JP2005126513A - Solid silicate composition, method for producing the same and powder coating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid silicate composition which is effective by only a small amount of an organic silicate compound to be added to a powder coating. <P>SOLUTION: The solid silicate composition comprises a solid material having a melting or softening point of 60-200°C and 5-25 mass% of an organic silicate compound. The solid silicate composition is obtained by adding 5-25 mass% of the organic silicate compound to the solid material and melt-kneading the mixture batch-wise. A coating film obtained by applying the powder coating containing the solid silicate composition has stain resistance. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a solid silicate composition, a method for producing the same, and a powder coating material containing the solid silicate composition.

  It is known that stain resistance can be imparted to the resulting coating film by adding an organic silicate compound to the paint. Many of the paints to be added have been mainly solvent type so far, but recently they have been applied to powder paints.

For the production of powder paint, a continuous kneader such as a kneader or an extruder is generally used. In order to produce a powder coating having a stain resistance function using these continuous kneaders, it is necessary to use a large amount of an organic silicate compound. This is because in melt kneading at the time of powder coating production, there are many components that cannot exhibit their functions due to adsorption of the organic silicate compound to the pigment contained in the coating or reaction with the functional group of the resin. is there.
In order to solve the former problem, production of a powder coating composition in which a component in which a silicate compound such as a pigment is deactivated is added to a component obtained by melt-kneading a binder resin and a silicate compound, and melt-kneading is performed. A method is disclosed (for example, see Patent Document 1). However, this method is not efficient because the silicate compound is sufficiently dispersed in the binder, and it is necessary to perform melt-kneading twice or more. Furthermore, since the time for heating the binder resin and the curing agent becomes longer, the performance of the powder coating material may be adversely affected.
JP 2002-294171 A (Claim 3)

  An object of the present invention is to provide a solid silicate composition that requires a small amount of an organic silicate compound to be added to a powder coating.

  The solid silicate composition of the present invention comprises a solid material having a melting point or softening point of 60 to 200 ° C. and an organic silicate compound of 5 to 25% by mass of the solid material. Here, the organic silicate compound may contain a resin portion. The raw material solid material may be a binder resin or a curing agent.

  The method for producing a solid silicate composition of the present invention is to add 5 to 25% by mass of an organic silicate compound of the above solid substance to a solid substance having a melting point or softening point of 60 to 200 ° C., and melt-knead in a batch system. It is a feature. Here, after the melt kneading, particles having an average primary particle diameter of 1 nm to 5 μm can be added and further melt kneaded. The solid silicate composition of the present invention is obtained by this production method.

The powder coating material of the present invention contains the solid silicate composition described above. Here, the powder coating material may contain the solid substance as a constituent component other than the solid silicate composition.
The coating film having stain resistance of the present invention is obtained from the above powder coating material.

  By using the solid silicate composition of the present invention, the amount of the organic silicate compound added to the powder coating can be reduced as compared with the direct addition. This is because the organic silicate compound is sufficiently kneaded into the solid substance by sufficiently performing melt-kneading in a batch system, and this kneaded organic silicate is in contact with the components constituting other powder coatings It is thought that it is because it does not.

  Moreover, since the solid silicate composition of the present invention can be melt kneaded at a time when added to the powder coating material, adverse effects on the performance of the powder coating material due to long-term heat history can be prevented.

  Furthermore, when the solid silicate composition of the present invention is produced, a product obtained by further adding particles having an average primary particle diameter of 1 nm to 5 μm as an antiblocking agent is excellent in stability and operability.

  The solid silicate composition of the present invention comprises a solid substance and an organic silicate compound. This solid material has a melting point or softening point of 60-200 ° C. In consideration of the fact that the solid silicate composition is usually added to a powder coating, the solid substance is preferably a component contained in the powder coating, in other words, a powder coating material. . Specific examples include binder resins having the melting point or softening point, curing agents, and various additives. In addition, if the material other than the powder coating material does not have an adverse effect when added to the powder coating, such as separation in the coating film or lowering of physical properties of the coating film, the solid It can be used as a substance. Examples thereof include petroleum resins and fatty acid esters of polyhydric alcohols. In addition, the said solid substance may mix 2 or more types, if reaction does not advance by heating etc. mutually.

  The organic silicate compound, which is another component of the solid silicate composition of the present invention, is a tetraalkoxysilane having an alkoxy group having 1 to 8 carbon atoms, a condensate thereof, and a modification of this condensate.

  Specific examples of the tetraalkoxysilane having an alkoxy group having 1 to 8 carbon atoms include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrahexyloxysilane, and tetraoctyloxysilane. Among these condensates, a tetramethoxysilane condensate and a tetraethoxysilane condensate are commercially available from Mitsubishi Chemical as the MKC silicate MS series and from Colcoat as the ethyl silicate series, respectively. As a kind of alkoxy group which the said tetraalkoxysilane and its condensate have, a C1-C4 thing is preferable from a reactive viewpoint, and a C1-C2 thing is especially preferable.

  On the other hand, examples of the modified condensate include those obtained by substituting the alkoxy group of the condensate with an alcohol and those modified with a polymer. Substitution of the alkoxy group of the condensate with an alcohol varies depending on whether the alcohol used is a monoalcohol or a diol. That is, in the case of a monoalcohol, by substituting the alkoxy group of the condensate with the alkoxy group of the monoalcohol, the hydrolyzability of the organic silicate compound and the compatibility in the paint and / or coating film The purpose of denaturation is to control each of these.

  On the other hand, when the alcohol used is a diol, a reaction between an alkoxy group of the condensate and an alkoxy group of the diol between one molecule of the diol and two molecules of the condensate results in two molecules of the condensate. A modified product in which is linked by a diol is obtained. Thus, by further repeating this reaction, the molecular weight of the organic silicate compound can be reduced without performing condensation, which is difficult to adjust, and without using a low-reactivity and bulky alkoxy group. Can be increased.

When the alkoxy group of the condensate is substituted with a monoalcohol, it can be obtained by performing an exchange reaction using 1 mol or more of monoalcohol with respect to 1 mol of the condensate. In terms of reactivity, the condensate is preferably a condensate of tetramethoxysilane and / or tetraethoxysilane. The amount of the monoalcohol can be appropriately increased in accordance with the number of target substituents. The above reaction is preferably performed by heating to about 150 ° C., for example. Moreover, in order to advance reaction, it is preferable to make the system pressure reduction and to distill off produced | generated methanol or ethanol out of the system. The reaction is terminated when a predetermined amount of substitution with alcohol is performed. After completion of the reaction, the target silicate compound can be obtained by performing separation and purification as necessary. The silicate compound thus obtained is generally a colorless to light yellow oily substance. In addition, the determination of the substitution amount with the alcohol is performed by checking the amount of methanol or ethanol produced or using an analytical instrument.
Examples of the monoalcohol include ethanol, propanol, butanol, benzyl alcohol, 2-butoxyethanol, 3-methoxy-1-propanol, 2-ethylhexanol, and octanol.

  On the other hand, when the alkoxy group of the condensate is substituted with a diol, it can be obtained by performing an exchange reaction using 1 mol of the condensate in an amount of 0.6 mol times or less. If the amount exceeds 0.6 mole times, gelation may occur. The reaction can be carried out in the same manner as for the monoalcohol, but the resulting product can be further reacted by adding a diol of 0.5 mol times or less. The modified product thus obtained is a silicate obtained by removing one alkoxy group from the condensate of tetraalkoxysilane to the oxygen atoms at both ends of the diol unit obtained by removing hydrogen atoms from the two hydroxyl groups of the diol. Although each unit has a structure bonded to each other, at least one of the silicate units may be bonded to another silicate unit via another diol unit.

  In addition, in the substitution of the alkoxy group of the condensate with an alcohol, a solvent is not particularly required. However, when used, the solvent may be 10 times or less with respect to the total mass of the condensate and the monoalcohol. preferable. Specific examples of the solvent include, for example, aromatic hydrocarbons such as toluene, benzene and xylene, halogenated hydrocarbons such as dichloroethane, ethers such as THF and dioxane, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate and Examples include esters such as butyl acetate, dimethyl carbonate, and acetonitrile.

  In the exchange reaction, an acid or a base can be used as a catalyst as necessary. Examples of the acid include Bronsted acids such as hydrochloric acid, sulfuric acid, phosphoric acid and sulfonic acid, and Lewis acids such as organotin compounds. Examples of the base include triethylamine, dimethylbenzylamine, diazabicyclo [2.2.2. A tertiary amine such as octane or 1,8-diazabicyclo [5.4.0] undecene-7 can be used.

  Another polymer modification of the condensate is to introduce a resin portion into the organic silicate compound by reacting the alkoxy group of the condensate with the hydroxyl group of the polyol. This modification is usually performed to adjust the compatibility with the paint or coating film components. The condensate modified here includes not only the above condensate but also one obtained by replacing this with an alcohol.

  Examples of the polyol include acrylic resins, polyester resins, polyether resins, polyurethane resins, and fluorine resins having a hydroxyl value of 5 to 300 and a number average molecular weight of 500 to 20000. The solid content mass ratio of the condensate (including alcohol substitution product) / polyol in the polymer modification can be 0.1 / 1 to 10/1. The reaction itself can be carried out based on the above monoalcohol substitution method.

  In the solid silicate composition of the present invention, the amount of the organic silicate compound relative to the solid substance is 5 to 25% by mass. A preferable lower limit is 10% by mass, and a preferable upper limit is 20% by mass. The solid silicate composition of the present invention preferably has a melting point or softening point of 60 to 200 ° C., but the melting point or softening point may have a width of about 5 to 10 ° C.

  The method for producing a solid silicate composition of the present invention is to add 5 to 25% by mass of an organic silicate compound of the above solid substance to a solid substance having a melting point or softening point of 60 to 200 ° C., and melt-knead in a batch system. It is a feature. When the melting point or softening point of the solid substance is outside the above range, it becomes difficult to melt and knead.

  Here, the batch type means a non-continuous type. In other words, it is a system in which kneading can be performed while simply heating and the kneading time can be arbitrarily set. Currently, in continuous extruders such as kneaders and extruders used in the production of general powder coatings, the kneaded material is extruded after a certain period of time, so the kneading time is limited, It is not suitable for the method for producing the solid silicate composition of the present invention. Of course, even in a continuous extruder, it is possible to obtain the target product by repeating the obtained kneaded product over and over, but this is not efficient. The batch type kneader is well known to those skilled in the art. For example, as a kneading method using a biaxial planetary system, T.K. K. Hibismix (registered trademark) series and the like.

  As the solid substance used in the method for producing a solid silicate composition of the present invention, a component contained in the powder coating to which the obtained solid silicate composition is to be added, for example, a binder resin or a curing agent is selected. You can also. About the other said solid substance and organic silicate compound, the description about the above-mentioned solid silicate composition is applied as it is.

  The melt-kneading in the method for producing a solid silicate composition of the present invention is carried out for an appropriate time at a temperature equal to or higher than the melting point or softening point of the solid substance, preferably about 20 to 100 ° C. higher than the melting point or softening point. If the temperature is too high, the solid substance and the organic silicate compound may be denatured. If the temperature is lower than the melting point or the softening point, mixing may not be performed sufficiently. The melt kneading time can be, for example, 10 minutes to 2 hours. After completion of this melt-kneading, the mixture is cooled to obtain a solid silicate composition. You may grind | pulverize to the target magnitude | size as needed. The solid silicate composition thus obtained preferably has a melting point or softening point of 60 to 200 ° C. Here, the melting point or softening point may have a width of about 5 to 10 ° C.

  In addition, in order to improve the stability and operability of the obtained solid silicate composition itself, after completion of the melt kneading, particles having an average primary particle diameter of 1 nm to 5 μm can be added and further melt kneaded. Here, the particles need to have a function capable of supporting an organic silicate compound. Those having an average primary particle diameter in the range of 1 nm to 5 μm are known to function as an anti-blocking agent for powder coatings. For these reasons, it is preferable to use an anti-blocking agent already prepared for powder coatings as the particles.

  As the antiblocking agent, organic or inorganic fine particles are well known. Examples of inorganic fine particles include barium sulfate, calcium carbonate, aluminum oxide, calcium silicate, magnesium silicate, antimony oxide, titanium dioxide, iron oxide, fine powder silica, and examples of organic fine particles include polyolefins and acrylic polymers. Can be mentioned. The acrylic polymer may or may not be crosslinked.

  The average particle diameter, which is well known as a characteristic value indicating the characteristics of the particles, can vary depending on the state of the particles and the measurement conditions at that time, but the average primary particle diameter is not affected by the measurement environment or the like. Therefore, the average primary particle diameter is used here as a special value representing the particles. The average primary particle diameter can be determined by a well-known measurement method such as electron microscope observation, depending on the material and type, and is described in the catalog if it is commercially available. It is also possible to adopt the determined values. In addition, the average particle diameter of the particles may be in a range that does not cause problems when added to the paint, that is, the film thickness of the coating film obtained from the paint, and a specific value is, for example, 40 μm or less. It is preferable.

  The amount of particles having an average primary particle size of 1 nm to 5 μm added after completion of the melt kneading is preferably 1 to 15% by mass of the raw material solid material. If it is less than 1% by mass, the purpose of addition is not achieved, and if it exceeds 15% by mass, an effect commensurate with it cannot be obtained.

  The powder coating material of the present invention contains the above-described solid silicate composition. The content of the organic silicate compound considered to be possessed by the solid silicate composition is 0. 0% relative to the total resin solid content of the binder resin and the curing agent contained in the powder coating material. It is preferable that it is 2-10 mass%. When the content is less than 0.2% by mass, the content of the organic silicate compound in the obtained powder coating composition becomes low, and there is a possibility that a coating film excellent in stain resistance cannot be obtained. Moreover, when it exceeds 10 mass%, there exists a possibility that a problem may arise in stability of a powder coating composition. A more preferable range is 1 to 5% by mass. The amount of the organic silicate compound considered to be possessed by the solid silicate composition is calculated on the assumption that all of the organic silicate compound used to produce the solid silicate composition is contained in the solid silicate composition. Shall be.

  The powder coating material of the present invention may contain the solid substance as a constituent component other than the solid silicate composition. In this case, the solid substance is one of raw material components constituting the powder coating material. Therefore, in consideration of the amount contained in the solid silicate composition, the formulation of the powder coating material can be adjusted. In addition, when the amount of the organic silicate compound contained in the solid silicate composition is large, the amount of the solid silicate composition added to the powder coating is small, and as a result, the amount of the solid substance to be added is Accordingly, the above blending may not be adjusted.

  The main components of the powder coating material of the present invention are a binder resin and a curing agent. Examples of the binder resin and the curing agent include those usually used for powder coatings. As the binder resin, a polyester resin, an epoxy resin, or an acrylic resin having a functional group capable of reacting with a curing agent is usually used. Further, these can be appropriately blended to be used as a polyester / epoxy resin, an acrylic / epoxy resin, or an acrylic / polyester resin.

  The polyester resin can be obtained by polycondensation using an ordinary method using an acid component mainly composed of a polyvalent carboxylic acid and an alcohol component mainly composed of a polyhydric alcohol as raw materials. The acid component is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid and anhydrides thereof, aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and the like. Anhydrides, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, saturated aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and their anhydrides, lactones such as γ-butyrolactone, ε-caprolactone, etc. And aromatic oxymonocarboxylic acids such as p-oxyethoxybenzoic acid, hydroxycarboxylic acids corresponding to these, and the like.

  The alcohol component is not particularly limited, and examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,5-hexanediol, diethylene glycol, and triethylene. Glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A alkylene oxide adduct, bisphenol S alkylene oxide adduct, 1,2-propanediol, neopentyl glycol, 1,2-butanediol, , 3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,4-hexanediol, 2,5-hexanediol, 3-methyl-1,5-pentane Diol, 1,2-dodecandioe It can be exemplified aliphatic glycols having a side chain such as 1,2-octadecanediol, trimethylolpropane, glycerin, a trivalent or higher polyhydric alcohols such as pentaerythritol or the like.

  By controlling the kind and amount of the compound contained in each of the acid component and the alcohol component, a polyester resin having a predetermined amount of functional groups capable of reacting with the curing agent can be obtained. In addition, a polyester resin with high weather resistance can be obtained by containing 50 mass% or more, preferably 80 mass% or more of isophthalic acid in the acid component.

  Moreover, the said acrylic resin can be obtained by mix | blending an ethylenically unsaturated group containing monomer, and copolymerizing this using a normal method. Examples of the ethylenically unsaturated group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, Plaxel FM and FA series (trade name, 2-hydroxyethyl (Meth) acrylate and polycaprolactone adduct, manufactured by Daicel Chemical Industries, Ltd.), hydroxyl group-containing monomers such as polyalkylene glycol mono (meth) acrylates, epoxy groups such as glycidyl acrylate, glycidyl methacrylate, and 2-methylglycidyl methacrylate Monomers, amino group-containing monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide Curing functional group-containing monomers such as acrylamide monomers such as N-butoxymethyl (meth) acrylamide and N-methylacrylamide, carboxylic acid group-containing monomers such as (meth) acrylic acid, acrylonitrile, vinyl acetate, (meth) acrylic Others such as methyl acid, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, styrene, vinyltoluene, p-chlorostyrene Neutral monomers can be exemplified. By appropriately blending these ethylenically unsaturated group-containing monomers, an acrylic resin having a predetermined amount of functional groups capable of reacting with the curing agent is obtained.

  Furthermore, the epoxy resin is a compound having an epoxy group as a functional group capable of reacting with two or more curing agents in one molecule, for example, glycidyl ester resin, bisphenol A and epichlorohydrin. Glycidyl ether type resins such as condensation reaction products and condensation reaction products of bisphenol F and epichlorohydrin, alicyclic epoxy resins, aliphatic epoxy resins, bromine-containing epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy Resin etc. can be illustrated.

On the other hand, when the functional group of the binder resin is a hydroxyl group, an aliphatic polyvalent carboxylic acid, an aliphatic acid anhydride, an amino resin, a polyepoxy compound, a blocked isocyanate compound, a glycoluril curing agent, or the like is used as the curing agent. It is done. When the functional group of the binder resin is a carboxyl group, examples of the curing agent include polyepoxy compounds, polyhydroxy compounds, and β-hydroxyalkylamide compounds. Furthermore, when the functional group of the binder resin is an epoxy group, the curing agent includes aliphatic polycarboxylic acids such as decanedicarboxylic acid and sebacic acid, polyvalent carboxylic acid anhydrides, dicyandiamide, blocked isocyanate compounds, and amine-based compounds. Examples thereof include a curing agent, a polyamide-based curing agent, a phenol resin, imidazoles, and imidazolines.
The ratio between the binder resin and the curing agent is preferably such that the functional groups involved in the curing do not deviate significantly from the stoichiometrically equivalent amount ratio.

  The powder coating material of the present invention may contain a pigment in addition to the main component. As the pigment, those commonly used can be used. Specifically, titanium dioxide, bengara, yellow iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, quinacridone pigments, azo pigments and other colored pigments, metallic pigments, pearl pigments, metal powders and surface treatments. And extender pigments such as talc, silica, calcium carbonate and precipitated barium sulfate. Although content in the powder coating material of the said pigment is not specifically limited, Generally it is preferable that it is the quantity of 30-100 mass% with respect to the total amount of the said binder resin and a hardening | curing agent.

  The powder coating of the present invention may further contain other components such as a curing catalyst such as a tin compound and additives. Examples of the additive include a surface conditioner, a plasticizer, an ultraviolet absorber, an antioxidant, a wax inhibitor, a charge control agent, and a fluidity imparting agent. These are preferably contained in such an amount that they can express the functions of each of them and do not cause any problems when added.

  There are two ways to obtain the powder coating of the present invention. One is to mix the raw material component of the powder coating material and the solid silicate composition, melt and knead, and then pulverize to a desired particle size through coarse pulverization and fine pulverization steps. How to add. The other is a so-called dry blending method in which the above-described solid silicate composition is added to an existing powder coating material. The latter dry blending method is preferable because the characteristics of the solid silicate composition of the present invention can be utilized.

  In addition, it is preferable that the powder coating finally obtained sets a volume average particle diameter to 5-50 micrometers. When using for thin film coating, it is more preferable to set to 5 to 30 μm, particularly when trying to obtain a smooth coating film with a thin film. These are performed by classification for removing large particles and fine particles and adjusting the particle size distribution.

  The coating film having stain resistance of the present invention is obtained from the above powder coating material. Specifically, a coating film having excellent stain resistance can be obtained by applying the previously obtained powder coating material to a substrate and baking it. The base material is not particularly limited as long as it does not cause defects such as deformation due to baking after coating, and specifically, iron plates, steel plates, aluminum plates, and the like, and surface treatments thereof may be mentioned. Can do. Since the coating film of the present invention has stain resistance, the substrate is preferably applied to vending machines, switchboards, building exterior materials, steel structures and the like installed outdoors. Note that an undercoat coating film obtained from an undercoat paint such as a primer may be formed on the substrate.

  The application is not particularly limited, and methods well known by those skilled in the art, such as an electrostatic coating method and a fluid dipping method, can be used. From the viewpoint of coating efficiency, the electrostatic coating method is preferable. Examples of the charging method in the electrostatic coating method include a corona charging method and a friction charging method. These methods can also be used in combination. Although a coating film thickness is not specifically limited, For example, it can be set as 20-200 micrometers. The baking after application can be performed at 140 to 220 ° C. for 5 to 40 minutes based on the type of binder resin and curing agent used. In this way, a coating film having stain resistance can be obtained.

  The following is an example of the production of materials for use in the examples of the present invention. Here, “part” and “%” in the production examples and the following examples are both based on mass.

Production Example 1 Production of Ethyl-Substituted Methyl Silicate 161 g of ethanol and 5 g of triethylamine were added to 735 g of MKC silicate 56 (manufactured by Mitsubishi Chemical Corporation), which is a condensate of tetramethoxysilane, and heated for 5 hours while refluxing. Thereafter, the alcohol was distilled off from the reaction solution, followed by concentration under reduced pressure to obtain 703 g of ethyl-substituted methyl silicate.

Example 1 Production of Solid Silicate Composition Using Blocked Isocyanate Compound 1
T.K. K. 100 g of B1530 (melting point 95 ° C.), which is an ε-caprolactam block isocyanate manufactured by Huls, was added to Hibismix f model 03, and then heated to 100 ° C. to be melted. To this, 10 g of the ethyl-substituted methyl silicate obtained in Production Example 1 was added, and kneading was performed at a temperature of 100 ° C. for about 20 minutes. The white solid obtained by cooling to room temperature was pulverized to obtain a solid silicate composition. The melting point of this product was 106-109 ° C.

Example 2 Production of Solid Silicate Composition Using Blocked Isocyanate Compound 2
A solid silicate composition was obtained in the same manner as in Example 1, except that the amount of ethyl-substituted methyl silicate was increased from 10 g to 20 g.

Example 3 Production of Solid Silicate Composition Containing Fine Particle Silica Using Blocked Isocyanate Compound In Example 2, Carplex FPS-1 (fine particle silica having an average particle size of 1.5 to 3.0 μm after completion of kneading) A solid silicate composition containing fine-particle silica was obtained in the same manner except that 5 g (manufactured by Shionogi & Co., Ltd.) was added and kneading was further performed at 100 ° C. for 1 hour.

Examples 4-8
Based on the formulation in Table 1 below, various solid silicate compositions were obtained in the same manner as in the previous examples. The melting point or softening point of the obtained solid silicate composition is also shown in Table 1.

実施例９ 固形シリケート組成物を含有した粉体塗料の調製
クリルコート６９０（ダイセルＵＣＢ社製ポリエステルポリオール）６００ｇ、Ｂ−１５３０（ヒュルスジャパン社製ブロックイソシアネート硬化剤）８０ｇ、ＴＥＰＩＣ−Ｇ（日産化学社製トリスグリシダルイソシアヌレート）５ｇ、ベンゾイン１０ｇ、Ａ−２４１（大日本インキ化学工業社製アクリル樹脂）２５ｇ、ＣＲ−９５（石原産業社製二酸化チタン）３００ｇをヘンシェルミキサーで混合したのち、ニーダーで混練、粉砕、分級して白色粉体塗料を得た。

Example 9 Preparation of powder coating material containing solid silicate composition Kurilcoat 690 (polyester polyol manufactured by Daicel UCB) 600 g, B-1530 (block isocyanate curing agent manufactured by Huls Japan) 80 g, TEPIC-G (Nissan Chemical) After mixing 5 g of Tris glycidal isocyanurate), 10 g of benzoin, 25 g of A-241 (acrylic resin manufactured by Dainippon Ink & Chemicals) and 300 g of CR-95 (titanium dioxide manufactured by Ishihara Sangyo Co., Ltd.) with a Henschel mixer, kneader The mixture was kneaded, pulverized, and classified to obtain a white powder paint.

  20 g of the solid silicate composition of Example 1 was added to 200 g of this paint, and the mixture was thoroughly shaken to obtain a solid silicate composition-containing powder paint. The obtained paint was applied to a test panel and baked at 180 ° C. for 20 minutes to obtain a coating film. When this coating film was exposed outdoors for 6 months, the stain resistance was good. Moreover, when the obtained coating material was stored at 35 ° C. for 4 weeks and its fluidity was evaluated, the fluidity was the same as that of the coating immediately after preparation.

Comparative Example 1 Powder coating example containing an organic silicate compound In Example 9, the amount of B-1530 was increased to 100 g, and the solid silicate composition was not used. Instead, it was contained in this solid silicate composition. A powder coating material was prepared in the same manner except that the same amount of MKC silicate 56 was added to the Henschel mixer together with other raw materials. The coating obtained in the same manner as in Example 9 from this powder paint had better stain resistance in outdoor exposure for 6 months than that containing no organic silicate component, but at a satisfactory level. It was not a thing. The fluidity of this paint after storage at 35 ° C. for 4 weeks was equivalent to that of the paint immediately after preparation.

Comparative Example 2 Powder coating material containing a large amount of an organic silicate compound In Example 9, a solid silicate composition was not used, and instead, the same amount of MKC silicate 56 as the solid silicate composition was added to the Henschel mixer together with other raw materials. A powder coating was prepared in the same manner except that it was added. The coating obtained from this powder coating in the same manner as in Example 9 had good stain resistance after 6 months of outdoor exposure, but the coating after storing at 35 ° C. for 4 weeks was moist and wet. As a result, it was confirmed that the fluidity was lower than that immediately after production.

  In Example 9, a powder coating excellent in stain resistance was obtained, whereas in Comparative Example 1 in which the same amount of the organic silicate compound as that contained in Example 9 was directly added, sufficient Contamination resistance was not expressed. On the other hand, in Comparative Example 2 in which the organic silicate compound to be added directly was greatly increased, it was found that the same stain resistance as in Example 9 was obtained, but there was a problem in the blocking property, and the powder paint Could not be used as. Thus, it has been confirmed that the amount of the organic silicate compound added to the powder coating can be reduced by using the solid silicate composition of the present invention.

  The solid silicate composition of the present invention is used for powder coatings as a material for imparting stain resistance to a coating film.

Claims (8)

  A solid silicate composition comprising a solid material having a melting point or softening point of 60 to 200 ° C. and an organic silicate compound of 5 to 25% by mass of the solid material.   The solid silicate composition according to claim 1, wherein the organic silicate compound includes a resin portion.   The solid silicate composition according to claim 1 or 2, wherein the solid substance is a binder resin.   The solid silicate composition according to claim 1 or 2, wherein the solid substance is a curing agent.   A method for producing a solid silicate composition, comprising adding an organic silicate compound of 5 to 25% by mass of the solid substance to a solid substance having a melting point or softening point of 60 to 200 ° C., and melt-kneading in a batch system.   The powder coating material containing the solid silicate composition as described in any one of Claims 1-5.   The powder coating material of Claim 6 which contains the said solid substance as components other than the said solid silicate composition.   A coating film having stain resistance obtained from the powder coating material according to claim 6 or 7.