JP5499233B2 - Fine particle slurry - Google Patents

Description

  The present invention relates to a fine particle slurry. More particularly, the present invention relates to a fine particle slurry suitable for applying a screen printing method to a support.

  Conventionally, a fine particle slurry containing inorganic fine particles {precipitation silica and / or vapor phase silica}, a water-soluble organic solvent, and a binder {water-soluble resin} such as polyvinyl alcohol is known (Patent Document 1).

JP 2007-098657 A

However, the conventional fine particle slurry has a problem that when the coating film is formed by a screen printing method or the like, the smoothness of the coating film is impaired due to irregularities due to spinnability, bubble marks due to foam, mesh marks during printing, etc. is there.
An object of the present invention is to provide a coating film excellent in smoothness even when the coating film is formed by a screen printing method or the like.

The fine particle slurry of the present invention is characterized by inorganic fine particles (A) composed of alumina fine particles (A1) and silica fine particles (A2), a binder resin (B), water (C), an aliphatic alcohol having 3 to 6 carbon atoms (D ) And carboxylic acid (salt) (co) polymer ( E ),
Carboxylic acid (salt) (co) polymer (E) is a homopolymer of aliphatic monocarboxylic acid (salt) or aliphatic monocarboxylic acid (salt) and maleic anhydride, (meth) acrylic acid alkyl ester, (meth) It is a copolymer with other monomers selected from hydroxyalkyl acrylate, vinyl group-containing amide, vinyl group-containing sulfonic acid, vinyl group-containing nitrile and styrene,
The gist is that the weight ratio (D / C) of the aliphatic alcohol (D) having 3 to 6 carbon atoms and water (C) is 0.01 to 0.9.

The fine particle slurry production method of the present invention is characterized in that after obtaining an aqueous dispersion of inorganic fine particles (A) composed of alumina fine particles (A1) and silica fine particles (A2), an aqueous solution of binder resin (B), water (C ), A C3-C6 aliphatic alcohol (D) and a carboxylic acid (salt) (co) polymer ( E ), and if necessary, an additive and an aqueous dispersion of inorganic fine particles (A) Including a step of mixing and dispersing,
Carboxylic acid (salt) (co) polymer (E) is a homopolymer of aliphatic monocarboxylic acid (salt) or aliphatic monocarboxylic acid (salt) and maleic anhydride, (meth) acrylic acid alkyl ester, (meth) It is a copolymer with other monomers selected from hydroxyalkyl acrylate, vinyl group-containing amide, vinyl group-containing sulfonic acid, vinyl group-containing nitrile and styrene,
The gist is that the weight ratio (D / C) of the aliphatic alcohol (D) having 3 to 6 carbon atoms and water (C) is 0.01 to 0.9.

  The fine particle slurry of the present invention can easily form a coating film remarkably excellent in smoothness. That is, if the fine particle slurry of the present invention is used, even when the coating film is formed by a screen printing method or the like, unevenness and bubble biting due to spinnability hardly occur, and a coating film excellent in smoothness can be easily obtained. can get. Therefore, when the coating film of the present invention is used, it becomes possible to have high smoothness even when printed on a support by various printing methods.

  By using the method for producing a fine particle slurry of the present invention, a fine particle slurry capable of easily forming a coating film with extremely excellent smoothness can be obtained.

  As the alumina fine particles (A1), a known gas phase method {(1) a method in which metal aluminum is melted and vaporized in a vacuum and introduced into an oxidizing atmosphere to obtain alumina fine particles; (2) a metal aluminum powder, A method of obtaining alumina fine particles by evaporating and oxidizing in a flame containing oxygen; and (3) a method of obtaining aluminum fine particles by vaporizing aluminum chloride and ejecting it into a burner flame and oxidizing it. Etc.), or a known liquid phase method {(4) Hydrolysis of alkylaluminum or alkoxyaluminum (Chemical Review No. 48, 1985, ultrafine particles (edited by the Chemical Society of Japan), pages 173 to 175; (Publishing Center, published in 1985); (5) Ammonium Alum Pyrolysis Method; (6) Ammonium Aluminum Carbonate Pyrolysis Method; (7) A How to alkaline neutralizing Miniumu salt; and (8) include alumina particles obtained aluminate by hydrolyzing the like} and the like.

  Alumina fine particles can be easily obtained from the market. For example, Aeroxide series {Alu-c and Al-65, Degussa, “Aeroxide” is a registered trademark of the company. }, SpctrAl series {51, 81, 100 etc., Cabot Corporation}, CAB-O-SPERSE series {SpctrAl series water dispersion, Cabot Corporation, AKP series {manufactured by Sumitomo Chemical Co., Ltd., "AKP" is registered by the company Trademark. }, Tymicron series {manufactured by Daimei Chemical Co., Ltd.}, DISPERAL series {Sasol, "DISPERAL" is a registered trademark of the same company. } And DISPAL series {Sasol, "DISPAL" is a registered trademark of the company. } Etc.} etc. are mentioned.

  The alumina fine particles (A1) can also be used in the form of a dispersion (for example, alumina sol) dispersed by a known dispersant (acetic acid, lactic acid, formic acid, nitric acid, etc.).

  Alumina fine particle dispersion (alumina sol) can be easily obtained from the market, and examples thereof include Cataloid-A series {manufactured by Catalyst Kasei Kogyo Co., Ltd.} and alumina sol series {manufactured by Nissan Chemical Industries Ltd.}.

  As silica fine particles (A2), a known method {(1) a method in which metal silicon is melted and vaporized in a vacuum and introduced into an oxidizing atmosphere to obtain silica fine particles; (2) metal silicon powder is mixed with oxygen A method of obtaining silica fine particles by evaporating and oxidizing in a containing flame; (3) A method of obtaining silica fine particles by vaporizing tetrachlorosilane and ejecting and oxidizing it in a burner flame (Japanese Patent Publication No. 47-46274, etc.) ); (4) Water glass method using alkali metal silicate (sodium silicate etc.) as a raw material; and (5) Alkoxysilane method etc. using alkoxysilane (tetraethoxysilane etc.) as a raw material} Contains fine particles.

  The silica fine particles (A2) can be easily obtained from the market. For example, Aerosil series {Nippon Aerosil Co., Ltd., “Aerosil” is a registered trademark of Degussa Aktiengesellschaft. }, Leoroseal series {Tokuyama Co., Ltd., "Leoroseal" is a registered trademark of the company. }, WACKER HDK series {Asahi Kasei Wacker Co., Ltd., “WACKER” is a registered trademark of Wacker Chemie Aktiengesellschaft. } And Cab-O-Sil series {Cabot Corporation, "Cab-O-Sil" is a registered trademark of the same company. } Etc. are mentioned.

  The silica fine particles (A2) can also be used in the form of a dispersion (for example, silica sol) dispersed by a known dispersant (acetic acid, lactic acid, formic acid, nitric acid, etc.). For example, Adelite series {Co., Ltd. ADEKA, “Adelite” is a registered trademark of the same company. }, Cataloid-S series {Catalytic Chemical Industry Co., Ltd., "Cataloid" is a registered trademark of the same company. }, Quartron series {Fuso Chemical Industry Co., Ltd., "Quartron" is a registered trademark of the company. } And Snowtex series {Nissan Chemical Industry Co., Ltd.} and the like.

  The weight ratio (A1 / A2) of the alumina fine particles (A1) to the silica fine particles (A2) is preferably 0.05 to 2.0, more preferably 0.1 to 1.5, and particularly preferably 0.15 to 1.0, most preferably 0.2 to 0.5. Within this range, the coating suitability (particularly screen printing suitability) is further improved, and the smoothness of the coating film is further improved.

As inorganic fine particles (A), in addition to alumina fine particles (A1) and silica fine particles (A2), known inorganic fine particles (for example, titanium dioxide, barium sulfate, calcium silicate, zeolite, kaolinite, halloysite, mica, talc, Calcium carbonate, magnesium carbonate, calcium sulfate, zinc oxide, zinc hydroxide, aluminum silicate, calcium silicate, magnesium silicate, zirconium oxide, zirconium hydroxide, cerium oxide, lanthanum oxide or yttrium oxide fine particles). .
Two or more inorganic fine particles other than the alumina fine particles (A1) and the silica fine particles (A2) can be used.

  In the case of containing known inorganic fine particles, the content (% by weight) of inorganic fine particles other than the alumina fine particles (A1) and silica fine particles (A2) is from the viewpoint of coating suitability (screen printing suitability). And 0.1 to 30 based on the weight of the mixture of silica fine particles (A2), more preferably 0.5 to 15 and particularly preferably 1 to 10.

  The average primary particle diameter (nm) of each of the alumina fine particles (A1) and the silica fine particles (A2) is preferably 7 to 40, more preferably 9 to 30, particularly preferably 12 to 20. Within this range, the smoothness of the coating film is further improved.

  When known inorganic fine particles other than the alumina fine particles (A1) and silica fine particles (A2) are contained, the average primary particle size (nm) of the inorganic fine particles is preferably 7 to 5000, more preferably 10 to 1000, and particularly preferably. Is 20-500. Within this range, the smoothness of the coating film is further improved.

  Note that the average primary particle size is in accordance with JIS Z8901-2006 “Testing Powder and Testing Particles” 5.44 Particle Distribution (c) Microscopy, and a sample prepared by a sprinkling method is used with a transmission electron microscope. It is a number average value of equivalent circle diameters calculated by observing 200 or more particles from an image observed by magnifying 50,000 to 1,000,000 times.

The BET specific surface area (m ² / g) of each of the alumina fine particles (A1) and the silica fine particles (A2) is preferably 50 to 400, and more preferably 90 to 300. Within this range, the coating suitability (particularly screen printing suitability) is further improved.

When known inorganic fine particles other than the alumina fine particles (A1) and silica fine particles (A2) are contained, the BET specific surface area (m ² / g) of the inorganic fine particles is preferably 5 to ²⁰⁰ , more preferably 10 to 100. It is. Within this range, the coating suitability (particularly screen printing suitability) is further improved.

  The BET specific surface area conforms to JIS Z8830-2001 “Method for measuring specific surface area of powder (solid) by gas adsorption” and JIS R1626-1996 “Method for measuring specific surface area of fine ceramic powder by gas adsorption BET method”. Then, the dried inorganic fine particles are measured by a gas adsorption method (flow method). A nitrogen-helium mixed gas was used as the carrier gas. The BET specific surface area can be calculated from the value of the desorption peak.

Polyvinyl alcohol can be used as the binder resin (B).
Examples of the polyvinyl alcohol include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, cation modified polyvinyl alcohol, anion modified polyvinyl alcohol, nonionic modified polyvinyl alcohol, and crosslinked polyvinyl alcohol.

  The completely saponified polyvinyl alcohol means a polyvinyl alcohol having a saponification degree exceeding 98 mol% and not more than 100 mol%. The partially saponified polyvinyl alcohol means polyvinyl alcohol having a saponification degree of 70 to 98 mol%. The cation-modified polyvinyl alcohol means a polymer having a structure obtained by saponifying, if necessary, a copolymer of an ethylenically unsaturated monomer having a primary to tertiary amino group or a quaternary ammonio group and vinyl acetate. To do. The anion-modified polyvinyl alcohol means a polymer having a structure obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a carboxy group or a sulfo group and vinyl acetate as necessary. Nonionic modified polyvinyl alcohol means a polymer having a structure obtained by saponifying, if necessary, a copolymer of an ethylenically unsaturated monomer having a mercapto group or keto group (carbonyl group) and vinyl acetate. Cross-linked polyvinyl alcohol is a polymer having a structure in which fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol or nonionic-modified polyvinyl alcohol is cross-linked in and / or between molecules. means.

  As the fully saponified polyvinyl alcohol and the partially saponified polyvinyl alcohol, known ones (for example, JP-A-2006-28233) can be used. As the cation-modified polyvinyl alcohol, known ones (for example, JP-A-10-119423) can be used. As the anion-modified polyvinyl alcohol, known ones (for example, JP-A-1-206088, JP-A-61-237681, JP-A-63-307979 and JP-A-7-285265) can be used. . As the nonionic modified polyvinyl alcohol, known ones (for example, JP-A-7-9758 and JP-A-8-25795) can be used.

  As the cross-linked polyvinyl alcohol, polyvinyl alcohol cross-linked by ionizing radiation or the like (JP-A-1-286886, JP-A-60-129742, or JP-A-2000-181062) can be used.

  Of these polyvinyl alcohols, partially saponified polyvinyl alcohol and fully saponified polyvinyl alcohol are preferable, more preferably partially saponified polyvinyl alcohol, particularly preferably from the viewpoint of the coating strength of the dry coating film to be formed. A partially saponified polyvinyl alcohol having a saponification degree of 72 to 96 {preferably 77 to 95, particularly preferably 78 to 90} mol%.

  The degree of saponification is measured according to JIS K6726-1994 “Polyvinyl alcohol test method 3.5 degree of saponification”.

  The average degree of polymerization of polyvinyl alcohol is preferably 1000 to 6000, more preferably 2000 to 5500, and particularly preferably 2500 to 5000. Within this range, the dimensional stability of the formed dry coating film is further improved.

  The average degree of polymerization is measured according to JIS K6726-1994 “Polyvinyl alcohol test method” 3.7 average degree of polymerization. The average degree of polymerization of the cation-modified polyvinyl alcohol is measured by the method described in Japanese Patent No. 3434055.

As the binder resin (B), a known hydrophilic polymer can be used in addition to polyvinyl alcohol.
As the known hydrophilic polymer, a hydrophilic polymer described in JP-A No. 2003-063131 and the like can be used.

  The content (% by weight) of the binder resin (B) is preferably 5 to 50 based on the weight of the inorganic fine particles (A), more preferably 10 to 40, particularly preferably 15 to 35, most preferably 18 to. 30. Within this range, the coating film strength and smoothness (balance between coating film strength and screen printing suitability) are further improved.

  As the water (C), ion exchange water, distilled water, ultrapure water, tap water, industrial water and the like can be used.

  Examples of the aliphatic alcohol (D) having 3 to 6 carbon atoms include aliphatic monoalcohols, aliphatic polyhydric alcohols, and polyoxyalkylene compounds.

  Examples of the aliphatic monoalcohol include 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3 -Pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2- Methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol and 4-methyl-2-pen And tanol.

  Aliphatic polyhydric alcohols include diols {for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,2- Hexanediol and 1,6-hexanediol, etc.}, trivalent to tetravalent polyhydric alcohols {glycerin, trimethylolpropane, pentaerythritol, 1,2,6-hexanetriol, diglycerin and the like}.

  Examples of the polyoxyalkylene compound include polyoxyalkylene glycol {for example, diethylene glycol, dipropylene glycol and triethylene glycol, etc.}, alkylene glycol monoalkyl ether {for example, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, Triethylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether (methoxypropanol) and the like}.

  The aliphatic alcohol (D) may be one kind or a mixture of two or more kinds, but it is preferable that at least two kinds are included from the viewpoint of the smoothness of the coating film to be formed, more preferably an aliphatic mono Containing at least two alcohols, particularly preferably 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, Including at least two selected from the group consisting of 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol and 3-methyl-2-butanol, and preferably 1- Consists of butanol, 2-methyl-1-propanol, 1-pentanol, 2-methyl-1-butanol and 3-methyl-1-butanol Includes at least two are more selected, and most preferably contains at least two of 1-butanol, selected from the group consisting of 2-methyl-1-propanol and 1-pentanol.

  The content (% by weight) of the aliphatic alcohol (D) is preferably 0.7 to 55 based on the weight of the inorganic fine particles (A), the binder resin (B), and water (C), and more preferably 1. It is 5-45, Most preferably, it is 3.0-30, Most preferably, it is 4.0-16. Within this range, the coating suitability (particularly screen printability) is further improved, and the smoothness of the formed coating film is further improved.

  The weight ratio (D / C) of the aliphatic alcohol (D) having 3 to 6 carbon atoms and water (C) is preferably 0.01 to 0.9, more preferably 0.02 to 0.75, particularly Preferably it is 0.03-0.5, Most preferably, it is 0.05-0.3. Within this range, any coating method, for example, a screen printing method, has less foam and the smoothness of the formed coating film is further improved.

  The fine particle slurry of the present invention preferably further contains a carboxylic acid (salt) (co) polymer (E). When the carboxylic acid (salt) (co) polymer (E) is contained, the smoothness of the formed coating film is further improved.

  The carboxylic acid (salt) (co) polymer (E) may be a homopolymer of a vinyl group-containing carboxylic acid (salt) as long as it is a polymer having a vinyl group-containing carboxylic acid (salt) as an essential constituent monomer. The vinyl group-containing carboxylic acid (salt) and other monomers {(meth) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl, vinyl group-containing amide, vinyl group-containing sulfonic acid, vinyl group It may be a copolymer with a contained nitrile, styrene or the like}.

In the present invention, “•• carboxylic acid (salt)” means “•• carboxylic acid”, “•• completely neutralized salt of carboxylic acid” or “•• partially neutralized salt of carboxylic acid”.
It does not specifically limit as a salt, A well-known thing can be used. Of these, alkali metal (lithium, sodium, potassium, etc.) salts and ammonium salts are preferred.

  The carboxylic acid (salt) (co) polymer (E) may be obtained by polymerizing a vinyl group-containing carboxylate as an essential constituent monomer. It may be obtained by polymerization as an essential constituent monomer, or may be a neutralized salt after polymerizing a vinyl group-containing carboxylic acid as an essential constituent monomer.

  Examples of vinyl group-containing carboxylic acids (salts) include aliphatic monocarboxylic acids (salts), alicyclic monocarboxylic acids (salts), and aromatic monocarboxylic acids (salts). For example, JP 2004-315359 A The thing etc. which are described in gazette number can be used. Of these, aliphatic monocarboxylic acids (salts) are preferred, acrylic acid (salts) and methacrylic acid (salts) are more preferred, and acrylic acid (salts) are particularly preferred.

  Among the other monomers, as the (meth) acrylic acid alkyl ester, known ones can be used, and examples include those described in JP-A-2006-045549. Among these, from the viewpoint of easy availability, monofunctional aliphatic (meth) acrylate is preferable, more preferably methyl (meth) acrylate, ethyl (meth) acrylate, n- or iso-propyl (meth) acrylate, n-, iso- or t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate.

  Examples of the hydroxyalkyl (meth) acrylate include hydroxyalkyl having 1 to 6 carbon atoms in the alkyl group, such as those described in JP-A-2006-045549. Of these, hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 6-hydroxyhexyl (meth) acrylate are preferred from the viewpoint of availability.

  As the vinyl group-containing amide, vinyl group-containing sulfonic acid, and vinyl group-containing nitrile, known ones can be used, and examples include those described in JP-A-2004-315359. Of these, from the viewpoint of easy availability, vinyl group-containing amides are preferable, (meth) acrylamide is more preferable, and dimethyl (meth) acrylamide and diethyl (meth) acrylamide are more preferable.

  When other monomers are included as constituent monomers, the carboxylic acid (salt) (co) polymer (E) may be in the form of a block, random or a combination thereof, from the viewpoint of productivity, etc. A random shape and a combination of a block shape and a random shape are preferable, and a random shape is more preferable.

  When other monomer is a constituent monomer, the content (mol%) of the other monomer unit is preferably 5 to 100 based on the number of moles of the vinyl group-containing carboxylic acid (salt) unit. More preferably, it is 10-95, Most preferably, it is 30-90.

  The carboxylic acid (salt) (co) polymer (E) is obtained using a known polymerization method {solution polymerization method, pearl polymerization method, reverse phase emulsion polymerization method, etc .; for example, JP-A-2004-315359, etc.}. However, it is not particularly limited.

When the carboxylic acid (salt) (co) polymer (E) is contained, the carboxylic acid (salt) (co) polymer (E) may be one kind or a mixture of two or more kinds.
In this case, the content (% by weight) of the carboxylic acid (salt) (co) polymer (E) is the inorganic fine particles (A), the binder resin (B), water (C), and 3 to 6 carbon atoms. Based on the weight of the aliphatic alcohol (D), 0.01 to 5.0 is preferable, more preferably 0.02 to 4, particularly preferably 0.05 to 3, and most preferably 0.1 to 2. . Within this range, the smoothness of the formed coating film is further improved (even if the screen printing method is applied, a mesh mark or the like does not remain and a highly smooth coating film can be obtained).

  In the fine particle slurry of the present invention, additives {dispersant (F), organic fine particles (G), antioxidant (H), ultraviolet absorber (I), crosslinking agent (J) and dye fixing as necessary Agent (K) etc.} can be added. Each additive can be used by mixing two or more kinds.

  As the dispersant (F), known ones (for example, a cationic polymer, a water-soluble polyvalent metal compound and a surfactant described in JP-A-2006-231596 are described in JP-A-2006-169321. And low molecular weight cationic molecules, and organic acids and inorganic acids described in JP-A No. 2003-251918 can be used.

  Of these, cationic polymers, water-soluble polyvalent metal compounds, low molecular weight cationic molecules, organic acids and inorganic acids are preferred, and more preferred are cationic polymers, low molecular weight cationic molecules, lactic acid, formic acid, acetic acid, hydrochloric acid and Nitric acid, particularly preferably a cationic polymer, a low molecular weight cationic molecule, lactic acid, acetic acid and nitric acid.

  From the viewpoint of improving the scratch resistance of the coating film, it is preferable to add organic fine particles (G).

  As the organic fine particles (G), known ones (for example, organic fine particles described in JP-A-2006-192634 and JP-A-2004-082729) can be used. Of these, crosslinked polyvinylpyrrolidone particles, acrylic polymers, styrene-acrylic copolymers and vinyl acetate-acrylic copolymers are preferred.

  As the antioxidant (H), a known one {for example, JP 2001-26178 A} can be used. Among these, a hindered amine antioxidant is preferable from the viewpoint of the weather resistance of the dried coating film.

  As the ultraviolet absorber (I), known ones {for example, the ultraviolet absorber described in JP-A No. 2000-42614 and the polymer type ultraviolet absorber described in JP-A No. 2004-42614} Etc. can be used. Of these, benzotriazole ultraviolet absorbers are preferred from the viewpoint of the weather resistance of the dried coating film.

  As a crosslinking agent (J), if it is a compound which can bridge | crosslink binder resin (B), it can be used without a restriction | limiting, A well-known thing (for example, Unexamined-Japanese-Patent No. 2000-335087) etc. can be used. Of these, from the viewpoint of coloring the dried coating film, boron compounds and metal-containing compounds are preferred, more preferably borax, boric acid, borate, zirconium acetate and zirconium nitrate, particularly preferably borax, boric acid and zirconium acetate. And zirconium nitrate.

  When the fine particle slurry is used as a composition for forming an ink jet receiving layer, it is preferable to add a dye fixing agent (K) from the viewpoint of improving the color developability of the printed image of the ink jet receiving layer to be formed.

  As the dye fixing agent (K), known ones (for example, JP-A-10-264511 and JP20000261) can be used. Among these, from the viewpoint of color developability of a printed image, allylamine and its polymer salt, diallylamine salt and / or alkyldiallylamine salt described in Japanese Patent No. 20000261, and a nonionic vinyl monomer (such as acrylamide) are used as structural units. Preferred is a polymer, diallylamine and its polymer salt, diallyldialkylammonium and its polymer salt, and diallylalkylamine and its polymer salt, more preferably diallylamine polymer salt, diallyldialkylammonium polymer salt, diallylalkylamine Polymer salt and diallylamine salt and / or polymer having alkyldiallylamine salt and nonionic vinyl monomer as structural units, particularly preferably diallylamine polymer hydrochloride, diallyldialkylammonium polymer hydrochloride, di Rylalkylamine polymer hydrochlorides and diallylamine salts and / or polymers comprising alkyldiallylamine salts and nonionic vinyl monomers, most preferably diallylamine polymer hydrochlorides, diallylalkylamine polymer hydrochlorides and diallylamine salts And / or a polymer having an alkyl diallylamine salt and a nonionic vinyl monomer as constituent units.

  When the dispersant (F) is contained, the content (% by weight) is the weight of the inorganic fine particles (A), the binder resin (B), water (C), and the aliphatic alcohol (D) having 3 to 6 carbon atoms. Is preferably 0.002 to 2, more preferably 0.02 to 1, particularly preferably 0.1 to 0.5.

  When the organic fine particles (G) are contained, the content (% by weight) is the weight of the inorganic fine particles (A), the binder resin (B), water (C), and the aliphatic alcohol (D) having 3 to 6 carbon atoms. Is preferably 0.002 to 2, more preferably 0.02 to 1, particularly preferably 0.1 to 0.5.

  When the antioxidant (H) is contained, the content (% by weight) of the inorganic fine particles (A), the binder resin (B), water (C), and the aliphatic alcohol (D) having 3 to 6 carbon atoms. Based on the weight, 0.002 to 2 is preferable, 0.02 to 1 is more preferable, and 0.1 to 0.5 is particularly preferable.

  When the ultraviolet absorber (I) is contained, the content (% by weight) of the inorganic fine particles (A), the binder resin (B), water (C), and the aliphatic alcohol (D) having 3 to 6 carbon atoms. Based on the weight, 0.002 to 2 is preferable, 0.02 to 1 is more preferable, and 0.1 to 0.5 is particularly preferable.

  When the crosslinking agent (J) is contained, the content (% by weight) is the weight of the inorganic fine particles (A), the binder resin (B), water (C), and the aliphatic alcohol (D) having 3 to 6 carbon atoms. Is preferably 0.002 to 2, more preferably 0.02 to 1, particularly preferably 0.05 to 0.5.

  When the dye fixing agent (K) is contained, the content (% by weight) of the inorganic fine particles (A), the binder resin (B), water (C), and the aliphatic alcohol (D) having 3 to 6 carbon atoms. Based on the weight, 0.002 to 10 is preferable, 0.02 to 5.0 is more preferable, and 0.05 to 2.0 is particularly preferable.

  When an additive is contained, the additive can be added and mixed in any stage.

  The fine particle slurry of the present invention can be easily obtained by the production methods of the following <Method 1> to <Method 3>.

<Method 1>
After obtaining an aqueous dispersion of inorganic fine particles (A) composed of alumina fine particles (A1) and silica fine particles (A2), an aqueous solution of binder resin (B), water (C), and an aliphatic alcohol having 3 to 6 carbon atoms ( D), and a process comprising uniformly mixing and dispersing a carboxylic acid (salt) (co) polymer (E) and / or an additive and an aqueous dispersion of inorganic fine particles (A) as necessary.

<Method 2>
In an aqueous solution containing the binder resin (B) in an aqueous solution, inorganic fine particles (A) composed of alumina fine particles (A1) and silica fine particles (A2), aliphatic alcohol (D) having 3 to 6 carbon atoms, water (C) and a production method comprising a step of uniformly mixing and dispersing the carboxylic acid (salt) (co) polymer (E) and / or the additive, if necessary.

<Method 3>
Inorganic fine particles (A) composed of alumina fine particles (A1) and silica fine particles (A2), binder resin (B), water (C), aliphatic alcohol (D) having 3 to 6 carbon atoms, and, if necessary, carboxylic acid (Salt) A production method comprising a step of uniformly mixing and dispersing a (co) polymer (E) and / or an additive.

  Among these, <Method 1> and <Method 2> are preferable from the viewpoint of the smoothness of the resulting dried coating film, and <Method 1> is more preferable.

  For the uniform mixing and dispersion, a known disperser {for example, a pressure disperser (such as a high-pressure homogenizer), a ball mill, a sand mill, a roll mill, a planetary mixer / disperser, a three-axis planetary mixer, etc.) can be used. Among these dispersers, a planetary mixer / disperser and a three-axis planetary mixer are preferable, and a three-axis planetary mixer is more preferable. The three-axis planetary mixer is composed of two blades that perform planetary motion and three axes of high-speed rotary blades. The two blades rotate and revolve, and the high-speed rotor blades are structured to rotate in synchronization with the rotation and revolution (for example, registered utility model No. 3026043).

  The dispersion temperature is not particularly limited, but is preferably 10 to 50 ° C, more preferably 20 to 45 ° C, and particularly preferably 25 to 35 ° C. Within this range, the storage stability is further improved. The dispersion time is not particularly limited, but is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. Within this range, the smoothness of the resulting coating film is further improved.

  The fine particle slurry of the present invention can be used as an ink receiving layer, an antioxidant coating, an insulating coating, a heat dissipation material, a phosphor light diffusion layer, and a catalyst support layer. Applicable supports include paper {paper with sizing, non-size paper, high quality paper, medium quality paper, coated paper, art paper, cast coated paper, one or both sides of the paper covered with resin (polyolefin, etc.) Resin-coated paper, etc.}, resin film (meaning including sheet) {polyethylene, polypropylene, polyester, polylactic acid, polystyrene, polyacetate, polycycloolefin, polyvinyl chloride, cellulose acetate, polyethylene terephthalate, polymethyl methacrylate Or films made of polycarbonate, etc., and metal-deposited films thereof, synthetic paper made of films made opaque by filling with inorganic substances or fine foam, etc.}, disc-shaped optical recording media, glass substrates, metal substrates, cloths and leathers Etc. Among these, it is suitable for resin films, disc-shaped optical recording media, glass substrates, and metal substrates.

  Prior to the step of applying the fine particle slurry of the present invention to the support to form the coating layer, the surface of the support to which the fine particle slurry is applied is applied in advance for the purpose of improving the adhesion between the support and the coating film. You may add the process of adhering, or the process of carrying out the adhesion process. In particular, when a resin-coated paper, a resin film, or a synthetic paper is used as the support, it is preferable to subject the surface to corona discharge treatment or to provide an undercoat layer made of gelatin or the like.

  In the step of forming the coating layer by applying the fine particle slurry of the present invention to the support, a screen printing method, a die coater method, a roll coater method, a blade coater method, a rod coater method, a bar coater method or a spin coater method is used. Can be applied.

  When the fine particle slurry of the present invention is used, even when the coating film is formed by the screen printing method, it is possible to prevent the occurrence of irregularities and mesh marks due to spinnability, and a smooth coating film is obtained. When the screen method is used, it is possible to form a coating pattern or a pattern that cannot be formed by other printing methods.

As the squeegee used in the screen printing method, any of resin squeegees such as silicone rubber and polyurethane rubber and metal squeegees can be used.
The squeegee hardness is preferably 55 to 95 degrees, more preferably 60 to 90 degrees, and particularly preferably 70 to 80 degrees.
The squeegee hardness is measured according to JIS K6253-1997 “Hardness test method of vulcanized rubber and thermoplastic rubber 5. Durometer hardness test (type A)”.
The head shape of the squeegee is not particularly limited, but the shape described in Japanese Patent Application Laid-Open No. 2004-042644 can be used, and any of a flat shape, a sword shape, a square shape, a flat shape, or the like may be used.

There is no restriction | limiting in particular as a material of the screen mesh mask used for a screen printing method, The thing etc. which formed the opening part with the photosensitive emulsion for the stainless mesh or the polyester mesh are mentioned.
The mesh opening (μm) is preferably 30 to 400, more preferably 40 to 300, and particularly preferably 50 to 250.
The mesh opening is measured according to JIS G3556-2002 “Industrial Woven Wire Mesh 7.2 Test Method Opening”.
The thickness of the screen mesh mask (total thickness of the mesh and the photosensitive emulsion) (μm) is preferably 30 to 200, more preferably 70 to 150, and particularly preferably 90 to 120.

  When the fine particle slurry of the present invention is used as a screen printing ink, the loss tangent at a frequency of 1 Hz at 25 ° C. is preferably 0.4 to 4.5, more preferably 0.6 to 4.0, particularly preferably 1. 0.0 to 3.6. Within these ranges, the screen printing characteristics are improved and a coating film with high smoothness can be obtained.

  Loss tangent is measured by the stress control method described in “Rheological engineering and its applied technology”, Fuji Techno System Co., Ltd., January 12, 2001, first edition, first printing, pages 204-206. It is determined using an apparatus (for example, trade name “Leostress RS75” (manufactured by HAAKE), and can be measured by, for example, the method described in JP-A-2006-241449.

When the fine particle slurry of the present invention is used as a screen printing ink, the viscosity (V ₁₀ , mPa · s) at ₁₀ rpm is preferably 2000 to 15000 in the cone-plate type rotational viscosity (E-type viscosity) at 25 ° C. More preferably, it is 3000-12000, Most preferably, it is 4000-10000. Similarly, the viscosity at 100 rpm (V ₁₀₀ , mPa · s) is preferably 300 to 4500, more preferably 500 to 4000, and particularly preferably 600 to 3000. The ratio (V ₁₀ / V ₁₀₀ ) of the viscosity at ₁₀ rpm (V ₁₀ ) and the viscosity at 100 rpm (V ₁₀₀ ) is preferably 1.1 to 4.0, more preferably 1.2 to 3. 5, particularly preferably 1.5 to 3.0. Within these ranges, the screen printing characteristics are improved and a coating film with high smoothness can be obtained.

  The cone-plate type rotational viscosity (E-type viscosity) is in accordance with JIS K7117-2 “Plastics—Liquid, Liquid, Emulsion or Dispersed Resin—Method of Measuring Viscosity at a Constant Shear Rate Using a Rotational Viscometer”. For example, it can be measured by “RE-80U” manufactured by Toki Sangyo Co., Ltd.

After apply | coating the fine particle slurry of this invention, a dry coating film is formed by drying the formed application layer.
In the step of drying the coating layer to form a dried coating film, the drying is preferably performed at 30 to 150 ° C. for 0.5 to 30 minutes, more preferably 40 to 125 ° C. for 1 to 20 minutes, particularly preferably. The conditions are 45 to 100 ° C. for 3 to 15 minutes, most preferably 50 to 95 ° C. and 4 to 10 minutes.

  The thickness of the dry coating film can be appropriately selected depending on the printing method on the coating film, the type of ink used for printing, the type of solvent used in the ink, the amount of ink, and the like, but preferably 1 to 100 μm. More preferably, it is 5-70 micrometers, Most preferably, it is 10-50 micrometers, Most preferably, it is 12-45 micrometers.

  When the formed coating film is used as an ink receiving layer, image formation can be performed by an inkjet printer, a thermal transfer printer, a laser printer, offset printing, a writing instrument (felt pen, etc.), and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these Examples at all. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.

<Production Example 1>
Into a stainless steel reactor for polymerization equipped with a thermometer, a stirrer, a condenser, and two dropping pumps, 81.4 parts (0.83 mol) of maleic anhydride and 293.9 parts of ion-exchanged water were added. Heat to 95 ° C. with stirring. Thereafter, under reflux (95 ° C.), a mixture of 260.0 parts (2.89 mol) of an 80% aqueous acrylic acid solution, 173.6 parts of a 48.5% aqueous sodium hydroxide solution and 156.0 parts of ion-exchanged water was previously mixed. The aqueous solution of the monomer was dropped from the dropping pump over 180 minutes, and at the same time, the mixed catalyst solution (11.6 parts of sodium persulfate, 47.0 parts of 35% hydrogen peroxide solution and 11.0 parts of ion-exchanged water) was added from the other dropping pump. The mixture was polymerized while dropping at a constant rate over the course of 180 minutes. After completion of the dropwise addition, the reflux (95 ° C.) was maintained for an additional 120 minutes to complete the polymerization reaction. Subsequently, after cooling to 40 ° C. or lower, the solution was neutralized with 152.4 parts of 48.5% aqueous sodium hydroxide solution while maintaining 40 ° C. or lower to obtain an aqueous solution of copolymer (1). Furthermore, water was distilled off from the aqueous solution of the copolymer (1) with an evaporator to obtain a carboxylate copolymer (e1).

<Production Example 2>
In the same manner as in Production Example 1, except that “81.4 parts (0.83 mol) of maleic anhydride” was changed to “18.6 parts (0.16 mol) of hydroxyethyl acrylate” A union (e2) was obtained.

<Production Example 3>
Changed 81.4 parts (0.83 mol) of maleic anhydride to 239.6 parts (1.3 mol) of 2-ethylhexyl monoacrylate and 166.7 parts (1.3 mol) of n-butyl acrylate In the same manner as in Production Example 1, except that “80% acrylic acid aqueous solution 260.0 parts (2.89 mol)” was changed to “80% acrylic acid aqueous solution 26.0 (0.29 mol)”. Thus, a carboxylate copolymer (e3) was obtained.

<Production Example 4>
“Maleic anhydride 81.4 parts (0.83 mol)” was changed to “styrene 270.9 parts (2.6 mol)”, “80% acrylic acid aqueous solution 260.0 parts (2.89 mol)” "To 80% acrylic acid aqueous solution 26.0 (0.29 mol)" and "48.5% sodium hydroxide aqueous solution 173.6 parts" to "25% aqueous ammonia 150.0 parts" A carboxylate copolymer (e4) was obtained in the same manner as in Production Example 1 except for the change.

<Example 1>
40 parts of water (c1) {ion-exchanged water} and 4 parts of polyvinyl alcohol (b1) {J-POVAL JP-50, manufactured by Nihon Vinegar Bipoval Co., Ltd., saponification degree 89 mol%, polymerization degree 5000} After dispersion at 15 ° C., the temperature was raised to 90 ° C. over 45 minutes under atmospheric pressure (about 1013 hPa), and the mixture was stirred at 90 ° C. for 6 hours to obtain 44 parts of an aqueous polyvinyl alcohol (b1) solution.

3-axis planetary mixer (Asada Tekko Co., Ltd., Planetary DESPA) with 23 parts of water (c2) {ion exchange water}, dispersant (f1) {lactic acid, Tokyo Kasei Co., Ltd., reagent grade 1} 2. 4 parts, dye fixing agent (k1) {methyldiallylamine polymer hydrochloride 50 wt% aqueous solution, PAS-M-1, manufactured by Nitto Boseki Co., Ltd.} 2.0 parts and silica fine particles (a5) {silica fine particles, Aerosil 200, Prepared by Nippon Aerosil Co., Ltd., gas phase method silica, primary particle size 7 nm, BET specific surface area 200 m ² / g} 18 parts are charged and maintained at 25-30 ° C., and the output of the stirrer of the disperser is fixed at 80%. 1 hour after stirring, 4 parts of alumina fine particles (a1) {alumina fine particles, Aeroxide Alu-c, Degussa, primary particle size 13 nm} were charged, and the output of the stirrer of the disperser was similarly set to 80 parts. The mixture was stirred for 1 hour and charged with 44 parts of an aqueous solution of polyvinyl alcohol (b1). The output of the stirrer of the disperser was fixed again at 80 percent and stirred for 1 hour, and then the aliphatic alcohol (d1) { 1-butanol, NBO, manufactured by Chisso Corporation} 5 parts, aliphatic alcohol (d3) {2-methyl-1-propanol, isobutanol, manufactured by Kyowa Hakko Chemical Co., Ltd.} 5 parts, aliphatic alcohol (d5) {1-pentanol, manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1} 1 part and 0.1 part of carboxylate copolymer (e1) were charged and further stirred for 1 hour under the same conditions. A fine particle slurry (1) was obtained.

<Examples 2 to 12>
“5 parts of aliphatic alcohol (d1)”, “5 parts of aliphatic alcohol (d3)”, “1 part of aliphatic alcohol (d5)”, “23 parts of water (c2)” and “carboxylate copolymer ( The fine particle slurries (2) to (12) of the present invention were obtained in the same manner as in Example 1 except that “e1) 0.1 part” was changed to the substances and amounts used listed in Table 1.

<Examples 13 to 21>
Fine particle slurries (13) to (21) of the present invention in the same manner as in Example 1, except that 0.1 parts of “carboxylate copolymer (e1)” was changed to the substances and amounts used in Table 2. )

<Examples 22 to 26>
The fine particle slurry (22) of the present invention was obtained in the same manner as in Example 1 except that the “silica fine particles (a5) 18 parts” and the “alumina fine particles (a1) 4 parts” were changed to the substances and amounts used in Table 3. ) To (26) were obtained.

<Examples 27 to 33>
Example 1 except that “silica fine particles (a5) 18 parts”, “alumina fine particles (a1) 4 parts” and “polyvinyl alcohol (b1) aqueous solution 44 parts” were changed to the substances and amounts used in Table 4. Similarly, fine particle slurries (27) to (33) of the present invention were obtained.

<Examples 34 to 40>
In the same manner as in Example 1 except that 18 parts of “silica fine particles (a5)” and “4 parts of alumina fine particles (a1)” were changed to the substances and amounts used in Table 5, the fine particle slurry (34 ) To (40) were obtained.

In addition, the numerical value corresponding to each component (a1)-(a7), (b1), (c1), (c2), (d1)-(d13) in Tables 1 to 4 represents parts by weight. The meaning of each abbreviation other than is as follows.
“E1”, “e2”, “e3”, and “e4” are carboxylic acids (salts) based on the weight of inorganic fine particles (A), binder resin (B), water (C) and aliphatic alcohol (D) ( The addition amount (% by weight) of the (co) polymers (e1) to (e4), where “f1” is the weight of the inorganic fine particles (A), the binder resin (B), water (C) and the aliphatic alcohol (D). The added amount (% by weight) of the dispersant (f1) based on “k1” is the added amount of the dye fixing agent (k1) based on the weight of the inorganic fine particles (A), the binder resin (B) and the water (C). (% By weight), “D / C” used was the weight ratio {(D) / (C)} of the aliphatic alcohol (D) having 3 to 6 carbon atoms and water (C), and “BET” was used. The BET specific surface area of the inorganic fine particles (A) (respectively listed in the upper and lower columns in order), the particle diameter is the average of the inorganic fine particles (A) used. “A1 / A2” is the weight ratio of alumina fine particles (A1) and silica fine particles (A2), and “B / A” is the weight of inorganic fine particles (A). The content (% by weight) of the binder resin (B) based on the “particle diameter” indicates the average primary particle diameter (nm) of (A1) and (A2).

a1; Aeroxide Alu-c {alumina fine particles, manufactured by Degussa, vapor phase method alumina, primary particle diameter 13 nm, BET specific surface area 100 m ² / g}
a2; Aerosil 380 {silica fine particles, manufactured by Nippon Aerosil Co., Ltd., vapor phase silica, primary particle diameter 7 nm, BET specific surface area 380 m ² / g}
a3; Aerosil TT600 {silica fine particles, manufactured by Nippon Aerosil Co., Ltd., vapor phase silica, primary particle diameter 40 nm, BET specific surface area 50 m ² / g}
a4; Aerosil 90G {silica fine particles, manufactured by Nippon Aerosil Co., Ltd., gas phase method silica, primary particle diameter 20 nm, BET specific surface area 90 m ² / g}
a5; Aerosil 200 {silica fine particles, manufactured by Nippon Aerosil Co., Ltd., vapor phase silica, primary particle size 7 nm, BET specific surface area 200 m ² / g}
a6; Aerosil 300 {silica fine particles, manufactured by Nippon Aerosil Co., Ltd., vapor phase silica, primary particle size 7 nm, BET specific surface area 300 m ² / g}
a7; NanoTek TiO ₂ {Titanium dioxide fine particles, manufactured by CI Kasei Co., Ltd., titanium dioxide, primary particle size 36 nm, BET specific surface area 50 m ² / g}

b1; {J-POVAL JP-35, manufactured by Nihon Vinegar Bipovar Co., Ltd., saponification degree 89 mol%, polymerization degree 3500}
c1, c2; ion exchange water

d1; 1-butanol {NBO, manufactured by Chisso Corporation}
d2; 2-butanol {manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1}
d3; 2-methyl-1-propanol {isobutanol, manufactured by Kyowa Hakko Chemical Co., Ltd.}
d4; 2-methyl-2-propanol {manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1}
d5; 1-pentanol {manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1}
d6; 2-pentanol {manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1}
d7; 3-pentanol {manufactured by Wako Pure Chemical Industries, Ltd., reagent grade 1}
d8; 2-methyl-1-butanol {Wako Pure Chemical Industries, Ltd., reagent grade 1}
d9; 3-methyl-1-butanol {Wako Pure Chemical Industries, Ltd., reagent grade 1}
d10; 2-methyl-2-butanol {Wako Pure Chemical Industries, Ltd., reagent grade 1}
d11; 3-methyl-2-butanol {Tokyo Chemical Industry Co., Ltd., reagent grade 1}
d12; 1-propanol {Wako Pure Chemical Industries, Ltd., reagent grade 1}
d13; 1-hexanol {Wako Pure Chemical Industries, Ltd., reagent grade 1}

e1; carboxylic acid (salt) (co) polymer e2 produced in Production Example 1; carboxylic acid (salt) (co) polymer e3 produced in Production Example 2; carboxylic acid (salt) produced in Production Example 3 ( Co) polymer e4; carboxylic acid (salt) (co) polymer produced in Production Example 4

f1; lactic acid, manufactured by Tokyo Chemical Industry Co., Ltd., reagent grade 1 k1; methyl diallylamine polymer hydrochloride 50% by weight aqueous solution, PAS-M-1, manufactured by Nittobo Co., Ltd.

<Comparative Example 1>
“Fatty alcohol (d1) 5 parts”, “Fatty alcohol (d3) 5 parts”, “Fatty alcohol (d5) 1 part” and “Water (c2) 23 parts” are replaced with “Water (c2) 35 parts”. A comparative fine particle slurry (H1) was obtained in the same manner as in Example 1 except that the change was changed to.

<Comparative example 2>
In 26.6 parts of water (c1), 2 parts of binder resin (b2) {PVA235, manufactured by Kuraray Co., Ltd., saponification degree 88 mol%, polymerization degree 3500} are dispersed in an air atmosphere at 15 ° C. The temperature was raised to 90 ° C. over 45 minutes under atmospheric pressure (about 1013 hPa), and the mixture was stirred at 90 ° C. for 6 hours to obtain 28.6 parts of an aqueous binder resin (b2) solution.

  Triaxial planetary mixer (Planetary DESPA, manufactured by Asada Tekko Co., Ltd.), water (c2) 64.8 parts, dispersant {Charol DC-902P, Daiichi Kogyo Seiyaku Co., Ltd.} 0.9 parts and inorganic fine particles (a5 ) {Aerosil 300CF, manufactured by Nippon Aerosil Co., Ltd.} 10 parts are charged, maintained at 25-30 ° C., the output of the stirrer of the disperser is fixed at 80% and stirred for 1 hour, and then polyvinyl alcohol (b2) After charging 28.6 parts of the aqueous solution, the output of the stirrer of the disperser was fixed to 80 percent and stirred for 1 hour, zirconyl nitrate {ZA-30, manufactured by Daiichi Rare Elemental Chemical Co., Ltd.} 0.5 part , Crosslinking agent {Boric acid, Wako Pure Chemical Industries, Ltd., reagent grade} 0.4 part, Water-soluble resin (binder) {Superflex 600, Daiichi Kogyo Seiyaku Co., Ltd.} 1 part, Polyoxyethylene Lauril -Ter {Emulgen 109P, Kao Co., Ltd.} 0.5 part and ethanol {Wako Pure Chemical Industries, Ltd., reagent grade} 2.5 parts were charged and stirred for 1 hour under the same conditions. A fine particle slurry (H2) was obtained.

The fine particle slurries obtained in the examples and comparative examples were evaluated as follows, and the results are shown in Tables 6 and 7.
<Preparation of coated film>
A screen mesh mask (emulsion thickness 120 μm, size 30 cm × 30 cm polyester mesh opening 173 μm mesh plate) is placed on 70 KOKUYO OHP film (product number VF-1) (printing gap: 1 5 mm) and mask-printed an evaluation sample {fine particle slurry} sealed in a 25 ° C. environment for 6 hours with a square squeegee having a hardness of 70 °, a length of 20 cm, and a thickness of 2 cm {squeegee angle of 15 °, moving speed of 150 mm / Sec, squeegee pressure (squeegee pressing load) 40 kg)} to obtain 70 coated films. Subsequently, the coated film was dried in a hot air drier at 70 ± 5 ° C. for 10 minutes to obtain 70 dried films.

<Glossiness (smoothness)>
The dried film was conditioned at 20 ° C. and 65% RH for 24 hours, and then JIS K5600-4-7: 1999, paint general test method, Part 4: Visual characteristics of coating film, Section 7: Based on the specular gloss, the gloss checker IG-320 {manufactured by Horiba Ltd.} was used to measure the 60 ° specular gloss of the film surface after drying placed on black felt, 70 sheets The arithmetic average value was taken as the glossiness.

<Bubble bubble>
In the production of the coating film, for the dried film mask-printed on the 11th to 60th sheets, the bubble marks were counted visually, and the arithmetic average value per sheet was taken as the number of bubble ridges.

<Loss tangent>
Loss tangent at 25 ° C. and 1 Hz was measured using “Rheostress RS75” (manufactured by HAAKE).

<E-type viscosity>
Using “RE-80U” (manufactured by Toki Sangyo Co., Ltd.), the viscosity at 10 rpm (V ₁₀ , mPa · s) and the viscosity at 100 rpm (V ₁₀₀ , mPa · s) at 25 ° C. were measured. It was calculated viscosity ratio of the viscosity _{(V 100)} in _{(V 10)} and _{100rpm (V 10 / V 100)} .

The fine particle slurry (Examples 1 to 40) of the present invention was remarkably superior in terms of glossiness (smoothness) and foaming compared to the comparative fine particle slurry (Comparative Examples 1 and 2).

  The fine particle slurry of the present invention is suitable as a material for forming an ink receiving layer, an antioxidant coating, an insulating coating, a heat dissipation material, a phosphor light diffusing layer, or a catalyst supporting layer. The fine particle slurry of the present invention can be applied (coated) to various supports and dried to form a coating film, whereby printability with aqueous ink can be imparted to the support. The formed coating film is excellent in smoothness, and when the coating film is used as an ink receiving layer, a glossy appearance is preferable. Examples of the support include leather, cloth, resin molded body, paper, metal, cardboard, and ceramic, and the support to which the fine particle slurry of the present invention is applied is ink jet printing compatible paper, ink jet printing compatible industrial advertising film, Prepaid cards, optical recording media (CD-R, CD-RW, DVD, BD, etc.), IC cards, magnetic cards, heat sinks, phosphors such as LEDs, electrodes carrying catalysts, acrylic resin sheets for electrical equipment, It can be used as a polycarbonate plate for building materials, signboards, display panels, nameplates, nameplates, packaging containers and bags.

Claims (11)

Inorganic fine particles (A) composed of alumina fine particles (A1) and silica fine particles (A2), binder resin (B), water (C), aliphatic alcohol (D) having 3 to 6 carbon atoms and carboxylic acid (salt) ) Polymer ( E ),
Carboxylic acid (salt) (co) polymer (E) is a homopolymer of aliphatic monocarboxylic acid (salt) or aliphatic monocarboxylic acid (salt) and maleic anhydride, (meth) acrylic acid alkyl ester, (meth) It is a copolymer with other monomers selected from hydroxyalkyl acrylate, vinyl group-containing amide, vinyl group-containing sulfonic acid, vinyl group-containing nitrile and styrene,
A fine particle slurry, wherein a weight ratio (D / C) of an aliphatic alcohol (D) having 3 to 6 carbon atoms and water (C) is 0.01 to 0.9. The fine particle slurry according to claim 1 , wherein the weight ratio (A1 / A2) of the alumina fine particles (A1) to the silica fine particles (A2) is 0.05 to 2.0. The fine particle slurry according to claim 1 or 2 , wherein the average primary particle diameter of the alumina fine particles (A1) and the silica fine particles (A2) is 7 to 40 nm. The fine particle slurry according to any one of claims 1 to 3 , wherein the aliphatic alcohol (D) is an aliphatic monoalcohol. The aliphatic alcohol (D) is 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl- 1-butanol, 3-methyl-1-butanol, according to claim 1-4 comprising at least two selected from the group consisting of 2-methyl-2-butanol and 3-methyl-2-butanol according to any Fine particle slurry. The fine particle slurry according to any one of claims 1 to 5 , wherein the binder resin (B) is polyvinyl alcohol. The fine particle slurry according to any one of claims 1 to 6 , wherein the content of the binder resin (B) is 5 to 50% by weight based on the weight of the inorganic fine particles (A). The carboxylic acid (salt) (co) polymer (E) content is alumina fine particles (A1) and silica fine particles (A2), binder resin (B), water (C) and monovalent fat having 3 to 6 carbon atoms. The fine particle slurry according to any one of claims 1 to 7 , which is 0.01 to 5.0% by weight based on the weight of the group alcohol (D). The fine particle slurry according to any one of claims 1 to 8 , wherein the inorganic fine particles (A) have a BET specific surface area of 50 to 400 m ² / g. The fine particle slurry according to any one of claims 1 to 9 , which is applied to a support by a screen printing method. After obtaining an aqueous dispersion of inorganic fine particles (A) composed of alumina fine particles (A1) and silica fine particles (A2), an aqueous solution of a binder resin (B), water (C), an aliphatic alcohol having 3 to 6 carbon atoms ( D) and a carboxylic acid (salt) (co) polymer ( E ), and if necessary, an additive and a step of uniformly mixing and dispersing an aqueous dispersion of inorganic fine particles (A),
Carboxylic acid (salt) (co) polymer (E) is a homopolymer of aliphatic monocarboxylic acid (salt) or aliphatic monocarboxylic acid (salt) and maleic anhydride, (meth) acrylic acid alkyl ester, (meth) It is a copolymer with other monomers selected from hydroxyalkyl acrylate, vinyl group-containing amide, vinyl group-containing sulfonic acid, vinyl group-containing nitrile and styrene,
A method for producing a fine particle slurry, wherein the weight ratio (D / C) of the aliphatic alcohol (D) having 3 to 6 carbon atoms and water (C) is 0.01 to 0.9.