JPH01310777A - Method for forming film in uniform thickness - Google Patents

Abstract

PURPOSE:To improve the hot water resistance, acid resistance, film hardness and film denseness of a uniform film by applying reaction curable type org. coating to the surface of a base material and subsequently applying alkoxide type inorg. coating to form the uniform film. CONSTITUTION:After the surface of a base material composed of a metal, plastic, paper, glass, ceramic or slate is coated with reaction curable type org. coating, alkoxide type inorg. coating is applied to form a uniform film. As the reaction curable org. coating polyester, epoxy, acrylic urethane, fluorocarbon resin coatings or the like are pref. The alkoxide type inorg. coating to be used is composed of an oligomer having a three-dimensional reticulated structure whose MW is usually 5000-15000 and pref. 7000-10000.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for forming a uniform coating film. More specifically, the present invention relates to a method for forming a uniform coating film that can also be formed on the surface of a porous substrate such as a building material.

[Prior art and its problems] Conventionally, paints include alkali metal salt-containing paints with excellent heat resistance, paints containing alkali metal salts and their curing agents that have high coating hardness after application, and heat-resistant and water-resistant paints. Paints containing acidic metal salts with excellent fire resistance and paints containing metal oxide sol with excellent fire resistance are used.

These paints are useful only for purposes according to their characteristics, such as hot water resistance, acid resistance, film hardness,
There is no one that satisfies all characteristics such as coating film density.
In addition, when these characteristics are required and the base material used is a basic porous base material, such as the wall of a concrete building, the paint may penetrate into the pores of the base material. However, there were drawbacks such as unevenness on the surface of the coating and the possibility of peeling off due to corrosion.

In addition, when using an evaporation-solidifying type of thermoplastic resin, the inorganic paint softens due to the heat generated during curing.
The drawback is that inorganic paints tend to crack.

In view of the problems of the prior art described above, the present inventors have therefore found a method that can solve these problems, that is, it has excellent hot water resistance, acid resistance, coating film hardness, and coating film density, and has a porous structure. We have conducted extensive research in order to develop a method for forming a uniform coating film that can be applied to the surface of the surface of the coating film (L7 or Ai) without any unevenness on the surface of the coating film. As a result, we have discovered a completely new method for forming a uniform coating film that can solve the above-mentioned problems, and have completed the present invention.

[Means for Solving the Problem] That is, the present invention provides a uniform coating film characterized in that after applying a reaction-curing organic paint to the surface of a specimen, an Alcoquine F-based inorganic paint 1 is applied. The present invention relates to a method of forming.

[Operations and Examples] According to the method for forming a uniform coating film of the present invention, after applying a reaction-curing organic paint on the surface of the specimen, an alkoxide-based inorganic paint is applied, thereby achieving hot water resistance and acid resistance. It is possible to form a uniform coating film with excellent properties in terms of hardness, coating hardness, and coating density.

In particular, the method for forming a coating film of the present invention can be suitably used for porous samples where a uniform coating film could not be formed using conventional paints.

The term "uniform coating film" as used herein refers to a smooth coating film with no irregularities, bubbles, or pinholes on the coating surface.

The coating film forming method of the present invention is applied to various materials such as metal, plastic, paper, glass, ceramic, clay, asbestos clay, concrete, and cement. The present invention is not limited only to groups (4) made of these cable materials, although the group (A) made of the ropes is mentioned.

In the reaction-curing organic paint, for example, a porous group O is used as the group +4, and the alkoxide-based inorganic paint, which will be described in detail later, is prevented from penetrating into the pores on the surface.
Furthermore, since alkoxide-based inorganic paints have low base resistance, they are applied to suppress corrosion and peeling that occur when directly applied to basic materials. In the present invention, specific examples of reaction-curing organic paints include polyester urethane paints, epoxy paints, acrylic urethane paints, and fluororesin paints, and these paints may be used alone or in combination of two types. A mixture of the above is used.

The polyester urethane paint is composed of a main ingredient consisting of a polyester resin varnish, a pigment, an additive, and a solvent, and a curing agent consisting of an isocyanate-1/resin varnish.

Typical examples of such polyester urethane paints include:
Polyester resin varnish 59% by weight, pigment 36% by weight,
Additives = 4 -- Examples include mixtures of a main ingredient consisting of 1% by weight and 4% by weight of a solvent and a curing agent consisting of an isocyanate resin varnish at a ratio of 75./25 (weight ratio), such as Polytan (Dainippon Paint Co., Ltd.) Manufactured by Nato (product name).

The epoxy paint is composed of a main ingredient consisting of an epoxy resin varnish, a pigment, an additive, and a solvent, and a curing agent consisting of a modified polyamide amine varnish. A typical example of such an epoxy paint is epoxy resin varnish 39 layers 1
872 (f
For example, Ebonix #10, Ebonix #20, and Ebonix #30 (hereinafter "-1" manufactured by Dainippon Paint Co., Ltd., trade name) are available.

The acrylic urethane paint includes acrylic resin varnish,
It consists of a main ingredient consisting of pigment, additives and a solvent, and a curing agent consisting of an isocyanate resin face and a solvent.

A typical example of the acrylic urethane paint is a base material consisting of 30% by weight of acrylic resin varnish, 44% by weight of pigment, 2% by weight of additives and 24% by weight of solvent, and 53% by weight of isocyanate resin varnish and 47% by weight of solvent. For example, V-Top #100 (manufactured by Dainippon Toyo Co., Ltd., trade name) is available.

The fluororesin paint is composed of a main ingredient consisting of a fluororesin varnish, a pigment, an additive, and a solvent, and a curing agent consisting of an isocyanate resin varnish. Typical examples of such fluororesin paints include fluororesin varnish 66% by weight;
One example is a mixture of a main ingredient consisting of 25% by weight of pigment, 1% by weight of additives, and 8% by weight of solvent, and a curing agent consisting of isocyanate resin varnish at a ratio of 8/2 (weight ratio). Manufactured by Nato (product name).

Among the reaction-curable organic paints, polyester urethane paints and acrylic urethane paints are preferred because they have excellent adhesion to the substrate.

Note that reaction-curing organic paints have a viscosity that varies depending on the temperature during application, the application method, the type of substrate to be applied, etc.
It is preferable to use one that has been adjusted in advance by adjusting the amount of solvent added so that the heating time is 5 to 25 seconds (25° C.) at 4.

When applying the reaction-curing organic paint to a porous substrate, for example, it is necessary to preheat the substrate in order to prevent the reaction-curing organic paint from penetrating into the pores of the substrate. is preferred.

When the substrate is preheated, the reaction-curing organic coating dries before entering the pores of the substrate, and the pores are covered with a coating film. The preheating temperature of the substrate cannot be determined generally, since it depends on the number of pores on the surface of the substrate and their size, as well as the temperature and humidity of the surrounding atmosphere, etc.

= 7 - As the method for applying the reaction-curing organic paint, is it possible to apply a conventionally commonly used method such as an air spray method, a curtain flow coater method, or a roll coater method? The coating is not limited to the above method, but may be applied by other methods. Further, depending on the necessity, for example, when applying to a substrate having a large number of holes on the surface, the coating may be coated one or more times.

The amount of the reaction-curing organic paint applied and the film thickness after drying vary depending on the type of base material used as mentioned above, so it cannot be determined generally, but the amount applied is Usually 10-2 per 30e111x30cm
It is preferable that the film thickness after drying is 30 to 75 g.

After the reaction-curable organic paint film thus formed is sufficiently dried, an alkoxide-based inorganic paint is applied onto the paint film.

Unlike other commonly used inorganic paints, the alkoxide-based inorganic paint forms a strong chemical bond with the coating film of the reaction-curing organic paint. The present inventors have discovered that the coating film applied on the coating film of the curable organic paint has excellent hot water resistance, acid resistance, hardness, and density.

That is, the coating film formed by the formation method of the present invention not only has the above-mentioned properties, but also has a uniform coating film even when provided on a porous substrate. It is formed.

The alkoxide-based inorganic paint is an oligomer with a three-dimensional network structure, and if its molecular weight exceeds about 15,000, it will gel and become difficult to apply. 10
000 molecular weight is used.

The molecular weight of the alkoxide-based inorganic paint used in the present invention is low as described above, and is much smaller than the molecular weight of commonly used organic paints (approximately 20,000 to several hundred thousand). If applied directly to a substrate, it will be absorbed into the pores of the substrate in a short period of time, so the reaction-curing organic paint is applied before the alkoxide inorganic paint is applied.

As the alkoxide-based inorganic paint, general 2M (OR) is used.
n (wherein H is Si, Ti, M, Zr5Sn,
Paints whose main component is a metal alkoxide represented by Pb and/or Pe, R is an alkyl group having 1 or more carbon atoms, and n is an integer from 1 to 1- are listed, and specific examples of such metal alkoxides include: is Sj (OCH3)4
, Sj (QC2+5)4, S i (OCII (
CHs )2 )4, Si (QC3+7 )4, S
i (QC4)+9 )4, Ti (OCH3)4, T
1(QC2+5)4, T i (OCII (CH
3)2)4, Ti (QC3+7)4, Ti (
QC4+9 )4, M (OCH3)4, Ai' (Q
C2+5 )4, M(OCII(CH3)2 )4, M
(QC3+7)4, M (QC4+9)4, Zr
(0CR3)4, Zr (QC2+5)4, Zr(
OCH(CI-b)2)4, Zr(QC3+7
)4, Zr (OC4H9)4, Sn (OCH3)4.
5n(QC2+5)4.5n(OCH(CHx)2
)4, Sn (QC387)4, Sn (QC4+9
)4, Pb (OCH3)2, Pb (QC2)Is
)2,Pb(OCH(CHa)2)2,PI)(
QC3+7)2, Pb(OC4H9)2, Fe(0
CR3)4, Fe(OC2H5)4, Fe(OCH(C
H3)2)4, Fe(QC3+7)4, Pe(QC
4+9)4, ZrSi (QC)13)4, ZrS
i (QC2+5)4, Zr5i(OCH(CH3)
2) 4, ZrSi (QC387) 4, ZrSi (
Examples include QC489)4, and these metal alkoxides may be used alone or in combination with others. Among the metal alkoxides, general formula M(O
I? ) Silicon alkoxides in which H is 81 in n are inexpensive and can be used particularly preferably.

Components other than the metal alkoxide contained in the alkoxide-based inorganic paint include, for example, chrome green, cobalt blue, red iron, amber, titanium yellow,
Inorganic pigments such as iron black, zinc white, titanium oxide, talc, and silica powder may be added to the alkoxide-based inorganic paint in an amount not exceeding 60% by weight.

Note that alcohols such as isopropyl alcohol, methyl alcohol, ethyl alcohol, methyl nityl ketone, toluene, and butyl cellosolve are used as the solvent for the alkoxide-based inorganic paint, and the solvent is used to adjust the viscosity of the alkoxide-based inorganic paint. It is added as appropriate. The amount of the solvent added varies depending on the molecular weight of the metal alkoxide, the presence or absence of an inorganic pigment, etc.
-Although it cannot be determined generally, it is usually adjusted so that the H content in the alkoxide-based inorganic paint is 40 to 80%.

The method for applying the alkoxide-based inorganic paint may be, for example, an air spray method, a curtain flow coater method, a roll coater method, or the like, but the present invention is not limited to these methods, and other methods may be used. You can.

The amount of the alkoxide-based inorganic paint applied and the thickness of the coating after drying vary depending on the type of group H used, etc., so it cannot be roughly determined, or the amount applied is usually 30 to 300 g. /rrr, the thickness of the coating film after drying is preferably 5 to 5011 m.

In addition, the reaction hardness of the alkoxide-based inorganic paint = 1
2 - When forming on a coating film of a reaction-curing organic paint, for example, after applying an alkoxide-based inorganic paint containing the inorganic pigment to the coating film of a reaction-curing organic paint, An alkoxide-based inorganic paint that does not contain an inorganic paint may be applied to the surface. In this case, the coating amount of the alkoxide-based inorganic paint containing the inorganic pigment and the alkoxide-based inorganic paint not containing the inorganic pigment is 30% each.
Preferably, it is ~300g/g/g and 30-150g/i.

The general 2 M(OR)+1 used in the present invention
The alkoxide-based inorganic paint represented by is one that is polymerized by a hydrolysis heating dehydration condensation reaction to form a coating film. The produced metal oxide MO2/n has excellent heat resistance, water resistance, acid resistance, coating film hardness, and coating film density. It is preferable to apply an alkoxide paint to the surface and then heat it.

Zunawaji applies an alkoxide-based inorganic paint to a reaction-curing organic paint film and cures it in air for about 5 minutes to 1[) hours, depending on the surrounding environment conditions such as ambient temperature and humidity. It is preferable to let it cool and then heat it.

The coating film of the alkoxide-based inorganic paint is heated to a temperature of 60 to 200 ℃ using, for example, a hot air dryer or a far infrared dryer.
℃ for 5 to 30 minutes.

Thus, a coating film formed by applying an alkoxide-based inorganic paint onto a reaction-curing organic paint film has excellent hot water resistance, coating hardness, and coating density, and the base material exhibits basicity. It can be particularly preferably applied to porous substrates.

Next, the forming method of the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.

Example 1 Asbestos slate, which is a basic substrate (PL+ 12-13) specified in JIS A 5403, was used as a base material (
Using asbestos slate (with a thickness of 6 cm), apply an acrylic urethane sealer (manufactured by Dainippon Paint Co., Ltd., V-Selan #100ST) as a reaction-curing organic paint on the surface of the asbestos slate board at a rate of 6 g per 30 cm x 30 cm. After applying using the air spray method as shown in the figure, it was applied at room temperature (approximately 25°C) for 24 hours.
Let dry for an hour.

Next, an alkoxide-based color inorganic paint (metal alkoxide: Si (OC2H5)4,
Molecule i: 10,000) was applied using an air spray method at a rate of 5 g per 30 cm x 30 cm, dried at room temperature (approximately 25°C) for 6 hours, and then an alkoxide-based clear inorganic paint (metal alkoxide: Si
(OC2H5)4, molecule R: 10000) at 30cm
It was applied by air spraying in an amount of 5 g per x 30 cm, and dried at room temperature (approximately 25° C.) for 1 hour.

The reaction-curable organic coating film and the alkoxide-based inorganic coating film applied to the asbestos slate board as described above were heated and baked at 100 to 150°C for LO minutes using a far-infrared dryer to prepare a test piece. did.

The physical properties of the coating film of the obtained test piece were examined for hot water resistance, coating hardness, and coating film density according to the following methods. The results are shown in Table 1.

(Hot water resistance) A test piece was cut into 75mm x 150+++m, boiled continuously for 7 days, then dried in a dryer (internal atmosphere temperature 260°C) for 3 days, and then tested according to JIS K 540.
0. Conduct a base peel test in accordance with 0. The criteria for this judgment are as follows.

(Judgment criteria) ○: No peeling △: Peeling] O ~ 40 pieces occurred ×: 41 or more pieces peeled off (acid resistance) The test is conducted in accordance with JIS K 54 (107.5 acid resistance. The judgment criteria are as shown.

(Judgment criteria) ○: No abnormalities △: Blisters, cracks, peeling, etc. occur in 5 or less places ×: Blisters, cracks, peeling, etc. occur in 6 or more places (paint film hardness) Based on JIS K 54006.14 pencil scratch test and perform the test.

(Denseness of the coating film) (() Cut the glossiness test piece of the coating film into 75 mm x 150 mm, and
"60" shown in IS Z 87415.4 gloss measurement
The degree of gloss is measured based on the specular gloss.

(b) Paint film water permeability test piece 80+nm x 8 (1mm x 60
Cut into m+n, and place a vinyl chloride pipe (inner diameter: 5Lmm) on the surface.

Height: 30++ on), after drying at 10℃ for 2 days, apply epoxy resin to the outer circumference of the PVC pipe, and then apply paint (Acrose Super) to the outer circumference of the test piece. , dry.Next, pour water into the PVC pipe and raise it to the height of water + 1 or about 25m.
After adjusting it so that it is +n, it is set for 71", and the water permeability (g/c!) is determined from the weight of the test piece before and after the test.
).

Example 2 Asbestos cement calcium silicate board (thickness 1
Example 1 except that 2mm, density 1.0g/ca) was used.
A test piece was prepared in the same manner as (.

The physical properties of the coating film of the obtained test piece were examined in the same manner as in Example 1 for hot water resistance, acid resistance, coating hardness, and coating film density. The results are shown in Table 1.

Example 3 Alkoxide-based color inorganic paint (metal alkoxide, Si (OC2H5)4 and Zr (OC3H7)) was used instead of the alkoginate-based color inorganic paint used in Example 1.
A test piece was prepared in the same manner as in Example 1 except that 4.5i02/Zr (h was 773 in molar ratio) was used.

The physical properties of the coating film of the obtained test piece were examined in the same manner as in Example 1 for hot water resistance, acid resistance, coating hardness, and coating film density. The results are shown in Table 1.

Example 4 A test piece was prepared in the same manner as in Example 1 except that the alkoxide color inorganic paint used in Example 2 was replaced with the alcoginte color inorganic paint used in Example 3.

The physical properties of the coating film of the obtained test piece (7) hot water resistance,
Acid resistance, coating film hardness, and coating film density were examined in the same manner as in Example 1. The results are shown in Table 1.

Examples 5 to 7 In Example 1, a polyester urethane paint (manufactured by Artificial Wood Co., Ltd., Polytan $1) was used as a reaction-curing organic paint.
000) with an application amount of 8g per 30cm x 30cm
(Example 5), 12g (Example 6) or 16g (Example 7) by air spray method, heated to G O'C with warm air and dried for 30 minutes, but the same. Tess!・Created a piece.

The physical properties of the coating film of the obtained test piece were investigated in the same manner as in Example 1. The results are shown in Table 1.

Examples 8 to JO In Example 1, an epoxy resin paint (Dai ['' manufactured by Honyo Paint ■, Eponix #10) was used as a reaction-curing organic paint.
) and its application amount is 8g per 30cm x 80cm.
(Example 8), 12g (Example 9), or 16g (Example 10) was applied by air spray method, and then heated to 60°C with warm air and dried for 30 minutes. A test piece was prepared.

The physical properties of the coating film of the obtained test piece were examined in the same manner as in Example 1. The results are shown in Table 1.

Examples 1] and 12 In Example 1, an asbestos cement calcium silicate board (thickness 12 mm) was used as the base material, and an epoxy resin paint was used as the reaction-curing organic paint = 20 - (manufactured by Dainippon Paint Co., Ltd., Eponix Co., Ltd.) #10) with a coating amount of 12g per 30cm x 30cm (Example 1)
Or, after applying it by air spray method so that it becomes 16g (Example 12), it is heated to 60°C with hot air and heated to 30°C.
A Tes I piece was prepared in the same manner except that it was dried for a minute.

The physical properties of the coating film of the obtained test piece were investigated in the same manner as in Example 1. The results are shown in Table 1.

Examples 13 and 14 In Example 1, acrylic urethane paint (Inu 1) manufactured by Hon Paint, ■Top $10 was used as the reaction-curing organic paint.
0) and its application amount is 12 per 30cm x 30cm.
g (Example 13) or 16 g (Example 14) by air spray method, and then heated at 60°C with hot air.
A test piece was prepared in the same manner except that it was heated to 30 minutes and dried for 30 minutes.

The physical properties of the coating film of the obtained test piece were investigated in the same manner as in Example 1. The results are shown in Table 1.

Examples] 5 and 16 In Example 1, an asbestos cement calcium silicate plate (thickness 12 nm) was used as the base material, and an acrylic urethane resin paint (Dainippon Paint Co., Ltd.) was used as the reaction-curing organic paint.
(Top #100) with a coating amount of 30cm
Test pieces were prepared in the same manner, except that 12 g (Example 15) or 16 g (Example 16) was applied per 30 cm using the air streak 1 no method, and then heated to 60°C with warm air and dried for 30 minutes. Created.

The physical properties of the coating film of the obtained test piece were investigated in the same manner as in Example 1. The results are shown in Table 1.

Examples 17 to 19 In Example 1, a fluororesin paint (manufactured by Dainippon Paint Co., Ltd., CFC $200) was applied as a reaction-curing organic paint in an amount of 8 g per 30 cm x 30 cm (Example 17). 12g (Example 18) or 1.6g (
A test piece was prepared in the same manner as in Example 19), except that it was applied by air spraying and then heated to 60°C with hot air and dried for 40 minutes.

The physical properties of the coating film of the obtained test piece were investigated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 A test piece was prepared by applying an alkoxide color inorganic paint and an alkoxide clear inorganic paint to an asbestos slate board in the same manner as in Example 1 except that the reaction-curing organic paint was not applied.

The physical properties of the coating film of the obtained test piece were examined in the same manner as in Example 1 for hot water resistance, acid resistance, coating hardness, and coating film density. The results are shown in Table 1.

Comparative Example 2 A chist piece was prepared in the same manner as in Example 2 except that the reaction-curing organic paint was not applied, by applying an alkoxide-based color inorganic paint and an alkoxide-based clear inorganic paint to an asbestos cement calcium silicate board.

The physical properties of the coating film of the obtained test piece were examined in the same manner as in Example 2, including hot water resistance, acid resistance, coating hardness, and coating film density. The results are shown in Table 1.

Comparative Examples 3 and 4 The asbestos straight plate used in Example 1 was used as the substrate, and the conventionally used acrylic paint (
Made by Dainippon Toyo ■, Acroze #LOOV) or acrylic urethane paint (made by Dainippon Toyo ■, ■Top #1
00) with an application amount of 20g per 30cm x 30cm
After applying by air spray method so that
A test piece was prepared by drying at 0 to 70°C for 15 minutes.

The physical properties of the coating film of the obtained test piece were examined in the same manner as in Example 1 for hot water resistance, acid resistance, coating hardness, and coating film density. The results are shown in Table 1.

Comparative Example 5 In Example 1, a reaction curing organic paint and an acrylic resin paint (Acroze $LOOV, manufactured by Dainippon Toyo ■) were used, and the coating amount was 6 g/shaku2. After applying it by air spray method to room temperature (25
A test piece was prepared in the same manner as in Example 1, except that the test piece was dried for 24 hours at (°C).

The replacement of the coating film on the obtained test piece was investigated in the same manner as in Example 1. The results are shown in Table 1.

[Left below] Example 1 is a case in which a reactively curing organic paint is applied on a basic substrate, and an alkoxide-based inorganic paint is further applied on the top surface of the basic substrate, but in the case where a reactive organic paint is not applied. It can be seen that compared to (Comparative Example 1), the hot water resistance is extremely excellent, and peeling does not occur over a long period of time.

Example 2 is a case in which a reaction-curing organic paint is applied on a porous substrate, and an alkoxide-based inorganic paint is further applied on the top surface of the porous substrate, but such a coating film is not coated with a reaction-curing organic paint. In the case of Comparative Example 2, the gloss was poor, that is, the surface was not uniform, and there were pinholes, resulting in a highly water-absorbing coating. I know that there is.

In addition, conventionally used paints do not satisfy all of the requirements of hot water resistance, acid resistance, film strength, and film density, but the paint film obtained by the forming method of the present invention has the physical properties as described above. It can be seen that it is extremely superior.

[Effects of the Invention] According to the method for forming a uniform coating film of the present invention, it satisfies all properties such as hot water resistance, acid resistance, coating hardness, and coating film density, and can be applied to porous substrates. It is possible to form a uniform coating film without pinholes or unevenness even in cases where conventional paints cannot be applied, such as on porous walls of concrete buildings. It can be suitably used for various purposes including as a plastic substrate.

Further, according to the method for forming a uniform coating film of the present invention, the organic paint is applied before the alkoxide-based inorganic paint is applied, so it can be preferably applied even if the base material is basic. can.

Claims (1)

[Scope of Claims] 1. A method for forming a uniform coating film, which comprises applying a reaction-curable organic paint onto the surface of a substrate, and then applying an alkoxide-based inorganic paint. 2. The method for forming a uniform coating film according to claim 1, wherein the reaction-curable organic paint is at least one selected from polyester urethane paints, epoxy paints, acrylic urethane paints, and fluororesin paints. 3. The method for forming a uniform coating film according to claim 1, wherein the base material exhibits basicity. 4. The method for forming a uniform coating film according to claim 1 or 3, wherein the base material is a porous base material.