WO2012128138A1 - 塩化ビニル系樹脂エマルジョン及びその製造方法並びに水性インキ及び記録用紙 - Google Patents
塩化ビニル系樹脂エマルジョン及びその製造方法並びに水性インキ及び記録用紙 Download PDFInfo
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- WO2012128138A1 WO2012128138A1 PCT/JP2012/056512 JP2012056512W WO2012128138A1 WO 2012128138 A1 WO2012128138 A1 WO 2012128138A1 JP 2012056512 W JP2012056512 W JP 2012056512W WO 2012128138 A1 WO2012128138 A1 WO 2012128138A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/08—Vinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
-
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
Definitions
- the present invention relates to a vinyl chloride resin emulsion that can be effectively used for binders such as inks, paints, inorganic substance dispersions, recording paper receiving layers, fiber treating agents, and the like.
- binders such as inks, paints, inorganic substance dispersions, recording paper receiving layers, fiber treating agents, and the like.
- binders such as inks, paints, inorganic substance dispersions, recording paper receiving layers, fiber treating agents, and the like.
- binders such as inks, paints, inorganic substance dispersions, recording paper receiving layers, fiber treating agents, and the like.
- binders such as inks, paints, inorganic substance dispersions, recording paper receiving layers, fiber treating agents, and the like.
- binders such as inks, paints, inorganic substance dispersions, recording paper receiving layers, fiber treating agents, and the like.
- the present invention relates to a vinyl chloride resin emulsion that exhibits high gloss and
- the gravure printing ink in general printing, its quality is determined by the printability and printing effect of the printing ink.
- Printability is a property related to the behavior of the ink from when the ink on the printing press is transferred to the substrate to form the printing surface.
- the main properties include ink fluidity, interface suitability, and drying properties.
- the printing effect is the quality of printing exhibited by the ink on which the printing surface is formed, and the characteristics include color tone, gloss, water resistance, blocking resistance and the like.
- the basic composition of ink is composed of colorants (dyes, pigments), vehicles, and auxiliary agents (fluidity modifiers, drying modifiers, etc.), among which the vehicle has a great influence on printability and printing effect. .
- the basic composition of the vehicle is a binder, a wax, a solvent, and the like. Therefore, the properties of the vehicle greatly change depending on the choice of the binder, and this greatly affects the printability and the printing effect.
- Binders are roughly classified into solvent-type binders and aqueous binders.
- the solvent-type binder include urethane resins proposed in Japanese Patent Laid-Open No. 9-12956 (Patent Document 1).
- Patent Document 1 Japanese Patent Laid-Open No. 9-12956
- aqueous binders that do not use organic solvents have attracted attention because of considerations such as air pollution, fire hazard, and occupational health.
- aqueous binders examples include alkali-soluble resins typified by styrene / acrylic resins, water-soluble resins typified by polyvinyl alcohol, urethane emulsions (Patent Document 2: JP-A-2-238015), and acrylic emulsions. It is roughly divided into water-dispersed resins.
- the ink when printing using water-based ink with a water-dispersible resin as a binder, the ink is applied to the printing surface at room temperature on a printing machine, and then dried to finish above the glass transition temperature of the water-dispersible resin. It is done. Thus, if it heats more than a glass transition temperature, resin particles will cause the whole to fuse
- the drying ink needs to maintain fluidity without being dried on the printing machine for as long as possible.
- Solvent-type resins, alkali-soluble resins, and water-soluble resins once formed into a dry film, will dissolve in the solvent, aqueous alkali solution or water and maintain the original fluidity.
- alkali-soluble resins have a problem of poor alkali resistance
- water-soluble resins have a problem of poor water resistance
- conventional binders are prepared by using alkali-soluble resins or water-soluble resins in combination with water-dispersed resins. There is a case.
- the alkali resistance and water resistance are poor, and when trying to improve the alkali resistance and water resistance, the printability is insufficient.
- Patent Document 3 selects from vinyl chloride, (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms and monoalkenylbenzenes.
- a water-based ink binder has been proposed comprising a monomer selected from an ethylenically unsaturated monomer having a functional group, an ethylenically unsaturated monomer having a functional group, and other ethylenically unsaturated monomers.
- moisture resistance and gloss there were problems in terms of moisture resistance and gloss.
- Patent Document 4 Japanese Patent Application Laid-Open No. 11-35866. Fluoropolymers are excellent in various aspects such as weather resistance and corrosion resistance, but cost problems still remain.
- the ink jet recording method is excellent in quietness, recording speed, printing quality, and running cost, and is generally widely used.
- the ink used in this method is water-based ink from the viewpoints of ink physical properties, safety, ease of handling, and the like.
- water-soluble dyes such as acid dyes, direct dyes, basic dyes, etc., dissolved in a glycol solvent and water (Patent Documents 5 to 7: JP-A-53-61412, JP-A-SHO) No. 54-89811 and JP-A-55-65269) are known, but have the disadvantage of poor water resistance.
- Patent Document 8 JP-A-61-61.
- Patent Document 9 Japanese Patent Laid-Open No. 8-253716.
- Patent Document 11 Japanese Patent Laid-Open No. 56-144854
- an ink receiving layer containing porous pigment particles is provided on both sides.
- Patent Document 12 Japanese Patent Laid-Open No. 62-2880766
- a water-insoluble resin obtained by reacting polyvinyl alcohol, acrylic acid and methyl methacrylate.
- the water-insoluble resin is anionic, the fixability of the same anionic water-based ink is poor, and no solution has been reached to improve ink bleeding or water resistance.
- a recording sheet containing a polycation polymer electrolyte (Patent Document 13: Japanese Patent Laid-Open No. 56-84992) and an ink receiving layer mainly composed of a cationic polymer binder having ink adsorption properties were provided.
- Recording sheets (Patent Document 14: Japanese Patent Laid-Open No. 58-24493) and recording sheets containing a cationic acrylic resin emulsion (Patent Documents 15 and 16: Japanese Patent Laid-Open Nos. 11-123867 and 2001-199152) Publication) has also been proposed, but it is not always satisfactory in terms of color development and water resistance.
- Patent Document 18 PCT / JP2010 / 59418
- the weight ratio of vinyl chloride in the polymer is low.
- the present invention has been made in view of the above circumstances, and when used in water-based ink, exhibits excellent water resistance, moisture resistance, high gloss, and alcohol resistance, and when used in recording paper, it is excellent. Excellent color development, water resistance, moisture resistance, color visibility, high gloss, releasability, etc. Effective for inks, paints, binders for dispersing inorganic substances, recording paper receiving layers, fiber treatment agents, etc.
- An object of the present invention is to provide a vinyl chloride resin emulsion that can be used and a method for producing the same.
- Another object of the present invention is to provide a water-based ink and recording paper using such a vinyl chloride resin emulsion.
- (B) vinyl chloride monomer or (B) vinyl chloride monomer and copolymerizable with (C) ethylenic monomer Chloride obtained by emulsion polymerization of 100 parts by weight of a monomer mixture with a saturated group-containing monomer in the presence of (A) styrene / acrylate oligomer and / or 40 to 500 parts by weight of acrylate oligomer.
- the present invention provides a vinyl chloride resin emulsion, a production method thereof, a water-based ink and a recording paper.
- 100 parts by mass of (B) a vinyl chloride monomer or (B) a vinyl chloride monomer and a monomer mixture of (C) an ethylenically unsaturated group-containing monomer copolymerizable therewith is used as (A) styrene
- a vinyl chloride polymer emulsion obtained by emulsion polymerization in the presence of 40 to 500 parts by mass of an acrylic ester oligomer and / or an acrylic ester oligomer is used as (D) seed
- 100 parts by mass of (E) vinyl chloride monomer or (E) monomer mixture of vinyl chloride monomer and (F) ethylenically unsaturated group-containing monomer copolymerizable therewith is the above (D)
- [4] 100 parts by mass of (B) a vinyl chloride monomer or (B) a vinyl chloride monomer and a monomer mixture of (C) an ethylenically unsaturated group-containing monomer copolymerizable therewith is used as (A) styrene -A seed (D) consisting of a vinyl chloride polymer emulsion is prepared by emulsion polymerization in the presence of 40 to 500 parts by mass of an acrylic ester oligomer and / or an acrylic ester oligomer; 100 parts by mass of (E) vinyl chloride monomer or (E) monomer mixture of vinyl chloride monomer and (F) ethylenically unsaturated group-containing monomer copolymerizable therewith is the above (D) A method for producing a vinyl chloride resin emulsion, wherein emulsion polymerization is performed using 3 to 50 parts by mass of a seed as a solid content.
- [5] The method for producing a vinyl chloride resin emulsion as described in [4], wherein the oligomer (A) has a number average molecular weight of 5,000 to 50,000. [6] [4] or [5], wherein the seed (D) has an average particle diameter of 20 to 800 nm. [7] A water-based ink containing the vinyl chloride resin emulsion according to any one of [1] to [3]. [8] The content of the vinyl chloride resin emulsion is 2 to 30% by mass as a solid content, further contains 3 to 40% by mass of a colorant, 0 to 50% by mass of a water-soluble organic solvent, and 5 to 95% by mass of water. The water-based ink according to [7].
- the coating film contains 2 to 30% by weight of the solid content of the vinyl chloride resin emulsion, further contains 0 to 30% by weight of pigment, 0 to 60% by weight of water-soluble organic solvent, and 5 to 98% by weight of water.
- the recording paper according to [9] or [10] which is formed from the composition as described above.
- the vinyl chloride resin emulsion of the present invention exhibits excellent water resistance, moisture resistance, high gloss and alcohol resistance when used in water-based inks, and excellent color developability when used in recording paper. It can be used effectively as a binder for ink, paint, inorganic substance dispersion, recording paper receiving layer, fiber treating agent, etc., exhibiting water resistance, moisture resistance, color visibility, high gloss, releasability, etc. .
- the vinyl chloride resin emulsion of the present invention is a single amount of (B) vinyl chloride monomer or (B) vinyl chloride monomer and (C) ethylenically unsaturated group-containing monomer copolymerizable therewith. 100 parts by mass of the body mixture is emulsion-polymerized in the presence of (A) styrene / acrylate oligomer and / or acrylate oligomer, particularly 40 to 500 parts by mass of an oligomer having a number average molecular weight of 5,000 to 50,000.
- (D) seed made of a vinyl chloride polymer emulsion 100 parts by mass of (E) vinyl chloride monomer or (E) monomer mixture of vinyl chloride monomer and (F) ethylenically unsaturated group-containing monomer copolymerizable therewith is the above (D)
- (D) the seed manufacturing method will be described.
- Examples of the acrylate monomer used in the styrene / acrylate oligomer and the acrylate oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.
- (meth) acryl is a general term for acrylic and methacrylic. Examples of commercially available products include JONCRYL JDX-6500, JONCRYL JDX-6102B, JONCRYL HPD-96J, and JONCRYL 52J (all manufactured by BASF), but are not limited thereto. Two or more are used.
- the mass ratio of styrene / acrylic acid ester is preferably 50/50 to 0/100.
- the oligomer is used in an amount of (B) a vinyl chloride monomer or a monomer mixture of (B) a vinyl chloride monomer and (C) an ethylenically unsaturated group-containing monomer copolymerizable therewith.
- the content is preferably 40 to 500 parts by mass, more preferably 100 to 300 parts by mass with respect to parts by mass. If the amount is less than 40 parts by mass, there may be a problem that aggregates are generated. If the amount exceeds 500 parts by mass, the reaction may be inactivated and stable production may not be possible.
- the number average molecular weight of the styrene / acrylic acid ester oligomer and acrylic acid ester oligomer is preferably 5,000 to 50,000, and more preferably 8,000 to 20,000. If the molecular weight is less than 5,000, there may be an inconvenience that aggregates are generated. If the molecular weight exceeds 50,000, a large amount of aggregates are generated, and in the worst case, inconveniences such as gelation may occur.
- the number average molecular weight is a polystyrene conversion value measured by GPC, and in the present invention, those having a number average molecular weight of 50,000 or less are called oligomers.
- the ethylenically unsaturated group-containing monomer copolymerizable with the vinyl chloride monomer (C) includes vinyl acetate, ethylene, propylene, vinylidene chloride, and vinyl carboxylates such as vinyl propionate.
- Aromatic vinyl monomers such as styrene and ⁇ -methylstyrene, conjugated diene monomers such as 1,3-butadiene and 2-methyl-1,3-butadiene, methyl acrylate, acrylic acid Ethylenic unsaturated monocarboxylic esters such as ethyl, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethylenic dimethyl itaconate, diethyl maleate, monobutyl maleate, monoethyl fumarate, dibutyl fumarate, etc.
- Ethylenic unsaturation such as unsaturated polycarboxylic acid esters, acrylic acid, methacrylic acid, crotonic acid Nocarboxylic acids, itaconic acid, maleic acid, fumaric acid and other ethylenically unsaturated dicarboxylic acids, glycidyl methacrylate and other epoxy group-containing monomers, 2-hydroxyethyl methacrylate and other alcoholic hydroxyl group-containing monomers, methoxyethyl Alkoxy group-containing monomers such as acrylate, nitrile group-containing monomers such as acrylonitrile, amide group-containing monomers such as acrylamide, amino group-containing monomers such as dimethylaminoethyl methacrylate, divinylbenzene, Examples include monomers having two or more ethylenically unsaturated groups in one molecule, such as allyl methacrylate, and one or more of these are selected. Vinyl acetate, ethylenically uns
- the ratio of (B) the vinyl chloride monomer and the (C) ethylenically unsaturated group-containing monomer copolymerizable therewith is 50:50 to 100: 0, particularly 70:30 as a mass ratio. Preferably it is ⁇ 100: 0. If the amount of vinyl chloride is too small, aggregates may be generated, and the vinyl chloride emulsion characteristic of the present invention cannot be obtained.
- the solid content of the obtained seed (D) is preferably 20 to 40% by mass, the average particle size is preferably 20 to 800 nm, and the average degree of polymerization is preferably 300 to 1,000. Create a seed.
- (E) vinyl chloride monomer or (E) vinyl chloride monomer and (F) ethylenically unsaturated group-containing monomer copolymerizable therewith A method for emulsion polymerization of the monomer mixture will be described.
- the ethylenically unsaturated group-containing monomer copolymerizable with the vinyl chloride monomer (F) include the same monomers as those described above in (C).
- the ratio of (E) vinyl chloride monomer and (F) ethylenically unsaturated group-containing monomer copolymerizable therewith is 50:50 to 100: 0, particularly 80:20 as a mass ratio. Preferably it is ⁇ 100: 0. If the amount of vinyl chloride is too small, aggregates may be generated.
- the amount of seed used is (E) vinyl chloride monomer or (E) monomer of vinyl chloride monomer and monomer copolymerizable with (F) ethylenically unsaturated group.
- the solid content is 3 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the mixture. If the amount is less than 3 parts by mass, there may be a problem that a large amount of aggregates are generated. If the amount exceeds 50 parts by mass, aggregates may be generated.
- the seed used in the present invention is preferably added before the polymerization reaction of the vinyl chloride emulsion (at the time of charging), and has characteristics without using an emulsifier in the polymerization (becomes polymerization by increasing the polymerization of vinyl chloride). An emulsion is obtained.
- Monomers and other polymerization aids for example, emulsifiers such as alkyl sulfate esters, polymerization initiators such as ammonium persulfate, chain transfer agents such as mercaptans, pH adjusters such as sodium carbonate, various antifoaming agents, etc.
- emulsifiers such as alkyl sulfate esters
- polymerization initiators such as ammonium persulfate
- chain transfer agents such as mercaptans
- pH adjusters such as sodium carbonate
- various antifoaming agents etc.
- a nonionic surfactant or an anionic emulsifier can be used in combination as long as the effects of the present invention are not impaired.
- Examples of the polymerization initiator used in the emulsion polymerization include persulfates such as ammonium persulfate and potassium persulfate, azo compounds such as 2,2′-diamidino-2,2′-azopropane dihydrochloride and azobisisobutyronitrile. , Cumene hydroperoxide, benzoyl peroxide, peroxides such as hydrogen peroxide, tartaric acid and the like. Moreover, a well-known redox-type initiator, for example, potassium persulfate, sodium hydrogensulfite, etc. are mentioned.
- the amount of the polymerization initiator used is usually 0.1 to 2.0% by mass, preferably 0.2 to 1.0% by mass, based on the monomer or monomer composition.
- the polymerization temperature for carrying out the emulsion polymerization is usually 40 to 80 ° C., preferably 50 to 70 ° C.
- the polymerization time may be appropriately set, but is preferably 10 to 15 hours. This polymerization is desirably performed in an atmosphere of an inert gas such as nitrogen gas.
- the evaporation residue is preferably 10 to 50% by mass, more preferably 20 to 40% by mass. If it is less than 10% by mass, aggregates may be generated, and if it exceeds 50% by mass, a large amount of aggregates may be generated.
- a plasticizer, an inorganic or organic filler, a thickener, etc. can be added within a range that does not impair the performance of the water-based ink binder of the present invention and the recording paper receiving layer.
- the average particle diameter of the emulsion is 50 to 2,000 nm, preferably 100 to 1,000 nm, and the viscosity is 5 to 2,000 mPa ⁇ s at 23 ° C.
- the resin emulsion according to the present invention can be used for various applications, but particularly when used for recording paper, it exhibits excellent color development, water resistance, moisture resistance, high gloss, and when used for water-based ink. Gives water resistance, moisture resistance, color visibility, high gloss, and excellent alcohol resistance.
- the vinyl chloride resin emulsion of the present invention when used in water-based ink, a colorant, a water-soluble organic solvent, various additives, water, and the like are blended in the vinyl chloride resin emulsion, and a known disperser, mixing It can be produced by dispersing and mixing with a machine, a kneader or the like.
- the content of the vinyl chloride resin emulsion in the water-based ink is preferably 2 to 30% by mass, particularly 5 to 20% by mass as a solid content. If it is less than 2% by mass, there may be a problem that the adhesion is deteriorated, and if it exceeds 30% by mass, there may be a problem that the viscosity is increased.
- Water-soluble organic solvents include ethylene glycol monoether, diethylene glycol monoether, propylene glycol monoether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol, diethylene glycol, propylene glycol, glycerin, methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, methyl cellosolve, Ethyl cellosolve, acetone, ethyl acetate, diacetone alcohol and the like can be used, and the content is preferably 0 to 50% by mass, particularly preferably 0 to 40% by mass in the aqueous ink.
- Water is preferably contained in the water-based ink in an amount of 5 to 95% by mass, particularly 10 to 90% by mass.
- the additive include a pigment dispersant, a leveling agent, an antifoaming agent, and the like, and these additives can be used at a normal dose in water-based ink.
- the vinyl chloride resin emulsion of the present invention when used for recording paper, it can be suitably used particularly for forming a receiving layer of recording paper.
- a pigment, a water-soluble organic solvent, various additives, water, and the like can be blended with the vinyl chloride resin emulsion, and dispersed and mixed by a known disperser, mixer, kneader, or the like.
- the composition for forming the receiving layer containing the vinyl chloride resin emulsion used for forming the receiving layer contains 2 to 30% by mass, particularly 5 to 20% by mass, of the solid content of the vinyl chloride resin emulsion. preferable.
- amorphous synthetic silica, aluminum silicate, magnesium silicate, precipitated calcium carbonate, heavy calcium carbonate, calcium silicate, aluminum hydroxide, zeolite, calcined clay, kaolin clay, talc, white carbon, etc. are blended. be able to.
- the blending amount of these components is preferably 0 to 30% by mass, particularly preferably 0 to 20% by mass.
- Water-soluble organic solvents include ethylene glycol monoether, diethylene glycol monoether, propylene glycol monoether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol, diethylene glycol, propylene glycol, glycerin, methanol, ethanol, isopropyl alcohol, methyl ethyl ketone, methyl cellosolve, Ethyl cellosolve, acetone, ethyl acetate, diacetone alcohol and the like can be used, and the content is preferably 0 to 60% by mass, particularly 0 to 50% by mass in the water-based ink. Water is preferably contained in the water-based ink in an amount of 5 to 98% by mass, particularly 10 to 90% by mass.
- a pigment dispersant, an antifoaming agent, a colorant, an antioxidant, an ultraviolet absorber, a viscosity modifier, a release agent, and the like can be blended.
- the receiving layer-forming composition is applied to a support such as commercially available paper by a coating method such as a brush coater, an air knife coater, a curtain coater, a Mayer bar coater, a gravure coater, or a roll coater. It can be produced by coating, spraying and drying so as to have a solid content of ⁇ 25 g / m 2 (dry polymerization solid content) (thickness of 0.5 to 100 ⁇ m), preferably 1 to 10 g / m 2 .
- a coating method such as a brush coater, an air knife coater, a curtain coater, a Mayer bar coater, a gravure coater, or a roll coater.
- the polymerization internal pressure reached 0 MPa
- the residual monomer was removed to 1,000 ppm in a vacuum, and then cooled to 40 ° C. or lower to obtain a polymer.
- the solid content was 30%
- the pH was 7.5
- the viscosity (23 ° C.) measured by a B-type viscometer was 10 mPa ⁇ s.
- the composition of the seeds 1 to 6 and the solid content, pH, average particle size, and viscosity measured by the following evaluation method are shown in Table 1 below.
- Average degree of polymerization The degree of polymerization can be obtained as a weight average degree of polymerization as a polystyrene conversion value by gel permeation chromatography (GPC) analysis.
- JONCRYL JDX-6500 BASF acrylic ester oligomer, number average molecular weight 10,000
- JONCRYL HPD-96J BASF styrene / acrylic acid ester oligomer, number average molecular weight 16,500
- Example 1 In a polymerization vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet, after nitrogen substitution, 64 parts of deionized water, 27 parts of vinyl chloride, and 19 parts of seed 19 (30% active ingredient) were charged and stirred. Warmed to 60 ° C. Further, 0.1 part of ammonium persulfate (initiator) was dissolved in 1 part of deionized water and added, and the polymerization reaction was carried out for 24 hours. When the polymerization internal pressure reached 0 MPa, the residual monomer was removed to 1,000 ppm in a vacuum, and then cooled to 40 ° C. or lower to obtain a polymer.
- initiator ammonium persulfate
- the solid content was 30%, the pH was 7.0, and the viscosity (23 ° C.) measured by a B-type viscometer was 10 mPa ⁇ s. In addition, it was measured by GPC that the obtained emulsion was a vinyl chloride resin. The results are shown in Table 2.
- Examples 2 to 13 Comparative Examples 1 to 7
- Polymerization similar to that of Example 1 was carried out with the compositions shown in Tables 2 and 3 to obtain a vinyl chloride resin emulsion.
- Tables 2 and 3 show the results of measuring the vinyl chloride resin emulsions obtained in Examples 1 to 13 and Comparative Examples 1 to 7 by the following evaluation method.
- ⁇ PH measurement method> The vinyl chloride resin emulsion was measured as it was using a pH meter according to JIS Z8802 (pH measurement method).
- ⁇ B type viscometer viscosity measurement method The liquid temperature of the vinyl chloride resin emulsion was maintained at 23 ⁇ 0.5 ° C. and measured with a BM viscometer (No. 1 rotor, 6 rpm).
- Glossy The printed part was measured with a gloss meter PG-1M (manufactured by Nippon Denshoku Industries Co., Ltd.), the value at a light projection / reception angle condition of 60 ° was read, and judged according to the following criteria.
- ⁇ Gloss value is 90 or more
- ⁇ Gloss value is 70 or more and less than 90
- ⁇ Gloss value is less than 70
- Sample 67 was prepared by mixing 67 parts of a vinyl chloride resin emulsion (solid content 30%), 20 parts of carbon black MA100 (manufactured by Mitsubishi Paper Industries), and 13 parts of water.
- JONCRYL JDX-6500 BASF acrylic ester oligomer, number average molecular weight 10,000 Neugen XL-6190: Nonionic emulsifier Perex SS-L manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Anionic emulsifier manufactured by Kao Corporation
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Abstract
Description
(E)塩化ビニル単量体又は(E)塩化ビニル単量体とこれと共重合可能な(F)エチレン性不飽和基含有単量体との単量体混合物を乳化重合させて得られることを特徴とする塩化ビニル系樹脂エマルジョンが、前述した課題を克服できることを見出し、本発明をなすに至った。
〔1〕
(B)塩化ビニル単量体又は(B)塩化ビニル単量体とこれと共重合可能な(C)エチレン性不飽和基含有単量体との単量体混合物100質量部を(A)スチレン・アクリル酸エステルオリゴマー及び/又はアクリル酸エステルオリゴマー40~500質量部の存在下で乳化重合させることによって得られる塩化ビニル系ポリマーエマルジョンを(D)シードとし、
(E)塩化ビニル単量体又は(E)塩化ビニル単量体とこれと共重合可能な(F)エチレン性不飽和基含有単量体との単量体混合物100質量部を上記(D)シードを固形分として3~50質量部用いて乳化重合させて得られることを特徴とする塩化ビニル系樹脂エマルジョン。
〔2〕
上記オリゴマー(A)の数平均分子量が5,000~50,000であることを特徴とする〔1〕に記載の塩化ビニル系樹脂エマルジョン。
〔3〕
シード(D)の平均粒子径が20~800nmであることを特徴とする〔1〕又は〔2〕に記載の塩化ビニル系樹脂エマルジョン。
〔4〕
(B)塩化ビニル単量体又は(B)塩化ビニル単量体とこれと共重合可能な(C)エチレン性不飽和基含有単量体との単量体混合物100質量部を(A)スチレン・アクリル酸エステルオリゴマー及び/又はアクリル酸エステルオリゴマー40~500質量部の存在下で乳化重合させることによって塩化ビニル系ポリマーエマルジョンからなる(D)シードを調製し、
(E)塩化ビニル単量体又は(E)塩化ビニル単量体とこれと共重合可能な(F)エチレン性不飽和基含有単量体との単量体混合物100質量部を上記(D)シードを固形分として3~50質量部用いて乳化重合させることを特徴とする塩化ビニル系樹脂エマルジョンの製造方法。
〔5〕
上記オリゴマー(A)の数平均分子量が5,000~50,000であることを特徴とする〔4〕に記載の塩化ビニル系樹脂エマルジョンの製造方法。
〔6〕
シード(D)の平均粒子径が20~800nmであることを特徴とする〔4〕又は〔5〕に記載の塩化ビニル系樹脂エマルジョンの製造方法。
〔7〕
〔1〕~〔3〕のいずれかに記載の塩化ビニル系樹脂エマルジョンを含有する水性インキ。
〔8〕
塩化ビニル系樹脂エマルジョンの含有量が固形分として2~30質量%であり、更に着色剤を3~40質量%、水可溶性有機溶剤を0~50質量%、水を5~95質量%含有してなる〔7〕に記載の水性インキ。
〔9〕
〔1〕~〔3〕のいずれかに記載の塩化ビニル系樹脂エマルジョンの塗膜を有する記録用紙。
〔10〕
上記塗膜が受容層を形成する〔9〕に記載の記録用紙。
〔11〕
上記塗膜が、塩化ビニル系樹脂エマルジョンの固形分2~30質量%を含み、更に顔料を0~30質量%、水可溶性有機溶剤を0~60質量%、水を5~98質量%含有してなる組成物から形成されたものである〔9〕又は〔10〕に記載の記録用紙。
(E)塩化ビニル単量体又は(E)塩化ビニル単量体とこれと共重合可能な(F)エチレン性不飽和基含有単量体との単量体混合物100質量部を上記(D)シードを固形分(即ち、塩化ビニル系ポリマー)として3~50質量部使用して乳化重合させて得られる塩化ビニル系樹脂エマルジョンである。
(A)スチレン・アクリル酸エステルオリゴマー、アクリル酸エステルオリゴマーに使用されるアクリル酸エステルモノマーとしては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル等が挙げられる。なお、(メタ)アクリルはアクリルとメタクリルの総称である。市販されているものとしては、JONCRYL JDX-6500、JONCRYL JDX-6102B、JONCRYL HPD-96J、JONCRYL 52J(いずれもBASF社製)等が挙げられるが、これに限定されるものではなく、1種又は2種以上が使用される。
また、スチレン/アクリル酸エステルの質量比率は50/50~0/100が好ましい。
(F)の塩化ビニル単量体と共重合可能なエチレン性不飽和基含有単量体としては、前述の(C)と同様の単量体が挙げられる。
この場合、(E)塩化ビニル単量体とこれと共重合可能な(F)エチレン性不飽和基含有単量体との割合は、質量比として50:50~100:0、特に80:20~100:0であることが好ましい。塩化ビニル量が少なすぎると、凝集物が発生するおそれがある。
2質量%未満であると密着性が悪化するといった不具合を生じる場合があり、30質量%を超えると高粘度化するといった不具合を生じる場合がある。
[シード1]
撹拌機、コンデンサー、温度計及び窒素ガス導入口を備えた重合容器に、窒素置換後、脱イオン水34部、塩化ビニル15部、JONCRYL JDX-6500(BASF社製アクリル酸エステルオリゴマー、数平均分子量10,000)50部(有効成分30%)を仕込み、撹拌しながら60℃に加温した。更に過硫酸アンモニウム(開始剤)0.1部を脱イオン水1部に溶解させて添加して24時間重合反応させた。
重合内圧が0MPaになった時点で、残存モノマーを真空にて1,000ppmまで除去し、その後40℃以下まで冷却して重合体を得た。固形分30%、pH7.5、B型粘度計による粘度(23℃)は10mPa・sであった。なお、得られたエマルジョンが塩化ビニル系樹脂であることはGPCにより測定した。
表1に示すような組成で、シード1と同様の重合を実施して、塩化ビニル系樹脂エマルジョンを得た。
平均重合度:重合度は、重量平均重合度として、ゲルパーミエーションクロマトグラフィー(GPC)分析によるポリスチレン換算値として求めることができる。
BASF社製アクリル酸エステルオリゴマー、数平均分子量10,000
JONCRYL HPD-96J:
BASF社製スチレン・アクリル酸エステルオリゴマー、数平均分子量16,500
撹拌機、コンデンサー、温度計及び窒素ガス導入口を備えた重合容器に、窒素置換後、脱イオン水64部、塩化ビニル27部、シード1 9部(有効成分30%)を仕込み、撹拌しながら60℃に加温した。更に過硫酸アンモニウム(開始剤)0.1部を脱イオン水1部に溶解させて添加して24時間重合反応させた。
重合内圧が0MPaになった時点で、残存モノマーを真空にて1,000ppmまで除去し、その後40℃以下まで冷却して重合体を得た。固形分30%、pH7.0、B型粘度計による粘度(23℃)は10mPa・sであった。なお、得られたエマルジョンが塩化ビニル系樹脂であることはGPCにより測定した。結果を表2に示す。
表2,3に示すような組成で、実施例1と同様の重合を実施して、塩化ビニル系樹脂エマルジョンを得た。
<固形分測定方法>
塩化ビニル系樹脂エマルジョン約1gをアルミニウム箔製の皿にはかり取り、105~110℃に保った乾燥器に入れて1時間加熱した後、乾燥器より取り出して、デシケーターの中にて放冷した。試料の乾燥後の重さをはかり、次の式により固形分を算出した。
W:乾燥前の試料を入れたアルミニウム箔皿の質量(g)
A:アルミニウム箔皿の質量(g)
D:乾燥後の試料を入れたアルミニウム箔皿の質量(g)
アルミニウム箔皿の寸法:70φ・12h(mm)
塩化ビニル系樹脂エマルジョンをそのまま、JIS Z8802(pH測定方法)によりpHメーターを用いて測定した。
塩化ビニル系樹脂エマルジョンの液温を23±0.5℃に保持し、BM型粘度計(No.1ローター、6rpm)にて測定した。
光散乱型粒子径測定装置を用いて測定した。
サンプル調製
1.ディスカップにサンプルを採取し、25℃純水にて希釈した。
2.希釈したサンプルを300メッシュ濾布にて濾過した。
測定液温 25℃
積算回数 100回
測定回数 1回
測定
適正濃度であることを確認し、上記測定条件にて測定した。
測定結果が良好であることを確認した。
塩化ビニル系樹脂エマルジョンを6ミル(mil)のドクターナイフでガラス板に塗布し、凝集物発生の有無を目視にて確認した。
○:凝集物は確認できなかった
×:凝集物が発生した
塩化ビニル系樹脂エマルジョン(固形分30%)を67部、顔料DISPERS RED SD-1011を5部、水を28部混合し、これを試料Aとした。
卓上印刷機(GRAVO-PROOF CM、日商グラビア社製)に試料をセットし、印刷ロールを1回転させ、市販の紙に印刷した。
印刷した紙を学振形染色摩擦堅ろう度試験機(安田精機製作所製)にセットし、水で湿らせたガーゼを用いて25回摩擦試験を実施し、下記の基準に従って目視で判定した。
○:ガーゼへの色移り無し
△:色移りが見られる
×:完全に色移りし、印刷面の色が落ちる
印刷した紙を50℃、湿度90%で1日静置し、下記の基準に従って目視で判定した。
○:印刷部位に滲みが無い
△:印刷部位から少し滲みが見られる
×:完全に滲む
印刷した部分をグロスメーターPG-1M(日本電色工業社製)で測定し、投受光角度条件60°の値を読み取り、下記の基準に従って判定した。
○:グロス値が90以上
△:グロス値が70以上90未満
×:グロス値が70未満
印刷した紙を学振形染色摩擦堅ろう度試験機(安田精機製作所製)にセットし、エタノールで湿らせたガーゼを用いて25回摩擦試験を実施し、下記の基準に従って目視で判定した。
○:ガーゼへの色移り無し
△:色移りが見られる
×:完全に色移りし、印刷面の色が落ちる
[インクの調製]
塩化ビニル系樹脂エマルジョン(固形分30%)を67部、カーボンブラックMA100(三菱製紙社製)を20部、水を13部混合し、これを試料Bとした。
調製した試料Bを、市販の紙にバーコーターNo.4にて厚さ9μm(乾燥重量固形分3.6g/m2)塗工し、40℃で30秒乾燥した。得られた塗工紙と調製した試料の外観を下記の基準で目視により判定した。
○:色調が同等
△:黒色濃度が不足する
×:色調が変化している
調製した試料Bを、軟質塩化ビニルフィルム・スーパーフィルムノンタックE(オカモト社製)にバーコーターNo.4にて厚さ9μm(乾燥重量固形分3.6g/m2)塗工し、40℃で30秒乾燥した。得られた塗工品に、セロテープ(ニチバン社製、登録商標)を貼り付けた後、150Paで剥離し、下記の基準で判定した。
○:剥離無し
△:一部剥離有り
×:完全剥離
調製した試料Bを常温で1週間放置し、経時沈降を下記の基準で目視により判定した。
○:沈降無し
△:沈降するが再撹拌可能
×:沈降し復元せず
[インクジェット用受容層の調製]
市販の紙に、塩化ビニル系樹脂エマルジョンをバーコーターNo.4にて厚さ9μm(乾燥重量固形分3.3g/m2)塗工し、40℃で30秒乾燥し試料Cとした。
EPSON PM-800Cで、イエロー、シアン、マゼンダの3色を印刷し、各色の色濃度を下記の基準で目視により判定した。
○:色抜けが無く鮮明に印刷されている
△:一部に色抜けがある
×:色抜けがあり、色褪せている
印刷した紙を学振形染色摩擦堅ろう度試験機(安田精機製作所製)にセットし、水で湿らせたガーゼを用いて25回摩擦試験を実施し、下記の基準に従って目視で判定した。
○:ガーゼへの色移り無し
△:色移りが見られる
×:完全に色移りし、印刷面の色が落ちる
印刷した紙を50℃、湿度90%で1日静置し、下記の基準に従って目視により判定した。
○:印刷部位に滲みが無い
△:印刷部位から少し滲みが見られる
×:完全に滲む
[染料拡散転写用受容層の調製]
試料CをCANON SELPHY CP-750で全面黒画像(黒ベタ画像)を印刷し、下記の基準で目視により判定した。
k.発色性
○:色抜けが無く鮮明に印刷されている
△:一部に色抜けがある
×:色抜けがあり、色褪せている
印刷した際のインクリボンと受容層の離型音を聞き取り、大小を評価した
○:問題無く、良好な結果が得られた
△:悪化傾向にあるが、許容範囲
×:問題であり、許容出来ないレベル
印刷した紙を50℃、湿度90%で1日静置し、下記の基準に従って目視により判定した。
○:印刷部位に滲みが無い
△:印刷部位から少し滲みが見られる
×:完全に滲む
Claims (11)
- (B)塩化ビニル単量体又は(B)塩化ビニル単量体とこれと共重合可能な(C)エチレン性不飽和基含有単量体との単量体混合物100質量部を(A)スチレン・アクリル酸エステルオリゴマー及び/又はアクリル酸エステルオリゴマー40~500質量部の存在下で乳化重合させることによって得られる塩化ビニル系ポリマーエマルジョンを(D)シードとし、
(E)塩化ビニル単量体又は(E)塩化ビニル単量体とこれと共重合可能な(F)エチレン性不飽和基含有単量体との単量体混合物100質量部を上記(D)シードを固形分として3~50質量部用いて乳化重合させて得られることを特徴とする塩化ビニル系樹脂エマルジョン。 - 上記オリゴマー(A)の数平均分子量が5,000~50,000であることを特徴とする請求項1に記載の塩化ビニル系樹脂エマルジョン。
- シード(D)の平均粒子径が20~800nmであることを特徴とする請求項1又は2に記載の塩化ビニル系樹脂エマルジョン。
- (B)塩化ビニル単量体又は(B)塩化ビニル単量体とこれと共重合可能な(C)エチレン性不飽和基含有単量体との単量体混合物100質量部を(A)スチレン・アクリル酸エステルオリゴマー及び/又はアクリル酸エステルオリゴマー40~500質量部の存在下で乳化重合させることによって塩化ビニル系ポリマーエマルジョンからなる(D)シードを調製し、
(E)塩化ビニル単量体又は(E)塩化ビニル単量体とこれと共重合可能な(F)エチレン性不飽和基含有単量体との単量体混合物100質量部を上記(D)シードを固形分として3~50質量部用いて乳化重合させることを特徴とする塩化ビニル系樹脂エマルジョンの製造方法。 - 上記オリゴマー(A)の数平均分子量が5,000~50,000であることを特徴とする請求項4に記載の塩化ビニル系樹脂エマルジョンの製造方法。
- シード(D)の平均粒子径が20~800nmであることを特徴とする請求項4又は5に記載の塩化ビニル系樹脂エマルジョンの製造方法。
- 請求項1~3のいずれか1項に記載の塩化ビニル系樹脂エマルジョンを含有する水性インキ。
- 塩化ビニル系樹脂エマルジョンの含有量が固形分として2~30質量%であり、更に着色剤を3~40質量%、水可溶性有機溶剤を0~50質量%、水を5~95質量%含有してなる請求項7に記載の水性インキ。
- 請求項1~3のいずれか1項に記載の塩化ビニル系樹脂エマルジョンの塗膜を有する記録用紙。
- 上記塗膜が受容層を形成する請求項9に記載の記録用紙。
- 上記塗膜が、塩化ビニル系樹脂エマルジョンの固形分2~30質量%を含み、更に顔料を0~30質量%、水可溶性有機溶剤を0~60質量%、水を5~98質量%含有してなる組成物から形成されたものである請求項9又は10に記載の記録用紙。
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JP2013505915A JP5664766B2 (ja) | 2011-03-18 | 2012-03-14 | 塩化ビニル系樹脂エマルジョン及びその製造方法並びに水性インキ及び記録用紙 |
US14/000,504 US8822587B2 (en) | 2011-03-18 | 2012-03-14 | Vinyl chloride-based resin emulsion, method for producing same, water-based ink, and recording paper |
EP12760384.3A EP2687550B1 (en) | 2011-03-18 | 2012-03-14 | Vinyl chloride-based resin emulsion, method for producing same, water-based ink, and recording paper |
KR1020137026829A KR101603512B1 (ko) | 2011-03-18 | 2012-03-14 | 염화비닐계 수지 에멀전 및 그 제조 방법, 및 수성 잉크 및 기록 용지 |
ES12760384T ES2743541T3 (es) | 2011-03-18 | 2012-03-14 | Emulsión de resina a base de cloruro de vinilo, método para producirla, tinta a base de agua y papel de registro |
CN201280013955.XA CN103443153B (zh) | 2011-03-18 | 2012-03-14 | 氯乙烯系树脂乳液及其制造方法以及水性墨和记录用纸 |
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WO2020166660A1 (ja) * | 2019-02-15 | 2020-08-20 | 日信化学工業株式会社 | 塩化ビニル系樹脂エマルジョン、水性インキ及び記録用紙 |
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WO2021249748A1 (en) | 2020-06-08 | 2021-12-16 | Basf Se | Method of producing printed matter by inkjet printing on a coated substrate |
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JPWO2020166660A1 (ja) * | 2019-02-15 | 2021-12-09 | 日信化学工業株式会社 | 塩化ビニル系樹脂エマルジョン、水性インキ及び記録用紙 |
JP7173177B2 (ja) | 2019-02-15 | 2022-11-16 | 日信化学工業株式会社 | 塩化ビニル系樹脂エマルジョン、水性インキ及び記録用紙 |
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JPWO2012128138A1 (ja) | 2014-07-24 |
EP2687550A1 (en) | 2014-01-22 |
CN103443153A (zh) | 2013-12-11 |
ES2743541T3 (es) | 2020-02-19 |
EP2687550A4 (en) | 2014-09-03 |
JP5664766B2 (ja) | 2015-02-04 |
US8822587B2 (en) | 2014-09-02 |
KR101603512B1 (ko) | 2016-03-15 |
US20130331504A1 (en) | 2013-12-12 |
CN103443153B (zh) | 2015-12-09 |
KR20140012723A (ko) | 2014-02-03 |
EP2687550B1 (en) | 2019-07-03 |
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