JP2014096231A - Inorganic fine particle slurry - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inorganic fine particle slurry capable of easily forming uniform coat.SOLUTION: An inorganic fine particle slurry is used, the inorganic fine particle slurry containing: an inorganic fine particle (A); a polyvinyl alcohol (B1) and/or a polyoxyalkylene compound (B2) represented by general formula (1); an amino alcohol (salt) (C); and water (D). {R-(OX)-}Q (1) Q represents a reaction residue obtained by removing a hydrogen atom from m primary hydroxyl groups of non-reductive disaccharides or trisaccharides, OX represents a 2-4C oxyalkylene group, R represents a 1-4C alkyl group and/or a hydrogen atom, m number of R and m number of (OX)may be the same or different, ni represents an integer of 0-100, m represents an integer of 2-4, i represents an integer of 1-m, m number of ni may be the same or different, but at least one of them is 1 or more, and the sum total (Σni×m) of OX is an integer of 20-100.

Description

  The present invention relates to an inorganic fine particle slurry.

  Conventionally, by applying inorganic fine particle slurry containing alumina particles or silica particles and laminating a protective film on the glass tube, the release of sodium from the glass tube is suppressed, and the formation of amalgam with mercury is suppressed and the life is extended. There are known fluorescent lamps (Patent Documents 1 and 2).

JP 2007-226988 A JP 2011-071027 A

  However, the conventional inorganic fine particle slurry is not easy to form a uniform coating film, and when used as a protective layer applied to the inner surface of a fluorescent lamp, uneven coating occurs and uneven brightness of the fluorescent lamp It can be a cause. In addition, when there is uneven coating, a uniform protective film cannot be formed, so that sufficient protection performance cannot be exhibited, and the life of the fluorescent lamp tends to be shortened.

  An object of the present invention is to provide an inorganic fine particle slurry capable of easily forming a uniform coating film.

  The inorganic fine particle slurry of the present invention comprises inorganic fine particles (A), polyvinyl alcohol (B1) and / or polyoxyalkylene compound (B2) represented by the general formula (1), amino alcohol (salt) (C) and water ( It is summarized that it contains D).

{R- (OX) _ni- } _m Q (1)

Q is a reaction residue obtained by removing a hydrogen atom from m primary hydroxyl groups of non-reducing di- or trisaccharides, OX is an oxyalkylene group having 2 to 4 carbon atoms, R is an alkyl group having 1 to 4 carbon atoms, and / Represents a hydrogen atom, m R and m (OX) _ni may be the same or different, ni is an integer of 0 to 100, m is an integer of 2 to 4, i is 1 to m Represents an integer, m ni may be the same or different, but at least one is 1 or more, and the total number of OX (Σni × m) is an integer of 20-100.

  The gist of the fluorescent lamp of the present invention is that the inorganic fine particle slurry is applied to the inner surface of the glass tube and dried.

  The inorganic fine particle slurry of the present invention can easily form a uniform coating film.

  Since the fluorescent lamp of the present invention is coated with the inorganic fine particle slurry, it has a uniform protective layer, has no unevenness in brightness, and has an excellent appearance and life.

<Inorganic fine particles (A)>
The inorganic fine particles (A) include silica fine particles, alumina fine particles and a mixture thereof.

  Examples of the silica fine particles include amorphous synthetic silica (precipitation method silica, gel method silica, gas phase method silica, and fusion method silica), crystalline synthetic silica, and natural silica. The alumina fine particles include vapor phase method alumina and calcined method alumina. Examples of the silica fine particles and alumina fine particles include the following products {in the form of a dispersion in which powdery or inorganic fine particles are dispersed in water}.

<Precipitated silica>
Nipsil series {Tosoh Silica Co., Ltd., “Nipsil” is a registered trademark of Tosoh Silica Co., Ltd. }, Sipernat series {Evonik Degussa Japan Co., Ltd., "Sipernat" is a registered trademark of Evonik Degussa GmbH. }, Carplex series {DSL. Japan Corporation, “Carplex” is a DSL. It is a registered trademark of Japan Corporation. }, FINESIL series {Tokuyama Corporation, "FINESIL" is a registered trademark of Tokuyama Corporation. }, TOKUSIL series {Tokuyama Corporation, “TOKUSIL” is a registered trademark of Tokuyama Corporation. }, Zeosil series {Rhodia, "Zeosil" is a registered trademark of Rhodia Simi. }, MIZUKASIL series {Mizusawa Chemical Industry Co., Ltd., "MIZUKASIL" is a registered trademark of Mizusawa Chemical Industry Co., Ltd. }etc.

<Gel method silica>
Carplex series, SYLYSIA series {Fuji Silysia Co., Ltd., "SYLYSIA" is a registered trademark of YK FF Ltd. }, Nippon Series {Tosoh Silica Co., Ltd., “Nipgel” is a registered trademark of Tosoh Silica Co., Ltd. }, MIZUKASIL series {Mizusawa Chemical Industry Co., Ltd., "MIZUKASIL" is a registered trademark of Mizusawa Chemical Industry Co., Ltd. }etc.

<Gas phase method silica>
Aerosil series {Nippon Aerosil Co., Ltd. and Evonik Degussa, "Aerosil" is a registered trademark of Evonik Degussa GmbH. }, Reolosil series {Tokuyama Corporation, “Reorosil” is a registered trademark of Tokuyama Corporation. }, Cab-O-Sil series {Cabot Corporation, "Cab-O-Sil" is a registered trademark of Cabot Corporation. }, WACKER HDK series {Asahi Kasei Wacker Co., Ltd., “WACKER” is a registered trademark of Wacker Chemie Aktiengesellschaft. }etc.

<Fused silica>
Admafine series {Admatechs, "Admafine" is a registered trademark of Admatex. }, Fuselex series {Tatsumori Co., Ltd.}, Denka fused silica series {Electrochemical Industry Co., Ltd.}, etc.

<Crystalline synthetic silica>
CRYSTALITE series {Tatsumori Corporation, “CRYSTALITE” is a registered trademark of Tatsumori Corporation. }, Imsil series {UNIMIN, "Isil" is a registered trademark of Unimin Specialty Minerals, Inc. }etc.

<Natural silica>
Mizuka Ace Series {Mizusawa Chemical Co., Ltd.} etc.

<Silica dispersion>
Cataloid-S series {Catalytic Chemical Industry Co., Ltd., "Cataloid" is a registered trademark of the company. }, Quartron series {Fuso Chemical Industry Co., Ltd., "Quartron" is a registered trademark of the company. } And Snowtex series {Nissan Chemical Co., Ltd.} etc.

<Gas phase alumina>
Aeroxide Al series {Nippon Aerosil Co., Ltd. and Evonik Degussa, "Aeroxide" is a registered trademark of Evonik Degussa GmbH. } And SpectrAl series {Cabot}.

<Baking alumina>
High-purity alumina AKP series {Sumitomo Chemical Co., Ltd.}, Alumina A series {Nihon Light Metal Co., Ltd.}, Tymicron series {manufactured by Daimei Chemical Co., Ltd.} and DISPAL series {Sasol "DISPAL" are registered trademarks of the company. }etc.

<Alumina dispersion>
Cataloid-A series {manufactured by Catalyst Kasei Kogyo Co., Ltd.} and alumina sol series {manufactured by Nissan Chemical Industries Ltd.}.

As inorganic fine particles (A), in addition to silica fine particles, alumina fine particles and mixtures thereof, the following inorganic fine particles can also be used.
Metal oxide fine particles {titanium dioxide (TiO ₂ ), chromium dioxide (CrO ₂ ), molybdenum dioxide (MoO ₂ ), molybdenum trioxide (MoO ₃ ), manganese dioxide (MnO ₂ ), zirconium dioxide (ZrO ₂ ), iron oxide (II) (FeO), iron oxide (III) (Fe ₂ O ₃ ), triiron tetroxide (Fe ₃ O ₄ ), cobalt dioxide (CoO ₂ ), copper oxide (II) (CuO), zinc oxide (ZnO ), Tin (II) oxide (SnO), tin oxide (IV) (SnO ₂ ), tin oxide (VI) (SnO ₃ ), barium titanate (BaO ₃ Ti), lead titanate (PbTiO ₃ ), titanate strontium (SrTiO _3), potassium niobate (KNbO _3), strontium aluminate (SrAl ₂ O _4), ammonium chromate ((N _{4) 2} Cr ₂ O ₄₎ or titanium ammonium _((NH 4) 2 TiO ₃₎ made of such fine particles}; metal hydroxide fine particles (fine particles of magnesium hydroxide or calcium hydroxide); fine particulate carbonate (Fine particles made of calcium carbonate or magnesium carbonate, etc.); layered mineral fine particles {kaolinite, halloysite, talc, smectite (montmorillonite, beidellite, hectorite, sabonite, etc.), vermiculite, mica (mica), chlorite, hydrotalcite or Layered polysilicate (fine particles such as kanemite, macatite, ialite, magadiite, and Kenyaite))}; and mixed fine particles of these fine particles and / or silica fine particles and alumina fine particles.

  The number average primary particle diameter (nm) of the inorganic fine particles (A) is preferably 7 to 3, more preferably 7 to 20. Within this range, the uniformity of the coating film is further facilitated, which is preferable. The number average primary particle size was determined according to JIS Z8901-2006 “Testing powder and testing particles”, 5.44 particle diameter distribution (c) microscopy, and a sample prepared by the sprinkling method was measured with a transmission electron microscope. It is an arithmetic average value of equivalent circle diameters calculated by observing 100 or more particles from an image observed with magnification of 10,000 to 1,000,000 times.

  The shape of the inorganic particles (A) is not particularly limited, but is preferably a needle shape, but may be a spherical shape, a spheroid shape (spindle shape), a polyhedral shape, an indefinite shape, or the like.

<Polyvinyl alcohol (B1)>
Examples of the polyvinyl alcohol (B1) include fully saponified polyvinyl alcohol (B11), partially saponified polyvinyl alcohol (B12), cation modified polyvinyl alcohol (B13), anion modified polyvinyl alcohol (B14), and nonionic modified polyvinyl alcohol (B15). ) Is included.

  The completely saponified polyvinyl alcohol means polyvinyl alcohol having a saponification degree of 98 mol% or more and 100 mol% or less. The partially saponified polyvinyl alcohol means polyvinyl alcohol having a saponification degree of 70 mol% or more and less than 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.

  As the fully saponified polyvinyl alcohol (B11) and the partially saponified polyvinyl alcohol (B12), known ones (for example, JP-A-2006-28233) can be used. As the cation-modified polyvinyl alcohol (B13), known ones (for example, JP-A-10-119423) can be used. Known anion-modified polyvinyl alcohol (B14) (for example, JP-A-1-206088, JP-A-61-237681, JP-A-63-307979 and JP-A-7-285265), etc. Can be used. As the nonionic modified polyvinyl alcohol (B15), known ones (for example, JP-A-7-9758 and JP-A-8-25795) can be used.

  Among these polyvinyl alcohols, partially saponified polyvinyl alcohol (B12) is preferable from the viewpoint of the uniformity of the coating film, more preferably partially saponified polyvinyl alcohol having a saponification degree of 70 to 96 mol%, particularly preferably. Is a partially saponified polyvinyl alcohol having a saponification degree of 80 to 89 mol%.

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

  300-5000 are preferable and, as for the average degree of polymerization of polyvinyl alcohol (B1), More preferably, it is 500-2000. Within this range, the uniformity of the coating film is further improved, which is preferable.

 The average degree of polymerization is measured according to JIS K6726-1994 “Polyvinyl alcohol test method 3.7 Average degree of polymerization”.

<Polyoxyalkylene compound (B2)>
In the general formula (1), the di- or trisaccharide that can constitute the reaction residue (Q) obtained by removing a hydrogen atom from m primary hydroxyl groups of a non-reducing di- or trisaccharide is sucrose (sucrose). ), Trehalose, isotrehalose, isosaccharose, gentianose, raffinose, meretitol and planteose.
Among these, sucrose, trehalose, raffinose, and meletitose are preferable from the viewpoint of the uniformity of the coating film.

  Examples of the oxyalkylene group having 2 to 4 carbon atoms (OX) include oxyethylene, oxypropylene, oxybutylene, and a mixture thereof.

The ni OXs may be the same or different, and the m (OX) _ni may be the same or different. (OX) When a plurality of types of oxyalkylene groups are contained in _ni , there is no limitation on the bonding order (block shape, random shape, and combinations thereof) and the content ratio of these oxyalkylene groups.

  Among R, examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, iso-propyl, n-butyl and iso-butyl. Of R, methyl, ethyl and hydrogen atoms are preferred. The m Rs may be the same or different.

  When an alkyl group is included in m R, the number of hydrogen atoms among all R is preferably 0 to 3, more preferably 0 to 2, particularly preferably 0 or 1 when m is 4. When m is 3, 0 to 2 are preferable, more preferably 0 or 1, and when m is 2, 0 or 1 is preferable.

  ni is preferably an integer of 0 to 100, more preferably an integer of 2 to 98. Within this range, the uniformity of the coating film is further improved.

  m is preferably an integer of 2 to 4, more preferably 3. Within this range, the uniformity of the coating film is further improved. This m corresponds to the number of primary hydroxyl groups of the non-reducing di- or trisaccharide.

  i represents an integer of 1 to m, and m ni may be the same value or different values, but at least one ni is 1 or more. That is, for example, when m = 4, ni means n1, n2, n3, and n4, all of which may be the same or different.

  The total number of OX (Σni × m) is preferably an integer of 20 to 100, more preferably an integer of 35 to 85. Within this range, the uniformity of the coating film is further improved.

  Preferred examples of the polyoxyalkylene compound (B2) include polyoxyalkylene compounds described in International Patent Application Pamphlet WO 2004/101103 (Republished 2004-101103).

  Examples of the polyoxyalkylene compound (B2) include a reaction product (B2 ′) of the polyoxyalkylene compound (B2) and diisocyanate and / or a reaction product (B2 ″) of the polyoxyalkylene compound (B2) and diglycidyl ether. Can be used.

  Examples of the reactant (B2 ′) include polyoxyalkylene compounds described in JP-A No. 2004-224945. Examples of the reactant (B2 ″) include polyoxyalkylene compounds described in JP-A-2005-170965.

<Amino alcohol (salt) (C)>
Amino alcohol (salt) (C) means amino alcohol (C1) and / or amino alcohol salt (C2).

  The amino alcohol (C1) includes alkanolamines having 2 to 9 carbon atoms, such as monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-1-propanol, diethanolamine, diisopropanolamine, triethanolamine and Examples include triisopropanolamine.

  As amino alcohol salt (C2), (co) polymer of amino alcohol (C1) and inorganic acid or organic acid {carboxylic acid having 1 to 10 carbon atoms, sulfonic acid having 1 to 7 carbon atoms, ethylenically unsaturated acid] Etc.} and the like.

  Examples of inorganic acids include hydrochloric acid, nitric acid, phosphoric acid, perchloric acid, bromic acid, and sulfuric acid.

  Examples of the carboxylic acid having 1 to 10 carbon atoms include monocarboxylic acids having 1 to 4 carbon atoms (such as formic acid, acetic acid, propionic acid, butanecarboxylic acid and acrylic acid), and dicarboxylic acids having 2 to 5 carbon atoms (oxalic acid and malon). Acid, succinic acid, glutaric acid, etc.) and C2-C6 hydroxycarboxylic acid (glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, ascorbic acid, etc.) and C7-10 aromatic carboxylic acid (benzoic acid) Acid, methylbenzoic acid, salicylic acid, phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, and the like.

  Examples of the sulfonic acid having 1 to 7 carbon atoms include methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid.

The (co) polymer of the ethylenically unsaturated acid is a (co) polymer comprising an ethylenically unsaturated acid as an essential constituent monomer.
Examples of the ethylenically unsaturated acid include ethylenically unsaturated monocarboxylic acid, ethylenically unsaturated dicarboxylic acid, monoester of ethylenically unsaturated dicarboxylic acid, and ethylenically unsaturated sulfonic acid.

  Examples of the ethylenically unsaturated monocarboxylic acid include acrylic acid and methacrylic acid.

  Examples of the ethylenically unsaturated dicarboxylic acid include itaconic acid, fumaric acid, maleic acid, and intramolecular anhydrides thereof.

  The monoester of ethylenically unsaturated dicarboxylic acid includes monoester of ethylenically unsaturated dicarboxylic acid and (poly) oxyalkylene alcohol or aliphatic alcohol.

  Examples of the (poly) oxyalkylene alcohol include alkylene (2 to 4 carbon atoms) glycol, monoalkyl (carbon numbers 1 to 18) ether of alkylene (2 to 4 carbon atoms) glycol, and poly (n = 2 to 90) oxyalkylene. Examples thereof include monoalkyl (carbon number 1 to 18) ethers of (carbon number 2 to 4) glycol and poly (n = 2 to 90) oxyalkylene (carbon number 2 to 4) glycol.

  Examples of the aliphatic alcohol include lower alcohols having 1 to 4 carbon atoms (such as methanol, ethanol, n-propanol, isopropanol, and butanol).

  When the (co) polymer of ethylenically unsaturated acid is a (co) polymer having a monoester of ethylenically unsaturated dicarboxylic acid as a structural unit, the (co) polymer of ethylenically unsaturated dicarboxylic acid is esterified. Alternatively, it may be obtained by (co) polymerizing a monoester of ethylenically unsaturated dicarboxylic acid as a structural unit.

  Examples of the ethylenically unsaturated sulfonic acid include styrene sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid.

  The copolymerizable monomer that can be copolymerized with the ethylenically unsaturated acid is not particularly limited as long as it can be copolymerized with the ethylenically unsaturated acid, and an aromatic vinyl monomer (styrene, α-methylstyrene, m- or p-). Vinyl toluene and mixtures thereof), ethylenically unsaturated carboxylic acid esters {methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate)}, olefins (ethylene, propylene, isobutylene, octylene and Non-decylene, etc.), ethylenically unsaturated nitriles {(meth) acrylonitrile, cyanopropene, etc.} and ethylenically unsaturated amides {(meth) acrylamide, N-methyl (meth) acrylamide, N- (2-aminoethyl) (meth) Acrylamide and N-vinylpyrrolidone etc.}.

  When the comonomer is included as a constituent unit, the content (mol%) of the comonomer unit is preferably 10 to 95, more preferably 50 based on the number of moles of the ethylenically unsaturated acid unit. ~ 90.

The weight average molecular weight (Mw) of the (co) polymer of the ethylenically unsaturated acid is preferably 3,000 to 100,000, more preferably 4,000 to 20,000.
The weight average molecular weight (Mw) can be measured by a gel permeation chromatography (GPC) method using polyethylene glycol having a known molecular weight as a standard substance (as examples of measurement conditions, columns: TSKgel GuardColumn SWXL, G4000SWXL, manufactured by Tosoh Corporation). And G2000SWXL connected in series, column temperature: 40 ° C., eluent: 0.1-MPB disodium hydrogenphosphate aqueous solution: 0.1-MPB sodium dihydrogenphosphate aqueous solution = 1: 1 (molar ratio) ), Flow rate 0.8 ml / min, sample concentration: 0.4 wt% eluent solution.

  The amino alcohol salt (C2) can be easily obtained by mixing the amino alcohol (C1) with an inorganic acid or an organic acid and causing a neutralization reaction. When the organic acid is a (co) polymer of an ethylenically unsaturated acid, the amino alcohol (C1) and the ethylenically unsaturated acid may be mixed and neutralized for (co) polymerization. Then, the (co) polymer of ethylenically unsaturated acid and amino alcohol (C1) may be mixed and neutralized.

  As amino alcohol (salt) (C), both amino alcohol (C1) and amino alcohol salt (C2) may be included. In this case, each amino alcohol may be the same or different. Also good. When both amino alcohol (C1) and amino alcohol salt (C2) are included, the content (% by weight) of amino alcohol (C1) is based on the total weight of amino alcohol (C1) and amino alcohol salt (C2). 5 to 95 is preferable, and 50 to 90 is more preferable. In this case, the content (% by weight) of the amino alcohol salt (C2) is preferably 5 to 95, more preferably 10 based on the total weight of the amino alcohol (C1) and the amino alcohol salt (C2). ~ 50.

<Water (D)>
As the water (D), ion-exchanged water, distilled water, ultrapure water, tap water, industrial water, and a mixture thereof can be used.
As water (D), in addition to the above water, water and aqueous solvents {monool (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, etc.), polyol (ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, glycerin, sorbit, sorbitan, etc.), glycol ether (methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, carbitol, butyl carbitol, etc.), glycol ester (methyl cellosolve acetate, cellosolve acetate, etc.), ketone (acetone and Methyl ethyl ketone, etc.), other polar solvents (formamide, acetamide, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, etc.) and mixtures thereof Aqueous solution of a mixture of equal} can also be used.
In the case of an aqueous solution of water and an aqueous solvent, the content (% by weight) of the aqueous solvent is preferably 1 to 80, more preferably 3 to 60, and particularly preferably 5 to 5 based on the total weight of water and the aqueous solvent. 50.

  The content (% by weight) of the inorganic fine particles (A) is that of the inorganic fine particles (A), polyvinyl alcohol (B1) and / or polyoxyalkylene compound (B2), amino alcohol (salt) (C) and water (D). Based on the total weight, 2 to 40 is preferable, and 5 to 20 is more preferable. Within this range, the dispersion of the inorganic fine particles (A) is further improved, especially the storage stability of the inorganic fine particle slurry is further improved, and a uniform coating film can be obtained for a longer period of time.

  The content of the polyvinyl alcohol (B1) and the polyoxyalkylene compound (B2) includes inorganic fine particles (A), polyvinyl alcohol (B1) and / or polyoxyalkylene compounds (B2), amino alcohol (salt) (C) and water. Based on the total weight of (D), 0.05 to 10 is preferable, and 0.1 to 2 is more preferable. Within this range, the dispersion of the inorganic fine particles (A) is further improved, especially the storage stability of the inorganic fine particle slurry is further improved, and a uniform coating film can be obtained for a longer period of time.

  The content of amino alcohol (salt) (C) is the sum of inorganic fine particles (A), polyvinyl alcohol (B1) and / or polyoxyalkylene compound (B2), amino alcohol (salt) (C) and water (D). Based on weight, 0.1-10 are preferable, More preferably, it is 0.5-5. Within this range, the dispersion of the inorganic fine particles (A) is further improved, especially the storage stability of the inorganic fine particle slurry is further improved, and a uniform coating film can be obtained for a longer period of time.

  The content (% by weight) of water (D) is preferably 100 to 5000, more preferably 250 to 500, based on the weight of the inorganic fine particles (A). Within this range, the dispersion of the inorganic fine particles (A) is further improved, especially the storage stability of the inorganic fine particle slurry is further improved, and a uniform coating film can be obtained for a longer period of time.

The inorganic fine particle slurry of the present invention may contain known additives {the following various dyes (colorants), resins, etc.} depending on the purpose.
(1) Colorant (disperse dye, acid dye, direct dye, basic dye, various organic or inorganic color pigments, etc.)
(2) Aqueous resin (acrylic resin, acrylic-styrene resin, vinyl acetate resin, epoxy resin, alkyd resin, acrylic modified alkyd resin, melamine resin, epoxy resin, hexamethylol melamine resin, urea-formaldehyde condensate, urea-melamine co Condensate)
(3) Thickener (methyl cellulose, hydroxyethyl cellulose, xanthan gum, etc.)
(4) UV absorber (5) Antioxidant (6) Antifungal agent (7) Antifoam agent (8) Drying inhibitor (9) Water resistance imparting agent (10) Thickener (11) Anti-repellent agent ( 12) Other surfactants

  When an additive is contained, the amount (% by weight) of these additives is not particularly limited, but inorganic fine particles (A), polyvinyl alcohol (B1) and / or polyoxyalkylene compound (B2), amino alcohol (salt) (C ) And water (D) based on the total weight, 0.1 to 40 is preferable, and 1 to 30 is more preferable.

  As a method for producing the inorganic fine particle slurry of the present invention, inorganic fine particles (A), polyvinyl alcohol (B1) and / or polyoxyalkylene compound (B2), amino alcohol (salt) (C) and water (D), and necessary There is no limitation as long as the additives can be uniformly mixed according to the conditions, but the polyvinyl alcohol (B1) and / or polyoxyalkylene compound (B2), amino alcohol (salt) (C) and water (D) are uniformly mixed to form an aqueous solution. After being obtained, it is preferable to obtain an inorganic fine particle slurry by uniformly mixing this aqueous solution with the inorganic fine particles (A) and, if necessary, additives.

  When the amino alcohol salt (C2) is contained in the inorganic fine particle slurry of the present invention, the amino alcohol salt (C2) may be uniformly mixed with the inorganic fine particles (A) or the like in the form of amino alcohol salt, or amino alcohol The amino alcohol salt may be formed in a mixture of (C1) and the organic acid or inorganic acid with the inorganic fine particles (A), etc., and the inorganic fine particles (A).

  Polyvinyl alcohol (B1), polyoxyalkylene compound (B2) and amino alcohol (salt) (C) can be mixed in the form of an aqueous solution. At this time, the water contained in the aqueous solution constitutes part or all of the water (D) which is one of the constituent components of the inorganic fine particle slurry of the present invention.

  There is no particular limitation on uniform mixing, and commonly used dispersers can be used. Dispersers such as paint shakers, homomixers, high-pressure homogenizers, disper mills, medium stirring type dispersers such as ball mills and sand mills, roll mills, A kneading disperser such as a planetary mixer can be used.

  The uniform mixing 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.

  The uniform mixing time is not particularly limited, but is preferably 0.5 to 24 hours, and more preferably 1 to 12 hours. Within this range, the uniformity of the obtained coating film is further improved.

  The viscosity of the inorganic fine particle slurry of the present invention is not particularly limited, but is generally preferably low viscosity, more preferably 0.5 to 800 mPa · s, and particularly preferably 1 to 500 mPa · s as the rotational viscosity at 25 ° C. It is. The rotational viscosity is measured according to JIS R1652: 2003 (Brookfield single cylinder rotational viscometer).

  The pH of the inorganic fine particle slurry of the present invention is generally selected according to the type of the inorganic fine particles (A), but particularly when silica fine particles and / or alumina fine particles are used as the inorganic fine particles (A), From the viewpoint of uniformity, the pH is preferably 6 to 11, and more preferably 7 to 10. In addition, when adjusting pH according to the kind of inorganic fine particle (A), you may add a well-known pH adjuster etc. in the range which does not inhibit the performance of the inorganic fine particle slurry of this invention. In accordance with JIS K0802-1996, the pH is measured at a measurement temperature of 25 ° C. with a glass electrode type pH measurement device using a silver / silver chloride electrode {for example, Castany LAB pH meter of Horiba, Ltd.). The

  The inorganic fine particle slurry of the present invention can be coated on a substrate to be coated to form a coating film, followed by heating and drying to form a uniform coating film. As a substrate to be coated, a resin film (meaning including a sheet) {polyethylene, polypropylene, polyester, polylactic acid, polystyrene, polyacetate, polycycloolefin, polyvinyl chloride, cellulose acetate, polyethylene terephthalate, polymethyl methacrylate or Synthetic resin films made of polycarbonate, etc., and these metal vapor-deposited films, resin-coated papers coated with paper with synthetic resin films, synthetic paper made of films made opaque by filling with inorganic substances or fine foam, etc.}, glass plates, A glass tube, a metal plate, cloth, leather, etc. are mentioned. In particular, when the inorganic fine particle slurry of the present invention is used for forming a protective film of a fluorescent lamp, it is preferable to use a glass tube that conforms to the specifications of the fluorescent lamp as a substrate to be coated.

  Before the inorganic fine particle slurry of the present invention is applied to a substrate to be coated to form a coating film, the adhesion between the coating film and the substrate to be coated is improved on the surface of the substrate to be coated. For this purpose, a step of hydrophilizing the surface of the substrate to be coated may be added in advance. In particular, when a resin-coated paper, a resin film, or a synthetic paper is used as the substrate to be coated, it is preferable to perform a corona discharge treatment on its surface or provide an undercoat layer made of gelatin or the like.

  The inorganic fine particle slurry of the present invention is necessary when a coated film is formed by applying to a substrate to be coated and then dried, and further when a coating film is formed on a heat-resistant coated substrate (glass or the like). Depending on the case, the coating film can be baked and used.

  As for the film thickness (micrometer) of the coating film after drying formed on a support body, 0.1-10 are preferable, More preferably, it is 1-5. Within this range, the uniformity and appearance of the coating film are further improved.

  When the inorganic fine particle slurry of the present invention is applied to a support to form a coating film, the inorganic fine particle slurry of the present invention is applied to the dip coater method, spray coater method, flow coater method, die coater method, roll coater method, blade coater. The coating can be performed using a known coating method such as a method, a rod coater method, a bar coater method, or a spin coater method. In particular, when applying to the inner surface of a cylindrical coated substrate such as a glass tube, the dip coater method, spray coater method (method of spraying a spray nozzle inserted inside the cylindrical coated substrate, etc.), flow coater method (Method of pouring or showering inorganic fine particle slurry inside cylindrical coated substrate), method of sucking and coating inorganic fine particle slurry inside cylindrical coated substrate (suction method), etc. Is preferably used.

  The drying after the application may be performed under the condition that the water (D) contained in the slurry and the aqueous solvent contained therein are volatilized, and may be a method of spraying hot air or normal temperature. Of the drying conditions, heating at 30 to 150 ° C. is preferably performed for 0.5 to 30 minutes, and more preferably heating at 50 to 95 ° C. is performed for 4 to 10 minutes.

  When the coating film is baked and used, the baking temperature is determined by the polyvinyl alcohol (B1) and / or the polyoxyalkylene compound (B2) represented by the general formula (1) and the amino alcohol (salt). (C) should just be the temperature which thermally decomposes, and it may carry out by blowing in air | atmosphere or oxygen even in an atmospheric condition. Among the firing conditions, it is preferable to perform heating at 200 to 800 ° C. for 1 to 30 minutes while blowing air or oxygen, and more preferably by performing heating at 300 to 700 ° C. for 2 to 20 minutes while blowing air or oxygen. is there.

When the inorganic fine particle slurry of the present invention is used to form a protective film for a fluorescent lamp, after coating and drying the inorganic fine particle slurry on the inner surface of the glass tube by the above method to form a coating film, the above method is then used. A protective film can be formed by baking.
In addition, the fluorescent lamp has a phosphor layer formed by applying, drying, and firing a slurry containing a phosphor on a protective film, and / or firing the coating film with the inorganic fine particle slurry of the present invention. It may be performed before applying the phosphor layer (separately from the firing of the phosphor layer), or may be performed together with the firing of the phosphor layer after the phosphor layer is formed.

  In addition, when applying the inorganic fine particle slurry of the present invention, a predetermined amount of water (D) is added to the inorganic fine particle slurry for the purpose of obtaining a viscosity suitable for the coating method and the thickness of the coating film after drying. Application may be performed after dilution.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these Examples at all. Unless otherwise specified, parts means parts by weight,% means% by weight, PO means propylene oxide, EO means ethylene oxide, and BO means butylene oxide.

The weight average molecular weights of the amino alcohol salts produced in Production Examples 7 to 9 were measured using the following apparatuses and conditions.
(Weight average molecular weight)
Model: Waters LCM1
Detector: Waters 410 Differential refraction detector analysis software: Waters Millenium Ver. 2.18
Dissolved solution: 0.1-MPB disodium hydrogen phosphate aqueous solution: 0.1-MPB sodium dihydrogen phosphate aqueous solution = 1: 1 (molar ratio)
Eluent flow rate: 0.8ml / min
Column temperature: 40 ° C
Sample concentration: 0.4% eluent solution column: TSKgel GuardColumn SWXL + G4000SWXL + G3000SWXL + G2000SWXL manufactured by Tosoh Corporation
Standard substance: Polyethylene glycol, weight average molecular weight (Mw) 272500, 219300, 85000, 46000, 24000, 12600, 4250, 7100, 1470

  In Production Examples 6 to 9, the dry weight was measured according to JIS K0067-1992, the weight loss and residue test method of chemical products 4.1 Drying loss test, 4.1.4 (1) “First method, heating under atmospheric pressure The drying was carried out at a drying temperature of 130 ± 3 ° C. according to “Method of drying”.

  In Examples 1 to 10 and Comparative Examples 1 and 2, the viscosity of the inorganic fine particle slurry was measured by using a BM viscometer manufactured by Toki Sangyo Co., Ltd. The fine particle slurry was measured at a measurement temperature of 25 ° C. according to JIS R1652: 2003 (Brookfield type single cylinder rotational viscometer).

  In Examples 1 to 10 and Comparative Examples 1 and 2, the pH of the inorganic fine particle slurry was measured at a measurement temperature of 25 ° C. according to JIS K0802-1996 using a Castany LAB pH meter manufactured by Horiba, Ltd.

<Production of polyoxyalkylene compound (B2)>
<Production Example 1>
In a reaction vessel capable of heating, stirring, cooling, dropping, pressurizing and depressurizing, 342 parts (1 mol) of sucrose (manufactured by Taiwan Sugar Co., Ltd.) and dimethylformamide (DMF) {special reagent grade, Wako Pure Chemical Industries ( Co., Ltd., the same below} After 3000 parts are uniformly mixed, an operation (pressurized nitrogen substitution) is performed three times using nitrogen gas and pressurizing until the pressure becomes 0.4 MPa with a gauge pressure until reaching 0.02 MPa. Repeated. Thereafter, the temperature was raised to 100 ° C. while stirring, and 754 parts (13 mole parts) of PO was dropped at the same temperature over 4 hours, and then stirring was continued for 30 minutes at the same temperature to react with the remaining PO. It was. Subsequently, after heating to 130 ° C., dehydration was performed at the same temperature under a reduced pressure of 0.01 to 0.1 MPa for 1 hour, and then 2948 parts (67 mole parts) of EO was added at 100 to 120 ° C. under the reduced pressure. It was dripped in 2 hours. Next, 360 parts (5 mole parts) of BO was added dropwise at 100 to 120 ° C. over 6 hours, and the remaining alkylene oxide was reacted at the same temperature for 4 hours. Next, after adding 85 parts of ion-exchanged water at 90 ° C., an alkaline adsorbent {KYOWARD 700, manufactured by Kyowa Chemical Industry Co., Ltd., “KYOWARD” is a registered trademark of the company. } 170 parts were added and stirred at the same temperature for 1 hour. Next, at the same temperature, no. 2 filter paper {manufactured by Toyo Filter Paper Co., Ltd.} to remove the alkali adsorbent, and further dehydrated at 120 ° C. under reduced pressure of 0.01 to 0.1 MPa for 1 hour to obtain a polyoxyalkylene compound (B21 ) (Sucrose PO 13 mol / EO 67 mol / BO 5 mol adduct).

<Production Example 2>
“2948 parts (67 mole parts) EO” was changed to “1188 parts (27 mole parts) EO” and “360 parts (5 mole parts) BO” was changed to “3480 parts (60 mole parts) PO”. The polyoxyalkylene compound (B22) (sucrose / PO13 mol / EO27 mol / PO60 mol adduct) was obtained in the same manner as in Production Example 1, except that the above was changed.

<Production Example 3>
In the same reaction vessel as in Production Example 1, raffinose {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.} 504 parts (1 mole part), and N-methylpyrrolidone {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd., Hereinafter, the same} 3000 parts were uniformly mixed, and thereafter, an operation (pressurized nitrogen substitution) of using nitrogen gas to pressurize to 0.4 MPa with a gauge pressure and discharge to 0.02 MPa was repeated three times. Then, the temperature was raised to 100 ° C. with stirring, 2030 parts (35 mole parts) of PO was dropped at the same temperature over 4 hours, and stirring was continued for 30 minutes at the same temperature to react with the remaining PO. It was. Next, the mixture was heated to 120 ° C., while maintaining the same temperature, DMF was distilled off under a reduced pressure of 0.01 to 0.1 MPa, then cooled to 90 ° C., 20 parts of ion-exchanged water was added, and alkali adsorption was performed. 100 parts of the agent was added and stirred at the same temperature for 1 hour. Next, at the same temperature, no. 2 filter paper {manufactured by Toyo Filter Paper Co., Ltd.} to remove the alkali adsorbent, and further dehydrated at 120 ° C. under reduced pressure of 0.01 to 0.02 MPa for 1 hour to obtain a polyoxyalkylene compound (B23) (Raffinose / PO35 mol adduct) was obtained.

<Production Example 4>
“Raffinose 504 parts (1 mole part)” was changed to “Meretito {reagent special grade, manufactured by Tokyo Chemical Industry Co., Ltd.} 504 parts (1 mole part)”; “N-methylpyrrolidone 3000 parts” was changed to “dimethylformamide” In the same manner as in Production Example 3, except that (DMF) 2500 parts "and" 4350 parts (75 mole parts PO) "were changed to" 1160 parts (20 mole parts PO) " An alkylene compound (B24) (meletitol / PO20 mol adduct) was obtained.

<Production Example 5>
342 parts (1 mol part) of sucrose and 1000 parts of dimethylformamide (DMF) were charged into the same reaction vessel as in Production Example 1, and then pressurized nitrogen substitution was carried out in the same manner as in Production Example 3. Then, the temperature was raised to 100 ° C. while stirring, and then 220 parts (5 parts by mole) of EO was added dropwise at the same temperature over 3 hours, followed by stirring for 30 minutes at the same temperature to react with the remaining EO. It was. Next, after the temperature was raised to 110 ° C., 2610 parts (45 moles) of PO was dropped at this temperature over 5 hours, and stirring was continued for 4 hours at the same temperature to react with the remaining PO. Thereafter, the temperature was raised to 120 ° C., and while maintaining the same temperature, DMF was distilled off under a reduced pressure of 0.01 to 0.1 MPa, then cooled to 50 ° C. or lower, and then sodium hydroxide {reagent special grade, Sigma Aldrich Japan Co., Ltd.} 112 parts was added. Subsequently, the temperature was raised to 80 ° C. with stirring under reduced pressure (0.01 to 0.1 MPa), and methyl chloride {reagent special grade, manufactured by Sigma Co., Ltd.} 126.3 parts (2. 5 mol parts) was added dropwise over 4 hours. The mixture was further stirred at the same temperature for 3 hours and then cooled to 40 ° C. 500 parts of the obtained reaction mixture is taken in a separatory funnel, 500 parts of ion-exchanged water and 500 parts of n-hexane {reagent special grade, manufactured by Sigma Co., Ltd.} are added and shaken, and then left to stand. , Separated into an aqueous phase and an n-hexane phase. The n-hexane was distilled off from the obtained n-hexane phase at 100 ° C. under a reduced pressure of 0.01 to 0.1 MPa, and then treated with 50 parts of an alkali adsorbent in the same manner as in Production Example 1. A polyoxyalkylene compound (B25) (sucrose / EO 5 mol / PO 45 mol / methyl chloride 2.5 mol) was obtained.

<Production of amino alcohol salt (C2)>
<Production Example 6>
To a stirrable container, 360 parts of a 50% aqueous lactic acid solution (Musashino Chemical Co., Ltd.) was added and cooled in an ice bath. Subsequently, 149 parts of amino alcohol (C11) {triethanolamine, manufactured by Wako Pure Chemical Industries, Ltd., JIS reagent special grade, the same shall apply hereinafter) are added while maintaining the temperature at 40 ° C. or lower with stirring to carry out a neutralization reaction. An aqueous solution containing 64% by dry weight of salt (C21) (triethanolamine lactate) was obtained.

<Production Example 7>
200 parts of ion-exchanged water and 300 parts of isopropyl alcohol are put into a pressure-resistant reaction vessel equipped with a dropping line, a stirrer, and a thermometer, and 300 parts of acrylic acid and 100 parts of 40% ammonium persulfate aqueous solution are added separately under stirring. The reaction was conducted in a sealed state while dropping at a constant rate over 3 hours. The reaction temperature was maintained at 65-100 ° C. After completion of the dropping, the temperature is kept at 90 to 100 ° C. for 3 hours, and then isopropyl alcohol is removed under reduced pressure while dropping 150 parts of ion-exchanged water, followed by cooling to 30 ° C. and an aqueous solution containing 50% polyacrylic acid. Obtained. Subsequently, 145 parts of this polyacrylic acid aqueous solution was transferred to another container, and while maintaining this at 40 ° C. or lower with stirring, gradually the amino alcohol (C12) (diethanolamine, manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade, The same applies hereinafter, 105 parts, and an aqueous solution containing 71% by weight of amino alcohol salt (C22) (polyacrylic acid diethanolamine salt) was obtained. The weight average molecular weight was 20,000.

<Production Example 8>
In a reaction vessel equipped with a dropping line, a reflux tube, a stirrer and a thermometer, 200 parts of methyl ethyl ketone, styrene-maleic anhydride copolymer (styrene: maleic anhydride = 1: 1 (molar ratio), weight average molecular weight: 5000) [ Sartomer, SAM-1000] (202 parts) and methoxypoly (n = 45) ethylene glycol (manufactured by NOF Corporation, UNIOX M-2000), 594 parts, were added at 60-80 ° C. with stirring under nitrogen gas flow. Heated for 3 hours. Subsequently, the mixture was heated to 80 to 100 ° C. in a sealed state, methyl ethyl ketone was distilled off while maintaining the pressure at 80 to 100 ° C., and 200 parts of ion-exchanged water was simultaneously added from the dropping line (ion-exchanged water). Was not controlled). After the distillation of methyl ethyl ketone was stopped, the mixture was cooled to 30 ° C. The total weight of distilled methyl ethyl ketone was 200 parts. Subsequently, 151 parts of aminoalcohol (C13) (2-amino-2-methyl-1-propanol, manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade, the same applies hereinafter) was gradually added dropwise with stirring so as not to exceed 40 ° C. . Subsequently, ion-exchanged water was added to adjust the concentration so that the dry weight was 40%, and amino alcohol salt (C23) {2-amino-2-methyl-1-propanol maleate (35 mol%) An aqueous solution containing 40% of a monomethoxypoly maleate (n = 45) ethylene glycol 2-amino-2-methyl-1-propanol salt (15 mol%)-styrene (50 mol%) copolymer} was obtained. The weight average molecular weight was 6,000.

<Production Example 9>
In a pressure resistant reaction vessel similar to Production Example 7, 500 parts of ion-exchanged water, 200 parts of isopropyl alcohol, and 3 parts of 2-mercaptoethanol were charged and heated to 80 to 100 ° C. with stirring in a sealed state. Subsequently, while stirring at 80 to 100 ° C., 50 parts of acrylic acid and 1000 parts of acrylic acid methoxypolyoxyethylene (oxyethylene: 2 mol) ester [Blemmer AE-90, manufactured by NOF Corporation] The mixed monomer and 100 parts of 40% ammonium persulfate aqueous solution were added dropwise from separate drop lines at a constant rate over 2 hours. After completion of the dropwise addition, the mixture was kept at 95 to 100 ° C. for 3 hours in a sealed state. Subsequently, 150 parts of ion-exchanged water was dropped while maintaining the temperature of 95 to 100 ° C. while maintaining the temperature of 95 to 100 ° C. while gradually releasing the pressure. Subsequently, isopropyl alcohol was distilled off under reduced pressure while maintaining 95-100 ° C. The mixture was cooled to 30 ° C. after the isopropyl alcohol was not distilled off. The total weight of distilled isopropyl alcohol was 200 parts. Subsequently, 62 parts of 2-amino-2-methyl-1-propanol were gradually added dropwise with stirring so as not to reach 40 ° C. or higher. Subsequently, ion-exchanged water was added to adjust the concentration so that the dry weight was 40%, and amino alcohol salt (C24) [acrylic acid 2-amino-2-methyl-1-propanol salt (10.8 mol%) ) -Acrylic acid methoxypolyoxyethylene (oxyethylene; 2 mol) ester (89.2 mol%) copolymer] was obtained. The weight average molecular weight was 4,000.

<Manufacture of inorganic fine particle slurry>
<Examples 1-10, Comparative Examples 1-3>
Inorganic fine particles (A), polyvinyl alcohol (B1) and / or polyoxyalkylene compound (B2), amino alcohol (C1) and / or amino alcohol salt (C2), water (D), and monocarboxylic acid (S), The wetting and dispersing agent (W) was added to a triaxial planetary mixer (Asada Tekko Co., Ltd., Planetary DESPA) with the blending amount (parts) shown in Table 1, and maintained at 25 to 30 ° C. Was fixed at 80 percent and stirred for 3 hours to obtain inorganic fine particle slurries (S1 to 10) of the present invention and comparative inorganic fine particle slurries (HS1 to 3). Table 1 shows the physical property values (viscosity and pH) of the inorganic fine particle slurry (S1 to 10) and the comparative inorganic fine particle slurry (HS1 to 3) of the present invention. In addition, each component used is as follows.

<Inorganic fine particles (A)>
Inorganic fine particles (A1); vapor phase method alumina fine particles, number average primary particle size 13 nm (trade name: AeroxideAlu-C, manufactured by Nippon Aerosil Co., Ltd.)
Inorganic fine particles (A2); gas phase method silica, number average primary particle size 7 nm (trade name: Aerosil 300, Nippon Aerosil Co., Ltd.)
Inorganic fine particles (A3): gas phase method silica, number average primary particle size 30 nm (trade name: Aerosil 50, manufactured by Nippon Aerosil Co., Ltd.)
Inorganic fine particles (A4); gas phase method silica, number average primary particle size 20 nm (trade name: Aerosil 90, Nippon Aerosil Co., Ltd.)
Inorganic fine particles (A5): calcium carbonate, number average primary particle size 0.5 μm (trade name: Brilliant 15, manufactured by Shiroishi Kogyo Co., Ltd.)
Inorganic fine particles (A6): precipitated silica, number average primary particle size 2 μm (trade name: Nipsil SS20, manufactured by Tosoh Silica Co., Ltd.)
Inorganic fine particles (A7); Yttrium oxide (reagent, manufactured by Merck)
Inorganic fine particles (A8); zinc oxide (reagent, manufactured by Merck & Co., Inc.)

<Polyvinyl alcohol (B1)>
Polyvinyl alcohol (B11); partially saponified poval, saponification degree 80%, polymerization degree 500 (J-POVAL JL-05, manufactured by Nihon Vinegar Bipovar Co., Ltd.)
Polyvinyl alcohol (B12); partially saponified poval, saponification degree 96%, polymerization degree 5000 (J-POVAL JP-50, manufactured by Nihon Vinegar Bipoval Co., Ltd.)
Polyvinyl alcohol (B13): completely saponified poval, degree of saponification 99%, degree of polymerization 300 (J-POVAL JF-03, manufactured by Nihon Vinegar Bipoval Co., Ltd.)
Polyvinyl alcohol (B14); partially saponified poval, saponification degree 70%, polymerization degree 500 (J-POVAL JR-05, manufactured by Nihon Vinegar Bipovar Co., Ltd.)
Polyvinyl alcohol (B15); partially saponified poval, degree of saponification 89%, degree of polymerization 2000 (J-POVAL JP-20, manufactured by Nihon Vinegar Bipoval Co., Ltd.)

<Polyoxyalkylene compound (B2)>
Polyoxyalkylene compound (B21): Sucrose PO 13 mol / EO 67 mol / BO 5 mol adduct obtained in Production Example 1 Polyoxyalkylene compound (B22); Sucrose obtained in Production Example 2 / PO 13 mol / EO 27 mol / PO 60 mol addition Product polyoxyalkylene compound (B23); raffinose / PO35 mol adduct polyoxyalkylene compound (B24) obtained in Production Example 3; meletitol / PO20 mol adduct polyoxyalkylene compound (B25) obtained in Production Example 4; Sucrose obtained in Example 5 / EO 5 mol / PO 45 mol / methyl chloride 2.5 mol

<Amino alcohol (C1)>
Amino alcohol (C11); Triethanolamine (Wako Pure Chemical Industries, Ltd., JIS reagent special grade)
Amino alcohol (C12); Diethanolamine (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade)
Amino alcohol (C13); 2-amino-2-methyl-1-propanol (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade)

<Amino alcohol salt (C2)>
Amino alcohol salt (C21); triethanolamine lactate obtained in Production Example 6 (used in 64% aqueous solution)
Amino alcohol salt (C22); polyacrylic acid diethanolamine salt obtained in Production Example 7 (weight average molecular weight 20,000) (used in 71% aqueous solution)
Amino alcohol salt (C23); 2-amino-2-methyl-1-propanol maleate (35 mol%)-monomethoxypoly maleate (n = 45) ethylene glycol 2-amino-2 obtained in Production Example 8 -Methyl-1-propanol salt (15 mol%)-styrene (50 mol%) copolymer (weight average molecular weight 6,000) (used in 40% aqueous solution)
Amino alcohol salt (C24); 2-amino-2-methyl-1-propanol acrylate (10.8 mol%)-acrylic acid methoxypolyoxyethylene (oxyethylene; 2 mol) ester obtained in Production Example 9 ( 89.2 mol%) copolymer (weight average molecular weight 4,000) (used in 40% aqueous solution)
Amino alcohol salt (C25); ethanolamine hydrochloride (manufactured by Showa Chemical Co., Ltd.)

<Monocarboxylic acid (K)>
Acetic acid (manufactured by Wako Pure Chemical Industries, Ltd., reagent grade)

<Wet dispersant (W)>
Wetting and dispersing agent (W1); SN Dispersant 5034 (Polycarboxylic acid sodium salt 40% aqueous solution, manufactured by San Nopco)
Wetting and dispersing agent (W2); Nopcowet SN-20T (nonionic surfactant, manufactured by San Nopco)

（Ｃ１）／（Ｃ１＋Ｃ２）は、アミノアルコール（Ｃ１）及びアミノアルコール塩（Ｃ２）の両方を含む場合のアミノアルコール（Ｃ１）の含有量（％）である。

(C1) / (C1 + C2) is the content (%) of the amino alcohol (C1) when both the amino alcohol (C1) and the amino alcohol salt (C2) are included.

<Application to glass tube and production of fluorescent tube>
<Example 11>
After adding water to the inorganic fine particle slurry (S1) of Example 1 and mixing uniformly to prepare a diluted solution having a specific gravity of 1.03 by a floating method at 25 ° C., fluorescence obtained from a fluorescent lamp manufacturer The diluted inorganic fine particle slurry was applied to the inner surface of a glass tube for lamp (inner diameter: 16 mm, length: 40 cm) at about 25 ° C. using a suction coating method. Next, this coated film was dried in the air at 90 ° C. for 10 minutes while air blowing to produce a coated glass tube (G1). The film thickness of the dried coating film was 1 μm. Next, a phosphor layer was formed on this coating film and baked at 800 ° C. for 30 minutes. Thereafter, electrodes and lead wires were attached to the glass tube and sealed to produce a fluorescent lamp (L1) of the present invention. As the phosphor layer, a mixture of a red light emitting phosphor, a green light emitting phosphor and a blue light emitting phosphor was used.
In addition, the specific gravity by the buoyancy method is the density and specific gravity measuring method of JIS K0061: 2001 chemical product. Measuring method of density and specific gravity of liquid It was measured according to 7.1 Flotation method.

<Examples 12 to 20, Comparative Examples 4 to 6>
The inorganic fine particle slurry (S1) was changed to either the inorganic fine particle slurry (S2 to 10) obtained in Examples 2 to 10 or the comparative inorganic fine particle slurry (HS1 to 3) obtained in Comparative Examples 1 and 2. In the same manner as in Example 11, the coated glass tube (G2 to 10), the comparative glass tube (HG1 to 3), the fluorescent lamp (L2 to 10) and the comparative fluorescent lamp (HL1 to HL1) of the present invention. 3) was produced.

<Evaluation>
Table 2 shows the appearance of the coated glass tubes (G1-10, HG1-3) prepared in Examples and Comparative Examples and the protective action of fluorescent lamps (L1-10, HL1-3). did.

<Appearance of coating film>
As for the appearance of the coating film, 20 coated glass tubes were produced, and the appearance of these glass tubes was visually evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: All 20 glass tubes are uniform and uniform.
○: Unevenness in 1 to 9 glass tubes.
Δ: Unevenness in 10 to 15 glass tubes.
X: Unevenness in 16 to 20 glass tubes.

<Protective action of fluorescent lamp>
Protective action was made by preparing 20 fluorescent lamps each, and measuring the initial brightness immediately after lighting these fluorescent lamps (initial value) and the brightness after 2000 hours of continuous lighting (2000 hours value). Evaluation was performed by calculating a percentage of an average value of 2000 hour values with respect to an average value of. In addition, if the good protective effect can be exhibited, since the fall of the brightness by continuous lighting can be suppressed, the value of the luminous flux maintenance factor becomes a value close to 100%. The brightness of the fluorescent lamp is measured according to JIS C7617-2: 2009 “Straight fluorescent lamp-Part 2: Performance specifications” 1.5.6 Optical characteristics and 1.5.7 Luminous flux maintenance factor Measured with

As is apparent from Table 2, when the inorganic fine particle slurry of the present invention was used, the appearance of the coating film was excellent compared to the case where the comparative inorganic fine particle slurry was used (the coating film was uniform and uniform). Excellent.) Further, the fluorescent lamp using the inorganic fine particle slurry of the present invention did not have a decrease in brightness due to continuous lighting as compared with the fluorescent lamp using the comparative inorganic fine particle slurry, and exhibited a good protective action.

Claims (6)

Containing inorganic fine particles (A), polyvinyl alcohol (B1) and / or polyoxyalkylene compound (B2) represented by general formula (1), amino alcohol (salt) (C) and water (D) An inorganic fine particle slurry.

{R- (OX) _ni- } _m Q (1)

Q is a reaction residue obtained by removing a hydrogen atom from m primary hydroxyl groups of non-reducing di- or trisaccharides, OX is an oxyalkylene group having 2 to 4 carbon atoms, R is an alkyl group having 1 to 4 carbon atoms, and / Represents a hydrogen atom, m R and m (OX) _ni may be the same or different, ni is an integer of 0 to 100, m is an integer of 2 to 4, i is 1 to m Represents an integer, m ni may be the same or different, but at least one is 1 or more, and the total number of OX (Σni × m) is an integer of 20-100. The inorganic fine particle slurry according to claim 1, wherein the inorganic fine particles (A) are silica fine particles and / or alumina fine particles produced by a gas phase method. The inorganic fine particle slurry according to claim 1 or 2, wherein the number average primary particle diameter of the inorganic fine particles (A) is 7 to 30 nm. The inorganic fine particle slurry according to any one of claims 1 to 3, which is used for forming a fluorescent lamp protective film.   A fluorescent lamp obtained by applying, drying, and firing the inorganic fine particle slurry according to any one of claims 1 to 4 to an inner surface of a glass tube. The inorganic fine particle slurry described in any one of claims 1 to 4 is applied to the inner surface of the glass tube, dried, and then heated to thermally decompose the polyvinyl alcohol (B1) and / or the polyoxyalkylene compound (B2). And a method for producing a fluorescent lamp, comprising a step of forming a protective film made of inorganic fine particles (A).