JP2019034985A - Stain coating composition, photocurable coating composition, coating material and manufacturing method of coated body of porous material - Google Patents

Abstract

To suppress blister or fuzz of a substrate in a water-based stain coating composition.SOLUTION: There is provided a stain coating composition containing polyvalent metal cation (A1), a counter anion to polyvalent metal cation (A2), a coloring pigment (B), an aqueous resin (C) and water (D). There is provided a photocurable coating composition for applying to a surface of a porous material coated by a stain coating composition, having a polymerizable monomer having one or two polymerizable functional group and a hydrophilic group in a molecule. There is provided a coating material containing a first container accommodating the stain coating composition and the photocurable coating composition accommodated in the second container.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a stain coating composition, a photocurable coating composition, a coating material, and a method for producing a coated body of a porous material.

As a paint for coloring a porous material such as wood, there is a stain paint composition having permeability to the porous material.
As the stain paint composition, an organic solvent-based one and an aqueous one are known, but recently, an aqueous stain paint composition has been studied from the viewpoint of environmental friendliness.
For example, Patent Document 1 discloses an aqueous stain composition comprising an aqueous resin, a water-dispersed colorant, and a powder of fibrous magnesium silicate minerals.
Patent Document 2 discloses an aqueous stain composition comprising an aqueous resin composed of an acrylic resin having a pH of 7 or less and a water-dispersed colorant, and having a pH of 7 or less. .

JP 2000-109741 A JP 2001-181552 A

As described above, water-based stain coating compositions have been studied from the viewpoint of environmental friendliness.
However, when wood is painted with an aqueous stain coating composition, depending on the type of wood, as shown in the left figure of FIG. 1, some of the wood fibers rise on the surface of the wood and solidify into protrusions. There was a case. Such an event is called “eye blurring”, “fluffing” or the like.
Wood is usually coated with a curable paint (prime coat, intermediate coat, top coat, etc.) for surface protection after applying the stain paint composition. A rough body with a low commercial value is produced. Therefore, when a protrusion is generated, an additional step of polishing the wood surface and scraping the protrusion must be provided before the curable paint is applied repeatedly. Such an additional process causes a cost increase.
Due to such problems, water-based stain paint compositions have been apt to be avoided, and there has been a situation in which organic solvent-based stain paint compositions have to be used even though there are environmental problems. .

  The present invention has been made in view of such circumstances. That is, one of the objects of the present invention is to suppress eye blur or fuzz in an aqueous stain coating composition.

  The inventors of the present invention have made various studies focusing on the components contained in the aqueous stain coating composition. As a result, the inventors have found that the invention provided below can be achieved and the above-described problems can be achieved.

According to the present invention,
A polyvalent metal cation (A1),
A counter anion (A2) of the polyvalent metal cation,
Coloring pigment (B),
Aqueous resin (C) and water (D)
A stain coating composition is provided.

Moreover, according to the present invention,
A photocurable coating composition for application to the surface of a porous material coated with the above-mentioned stain coating composition,
There is provided a photocurable coating composition comprising a polymerizable monomer having one or two polymerizable functional groups and a hydrophilic group in one molecule.

Moreover, according to the present invention,
A coating material comprising a first coating composition contained in a first container and a second coating composition contained in a second container,
The first coating composition is a stain coating composition comprising a polyvalent metal cation (A1), a counter anion (A2) of the polyvalent metal cation, a color pigment (B), an aqueous resin (C) and water (E). ,
There is provided a coating material, wherein the second coating composition is a photocurable coating composition comprising a polymerizable monomer having one or two polymerizable functional groups and a hydrophilic group.

Moreover, according to the present invention,
A porous material coated body comprising a first coating step of coating a porous material with the above-mentioned stain coating composition and a second coating step of coating the porous material with the above-mentioned photocurable coating composition in this order. A manufacturing method is provided.

  According to the present invention, eye blur or fuzz can be suppressed in an aqueous stain coating composition.

It is a photograph for demonstrating "eye blurring". The photograph on the left side of FIG. 1 is a photograph of the wood surface when wood is applied using a conventional aqueous stain paint composition, and many “eye blurs” are generated. The photograph on the right side of FIG. 1 is a photograph of the wood surface when wood is applied using the stain coating composition of the present invention, and a colored wood having a smooth surface without eye blur is obtained.

Hereinafter, embodiments of the present invention will be described in detail.
In the present specification, the notation “ab” in the description of the component amount, temperature, and the like represents from a to b unless otherwise specified.
In the present specification, the expression “(meth) acryl” represents a concept including acrylic and methacrylic unless otherwise specified. The same applies to similar expressions such as “(meth) acrylate”.
Regarding the notation of a group (atomic group) in this specification, the notation that does not indicate substitution or non-substitution includes both those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

<Stain coating composition>
An embodiment of the stain coating composition will be described.
The stain coating composition of the present embodiment includes a polyvalent metal cation (A1), a counter anion (A2) of the polyvalent metal cation, a color pigment (B), an aqueous resin (C), and water (D).

  The stain coating composition of the present embodiment can suppress eye blur or fuzz due to the above configuration. The reason for this is not necessarily clear, but can be explained as follows.

In the conventional water-based stain paint composition, the cause of eye dings and fluffing is that there is a lot of water inside the porous material (especially, when the porous material is wood, the portion that corresponds to the wood conduit). It is thought to invade.
However, when a polyvalent metal cation or its counter anion is present in the aqueous stain coating composition, water permeation into the porous material is moderately suppressed due to osmotic pressure and the like. Presumed. That is, a condition is created in which it is thermodynamically advantageous that the moisture in the wood conduit moves out of the conduit rather than the water in the stain coating composition penetrates into the porous material. The penetration of the stain coating composition is suppressed. As a result, it is presumed that eye blur or fuzz is suppressed.
It should be noted that wood is not a perfect semipermeable membrane, so that a certain amount of the stain coating composition penetrates into the wood regardless of the osmotic pressure.

Here, in theory, the osmotic pressure of an ideal dilute solution depends only on the number of solute molecules present in the solution, and does not depend on the kind of solute (unity property). Therefore, not only the polyvalent metal cation and its counter anion but also an arbitrary substance dissolved in the water-based stain coating composition seems to suppress the penetration of the stain coating composition into wood. However, in this embodiment, when the composition contains a polyvalent metal cation and a counter anion thereof in particular, the effect of suppressing eye burr or fuzzing is remarkably obtained.
The reason for this is not clear, but, for example, (1) water in the composition moderately interacts and associates with the polyvalent metal cation, so that it is difficult for water to penetrate into a porous micro structure such as wood. It is presumed that (2) the material permeability of the cell membrane of wood has some specificity and selectivity.

  In other words, because the composition contains a polyvalent metal cation and its counter anion, the macroscopic properties (osmotic pressure) of the solution change and the micro interaction between the polyvalent metal cation and water or wood causes a blurring. Or it is estimated that the effect of suppression of fuzz is acquired. Such suppression of eye blur or fuzz due to the technical idea is unique to the present invention, which has never been present in the field of stain coating compositions.

  In the field of coating compositions, when the composition contains a polyvalent metal cation or the like, the polyvalent metal cation or the like aggregates components dispersed in the composition, resulting in poor storage stability. Concern such as to be considered. However, according to the knowledge of the present inventors, the stain coating composition of the present embodiment has practically sufficient storage stability, and no significant deterioration in storage stability is observed.

  Further, according to the theory of “vapor pressure drop”, the stain coating composition of this embodiment containing a polyvalent metal cation and its counter anion is a stain coating composition not containing a polyvalent metal cation and its counter anion. Compared to the above, there is a concern that the drying property becomes worse and a practical drying rate cannot be obtained. However, according to the knowledge of the present inventors, the stain coating composition of the present embodiment dries fast enough for practical use, and no significant deterioration in drying property is observed.

  Furthermore, some salts that can be considered as a supply source for the polyvalent metal cation and its counter anion have deliquescence, and there are also concerns from the viewpoint of water resistance. However, according to the knowledge of the present inventors, the water resistance performance of the stain coating composition of this embodiment is not particularly problematic.

  Hereinafter, components that can be contained in the stain coating composition of the present embodiment will be described.

(Polyvalent metal cation (A1) and counter anion (A2))
The stain coating composition of the present embodiment includes a polyvalent metal cation (A1) and a counter anion (A2) of the polyvalent metal cation. Hereinafter, the counter anion (A2) of the polyvalent metal cation is also simply referred to as “counter anion (A2)”.
The polyvalent metal cation (A1) that can be contained in the composition is not particularly limited. The polyvalent metal cation (A1) preferably contains at least one selected from the group consisting of magnesium ions, calcium ions, scandium ions, titanium ions, vanadium ions, chromium ions, manganese ions, strontium ions, and barium ions.

The counter anion (A2) is not particularly limited, but preferably contains at least one selected from the group consisting of chloride ions and bromide ions.
Note that as one embodiment, the counter anion (A2) is preferably a monovalent anion. Thereby, when the amount of the polyvalent metal cation (A1) is constant, the number of ions (number of moles) existing in the system can be increased. In other words, since the osmotic pressure can be further increased, it is considered that the effect of suppressing eye blurring or fluffing can be further obtained.

The lower limit of the amount of the polyvalent metal cation (A1) in the stain coating composition is not particularly limited, but is usually 0.05 mol / 100 g or more, preferably 0.1 mol / 100 g or more, more preferably 0. .15 mol / 100 g or more. It is preferable that the stain coating composition contains a certain amount or more of the polyvalent metal cation because the above-described osmotic pressure effect can be sufficiently obtained.
Further, the upper limit of the amount of the polyvalent metal cation (A1) in the stain coating composition is not particularly limited, but is usually 0.5 mol / 100 g from the viewpoint of cost and balance with other components, etc. Is 0.4 mol / 100 g, more preferably 0.35 mol / 100 g.

  The amount of counter anion (A2) in the stain coating composition is usually an amount that neutralizes the charge of the polyvalent metal cation (A1).

  The stain coating composition may contain only one type of polyvalent metal cation (A1), or may contain two or more types. Moreover, about a counter anion (A2), only 1 type may be included and 2 or more types may be included.

In the present embodiment, a stain coating composition can be usually prepared by dissolving a salt composed of a polyvalent metal cation (A1) and a counter anion (A2) in the composition. Such a salt is available from, for example, Wako Pure Chemical Industries, Ltd.
The amount of the polyvalent metal cation (A1) in the composition is as described above, but the content as a salt is preferably 2 to 40% by mass in the total amount of the composition, More preferably, it is 35 mass%, and it is further more preferable that it is 7-30 mass%.

(Coloring pigment (B))
The stain coating composition of this embodiment contains a color pigment (B).
As the color pigment (B), a known pigment can be appropriately selected according to the color tone to be obtained by painting. For example, white pigments such as titanium white, zinc white, lead white, basic lead sulfate, lead sulfate, lithopone, zinc sulfide, antimony white; carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black Black pigments such as Naphthol Yellow S, Hansa Yellow, Pigment Yellow L, Benzidine Yellow, Permanent Yellow, etc .; Orange pigments such as Chrome Orange, Chrome Vermilion, Permanent Orange; Brown pigments such as Iron Oxide, Amber; Bengala, Red pigments such as red lead, permanent red and quinacridone red pigments; purple pigments such as cobalt violet, fast violet and methyl violet lake, blue pigments such as ultramarine, bitumen, cobalt blue, phthalocyanine blue and indigo; chrome green, pig Cement Green B, and the like green pigment such as phthalocyanine green and the like, nor is it intended to be limited thereto.
For the purpose of adjusting the color, etc., a plurality of types of color pigments (B) may be used in combination.

  If necessary, barita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, hydrous magnesium silicate, alumina white, gloss white, mica powder, etc. The extender pigment may be used.

  The color pigment (B) preferably contains a pigment dispersed by a dispersant. Moreover, as a dispersing agent, it is preferable that a nonionic dispersing agent is included. Thereby, possibility that a color pigment (B) will aggregate by the polyvalent metal cation etc. which are contained in a composition can be reduced further. That is, it can be expected that a more uniform stain coating composition can be obtained, color unevenness during coating can be reduced, and storage stability can be further enhanced.

  The nonionic dispersant is not particularly limited as long as the hydrophilic group is a nonionic dispersant. For example, polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether; polyoxyethylene alkyl phenyl ethers; polyoxyalkylene ethers of sorbitan such as polyoxyethylene sorbitan stearate and / or Or fatty acid esters; oxyalkylene copolymers such as oxyethyleneoxypropylene block copolymers; glycerin polyoxyalkylene ethers such as polyoxyethylene glycerides and / or fatty acid esters.

  The nonionic dispersant may be used in combination with other dispersants (cationic dispersant or anionic dispersant). However, when used in combination, from the viewpoint of obtaining the maximum effect of the nonionic dispersant, the amount of the color pigment dispersed with the cationic dispersant or the anionic dispersant is based on the total amount of the color pigment (B). It is preferable that it is 50 mass% or less, and it is preferable that it is 40 mass% or less. Of course, only a nonionic dispersant may be used as the dispersant.

  As a method for obtaining a colored pigment dispersed by a dispersant, for example, a method of mixing the above-described pigment and dispersant with glass beads, zirconia beads, ceramic balls, and the like and then mixing them with a disperser can be mentioned. Examples of the disperser include a kneader, a roll mill, a ball mill, a paint shaker, a dissolver, an attritor, a sand mill, and a high speed mill.

  Moreover, you may use a commercial item as a color pigment disperse | distributed with dispersing agents, such as a nonionic dispersing agent. For example, trade names EP-130 Yellow (monoazo), EP-910 Yellow FR (disazo), EP-720 Red 2B (naphthol AS), EP-1500 Violet 3RN (dioxazine) manufactured by Dainichi Seika Kogyo Co., Ltd. Series), EP-520 Blue 2B (copper phthalocyanine blue (α)), EP-700 Blue GA (copper phthalocyanine blue (β)), EP-510 Green B (Cl-copper phthalocyanine green), EP-510 Black TR ( Carbon black), EP-65 White (titanium oxide), or the like may be used.

  The content of the color pigment (B) in the stain coating composition is usually 1 to 40% by mass, preferably 1 to 35% by mass, and more preferably 1 to 30% by mass based on the total amount of the composition. This amount represents the amount including the dispersant when the color pigment (B) is dispersed with the dispersant.

(Water-based resin (C))
The stain coating composition of the present embodiment contains an aqueous resin (C), that is, a resin dissolved or dispersed in water.

Examples of the aqueous resin (C) include water-soluble resins such as polyvinyl alcohol, polyacrylamide, polyacrylic acid, and polyacrylate.
1 type of water-soluble resin may be contained in the composition, and may be contained 2 or more types.

Another example of the aqueous resin (C) is resin emulsion particles (fine resin particles dispersed in water).
In the stain coating composition of the present embodiment, the aqueous resin (C) preferably contains resin emulsion particles.

  When the aqueous resin (C) contains resin emulsion particles, specific examples thereof include (meth) acrylic resin emulsion particles, urethane resin emulsion particles, fluororesin emulsion particles, epoxy resin emulsion particles, polyester resin emulsion particles, and alkyd resins. Examples include emulsion particles and melamine resin emulsion particles.

Among these, (meth) acrylic resin emulsion particles are preferable because of high cost and high design freedom. The (meth) acrylic resin emulsion particles may contain only structural units derived from (meth) acrylic monomers, or (meth) acrylic monomers and other monomers (for example, styrene). , Α-methylstyrene, chlorostyrene, and aromatic hydrocarbon vinyl monomers such as vinyltoluene).
Only one kind of resin emulsion particles may be contained in the composition, or two or more kinds thereof may be contained.

As another aspect, the resin emulsion particles may include anionic resin emulsion particles and / or nonionic resin emulsion particles. Among these, the resin emulsion particles preferably include nonionic resin emulsion particles.
Since nonionic resin emulsion particles have a neutral charge, it is considered that the nonionic resin emulsion particles basically do not interact electrostatically with the polyvalent metal cation (A1) or its counter anion (A2). Therefore, it is possible to expect a reduction in the possibility of problems such as aggregation. That is, it can be expected that a more uniform stain coating composition can be obtained, color unevenness during coating can be reduced, and storage stability can be further enhanced.

  When the stain coating composition of the present embodiment includes nonionic resin emulsion particles, 50% by mass or more is preferably nonionic resin emulsion particles, and 70% by mass or more is nonionic resin emulsion in the total amount of resin emulsion particles. More preferably, it is a particle, and 90% by mass or more is particularly preferably a nonionic resin emulsion particle.

  Commercially available products may be appropriately used as the resin emulsion particles. As a commercial item, the Polysol (trademark) series etc. of Showa Denko KK etc. are mentioned, for example.

  The content of the aqueous resin (C) in the stain coating composition is usually 1 to 45% by mass, preferably 2 to 40% by mass, more preferably 4 to 35% by mass, based on the total amount of the composition. In addition, about water-based resin (C), water-soluble resin and resin emulsion particle | grains may be used together.

(Water (D))
The stain coating composition of this embodiment contains water (D). As a result, a stain coating composition having excellent environmental performance can be obtained as described above.
The amount of water (D) in the composition is not particularly limited, but is usually 5 to 95% by mass, preferably 10 to 90% by mass, and more preferably 20 to 80% by mass in the total amount of the composition. Preferably (D) is used.

(Defoamer (E))
It is preferable that the stain coating composition of this embodiment contains an antifoamer (E). Thereby, bubbles in the composition are reduced, and it becomes easy to perform uniform and uniform coating without color unevenness.
As the antifoaming agent, any of a mineral oil-based antifoaming agent, a polyether-based antifoaming agent, a silicone-based antifoaming agent, an acrylic defoaming agent and the like may be used.

  A well-known thing can be used suitably as an antifoamer (E). For example, SN deformer 154, SN deformer 154S, SN deformer 317, SN deformer 777, Nopco 8034, Nopco 8034-L, Nopco DF-122-NS (above, mineral oil-based antifoaming agent) sold by San Nopco Co., Ltd. SN deformer 180, SN deformer 265, SN deformer 396 (polyether antifoaming agent), SN deformer 121N, SN deformer 1311, SN deformer 1312, SN deformer 1314, SN deformer 1315, SN deformer 1316, SN deformer 380 SN deformer 381, SN deformer 391, SN deformer 393, SN deformer 399, SN deformer 5016 (above, silicone antifoaming agent), etc. It is possible.

Moreover, the product numbers OX-880EF, OX-881, OX-883HF, OX-70, OX-77EF, OX-60, OX of Disparon (registered trademark) series, which are acrylic antifoams manufactured by Enomoto Kasei Kogyo Co., Ltd. -710, OX-750HF, AQ-7503, AQ-7533, AQ-7552, etc. can also be used.
When using an antifoamer, only 1 type may be used and 2 or more types may be used.

  When the stain coating composition contains the antifoaming agent (E), the content thereof is usually 0.05 to 15% by mass, preferably 0.1 to 10% by mass with respect to the total amount in the composition.

(Leveling agent (F))
The stain coating composition of this embodiment preferably contains a leveling agent (F). Thereby, it becomes easy to apply | coat a coating composition uniformly.

A well-known thing can be used suitably as a leveling agent (F). Examples thereof include silicone resins such as polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, polyether-modified methylalkylpolysiloxane copolymer, and aralkyl-modified methylalkylpolysiloxane copolymer. Also included are acetylene glycol surfactants (for example, Surfinol (registered trademark) series available from Nissin Chemical Industry Co., Ltd.).
When using a leveling agent (F), only 1 type may be used and 2 or more types may be used.

  When a stain coating composition contains a leveling agent (F), the content is 0.05-15 mass% normally with respect to the whole quantity in a composition, Preferably it is 0.1-10 mass%.

  In addition, depending on the kind of substance, one substance may correspond to both an antifoamer (E) and a leveling agent (F). For example, some products of the Dispalon series manufactured by Enomoto Kasei Kogyo Co., Ltd. have both defoaming performance and leveling performance. When the stain paint composition of this embodiment contains only one such substance, the stain paint composition of this embodiment shall contain both an antifoamer (E) and a leveling agent (F).

(Rheology control agent (G))
The stain coating composition of the present embodiment preferably contains a rheology control agent (G). By using the rheology control agent (G), viscosity and thixotropy can be appropriately adjusted, and unintentional dripping can be reduced or coating properties can be improved.

  As the rheology control agent, for example, a water-soluble polymer can be used. Specifically, gum arabic, arabinogalactan, alginic acid and its salts, curdlan, gutty gum, carrageenan, caraya gum, agar, xanthan gum, guar gum, enzymatic degradation guar gum, quince seed gum, gellan gum, gelatin, tamarind seed gum, difficulty Digestible dextrin, tragacanth gum, fercellan, pullulan, pectin, polydextrose, galactomannan, locust bean gum, water-soluble soybean polysaccharide, carboxymethylcellulose, metal salt of carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, sodium polyacrylate, etc. Water-soluble polymers can be used as rheology control agents.

Examples of the rheology control agent include products of BYK Japan, Inc., trade names BYK-410, BYK-E410, BYK-415, BYK-420, BYK-E420, BYK-D410, BYK-430, and the like. Yes ("BYK" is a registered trademark).
When using a rheology control agent (G), only 1 type may be used and 2 or more types may be used.

  When a stain paint composition contains a rheology control agent (G), the content is 0.05-15 mass% normally with respect to the whole quantity of a composition, Preferably it is 0.1-10 mass%.

(Preservative (H))
The stain coating composition of the present embodiment preferably contains a preservative (H). Thereby, improvement of the storage stability of the stain coating composition can be expected.

As the preservative (H), known ones can be used without particular limitation. For example, organic nitrogen sulfur compound type preservatives, organic sulfur halide type preservatives and the like can be mentioned.
When using a preservative (H), only 1 type may be used and 2 or more types may be used.

  When the stain coating composition contains a preservative (H), the content is usually 0.05 to 15% by mass, preferably 0.1 to 10% by mass, based on the total amount of the composition.

  Note that, as a precaution, the stain coating composition of the present embodiment does not exclude the inclusion of components other than those described above. For example, it may contain known thickeners, plasticizers, drying regulators, ultraviolet absorbers, antioxidants, fungicides, preservatives, film-forming aids, and the like.

(Physical properties of stain coating composition)
The physical properties of the stain coating composition of the present embodiment may be appropriately adjusted according to the desired coating properties, the surface properties of the base material (porous material) to be coated, and the like.
For example, the viscosity of the composition is not particularly limited, and may be appropriately adjusted by using the rheology control agent (G) described above.
As another aspect, the pH of the composition is not particularly limited. Unless it is extremely acidic or alkaline, any pH (for example, about pH 4 to 10) may be used.

<Photocurable coating composition>
An embodiment of the photocurable coating composition will be described.
The photocurable coating composition of the present embodiment is for application to the surface of a porous material coated with the aforementioned stain coating composition, and one or two polymerizable functional groups in one molecule. And a polymerizable monomer having a hydrophilic group (hereinafter also referred to as “specific monomer”).

In the painting of porous materials such as wood, after painting (coloring) with a stain paint composition, additional painting is performed using a photocurable paint composition or the like for the purpose of surface protection or waterproofing. . This additional painting is also called “priming”.
For purposes such as surface protection and waterproofing, it is desirable that the photocurable coating composition is sufficiently adhered to the surface of the porous material.

  As described above, the above-mentioned stain coating composition can be expected to suppress eye blurring and fuzzing. However, according to the knowledge of the present inventors, when the surface of the porous material coated with the above-mentioned stain coating composition is coated with a conventional photocurable coating composition, sufficient adhesion is obtained. It may not be obtained. The details of why sufficient adhesion cannot be obtained are unknown, but penetration of the photocurable coating composition into the porous material is hindered by polyvalent metal cations or salts existing inside the porous material. It is presumed that this is due.

  The present inventors have studied a photocurable coating composition that can provide sufficient adhesion even when the porous material is coated with the above-described stain coating composition. As a result of examination, sufficient adhesion could be obtained by using a photocurable coating composition containing a specific monomer. Details of the reason why this good result was obtained are not necessarily clear, but can be explained as (1) and (2) below.

(1) When the porous material contains a polyvalent metal cation or salt, it is considered that water molecules such as hydrated water exist around the cation or salt. Therefore, it is estimated that sufficient adhesion can be obtained by using a polymerizable monomer having a group that interacts with the water molecule (that is, a hydrophilic group).

(2) If the number of polymerizable functional groups in one molecule of the polymerizable monomer is too large, shrinkage of the coating film during curing becomes too large, and the coating film may be easily peeled off. Also, when the porous material is wood in particular, the coating film is required to be flexible enough to follow the expansion / contraction of the wood (depending on temperature and humidity). If the number of polymerizable functional groups is too large, the cured film will be It may become too hard to obtain sufficient flexibility. By reducing the number of polymerizable functional groups in one molecule of the polymerizable monomer (specifically, 1 or 2 and not 3 or more), shrinkage of the coating film during curing can be suppressed. It is considered that a moderate flexibility of the cured film can be obtained. As a result, it is estimated that sufficient adhesion can be obtained.

  From the viewpoint of (2) above, the number of polymerizable functional groups that the specific monomer has in one molecule is more preferably one.

A specific embodiment of the specific monomer will be described.
The polymerizable functional group possessed by the specific monomer is not particularly limited as long as it is a known functional group exhibiting polymerizability. Specific examples include a group containing an ethylenic double bond (such as a vinyl group and a (meth) acryloyl group), an epoxy group, and an oxetane group. A group containing an ethylenic double bond is preferred.

Examples of the hydrophilic group possessed by the specific monomer include a nitrogen atom-containing group, a hydroxy group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and a polyoxyethylene group. Among these, from the viewpoint of the balance between availability and performance (adhesion), it is preferably any of a nitrogen atom-containing group, a hydroxy group and a polyoxyethylene group.
Here, the “nitrogen atom-containing group” includes an amino group (a monovalent functional group obtained by removing hydrogen from ammonia, a primary amine or a secondary amine), or a monovalent group obtained by removing hydrogen from a nitrogen-containing heterocyclic compound. Examples of the functional group include: an atomic group containing an amide bond.

  More specifically, the specific monomer is preferably a compound corresponding to any of the following general formulas (m-1) to (m-4).

In general formula (m-1),
R is a hydrogen atom or a methyl group;
R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group, and R ¹ and R ² may be bonded to each other to form a ring structure;
A is a divalent organic group,
a is 0 or 1,
b is 0 when a is 0, and 0 or 1 when a is 1.

Examples of the monovalent organic group for R ¹ and R ² include an alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group (preferably having 6 to 10 carbon atoms). And an aralkyl group (preferably having 7 to 11 carbon atoms).
When R ¹ and R ² are bonded to each other to form a ring structure, the ring structure is preferably a 5- to 8-membered ring, and more preferably a 5- to 6-membered ring. In addition to the N atom shown in the formula, the ring structure may contain a heteroatom such as an O atom.
Examples of the divalent organic group for A include an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an arylene group (preferably having 6 to 10 carbon atoms), a carbonyl group, Examples thereof include an ester group, an ether group, and a group in which these are linked.

In general formula (m-2),
R is a hydrogen atom or a methyl group;
X is an ester group (—COO—) or an amide group (—CONH—),
A is an (n + 1) -valent organic group,
a is 0 or 1,
n is an integer of 1 or more.

X is preferably an ester group (—COO—).
About the (n + 1) valent organic group of A, when n = 1, the same thing as A in General formula (m-1) is mentioned. Moreover, in the case of n = 2 or 3, the group which remove | eliminated one or two hydrogen atoms further from the bivalent group demonstrated as A in general formula (m-1) is mentioned.
a is preferably 1.
n is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.

In general formula (m-3),
R is a hydrogen atom or a methyl group;
R ¹ is a hydrogen atom or a monovalent organic group,
n is an integer of 2 or more.

Examples of the monovalent organic group for R ¹ include the same groups as those for R ¹ in formula (m-1).
n is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 15.

In general formula (m-4),
Each R is independently a hydrogen atom or a methyl group;
n is an integer of 2 or more.

  n is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 15.

  Specific examples of the specific monomer are listed. The specific monomer is not limited to these.

Specific monomers having nitrogen atom-containing groups as hydrophilic groups N-methyl (meth) acrylamide, N-methylol (meth) acrylamide butyl ether, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N- Isopropyl (meth) acrylamide, N-cyclopropyl (meth) acrylamide, diacetone (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methyl, N-ethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-methylol (meth) acrylamide methyl ether, N-methylol (methyl) T) Acrylamide ethyl ether, N-methylol (meth) acrylamide propyl ether, (meth) acryloylmorpholine, N-vinyl-2-pyrrolidone.

Specific monomers having a hydroxy group as a hydrophilic group: hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate.

Specific monomers having a polyoxyethylene group as a hydrophilic group: tetraethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, n-butoxytriethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, and polyethylene glycol di (meth) acrylate.

-Specific monomers having hydrophilic groups other than the above (meth) acrylic acid, 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxyethyl phosphate, 2- (meth) acryloyloxyethyl succinic acid 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meta Acryloyloxyethyl-succinic acid.

Only 1 type may be used for a specific monomer and it may use 2 or more types together.
The content of the specific monomer in the photocurable coating composition is preferably 10 to 85 mass%, more preferably 15 to 70 mass%, based on the coating film forming component (nonvolatile component) in the composition.

  In addition to the specific monomer, components that may be contained in the photocurable coating composition of the present embodiment will be described.

(Photopolymerization initiator)
The photocurable coating composition of this embodiment preferably contains a photopolymerization initiator. The photopolymerization initiator preferably contains a radical photopolymerization initiator.
As the photopolymerization initiator, known ones such as alkylphenone photopolymerization initiators, acylphosphine oxide photopolymerization initiators, intramolecular hydrogen abstraction photopolymerization initiators, and oxime ester photopolymerization agents should be used as appropriate. Can do.

Specific examples of the photopolymerization initiator include, for example, IRGACURE 651, IRGACURE 184, IRGACURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369ERU, IRGACURE 379UREG, IRGACURE 379UREG, IRGACURE 379 EGEG, IRGACURE 379 IRGACURE MBF, IRGACURE 754, IRGACURE OXE 01, IRGACURE OXE 02, and the like.
Only 1 type may be used for a photoinitiator and it may use 2 or more types together.

  The content of the photopolymerization initiator is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and further preferably 3 to 10% by mass based on the coating film forming component (nonvolatile component) in the composition. It is.

(resin)
The photocurable coating composition of this embodiment preferably contains a resin. When a photocurable coating composition contains resin, it becomes easy to obtain the composition which has moderate applicability with moderate viscosity. Moreover, it becomes easy to improve the performance (adhesion and water resistance) as a coating film.

  The resin preferably has a polymerizable group. As a result, the resin is also directly involved in the curing reaction, and effects such as improved adhesion are expected. In addition, as a polymeric group here, the thing similar to the polymeric group which the above-mentioned specific monomer has is mentioned.

Examples of the resin having a polymerizable group include urethane (meth) acrylate and epoxy (meth) acrylate. Of these two types, urethane (meth) acrylate is particularly preferable from the viewpoint of the flexibility of the coating film.
When the resin has a polymerizable group, the number of polymerizable groups per resin chain is preferably 2 to 10, more preferably 2 to 6, and further preferably 2 to 4.

The weight average molecular weight of the resin is preferably 250 to 1,000,000, more preferably 500 to 500,000, and still more preferably 700 to 100,000.
Resins such as urethane (meth) acrylate are commercially available from Daicel Ornex Co., Ltd. under the product name EBECRYL series.

  When the photocurable coating composition contains a resin, the amount thereof is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on the coating film forming component (nonvolatile component) in the composition. .

(External pigment)
The photocurable coating composition of this embodiment may contain extender pigments. By including the extender pigment in the photocurable coating composition, the concentration (density) of the polymerizable group in the composition can be reduced. If it does so, an excessive polymerization reaction can be suppressed and the effect that it becomes easy to obtain a more flexible coating film as a result can be anticipated. In addition, extender pigments are advantageous because they do not significantly affect the color.

As the extender pigment, known pigments can be appropriately used. For example, silica sand, diatomaceous earth, talc, barium sulfate, barium carbonate, heavy calcium carbonate, light calcium carbonate, calcium carbonate whisker, aluminum borate whisker, clay, porcelain clay, zinc white, kaolin and the like can be mentioned.
The extender pigment may be used alone or in combination of two or more.

  The content of the extender is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, based on the coating film forming component (nonvolatile component) in the composition.

(Other ingredients)
The photocurable coating composition of the present embodiment includes components other than those described above, for example, an ultraviolet absorber, a light stabilizer, an organic solvent, a thickener, an antifoaming agent, a plasticizer, a dispersant, an antiseptic, and a rust inhibitor. Etc. may be appropriately included depending on the purpose.
The photocurable coating composition contains a polymerizable compound having no hydrophilic group and a polymerizable compound having three or more polymerizable groups in one molecule as long as sufficient adhesion and the like are exhibited. May be.

As a precaution, the stain coating composition of the present embodiment is combined with a photocurable coating composition that is not a photocurable coating composition or a coating composition that is not photocurable. It may be used.
In the description up to the previous paragraph, as one of the findings of the present inventors, it is possible to use a photocurable coating composition containing a specific monomer in combination with the above-described stain coating composition, such as adhesion of an undercoat layer. It only stated that it was preferable in terms of points. It is not denied that a photocurable coating composition other than the above is used in combination with the above-mentioned stain coating composition.
Moreover, about said photocurable coating composition, it uses independently (it is not combined with a stain coating composition), or a stain coating composition other than having demonstrated above (for example, a stain coating which does not contain a polyvalent metal cation) Use in combination with the composition) is not denied.

<Paint materials>
An embodiment of the coating material will be described.
The coating material of this embodiment is
A coating material comprising a first coating composition contained in a first container and a second coating composition contained in a second container,
The first coating composition is a stain coating composition comprising a polyvalent metal cation (A1), a counter anion (A2) of the polyvalent metal cation, a color pigment (B), an aqueous resin (C) and water (E). Yes,
The second coating composition is a photocurable coating composition containing a polymerizable monomer having one or two polymerizable functional groups and a hydrophilic group.

Here, the first coating composition is the composition described above as <stain coating composition>. Further, the second coating composition is the composition described above as <photocurable coating composition>.
According to the coating material containing the first coating composition and the second coating composition, it is possible to suppress eye blur or fuzz when coloring a porous material such as wood. Further, after coloring the porous material, an undercoat layer having high adhesion can be provided on the surface of the porous material. That is, by using the coating material of the present embodiment, a porous material coated body having a high commercial value can be obtained.

<Manufacturing method of coated body of porous material>
Embodiment of the manufacturing method of the coating body of a porous material is described.
The manufacturing method of the coated body of the porous material of the present embodiment,
A first coating step for coating the porous material with the above-described stain coating composition and a second coating step for coating the porous material with the above-described photocurable coating composition are included in this order.

  Specific embodiments of the “stain coating composition” and “photocurable coating composition” are as described above. By the first painting step, the porous material can be colored while suppressing the irregularity or fluffing of the porous material. Moreover, an undercoat layer with good adhesion can be provided by the second coating step.

The porous material will be described.
The porous material should just be porous at least in the surface (surface which applies a coating material). Typical porous materials include wood, paper, concrete, cement products and the like. In the present embodiment, the porous material preferably includes wood or paper, and more preferably includes wood.
The shape of the porous material is not particularly limited, and may be a plate shape, a sheet shape, a rod shape, or any other shape.

  When the porous material includes wood, the porous material may be a plywood, that is, a plate-like material having a sliced thin wood (commonly called a veneer) attached to the surface.

  In particular, a plywood having a protruding plate thickness of 0.25 mm or more (more specifically, 0.25 to 5 mm) has a high-grade appearance and texture close to natural wood. There was a problem that fuzz was likely to occur. This is because when the veneer is thin, such as less than 0.25 mm, the adhesive when producing the plywood penetrates into the veneer and the conduit is fixed by the adhesive, etc. On the other hand, when the thickness of the veneer is 0.25 mm or more, the adhesive is difficult to penetrate to the surface of the veneer, and the nature of the wood itself is likely to appear on the surface of the plywood.

However, according to the method for manufacturing a coated body of the porous material of the present embodiment, even for the plywood having the above-described protruding plate, it is possible to effectively suppress the eyes blisters or fuzzing. In other words, the commercial value of plywood with a high-class feeling can be further increased by painting.
The wood used for the veneer includes zelkova, oak, yachidamo, drill, hinoki, cedar, mahogany, walnut, oak, teak, rosewood, tochi, blackboard, shioji, elm, hippo and the like.

  The porous material may be natural wood that is not plywood. Also in this case, eye blurring or fluffing has been easy to occur in the past, but by applying coating based on the method of the present embodiment, eye blurring or fluffing can be suppressed.

The method of coating the stain coating composition on the surface of the porous material in the first coating step and the second coating step is not particularly limited, and may be any method such as roll coating, spray coating, and brush hand coating. Good. In particular, when the porous material has a flat plate shape, roll coating is preferable from the viewpoint of mass productivity and uniform coating.
As an apparatus for roll coating, those known in this technical field can be appropriately used.

In the first coating step, the coating amount of the stain coating composition is not particularly limited as long as the desired coloring is achieved. However, from the viewpoint of obtaining sufficiently dark coloring while reliably obtaining the effects of the present invention (suppression of eye blur or fuzz), for example, a polyvalent metal salt (polyvalent metal cation and counter anion per 1 m ^{2 of} coated area). It is preferable to adjust the coating amount of the stain coating composition so that the mass of Further, the coating amount as a whole stain coating composition is preferably a coating area 1 m ² per 5.0～100G, more preferably 10~50g per coating area 1 m ^2.

The method for producing a porous material coated body of the present embodiment may include a third coating step for providing an intermediate coating layer and a fourth coating step for providing a top coating layer after the second coating step.
Examples of paints that can be used in the third coating process and the fourth coating process include paints similar to those described in the above <photocurable paint composition>, that is, polymerizable monomers, photopolymerization initiators, resins, and the like. A photocurable coating composition is mentioned.

The application amount of each paint in the second to fourth coating steps can be adjusted as appropriate.
As an example, the coating amount of the coating material in the second coating step is preferably 20 to 80 g / ^{m 2,} and more preferably 25~70g / ^{m 2.}
Further, the coating amount of the coating material in the third coating step and the fourth coating step is preferably 3~30g per 1 m ^2, and more preferably 5~20g per 1 m ^2.

  It is preferable to provide a drying (curing) step before and after each coating step. For example, it is preferable to apply hot air (about 30 to 150 ° C.) to the surface of the porous material to dry the volatile component (water) after the first coating step and before the second coating step. The time for this step is, for example, about 10 seconds to 30 minutes. Moreover, in the 2nd-4th coating process, it is preferable to accelerate | stimulate hardening of a coating film by irradiating an ultraviolet light using an ultraviolet lamp etc. after application | coating of a photocurable coating composition. The irradiation time of ultraviolet rays is, for example, 0.1 second to 1 minute.

In addition to the drying (curing) step, there may be a step of physically and mechanically removing excess paint. For example, there may be a process of scraping excess paint with a reverse roll.
Furthermore, before and after each coating step, there may be a polishing step using polishing paper or the like.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and can employ | adopt various structures other than the above. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  Embodiments of the present invention will be described in detail based on examples and comparative examples. In addition, this invention is not limited to an Example.

1. Preparation and Evaluation of Stain Paint Composition (Preparation of Composition of Example 1-1)
First, 52 parts by mass of pure water, 20 parts by mass of calcium chloride, and 13 parts by mass of an acrylic ester resin aqueous emulsion (manufactured by Showa Denko KK, Polysol AE-710WF, resin solid content 41 to 44% by mass) are mixed, Stir for 30 minutes.

  Next, a white pigment aqueous dispersion (manufactured by Dainichi Seika Co., Ltd., EP-65 white, content of titanium oxide 55 to 60% by mass, containing nonionic surfactant and anionic surfactant) is added to the above mixture. 5 2 parts by mass of red pigment aqueous dispersion (manufactured by Dainichi Seika Co., Ltd., EP-1100 Red FGN, condensed azo red content 31% by mass, nonionic surfactant), yellow pigment aqueous dispersion (Daisen Seika Co., Ltd.) 4 parts by mass, EP-910 Yellow FR, disazo yellow content 24% by weight, nonionic surfactant content, and black pigment aqueous dispersion (manufactured by Dainichi Seika Co., Ltd., EP-510 Black TR, carbon) 1 part by weight of black content 37% by mass and nonionic surfactant) was mixed and further stirred for 30 minutes.

  Thereafter, 1 part by mass of an antifoaming agent (manufactured by Enomoto Kasei Co., Ltd., Disparon AQ-7552, non-silicone antifoaming agent) and a leveling agent (manufactured by Nissin Chemical Industry Co., Ltd., Surfynol 104E, non-silicone level) 1 part by mass of a ring agent) and 1 part by mass of a thickener (xanthan gum) were added and stirred for 30 minutes to obtain a stain coating composition of Example 1-1.

(Preparation of compositions of Examples 1-2 to 1-17 and Comparative Examples 1-1 to 1-5)
According to the process of Example 1-1, a stain coating composition having the component composition shown in Tables 1 to 4 was obtained.
Tables 1 to 4 also list the metal cation concentration in each composition (assuming that the total amount of metal salt used was ionized).

(Evaluation of paint stability: Average particle diameter change rate of colored pigment)
Each stain coating composition was diluted 1000 times with water, and a water refraction index of 1.33 and a liquid temperature of 25 using a granulometer (model number: Zetasizer Nano ZSP) manufactured by MALVERN using a dynamic light scattering method. The average particle diameter P of the pigment was measured under the condition of ° C.
In addition, for each stain coating composition, without using the polyvalent metal salt in the composition, prepared by replacing the polyvalent metal salt with the same mass of pure water, also in the same measurement conditions as described above The average particle size Q of the pigment was measured.
Then, R defined by the following equation was calculated from P and Q.
R = {(PQ) / Q} × 100
Evaluation was performed based on the following criteria using the value of R. A smaller R means that the change in the particle size of the pigment is small (that is, the pigment does not aggregate), and the coating composition is stable.

5: R is less than 10 4: R is 10 or more and less than 20 3: R is 20 or more and less than 40 2: R is 40 or more and less than 60 1: R is 60 or more

(Evaluation of eye blurring and fluffing)
Roll coater with plywood (2 mm thick oak veneer pasted on the surface, total thickness 12 mm) and the coating composition of each example and comparative example to a coating amount of 33 g / m ² respectively. Painted with Thereafter, drying was performed with hot air at 100 ° C. for 60 seconds to obtain a colored plywood. Each obtained plywood was visually observed, and the condition of the presence or absence of eye burr and fuzz on the surface of the plywood was evaluated according to the following criteria.

5: Neither eyes blur nor fuzz is observed at all.
4: Although eye blurring or fluffing is observed, it is observed that it is less than 5% of the conduit area.
3: Eye blurring or fluffing is observed in a region of 5% or more and less than 20% of the conduit area.
2: Eye blurring or fluffing is observed in a region of 15% or more and less than 50% of the conduit area.
1: Eye blurring or fluffing is observed in a region of 50% or more of the conduit area.

  In this evaluation, the stain coating composition of any Example was sufficiently dried by drying with hot air at 100 ° C. for 60 seconds.

  Details, sources, etc. of the components described in Tables 1 to 4 are as follows.

Metal salt:
-Calcium chloride: Wako Pure Chemical Industries, Ltd.-Barium chloride: Wako Pure Chemical Industries, Ltd.-Magnesium chloride: Wako Pure Chemical Industries, Ltd.-Manganese (II) chloride tetrahydrate: Wako Pure Chemical Industries, Ltd., bromide Calcium: Wako Pure Chemical Industries, Ltd./Ammonium chloride: Wako Pure Chemical Company
-Potassium chloride: Wako Pure Chemical Industries, Ltd.-Sodium chloride: Wako Pure Chemical Industries, Ltd.

Aqueous resin:
Polysol AE-710WF: Showa Denko Co., Ltd., acrylic ester copolymer aqueous emulsion (nonionic, resin solid content 41-44 mass%)
Polysol AP-815N: Showa Denko Co., Ltd., acrylic ester copolymer aqueous emulsion (nonionic, resin solid content 55-57 mass%)
Polysol AP-7681: Styrene acrylate copolymer aqueous emulsion manufactured by Showa Denko Co., Ltd. (anionic, resin solid content 46-50 mass%)

Colored pigment dispersion:
EP-65 White: manufactured by Dainichi Seika Kogyo Co., Ltd., white pigment aqueous dispersion (dispersed with a titanium oxide content of 55-60% by mass, nonionic surfactant and anionic surfactant)
EP-1100 Red FGN: manufactured by Dainichi Seika Kogyo Co., Ltd., red pigment aqueous dispersion (condensed azo red content 31% by mass, dispersed with nonionic surfactant)
EP-910FR Yellow FR: manufactured by Dainichi Seika Kogyo Co., Ltd., yellow pigment aqueous dispersion (disazo yellow content 24% by weight, dispersed with nonionic surfactant)
EP-510 Black TR: manufactured by Dainichi Seika Kogyo Co., Ltd., black pigment aqueous dispersion (carbon black content: 37% by mass, dispersed with nonionic surfactant)

Dispalon AQ-7552: manufactured by Enomoto Kasei Co., Ltd., non-silicon antifoaming agent (active ingredient 100% by mass)
Surfynol 104E: manufactured by Nissin Chemical Industry Co., Ltd., acetylene glycol compound (active ingredient 100% by mass)
Xanthan gum: manufactured by Sanki Co., Ltd., KELZAN (product name) (active ingredient 100% by mass)

  As shown in Tables 1 to 3, the stain coating compositions of Examples 1-1 to 1-17 containing a polyvalent metal cation are capable of suppressing the aggregation of pigments, and are also effective when the plywood is coated. And fuzz were highly suppressed. On the other hand, as shown in Table 4, the stain coating composition of Comparative Examples 1-1 to 1-5 that does not contain a polyvalent metal cation (does not contain a metal salt itself or contains a monovalent metal cation). Could not sufficiently suppress the occurrence of eye blurring and fuzzing.

2. Preparation and evaluation of photocurable coating composition (Preparation of photocurable coating composition (for undercoat))
Each component shown as "the composition of a photocurable coating composition (for undercoat)" in Tables 5 to 8 was mixed and stirred for 1 hour to obtain a photocurable coating composition (for undercoat). .

(Preparation of photocurable coating composition (for intermediate coating))
55 parts by mass of epoxy acrylate (manufactured by DIC Corporation, V-5500), 30 parts by mass of tripropylene glycol diacrylate, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by BASF, Irgacure 1173) 5 parts by mass and 10 parts by mass of talc (product name MS-P, manufactured by Nippon Talc Co., Ltd.) were mixed and stirred for 1 hour to obtain a photocurable coating composition (for intermediate coating).

(Preparation of photocurable coating composition (for top coating))
20 parts by mass of urethane acrylate (manufactured by Daicel Ornex, EBECRYL 4858), 30 parts by mass of trimethylolpropane ethoxytriacrylate (manufactured by Daicel Ornex, TMPEOTA), 20 parts by mass of tripropylene glycol diacrylate, acryloylmorpholine (KJ Chemicals) ACMO (registered trademark) 20 parts by mass, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (BASF, Irgacure 1173) 5 parts by mass, and silica (Fuji Silysia Chemical Ltd.) 5 parts by mass were mixed and stirred for 1 hour to obtain a photocurable coating composition (for top coating).

(Creation of test plates: Examples 2-1 to 2-14, Comparative examples 2-1 to 2-4, Reference examples 2-1 to 2-9)
Roll the plywood (with a 2 mm thick oak veneer pasted on the surface, total thickness 12 mm) with the stain coating composition shown in Tables 5 to 8 so that the coating amount is 33 g / m ² It was painted using a coater. Thereafter, drying was performed with hot air at 100 ° C. for 60 seconds to obtain a colored plywood.

The obtained plywood was coated with a photocurable coating composition (for undercoating) having the composition shown in Tables 5 to 8 so that the coating amount was 44 g / m ² . This was irradiated with ultraviolet rays (irradiation dose of 100 mJ / cm ² ) to cure the coated composition.

Next, the photocurable coating composition (for intermediate coating) was applied so that the coating amount was 11 g / m ² . This was irradiated with ultraviolet rays (irradiation dose 100 mJ / cm ² ) to cure the coated composition. The cured film on the obtained plywood was polished with # 320 water-resistant abrasive paper.

And said photocurable coating composition (for topcoat) was apply | coated so that the application quantity might be 11 g / m < ² >. This was irradiated with ultraviolet rays (irradiation dose of 300 mJ / cm ² ) to cure the coated composition.

  Then, it left still at room temperature for 24 hours, and the test board provided with 3 layers of cured films of a photocurable coating composition was obtained.

(Adhesion evaluation)
About each obtained test board, the adhesion test based on JISK5600-5-6 (1999) "Mechanical property of a coating-adhesion (cross-cut method)" was done, and it evaluated based on the following evaluation criteria.
5: The edges of the cut are completely smooth and there is no peeling in any lattice eye.
4: There is a small peeling of the coating film at the cut intersection, and the area of the peeled portion is less than 5%.
3: The area of the peeled portion is 5% or more and less than 15%.
2: The area of the peeled portion is 15% or more and less than 35%.
1: The area of the peeled portion is 35% or more.

(Water resistance evaluation)
Each test plate (cut to 150 mm × 150 mm × 12 mm in size) was immersed in water at 20 ° C. 24 hours after the start of immersion, the test plate was taken out of water, dried at 60 ° C. for 2 hours, and gradually cooled at room temperature for 2 hours. Using the test plate (test plate for water resistance evaluation) obtained by this series of steps, the following appearance evaluation and adhesion evaluation (after the water resistance test) were performed.

Appearance evaluation: The state of the coating film on the test plate for water resistance evaluation was visually observed and evaluated based on the following criteria.
5: There is no whitening at all.
4: Although whitening is observed, the area is less than 5%.
3: The whitened area is 5% or more and less than 25%.
2: The whitened area is 25% or more and less than 50%.
1: The whitened area is 50% or more.

Adhesion evaluation (after water resistance test): JIS K5600-5-6 (1999) “Mechanical properties of coating film” was applied to the test plate for water resistance evaluation in the same manner as in (Adhesion evaluation) described above. An adhesion test based on “adhesiveness (cross-cut method)” was performed and evaluated based on the following criteria.
5: The edges of the cut are completely smooth and there is no peeling in any lattice eye.
4: There is a small peeling of the coating film at the cut intersection, and the area of the peeled portion is less than 5%.
3: The area of the peeled portion is 5% or more and less than 15%.
2: The area of the peeled portion is 15% or more and less than 35%.
1: The area of the peeled portion is 35% or more.

  Details of the compounds used in the preparation of the photocurable coating compositions (for undercoating), photocurable coating compositions (for intermediate coating) and photocurable coating compositions (for topcoating) in Tables 5 to 8 and their sources Etc. are as follows.

Urethane acrylate: Daicel Ornex Co., Ltd., trade name EBECRYL210

・ Dimethylacrylamide: KJ Chemicals Co., Ltd. ・ N-Vinyl-2-pyrrolidone: Nippon Shokubai Co., Ltd. ・ Acroylmorpholine: KJ Chemicals Co., Ltd. ・ Hydroxyethyl acrylate: Osaka Organic Chemical Industry Co., Ltd. ・ Hydroxypropyl acrylate : Osaka Organic Chemical Industry Co., Ltd., 4-Hydroxybutyl Acrylate: Osaka Organic Chemical Industry Co., Ltd., Polyethylene Glycol Diacrylate: Kyoeisha Chemical Co., Ltd., trade name Light Acrylate 9EG-A
・ Isobornyl acrylate: Osaka Organic Chemical Industry Co., Ltd. ・ Tripropylene glycol diacrylate: Daicel Ornex Co., Ltd.

・ Talc: Made by Nippon Talc Co., Ltd., product name MS-P

Irgacure 1173: manufactured by BASF, 2-hydroxy-2-methyl-1-phenyl-propan-1-one

As shown in Tables 5 and 6, the porous material coated with a stain coating composition (Examples 1-8 and 1-9) containing a polyvalent metal cation, its counter anion, a color pigment, an aqueous resin and water. Undercoat with a photocurable coating composition (for undercoat) containing a specific monomer (polymerizable monomer having one or two polymerizable functional groups and a hydrophilic group in one molecule) When done, good results were obtained for adhesion and water resistance (Examples 2-1 to 2-14).
In particular, as can be seen from the comparison between Example 2-14 and Examples 2-8 to 2-13, by using a compound having only one polymerizable group in one molecule as a specific monomer, Better water resistance was obtained than when a specific monomer having two polymerizable groups was used.

  On the other hand, as shown in Table 7, a porous material coated with a stain coating composition (Example 1-8 and Example 1-9) containing a polyvalent metal cation, its counter anion, a color pigment, an aqueous resin and water. When the material was undercoated with a photocurable coating composition having no hydrophilic group (for undercoating), sufficient adhesion was not obtained (Comparative Examples 2-1 to 2-4).

  As shown in Table 8, the porous material coated with the stain coating composition containing no polyvalent metal cation was primed with a photocurable coating composition (for undercoating) containing a specific monomer. In this case, good adhesion and water resistance are obtained (Reference Examples 2-1 to 2-9).

3. Evaluation of combination of stain coating composition and photocurable coating composition Stain coating composition of this embodiment (containing polyvalent metal cations, etc.) and photocurable coating composition of this embodiment (containing specific monomers, etc.) Further examples show that adhesion and water resistance are good when used in combination.

Stain paint compositions of Examples 1-1 to 1-17 and Comparative Examples 1-1 to 1-5 described above on plywood (a 2 mm thick oak veneer stuck on the surface, total thickness 12 mm) The product was coated using a roll coater so that the coating amount was 33 g / m ² . Thereafter, drying was performed with hot air at 100 ° C. for 60 seconds to obtain a colored plywood.

  Using this colored plywood, a test plate having three layers of a cured product of the photocurable coating composition was obtained in the same procedure as in Example 2-1. However, the following were used for the photocurable coating composition (for undercoating, intermediate coating and overcoating).

・ Photo-curable coating composition (for undercoat)
45 parts by mass of urethane acrylate (Daicel Ornex, EBECRYL 210), 30 parts by mass of acryloylmorpholine (manufactured by KJ Chemicals, ACMO (registered trademark)), 2-hydroxy-2-methyl-1-phenyl-propane-1 -5 mass parts of ON (made by BASF, Irgacure 1173) and 20 mass parts of talc (made by Nippon Talc Co., Ltd.) were mixed and stirred for 1 hour to obtain a composition.

・ Photo-curable coating composition (for intermediate coating)
55 parts by mass of epoxy acrylate (manufactured by DIC Corporation, V-5500), 30 parts by mass of tripropylene glycol diacrylate, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by BASF, Irgacure 1173) 5 parts by mass and 10 parts by mass of talc (product name MS-P, manufactured by Nippon Talc Co., Ltd.) were mixed and stirred for 1 hour to obtain a composition.

・ Photocurable coating composition (for top coating)
20 parts by mass of urethane acrylate (manufactured by Daicel Ornex, EBECRYL 4858), 30 parts by mass of trimethylolpropane ethoxytriacrylate (manufactured by Daicel Ornex, TMPEOTA), 20 parts by mass of tripropylene glycol diacrylate, acryloylmorpholine (KJ Chemicals) ACMO (registered trademark) 20 parts by mass, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (BASF, Irgacure 1173) 5 parts by mass, and silica (Fuji Silysia Chemical Ltd.) 5 parts by mass were mixed and stirred for 1 hour to obtain a composition.

(Evaluation)
Using the obtained test plates, the same evaluations (adhesion evaluation and water resistance evaluation) as those performed in “2. Preparation and evaluation of photocurable coating composition” were performed. The evaluation results are shown in Tables 9 to 11.

As shown in Table 9 and Table 10, when a stain coating composition containing a polyvalent metal cation or its counter anion and a photocurable coating composition containing a specific monomer (for undercoating) are used in combination, the surface A coated body of porous material with few protrusions (blurred eyes or fuzz) and good adhesion and water resistance of the undercoat was obtained (Examples 3-1 to 3-17).
However, as shown in Table 11, when a stain coating composition that does not contain a polyvalent metal cation or the like was used, satisfactory results were not obtained at least in terms of eye blurring and fuzzing (comparison). Examples 3-1 to 3-5).

Claims (13)

A polyvalent metal cation (A1),
A counter anion (A2) of the polyvalent metal cation,
Coloring pigment (B),
Aqueous resin (C) and water (D)
A stain coating composition comprising: A stain coating composition according to claim 1,
A stain coating composition containing the pigment in which the color pigment (B) is dispersed by a nonionic dispersant. The stain paint composition according to claim 1 or 2,
The stain paint composition in which the water-based resin (C) includes nonionic resin emulsion particles. The stain paint composition according to any one of claims 1 to 3,
The stain coating composition whose content of the said polyvalent metal cation (A1) in a composition is 0.1 mol / 100g or more. The stain paint composition according to any one of claims 1 to 4,
Furthermore, the stain coating composition containing an antifoamer (E). A stain paint composition according to any one of claims 1 to 5,
Furthermore, the stain coating composition containing a leveling agent (F). The stain paint composition according to any one of claims 1 to 6,
Furthermore, the stain coating composition containing a rheology control agent (G). The stain paint composition according to any one of claims 1 to 7,
The polyvalent metal cation (A1) contains at least one selected from the group consisting of magnesium ion, calcium ion, scandium ion, titanium ion, vanadium ion, chromium ion, manganese ion, strontium ion, and barium ion,
A stain coating composition, wherein the counter anion (A2) comprises at least one selected from the group consisting of chloride ions and bromide ions. A photocurable coating composition for applying to the surface of a porous material coated with the stain coating composition according to any one of claims 1 to 8,
A photocurable coating composition comprising a polymerizable monomer having one or two polymerizable functional groups and a hydrophilic group in one molecule. The photocurable coating composition according to claim 9,
A photocurable coating composition wherein the hydrophilic group is at least one selected from the group consisting of a nitrogen atom-containing group, a hydroxy group and a polyoxyethylene group. A coating material comprising a first coating composition contained in a first container and a second coating composition contained in a second container,
The first coating composition includes a polyvalent metal cation (A1), a counter anion (A2) of the polyvalent metal cation, a color pigment (B), an aqueous resin (C), and water (E). And
A coating material, wherein the second coating composition is a photocurable coating composition containing a polymerizable monomer having one or two polymerizable functional groups and a hydrophilic group. A first coating step of coating a porous material with the stain coating composition according to any one of claims 1 to 8, and a coating of the porous material with the photocurable coating composition according to claim 9 or 10. The manufacturing method of the coating body of a porous material including the 2nd coating process to perform in this order. It is a manufacturing method of the coating object of the porous material according to claim 12,
A method for producing a coated body, wherein the porous material is wood.