JP4765300B2 - Coating composition and method for producing the same. - Google Patents

Description

  The present invention relates to an antistatic and infrared shielding coating composition using a metal oxide having conductivity and infrared shielding ability, and relates to a coating composition having excellent dispersion stability and transparency when formed into a coating film. .

  Many metal oxides have electrical and optical characteristics such as electrical conductivity, low to high and wide refractive index, and heat ray / ultraviolet ray shielding ability. In recent years, display panels, functional glass, functional films, etc. Expectations are growing as a processing material. Among them, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), etc. are heat-resistant cuts using dust-proof films that use their conductivity and the ability to absorb and reflect near-infrared heat rays. Development to glass and film is under consideration. However, when these materials are used at a high concentration in order to obtain a high function, there is a problem that transparency when formed into a coating film cannot be obtained due to a high refractive index of the materials themselves.

  The visible light scattering intensity of a fine particle depends on the refractive index of the particle and the medium, but generally the particle size is maximized in the vicinity of half of the wavelength, and when the particle size is smaller than that, the Rayleigh scattering formula As shown in FIG. 4, the scattering intensity decreases in proportion to the sixth power of the particle size. Therefore, for visible light (wavelength: 400 to 800 nm), the scattering intensity is maximum when the particle diameter is 200 to 400 nm, and the scattering intensity is reduced (transparent) as the particle intensity becomes lower. That is, it is indispensable to highly disperse particles having a small primary particle diameter in order to ensure transparency.

  However, when considering dispersion of inorganic particles such as metal oxides in a solvent or polymer, the surface tension of the inorganic particles is larger than the surface tension of the medium, so the difference in surface tension between the two is large. The interfacial energy between the particles and the medium increases and the particles aggregate. In addition, the use of inorganic particles having a small primary particle size means that the specific surface area of the particles is increased at the same time. As a result, the opportunity for contact between particles increases, the tendency to agglomerate increases, and a stable dispersion is obtained. It becomes more difficult to obtain.

Patent Document 1 exemplifies a method of dispersing tin-doped indium powder, a dispersion resin, a solvent, and the like with a media-type disperser such as a paint conditioner, but the transparency is insufficient. Patent Document 2 exemplifies a method in which tin oxide powder doped with antimony and water are dispersed in a sand mill for 16 hours. However, these methods require a long time for dispersion, and are long for a media-type disperser. When time dispersion is performed, there is a concern that contamination due to wear of the media and the vessel occurs, and that a complicated filtration step is required. Also, Patent Document 3 exemplifies dispersion by an ultrasonic disperser, but a general ultrasonic disperser has a weak dispersion force and often cannot obtain sufficient dispersion. Even when a media-type disperser is used, there is a problem that particles are easily re-aggregated if the surfactant or the dispersant is not sufficiently adsorbed to the filler.

JP-A-10-218917 JP-A-8-54502 Japanese Patent Laid-Open No. 10-8010

Conductive transparent film or infrared shielding transparent film with good dispersibility and temporal stability of paint using tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO), and excellent transparency when formed into a coating film It is to provide a dispersion for forming.

That is, the present invention includes 100 parts by weight of a metal oxide having a specific surface area of 30 to 100 m ² / g selected from tin-doped indium oxide or antimony-doped tin oxide and a dispersion resin of 5 to 50. A kneaded product obtained by kneading a mixture of parts by weight and a solvent of 0 to 50 parts by weight using a two-roll or dry pulverizer is blended in 5 to 95 parts by weight of the film-forming material. Furthermore, the present invention relates to a method for producing a coating composition having a haze value of 1% or less when a dry film having a film thickness of 2 to 5 μm is used .

  The present invention also relates to a coating composition comprising a silicon alkoxide compound or a metal alkoxide compound as the coating film-forming material.

  The present invention also relates to a coating composition comprising an active energy ray-curable resin or monomer as the coating film-forming material.

Further, the present invention provides 100 parts by weight of a metal oxide selected from tin-doped indium oxide or antimony-doped tin oxide and having a specific surface area of 30 to 100 m ² / g by nitrogen adsorption method (BET method), and 5 to 50 dispersion resins. It is related with the manufacturing method of the composition for coating which mix | blends the kneaded material obtained by knead | mixing the mixture which consists of a weight part and 0-50 weight part of solvents with the said film-forming material.

  The present invention also relates to a method for producing a coating composition, wherein the kneading treatment is carried out with a two-roll or a dry pulverizer.

Furthermore, the present invention relates to a method for producing a coating composition in which the kneaded product is dispersed in the coating film-forming material and the solvent by a media type disperser.

Due to the shearing action of the two rolls in the kneading process or the impact force of the grinding media, the aggregation of the metal oxide particles is crushed and at the same time the resin is strongly adsorbed on the surface of the particles. A good dispersion can be obtained. In addition, since the kneading process using a two-roll or dry pulverizer and the dispersion process using a wet media type disperser are used in combination, the dispersion time is significantly shortened compared to the case where a media type disperser alone is used for long time dispersion. In addition, contamination caused by wear of vessels and media can be greatly reduced.

As the metal oxide used in the present invention, tin-doped indium oxide (ITO) or antimony-doped tin oxide (ATO) is preferably used, but these may be used alone or in combination.

When considering the transparency of the coating film to visible light (wavelength: 400 to 800 nm), it is generally preferable that the dispersed particle diameter of the filler is ½ (200 to 400 nm) or less, more preferably 100 nm or less of the wavelength. That is, it is indispensable to highly disperse the filler having a small primary particle size in order to ensure transparency. Therefore, in this invention, the metal oxide powder whose specific surface area calculated | required by the nitrogen adsorption method (BET method) is 30-100 m < ² > / g is used. When the specific surface area is less than 30 m ² / g, light scattering by the metal oxide particles becomes remarkable, and it becomes difficult to obtain a transparent coating film.

  The ITO and ATO powders used in the present invention may be previously hydrophobized with a coupling agent, organosilicone, higher fatty acid, phosphate ester, higher alcohol and the like. For example, the coupling agent may be any of silane, titanate, and aluminum chelate. Specifically, methyltriethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxylane, tetraethoxysilane, tetramethoxysilane , Phenyltriethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N (2-aminoethyl) -3- Aminopropylmethyldimethoxysilane, N (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, isopropyltri Isostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate , Bis (dioctylpyrophosphate) ethylene titanate, isopropyl trioctanoyl tita Isopropyl dimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-amidoethyl aminoethyl) titanate, dicumyl phenyloxyacetate titanate, di Examples include isostearoyl ethylene titanate acetoalkoxy aluminum diisopropylate.

As a method for hydrophobizing a metal oxide in the present invention, a conventionally known method can be used. That is, a treatment agent such as a coupling agent and metal oxide particles are wet, dry, or mixed, pulverized, or heated by various mixing and dispersing machines. Specifically, in wet processing, paint conditioner (manufactured by Red Devil), ball mill, sand mill (such as “Dynomill” manufactured by Shinmaru Enterprises), attritor, pearl mill (such as “DCP mill” manufactured by Eirich), coball mill, Homomixers, homogenizers (such as “Clearmix” manufactured by M Technique), wet jet mills (such as “Genus PY” manufactured by Genus, “Nanomizer” manufactured by Nanomizer, etc.), etc. can be used. Conditioner (manufactured by Red Devil), ball mill, attritor, kneader, roller mill, millstone mill, hybridizer (Nara Machinery Co., Ltd.), Mechano Micros (Nara Machinery Co., Ltd.), Mechano Fusion System AMS ( Hosokawa Micron Corporation) But it is not intended to be limited to be come available.

The dispersion resin used in the present invention is a polymer or copolymer containing vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylate ester, acrylonitrile, styrene, vinyl butyral, vinyl acetal or the like as a structural unit. Examples thereof include polyurethane resins, polyester resins, phenol resins, epoxy resins, phenoxy resins, urea resins, melamine resins, alkyd resins, acrylic resins, formaldehyde resins, silicon resins, and fiber-based resins such as nitrified cotton. These dispersion resins have a molecular weight of 500 to 100,000, more preferably 500 to 50,000, and —COOM, —SO ₃ M, —PO (OM) ₂ (M is a hydrogen atom or an alkali metal) ), -OH, -NRn (wherein R is a hydrocarbon, n is an integer of 2 to 3), an epoxy group, a sulfobetaine group, and the like. By having these polar functional groups, the interaction between the dispersion resin and the metal oxide particles is strengthened, and the dispersibility is improved. Moreover, in order to finally obtain a transparent coating film, these dispersion resins are preferably transparent. A commercially available resin-type dispersant can also be used as the dispersing resin. Specifically, “EFKA 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766” manufactured by EFKA CHEMICALS, “EFCA Polymer 100 (modified polyacrylate), 150” (Aliphatic modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate) ”,“ Solsperse 20000 (polymer containing a basic group) ”manufactured by Avicia, 24000SC, 24000GR, 28000, 32000, 21000 (polymer copolymer having acid group), 36000, 41000 "," Ajisper PB-711 (polymer copolymer containing basic group) "manufactured by Ajinomoto Fine Techno Co., Ltd. 821 (a high molecular copolymer containing a basic group and an acidic group), 822, PA-411 ( Polymer copolymer containing acidic group), PN-411 ”,“ Floren TG-710 (urethane oligomer) ”manufactured by Kyoeisha Chemical Co., Ltd.,“ Flownon SH-290, SP-1000 ”,“ Polyflow No. 50E, No .300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874 (polymer dispersant), # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester type) manufactured by Enomoto Kasei Co., Ltd. "BY-Chemie" Anti-Terra-U (polyaminoamide phosphate) "," Anti-Terra-203 / 204 (high molecular weight polycarboxylate) "," Disperbyk-101 (polyaminoamide phosphate and acid ester) ), 107 (hydroxyl group-containing carboxylic acid ester), 110 (copolymer containing an acid group), 11, 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), 180, 185 "," 400 "," Bykumen "(high molecular weight unsaturated acid ester)," BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) "," P104S, 240S (high molecular weight unsaturated acid polycarboxylic acid and silicon-based) "," Lactimon (long chain amine and unsaturated acid polycarboxylic acid and Silicon) ”and the like, but is not limited thereto. These dispersion resins may be used alone or in combination of two or more. These dispersion resins may be used in the form of a solid, or may be used as a varnish dissolved in an appropriate solvent.

  Further, when the present invention is used as an active energy ray-curable coating material such as an ultraviolet ray or an electron beam, active energy ray curing such as acryloyl acrylate, urethane acrylate, epoxy acrylate, polyester acrylate, and polyether acrylate is used as the dispersion resin. A resin or a monomer having a viscosity of 1000 mPa · s or more may be added.

  Next, the kneading process using two rolls of metal oxide powder and dispersion resin will be described. The kneading treatment with two rolls in the present invention is to adsorb the dispersion resin on the particle surfaces while crushing the aggregates of metal oxide particles using the shearing force of the two rolls. First, 5 to 50 parts by weight (in terms of solid content), preferably 10 to 40 parts by weight of a dispersion resin are mixed with 100 parts by weight of metal oxide powder at room temperature or under heating to form a homogeneous mixture. At this time, a solvent may be added to form a wet mixture. Solvents include ketones such as methyl ethyl ketone, alcohols such as ethyl alcohol, esters such as ethyl acetate, other organic solvents such as ethers and aromatics, but are not particularly limited, and the surface is particularly hydrophobized. If a metal oxide not used is used, water may be used, but it is preferable to select a solvent in accordance with the final use. Although the addition amount of a solvent changes with powders and resin to be used, 0-50 weight part of solvent is added with respect to 100 weight part of inorganic powder. When the weight ratio of the metal oxide powder, the dispersion resin, and the solvent exceeds the above range, the workability of the next kneading process step with two rolls deteriorates. In particular, when the amount of the dispersed resin is small with respect to the metal oxide powder, the dispersion stability of the paint is lowered. The mixture thus obtained is kneaded a plurality of times with two rolls at a heating temperature of 40 to 200 ° C. and a rotation speed of 10 to 50 rpm to obtain a fragment-like or sheet-like kneaded product. The number of kneading can be arbitrarily set according to the desired degree of kneading. When the obtained kneaded material is in the form of a sheet, it is preferably used in the subsequent dissolution and dispersion steps after being pulverized into powder or fragments. A method for pulverizing the sheet-like kneaded material is not particularly limited, and an ordinary pulverizer may be used.

  Subsequently, a kneading process of the metal oxide powder and the dispersion resin by a dry pulverizer will be described. In the kneading treatment by the dry pulverizer in the present invention, 5 to 50 parts by weight (in terms of solid content) of the dispersion resin is added to 100 parts by weight of the metal oxide powder, preferably 10 to 40 parts by weight, at room temperature or under heating, It is performed using a pulverizer with a built-in pulverization medium such as beads. That is, the dispersion resin is adsorbed on the particle surface while pulverizing the aggregate of the metal oxide particles using the impact force of the pulverizing media. As the dry pulverizer, known methods such as a dry attritor, a ball mill, and a vibration mill can be used. If necessary, the inside of the dry pulverization apparatus may be subjected to a deoxidizing atmosphere by flowing nitrogen gas or the like to perform the kneading process. Moreover, when using solid dispersion resin, you may add a solvent at the time of a grinding | pulverization process. The softening of the resin by the addition of the solvent and the improvement of the wetness of the metal oxide powder to the resin are expected to have an effect of promoting pulverization. The amount of the solvent added in this case varies depending on the material used, but is 0.5 to 20% by weight based on the amount of the added resin. Examples of the solvent to be used include ketones such as methyl ethyl ketone, alcohols such as ethyl alcohol, esters such as ethyl acetate, and other organic solvents such as ethers and aromatics, but are not particularly limited. The kneading treatment time can be arbitrarily set depending on the apparatus used and the desired degree of kneading. By performing these treatments, a powdery or lump kneaded product can be obtained.

A liquid coating composition is obtained by dispersing the kneaded material obtained by the kneading treatment with the two rolls or the dry pulverizer in a solvent and a film-forming material.

  The solvent used is not particularly limited as long as it dissolves the film-forming material, and various solvents such as ketones, ethers, esters, alcohols, and aromatic organic solvents can be used.

  In addition, when the present invention is used as an active energy ray-curable coating material such as an ultraviolet ray or an electron beam, a monomer having a viscosity of 200 mPa · s or less may be used in place of the solvent.

Examples of the film-forming material include silicon alkoxide compounds and / or metal alkoxide compounds represented by the following general formulas (1) to (3).
(R _a ) _p Si (OR _b ) _4-p (1)
R _b (OSi (OR _b ) ₂ ) _q OR _b (2)
M (OR _c ) _r (3)
Where
R _a is an alkyl group having 1 to 4 carbon atoms and / or a polymerizable organic group,
R _b and R _c are alkyl groups having 1 to 4 carbon atoms,
p is an integer from 1 to 3,
q is an integer from 1 to 10,
M is a trivalent or tetravalent metal ion,
r is an integer of 3 or 4 depending on the valence of M;
When each compound contains a plurality of R _a , R _b , or R _c , they may be the same or different.

  The compound represented by the general formula (1) is an alkoxysilane compound having an alkyl group and / or a polymerizable organic group. The polymerizable organic group is an organic group having an unsaturated double bond and repeating polymerization addition, or an organic group having a ring-opening cyclic group, which has the property of being cleaved and repeating addition. Examples of such a polymerizable organic group include a vinyl group, a 2-propenyl group, an isopropenyl group, an acryloyl group, a methacryloyl group, a γ-methacryloxypropyl group, a group having a polymerizable unsaturated double bond. Cyclic cyclic groups include cyclic ether groups, especially cyclic monoether groups, lactone groups, lactam groups, acid anhydrides, isocyanate groups (and hydroxyl groups), and others. Among these, a vinyl group or a γ-methacryloxypropyl group is preferable.

  In such a compound, specifically, vinyltrimethoxysilane, vinyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane are preferable. Moreover, you may use it in combination of several of these.

  The alkoxysilane compound represented by the general formula (2) is combined with the compound of the general formula (1) and has an effect of making the matrix material affinity with the substrate surface.

  Any compound having the general formula (2) can be used as such a compound, but tetramethoxysilane or tetraethoxysilane is particularly preferable. However, from the viewpoint of safety and health, when these monomers are difficult to use, a polymerized silicate of these monomers, specifically, ethyl silicate 40 or methyl silicate 51 (both trade names: manufactured by Mitsubishi Chemical Corporation) can be used. .

  Examples of the metal alkoxide compound used in the present invention include metal alkoxide, condensation multimer of metal alkoxide, metal alkoxide modified with an organic functional group and / or organic resin, and condensation of metal alkoxide modified with an organic functional group and / or organic resin. Multimers and the like are preferably used.

  The metal ion in the general formula (3) is generally a trivalent or tetravalent one, and includes Si, Ti, Ni, Zr, Zn, Al, Fe, Co, etc. Zr or Al is preferred. These metal alkoxides can be used alone or in combination according to the purpose. Metal alkoxides can also be used as condensed multimers due to problems such as toxicity and stability.

Also, R _b or R _c are in the general formula (1) to (3), when the too large number of carbon atoms, is to deteriorated organic solvent resistance of the coating film after curing, usually in R _b is The carbon number is 2 or less, and the carbon number in R _c is 4 or less.

These compounds are mixed by an arbitrary method to form a film-forming material. Usually, if the compound is liquid, the coating-forming material is obtained by dissolving or dispersing the compound in an appropriate solvent and mixing if the compound is solid. Further, these compounds may be mixed and then dissolved or dispersed in a suitable solvent. The solvent used at this time is selected depending on the type of the compound used or the dispersion conditions, and is generally methanol, ethanol, propanol, and others. Moreover, you may use an organic acid, an inorganic acid, etc. as a catalyst.

  Further, when the present invention is a coating composition of a type that is cured with active energy rays such as ultraviolet rays and electron beams, the coating film forming material can be polymerized with an active energy ray curable resin, and further with active energy rays. Use monomers.

  Examples of the active energy ray curable resin include urethane acrylate, epoxy acrylate, polyester acrylate, and polyether acrylate.

  Moreover, as a monomer which can be polymerized by active energy rays, monofunctional monomers include butanediol monoacrylate, N, N-dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, 2- Methoxyethyl acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, acryloylmorpholine, N-vinylformamide, cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, glycidyl acrylate, isobornyl acrylate, isodecyl acrylate, phenoxy methacrylate, Stearyl acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl acrylate 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, isobutyl acrylate, t-butyl acrylate, isooctyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy Butyl acrylate, benzyl acrylate, ethoxyethoxyethyl acrylate, butoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxydipropylene glycol acrylate, methylphenoxyethyl acrylate, dipropylene glycol acrylate, ethylene glycol monovinyl ether, triethylene glycol monovinyl ether, hydroxyethyl monovinyl Ether, hydroxynonyl monovinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexanedimethanol monovinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, isopropenyl ether Examples thereof include monovinyl ether compounds such as —O-propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, octadecyl vinyl ether, monofunctional alicyclic epoxy, and monofunctional oxetane, but are not limited thereto.

  Examples of the bifunctional monomer that can be polymerized by active energy rays include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. , Ethoxylated 1,6-hexanediol diacrylate, propoxylated 1,6-hexanediol diacrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di ( (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol diacrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanedioldia Relate, tetraethylene glycol diacrylate, 2-n-butyl-2-ethyl-1,3-propanediol diacrylate, dimethylol-tricyclodecane diacrylate, hydroxypivalate neopentyl glycol diacrylate, 1,3-butylene glycol diacrylate (Meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol dicyclopentane diacrylate, ethylene glycol divinyl ether, diethylene glycol divinyl ether , Triethylene glycol divinyl ether, butanediol divinyl ether, propylene glycol divinyl ether, dipropylene Recall divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, bifunctional alicyclic epoxy, 2 but functional oxetane, and the like is not limited to these.

  Furthermore, as a trifunctional monomer that can be polymerized by active energy rays, specifically, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, Tetramethylolpropane triacrylate, tetramethylolmethane triacrylate, caprolactone-modified trimethylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, tri (2-hydroxyethyl isocyanurate) triacrylate, propoxylate glyceryl triacrylate, trimethylolpropane triacrylate Examples include vinyl ether, trifunctional alicyclic epoxy, trifunctional oxetane, etc. Not.

  In addition, specific examples of monomers having four or more functionalities that can be polymerized by active energy rays include pentaerythritol ethoxytetraacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate. It is not limited to these.

  These active energy ray-curable resins and monomers may be used alone or in combination of two or more as required.

  In the present invention, when a radical polymerization type coating composition using ultraviolet rays as active energy rays is used, a radical photopolymerization initiator is further blended. As radical photopolymerization initiators, benzophenone, 4,4-diethylaminobenzophenone, diethylthioxanthone, 2-methyl-1- (4-methylthio) phenyl-2-morpholinopropan-1-one, 4-benzoyl-4′- Methyldiphenyl sulfide, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenylketone, bis-2,6-dimethoxybenzoyl -2,4,4-trimethylpentylphosphine oxide, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2,2-dimethyl- 2-hydroxyacetophenone, 2,2- Methoxy-2-phenyl acetophenone, 2,4,6-trimethyl-benzyl - diphenyl phosphine oxide, 2-benzyl-2-dimethylamino-1- (morpholinophenyl) - butan-1-one, and the like. These radical photopolymerization initiators can be used alone or in combination. Examples of the photopolymerization accelerator used in combination with the radical photopolymerization initiator include p-dimethylaminobenzoic acid ethyl ester and benzyl 4-dimethylaminobenzoate. These radical photopolymerization accelerators can be used alone or in combination. In the case of cationic polymerization, the cationic polymerization initiator is an essential component regardless of the type of active energy ray. Specifically, as the cationic polymerization initiator, arylsulfonium salt derivatives (for example, Cyracure UVI-6990, Union Carbide, Silacure) UVI-6974, Adeka optomer SP-150, Adeka optomer SP-152, Adeka optomer SP-170, Adeka optomer SP-172 manufactured by Asahi Denka Kogyo Co., Ltd., allyl iodonium salt derivatives (for example, RP manufactured by Rhodia) -2074), allene-ion complex derivatives (for example, Irgacure 261 manufactured by Ciba Geigy), diazonium salt derivatives, triazine initiators and other acid generators such as other halides. Examples of the photopolymerization accelerator used in combination with the cationic photopolymerization initiator include anthracene and anthracene derivatives (for example, Adekaoptomer SP-100 manufactured by Asahi Denka Kogyo Co., Ltd., 9,10-dibutoxyanthracene produced by Kawasaki Kasei, 10-ethoxyanthracene, 9,10-dipropoxyanthracene). These cationic photopolymerization initiators and cationic photopolymerization accelerators can be used alone or in combination.

  In addition, as a film-forming material in the present invention, a thermosetting type or an acrylic resin, a urethane resin, a polyester resin, an epoxy resin, a butyral resin, a silicone resin, a fluorine resin, or the like that is cured by evaporation of a solvent, is generally used for coatings. It is also possible to use the resin used in the above.

  As a method of dispersing the kneaded material obtained by the kneading treatment with the two rolls or the dry pulverizer in the solvent and the film-forming material, the kneaded material is formed using a high-speed stirrer such as a dissolver. Although it disperses | distributes to material, it is preferable after that it is further disperse-processed with various dispersers to obtain a uniform and fine dispersion. Alternatively, the kneaded product obtained by the kneading treatment may be mixed with a film-forming material after being dispersed in a solvent.

  As a dispersing machine to be used, a dispersing machine usually used for pigment dispersion can be used. Although a specific example is given below, it is not limited to them. For example, paint conditioner (manufactured by Red Devil), ball mill, sand mill (such as “Dynomill” manufactured by Shinmaru Enterprises), attritor, pearl mill (such as “DCP mill” manufactured by Eirich), coball mill, homomixer, homogenizer (M -"Clairemix" manufactured by Technic Co., Ltd.), wet jet mill (such as "Genus PY" manufactured by Genus, "Nanomizer" manufactured by Nanomizer, etc.) can be used. In view of cost, processing capability, etc., it is preferable to use a media type dispersing machine. As the media, glass beads, zirconia beads, alumina beads, magnetic beads, stainless beads, etc. can be used.

Due to the strong shearing action of the two rolls in the kneading process or the strong impact force of the grinding media, the agglomerated metal oxide particles are crushed and at the same time the resin is strongly adsorbed onto the particle surfaces. A fine dispersion having good dispersion stability can be obtained. In addition, since the kneading process using a two-roll or dry pulverizer and the dispersion process using a wet media type disperser are used in combination, the dispersion time is significantly shortened compared to the case where a media type disperser alone is used for long time dispersion. At the same time, it is expected that contamination caused by vessel and media wear will be greatly reduced.

(Example)

EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is not limited to an Example. In the examples, parts represent parts by weight, and% represents% by weight. The non-volatile content of the kneaded product obtained by the two-roll treatment or the dry pulverization treatment was determined from the weight difference before and after drying when the kneaded product was dried in a hot air oven at 140 ° C. for 1 hour. Dispersion particle size was measured using a (average particle size (D ₅₀₎₎ particle size distribution analyzer of the dynamic light scattering method (the Nikkiso Co., Microtrac UPA). Moreover, about the transparency (haze) of a coating film, the coating film apply | coated to the base material (100 micrometer PET film or 1.3 mm thickness glass plate) was evaluated with the haze meter (Nippon Denshoku Co., Ltd. COH-300A). . At this time, the haze of only the film | membrane was calculated | required on the basis of the PET film or glass plate which is a base material.

<Preparation of metal alkoxide binder solution>
18.5 parts of tetraethoxysilane, 15.3 parts of ethyl silicate 40 (manufactured by Mitsubishi Chemical Corporation), 6.2 parts of vinyltrimethoxysilane, 2.9 parts of purified water, 2.5 parts of nitric acid, 4.9 parts of methanol, 44.6 parts of ethanol and 5.1 parts of isopropyl alcohol were stirred and mixed for 3 hours to obtain a binder liquid (sol-gel binder).

100 parts of ITO (tin-doped indium oxide, BET specific surface area 34 m ² / g, manufactured by Mitsubishi Materials), 20 parts of dispersion resin A (polymer copolymer having a phosphoric acid group, molecular weight 5000, acid value 100) and purified water 10 Parts were mixed at room temperature to obtain a homogeneous wet mixture. This wet mixture was repeatedly kneaded with two rolls heated to 80 ° C. to obtain a solid kneaded product A. The non-volatile content of the kneaded material A was 99.6%. Subsequently, 33.2 parts of methyl ethyl ketone, 14 parts of trimethylolpropane triacrylate, 9.4 parts of 1,6-hexanediol diacrylate, 23.4 parts of Ebecryl 600 (epoxy acrylate, manufactured by Daicel UC Corporation), and SH28PA ( Paint additive, manufactured by Toray Dow Corning Silicone Co., Ltd.) In a mixed solution of 0.1 part, 120.5 parts of kneaded product A are dispersed using a high-speed disperser and charged into a glass bottle, and paint shaker using zirconia beads as media Was further dispersed for 2 hours to obtain a coating composition A having an average particle size (D50) of 64 nm.

Next, coating composition A is applied to a 100 μm PET film, dried at 70 ° C. for 3 minutes, and then irradiated with an electron beam irradiation device (device name: Min-EB, manufactured by Toyo Ink Manufacturing Co., Ltd.) with 40 KGy electron beam. Thus, a coating film A having a thickness of 4 μm was obtained. The haze of the coating film A was 0.1.

  120.5 parts of the kneaded product A obtained in Example 1 was dispersed in 46.7 parts of methyl ethyl ketone using a high-speed disper, then charged into a glass bottle, and further dispersed for 2 hours with a paint shaker using zirconia beads as a medium. Dispersion B having a diameter (D50) of 60 nm was obtained. The dispersion B was applied to a 100 μm PET film and dried at 140 ° C. for 2 minutes. The coating film having a thickness of 2 μm had a haze of 0.

  Subsequently, in dispersion B, 14 parts of trimethylolpropane triacrylate, 9.4 parts of 1,6-hexanediol diacrylate, 23.4 parts of Ebecryl 600 (epoxy acrylate, manufactured by Daicel UCB), and SH28PA (addition of paint) A coating composition B having a uniform particle size (D50) of 68 nm was obtained by adding 0.1 part of an agent (manufactured by Toray Dow Corning Silicone) and stirring with a high-speed disper.

  Coating composition B is applied to a 100 μm PET film, dried at 70 ° C. for 3 minutes, and then irradiated with an electron beam irradiation device (device name: Min-EB, manufactured by Toyo Ink Manufacturing Co., Ltd.) to irradiate 40 KGy electron beam. A coating film B of 3 μm was obtained. The haze of the coating film B was 0.1.

  120.5 parts of the kneaded product A obtained in Example 1 was dispersed in 200 parts of a sol-gel binder using a high-speed disper, and then charged into a glass bottle, and further dispersed for 2 hours with a paint shaker using zirconia beads as a medium. A coating composition C having an average particle diameter (D50) of 71 nm was obtained.

Coating composition C was applied to a glass plate, preliminarily dried at 70 ° C. for 5 minutes, and then baked at 200 ° C. for 15 minutes. The coating film having a film thickness of 2 μm had a haze of 0.5.

100 parts of ITO (tin-doped indium oxide, BET specific surface area 34 m ² / g, manufactured by Mitsubishi Materials Corporation) and 15 parts of Solsperse 41000 (polymer copolymer having an acid value, manufactured by Avicia) were charged, and the diameter was 3/8 inch. A kneaded product D was obtained by kneading for 20 minutes with a dry attritor filled with the above suspension beads. Subsequently, 57 parts of methyl ethyl ketone, 8.4 parts of trimethylolpropane triacrylate, 5.6 parts of 1,6-hexanediol diacrylate, 14 parts of Ebecryl 600 (epoxy acrylate, manufactured by Daicel UCB), and SH28PA (addition of paint) 115 parts of the kneaded product D is dispersed in 0.1 parts of a mixture using a high-speed disper, and charged in a glass bottle with a zirconia bead as a medium for another 2 hours with a paint shaker. Dispersion was performed to obtain a coating composition D having an average particle diameter (D50) of 60 nm.

Next, the coating composition D was applied to a 100 μm PET film, dried at 70 ° C. for 3 minutes, and then irradiated with an electron beam irradiation device (device name: Min-EB, manufactured by Toyo Ink Manufacturing Co., Ltd.) with 40 KGy electron beam. Thus, a coating film D having a thickness of 3 μm was obtained. The haze of the coating film D was 0.2.

100 parts of ATO (antimony-doped tin oxide, BET specific surface area 70 m ² / g, manufactured by Ishihara Techno Co.), Disperbyk 180 (polymer having acid value and amine value, manufactured by BYK Chemie) 20 parts and ethanol 15 parts Mixing at room temperature gave a homogeneous wet mixture. This wet mixture was repeatedly kneaded with two rolls heated to 80 ° C. to obtain a solid kneaded product E. The non-volatile content of the kneaded material E was 99.8%. Subsequently, 19.6 parts of methyl ethyl ketone, 14 parts of trimethylolpropane triacrylate, 9.4 parts of 1,6-hexanediol diacrylate, 23.4 parts of Ebecryl 600 (epoxy acrylate, manufactured by Daicel UC Corporation), and SH28PA ( Paint additive, manufactured by Toray Dow Corning Silicone Co., Ltd.) In a mixed solution of 0.1 part, 120.2 parts of kneaded product E is dispersed using a high-speed disperser and charged into a glass bottle, and paint shaker using zirconia beads as a medium And further dispersed for 2 hours. Thereafter, 6 parts of Irgacure 907 (polymerization initiator, manufactured by Ciba Specialty Chemicals) and 3 parts of isopropylthioxanthone were added and stirred with a high speed disper to obtain a coating composition E having an average particle size (D50) of 57 nm.

Next, the coating composition E was applied to a 100 μm PET film, dried at 70 ° C. for 3 minutes, and then under a nitrogen atmosphere, using an ultraviolet irradiation device (Fusion UV system Japan, electrodeless type), 200 W, 1 m / A coating film E having a film thickness of 5 μm was obtained by irradiating ultraviolet rays under the condition of min. The haze of the coating film E was 0.2.

ATO (antimony-doped tin oxide, BET specific surface area 70 m ² / g, manufactured by Ishihara Techno Co., Ltd.) 100 parts and BYK180 (polymer having acid value and amine value, manufactured by BYK Chemie) 15 parts, diameter 3 A kneaded product F was obtained by kneading with a dry attritor filled with / 8 inch suspension beads for 20 minutes. 115 parts of the kneaded product F was dispersed in 212 parts of a sol-gel binder using a high-speed disper, and then charged into a glass bottle, and dispersed with a paint shaker for 2 hours using zirconia beads as a medium. The average particle diameter (D50) was 70 nm Coating composition F was obtained.

Coating composition F was applied to a glass plate, pre-dried at 70 ° C. for 5 minutes, and then fired at 200 ° C. for 15 minutes. The coating film having a thickness of 2 μm obtained had a haze of 0.6.
(Comparative Example 1)

100 parts of ITO (tin-doped indium oxide, BET specific surface area 34 m ² / g, manufactured by Mitsubishi Materials Corporation), 20 parts of dispersion resin A (polymer copolymer having phosphoric acid group, molecular weight 5000, acid value 100), methyl ethyl ketone 33. 2 parts, 14 parts of trimethylolpropane triacrylate, 9.4 parts of 1,6-hexanediol diacrylate, 23.4 parts of Ebecryl 600 (epoxy acrylate, manufactured by Daicel UC), and SH28PA (paint additive, Toray Industries, Inc.) 0.1 part of Dow Corning Silicone Co., Ltd.) was charged into a glass bottle and dispersed with a paint shaker for 2 hours using zirconia beads as a medium to obtain a coating composition G having an average particle size (D50) of 173 nm.

Next, the coating composition G was applied to a 100 μm PET film, dried at 70 ° C. for 3 minutes, and then irradiated with an electron beam irradiation device (device name: Min-EB, manufactured by Toyo Ink Manufacturing Co., Ltd.) with 40 KGy electron beam. Thus, a coating film G having a film thickness of 4 μm was obtained. The haze of the coating film G was 18.
(Comparative Example 2)

  A coating composition H having an average particle size (D50) of 113 nm was obtained in the same manner as in Comparative Example 1 except that the dispersion time on the paint shaker was 10 hours.

Next, the coating composition H was applied to a 100 μm PET film, dried at 70 ° C. for 3 minutes, and then irradiated with an electron beam irradiation device (device name: Min-EB, manufactured by Toyo Ink Manufacturing Co., Ltd.) with 40 KGy electron beam. Thus, a coating film H having a film thickness of 4 μm was obtained. The haze of the coating film H was 6.
(Comparative Example 3)

ATO (antimony-doped tin oxide, BET specific surface area 70 m ² / g, manufactured by Ishihara Techno Co.) 100 parts, BYK180 (polymer having acid value and amine value, manufactured by BYK Chemie) 15 parts, sol-gel binder 212 parts were charged into a glass bottle and dispersed with a paint shaker for 10 hours using zirconia beads as a medium to obtain a coating composition I having an average particle size (D50) of 122 nm.

Coating composition I was applied to a glass plate, preliminarily dried at 70 ° C. for 5 minutes, and then fired at 200 ° C. for 15 minutes. The coating film having a film thickness of 2 μm had a haze of 8.

  The average particle size (D50) of the coating compositions obtained in Examples 1 to 6 and Comparative Examples 1 to 3, the haze of the coating film, and the average particle size when the composition was aged at 40 ° C. for 10 days Is shown in Table 1.

Claims (4)

100 parts by weight of a metal oxide having a specific surface area of 30 to 100 m ² / g selected from tin-doped indium oxide or antimony-doped tin oxide by a nitrogen adsorption method (BET method), 5 to 50 parts by weight of a dispersion resin, and a solvent A kneaded product obtained by kneading a mixture of 0 to 50 parts by weight using a two-roll or dry pulverizer is blended with 5 to 95 parts by weight of a film-forming material, and a film A method for producing a coating composition having a haze value of 1% or less when a dry film having a thickness of 2 to 5 μm is formed. The method for producing a coating composition according to claim 1, wherein the film-forming material contains a silicon alkoxide compound or a metal alkoxide compound. The method for producing a coating composition according to claim 1, wherein the film forming material comprises an active energy ray curable resin or a monomer. The manufacturing method of the coating composition in any one of Claims 1-3 which disperse | distribute a kneaded material to a film-forming material and a solvent with a media type disperser.