JP2005225928A - Method for forming mat coating film excellent in durability - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming a mat coating film excellent in smoothness, which uses a paint showing little increase in viscosity, and to prepare the mat coating film obtained which is excellent in durability and is hardly damaged by nails, collision of articles, and the like. <P>SOLUTION: In the method for forming the mat coating film, the paint containing a gel method-derived silica particle and a binder component is applied onto a substrate, wherein the gel method-derived silica particle has an average particle size of 2-20 μm, an amount of particles with a particle size of ≥40 μm of ≤0.3 mass%, a pore volume of 1.2-2.5 ml/g and a BET specific surface area of 200-400 m<SP>2</SP>/g. Preferably, the paint further contains at least one selected from the group consisting of a crosslinking resin particle, a spherical silica particle and diatomaceous earth. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a matte coating film forming method used for interior and exterior of a building, and a matte coating film excellent in durability obtained therefrom.

In order to obtain a high-class and calm space on the walls and ceilings inside and outside the building, a matte paint film may be formed on the surface. This matte coating film is formed by applying a paint containing a binder component and a matting agent, for example, extender pigments and resin particles. (For example, see Patent Document 1, Patent Document 2, and Patent Document 3.)
However, such paints have a very high matting agent content, which increases the viscosity of the paint and requires a large amount of dilution at the time of application. As a result, the coating workability may be reduced.

Also, the matte coating obtained is brittle due to the small amount of resin component, and because the surface is not very smooth, it catches on the unevenness of the coating when touched by nails or articles in daily life, In some cases, the coating film was scraped off, resulting in scratches.
JP 2003-49111 A JP 2003-119426 A JP 2003-147275 A

  The present invention is a method for forming a matte coating film with a small increase in paint viscosity to be used and excellent in smoothness, and a matte coating film obtained therefrom, which is resistant to scratches due to collisions with nails and articles, etc. and excellent in durability. The purpose is to provide.

In the present invention, the average particle size is 2 to 20 μm, the content of particles having a particle size of 40 μm or more is 0.3% by mass or less, the pore volume is 1.2 to 2.5 ml / g, and the BET specific surface area It is a method for forming a matte coating film, characterized in that it is applied to a base material with a gel method silica particle having a particle size of 200 to 400 m ² / g and a binder component. The paint further comprises crosslinked resin particles. It is preferable that at least one selected from the group consisting of spherical silica particles and diatomaceous earth is included.

  Here, the paint is preferably an aqueous paint, and the content of the volatile organic compound is preferably 1% by mass or less.

  The matte coating film has, for example, a 60 degree gloss value of 50 or less and an 85 degree gloss value of 70 or less.

  Moreover, this invention is a matte coating film excellent in durability characterized by being obtained by the formation method of said matting coating film.

  Furthermore, the present invention is a paint comprising gel method silica particles and a binder component used in the above-described method for forming a matte coating film.

  The matte coating film forming method of the present invention uses a paint containing predetermined gel method silica particles, so that it is excellent in smoothness, but is not easily damaged by claws or articles, etc. An excellent matte coating can be obtained. This is because the gel method silica particles used as a matting agent retain its structure even during the preparation of the paint, so that the amount of matting agent used is small and the amount of resin contained in the coating film increases. This is probably because the film surface is smoothed by the resin and a coating film having high viscoelasticity can be formed.

  By further including at least one selected from the group consisting of crosslinked resin particles, spherical silica particles, and diatomaceous earth, the paint obtains a matte paint film having a high matte effect without reducing the smoothness of the paint film. be able to.

  Moreover, the matte coating film excellent in durability of the present invention is obtained from the above-described method for forming a matte coating film, and has good smoothness as well as durability.

  Furthermore, the paint of the present invention has a small increase in paint viscosity as found in conventional products. This is presumably because the gel method silica particles used as a matting agent maintain the structure even during the preparation of the paint, and the adsorption amount of various components in the paint does not change. Therefore, since this paint does not require a large amount of dilution at the time of application, the application workability is good. In addition, the paint is water-based, and the VOC (volatile organic compound) content is 1% by mass or less, so that the environment can be considered.

  The matte coating film forming method of the present invention is characterized in that a coating material containing specific gel method silica particles and a binder component is applied to a substrate.

  The said coating material used for the formation method of the matt coating film of this invention contains resin, for example as a binder component. The resin is not particularly limited, and specific examples include an acrylic resin, a polyester resin, an alkyd resin, a polyurethane resin, and an epoxy resin. The resin may have a curable functional group.

  Furthermore, a curing agent may be included as the binder component. The curing agent is not particularly limited, and examples thereof include a curing functional group having a reactive functional group and a curable functional group, and specifically, when the resin has a hydroxyl group. An amino resin, a (blocked) polyisocyanate compound, etc., and if the resin has a carboxylic acid group, a resin having an epoxy group or a compound having a carbodiimide group, etc., and the resin has a carbonyl group. In the case of hydrazide, hydrazide compounds and the like can be mentioned.

  The gel method silica particles contained in the paint is different from the silica particles obtained by a precipitation method usually used as a matting agent among silica particles produced by a wet method, and the raw materials are reacted in an acidic pH region, It is obtained by agglomerating in a state where the growth of primary particles is suppressed to form a three-dimensional network structure. Such gel method silica particles are aggregates having relatively strong cohesive strength. Therefore, unlike silica particles obtained by the precipitation method, the gel method silica particles are not easily destroyed even when dispersed in a paint, and therefore, the matt effect is very high even in a relatively small amount. Moreover, since the structure of the aggregate is not destroyed, the increase in the viscosity of the paint is small.

The gel method silica particles contained in the coating material have an average particle size of 2 μm or more and 20 μm or less, the content of particles having a particle size of 40 μm or more is 0.3% by mass or less, and the pore volume is 1. 2 ml / g or more and 2.5 ml / g or less, and BET specific surface area is 200 m ² / g or more and 400 m ² / g or less.

  If the average particle diameter of the gel method silica particles is outside the above range, it is impossible to achieve both the matte effect and the smoothness of the resulting coating film. On the other hand, when the content of particles having a particle diameter of 40 μm or more exceeds 0.3% by mass, the smoothness of the coating film is lowered. Examples of the average particle size and the method for measuring the particle size include methods well known by those skilled in the art, such as a light scattering method.

  When the pore volume is less than 1.2 ml / g, the matting effect is reduced, and when it exceeds 2.5 ml / g, the viscosity of the paint is remarkably increased. Preferably they are 1.7 ml / g or more and 2.3 ml / g or less. Examples of the method for measuring the pore volume include a nitrogen adsorption method.

When the BET specific surface area is less than 200 m ² / g, the smoothness of the resulting coating film is lowered, and when it exceeds 400 m ² / g, the matte effect and the dispersibility in the paint are lowered. Examples of the method for measuring the BET specific surface area include methods well known by those skilled in the art, such as a nitrogen adsorption method.

  Examples of such commercially available silica gel particles include the NIPGEL series (manufactured by Tosoh Silica), the Syloid C series (manufactured by Grace Japan), and the silicia series (manufactured by Fuji Silysia). be able to.

  It is preferable that content of the said gel method silica particle in the said coating material is 2-20 mass% with respect to coating resin solid content. If it is less than 2% by mass, the resulting coating film may have an insufficient matting effect, and if it exceeds 20% by mass, the viscosity of the paint may increase.

  The said coating material used for the formation method of the matt coating film of this invention may further contain at least 1 chosen from the group which consists of a crosslinked resin particle, spherical silica particle, and diatomaceous earth. By including these, the matte effect can be enhanced without deteriorating the smoothness of the coating film obtained. These preferably have an average particle diameter of 2 to 25 μm. If the average particle size is outside the above range, it may be difficult to achieve both the matte effect and the smoothness of the resulting coating film. Specific examples of the method for measuring the average particle diameter include the methods described above for the gel method silica particles.

  The cross-linked resin particles are not particularly limited, and examples thereof include polystyrene-based and polymethacrylic acid ester-based spherical organic fine particles. Examples of such crosslinked resin particles that are commercially available include Ganzpearl series (manufactured by Ganz Kasei Co., Ltd.), Art Pearl (manufactured by Negami Kogyo Co., Ltd.), and the like.

  The spherical silica particles are not particularly limited, and examples thereof include spheroidized fused silica particles and silica particles obtained by a sol-gel method. Examples of such spherical silica particles that are commercially available include FB-35, FB-48 (both manufactured by Denki Kagaku Kogyo Co., Ltd.), SP-25B (manufactured by Fuso Chemical Co., Ltd.), and the like. Can do.

  It does not specifically limit as said diatomaceous earth, For example, what was baked at 800-1200 degreeC and was made into the powder can be mentioned. Examples of such diatomaceous earth include silica series (manufactured by Chuo Silica), celite series (manufactured by Celite), and the like.

  When the paint contains at least one selected from the group consisting of the crosslinked resin particles, the spherical silica particles, and the diatomaceous earth, the mass of the gel method silica particles / (the crosslinked resin particles, the spherical silica particles, and the diatomaceous earth The ratio of the sum of the masses is preferably 5/5 or more and 8/2 or less. If the ratio is out of the above range, it may be difficult to achieve both the matte effect and the smoothness of the resulting coating film.

  The total content of the gel method silica particles, the crosslinked resin particles, the spherical silica particles, and the diatomaceous earth in the matte paint is 2% by mass or more and 35% by mass or less based on the solid content of the paint resin. If the total content is less than 2% by mass, the effect of containing these may be insufficient, and if it exceeds 35% by mass, the film forming property may be deteriorated.

  The paint may be an organic solvent type or an aqueous type, but is preferably an aqueous type from the viewpoint of consideration for the environment, and in particular, a VOC content of 1% by mass or less. Further preferred. Examples of the method for measuring the VOC content include methods well known by those skilled in the art, such as analysis by gas chromatography with a flame ionization detector (FID detector).

In the present specification, VOC, that is, a volatile organic compound means an organic compound having volatility at normal pressure.
When the paint is water-based, the binder component preferably contains an emulsion resin. From the viewpoint of minimizing the amount of organic solvent contained, the emulsion resin is preferably obtained, for example, by emulsion polymerization of a monomer mixture.

  In addition to the above components, the paint used in the method for forming a matte coating film of the present invention may include a color pigment, an extender pigment, a pigment dispersant, an antifoaming agent, a thickener, an ultraviolet absorber, and a light stabilizer. An agent etc. can be mentioned.

  The color pigment is not particularly limited, and examples thereof include inorganic pigments such as yellow iron oxide, iron oxide, carbon black, and titanium dioxide; azo chelate pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, indigo pigments, Examples thereof include organic pigments such as perinone pigments, perylene pigments, dioxane pigments, quinacridone pigments, isoindolinone pigments, and metal complex pigments. Examples of the extender pigment include calcium bicarbonate, calcium carbonate, precipitated barium sulfate, clay, and talc.

  In addition, it is preferable that the pigment volume concentration of the said coating material used for the formation method of the matt coating film of this invention is 10 to 50%. If it is less than 10%, various performances may be deteriorated, and if it exceeds 50%, the low-temperature film-forming property may be deteriorated.

  When the paint is water-based, it can further contain an antifreezing agent, a film-forming aid, and the like. However, the anti-freezing agent and the film-forming aid often fall under VOC and are environmentally friendly. From the viewpoint, it is preferable not to include them.

  The matte coating film forming method of the present invention is a method in which the coating material is applied to a substrate. The above-mentioned base material forms the outer walls, inner walls, ceilings, etc. of buildings and structures. For example, iron, stainless steel, aluminum, etc. and metal substrates of surface treated products thereof, cements, limes, plasters, etc. Cement-based substrates such as polyvinyl chlorides, polyesters, polycarbonates, acrylics, and the like. An undercoat such as a sealer may be formed on these.

  The coating method is not particularly limited, and examples thereof include brush coating, roller coating, and spray coating. After coating, it can be left at room temperature or forcibly heated and dried to obtain a matte coating. The coating amount, coating film thickness, and drying time can be arbitrarily set according to the type of coating material and the substrate to be applied.

  The matte coating film preferably has a 60 degree gloss value of 50 or less and an 85 degree gloss value of 70 or less. The method for obtaining the gloss value is not particularly limited. For example, the gloss value is applied on a glass plate with an applicator so that the dry film thickness is 50 μm, and then allowed to stand for one day under the standard conditions defined in JIS K 5600. The method of measuring the coating film obtained can be mentioned. The measurement method is not particularly limited, and examples thereof include a gloss meter measurement method well known by those skilled in the art. More preferably, the 60 degree gloss value is 40 or less and the 85 degree gloss value is 50 or less.

  The matte coating film excellent in durability of the present invention is obtained by the above-described method for forming a matte coating film. Therefore, it is excellent in smoothness and is hardly damaged by a collision of a nail or an article.

  The paint of the present invention is characterized by being used in the above-described method for forming a matte coating film. Accordingly, the increase in the viscosity of the paint is small and a large amount of dilution is not required at the time of application, so that the decrease in sagging property is small, and as a result, the application workability is not deteriorated. Moreover, the matte coating film obtained is excellent in smoothness, and is hardly damaged by collision of nails or articles. Specific examples of the coating material include those described in the method for forming the matte coating film.

  EXAMPLES Hereinafter, although a specific Example is given and this invention is demonstrated in detail, this invention is not limited by a following example. In the following description, “part” means “part by mass”.

Production Example 1 Production of Emulsion Resin A separable flask equipped with a dropping funnel, a thermometer, a nitrogen inlet tube, a reflux condenser and a stirrer was charged with 34.5 parts of ion-exchanged water, Perex SS-H (Kao Co., Ltd. alkyldiphenyl ether disulfonic acid). Sodium) 0.3 part was charged and heated to 80 ° C. under a nitrogen atmosphere. Dodecyl was added to a monomer mixture consisting of 14 parts of styrene, 57 parts of 2-ethylhexyl acrylate, 22 parts of methyl methacrylate, 4 parts of ethylene glycol dimethacrylate, 1 part of diacetone acrylamide and 2 parts of methacrylic acid. After adding 0.6 parts of mercaptan, this was added to an emulsifier aqueous solution in which 1.2 parts of PELEX SS-H was dissolved in 50 parts of ion-exchanged water, and emulsified using a mixer to prepare a pre-emulsion. An initiator aqueous solution prepared by dissolving the pre-emulsion thus obtained and 0.3 part of ammonium persulfate in 13 parts of ion-exchanged water was simultaneously added dropwise from a separate dropping funnel. The former started to drip evenly over 120 minutes and the latter over 150 minutes. After completion of the dropwise addition, the reaction was continued for an additional 120 minutes at the same temperature. After cooling, the solution was neutralized with aqueous ammonia corresponding to 10 mol% of the methacrylic acid used. The neutralized product was filtered through a 200-mesh wire mesh to obtain an emulsion resin having a solid content of 50%.

Production Example 2 Production of Pigment Dispersion Paste 200 parts of Taipei CR-50 (Titanium Dioxide manufactured by Ishihara Sangyo Co., Ltd.), 1 part of SP-600N (Hydroxycellulose-based thickener manufactured by Daicel Corporation), SN deformer 1070 (Defoamer manufactured by San Nopco) ) 1 part, 15 parts of Dispersic 190 (Pig Dispersant manufactured by Big Chemie) and 53 parts of ion-exchanged water were mixed, and then dispersed with Disper using glass beads to obtain a pigment dispersion paste.

Production Example 3 Production of Emulsion Coating Material 290 parts of the emulsion resin obtained in Production Example 1, 150 parts of the pigment dispersion paste obtained in Production Example 2, 5 parts of SN deformer 1070, 14 parts of a 5% aqueous solution of adipic acid dihydrazide, 6 parts of Adecanol UH-420 (Asahi Denka Co., Ltd. urethane thickener) and 35 parts of ion-exchanged water were mixed to obtain an emulsion coating material. It was 90 KU when the viscosity at 25 degrees C of this emulsion coating material was measured with the stoma viscometer.

Production Example 4 Production of extender pigment dispersion paste 120 parts heavy charcoal (calcium bicarbonate manufactured by Maruo Calcium Co., Ltd.), 0.1 part SP-600N (hydroxycellulosic thickener made by Daicel), SN deformer 769 (manufactured by San Nopco Co., Ltd.) After mixing 1 part of foaming agent, 18 parts of Dispersic 191 (pigment dispersant manufactured by Big Chemie) and 79 parts of ion-exchanged water, the mixture was dispersed with Disper using glass beads to obtain an extender pigment dispersion paste.

Example 1
500 parts of the emulsion paint material obtained in Production Example 3 and NIPGEL AZ-460 (gel silica particles manufactured by Tosoh Silica Co., Ltd., average particle size of 3.8 μm, pore volume of 1.8 ml / g, BET specific surface area of A paint was obtained by stirring and mixing 20 parts with a disper (214 m ² / g, content of particles having a particle size of 40 μm or more is 0.1 mass% or less) with a disper. The VOC content of this paint was analyzed with HP-5890 with a FID detector (gas chromatography manufactured by Hewlett-Packard Company), and the total peak area of the detected volatile components was substituted into the calibration curve formula of the prepared toluene standard sample. And found to be 0.1% by mass.
This paint was applied on a glass plate under the standard conditions of JIS K 5600 using an applicator so that the dry film thickness became 50 μm, and then left as it was for 1 day to obtain a gloss test plate.

Also, under the same conditions, Nippe Ultra Sealer III (Nippon Paint Co., Ltd. carboxylic acid group-containing styrene-acrylic resin-based aqueous sealer) was applied to a flexible plate in accordance with JIS A 5403 at a coating amount of 100 g / m ² using a wool roller. The coating material obtained was applied ^twice at a coating amount of 120 g / m ² using a wool roller for an interval of 3 hours. Thereafter, a test plate was obtained by curing in a thermostatic chamber at 20 ° C. for 3 days.

Example 2
A paint was obtained in the same manner as in Example 1, except that 15 parts of NIPGEL AZ-460 and 7.5 parts of Gantz Pearl GM1702H (cross-linked resin particles manufactured by Gantz Kasei Co., Ltd., average particle diameter: 17 μm) were used. When the VOC content of this paint was analyzed in the same manner as in Example 1, it was 0.1% by mass.
Further, each test plate was obtained in the same manner as in Example 1.

Example 3
A paint was obtained in the same manner as in Example 2 except that 7.5 parts of FB-48 (spherical silica particles manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size 13.3 μm) was used instead of Gantzpearl GM1702H. When the VOC content of this paint was analyzed in the same manner as in Example 1, it was 0.1% by mass.
Further, each test plate was obtained in the same manner as in Example 1.

Example 4
A paint was obtained in the same manner as in Example 2 except that 4 parts of silica # 6B (diatomaceous earth manufactured by Chuo Silica Co., Ltd., average particle size 5.5 μm) was used instead of Gantzpearl GM1702H. When the VOC content of this paint was analyzed in the same manner as in Example 1, it was 0.1% by mass.
Further, each test plate was obtained in the same manner as in Example 1.

Example 5
Instead of NIPGEL AZ-460, NIPGEL AY-601 (gel method silica particles manufactured by Tosoh Silica Co., Ltd., average particle size 6.0 μm, pore volume 1.6 ml / g, BET specific surface area 300 m ² / g, particles A paint was obtained in the same manner as in Example 2, except that 20 parts of particles having a diameter of 40 μm or more were contained in an amount of 0.1% by mass or less. When the VOC content of this paint was analyzed in the same manner as in Example 1, it was 0.1% by mass.
Further, each test plate was obtained in the same manner as in Example 1.

Comparative Examples 1-3
In place of NIPGEL AZ-460, NIPGEL BY-001 (gel method silica particles manufactured by Tosoh Silica Co., Ltd., average particle diameter of 14 μm, pore volume of 1.3 ml / g, BET specific surface area of 450 m ² / g, Content of particles having a particle diameter of 40 μm or more is 0.1% by mass or less), NIPGEL CX-200 (gel method silica particles manufactured by Tosoh Silica Co., Ltd., average particle diameter is 1.7 μm, pore volume is 0.5 ml / g, BET specific surface area of 750 m ² / g, content of particles having a particle size of 40 μm or more is 0.1% by mass or less, NIPSIL E-200A (precipitated silica particles manufactured by Tosoh Silica Co., average particle size is 2) 0.8 μm, pore volume of 0.8 ml / g, BET specific surface area of 140 m ² / g, particle size of 40 μm or more is 0.1% by mass or less) In the same manner as in Example 1, each paint was obtained. When the VOC content contained in these paints was analyzed in the same manner as in Example 1, they were all 0.1% by mass.
Further, each test plate was obtained in the same manner as in Example 1. In Comparative Examples 2 and 3, the obtained paint had a high viscosity, and dilution with water was necessary.

Comparative Example 4
A paint was obtained in the same manner as in Example 1 except that 300 parts of the extender pigment paste obtained in Production Example 4 was used instead of NIPGEL AZ-460. When the VOC content of this paint was analyzed in the same manner as in Example 1, it was 0.1% by mass.
Further, each test plate was obtained in the same manner as in Example 1.

Evaluation Tests The following evaluation tests were performed on the paints and test plates obtained in Examples 1 to 5 and Comparative Examples 1 to 4. The blending and evaluation results are shown in Table 1.

(1) Viscosity increase value of paint The paint viscosity at 25 ° C. was measured with a stoma viscometer, and the increase obtained from (obtained value) − (viscosity value of emulsion paint material obtained in Production Example 3). The value was determined. An increase value of 20 KU or less was accepted.

(2) Gloss value The 60-degree gloss value and the 85-degree gloss value were measured with respect to the obtained gloss test plate using a microtrigloss (Gloss meter manufactured by Big Chemie).

(3) Smoothness The smoothness of the coating film of the obtained process test plate was evaluated by touching with a finger. The evaluation criteria were as follows.
○: There is no catch and it is smooth ×: There is a catch and it is rough

(4) Scratch resistance After the nail was set up so that it might become 90 degrees with respect to the coating-film surface with respect to the obtained process test board, it was made to reciprocate 5 times and was scratched. The obtained scratch marks were visually evaluated. The evaluation criteria were as follows.
◎: Scratch marks can hardly be confirmed. ○: Scratch marks can be confirmed slightly but are not conspicuous. ×: Scratch marks can be clearly confirmed.

  As described above, the method for forming a matte paint film using a paint containing gel method silica particles having a predetermined characteristic value according to the present invention has a small increase in viscosity of the paint used and good smoothness of the obtained paint film. It was found that scratch marks were difficult to be attached (Examples 1 to 5). In particular, the coating material further containing at least one selected from the group consisting of crosslinked resin particles, spherical silica particles and diatomaceous earth has a smaller increase in viscosity (Examples 2 to 4), and the crosslinked resin particles and spherical silica having high hardness. The matte coating obtained from the paint containing particles was found to be less susceptible to scratch marks (Examples 2 and 3).

  However, when a paint containing gel method silica particles deviating from a predetermined characteristic value is used, the viscosity of the paint is significantly increased (Comparative Examples 2 and 3), and the resulting matte coating film is less smooth (Comparative Example). 1) Do it. Further, the matte coating film obtained from the paint containing a large amount of extender pigment was easily scratched (Comparative Example 4).

  The matte coating film forming method of the present invention is suitable for the interior and exterior of buildings.

Claims (7)

The average particle size is 2 to 20 μm, the content of particles having a particle size of 40 μm or more is 0.3 mass% or less, the pore volume is 1.2 to 2.5 ml / g, and the BET specific surface area is 200 to 400 m. ^A method for forming a matte coating film, which comprises applying a coating material containing gel method silica particles of ² / g and a binder component to a substrate.   The matte coating film forming method according to claim 1, wherein the paint further contains at least one selected from the group consisting of crosslinked resin particles, spherical silica particles, and diatomaceous earth.   The method for forming a matte coating film according to claim 1, wherein the paint is a water-based paint.   The method for forming a matte coating film according to any one of claims 1 to 3, wherein the content of the volatile organic compound is 1% by mass or less.   The method for forming a matte coating film according to any one of claims 1 to 4, wherein the matte coating film has a 60-degree gloss value of 50 or less and an 85-degree gloss value of 70 or less.   A matte coating film excellent in durability, which is obtained by the method for forming a matte coating film according to any one of claims 1 to 5.   A paint comprising gel method silica particles and a binder component used in the method for forming a matte coating film according to any one of claims 1 to 5.