Classifications

• • 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
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds

Definitions

• the present invention relates to a UV curable printing ink composition, a method for producing the same, and a cured film.
• UV-curable resin compositions in which an ultraviolet-curable resin, a pigment, etc. are mixed are known (for example, Patent Documents 1 to 3).
• Patent Document 1 describes a photocurable ink composition for a solder resist containing a photocurable resin as an essential component, characterized in that polymer fine particles having a Tg of 20° C. or less are dispersed in the composition.
• An ink composition for a liquid solder resist is disclosed.
• Patent Document 2 discloses a polymerizable compound characterized by being represented by a characteristic general formula.
• Patent Document 3 discloses a resin composition for liquid crystal sealing, which is characterized by containing a rubber-modified unsaturated compound, a coupling agent, a filler, and a photopolymerization initiator as essential components.
• One embodiment of the present invention was made in view of the above problems, and its purpose is to provide a UV curable printing ink composition that has excellent adhesion to a substrate.
• the present inventors have completed the present invention as a result of intensive studies to solve the above problems.
• a UV curable printing ink composition includes the following composition: A UV curable printing ink composition, which includes polymer fine particles (A) and a pigment (D), wherein the polymer fine particles (A) include an elastic body and a graft portion grafted to the elastic body.
• the elastic body includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber
• the graft portion includes a rubber-containing graft copolymer having: , an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate monomer.
• a UV curable printing ink composition, wherein the content of the pigment (D) in the curable printing ink composition is 1% by weight or more based on 100% by weight of the UV curable printing ink composition.
• UV curable printing ink composition that has excellent adhesion to a substrate.
• Water-based printing ink compositions can be printed on paper, but they cannot be printed on materials that the water-based printing ink compositions do not penetrate, such as plastic materials such as films and molded products, metal materials, and glass materials. I can't. Therefore, when printing on non-permeable substrates such as plastic materials, metal materials, and glass materials, inks containing solvents and UV-curable printing inks are often used.
• printing ink compositions containing aqueous printing ink compositions and solvents have the disadvantage of requiring a large amount of energy for evaporation and drying.
• UV-curable printing ink compositions have the advantage of being excellent in productivity because they are immediately cured by UV irradiation after the printing ink composition is applied to a substrate.
• UV-curable printing ink compositions do not require evaporation of the solvent after application, and the working environment is such that no solvent is contained in the waste liquid generated during the manufacturing process. It is also excellent from the viewpoint of improving environmental conditions and reducing environmental impact.
• UV curable printing ink compositions still have problems from the viewpoint of adhesion to substrates.
• the UV curable printing ink composition is cured by radical polymerization.
• radical polymerization ethylenic double bonds contained in monomers serving as reaction diluents react with each other to generate -CC- bonds, and the monomers are interconnected.
• significant volumetric shrinkage of about 10% occurs before and after curing of the UV-curable printing ink composition. Therefore, due to residual stress in the cured film (coating) obtained after curing of the UV-curable printing ink composition, the cured film may peel off from the substrate. That is, conventional UV curable printing ink compositions have the drawback of not having sufficient adhesion to substrates.
• One embodiment of the present invention was made in view of the above problems, and its purpose is to provide a novel UV curable printing ink composition that has excellent adhesion to a substrate.
• a UV-curable printing ink composition containing polymer fine particles (A), wherein the polymer fine particles (A) are composed of an elastic body and a UV-curable printing ink composition.
• a rubber-containing graft copolymer having a graft portion graft-bonded to an elastic body, the elastic body being selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber.
• the graft portion is derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers.
• the UV curable printing ink composition further includes a pigment (D), and the content of the pigment (D) in the UV curable printing ink composition is such that the UV curable printing ink composition further includes a pigment (D).
• a UV curable printing ink composition with excellent adhesion to a substrate can be obtained by making the UV curable printing ink composition 1% by weight or more based on 100% by weight of the mold printing ink composition. We have newly discovered this and completed the present invention.
• the present inventors have achieved the adhesion of the UV curable printing ink composition to the substrate and the color development of the cured film, which had been difficult until now, by having the UV curable printing ink composition having the above-mentioned structure. We have also found new knowledge that it is possible to achieve both.
• the UV curable printing ink composition is a UV curable printing ink composition, and includes polymer fine particles (A) and a pigment (D), and the polymer fine particles (A) are A rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body, the elastic body comprising a diene rubber, a (meth)acrylate rubber, and an organosiloxane rubber.
• the graft portion contains one or more selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers.
• the pigment (D) in the UV curable printing ink composition contains a polymer containing a structural unit derived from a monomer, and the content of the pigment (D) in the UV curable printing ink composition is 1% by weight based on 100% by weight of the UV curable printing ink composition. % or more.
• UV curable printing ink composition may be referred to as a "printing ink composition”
• a “UV curable printing ink composition according to an embodiment of the present invention” may be referred to as “this printing ink composition”.
• this printing ink composition Sometimes referred to as “things”.
• the UV curable printing ink composition can also be referred to as a UV curable printing ink composition or a UV curable printing ink composition.
• a substance obtained by curing a printing ink composition is referred to as a cured film.
• a cured film obtained by curing the present printing ink composition is also an embodiment of the present invention.
• the cured film according to an embodiment of the present invention may be referred to as "main cured film”.
• the cured film may also be referred to as a cured film, an ink film, or an ink film, and these terms have the same meaning.
• the present printing ink composition has the above-described structure, it has the advantage of excellent adhesion to the substrate.
• excellent adhesion to a base material means that when the adhesion test described later in Examples is conducted on a base material (for example, a PMMA (polymethyl methacrylate) sheet), It is intended that the result be 1 (fair) or higher, ie 2 (good) or 1 (fair).
• a base material for example, a PMMA (polymethyl methacrylate) sheet
• the result was 1 (fair) or higher, that is, 2 (good) or 1 ( It has the advantage of being (possible).
• the present printing ink composition may contain a solvent, it is preferable that the content of the solvent (for example, an organic solvent) is small.
• the content of the solvent (e.g., organic solvent) contained in the printing ink composition is preferably 10% by weight or less, more preferably 5% by weight or less, and 3% by weight based on 100% by weight of the printing ink composition. % or less, even more preferably 1% by weight or less, particularly preferably 0.1% by weight.
• the content of the solvent (e.g., organic solvent) in the present printing ink composition is within the above-mentioned range, there are the following advantages: (a) the amount of solvent discharged is reduced or eliminated, resulting in a reduction in environmental burden; (b) Since the drying step for removing the solvent is shortened or unnecessary, there is an advantage that productivity can be improved.
• the solvent e.g., organic solvent
• the polymer fine particles (A) include a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body.
• This printing ink composition has the advantage of being able to provide a cured film with excellent adhesion by containing the polymer fine particles (A). Although the reason for this is not clear, it is thought that the polymer fine particles (A) can reduce the residual stress in the cured film caused by the volumetric shrinkage that occurs in the cured film when the printing ink composition is cured.
• One embodiment is not limited to such speculation.
• the elastic body includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber.
• the elastic body may contain natural rubber in addition to the above-mentioned rubber.
• the elastic body can also be referred to as an elastic part or rubber particles.
• (Meth)acrylate as used herein means acrylate and/or methacrylate.
• the printing ink composition containing the polymer fine particles (A) can provide a cured film with excellent toughness and impact resistance.
• a cured film with excellent toughness and/or impact resistance can also be said to be a cured film with excellent durability.
• the diene rubber is an elastic body containing a structural unit derived from a diene monomer as a structural unit.
• the diene monomer can also be referred to as a conjugated diene monomer.
• the diene rubber contains 50 to 100% by weight of structural units derived from diene monomers out of 100% by weight of structural units, and other than diene monomers copolymerizable with diene monomers. It may contain 0 to 50% by weight of structural units derived from vinyl monomers.
• the diene rubber may contain, as a structural unit, a structural unit derived from a (meth)acrylate monomer in a smaller amount than the structural unit derived from a diene monomer.
• diene monomer examples include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), and 2-chloro-1,3-butadiene. These diene monomers may be used alone or in combination of two or more.
• vinyl monomers other than diene monomers examples include (a) styrene, ⁇ -methylstyrene; , vinyl arenes such as monochlorostyrene and dichlorostyrene; (b) vinyl carboxylic acids such as acrylic acid and methacrylic acid; (c) vinyl cyanates such as acrylonitrile and methacrylonitrile; (d) vinyl chloride, vinyl bromide, Vinyl halides such as chloroprene; (e) vinyl acetate; (f) alkenes such as ethylene, propylene, butylene, and isobutylene; (g) polyvinyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, Functional monomers, etc.
• the vinyl monomer A mentioned above may be used alone or in combination of two or more types. Among the vinyl monomers A mentioned above,
• the diene rubber is butadiene rubber (also referred to as polybutadiene rubber) consisting of constitutional units derived from 1,3-butadiene, or butadiene rubber which is a copolymer of 1,3-butadiene and styrene. Styrene rubber (also called polystyrene-butadiene) is preferred.
• the diene rubber butadiene rubber is more preferred. That is, it is preferable that the elastic body is butadiene rubber. According to the above configuration, the desired effect due to the elastic body of the polymer fine particles (A) containing the diene rubber can be further exhibited. Further, butadiene-styrene rubber is more preferable in that the transparency of the resulting cured film can be improved by adjusting the refractive index.
• case B A case where the elastic body contains (meth)acrylate rubber (case B) will be explained.
• case B the combination of various monomers allows a wide range of polymer designs for the elastomer.
• the (meth)acrylate rubber is an elastic body containing a structural unit derived from a (meth)acrylate monomer as a structural unit.
• the (meth)acrylate rubber contains 50 to 100% by weight of the structural units derived from the (meth)acrylate monomer out of 100% by weight of the structural units, and co-contains the (meth)acrylate monomer with the structural units derived from the (meth)acrylate monomer. It may contain 0 to 50% by weight of structural units derived from vinyl monomers other than polymerizable (meth)acrylate monomers.
• the (meth)acrylate rubber may contain, as a structural unit, a structural unit derived from a diene monomer in a smaller amount than the structural unit derived from a (meth)acrylate monomer. good.
• Examples of (meth)acrylate monomers include (a) methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl ( Alkyl (meth)acrylates such as meth)acrylate, stearyl (meth)acrylate, and behenyl (meth)acrylate; (b) Aromatic ring-containing (meth)acrylates such as phenoxyethyl (meth)acrylate and benzyl (meth)acrylate; (c) Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; (d) Glycidyl (meth)acrylates such as glycidyl (meth)acrylate and glycidyl alkyl (meth)acrylate; ) acrylates;
• (meth)acrylate monomers may be used alone or in combination of two or more.
• ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred, and butyl (meth)acrylate is more preferred.
• the (meth)acrylate rubber is preferably one or more selected from the group consisting of ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, and 2-ethylhexyl (meth)acrylate rubber.
• butyl (meth)acrylate rubber is more preferred.
• Ethyl (meth)acrylate rubber is a rubber consisting of constitutional units derived from ethyl (meth)acrylate
• butyl (meth)acrylate rubber is a rubber consisting of constitutional units derived from butyl (meth)acrylate.
• Meth)acrylate rubber is a rubber composed of structural units derived from 2-ethylhexyl (meth)acrylate.
• the glass transition temperature (Tg) of the elastic body is lowered, polymer fine particles (A) having a lower Tg can be obtained.
• the resulting printing ink composition containing the polymer fine particles (A) can provide a cured film with excellent toughness, and (b) the viscosity of the printing ink composition can be lowered. can.
• Vinyl monomers other than (meth)acrylate monomers that can be copolymerized with (meth)acrylate monomers include the vinyl monomers mentioned above. Examples include the monomers listed as Form A. Only one type of vinyl monomer B may be used, or two or more types may be used in combination. Among the vinyl monomers B, styrene is particularly preferred.
• case C A case where the elastic body contains an organosiloxane rubber (case C) will be explained.
• the printing ink composition can provide a cured film that has sufficient heat resistance and has excellent impact resistance at low temperatures.
• organosiloxane-based rubbers include (a) rubbers composed of alkyl- or aryl-disubstituted silyloxy units, such as (a) dimethylsilyloxy, diethylsilyloxy, methylphenylsilyloxy, diphenylsilyloxy, dimethylsilyloxy-diphenylsilyloxy; organosiloxane-based polymers, and (b) organosiloxane-based polymers composed of alkyl or aryl monosubstituted silyloxy units, such as organohydrogensilyloxy in which some of the alkyls in the side chains are substituted with hydrogen atoms. Can be mentioned. These organosiloxane polymers may be used alone or in combination of two or more.
• a polymer composed of dimethylsilyloxy units is referred to as dimethylsilyloxy rubber
• a polymer composed of methylphenylsilyloxy units is referred to as methylphenylsilyloxy rubber
• a polymer composed of dimethylsilyloxy units and diphenylsilyl A polymer composed of oxy units is called dimethylsilyloxy-diphenylsilyloxy rubber.
• the organosiloxane rubber (a) dimethylsilyloxy rubber, methylphenylsilyloxy rubber, and dimethylsilyloxy-diphenylsilyl are used because the printing ink composition can provide a cured film with excellent heat resistance. It is preferable to use one or more types selected from the group consisting of oxy rubbers, and (b) dimethylsilyloxy rubber is more preferable because it is easily available and economical.
• the polymer fine particles (A) preferably contain 80 wt% or more of organosiloxane rubber, and preferably contain 90 wt% or more of organosiloxane rubber based on 100 wt% of the elastic body contained in the polymer fine particles (A). It is more preferable that you do so.
• the printing ink composition can provide a cured film with excellent heat resistance.
• the elastic body includes butadiene rubber, butadiene-styrene rubber, butadiene-(meth)acrylate rubber, ethyl (meth)acrylate rubber, butyl (meth)acrylate rubber, and 2-ethylhexyl (meth)acrylate rubber.
• dimethylsilyloxy rubber, methylphenylsilyloxy rubber, and dimethylsilyloxy-diphenylsilyloxy rubber preferably one or more selected from the group consisting of butadiene rubber, butadiene-styrene rubber, butyl (meth)acrylate. More preferably, it is one or more selected from the group consisting of rubber and dimethylsilyloxy rubber.
• Crosslinked structure of elastic body Since the dispersion stability of the polymer fine particles (A) in the printing ink composition can be maintained, it is preferable that a crosslinked structure is introduced into the elastic body.
• a method for introducing a crosslinked structure into an elastic body commonly used methods can be employed, and examples include the following method. That is, in the production of an elastic body, there is a method in which a crosslinkable monomer such as a polyfunctional monomer and/or a mercapto group-containing compound is mixed with a monomer that can constitute the elastic body, and then polymerized. . In this specification, producing a polymer such as an elastomer is also referred to as polymerizing the polymer.
• methods for introducing a crosslinked structure into organosiloxane rubber include the following methods: (a) When polymerizing organosiloxane rubber, a polyfunctional alkoxysilane compound and other materials are combined. (b) A method in which a reactive group (for example, (a) a mercapto group and (b) a reactive vinyl group, etc.) is introduced into an organosiloxane rubber, and then the resulting reaction product is (a) A method of adding an organic peroxide or (b) a polymerizable vinyl monomer to cause a radical reaction, or (c) a method of adding a polyfunctional monomer when polymerizing an organosiloxane rubber. and/or a method in which a crosslinkable monomer such as a mercapto group-containing compound is mixed with other materials and then polymerized.
• a reactive group for example, (a) a mercapto group and (b) a reactive vinyl group, etc.
• a polyfunctional monomer can also be said to be a monomer that has two or more radically polymerizable reactive groups within the same molecule.
• the radically polymerizable reactive group is preferably a carbon-carbon double bond.
• Examples of polyfunctional monomers include (meth)acrylates having ethylenically unsaturated double bonds, such as allyl alkyl (meth) acrylates and allyloxyalkyl (meth) acrylates, but do not include butadiene. be done.
• Monomers having two (meth)acrylic groups include ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, and cyclohexanedimethanol.
• Di(meth)acrylates and polyethylene glycol di(meth)acrylates are mentioned.
• Examples of the polyethylene glycol di(meth)acrylates include triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol (600) di(meth)acrylate, etc. is exemplified.
• monomers having three (meth)acrylic groups include alkoxylated trimethylolpropane tri(meth)acrylates, glycerolpropoxytri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxy Examples include ethyl)isocyanurate tri(meth)acrylate.
• alkoxylated trimethylolpropane tri(meth)acrylates include trimethylolpropane tri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, and the like.
• examples of the monomer having four (meth)acrylic groups include pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and the like. Furthermore, examples of the monomer having five (meth)acrylic groups include dipentaerythritol penta(meth)acrylate. Furthermore, examples of the monomer having six (meth)acrylic groups include ditrimethylolpropane hexa(meth)acrylate. Examples of the polyfunctional monomer include diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, and the like.
• Examples of mercapto group-containing compounds include alkyl-substituted mercaptans, allyl-substituted mercaptans, aryl-substituted mercaptans, hydroxy-substituted mercaptans, alkoxy-substituted mercaptans, cyano-substituted mercaptans, amino-substituted mercaptans, silyl-substituted mercaptans, and acid-substituted mercaptans.
• Examples include mercaptan, halo group-substituted mercaptan, and acyl group-substituted mercaptan.
• the alkyl group-substituted mercaptan is preferably an alkyl group-substituted mercaptan having 1 to 20 carbon atoms, more preferably an alkyl group-substituted mercaptan having 1 to 10 carbon atoms.
• aryl group-substituted mercaptan phenyl group-substituted mercaptan is preferred.
• the alkoxy-substituted mercaptan is preferably an alkoxy-substituted mercaptan having 1 to 20 carbon atoms, more preferably an alkoxy-substituted mercaptan having 1 to 10 carbon atoms.
• the acid group-substituted mercaptan is preferably an alkyl group-substituted mercaptan having a carboxyl group and having 1 to 10 carbon atoms, or a mercaptan having a carboxyl group and having an aryl group having 1 to 12 carbon atoms.
• the glass transition temperature of the elastic body is preferably 80°C or lower, more preferably 70°C or lower, more preferably 60°C or lower, more preferably 50°C or lower, more preferably 40°C or lower, more preferably 30°C or lower, and 20°C or lower. °C or less, more preferably 10 °C or less, more preferably 0 °C or less, more preferably -20 °C or less, more preferably -40 °C or less, more preferably -45 °C or less, more preferably -50 °C or less.
• -55°C or less is more preferably -60°C or less, more preferably -65°C or less, more preferably -70°C or less, more preferably -75°C or less, more preferably -80°C or less, -85°C or lower is more preferred, -90°C or lower is more preferred, -95°C or lower is more preferred, -100°C or lower is more preferred, -105°C or lower is more preferred, -110°C or lower is more preferred, -115°C or lower
• the temperature is more preferably at most .degree. C., even more preferably at most -120.degree. C., particularly preferably at most -125.degree.
• glass transition temperature may be referred to as "Tg".
• Tg glass transition temperature
• polymer fine particles (A) having a low Tg can be obtained.
• the printing ink composition can provide a cured film with excellent toughness.
• the viscosity of the printing ink composition can be lowered.
• the Tg of the elastic body can be obtained by measuring viscoelasticity using a flat plate made of polymer fine particles (A). Specifically, Tg can be measured as follows: (1) A flat plate made of polymer fine particles (A) is measured using a dynamic viscoelasticity measuring device (for example, DVA-200 manufactured by IT Keizai Control Co., Ltd.).
• the peak temperature of tan ⁇ is taken as the glass transition temperature.
• the lowest peak temperature is taken as the glass transition temperature of the elastic body.
• the Tg of the elastic body is higher than 0°C because it is possible to suppress a decrease in the elastic modulus (rigidity) of the resulting cured film, that is, a cured film with sufficient elastic modulus (rigidity) can be obtained.
• the temperature is preferably 20°C or higher, even more preferably 50°C or higher, particularly preferably 80°C or higher, and most preferably 120°C or higher.
• the Tg of the elastic body can be determined by the composition of the structural units contained in the elastic body. In other words, by changing the composition of the monomers used when producing (polymerizing) the elastic body, the Tg of the resulting elastic body can be adjusted.
• the group of monomers that provides a homopolymer having a Tg larger than 0°C is defined as monomer group a.
• a group of monomers that provides a homopolymer having a Tg of less than 0° C. is referred to as monomer group b. 50 to 100% by weight (more preferably 65 to 99% by weight) of structural units derived from at least one monomer selected from monomer group a, and at least one selected from monomer group b.
• elastic body X An elastic body containing 0 to 50% by weight (more preferably 1 to 35% by weight) of structural units derived from one type of monomer is referred to as elastic body X.
• the elastic body X has a Tg greater than 0°C.
• the printing ink composition can provide a cured film having sufficient rigidity.
• a crosslinked structure is introduced into the elastic body.
• Examples of the method for introducing the crosslinked structure include the methods described above.
• Examples of monomers that can be included in the monomer group a include, but are not limited to, unsubstituted vinyl aromatic compounds such as styrene and 2-vinylnaphthalene; vinyl substituted compounds such as ⁇ -methylstyrene; Aromatic compounds; ring alkylated vinyl such as 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, etc.
• Aromatic compounds Ring alkoxylated vinyl aromatic compounds such as 4-methoxystyrene and 4-ethoxystyrene; Ring halogenated vinyl aromatic compounds such as 2-chlorostyrene and 3-chlorostyrene; 4-acetoxystyrene, etc.
• ring ester substituted vinyl aromatic compounds ring hydroxylated vinyl aromatic compounds such as 4-hydroxystyrene; vinyl esters such as vinyl benzoate and vinyl cyclohexanoate; vinyl halides such as vinyl chloride; acenaphthalene , aromatic monomers such as indene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and isopropyl methacrylate; aromatic methacrylates such as phenyl methacrylate; methacrylates such as isobornyl methacrylate and trimethylsilyl methacrylate; Examples include methacrylic monomers including methacrylic acid derivatives; certain acrylic esters such as isobornyl acrylate and tert-butyl acrylate; acrylic monomers including acrylic acid derivatives such as acrylonitrile; and the like.
• monomers that can be included in the monomer group a include acrylamide, isopropylacrylamide, N-vinylpyrrolidone, isobornyl methacrylate, dicyclopentanyl methacrylate, 2-methyl-2-adamantyl methacrylate, 1- Examples include monomers that can provide a homopolymer having a Tg of 120° C. or higher, such as adamantyl acrylate and 1-adamantyl methacrylate. These monomers a may be used alone or in combination of two or more.
• Examples of the monomer b include ethyl acrylate, butyl acrylate (also known as butyl acrylate), 2-ethylhexyl acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, etc. can be mentioned. These monomers b may be used alone or in combination of two or more. Among these monomers b, particularly preferred are ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate.
• the volume average particle diameter of the elastic body is preferably 0.03 ⁇ m to 50.00 ⁇ m, more preferably 0.05 ⁇ m to 10.00 ⁇ m, more preferably 0.08 ⁇ m to 2.00 ⁇ m, and even more preferably 0.10 ⁇ m to 1.00 ⁇ m. It is preferably 0.10 ⁇ m to 0.80 ⁇ m, even more preferably 0.10 ⁇ m to 0.50 ⁇ m.
• the volume average particle size of the elastic body is (a) 0.03 ⁇ m or more, an elastic body having a desired volume average particle size can be stably obtained; (b) when it is 50.00 ⁇ m or less, the elastic body can be obtained stably.
• the resulting cured film has good heat resistance and impact resistance.
• the volume average particle diameter of the elastic body can be measured using a dynamic light scattering particle size distribution measuring device or the like using an aqueous latex containing the elastic body as a sample.
• the method for measuring the volume average particle diameter of the elastic body will be described in detail in the Examples below.
• the proportion of the elastic body in the polymer microparticles (A) is preferably 40 to 97% by weight, more preferably 60 to 95% by weight, and more preferably 70 to 93% by weight, with the entire polymer microparticles (A) being 100% by weight. is even more preferable.
• the proportion of the elastic body is 40% by weight or more, the printing ink composition can provide a cured film with excellent toughness and impact resistance.
• the proportion of the elastic body is 97% by weight or less, the polymer fine particles (A) do not easily aggregate (do not easily aggregate), and therefore the printing ink composition does not have high viscosity. As a result, the printing ink composition may be easy to handle.
• the elastic body is preferably one that can swell in a suitable solvent but does not substantially dissolve in it.
• the elastic body is made of a low molecular compound (C), a radically polymerizable It is preferable that it is insoluble in the oligomer resin and inert resin (E).
• the elastic body preferably has a gel content of 60% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, and particularly preferably 95% by weight or more.
• the printing ink composition can provide a cured film with excellent toughness.
• the method for calculating gel content is as follows. First, an aqueous latex containing the polymer fine particles (A) is obtained, and then a granular material of the polymer fine particles (A) is obtained from the aqueous latex.
• the method for obtaining powdery particles of polymer fine particles (A) from aqueous latex is not particularly limited, but includes, for example, (i) agglomerating polymer fine particles (A) in the aqueous latex, and (ii) resulting Examples include a method of obtaining granular material of the polymer fine particles (A) by dehydrating the material and (iii) further drying the aggregate.
• MEK methyl ethyl ketone
• the obtained MEK melt is separated into a component soluble in MEK (MEK soluble component) and a component insoluble in MEK (MEK insoluble component).
• MEK soluble component component soluble in MEK
• MEK insoluble component component insoluble in MEK
• the obtained MEK lysate was subjected to centrifugation using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP60E) at a rotation speed of 30,000 rpm for 1 hour, and the lysate was then Separate into soluble and MEK-insoluble components.
• a centrifuge manufactured by Hitachi Koki Co., Ltd., CP60E
• the weight of the obtained MEK soluble content and MEK insoluble content is measured, and the gel content is calculated from the following formula.
• Gel content (%) (Weight of methyl ethyl ketone insoluble matter)/ ⁇ (Weight of methyl ethyl ketone insoluble matter)+(Weight of methyl ethyl ketone soluble matter) ⁇ 100.
• a polymer grafted to an elastic body is referred to as a graft portion.
• the graft portion contains, as a structural unit, a structural unit derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers. Contains polymers. Since the graft section has the above configuration, it can play various roles. "Various roles" include, for example, (a) improving the compatibility between the resin component in the printing ink composition and the polymer fine particles (A), (b) in the printing ink composition and in the cured film. (c) to improve the dispersibility of the polymer fine particles (A), and (c) to enable the polymer fine particles (A) to be dispersed in the state of primary particles in the printing ink composition and the cured film; etc.
• aromatic vinyl monomers include styrene, ⁇ -methylstyrene, p-methylstyrene, and divinylbenzene.
• vinyl cyan monomers include acrylonitrile and methacrylonitrile.
• the (meth)acrylate monomer examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxybutyl (meth)acrylate.
• the above-mentioned one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers may be used alone; You may use combinations of more than one species.
• the grafting part is composed of a total of structural units derived from an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate monomer as structural units.
• the content is preferably 10 to 95% by weight, more preferably 30 to 92% by weight, even more preferably 50 to 90% by weight, particularly preferably 60 to 87% by weight, and 70% by weight. Most preferably, the content is 85% by weight.
• the graft portion contains, as a structural unit, a structural unit derived from a monomer having a reactive group.
• the monomer having the reactive group includes an epoxy group, an oxetane group, a hydroxyl group, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester, a cyclic amide, a benzoxazine group, and a cyanate ester group.
• the monomer preferably has one or more reactive groups selected from the group consisting of epoxy groups, hydroxyl groups, and carboxylic acid groups. A monomer is more preferable, and a monomer having an epoxy group is most preferable.
• monomers having epoxy groups include glycidyl group-containing vinyl monomers such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and allyl glycidyl ether.
• monomers having hydroxyl groups include (a) hydroxy linear alkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; Acrylate (especially hydroxy linear C1-6 alkyl (meth)acrylate); (b) caprolactone-modified hydroxy (meth)acrylate; (c) methyl ⁇ -(hydroxymethyl)acrylate, ethyl ⁇ -(hydroxymethyl)acrylate Hydroxy branched alkyl (meth)acrylates such as (d) mono(meth)acrylates of polyester diols (especially saturated polyester diols) obtained from divalent carboxylic acids (phthalic acid, etc.) and dihydric alcohols (propylene glycol, etc.), etc. Examples include hydroxyl group-containing (meth)acrylates.
• hydroxy linear alkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, hydroxypropy
• monomers having carboxylic acid groups include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, and dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid.
• monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid
• dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid.
• the monomer having a carboxylic acid group the monocarboxylic acids mentioned above are preferably used.
• the monomers having the above-mentioned reactive groups may be used alone or in combination of two or more.
• the graft portion preferably contains 0.5 to 90 weight %, more preferably 1 to 50 weight %, of a structural unit derived from a monomer having a reactive group based on 100 weight % of the graft portion. It is more preferably contained in an amount of up to 35% by weight, and particularly preferably in an amount of 3 to 20% by weight.
• the printing ink composition can form a cured film having sufficient impact resistance. can be provided.
• the printing ink composition provides a cured film having sufficient impact resistance. It has the advantage that the printing ink composition can have good storage stability.
• the structural unit derived from a monomer having a reactive group is preferably contained in the graft portion, and more preferably contained only in the graft portion.
• the graft portion may contain a structural unit derived from a polyfunctional monomer as a structural unit.
• a structural unit derived from a polyfunctional monomer swelling of the polymer fine particles (A) can be prevented in the printing ink composition, (b) printing ink composition Because the viscosity of the printing ink composition is lower, the handling properties of the printing ink composition tend to be better, and (c) the dispersibility of the polymer fine particles (A) in the printing ink composition is improved.
• the printing ink composition has better toughness and durability than when the graft part contains a structural unit derived from a polyfunctional monomer.
• a cured film with better impact resistance can be provided.
• polyfunctional monomer examples include the same monomers as the above-mentioned polyfunctional monomers.
• these polyfunctional monomers allyl methacrylate, butylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, butane diol di (meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and polyethylene glycol di(meth)acrylates.
• These polyfunctional monomers may be used alone or in combination of two or more.
• the graft portion preferably contains 1 to 20 weight %, more preferably 5 to 15 weight %, of a structural unit derived from a polyfunctional monomer based on 100 weight % of the graft portion.
• the above-mentioned monomers may be used alone or in combination of two or more.
• the graft portion may contain structural units derived from other monomers.
• the glass transition temperature of the graft portion is preferably 190°C or lower, more preferably 160°C or lower, more preferably 140°C or lower, more preferably 120°C or lower, preferably 80°C or lower, more preferably 70°C or lower, and 60°C or lower.
• the following are more preferred, more preferably 50°C or less, more preferably 40°C or less, more preferably 30°C or less, more preferably 20°C or less, more preferably 10°C or less, more preferably 0°C or less, -20°C
• the following are more preferred, more preferably -40°C or lower, more preferably -45°C or lower, more preferably -50°C or lower, more preferably -55°C or lower, more preferably -60°C or lower, and -65°C or lower.
• the glass transition temperature of the graft portion is preferably 0°C or higher, more preferably 30°C or higher, more preferably 50°C or higher, even more preferably 70°C or higher, even more preferably 90°C or higher, and particularly preferably 110°C or lower. preferable.
• the Tg of the graft portion can be determined by the composition of the structural units contained in the graft portion. In other words, by changing the composition of the monomers used when producing (polymerizing) the graft part, the Tg of the resulting graft part can be adjusted.
• the Tg of the graft portion can be obtained by measuring viscoelasticity using a flat plate made of polymer fine particles (A). Specifically, Tg can be measured as follows: (1) A flat plate made of polymer fine particles (A) is measured using a dynamic viscoelasticity measuring device (for example, DVA-200 manufactured by IT Keizai Control Co., Ltd.). ) to perform dynamic viscoelasticity measurement under tensile conditions to obtain a tan ⁇ graph; (2) Regarding the obtained tan ⁇ graph, the peak temperature of tan ⁇ is taken as the glass transition temperature.
• the highest peak temperature is taken as the glass transition temperature of the graft portion.
• the polymer fine particles (A) are polymers having the same structure as the graft portion, and may include a polymer that is not grafted to the elastic body.
• a polymer having the same structure as the graft portion and not grafted to the elastic body is also referred to as a non-grafted polymer.
• the non-grafted polymer also constitutes a part of the polymer fine particles (A) according to one embodiment of the present invention.
• the non-grafted polymer can also be said to be a polymer that is not graft-bonded to the elastic body among the polymers produced in the polymerization of the graft portion.
• the proportion of the polymer grafted to the elastic body that is, the proportion of the graft portion is referred to as the graft ratio.
• the graft ratio can also be said to be a value expressed by (weight of grafted part)/ ⁇ (weight of grafted part)+(weight of non-grafted polymer) ⁇ 100.
• the graft ratio of the graft portion is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
• the grafting rate is 70% or more, there is an advantage that the viscosity of the printing ink composition does not become too high.
• the method for calculating the graft ratio is as follows. First, an aqueous latex containing the polymer fine particles (A) is obtained, and then a granular material of the polymer fine particles (A) is obtained from the aqueous latex. Specifically, the method for obtaining granular material of polymer fine particles (A) from aqueous latex includes (i) coagulating the polymer fine particles (A) in the aqueous latex, and (ii) coagulating the resulting coagulation. Examples include a method of obtaining granular material of the polymer fine particles (A) by dehydrating the material and (iii) further drying the coagulated material.
• MEK methyl ethyl ketone
• the obtained MEK melt is separated into a component soluble in MEK (MEK soluble component) and a component insoluble in MEK (MEK insoluble component).
• MEK soluble component component soluble in MEK
• MEK insoluble component component insoluble in MEK
• the obtained MEK lysate was subjected to centrifugation using a centrifuge (manufactured by Hitachi Koki Co., Ltd., CP60E) at a rotation speed of 30,000 rpm for 1 hour, and the lysate was then Separate into soluble and MEK-insoluble components.
• a centrifuge manufactured by Hitachi Koki Co., Ltd., CP60E
• Grafting ratio (%) 100-[(FP amount)/ ⁇ (FP amount)+(weight of MEK insoluble matter) ⁇ ]/(weight of polymer in grafted part) ⁇ 10,000.
• the weight of the polymer other than the graft portion is the charged amount of the monomer constituting the polymer other than the graft portion.
• the polymer other than the graft portion is, for example, an elastic body.
• the polymer fine particles (A) include a surface crosslinked polymer described below, the polymer other than the graft portion includes both the elastic body and the surface crosslinked polymer.
• the weight of the polymer in the graft section is the amount of monomers constituting the polymer in the graft section.
• the method of coagulating the polymer fine particles (A) is not particularly limited, and a method using a solvent, a method using a coagulant, a method of spraying an aqueous latex, etc. may be used.
• the elastic body and the graft portion are polymerized in this order in the production of the polymer fine particles (A)
• at least a portion of the graft portion can cover at least a portion of the elastic body in the obtained polymer fine particles (A).
• the polymer fine particles (A) obtained by multistage polymerization of an elastic body and a graft portion can also be called a multistage polymer.
• the graft portion may cover at least a portion of the elastic body or may cover the entire elastic body.
• the polymer fine particles (A) are a multistage polymer, a part of the graft portion may enter inside the elastic body.
• the elastic body and the graft portion may form a layered structure.
• the elastic body forms the innermost layer (also referred to as a core layer) and a layer of the graft portion is formed as the outermost layer (also referred to as a shell layer) on the outside of the elastic body is also an aspect of the present invention.
• a structure in which the elastic body is the core layer and the graft portion is the shell layer can also be called a core-shell structure.
• the polymer particles (A) in which the elastic body and the graft portion form a layered structure (core-shell structure) can also be said to be a multilayer polymer or a core-shell polymer. That is, in one embodiment of the present invention, the polymer fine particles (A) may be a multistage polymer, and/or a multilayer polymer or a core-shell polymer. However, as long as the graft portion is graft-bonded to the elastic body, the polymer fine particles (A) are not limited to the above configuration.
• At least a portion of the graft portion covers at least a portion of the elastic body.
• at least a portion of the graft portion is preferably present on the outermost side of the polymer fine particles (A).
• the rubber-containing graft copolymer further includes a surface crosslinked polymer in addition to the elastic body and the graft portion grafted to the elastic body.
• the polymer fine particles (A) further include a surface crosslinked polymer in addition to the elastic body and the graft portion grafted to the elastic body.
• the blocking resistance can be improved in the production of the polymer fine particles (A)
• the dispersibility of the polymer fine particles (A) in the printing ink composition can be improved.
• the polymer fine particles (A) may also have the following effects: (a) an effect of lowering the viscosity of the printing ink composition, (b) an effect of increasing the crosslinking density in the elastic body. , and (c) the effect of increasing the graft efficiency of the graft section.
• the crosslinking density in an elastic body means the number of crosslinked structures in the entire elastic body.
• the surface crosslinked polymer contains, as structural units, 30 to 100% by weight of structural units derived from polyfunctional monomers and 0 to 70% by weight of structural units derived from other vinyl monomers, totaling 100% by weight. It consists of a polymer containing % by weight.
• polyfunctional monomers that can be used in the polymerization of the surface-crosslinked polymer include the same monomers as the above-mentioned polyfunctional monomers.
• polyfunctional monomers that can be preferably used for polymerization of surface crosslinked polymers include allyl methacrylate, ethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate (e.g. (1,3-butylene glycol dimethacrylate, etc.), butanediol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, and polyethylene glycol di(meth)acrylates.
• These polyfunctional monomers may be used alone or in combination of two or more.
• the polymer fine particles (A) may contain a surface crosslinked polymer polymerized independently of the polymerization of the rubber-containing graft copolymer, or a surface crosslinked polymer polymerized together with the rubber-containing graft copolymer. May include merging.
• the polymer fine particles (A) may be a multistage polymer obtained by performing multistage polymerization of an elastic body, a surface crosslinked polymer, and a graft portion in this order. In any of these embodiments, the surface crosslinked polymer may cover at least a portion of the elastic body.
• the surface crosslinked polymer can also be considered as part of the elastic body.
• the surface crosslinked polymer can be regarded as a part of the rubber-containing graft copolymer, and can also be said to be a surface crosslinked polymer portion.
• the graft portion may be (a) graft-bonded to an elastic body other than the surface-crosslinked polymer, and (b) graft-bonded to the surface-crosslinked polymer. (c) It may be graft-bonded to both the elastic body other than the surface-crosslinked polymer and the surface-crosslinked polymer.
• the polymer fine particles (A) contain a surface crosslinked polymer
• the volume average particle diameter of the elastic body mentioned above is intended to be the volume average particle diameter of the elastic body containing the surface crosslinked polymer.
• case D in which the polymer fine particles (A) are a multistage polymer obtained by performing multistage polymerization of an elastic body, a surface crosslinked polymer, and a graft portion in this order will be described.
• the surface crosslinked polymer may cover a portion of the elastic body or may cover the entire elastic body.
• a part of the surface crosslinked polymer may have entered the inside of the elastic body.
• the graft portion may cover a portion of the surface-crosslinked polymer or may cover the entire surface-crosslinked polymer.
• a part of the graft portion may be inside the surface crosslinked polymer.
• the elastic body, surface crosslinked polymer, and graft portion may have a layered structure.
• the elastic body is the innermost layer (core layer)
• the surface crosslinked polymer layer is present as an intermediate layer on the outside of the elastic body
• the graft portion layer is the outermost layer (shell layer) outside the surface crosslinked polymer.
• the present embodiment is also an embodiment of the present invention.
• the volume average particle diameter (Mv) of the polymer fine particles (A) is preferably 0.03 ⁇ m to 50.00 ⁇ m, and 0.03 ⁇ m to 50.00 ⁇ m, since it is possible to obtain a highly stable printing ink composition having a desired viscosity. More preferably 0.05 ⁇ m to 10.00 ⁇ m, more preferably 0.08 ⁇ m to 2.00 ⁇ m, even more preferably 0.10 ⁇ m to 1.00 ⁇ m, even more preferably 0.10 ⁇ m to 0.80 ⁇ m, even more preferably 0.10 ⁇ m to 0.00 ⁇ m. Particularly preferred is 50 ⁇ m.
• the volume average particle diameter (Mv) of the polymer fine particles (A) is intended to mean the volume average particle diameter of the primary particles of the polymer fine particles (A), unless otherwise specified. do.
• the volume average particle diameter of the polymer fine particles (A) can be measured using a dynamic light scattering particle size distribution measuring device or the like using an aqueous latex containing the polymer fine particles (A) as a sample.
• the volume average particle diameter of the polymer fine particles (A) will be described in detail in the Examples below.
• the volume average particle diameter of the polymer fine particles (A) is measured by cutting the cured film of the printing ink composition, imaging the cut surface using an electron microscope, etc., and using the obtained imaging data (imaged image). You can also do that.
• the number distribution of the volume average particle diameter of the polymer fine particles (A) has a half width of 0.5 times or more and 1 time or less of the volume average particle diameter, since a printing ink composition with low viscosity and easy to handle is obtained. It is preferable.
• the polymer fine particles (A) can be produced by polymerizing an elastic body and then graft-polymerizing a polymer constituting the graft portion to the elastic body in the presence of the elastic body.
• the method for producing the polymer fine particles (A) (polymerization method) will be explained by taking as an example the method for producing an aqueous latex of the polymer fine particles (A) that can be suitably used for producing the printing ink composition described later. do.
• the polymer fine particles (A) can be produced by a known method, for example, an emulsion polymerization method, a suspension polymerization method, a microsuspension polymerization method, or the like.
• the polymerization of the elastic body, the polymerization of the graft portion (graft polymerization), and the polymerization of the surface crosslinked polymer in the polymer fine particles (A) can be carried out using known methods such as emulsion polymerization, suspension polymerization, This can be carried out by a method such as a microsuspension polymerization method.
• the emulsion polymerization method is particularly preferred as a method for producing the polymer fine particles (A).
• compositional design of the polymer fine particles (A) is easy
• industrial production of the polymer fine particles (A) is easy
• manufacturing of printing ink compositions It has the advantage that an aqueous latex of polymer fine particles (A) that can be suitably used for is easily obtained.
• a method for producing an elastic body, a graft portion, and a surface crosslinked polymer having an arbitrary structure that may be included in the polymer fine particles (A) will be described.
• the elastic body contains at least one selected from the group consisting of diene rubber and (meth)acrylate rubber.
• the elastic body can be manufactured, for example, by a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization, and the method described in WO2005/028546 can be used as the manufacturing method. .
• the elastic body contains organosiloxane rubber.
• the elastic body can be manufactured by a method such as emulsion polymerization, suspension polymerization, or microsuspension polymerization, and the method described in WO2006/070664 can be used as the manufacturing method. .
• the graft portion can be formed, for example, by polymerizing monomers used for forming the graft portion by known radical polymerization.
• the polymerization of the graft portion is preferably carried out by an emulsion polymerization method.
• the graft portion can be manufactured, for example, according to the method described in WO2005/028546.
• a method for manufacturing a graft section will be described when the graft section is composed of a plurality of types of graft sections (for example, graft section 1 , graft section 2 , . . . , graft section n ).
• graft part 1 , graft part 2 , ..., graft part n are each polymerized separately by the above-mentioned method, and then mixed and composited to form a graft part consisting of multiple types of graft parts. (composite) may be produced.
• the surface crosslinked polymer can be formed by polymerizing monomers used for forming the surface crosslinked polymer by known radical polymerization.
• the surface crosslinked polymer is preferably polymerized by emulsion polymerization.
• a known emulsifier can be used for producing the polymer microparticles (A).
• emulsifiers include anionic emulsifiers, nonionic emulsifiers, polyvinyl alcohol, alkyl-substituted cellulose, polyvinylpyrrolidone, polyacrylic acid derivatives, and the like.
• anionic emulsifier include sulfur-based emulsifiers, phosphorus-based emulsifiers, sarcosic acid-based emulsifiers, and carboxylic acid-based emulsifiers.
• sulfur emulsifier include sodium dodecylbenzenesulfonate (abbreviation: SDBS).
• examples of the phosphorus emulsifier include polyoxyethylene lauryl ether sodium phosphate.
• a thermal decomposition type initiator can be used for producing the polymer fine particles (A).
• the thermal decomposition type initiator may be a known initiator such as (a) 2,2'-azobisisobutyronitrile, and (b) peroxides such as organic peroxides and inorganic peroxides. Agents can be mentioned.
• the organic peroxides include t-butyl peroxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and t-butyl peroxide. Examples include hexyl peroxide.
• the inorganic peroxide include hydrogen peroxide, potassium persulfate, ammonium persulfate, and the like.
• a redox type initiator can also be used in the production of the polymer fine particles (A).
• the redox type initiator includes (a) peroxides such as organic peroxides and inorganic peroxides, and (b) transition metal salts such as iron (II) sulfate, sodium formaldehyde sulfoxylate, glucose, etc. This is an initiator used in combination with a reducing agent. Further, if necessary, a chelating agent such as disodium ethylenediaminetetraacetate, and a phosphorus-containing compound such as sodium pyrophosphate may be used in combination.
• a redox type initiator When a redox type initiator is used, polymerization can be carried out even at a low temperature at which the peroxide is not substantially thermally decomposed, and the polymerization temperature can be set within a wide range. Therefore, it is preferable to use a redox type initiator.
• redox type initiators using organic peroxides such as cumene hydroperoxide, dicumyl peroxide, paramenthane hydroperoxide, and t-butyl hydroperoxide as peroxides are preferred.
• the amount of the initiator used, and when a redox type initiator is used, the amount of the reducing agent, transition metal salt, chelating agent, etc. used can be within known ranges.
• chain transfer agents When using a polyfunctional monomer in the polymerization of an elastomer, graft portion, or surface crosslinked polymer for the purpose of introducing a crosslinked structure into the elastomer, graft portion, or surface crosslinked polymer, known chain transfer agents may be used. It can be used within the range of usage amount. By using a chain transfer agent, the molecular weight and/or degree of crosslinking of the resulting elastic body, graft portion, or surface crosslinked polymer can be easily adjusted.
• a surfactant can be used in the production of the polymer fine particles (A).
• the type and amount of the surfactant used are within known ranges.
• the content of the polymer fine particles (A) is preferably 1.0% by weight or more, and 1.5% by weight based on 100% by weight of the UV curable printing ink composition. % or more, more preferably 2.0% by weight or more, and particularly preferably 2.5% by weight or more.
• This configuration has the advantage that the adhesiveness of the cured film to the base material is excellent.
• the content of the polymer fine particles (A) is preferably 10.0% by weight or less, and 8.0% by weight or less based on 100% by weight of the UV curable printing ink composition. % or less, even more preferably 6.0% by weight or less, particularly preferably 4.0% by weight or less.
• This configuration has the advantage that the hardness of the cured film can be maintained at a high level.
• the present printing ink composition further contains a resin (B).
• the resin (B) is preferably contained in the powder of the polymer fine particles (A) described below.
• the granular material of the polymer fine particles (A) contains the resin (B).
• the resin (B) may be, for example, a thermosetting resin, a thermoplastic resin, or any combination of a thermosetting resin and a thermoplastic resin.
• thermosetting resin in resin (B) is not particularly limited, but preferably includes at least one selected from the group consisting of epoxy resins, phenol resins, polyol resins, and amino-formaldehyde resins.
• examples of the thermosetting resin in the resin (B) include resins containing polymers obtained by polymerizing aromatic polyester raw materials. In the resin (B), only one type of thermosetting resin may be used, or two or more types may be used in combination.
• Epoxy resin The epoxy resin is not particularly limited as long as it has at least one epoxy group in its molecule.
• epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, novolac epoxy resin, Glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, hydrogenated bisphenol A (or F) type epoxy resin, fluorinated epoxy resin, rubber modified epoxy resin containing polybutadiene or NBR, glycidyl ether of tetrabromobisphenol A, etc.
• Flame-retardant epoxy resin p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane-modified epoxy resin with urethane bond, various alicyclic epoxy resins, polyvalent Examples include glycidyl ethers of alcohols, hydantoin type epoxy resins, epoxidized products of unsaturated polymers such as petroleum resins, and aminoglycidyl ether resins.
• Examples of the polyhydric alcohol include N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, and glycerin.
• Examples of the epoxy resin include epoxy compounds obtained by adding bisphenols A (or F), polybasic acids, or the like to the above-mentioned epoxy resin.
• the epoxy resin is not limited to these, and commonly used epoxy resins may be used. These epoxy resins may be used alone or in combination of two or more.
• epoxy resins those having at least two epoxy groups in one molecule have high reactivity in curing the printing ink composition, and the resulting cured film tends to form a three-dimensional network.
• epoxy resins having at least two epoxy groups in one molecule epoxy resins containing bisphenol type epoxy resins as a main component are preferred because they are economical and easily available.
• the phenol resin is not particularly limited as long as it is a compound obtained by reacting phenols and aldehydes.
• Phenols are not particularly limited, but include, for example, phenol, orthocresol, metacresol, para-cresol, xylenol, para-tert-butylphenol, para-octylphenol, para-phenylphenol, bisphenol A, bisphenol F, and resorcinol.
• Particularly preferred phenols include phenol and cresol.
• the aldehydes are not particularly limited, but include, for example, formaldehyde, acetaldehyde, butyraldehyde, acrolein, and mixtures thereof.
• the aldehydes the above-mentioned substances that are sources of aldehydes or solutions of these aldehydes can also be used.
• formaldehyde is preferable because it is easy to operate when reacting phenols and aldehydes.
• the molar ratio (F/R) between phenols (P) and aldehydes (R) is not particularly limited.
• the reaction molar ratio (F/R) is preferably from 0.4 to 1.0, more preferably from 0.5 to 0.8.
• the reaction molar ratio (F/R) is preferably from 0.4 to 4.0, more preferably from 0.8 to 2.5.
• the reaction molar ratio when the reaction molar ratio is below the upper limit, the molecular weight of the phenol resin does not become too large and the softening point does not become too high, so that sufficient fluidity can be obtained during heating. Furthermore, when the reaction molar ratio is below the upper limit, the molecular weight can be easily controlled and there is no possibility of gelation or partial gelation due to reaction conditions.
• a polyol resin is a compound having two or more active hydrogen atoms at its terminal, and is a bifunctional or higher-functional polyol with a molecular weight of about 50 to 20,000.
• Examples of the polyol resin include aliphatic alcohols, aromatic alcohols, polyether polyols, polyester polyols, polyolefin polyols, and acrylic polyols.
• the aliphatic alcohol may be either a dihydric alcohol or a trihydric or higher alcohol (trihydric alcohol, tetrahydric alcohol, etc.).
• dihydric alcohols include (a) ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Alkylene glycols (especially alkylene glycols having about 1 to 6 carbon atoms) such as 3-methyl-1,5-pentanediol and neopentyl glycol, and (b) two or more molecules of the alkylene glycol compound (e.g.
• trihydric alcohol examples include glycerin, trimethylolpropane, trimethylolethane, and 1,2,6-hexanetriol (particularly trihydric alcohols having about 3 to 10 carbon atoms).
• tetrahydric alcohol examples include pentaerythritol and diglycerin.
• saccharides such as monosaccharides, oligosaccharides, and polysaccharides.
• aromatic alcohol examples include bisphenols such as bisphenol A and bisphenol F; biphenyls such as dihydroxybiphenyl; polyhydric phenols such as hydroquinone and phenol formaldehyde condensate; naphthalene diol, and the like.
• polyether type polyols include those obtained by ring-opening polymerization of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc. in the presence of (a) one or more initiators containing active hydrogen. Examples include random copolymers, block copolymers, and (b) mixtures of these copolymers.
• initiators containing active hydrogen used in ring-opening polymerization of polyether type polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1, Diols such as 6-hexanediol, neopentyl glycol, and bisphenol A; Triols such as trimethylolethane, trimethylolpropane, and glycerin; Saccharides such as monosaccharide, oligosaccharide, and polysaccharide; Sorbitol; Ammonia, ethylenediamine, urea, and monomethyl Examples include amines such as diethanolamine and monoethyldiethanolamine.
• polyester-type polyols include polycondensates obtained by polycondensing a polybasic acid and/or anhydride of a polybasic acid with a polyhydric alcohol in the presence of an esterification catalyst in a temperature range of 150 to 270°C.
• One example is merging.
• the polybasic acid include maleic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, dodecanedioic acid, isophthalic acid, and azelaic acid.
• polyester polyols examples include (a) ring-opening polymers such as ⁇ -caprolactone and valerolactone, and (b) active hydrogen compounds having two or more active hydrogens such as polycarbonate diol and castor oil. It will be done.
• polyolefin polyols examples include polybutadiene polyols, polyisoprene polyols, and hydrogenated products thereof.
• acrylic polyols examples include (a) hydroxyl group-containing monomers such as hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylate, and vinylphenol, and (b) n-butyl (meth)acrylate and 2-ethylhexyl. Examples include copolymers with general-purpose monomers such as (meth)acrylate, and mixtures of these copolymers.
• polyether-type polyols are preferred because the printing ink composition has a low viscosity and is excellent in workability, and the printing ink composition can provide a cured film with an excellent balance between hardness and toughness.
• polyester type polyols are preferred because the printing ink composition can provide a cured film with excellent adhesiveness.
• the amino-formaldehyde resin is not particularly limited as long as it is a compound obtained by reacting an amino compound and an aldehyde under an alkaline catalyst.
• the amino compounds include melamine; 6-substituted guanamines such as guanamine, acetoguanamine, and benzoguanamine; CTU guanamine (3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)); ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane), CMTU guanamine (3,9-bis[(3,5-diamino-2,4,6-diazaphenyl)methyl]- Examples include amine-substituted triazine compounds such as 2,4,8,10-tetraoxaspiro[5,5]undecane); ureas such as urea, thiourea, and
• amino compound (a) a substituted melamine compound in which the hydrogen of the amino group of melamine is substituted with an alkyl group, an alkenyl group, and/or a phenyl group (U.S. Pat. No. 5,998,573 (corresponding Japanese publication) ), and (b) substituted melamine in which the hydrogen of the amino group of melamine is substituted with a hydroxyalkyl group, a hydroxyalkyloxyalkyl group, and/or an aminoalkyl group.
• Compounds (described in US Pat. No. 5,322,915 (corresponding Japanese publication: JP-A-5-202157)) can also be used.
• the amino compounds are preferably polyfunctional amino compounds such as melamine, guanamine, acetoguanamine, and benzoguanamine, and melamine is particularly preferred, since they are industrially produced and inexpensive.
• the above-mentioned amino compounds may be used alone or in combination of two or more.
• phenols such as phenol, cresol, alkylphenol, resorcinol, hydroquinone, and pyrogallol
• aniline, etc. may be additionally used.
• aldehydes examples include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde, and furfural.
• formaldehyde and paraformaldehyde are preferred because they are inexpensive and have good reactivity with the above-mentioned amino compounds.
• the aldehyde is preferably used in an amount of 1.1 to 6.0 mol, preferably 1.2 to 4.0 mol, per effective aldehyde group per 1 mol of the amino compound. It is particularly preferable.
• aromatic polyester raw material examples include aromatic vinyl compounds, (meth)acrylic acid derivatives, vinyl cyanide compounds, radically polymerizable monomers such as maleimide compounds, dimethyl terephthalate, alkylene glycols, and the like.
• (meth)acrylic acid means acrylic acid and/or methacrylic acid.
• the thermosetting resin in the resin (B) includes a reactive group (for example, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester, a cyclic amide, a benzoxazine
• a reactive group for example, an epoxy group, an oxetane group, a hydroxyl group, an amino group, an imide group, a carboxylic acid group, a carboxylic acid anhydride group, a cyclic ester, a cyclic amide, a benzoxazine
• Compounds having one compound are also included.
• thermosetting resin in resin (B) also contains a reactive group-ethylenically unsaturated bond-containing monomer.
• Compounds having reactive groups also include thermosetting resins such as the above-mentioned epoxy resins, phenol resins, polyol resins, amino-formaldehyde resins, and resins containing polymers obtained by polymerizing aromatic polyester raw materials.
• the reactive group-ethylenically unsaturated bond-containing monomer is one or more selected from the group consisting of epoxy resins, phenol resins, polyol resins, amino-formaldehyde resins, and polymers obtained by polymerizing aromatic polyester raw materials.
• it may be a compound obtained by bonding ethylenically unsaturated monomers by a method other than radical polymerization.
• Examples of the reactive group-ethylenically unsaturated bond-containing monomer include unsaturated polyester resin, vinyl ester resin, and epoxy acrylate. These may be used alone or in combination of two or more.
• thermoplastic resin in the resin (B) examples include acrylic polymers, vinyl copolymers, polycarbonates, polyamides, polyesters, polyphenylene ethers, polyurethanes, and polyvinyl acetates. These may be used alone or in combination of two or more.
• the acrylic polymer is a polymer whose main component is a structural unit consisting of an acrylic acid ester monomer.
• the acrylic acid ester monomer preferably has 1 to 20 carbon atoms in the ester moiety.
• the acrylic polymer includes (a) a homopolymer of an acrylic ester monomer, (b) an acrylic ester monomer, an unsaturated fatty acid, an acrylamide monomer, a maleimide monomer, and acetic acid.
• Examples include monomers such as vinyl or copolymers with vinyl copolymers (hereinafter also referred to as acrylic copolymers).
• acrylic acid ester monomers examples include methyl acrylate (MA), ethyl acrylate (EA), 2-ethylhexyl acrylate (2EHA), acrylic acid (AA), methacrylic acid (MAA), and 2-acrylic acid.
• the acrylic copolymer (a) a structural unit derived from an acrylic acid ester monomer (structural unit (a)), and (b) an unsaturated fatty acid, an acrylamide monomer, a maleimide monomer, and acetic acid.
• the ratio of the structural unit (b) derived from a monomer such as vinyl or a vinyl copolymer is 50% to 100% by weight for the structural unit (a), and 50% to 100% by weight for the structural unit (b). 0% to 50% by weight is preferred.
• the acrylic polymer preferably contains structural units derived from butyl acrylate (BA) in an amount of 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, and 80% by weight or more. It is particularly preferably contained in an amount of 90% by weight or more, most preferably 90% by weight or more.
• BA butyl acrylate
• the vinyl copolymer is a vinyl monomer containing one or more selected from the group consisting of an aromatic vinyl monomer, a cyanide vinyl monomer, and an unsaturated carboxylic acid alkyl ester monomer. obtained by copolymerizing a mixture of The vinyl monomer mixture may further contain other monomers (hereinafter also referred to as monomer C) that are copolymerizable with the above-mentioned monomers.
• aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, t-butylstyrene, vinyltoluene, and the like. These vinyl monomers may be used alone or in combination of two or more. Among these, aromatic vinyl monomers are preferred, and styrene is more preferred, from the viewpoint that the refractive index can be easily increased.
• the unsaturated carboxylic acid alkyl ester monomer is not particularly limited.
• esters of alcohols having 1 to 6 carbon atoms and acrylic acid or methacrylic acid are preferred.
• the ester of an alcohol having 1 to 6 carbon atoms and acrylic acid or methacrylic acid may further have a substituent such as a hydroxyl group or a halogen group.
• esters of alcohols having 1 to 6 carbon atoms and acrylic acid or methacrylic acid include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid.
• Examples include 2,3,4,5,6-pentahydroxyhexyl acrylate and 2,3,4,5-tetrahydroxypentyl (meth)acrylate. These may be used alone or in combination of two or more.
• vinyl cyanide monomers examples include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like. These may be used alone or in combination of two or more.
• Monomer C is a vinyl monomer other than the aromatic vinyl monomer, unsaturated carboxylic acid alkyl ester monomer, and vinyl cyanide monomer, and does not impair the effects of the present invention. There is no particular restriction as long as there is no such thing. Specific examples of monomer C include unsaturated fatty acids, acrylamide monomers, maleimide monomers, vinyl acetate, and acrylic ester monomers. These may be used alone or in combination of two or more.
• the unsaturated fatty acid may be selected from, for example, itaconic acid, maleic acid, fumaric acid, butenoic acid, acrylic acid, methacrylic acid, and the like.
• the acrylamide monomer may be selected from, for example, acrylamide, methacrylamide, N-methylacrylamide, and the like.
• maleimide monomers include N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and the like.
• the method for producing the vinyl copolymer is not particularly limited, and examples include emulsion polymerization, suspension polymerization, bulk polymerization, and solution polymerization.
• a polymerization initiator may be used if necessary.
• the polymerization initiator include peroxides, azo compounds, potassium persulfate, etc. One or more types may be selected as appropriate.
• the amount of the polymerization initiator added is not particularly limited.
• peroxides examples include benzoyl peroxide, cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, and t-butyl peroxybenzoate.
• azo compounds include azobisisobutyronitrile, azobis(2,4-dimethylvaleronitrile), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano-2-propylazo Formamide, 1,1'-azobiscyclohexane-1-carbonitrile, azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 1-t-butylazo-2 -cyanobutane, and 2-t-butylazo-2-cyano-4-methoxy-4-methylpentane.
• 1,1'-azobiscyclohexane-1-carbonitrile is particularly preferably used.
• vinyl copolymers include polyvinyl chloride, chlorinated polyvinyl chloride, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-N-phenylmaleimide copolymer, and ⁇ -methylstyrene-acrylonitrile copolymer.
• examples include polymethyl methacrylate, methyl methacrylate-styrene copolymer, and the like. These may be used alone or in combination of two or more.
• polyesters include polyethylene terephthalate and polybutylene terephthalate.
• the resin (B) may be the same resin (resin having the same composition) as the component (E) (radically polymerizable oligomer resin or inert resin) described later, or it may be a resin different from the component (E). You can. In the printing ink composition, it is preferable that component (E) and resin (B) do not undergo phase separation.
• the resin (B) is preferably a resin that is compatible with the component (E).
• the resin (B) is the same resin as the component (E) described below, the resin (B) does not affect various physical properties of the resulting printing ink composition or cured film containing the powder. It has the advantage of
• the printing ink composition has (a) component (E) but no resin (B), or (b) resin (B) but ( E) Appears to have no ingredients.
• the printing ink composition contains the (E) component, and may also contain the resin (B) as a resin other than the (E) component.
• fats and oils and fatty acid esters are also included in resin (B).
• the resin (B) preferably contains oil and fat, and more preferably consists of oil and fat.
• examples of fats and oils that can be suitably used as the resin (B) include epoxidized fats and oils such as epoxidized soybean oil and epoxidized linseed oil. These resins may be used alone or in combination of two or more.
• the resin (B) preferably contains epoxidized soybean oil, and more preferably consists of epoxidized soybean oil.
• ADEKAISER O-130P manufactured by ADEKA.
• fatty acid esters that can be suitably used as the resin (B) include epoxidized fatty acid esters such as epoxidized butyl fatty acid, epoxidized fatty acid 2-ethylhexyl, epoxidized fatty acid octyl ester, and epoxidized fatty acid alkyl ester.
• epoxidized fatty acid esters such as epoxidized butyl fatty acid, epoxidized fatty acid 2-ethylhexyl, epoxidized fatty acid octyl ester, and epoxidized fatty acid alkyl ester.
• Epoxidized fats and oils and epoxidized fatty acid esters are sometimes referred to as epoxy plasticizers. That is, in this specification, an epoxy plasticizer is also included in the resin (B).
• epoxy plasticizers other than epoxidized fats and oils and epoxidized fatty acid esters include diepoxystearyl epoxyhexahydrophthalate and di2-ethylhexyl epoxyhexahydrophthalate.
• thermosetting resins thermoplastic resins, mixtures of thermosetting resins and thermoplastic resins, oils and fats, and fatty acid esters can be used in combination with an antioxidant.
• the antioxidant is considered to be part of the resin (B) only when used in combination with each of the above-mentioned substances.
• the antioxidant is not considered resin (B).
• a case where only an antioxidant is used instead of resin (B) will be explained. Since the antioxidant is a component that does not contribute to crosslinking, the physical properties of the cured film obtained by curing the printing ink composition tend to be poor. For example, there may be cases where the Tg of the cured film decreases or the impact resistance becomes poor.
• the antioxidant is not particularly limited.
• examples of antioxidants include (a) primary antioxidants such as phenolic antioxidants, amine antioxidants, lactone antioxidants, and hydroxylamine antioxidants, and (b) sulfur antioxidants. and secondary antioxidants such as phosphorus-based antioxidants.
• phenolic antioxidant examples include hindered phenolic antioxidants.
• hindered phenol antioxidant examples include compounds having a hindered phenol structure or a single hindered phenol structure in the molecule.
• commercially available products can be used, such as Irganox 245 manufactured by BASF Japan Co., Ltd., and the like.
• the amine antioxidant is not particularly limited, and a wide variety of conventionally known antioxidants can be used. Specific examples of amine antioxidants include 2,2,4-trimethyl-1,2-dihydroquinoline polymer and 6-ethoxy-1,2-dihydro-2,2,4 as amine-ketone compounds. -trimethylquinoline, and a reaction product of diphenylamine and acetone.
• the amine antioxidants also include aromatic amine compounds.
• aromatic amine compounds include naphthylamine antioxidants, diphenylamine antioxidants, and p-phenylenediamine antioxidants.
• the lactone antioxidant, hydroxylamine antioxidant, and sulfur antioxidant are not particularly limited, and a wide variety of conventionally known antioxidants can be used.
• the phosphorus antioxidant is not particularly limited, and a wide variety of conventionally known antioxidants can be used. Phosphoric acids and phosphoric acid esters containing active hydrogen can adversely affect the storage stability of printing ink compositions and the heat resistance of cured films provided by the printing ink compositions. Therefore, as the phosphorus antioxidant, alkyl phosphite, aryl phosphite, alkylaryl phosphite compounds, etc., which do not contain phosphoric acid or phosphoric acid ester in the molecule, are preferable.
• antioxidant other conventionally known substances may be used.
• antioxidants include the "Antioxidant Handbook” published by Taiseisha (first edition published October 25, 1976), and the “Polymer Additives Handbook” published by CMC Publishing (edited and written by Toru Haruna, November 2010). You may use various substances described in, for example, the 1st edition published on the 7th.
• Resin (B) is a thermosetting resin, a mixture of a thermosetting resin and an antioxidant, a thermoplastic resin, a mixture of a thermoplastic resin and an antioxidant, an oil or fat, a mixture of an oil or fat and an antioxidant, or a fatty acid. It is preferably one or more selected from the group consisting of esters, mixtures of fatty acid esters and antioxidants, epoxy hardeners, and mixtures of epoxy hardeners and antioxidants, and epoxy resins, acrylic heavy one or more selected from the group consisting of a mixture of an epoxy resin and an antioxidant, a mixture of an acrylic polymer and an antioxidant, and a mixture of an epoxy plasticizer and an antioxidant.
• the printing ink composition has the advantage that it can provide a cured film with excellent heat resistance and can improve the dispersibility of the polymer fine particles (A) in the printing ink composition.
• the viscosity of the resin (B) at 25°C is preferably 750,000 mPa ⁇ s or less, more preferably 700,000 mPa ⁇ s or less, and 500,000 mPa ⁇ s or less. - It is more preferable that it is below 350,000 mPa ⁇ s, it is more preferable that it is below 300,000 mPa ⁇ s, it is more preferable that it is below 250,000 mPa ⁇ s, and 100 ,000 mPa ⁇ s or less, more preferably 75,000 mPa ⁇ s or less, more preferably 50,000 mPa ⁇ s or less, and even more preferably 30,000 mPa ⁇ s or less.
• the resin (B) has an advantage of excellent fluidity.
• the viscosity of the resin (B) at 25° C. is more preferably 100 mPa ⁇ s or more, more preferably 200 mPa ⁇ s or more, more preferably 300 mPa ⁇ s or more, and 400 mPa ⁇ s or more. It is more preferable that it is 500 mPa ⁇ s or more, it is still more preferable that it is 750 mPa ⁇ s or more, it is even more preferable that it is 1000 mPa ⁇ s or more, and it is particularly preferable that it is 1500 mPa ⁇ s or more. preferable.
• the resin (B) is not impregnated into the polymer fine particles (B). Therefore, the resin (B) can prevent the polymer particles (B) from fusing together.
• the viscosity of the resin (B) at 25° C. is more preferably 100 mPa ⁇ s to 750,000 mPa ⁇ s, more preferably 100 mPa ⁇ s to 700,000 mPa ⁇ s, and more preferably 100 mPa ⁇ s to 350,000 mPa ⁇ s. , more preferably from 100 mPa ⁇ s to 300,000 mPa ⁇ s, more preferably from 100 mPa ⁇ s to 50,000 mPa ⁇ s, even more preferably from 100 mPa ⁇ s to 30,000 mPa ⁇ s, and from 100 mPa ⁇ s to 15,000 mPa ⁇ s. Particularly preferred.
• the resin (B) is semi-solid at 25°C, it can also be said that the resin (B) is semi-liquid at 25°C, and the resin (B) has a viscosity greater than 1,000,000 mPa ⁇ s at 25°C. It can be said that they are doing so.
• the resin (B) is semi-solid or solid at 25°C, the resulting composition has the advantage of being less sticky and easier to handle.
• the viscosity of the resin (B) can be measured with a viscometer.
• the method for measuring the viscosity of resin (B) will be described in detail in the Examples below.
• the resin (B) is preferably a resin whose differential scanning calorimetry (DSC) thermogram has an endothermic peak of 25°C or less, and more preferably a resin that has an endothermic peak of 0°C or less.
• DSC differential scanning calorimetry
• the printing ink composition preferably contains a radically polymerizable oligomer resin and/or an inert resin (E).
• This configuration has the advantage that it is possible to provide a printing ink composition and a cured film that are excellent in chemical properties such as the viscosity and fluidity of the printing ink composition, the film strength and adhesion of the cured film, and printability.
• “radical polymerizable oligomer resin and/or inert resin (E)” may be referred to as "component (E)."
• the radically polymerizable oligomer resin in component (E) is intended to be a resin that can be polymerized by radicals and has a molecular weight of 10,000 or less.
• a radically polymerizable oligomer photocrosslinkable groups such as (meth)acryloyl groups and An oligomer resin obtained by introducing a photopolymerizable group into the linear polymer is used.
• reactive substituents in linear polymers having reactive substituents include functional groups such as hydroxyl groups, carboxyl groups, and amino groups, as well as structures derived from acid anhydrides.
• Examples of the reactive substituent in the (meth)acrylic compound include a hydroxyl group, an isocyanate group, an aldehyde group, an epoxy group, and the like.
• a radically polymerizable oligomer resin (a) a linear polymer containing a structure derived from an acid anhydride such as a styrene-maleic anhydride copolymer and an ⁇ -olefin-maleic anhydride copolymer; , (b) A half-esterified compound obtained by reacting a (meth)acrylic compound having a hydroxyl group such as hydroxyalkyl (meth)acrylate.
• the radically polymerizable oligomer resin is not particularly limited, (a) the physical and chemical properties of the cured film (ink film), and (b) the printability of the printing ink composition itself (ease of application or spraying, From the viewpoint of (viscosity, etc.), it is preferable to contain one or more selected from the group consisting of alkyd acrylate, urethane-modified acrylate, polyester acrylate, and epoxy acrylate, and is composed only of one or more selected from the group. It is more preferable that
• the inert resin in component (E) is intended to be a solid resin that is itself non-reactive.
• Inert resins include, but are not limited to, (a) physical and chemical properties of the cured film (ink film), and (b) printability of the printing ink composition itself (ease of application, viscosity, etc.).
• the total content of the radically polymerizable oligomer resin and inert resin in the present printing ink composition is preferably 0.5% by weight or more and 50.0% by weight or less, based on 100% by weight of the printing ink composition, and 1 It is more preferably .0 weight % or more and 30.0 weight % or less, even more preferably 1.0 weight % or more and 20.0 weight % or less, and 1.0 weight % or more and 10.0 weight % or less. It is particularly preferable that there be.
• This configuration has the advantage that (a) the physical and chemical properties of the cured film (ink film) and (b) the printability of the printing ink composition itself (ease of application, viscosity, etc.) are excellent. .
• the printing ink composition preferably contains a low molecular compound (C).
• low molecular compound (C) may be referred to as “component (C).”
• the low molecular compound (C) has at least one polymerizable unsaturated bond within the molecule. Because of this configuration, the low molecular compound (C) can also be cured itself when the printing ink composition is cured. Furthermore, when a radically polymerizable oligomer resin is included as the component (E), a curing reaction may also occur between the component (C) and the radically polymerizable oligomer resin of the component (E) during curing of the printing ink composition. Therefore, the low molecular compound (C) can also function as a polymerizable monomer that crosslinks the cured film.
• the low molecular compound (C) preferably has at least one polymerizable unsaturated bond in the molecule, more preferably two polymerizable unsaturated bonds in the molecule, and three polymerizable unsaturated bonds in the molecule. It is more preferable to have a polymerizable unsaturated bond, and it is particularly preferable to have 6 polymerizable unsaturated bonds in the molecule. This configuration has the advantage that the curing speed becomes faster.
• the low molecular weight compound (C) has a molecular weight of less than 1000. Because of this configuration, the low molecular compound (C) can function as a reactive diluent in the printing ink composition. For example, the low molecular weight compound (C) can function as a diluent (solvent) for adjusting the printing ink composition to an appropriate viscosity (lowering it to an appropriate viscosity). That is, since the printing ink composition contains the low-molecular-weight compound (C), the printing ink composition has the advantage of being excellent in handleability.
• the molecular weight of the low molecular weight compound (C) is preferably less than 1000, more preferably less than 900, even more preferably less than 800, and particularly preferably less than 700. This configuration has the advantage that the viscosity of the printing ink composition can be easily adjusted.
• a low-molecular compound (C) having at least three or more polymerizable unsaturated bonds in one molecule As a reaction diluent, it is preferable to use a low-molecular compound (C) having at least three or more polymerizable unsaturated bonds in one molecule as a reaction diluent.
• a low molecular weight compound (C) having at least three or more polymerizable unsaturated bonds in one molecule is used in a large amount (for example, 10 parts by weight or more in 100 parts by weight of a printing ink composition).
• the cured film shrinks significantly, and residual stress generated in the cured film tends to deteriorate the adhesion of the cured film.
• the present printing ink composition may contain a large amount of a low molecular compound (C) having at least three or more polymerizable unsaturated bonds in one molecule. Even if there is, residual stress in the cured film can be reduced. Therefore, this printing ink composition has the advantage of being excellent in curing speed and hardness of the cured film, as well as being excellent in adhesiveness to the substrate.
• a low molecular compound (C) having at least three or more polymerizable unsaturated bonds in one molecule. Even if there is, residual stress in the cured film can be reduced. Therefore, this printing ink composition has the advantage of being excellent in curing speed and hardness of the cured film, as well as being excellent in adhesiveness to the substrate.
• the low-molecular compound (C) contains 5% by weight of a low-molecular compound having at least 3 or more polymerizable unsaturated bonds in one molecule based on 100% by weight of the low-molecular compound (C). % or more, more preferably 10% by weight or more, even more preferably 15% by weight or more, particularly preferably 20% by weight or more. This configuration has the advantage that the curing speed becomes faster.
• the low molecular compound (C) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and ethoxylated 1,6-hexanediol diacrylate, neopentyl glycol di(meth)acrylate, polypropylene glycol diacrylate, 1,4-butanediol di(meth)acrylate, 1,9-nonanediol diacrylate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, dimethylol tricyclodecane diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, 1,3-butylene glycol di(meth)acrylate, ethoxy Bisphenol A di(meth)acrylate, propoxyl
• Component (C) is not limited to this. One type of these compounds may be used alone, or two or more types may be used in combination as necessary. Component (C) contains one or more selected from the group consisting of low molecular weight compounds having at least three or more polymerizable unsaturated bonds in one molecule, or consists only of one or more selected from the group. It is particularly preferred that the configuration is configured. This configuration has the advantage that the curing speed becomes faster.
• the content of the low molecular weight compound (C) is not particularly limited, but is preferably 5% to 90% by weight, and preferably 7% to 80% by weight based on 100% by weight of the printing ink composition. It is more preferable that the amount is 10% to 70% by weight, more preferably 15% to 60% by weight, even more preferably 15% to 50% by weight, even more preferably 20% by weight. % to 40% by weight is particularly preferred.
• the content of the low molecular weight compound (C) may be 30% by weight or more, or 40% by weight or more based on 100% by weight of the printing ink composition. This configuration has the advantage that the viscosity of the printing ink composition can be easily adjusted.
• the printing ink composition includes a pigment (D).
• This configuration has the advantage that the printing ink composition can be colored.
• pigment (D) may be referred to as “component (D).”
• the pigment (D) used in one embodiment of the present invention is not particularly limited, and any known pigment can be used.
• "Dictionary of Pigments” edited by Seishiro Ito (published in 2000), W. Herbst, K. Hunger “Industrial Organic Pigments” pigments described in Japanese Patent Publication No. 2002-12607, Japanese Patent Application Publication No. 2002-188025, Japanese Patent Application Publication No. 2003-26978, and Japanese Patent Application Publication No. 2003-342503 can be used.
• the content of the pigment (D) in the present printing ink composition is 1% by weight or more, preferably 2% by weight or more, and preferably 3% by weight or more based on 100% by weight of the printing ink composition. More preferably, it is 5% by weight or more.
• This configuration has the advantage that the cured film obtained by curing the printing ink composition has excellent color development.
• the printing ink composition preferably contains a photopolymerization initiator (F).
• a photopolymerization initiator (F) may be referred to as “component (F).”
• the photopolymerization initiator (F) used in one embodiment of the present invention is not particularly limited, and any known photopolymerization initiator can be used.
• any known photopolymerization initiator can be used.
• Ya, M. Tsunooka et al. Prog. Polym. Sci. , 21, 1 (1996). You can use many of the ones listed in .
• the photopolymerization initiator (F) includes an alkyl acetophenone polymerization initiator, an alkylphenyl ketone polymerization initiator, a benzoin alkyl ether polymerization initiator, a benzophenone polymerization initiator, a thioxanthone polymerization initiator, and anthraquinone-based polymerization initiators, or is preferably composed of only one or more types selected from the group.
• the content of the photopolymerization initiator (F) in the present printing ink composition is preferably 0.1% to 30.0% by weight, and 0.5% by weight based on 100% by weight of the printing ink composition. It is more preferably from 1.0% to 20.0% by weight, and even more preferably from 1.0% to 20.0% by weight. This configuration has the advantage of good curability.
• the content of the photopolymerization initiator (F) in the printing ink composition is preferably 0.1% by weight or more, and preferably 0.5% by weight or more based on 100% by weight of the printing ink composition. More preferably, it is 1.0% by weight or more, more preferably 1.5% by weight or more, even more preferably 2.0% by weight or more, and even more preferably 2.5% by weight or more. It is particularly preferable. This configuration has the advantage that both the curability and adhesion of the curable composition are excellent.
• the content of the low molecular weight compound (C) having at least three or more polymerizable unsaturated bonds in one molecule is 2% by weight or more based on 100% by weight of the printing ink composition. It is preferably at least 5% by weight, more preferably at least 7.5% by weight, particularly preferably at least 10% by weight.
• This configuration has the advantage that both the curability and adhesion of the curable composition are excellent.
• the printing ink composition may contain other optional components other than the above-mentioned components, if necessary.
• Other optional components include photopolymerization inhibitors, waxes, leveling agents, photoinitiation aids, sensitizers, active energy ray curing catalysts, fillers, matting agents, antifoaming agents, dispersants, surface conditioners, Examples include antistatic agents, antioxidants, conductive agents, silicones, flame retardants, plasticizers, thermal conductivity improvers, and silane coupling agents.
• Preferred commercial products include offset UV ink (manufactured by Toyo Ink Co., Ltd., FD LPC PR Eye CM) and inkjet UV ink (manufactured by Mimaki Engineering Co., Ltd., LH-100). This configuration has the advantage that good printed matter can be obtained.
• the printing ink composition can be manufactured by mixing the above-mentioned components.
• a method for producing a UV curable printing ink composition may have the following configuration: A step of preparing a granular material containing polymer fine particles (A); A step of mixing the powder and the pigment (D) to prepare a UV curable printing ink composition,
• the polymer fine particles (A) include a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body,
• the elastic body includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber
• the graft portion comprises a polymer containing a structural unit derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers.
• the content of the pigment (D) in the UV curable printing ink composition is 1% by weight or more based on 100% by weight of the UV curable printing ink composition.
• a method for producing a UV curable printing ink composition may have the following configuration: A step of preparing a dispersion containing polymer fine particles (A); a step of mixing the dispersion and the pigment (D) to prepare a UV curable printing ink composition,
• the polymer fine particles (A) include a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body,
• the elastic body includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber
• the graft portion comprises a polymer containing a structural unit derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers.
• the content of the pigment (D) in the UV curable printing ink composition is 1% by weight or more based on 100% by weight of the UV curable printing ink composition.
• this printing ink composition may be produced by either method 1 or method 2.
• Method 1 is preferred from the viewpoint of no restrictions on blending.
• the UV curable printing ink composition may have the following aspect:
• the granular material of the polymer fine particles (A) is added to the printing ink composition.
• the fine polymer particles (A) contain a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body.
• the elastic body contains one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber, and the graft portion contains an aromatic vinyl monomer, vinyl cyanide rubber, and an aromatic vinyl monomer.
• the pigment ( A UV curable printing ink composition in which the content of D) is 1% by weight or more based on 100% by weight of the UV curable printing ink composition.
• binder includes both powder and granules, and means an aggregate of powder, grains, etc. Further, when specifically distinguished, “powder” means one with a volume average particle diameter of 0.01 mm to 0.1 mm, and “granule” means one with a volume average particle diameter of 0.1 mm to 10 mm. However, the granular material may contain coarse particles of 10 mm or more.
• volume average particle diameter in the range of less than 10 ⁇ m can be measured using a dynamic light scattering (DLS) particle size distribution analyzer Nanotrac Wave II-EX150 (manufactured by Microtrac Bell Co., Ltd.), and "volume average particle diameter” in the range of 10 ⁇ m or more The volume average particle diameter can be measured using a laser diffraction particle size distribution analyzer Microtrac MT3000II (manufactured by Microtrac Bell Co., Ltd.).
• DLS dynamic light scattering
• the method for producing a powder or granule is an aggregation step of preparing an aggregate containing polymer fine particles (A). and a drying step of air drying or freeze drying the aggregate.
• the polymer fine particles (A) include a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body.
• the elastic body includes one or more selected from the group consisting of diene rubber, (meth)acrylate rubber, and organosiloxane rubber.
• the graft portion includes, as a structural unit, a structural unit derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers. It is preferable to include a polymer containing.
• the "method for producing powder or granular material according to an embodiment of the present invention” may also be referred to as "the present production method”.
• the present manufacturing method has the above-mentioned structure, it has the advantage that it can provide powder particles having excellent dispersibility of the polymer fine particles (A) in the printing ink composition.
• the present manufacturing method since the present manufacturing method has the above-mentioned structure, it has the advantage of being able to provide a granular material that can provide a printing ink composition in which the polymer fine particles (A) are uniformly dispersed.
• the granular material further contains resin (B).
• resin (B) a method for producing powder containing resin (B) will be described in detail by giving an example.
• the aggregation step As long as it is possible to finally obtain an aggregate containing the polymer fine particles (A) and the resin (B), in other words, the finally obtained aggregate contains the polymer fine particles (A) and the resin ( There is no particular limitation as long as B) is included.
• the aggregation step may include, for example, the following steps in order: a preparation step (a1) of preparing an aqueous latex containing the polymer fine particles (A) and the resin (B); A coagulation step (a2) in which the polymer fine particles (A) and the resin (B) in the aqueous latex are coagulated together.
• the preparation step (a1) is not particularly limited as long as an aqueous latex containing the polymer fine particles (A) and the resin (B) can be obtained.
• a method for obtaining an aqueous latex containing polymer fine particles (A) and resin (B) for example, (i) during the polymerization step of polymer fine particles (A), resin (B) is added to the reaction solution. (ii) adding the resin (B) to the aqueous latex of the polymer fine particles (A); and (iii) polymerizing the resin (B) in the aqueous latex of the polymer fine particles (A). methods, etc.
• the method of adding the resin (B) to the reaction solution during the polymerization step of the polymer fine particles (A) or to the aqueous latex of the polymer fine particles (A) is not particularly limited.
• a method of directly adding the resin (B) to the reaction solution or the aqueous latex (ii) a method of separately preparing an aqueous latex containing the resin (B), and then adding the aqueous latex containing the resin (B)
• Examples include a method of adding latex, and (iii) a method of separately preparing a solution containing resin (B) and then adding a solution containing resin (B).
• a method for adding the resin (B) a method is preferred in which an aqueous latex containing the resin (B) is separately prepared and then the aqueous latex containing the resin (B) is added to the reaction solution or the aqueous latex.
• the resin (B) may be added to the aqueous latex of the polymer particles (A) before the coagulant is added. , or the resin (B) may be added to the polymer fine particles (A) together with the coagulant.
• a method for obtaining an aqueous latex containing the polymer fine particles (A) and the resin (B) a method of adding the resin (B) in an aqueous latex state to the aqueous latex of the polymer fine particles (A) is preferable.
• the aggregation step (a2) is not particularly limited as long as an aggregate containing the polymer fine particles (A) and the resin (B) can be obtained.
• the method of coagulating the polymer particles (A) and the resin (B) in the aqueous latex is not particularly limited. Examples of the method include known methods such as a method using a coagulant, a method using a solvent, and a method of spraying an aqueous latex. Examples of known methods include: Here, a mixture containing an aqueous solvent and an aggregate containing polymer particles (A) and resin (B) obtained by coagulating polymer particles (A) and resin (B) in aqueous latex, Also called slurry.
• the aggregation of the polymer fine particles (A) and the resin (B) in the aqueous latex can prevent blocking.
• the reaction is carried out in the presence of an agent.
• the aggregation step (a2) employs a method using a coagulant. In other words, it is preferable to use a coagulant in the aggregation step in this production method.
• the coagulant is used to coagulate (also known as coagulation and coagulation) the polymer particles (A) and resin (B) in the aqueous latex by bringing them into contact with the aqueous latex containing the polymer particles (A) and the resin (B).
• coagulant include an aqueous solution of an inorganic salt, an aqueous solution of an inorganic acid, an aqueous solution of an organic salt, an aqueous solution of an organic acid, and a polymer coagulant.
• inorganic salts include chloride salts, bromide salts, iodide salts, sulfates, nitrates, ammonium salts, phosphates, and the like.
• Specific inorganic salts include sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide, potassium iodide, sodium iodide, potassium sulfate, sodium sulfate, ammonium sulfate, ammonium chloride, and sodium nitrate.
• potassium nitrate calcium chloride, ferrous sulfate, magnesium sulfate, zinc sulfate, copper sulfate, barium chloride, ferrous chloride, ferric chloride, magnesium chloride, ferric sulfate, aluminum sulfate, potassium alum, iron alum, etc. can be mentioned.
• inorganic acids examples include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
• organic salts include acetates, citrates, formates, gluconates, lactates, oxalates, and tartrates of alkali metals or alkaline earth metals.
• organic acid salts include sodium acetate, calcium acetate, sodium formate, and calcium formate.
• organic acids examples include acetic acid and formic acid.
• the polymer coagulant is not particularly limited as long as it is a polymer compound having a hydrophilic group and a hydrophobic group, and may be any anionic, cationic, or nonionic polymer coagulant.
• a cationic polymer coagulant is preferable because it can further enhance the effects of the embodiment of the present invention.
• the cationic polymer coagulant may be any polymer coagulant that has a cationic group in its molecule, that is, a polymer coagulant that exhibits cationic properties when dissolved in water.
• cationic polymer coagulants include polyamines, polydicyandiamides, cationized starch, cationic poly(meth)acrylamide, water-soluble aniline resin, polythiourea, polyethyleneimine, quaternary ammonium salts, and polyvinylpyridine. and chitosan.
• coagulants include monovalent or divalent inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, ammonium chloride, calcium chloride, magnesium chloride, magnesium sulfate, barium chloride, hydrochloric acid, sulfuric acid, or inorganic Aqueous acid solutions can be suitably used.
• monovalent or divalent inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, ammonium chloride, calcium chloride, magnesium chloride, magnesium sulfate, barium chloride, hydrochloric acid, sulfuric acid, or inorganic Aqueous acid solutions can be suitably used.
• Agglomerating the polymer particles (A) and the resin (B) by bringing the aqueous latex containing the polymer particles (A) and the resin (B) into contact with a coagulant or a solution of a coagulant e.g., an aqueous solution.
• a coagulant or a solution of a coagulant e.g., an aqueous solution.
• the method of bringing the aqueous latex containing the polymer particles (A) and the resin (B) into contact with a coagulant or a solution of a coagulant is not particularly limited.
• Examples of the method include (i) a method in which an aqueous latex containing polymer particles (A) and a resin (B) is brought into contact with a coagulant or a solution of a coagulant (hereinafter referred to as aggregation method 1), and (ii) Droplets containing polymer particles (A) and resin (B) obtained by spraying an aqueous latex containing polymer particles (A) and resin (B) are brought into contact with a coagulant or a solution of a coagulant. (hereinafter referred to as aggregation method 2).
• Aggregation method 1 is a method in which an aqueous latex containing polymer fine particles (A) and a resin (B) is used as a liquid phase, in other words, a method in which the aqueous latex containing polymer fine particles (A) and resin (B) is not sprayed. It is. In this specification, aggregation method 1 is also referred to as "liquid phase coagulation.”
• the aggregation method 1 includes (1-i) a method of adding a coagulant into an aqueous latex containing polymer fine particles (A) and resin (B), and (1-ii) a method of adding a coagulant to an aqueous latex containing polymer fine particles (A) and a resin (B).
• the method (1-iii) above can also be said to be a method in which a coagulant or a solution of a coagulant is sprayed in the presence of the polymer fine particles (A) and the resin (B).
• a coagulant or a solution of a coagulant is sprayed in the presence of the polymer fine particles (A) and the resin (B).
• the aggregation method 1 an aqueous latex containing polymer fine particles (A), a resin (B), and a coagulant is obtained.
• Coagulation method 1 may further include the step of heating the obtained aqueous latex (aqueous latex containing polymer fine particles (A), resin (B), and coagulant).
• the step of heating the aqueous latex containing the polymer fine particles (A), the resin (B), and the coagulant is advantageous in that the moisture content of the resulting aggregates can be lowered, and/or the resulting granular material can be reduced. It has the advantage of being able to reduce the amount of fine powder inside.
• the temperature (heating temperature) of the aqueous latex obtained by heating the aqueous latex containing the polymer particles (A), the resin (B), and the coagulant is not particularly limited.
• Aggregation method 2 is a method of spraying an aqueous latex containing polymer particles (A) and a resin (B), in other words, a method of using an aqueous latex containing polymer particles (A) and a resin (B) as droplets. It is. In this specification, aggregation method 2 is also referred to as "vapor phase coagulation.”
• the aggregation method 2 includes (2-i) a method of spraying an aqueous latex containing polymer fine particles (A) and a resin (B) into a coagulant or a solution of a coagulant; (2-ii) ) A method of spraying an aqueous latex containing the polymer fine particles (A) and the resin (B) and spraying a coagulant or a solution of the coagulant.
• the method (2-i) can also be said to include a polymer fine particle spraying step of spraying an aqueous latex containing polymer fine particles (A) and resin (B) in the presence of a coagulant.
• the method (2-ii) above will be specifically explained.
• the method (2-ii) above may include the following embodiments: (2-ii-a) droplets containing polymer fine particles (A) and/or resin (B) obtained by spraying; (2-ii-b) A method of bringing the polymer fine particles (A) and the resin (B) into contact with the droplets containing the coagulant obtained by spraying; and (2-ii-c) a method of spraying an aqueous latex containing a solution of a coagulant in a region (space) where droplets containing polymer fine particles (A) and/or resin (B) obtained by spraying exist. How to spray.
• the region (space) in which droplets containing a coagulant exist can also be said to be in the presence of a coagulant.
• the region (space) where droplets containing the polymer fine particles (A) and/or the resin (B) exist can also be said to be in the presence of the polymer fine particles (A) and the resin (B).
• the method (2-ii) includes a polymer fine particle spraying step of spraying an aqueous latex containing polymer fine particles (A) and resin (B) in the presence of a coagulant, and Alternatively, it can also be said to be a method including a coagulant spraying step of spraying a solution containing a coagulant into the presence of the polymer fine particles (A) and the resin (B).
• the aggregation step in this production method is preferably performed by aggregation method 2, that is, "vapor phase coagulation.”
• the aggregation step in the present production method preferably further includes a polymer fine particle spraying step of spraying an aqueous latex containing the polymer fine particles (A) and the resin (B) in the presence of a coagulant.
• a polymer fine particle spraying step of spraying an aqueous latex containing the polymer fine particles (A) and the resin (B) in the presence of a coagulant.
• the aggregation step in this production method further includes a coagulant spraying step of spraying a coagulant or a solution containing a coagulant into the presence of the polymer fine particles (A) and the resin (B). It is more preferable to include. According to this configuration, there is an advantage that it is possible to obtain a powder or granule in which the proportion of particles having a volume average particle diameter of 1000 ⁇ m or more or 600 ⁇ m or more relative to the total amount of powder or granule is smaller.
• a slurry containing aggregates containing polymer fine particles (A) and resin (B) can be obtained.
• the aggregation step may further include a recovery step (a3) of recovering the obtained aggregates, that is, the aggregates containing the polymer fine particles (A) and the resin (B), from the slurry.
• the recovery step (a3) is not particularly limited, and any known method can be used as long as the aqueous solvent of the slurry and the aggregates can be separated.
• Examples of the recovery step (a3) include a method of filtering the slurry, a method of centrifugally dehydrating the slurry, and the like.
• the aggregation step include, for example, those including the following steps in order: Using an aqueous latex containing only the polymer fine particles (A), the polymer fine particles (A) in the aqueous latex are an aggregation step (b1) of aggregating the obtained polymer fine particles (A); a recovery step (b2) of recovering aggregates of the obtained polymer fine particles (A); and a collection step of collecting the aggregates of the polymer fine particles (A) and the resin (B).
• a mixing step (b3) of mixing is a mixing step (b3) of mixing.
• the aggregation step (b1) includes the preferred embodiments described above, except that instead of the aqueous latex containing the polymer microparticles (A) and the resin (B), an aqueous latex containing only the polymer microparticles (A) is used.
• the same aspect as the aggregation step (a2) may be used.
• the recovery step (b2) includes a preferred embodiment except that the aggregate contains only the polymer particles (A) instead of the polymer particles (A) and the resin (B), and is similar to the recovery step (a3) described above. The same mode may be used.
• the mixing step (b3) there are no particular limitations on the method for mixing the aggregates of the recovered polymer particles (A) and the resin (B). Examples of such methods include mechanical mixing methods using a rotation-revolution mixer, a planetary mixer, a disperser, and the like.
• the aggregate containing the polymer fine particles (A) and the resin (B) obtained in the aggregation step may contain water.
• the moisture content of the aggregate is preferably 10% to 70%, more preferably 20% to 60%, more preferably 30% to 60%, and more preferably 30% to 60%, based on the total weight (100% by weight) of the aggregate. 50% is more preferred, and 30% to 40% is particularly preferred.
• the moisture content of the aggregate can be measured by drying the obtained aggregate in an oven at 120° C. for 1 hour and comparing the weight before and after drying.
• the drying step is a step of drying the aggregate containing the polymer fine particles (A) and the resin (B) obtained by the above-mentioned aggregation step.
• the aggregate is air-flow dried or freeze-dried.
• flash drying means drying while causing the aggregates to float in a certain space.
• the flash drying method is not particularly limited, and conventionally known methods can be employed.
• An example of airflow drying is a method in which aggregates are housed in a container, and gas at a predetermined temperature is fed into the container to cause the aggregates to float inside the container while being dried.
• the atmospheric temperature when the drying step is carried out is not particularly limited.
• the drying step is preferably carried out at 100°C or lower, more preferably at 90°C or lower, since the resulting powder can provide a printing ink composition with better dispersibility than the polymer fine particles (A).
• it is carried out at 80 °C or lower, more preferably at 70 °C or lower, more preferably at 60 °C or lower, more preferably at 50 °C or lower, and more preferably at 40 °C or lower. It is more preferably carried out at 30°C or lower, more preferably at 20°C or lower, even more preferably at 10°C or lower, and particularly preferably at 0°C or lower. .
• the ambient temperature when the drying step is carried out can be adjusted by changing the temperature inside the container housing the aggregates and/or the temperature of the gas sent into the container.
• the gas sent into the container is not particularly limited.
• the gas include air, nitrogen, a mixture of nitrogen and air, a mixture of nitrogen and oxygen, and rare gases.
• the freeze-drying method is not particularly limited, and conventionally known methods can be employed. When freeze drying is employed as the drying process, the drying process can be easily carried out at 0°C or lower.
• the time for the drying step is not particularly limited and can be set as appropriate depending on the degree of drying of the aggregates.
• the drying time can be, for example, 1 minute to 3 hours, preferably 1 minute to 1 hour, more preferably 1 minute to 30 minutes, even more preferably 1 minute to 20 minutes, and even more preferably 1 minute to 10 minutes. Particularly preferred.
• the drying step may be carried out, for example, until the temperature of the aggregate (powder) reaches 40°C.
• the present manufacturing method further includes a step of washing the aggregate obtained in the aggregation step between the aggregation step and the drying step.
• a step of washing the aggregate obtained in the aggregation step between the aggregation step and the drying step.
• the washing step it is more preferable to wash the aggregates with water, and even more preferably with ion-exchanged water or pure water.
• the washing step may be any step of washing the aggregates, and the specific method is not particularly limited.
• Specific methods for the cleaning process include, for example, mixing the aggregates and water and stirring with a stirrer, kneading the aggregates and water using a kneader, and mixing the aggregates and water with a rotation-revolution mixer. Examples include a method of mixing with water, a method of spraying water onto the aggregate, and a method of washing the cake with a pressure filter.
• the kneader various types can be used, such as a batch type kneader, a continuous type kneader, an extrusion type kneader, and an extruder.
• the washing time is not particularly limited, and can be, for example, 1 second to 60 minutes.
• the washing time is preferably 1 second to 45 minutes, more preferably 1 second to 30 minutes, more preferably 1 minute to 30 minutes, and even more preferably 3 minutes to 30 minutes.
• the time period is preferably 5 minutes to 30 minutes, particularly preferably 10 minutes to 30 minutes.
• the number of times of washing is not particularly limited, and can be, for example, 1 to 10 times (cycles).
• the number of times of washing is preferably 1 to 6 times (cycle), more preferably 1 to 5 times (cycle), even more preferably 1 to 4 times (cycle), and 1 to 5 times (cycle).
• Most preferably, the number of cycles is 3 times to 3 times (cycles).
• the amount of washing water is not particularly limited, and may be, for example, 0.1 parts by weight to 1000 parts by weight per 1 part by weight of the aggregate.
• the amount of washing water is preferably 1 part by weight to 1000 parts by weight, more preferably 1 part to 500 parts by weight, and 1 part to 200 parts by weight, based on 1 part by weight of the aggregate. More preferably, the amount is from 10 parts by weight to 200 parts by weight, even more preferably from 15 parts by weight to 200 parts by weight, and particularly preferably from 20 parts by weight to 200 parts by weight.
• the amount of washing water is preferably 1 to 10 parts by weight, preferably 2 to 10 parts by weight, and also preferably 2 to 5 parts by weight, per 1 part by weight of the aggregate. preferable. Further, when washing is performed by kneading the aggregate and water using a kneader, the amount of washing water can be reduced, which is more preferable.
• the temperature of the washing water is also not limited, and for example, room temperature water or heated water may be used as appropriate. Since hot water has a higher cleaning effect, it is preferable to use heated cleaning water.
• the temperature of the washing water can be, for example, 10°C to 100°C, preferably 15°C to 100°C, more preferably 20°C to 100°C, and preferably 40°C to 100°C. It is more preferably from 40°C to 90°C, even more preferably from 40°C to 85°C, even more preferably from 40°C to 80°C, even more preferably from 40°C to 70°C. It is particularly preferable.
• the method for removing the washed water is not limited, and examples include methods such as discharging washing water, vacuum filtration, oil/water separation, filter press, centrifugation, belt press, screw press, membrane separation, and compression dehydration. be able to.
• the object to be cleaned is intended to be all impurities contained in the aggregate, and is not particularly limited.
• impurities derived from emulsifiers for example, phosphorus emulsifiers, sulfonic acid emulsifiers
• impurities derived from the coagulant, etc. can be mentioned.
• the aggregates and powder containing the polymer fine particles (A) and the resin (B) are operated (handled) in a temperature environment below the glass transition temperature of the grafted part of the polymer fine particles (A). is preferred.
• the aggregates and powder containing the polymer fine particles (A) and the resin (B) are exposed to a temperature environment higher than the glass transition temperature of the grafted portion of the polymer fine particles (A). The shorter the time, the better.
• the obtained powder can provide a printing ink composition that has better dispersibility than the polymer fine particles (A) (that is, the polymer fine particles (A) are more uniformly dispersed).
• the aggregates and powder containing the polymer fine particles (A) and the resin (B) are heated to the glass transition temperature of the grafted part of the polymer fine particles (A).
• the time (period) during which the aqueous latex containing the polymer fine particles (A) is exposed to the above temperature environment can be shortened.
• the temperature of the aqueous latex (before addition of the agent), the temperature of the aqueous solution of the coagulant, the temperature of the aqueous latex containing the polymer particles (A), the resin (B), and the coagulant, the heating temperature in the heating step, the drying temperature in the drying step, The temperature of the cleaning water in the cleaning process, etc.
• the temperature below the glass transition temperature of the grafted part of the polymer fine particles (A) varies depending on the composition of the grafted part, and is appropriately set depending on the composition of the grafted part.
• the aggregates and powder containing the polymer fine particles (A) and the resin (B) are preferably handled in an environment of less than 90°C, more preferably less than 80°C, throughout the manufacturing method. Preferably, it is more preferably handled in an environment of less than 70°C. That is, each temperature mentioned above is preferably less than 90°C, more preferably less than 80°C, more preferably less than 70°C, more preferably less than 60°C, more preferably less than 50°C, and even more preferably less than 40°C.
• the content of the resin (B) in the powder is 50 to 99% by weight when the total of the polymer fine particles (A) and the resin (B) is 100% by weight. %, and the resin (B) is preferably 1 to 50% by weight.
• the content of resin (B) in the powder and granules varies within the numerical range mentioned above, depending on the type of resin (B) and the physical properties of resin (B) (solid, semi-solid, liquid, viscosity, etc.). , may be set as appropriate.
• the resin (B) is liquid at 25° C. and the content of the resin (B) in the granular material is large, the granular material may not be obtained.
• the fluidity (smooth feel) of the powder may deteriorate.
• the content of the resin (B) in the powder will be explained from the point of view of its excellent blocking resistance.
• the polymer fine particles (A) account for 55 to 99 weight%
• the resin (B) accounts for 1 to 45 weight%.
• the polymer fine particles (A) be 60 to 99 weight %, and the resin (B) be 1 to 40 weight %, and the polymer fine particles (A) be 65 to 99 weight %, and the resin ( B) is more preferably 1 to 35% by weight, polymer fine particles (A) is 70 to 99% by weight, resin (B) is 1 to 30% by weight, and polymer fine particles (A) are more preferably 1 to 35% by weight.
• ) is more preferably 75 to 99% by weight, resin (B) is more preferably 1 to 25% by weight, polymer fine particles (A) is 80 to 99% by weight, and resin (B) is 1 to 20% by weight.
• the polymer fine particles (A) be 85 to 99 weight %, and the resin (B) be 1 to 15 weight %, and the polymer fine particles (A) be 90 to 99 weight %, and the resin ( It is even more preferable that B) be 1 to 10% by weight, particularly preferably 95 to 99% by weight of polymer fine particles (A), and 1 to 5% by weight of resin (B).
• the content of the resin (B) in the powder will be explained from the viewpoint of improving the dispersibility of the polymer particles (A) in the printing ink composition.
• the polymer particles (A) should be 50 to 97% by weight and the resin (B) should be 3 to 50% by weight.
• the polymer fine particles (A) is 50 to 95% by weight, and the resin (B) is more preferably 50 to 50% by weight, and the polymer fine particles (A) is 50 to 92% by weight, and the resin (B) is 50 to 92% by weight.
• the polymer fine particles (A) are 50 to 82 weight %, and the resin (B) is more preferably 18 to 50 weight %, and the polymer fine particles (A) are 50 to 80 weight %, and the resin (B) is 50 to 82 weight %. It is even more preferably 20 to 50% by weight, and particularly preferably 60 to 80% by weight of the polymer fine particles (A) and 20 to 40% by weight of the resin (B).
• the content of the resin (B) in the printing ink composition (when the total of the polymer fine particles (A) and the resin (B) is 100% by weight) Resin (B) content) is the resin (B) content in the powder (resin (B) content when the total of polymer fine particles (A) and resin (B) is 100% by weight). content).
• the obtained powder material has (a) excellent blocking resistance, and (b) excellent dispersibility of the polymer fine particles (A) in the printing ink composition.
• Anti-blocking agents include inorganic fine particles such as silicon dioxide, titanium oxide, aluminum oxide, zirconium oxide, aluminum silicate, diatomaceous earth, zeolite, kaolin, talc, calcium carbonate, calcium phosphate, barium sulfate, and magnesium hydrosilicate. ; Anti-blocking agents made of organic fine particles; Oil-based anti-blocking agents such as polyethylene wax, higher fatty acid amides, metal soaps, and silicone oils. Among these, antiblocking agents made of fine particles are preferred, and antiblocking agents made of organic fine particles are more preferred.
• the antiblocking agent made of organic fine particles has a structure derived from one or more monomers selected from aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers as structural units. Particularly preferred is an antiblocking agent made of organic fine particles of a polymer containing units.
• the antiblocking agent made of fine particles is generally one in which fine particles are dispersed in a liquid or in the form of a colloid.
• the fine particles in the antiblocking agent have a volume average particle diameter (Mv) of usually 10 ⁇ m or less, preferably 0.05 ⁇ m to 10.00 ⁇ m.
• Mv volume average particle diameter
• the content of the antiblocking agent is preferably 0.01% to 5.00% by weight, more preferably 0.50% to 3.00% by weight, based on the total weight (100% by weight) of the powder. preferable.
• the powder or granular material may contain other optional components other than the above-mentioned components, if necessary.
• Other optional components include various components described in the section (2-2-5. Additives) below.
• the antiblocking agent and other optional components can be added as appropriate during any step in the method for producing the present powder or granule.
• the antiblocking agent and other optional components may be added to an aqueous suspension (aqueous latex) of the polymer fine particles (A) or the polymer fine particles (A) and the resin (B) before or after coagulation. Can be added.
• the antiblocking agent and other optional components can also be added to the fine polymer particles (A), the resin (B), or the powder containing the fine polymer particles (A) and the resin (B).
• a preferred embodiment of the method for producing a dispersion includes, in order: (i) preparing an aqueous latex containing fine polymer particles (A); (In other words, the first step is to prepare the polymer fine particles (A) by emulsion polymerization), (ii) the aqueous latex containing the polymer fine particles (A) (in detail, the polymer fine particles (A) are prepared by emulsion polymerization); (reaction mixture after producing) with an organic solvent whose solubility in water at 20 ° C.
• the method for producing the UV curable printing ink composition according to an embodiment of the present invention is performed using the powder or granule described in the section (Powder or granule) or the method described in the section (2-8-2. Method 2). and components other than the polymer fine particles (A) and the resin (B).
• a method for producing a printing ink composition according to an embodiment of the present invention includes a powder or granule obtained by the method for producing a powder or granule described in the section (Method for producing a powder or granule) or (2-8-2) The method may include a step of mixing the dispersion described in Method 2) with components other than the polymer particles (A) and the resin (B). According to these configurations, it is possible to obtain a printing ink composition in which the polymer particles (A) are uniformly dispersed in components other than the polymer particles (A) and the resin (B).
• the method (step) include methods using a rotation/revolution mixer, a planetary mixer, a disperser, and the like.
• a preferred method for mixing the powder and granules with components other than the polymer particles (A) and the resin (B) is, for example, a method of mixing at 2000 rpm for 40 minutes using a rotation/revolution mixer.
• UV curable printing ink composition according to one embodiment of the present invention can be suitably used as a printing ink (printing ink).
• the cured film according to one embodiment of the present invention includes [2. UV curable printing ink composition] is preferably obtained by curing the UV curable printing ink composition described in [UV curable printing ink composition]. According to this configuration, the main cured film has the advantage that it is difficult to peel off from the base material.
• a UV curable printing ink composition must contain a large amount of a photopolymerization initiator and a polyfunctional monomer, and must have excellent curability (high sensitivity). There is.
• curability and adhesion in a curable composition there is a trade-off between curability and adhesion in a curable composition, and photopolymerization initiators and polyfunctional monomers (for example, low-molecular compounds having at least three or more polymerizable unsaturated bonds in one molecule) UV curable printing ink compositions containing large amounts of C)) and the like have a drawback of low adhesion to substrates.
• photopolymerization initiators and polyfunctional monomers for example, low-molecular compounds having at least three or more polymerizable unsaturated bonds in one molecule
• this printing ink composition solves the above problems and has the advantage of having excellent adhesion to the substrate. In other words, it can be said that the cured film is difficult to peel off from the base material.
• the light source for curing the printing ink composition that is, the light source for obtaining a cured film from the printing ink composition, is not particularly limited, but a high-pressure mercury lamp, a metal halide lamp, and a UV-LED lamp are preferred. Note that it is also possible to use an EB (electron beam) lamp as the light source. When using an EB (electron beam) lamp, the electron beam can decompose organic molecules and initiate radical polymerization, so there is no need to include a photopolymerization initiator.
• the method of printing the UV curable printing ink composition on the base material is not particularly limited, and examples thereof include offset printing, screen printing, flexo printing, and IJ printing.
• An embodiment of the present invention may have the following configuration.
• a UV curable printing ink composition comprising a polymer fine particle (A) and a pigment (D), wherein the polymer fine particle (A) is attached to an elastic body and is graft-bonded to the elastic body.
• a rubber-containing graft copolymer having a graft portion, the elastic body containing one or more selected from the group consisting of a diene rubber, a (meth)acrylate rubber, and an organosiloxane rubber;
• the graft portion includes a polymer containing a structural unit derived from one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers.
• a UV curable printing ink composition wherein the content of the pigment (D) in the UV curable printing ink composition is 1% by weight or more based on 100% by weight of the UV curable printing ink composition.
• the UV curable printing ink composition further contains a low molecular compound (C),
• the low molecular compound (C) is The UV-curable printing ink composition according to [1] or [2], which (i) has at least one polymerizable unsaturated bond in the molecule, and (ii) has a molecular weight of less than 1000.
• the low-molecular compound (C) contains 5% by weight or more of a low-molecular compound having at least 3 or more polymerizable unsaturated bonds in one molecule based on 100% by weight of the low-molecular compound (C),
• the UV curable printing ink composition further includes a radically polymerizable oligomer resin and/or an inert resin (E), and the radically polymerizable oligomer resin and the inert resin in the UV curable printing ink composition
• E radically polymerizable oligomer resin and/or an inert resin
• the UV curable type according to any one of [1] to [4], wherein the total content of (E) is 0.5% by weight or more based on 100% by weight of the UV curable printing ink composition. Printing ink composition.
• the UV curable printing ink composition further includes a photopolymerization initiator (F), and the content of the photopolymerization initiator (F) in the UV curable printing ink composition is such that the UV curable printing ink composition further includes a photopolymerization initiator (F).
• the UV-curable printing ink composition according to any one of [1] to [5], which is 1.0% by weight or more based on 100% by weight of the printing ink composition.
• a step of preparing a powder containing the polymer fine particles (A), and a step of mixing the powder and the pigment (D) to prepare a UV curable printing ink composition
• the polymer fine particles (A) include a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body, and the elastic body includes diene rubber, (meth)acrylate, etc.
• the graft portion contains one or more selected from the group consisting of aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers.
• the content of the pigment (D) in the UV curable printing ink composition includes a polymer containing a structural unit derived from one or more monomers selected from the UV curable printing ink composition.
• a step of preparing a dispersion containing the polymer fine particles (A), and a step of mixing the dispersion and the pigment (D) to prepare a UV curable printing ink composition
• the fine particles (A) include a rubber-containing graft copolymer having an elastic body and a graft portion grafted to the elastic body, and the elastic body is made of diene rubber, (meth)acrylate rubber, etc. , and an organosiloxane rubber, and the graft portion is selected from the group consisting of an aromatic vinyl monomer, a vinyl cyan monomer, and a (meth)acrylate monomer.
• the content of the pigment (D) in the UV curable printing ink composition is 100% by weight of the UV curable printing ink composition. % or more by weight of UV curable printing ink composition.
• polymer fine particles refers to polymer fine particles (A) which are polymer fine particles according to one embodiment of the present invention, and polymer fine particles outside the scope of the present invention. Includes all.
• the printing ink compositions obtained in each example and comparative example were applied to a PMMA sheet to a thickness of 30 ⁇ m.
• the obtained PMMA sheet was irradiated with ultraviolet rays to cure the printing ink composition, and a cured film made of the printing ink composition was formed on the PMMA sheet.
• the cured film formed on the PMMA sheet is cut using a cutter into a checkerboard shape consisting of squares each measuring 1 mm in length x 1 mm in width (10 vertical cuts ⁇ 10 pieces horizontally) were formed.
• cellophane tape manufactured by Nichiban Co., Ltd.
• the cellophane tape was peeled off from the cured film, and the number of squares on the PMMA sheet in which the cured film remained in an area of 80% or more of the total area of one square was visually counted.
• the adhesion of the printing ink composition was determined using the following criteria. The results are shown in Table 1. 2 (Good): The number of squares on the PMMA sheet is 80 or more, in which the cured film remains on 80% or more of the total area of one square. 1 (Acceptable): The cured film remains on one square. The number of squares on the PMMA sheet remaining in 80% or more of the total area of The number of squares remaining on the PMMA sheet by area is 50 or less.
• each of PHP, EDTA, and ferrous sulfate heptahydrate was added in arbitrary amounts and at arbitrary times into the pressure-resistant polymerization vessel.
• an aqueous latex (R-1) containing an elastic body mainly composed of polybutadiene rubber was obtained.
• the volume average particle diameter of the elastic body contained in the obtained aqueous latex was 70 nm.
• EDTA 0.003 parts by weight of EDTA, 0.0007 parts by weight of ferrous sulfate heptahydrate, and 0.14 parts by weight of SFS were added into the glass reactor and stirred for 10 minutes. Thereafter, a mixture of 19 parts by weight of methyl methacrylate (MMA), 1 part by weight of butyl acrylate, and 0.1 part by weight of t-butyl hydroperoxide (BHP) was continuously added into the glass reactor over a period of 80 minutes. did. Thereafter, 0.012 parts by weight of BHP was added into the glass reactor, and the mixture in the glass reactor was continued to be stirred for an additional hour to complete the polymerization.
• MMA methyl methacrylate
• BHP t-butyl hydroperoxide
• an aqueous latex (L-1) containing polymer fine particles (A) was obtained.
• the polymerization conversion rate of the monomer components was 99% or more.
• the volume average particle diameter of the polymer fine particles (A) contained in the obtained aqueous latex was 200 nm.
• the solid content concentration (concentration of polymer fine particles (A)) in the obtained aqueous latex (L-1) was 30%.
• Powder (P-1) contains 90% by weight of polymeric particles (A) and 10% by weight of resin (B), when the total of polymeric particles (A) and resin (B) is 100% by weight. It contained % by weight.
• a mixing tank (volume 1 L) equipped with a stirrer was used. Furthermore, methyl ethyl ketone (MEK) was used as an organic solvent that shows partial solubility in water. After the temperature in the mixing tank was set to 30° C., 126 parts by weight of MEK was put into the mixing tank. Thereafter, while stirring the MEK in the mixing tank, 143 parts by weight of latex (L-1) of polymer fine particles (A) was added to the mixing tank. By uniformly mixing the charged raw materials, a mixture (mixture M) of an aqueous latex containing polymer fine particles (A) and an organic solvent partially soluble in water was obtained.
• MEK methyl ethyl ketone
• the aggregates were then separated and recovered from the aqueous phase. Specifically, the aggregates were obtained by discharging 350 parts by weight of the aqueous phase from the outlet at the bottom of the mixing tank while leaving the aggregates in the mixing tank. 150 parts by weight of MEK was added to the obtained aggregate (polymer fine particles (A) dope) and mixed to obtain a first organic solvent dispersion containing polymer fine particles (A). The obtained first organic solvent solution was 277 parts by weight (containing 42.9 parts by weight of polymer fine particles (A)).
• the polymer fine particles (A) account for 40 weight percent, and the low molecular compound (C)
• the polymer fine particles (A) and the low molecular weight compound (C) were mixed at a blending ratio of 60% by weight.
• MEK was distilled off under reduced pressure from the obtained second organic solvent dispersion to obtain a masterbatch (M-1).
• the masterbatch (M-1) contains 40% by weight of the polymeric particles (A) and the low-molecular compound (C), when the total of the polymeric particles (A) and the low-molecular compound (C) is 100% by weight. ) contained 60% by weight.
• Example 1 Production of UV curable printing ink composition> (Example 1) A printing ink composition was produced by mixing 100% by weight of offset UV ink (manufactured by Toyo Ink Co., Ltd., FD LPC PR Eye CM) with 2.0% by weight of powder (P-1) using a three-roll mill. did.
• the offset UV ink contains 20% by weight or more of component (C), 1% or more of pigment as component (D), 1.0% by weight or more of component (E), out of 100% by weight of the offset UV ink. and (F) component at 1.0% by weight or more.
• Example 2 A printing ink composition was produced by mixing 100% by weight of offset UV ink (manufactured by Toyo Ink Co., Ltd., FD LPC PR Eye CM) with 5.0% by weight of masterbatch (M-1) using a three-roll mill. .
• Example 3 A printing ink composition was prepared by mixing 1.0% by weight of powder (P-1) with 100% by weight of inkjet UV ink (manufactured by Mimaki Engineering Co., Ltd., LH-100) in a three-roll mill.
• the component (C) is 20% by weight or more
• the pigment as the (D) component is 1% by weight or more
• the component (E) is 0.5% by weight or more
• (F) component at 1.0% by weight or more.
• Example 4 A printing ink composition was prepared by mixing 100% by weight of inkjet UV ink (manufactured by Mimaki Engineering Co., Ltd., LH-100) with 2.0% by weight of powder (P-1) in a three-roll mill.
• the UV curable printing ink composition according to one embodiment of the present invention can be suitably used as a printing ink (printing ink).

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• 2023
  • 2023-07-07 JP JP2024532642A patent/JPWO2024010080A1/ja active Pending
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