JP4656993B2 - Painting method - Google Patents

Description

  The present invention relates to a coating method that can be suitably used on the surface of a material containing a plasticizer, such as a sealing material, a vinyl-based interior material, and a vinyl-based building material.

  Conventionally, in building interiors and exteriors, various types of coating have been frequently used to protect the housing and improve the aesthetics.

  In the case of such coating, when various building materials such as ceramics or metal are used on the surface of the building to be coated, a sealing material is used at the joint portion of the building material in order to provide waterproof properties. It has been cast. When the entire surface to be coated including the joint portion of the building material is coated, the joint portion can be protected. Furthermore, there is an advantage that the overall design is unified and the aesthetics can be improved.

  In order to perform such coating, it is usually necessary to form a coating film so as to cover both the building material portion and the seam sealing material portion. However, most of such sealants contain a plasticizer in their components. For this reason, when the surface of the sealant is directly applied, the plasticizer in the sealant moves over time to plasticize and soften the paint on the sealant, which softens air pollutants. It may adhere to the surface of the coated film and reduce its aesthetics.

  Further, the sealing material has a function of following expansion and contraction due to a difference in temperature between various building materials, and this function is exhibited by the expansion and contraction of the sealing material itself. Therefore, if the coating film on the sealing material cannot follow the expansion and contraction of the sealing material, that is, has a relatively poor elasticity, the coating film may be cracked. On the other hand, cracking can be solved by using a highly elastic coating film on the sealing material, but in addition to the above-mentioned problem of softening the coating film due to the migration of plasticizer, There is also a problem that the pollutant is more likely to adhere than the hard coating originally, and the aesthetics are easily impaired.

  On the other hand, in interiors of buildings, so-called vinyl materials such as wallpaper, ceiling materials, floor materials, etc. mainly composed of vinyl chloride are used because they are relatively inexpensive and have good workability. When deterioration or contamination progresses over time, or when there is a request for a change in design, there is a need for refurbishment. As a refurbishment method for these, a method of replacing an old vinyl-based interior material with a new one is generally used. However, in this method, there is a concern about a problem of waste disposal such as a problem of dioxin generation. Recently, renovation by painting has been attracting attention as an alternative method. However, if the surface of such a vinyl-based material is applied directly, as in the case of the above-mentioned sealing material, the plasticizer contained in the component may be transferred to the coating film to easily cause contaminants to adhere. There is.

  Further, since the vinyl-based interior material itself has flexibility, when the coating film formed thereon is hard, the coating film is likely to be cracked. On the other hand, the use of a highly elastic coating film on the vinyl interior material can solve the problem of cracking, but this time the contamination resistance of the coating film is reduced.

  In order to solve the above problems, some treatment agents are applied on the surface of sealing materials and vinyl interior materials to prevent plasticizer migration and coating cracking. is there. However, most of such materials are so-called solvent-based materials mainly composed of an organic solvent as a medium, and it is difficult to say that it is preferable in view of safety in work and environmental hygiene (Patent Document 1). etc). In contrast, water-based materials have been proposed in part, but there is still room for improvement in terms of plasticizer migration prevention and crack prevention.

Japanese Patent Laid-Open No. 11-92711

  The present invention has been made in view of the above-described problems, and the plasticizer in such a material is applied by applying it to the surface of a sealing material or a vinyl interior material containing a plasticizer. An object of the present invention is to obtain a coating method capable of preventing transition to a film and further preventing the occurrence of cracks in a coating film due to expansion and contraction of a sealing material, a vinyl-based interior material or the like.

  As a result of intensive studies to achieve the above object, the present inventor has achieved the effect of preventing the migration of plasticizers, sealing materials and vinyl-based materials by using an aqueous paint containing a specific aqueous resin and a specific organic powder. The present inventors have found that an effect of preventing cracking against displacement of an interior material or the like can be obtained, and have completed the present invention. That is, the present invention has the following characteristics.

1. On the surface of the material containing the plasticizer,
100 parts by weight of an aqueous resin (I) having an average particle diameter of 0.1 μm or less and an elongation of the film of 500% or less, in terms of solid content,
Organic powder (a) made of a polymer having an average particle diameter of 0.1 to 100 μm and a glass transition temperature of −60 to 60 ° C. and / or an average particle diameter of 0.1 to 100 μm and a glass transition temperature An aqueous paint comprising 3 to 400 parts by weight of an organic powder (II) comprising an organic powder (b) having a core part comprising a polymer of less than 30 ° C and a shell part comprising a polymer having a glass transition temperature of 30 ° C or higher. A painting method characterized by painting.
2. The water-based resin (I) in the water-based paint includes a tertiary amine base, a quaternary ammonium base, an acrylic resin having at least one functional group selected from nitrile groups, and / or a polycarbonate urethane resin. 1. The coating method as described in 4.
3. 1. The water-based resin (I) in the water-based paint is a crosslinking reaction type water-based resin. Or 2. The coating method as described in 4.

  In this invention, the performance outstanding in the plasticizer transfer prevention property and the crack prevention property of a coating film can be exhibited. Therefore, the present invention is suitable for surface coating of a material containing a plasticizer such as a sealing material, a vinyl-based interior material, and a vinyl-based building material.

  Hereinafter, the best mode for carrying out the present invention will be described.

[Water-based paint]
In the aqueous paint of the present invention, an aqueous resin (I) (hereinafter referred to as “component (I)”) having an average particle size of 0.1 μm or less and a coating elongation of 500% or less is used as a binder. In this invention, plasticizer transfer prevention property can be exhibited by the effect | action of this (I) component. When the average particle diameter of the component (I) is larger than 0.1 μm, or when the elongation of the coating exceeds 500%, a sufficient plasticizer migration preventing effect cannot be obtained. The average particle size of the component (I) is 0.1 μm or less, preferably 0.01 μm or more and 0.08 μm or less. The elongation of the coating film of component (I) is 500% or less, preferably 400% or less, more preferably 3% or more and 300% or less.
The average particle diameter is a value measured by a dynamic light scattering method. Specifically, as a dynamic light scattering measurement device, using a Microtrac particle size analyzer (for example, UPA150, Nikkiso Co., Ltd.), the detected scattering intensity is a value analyzed by the Marquardt method of the histogram analysis method, The measurement temperature is 25 ° C.
Moreover, the elongation of the coating film of component (I) is a value measured by the method of JIS K6301: 1995. The measurement temperature is 20 ° C. However, as a test piece, the coating (Dry) obtained by casting component (I) on a glass plate and drying it under standard conditions (temperature 23 ° C., relative humidity 50%) for 24 hours and further at 80 ° C. for 48 hours. A film having a thickness of 300 μm) punched out into a No. 3 dumbbell piece is used.

  Specifically, as the resin constituting the component (I), for example, vinyl acetate resin, vinyl chloride resin, polyester resin, epoxy resin, acrylic resin, urethane resin, acrylic silicon resin, fluorine resin, or a composite system thereof Can be mentioned. These can be used alone or in combination of two or more. In particular, the component (I) desirably includes a tertiary amine base, a quaternary ammonium base, an acrylic resin having at least one functional group selected from a nitrile group, and / or a polycarbonate urethane resin.

  The acrylic resin having such a functional group can be obtained, for example, by polymerizing an acrylic monomer mixture containing a monomer selected from a tertiary amine base-containing monomer, a quaternary ammonium base-containing monomer, and a nitrile group-containing monomer. .

As the tertiary amine base-containing monomer, a tertiary amino group-containing monomer that has been converted to a tertiary amine salt with an acid or salt can be used. Examples of the tertiary amino group-containing monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and N, N. -Dimethylaminohydroxypropyl (meth) acrylate, N-methyl, N-ethylaminoethyl (meth) acrylate, N, N-diphenylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and the like can be mentioned.
Examples of the quaternary ammonium base-containing monomer include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, and (meth) acryloyl. Oxyethyldiethylbenzylammonium chloride, (meth) acrylamidopropyltrimethylammonium chloride, (meth) acrylamidopropyltriethylammonium chloride, (meth) acrylamidopropyldimethylbenzylammonium chloride, diallyldimethylammonium chloride, diallyldiethylammonium chloride, (meth) acryloyl Oxyethyltrimethylammonium sulfate, etc. And the like.
Examples of the nitrile group-containing monomer include acrylonitrile and methacrylonitrile.

  Examples of acrylic monomers other than the above monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate. In addition to (meth) acrylic acid alkyl esters such as 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate, carboxyl group-containing acrylic monomers, hydroxyl group-containing acrylic monomers, amide group-containing acrylic monomers, epoxy groups Examples thereof include an acrylic monomer containing carbonyl group, an acrylic monomer containing carbonyl group, and an acrylic monomer containing alkoxysilyl group.

Polycarbonate urethane resin is a resin obtained by reaction of polycarbonate polyol and polyisocyanate. The polycarbonate polyol can be obtained by condensation of polyhydric alcohol with phosgene, chloroformate ester, dialkyl carbonate or diallyl carbonate. Examples of the polyisocyanate include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), hydrogenated TDI, hydrogenated MDI, and isophorone diisocyanate (IPDI). ) And the like.
In order to produce a polycarbonate urethane resin by reacting a polycarbonate polyol and a polyisocyanate, a chain extender may be used in combination as necessary. Examples of the chain extender include polyhydric alcohols, aliphatic polyamines, and aromatic polyamines.

  In the present invention, the component (I) may have crosslinking reactivity. When the component (I) is a cross-linking aqueous resin, it is possible to improve the plasticizer migration prevention property, and further the water resistance and adhesion of the coating film. The crosslinking reaction-type aqueous resin may be either one that causes a crosslinking reaction by itself or one that causes a crosslinking reaction by a separately mixed crosslinking agent. Such crosslinking reactivity includes, for example, carboxyl group and metal ion, carboxyl group and carbodiimide group, carboxyl group and epoxy group, carboxyl group and aziridine group, carboxyl group and oxazoline group, hydroxyl group and isocyanate group, carbonyl group and hydrazide group. It can be imparted by combining reactive functional groups such as epoxy groups and amino groups, aldo groups and semicarbazide groups, keto groups and semicarbazide groups, and alkoxyl groups.

In the present invention, organic powder (II) (hereinafter referred to as “component (II)”) is mixed with the component (I). By mixing the component (II), the effect of preventing cracking of the coating film can be obtained. Specifically, as the component (II),
An organic powder (hereinafter referred to as “component (a)”) having an average particle size of 0.1 to 100 μm and a polymer having a Tg of 60 to 60 ° C. and / or an average particle size of 0.1 to 100 μm Yes, an organic powder (hereinafter referred to as “component (b)”) having a core part made of a polymer having a Tg of less than 30 ° C. and a shell part made of a polymer having a Tg of 30 ° C. or higher is used.
The average particle diameter of the component (a) and the component (b) is usually 0.1 to 100 μm, preferably 0.5 to 50 μm, more preferably 1 to 30 μm.

  The polymer of component (a) is formed by copolymerizing various polymerizable monomers. Examples of the polymerizable monomer that can be used include ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, and lauroyl. Examples include alkyl (meth) acrylate styrene such as (meth) acrylate and stearyl (meth) acrylate, aromatic vinyl monomers such as vinyltoluene and α-methylstyrene. A polyfunctional monomer having two or more vinyl groups in the molecule can also be used.

  (A) Tg of a component is -60-60 degreeC normally, Preferably it is -50-50 degreeC, More preferably, it is -40-40 degreeC. (A) Tg of a component can be adjusted by setting suitably the kind and ratio of the monomer which comprise a polymer. When Tg is too high, sufficient performance cannot be obtained in terms of preventing cracking of the coating film, and when Tg is too low, it is disadvantageous in terms of contamination resistance and the like.

  In the present invention, the crack prevention effect can be further enhanced by using the component (b). In this case, the component (a) and the component (b) can be mixed and used.

(B) Tg of the core part of a component is usually less than 30 degreeC, Preferably it is -60-20 degreeC, More preferably, it is -60-10 degreeC. The Tg of the shell part is usually 30 ° C. or higher, preferably 50 to 140 ° C., more preferably 60 to 130 ° C.
In the component (b), as long as the Tg of the core part and the shell part is within a predetermined range, the monomer constituting the polymer is not particularly limited, and the same monomer as the component (a) is used. it can.
The component (a) and the component (b) are both non-film-forming powders and are different materials from the component (I) having film-forming properties.

  The mixing ratio of the component (II) is usually 3 to 400 parts by weight, preferably 4 to 300 parts by weight, more preferably 5 to 200 parts by weight with respect to 100 parts by weight of the solid content of the component (I). When the mixing ratio of the component (II) is within such a range, a sufficient crack prevention effect can be obtained while securing the plasticizer migration preventing property.

In the water-based paint in the present invention, components other than the above-mentioned components can be mixed. Examples of such components include extender pigments, color pigments, aggregates, fibers, thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusting agents, preservatives, and antifungal agents. Algae-proofing agents, antibacterial agents, dispersants, antifoaming agents, ultraviolet absorbers, antioxidants, catalysts, crosslinking agents, adsorbents, and the like can be used.
Among these, if an inorganic powder having an average particle size of 0.1 to 100 μm, a hollow powder, an organic powder (excluding those having a polymer having a glass transition temperature of 60 ° C. or less), etc. are used as extender pigments, While maintaining the effects of the present invention, the matting effect can be enhanced, and the strength and thickness of the coating film, workability during coating, and the like can also be enhanced.

[Coating method]
The present invention is applied to a material containing a plasticizer (sealing material, vinyl interior material, etc.), and can be applied mainly to the interior and exterior of buildings. Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate and butyl benzyl phthalate, dicarboxylic acid adipate, diisodecyl succinate, dibutyl sebacate and butyl oleate, Examples include alcohol esters such as pentaerythritol ester, phosphate esters such as trioctyl phosphate and tricresyl phosphate, and chlorinated paraffin.

  In the present invention, when coating is performed on the sealing material using the water-based paint, it can be carried out as follows.

As the sealing material, those containing a plasticizer are targeted. Specifically, silicone-based sealing materials, modified silicone-based sealing materials, polysulfide-based sealing materials, modified polysulfide-based sealing materials, acrylic urethane-based sealing materials, Examples thereof include a polyurethane sealant, an SBR sealant, and a butyl rubber sealant. These may be either a one-component form or a two-component form.
The method for applying the water-based paint of the present invention onto such a sealing material is not particularly limited. However, when only the surface treatment of the sealing material is intended, the surface of the sealing material and its surroundings are usually applied by brush coating. What is necessary is just to apply about 3-10 mm wider than the laid width. Of course, the entire surface to be coated including the surface of the sealing material can be applied. The coating amount of the water-based paint is usually about 30 to 300 g / m ^{2 in} terms of solid content, although it depends on the form of the water-based paint.

After coating on the sealing material using the water-based paint, a finish coating material can be applied. Such a finish coating material may be any material that can be generally used for painting buildings and the like. For example, JIS
K 5654 “Acrylic resin enamel”, JIS K 5656 “Polyurethane resin paint for construction”, JIS
K 5658 "Fluorine resin paint for construction", JIS K 5660 "Glossy synthetic resin emulsion paint", JIS
K 5663 "Synthetic resin emulsion paint", JIS K 5667 "Multi-color paint", JIS
K 5668 “synthetic resin emulsion pattern paint”, JIS A 6909 “finishing coating material for construction” and the like can be suitably used. In particular, considering the problem of contamination, a hard system is preferable, but an elastic system can also be used depending on the purpose. In addition, before the finish coating material is applied, coating with various undercoat materials can be performed.

  The process interval time until the finish coating material is applied is usually about 2 hours to 7 days. Under the present circumstances, the coating film which does not have a problem of dirt, a crack, a peeling, a swelling, etc. can be formed by coating various finishing coating materials suitably based on each construction specification. In addition, it is also possible to use a large wall construction method by using a putty or a cold chiller as an auxiliary member.

  Moreover, when painting on a vinyl type interior material using the said water-based coating material, it can implement as follows.

Examples of the vinyl interior material include wall materials, ceiling materials, floor materials, and the like that contain a vinyl chloride resin as a main component and further contain a plasticizer. The method for applying the water-based paint of the present invention on such an interior material is not particularly limited, and the entire interior material may be painted using a brush, a spray, a roller, or the like. The coating amount at this time is usually about 30 to 300 g / m ^{2 in} terms of solid content.

After coating on the vinyl interior material using the water-based paint, various finishing coating materials can be appropriately coated based on the respective construction specifications. The process interval time until the finish coating material is applied may be usually about 2 hours to 7 days.
When the water-based paint itself corresponds to, for example, JIS K 5663 “synthetic resin emulsion paint” or the like, finishing can be performed only by applying the water-based paint.

  The present invention can be applied to various materials containing a plasticizer such as a vinyl chloride coated product and a vinyl chloride molded product in addition to the sealing material and the vinyl interior material.

  Examples are given below to clarify the features of the present invention.

(Manufacture of paint)
According to the formulations shown in Tables 1 and 2, paints were produced by mixing and stirring the respective raw materials by a conventional method. The following were used as raw materials.

Aqueous resin 1: methyl methacrylate-styrene-2-ethylhexyl acrylate-methacrylic acid-acrylonitrile copolymer, solid content 50% by weight, average particle size 0.06 μm, elongation 200%
Aqueous resin 2: methyl methacrylate-styrene-2-ethylhexyl acrylate-methacrylic acid-acrylonitrile copolymer, solid content 50% by weight, average particle size 0.1 μm, elongation 700%
Aqueous resin 3: methyl methacrylate-butyl acrylate-methacrylamide propyl trimethyl ammonium chloride copolymer, solid content 50% by weight, average particle size 0.04 μm, elongation 60%
Aqueous resin 4: A mixture of methyl methacrylate-2-ethylhexyl acrylate-diacetone acrylamide-acrylic acid copolymer and adipic acid dihydrazide, solid content 50% by weight, average particle size 0.08 μm, elongation 300%)
Aqueous resin 5: methyl methacrylate-styrene-2-ethylhexyl acrylate-methacrylic acid copolymer, solid content 50% by weight, average particle size 0.15 μm, elongation 1200%
Aqueous resin 6: polycarbonate urethane resin, solid content 30% by weight, average particle size 0.03 μm, elongation 20%
Organic powder 1: acrylic polymer powder (average particle size 8 μm, Tg 20 ° C., specific gravity 1.0)
Organic powder 2: Core-shell type acrylic polymer powder (average particle size 8 μm, core portion Tg-54 ° C., shell portion Tg 105 ° C., specific gravity 1.0)
Organic powder 3: Acrylic polymer powder (average particle diameter 8 μm, Tg 105 ° C., specific gravity 1.0)
・ Defoamer: Silicone-based defoamer

Example 1
Two ceramic siding boards measuring 300 mm in length, 140 mm in width, and 12 mm in thickness were mounted on a slate plate having a length of 300 mm, a width of 300 mm, and a thickness of 3 mm, with an interval of 20 mm. The joints between the boards were filled with a polyurethane sealant (containing 30% by weight of a phthalate ester plasticizer) with a spatula and cured for 7 days. Then, the aqueous coating 1 was spray painted with coat-weight 0.15 kg / ^{m 2,} after 2 hours curing were spray-coated and cured for 14 days of hard acrylic emulsion paint coat-weight 0.3 kg / ^{m 2.} The coating, curing, and the like were all performed under standard conditions (temperature 23 ° C., relative humidity 50%).

The test plate obtained by the above method was left for 7 days in an 80 ° C. environment and then taken out and allowed to cool in a standard state. Next, after placing the test body horizontally and spraying No. 8 black silica sand, the test plate was set up vertically to allow the silica sand to fall naturally. At this time, the plasticizer migration preventing property was evaluated by visually confirming the degree of adhered No. 8 black silica sand (the ratio of the adhered area to the sprinkled area). Evaluation criteria were as follows: ◎: Adhered area 20% or less, ○: Adhered area 20-50%, Δ: Adhered area 50-80%, X: Adhered area 80% or more.
Moreover, about the test body obtained by the said method, after carrying out the total 10 cycles of the warm-cool repetition test which makes water immersion (23 degreeC) 18 hours->-20 degreeC 3 hours-> 50 degreeC 3 hours 1 cycle, Appearance was confirmed. As the evaluation criteria, “O” indicates that the coating film is not cracked, and “X” indicates that the crack is generated.
The test results are shown in Table 3.

(Example 2)
The test was performed in the same manner as in Example 1 except that the water-based paint 2 was used instead of the water-based paint 1. The test results are shown in Table 3.

(Example 3)
The test was performed in the same manner as in Example 1 except that the water-based paint 3 was used in place of the water-based paint 1. The test results are shown in Table 3.

Example 4
The test was performed in the same manner as in Example 1 except that the water-based paint 4 was used instead of the water-based paint 1. The test results are shown in Table 3.

(Example 5)
The test was performed in the same manner as in Example 1 except that the water-based paint 5 was used instead of the water-based paint 1. The test results are shown in Table 3.

(Example 6)
The test was performed in the same manner as in Example 1 except that the water-based paint 6 was used instead of the water-based paint 1. The test results are shown in Table 3.

(Example 7)
The test was performed in the same manner as in Example 1 except that the water-based paint 7 was used instead of the water-based paint 1. The test results are shown in Table 3.

(Example 8)
The test was performed in the same manner as in Example 1 except that the water-based paint 8 was used instead of the water-based paint 1. The test results are shown in Table 3.

Example 9
The test was performed in the same manner as in Example 1 except that the water-based paint 9 was used instead of the water-based paint 1. The test results are shown in Table 3.

(Comparative Example 1)
The test was performed in the same manner as in Example 1 except that the water-based paint 10 was used instead of the water-based paint 1. The test results are shown in Table 4.

(Comparative Example 2)
The test was performed in the same manner as in Example 1 except that the water-based paint 11 was used instead of the water-based paint 1. The test results are shown in Table 4.

(Comparative Example 3)
The test was performed in the same manner as in Example 1 except that the water-based paint 12 was used instead of the water-based paint 1. The test results are shown in Table 4.

(Comparative Example 4)
The test was performed in the same manner as in Example 1 except that the water-based paint 13 was used instead of the water-based paint 1. The test results are shown in Table 4.

(Comparative Example 5)
The test was performed in the same manner as in Example 1 except that the water-based paint 14 was used instead of the water-based paint 1. The test results are shown in Table 4.

Claims (3)

On the surface of the material containing the plasticizer,
100 parts by weight of an aqueous resin (I) having an average particle diameter of 0.1 μm or less and an elongation of the film of 500% or less, in terms of solid content,
Organic powder (a) made of a polymer having an average particle diameter of 0.1 to 100 μm and a glass transition temperature of −60 to 60 ° C. and / or an average particle diameter of 0.1 to 100 μm and a glass transition temperature An aqueous paint comprising 3 to 400 parts by weight of an organic powder (II) comprising an organic powder (b) having a core part comprising a polymer of less than 30 ° C and a shell part comprising a polymer having a glass transition temperature of 30 ° C or higher. A painting method characterized by painting.   The water-based resin (I) in the water-based paint includes a tertiary amine base, a quaternary ammonium base, an acrylic resin having at least one functional group selected from nitrile groups, and / or a polycarbonate urethane resin. The coating method according to claim 1.   The coating method according to claim 1 or 2, wherein the water-based resin (I) in the water-based paint is a cross-linking reaction type water-based resin.