JP5547365B2 - Surface treatment agent and surface treatment method by applying the treatment agent - Google Patents

Description

  The present invention relates to a surface treatment agent suitable for a substrate such as a wooden substrate in consideration of the global environment, and a surface treatment method obtained by applying the treatment agent.

  Conventionally, wooden substrates that are widely used in floors, wall surfaces, doors, window frames, etc., and processed wood products in buildings and civil engineering structures are subjected to various surface treatments for the purpose of protecting the surface and aesthetics. Has been. In recent years, in the treatment of such wooden base materials, various paints using renewable raw materials such as plant resources have been proposed due to the growing awareness of global environmental conservation.

  For example, Patent Document 1 discloses a wood protective coating composition containing natural hiba oil and vegetable oil. According to such a coating composition, it is possible to form a coating film that can exhibit antibacterial / antifungal, insecticidal and aromatic properties for a long period of time, but there is a possibility that the waste used during the painting operation may spontaneously ignite, and further dilution There is also a problem that an organic solvent must be used when performing the above.

  Under such circumstances, water-based materials have also been developed. For example, Patent Document 2 describes a paint finishing method in which a normally dry water-based paint having a water-based alkyd resin as a base resin component is applied as an undercoat. Yes. The water-based paint used in such a paint finishing method is a one-pack type, is very easy to adapt to wood, and can form a smooth coating film at room temperature. There are problems such as the use of odors and low amounts of renewable raw materials, and it is necessary to develop a surface treatment agent suitable for a base material such as a wooden base material using a water-based material that is more considered in consideration of the human body and the environment.

JP-A-10-212457 JP 2004-238524 A

  An object of the present invention is to provide a surface treatment agent that is suitable for protecting a substrate such as a wooden substrate and maintaining aesthetics, and that is conscious of the human body and the environment, and a surface treatment method by applying the treatment agent.

As a result of intensive studies on the above-described problems, the present inventors have dispersed a composition containing a specific amount of a biodegradable resin and a fatty acid ester of a specific glycerin derivative, and further containing a specific oil and / or fatty acid in water. The present inventors have found that the dispersion does not adversely affect the environment and is suitable as a surface treatment agent for a substrate surface such as a wooden substrate, and reached the present invention.
That is, the present invention
1.
A biodegradable resin (a), a polyglycerin partial fatty acid ester (b ) and a composition containing oil and fat and / or fatty acid (d) are dispersed in water, and the biodegradable resin (a) and the polyglycerin part the total amount of der entire solid content 60% by mass or more of the treatment agent fatty acid ester (b) is, and the fats and / or fatty acid (d) is an iodine value of 100 or more, drying oils, semi-drying oil, drying oil A room temperature drying type surface treatment agent characterized by being selected from fatty acids and semi-drying oil fatty acids ;
2.
The surface treating agent according to 1, wherein the biodegradable resin (a) is a modified starch,
3.
The ratio of biodegradable resin (a) and partial fatty acid esters of polyglycerol (b) is a biodegradable resin (a) / poly partial fatty acid esters of glycerol (b) weight ratio of 99/1 to 80/20 The surface treatment agent according to item 1 or 2, which is within a range,
4).
The surface treatment agent according to any one of 1 to 3, further comprising an anionic surfactant (c) having a polyoxyethylene group,
5.
The surface treatment agent according to any one of items 1 to 4, further comprising a metal dryer ,
6).
The surface treatment agent according to any one of 1 to 5, further comprising a plasticizer (e) (excluding a partial fatty acid ester (b) of polyglycerin ),
7).
A surface treatment method comprising applying the surface treatment agent according to any one of items 1 to 6 to a substrate surface,
About.

  The surface treatment agent according to the present invention has an advantage that does not adversely affect the environment and the human body, and can form a film while penetrating the base material. In addition to being able to be modified and protected, it is possible to exhibit the effect of further enhancing the texture of the substrate.

Biodegradable resin (a);
In the present invention, the biodegradable resin (a) can be a film-forming component of the surface treatment agent (hereinafter referred to as a treatment agent) of the present invention, and conventionally known ones can be used without limitation. Specific examples thereof include starch derivatives such as starch and modified starch; cellulose acetate derivatives such as cellulose acetate, cellulose acetate butyrate and cellulose acetate propionate; polysaccharides such as chitin and chitosan; polylactic acid, lactic acid and other hydroxy Polylactic acids such as copolymers with carboxylic acids; dibasic acid polyesters such as polybutylene succinate, polyethylene succinate and polybutylene adipate; polycaprolactones such as polycaprolactone and copolymers of caprolactone and hydroxycarboxylic acid Polyhydroxybutyrates such as polyhydroxybutyrate and copolymers of polyhydroxybutyrate and hydroxycarboxylic acid; Aliphatics such as polyhydroxybutyric acid and copolymers of polyhydroxybutyric acid and other hydroxycarboxylic acids Po Examples include esters; polyamino acids; polyester polycarbonates; water-soluble polymers such as polyethylene glycol and polyvinyl alcohol; natural resins such as shellac and rosin; and the like, which are used alone or in combination of two or more. Can do.

  The biodegradable resin (A) has a weight average molecular weight of, for example, 5,000 to 2,000,000, preferably 10,000 to 1,000,000.

  In the present specification, the weight average molecular weight is a value obtained by converting the weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent based on the weight average molecular weight of polystyrene. As the column, “TSKgel G-4000H × L”, “TSKgel G-3000H × L”, “TSKgel G-2500H × L”, “TSKgel G-2000H × L” (all manufactured by Tosoh Corporation) were used. Can be mentioned.

  In the present invention, when modified starch is used as the biodegradable resin (A), it is possible to form a treated film having good affinity and film-forming property to a substrate such as a wooden substrate and having good water resistance. Therefore, it is preferable.

  Examples of the modified starch include starch obtained from corn, rice, rice bran, potato, wheat and the like, and natural fats and oils, etc., or starch as a main component, sugars such as lactose, glucose, molasses, casein and the like Modified with a substance; an aliphatic saturated hydrocarbon group, an aliphatic unsaturated hydrocarbon group, an aromatic hydrocarbon group or the like is bonded to starch or starch degradation product via an ester bond and / or an ether bond. The modified starch is included.

  Here, as a raw material starch, for example, a blend of one or more of various natural starches such as corn starch, potato starch, wheat starch, tapioca starch, sweet potato starch, and rice starch is used. Examples of the degradation product include those obtained by subjecting the starch to a low molecular weight treatment with an enzyme, an acid, or an oxidizing agent. Among them, the starch having a weight average molecular weight in the range of 5,000 to 2,000,000, particularly 10,000 to 1,000,000, or a starch degradation product has a film forming property, durability, etc. It is preferable from the point.

  A preferred modification method of the modified starch is esterification modification, and a preferred modifying group is an acyl group having 2 to 18 carbon atoms. Modification | denaturation can be performed by using a C2-C18 organic acid individually or in combination of 2 or more types.

Fatty acid esters of glycerin derivatives (b);
In the present invention, the fatty acid ester (b) of the glycerin derivative is used to disperse the biodegradable resin (a) in water. By using this, the treating agent according to the present invention is a wooden substrate. The surface layer can be improved, and the surface layer can be modified and the material appearance such as wood grain can be further enhanced as the appearance after the treatment.

  In the present invention, the fatty acid ester (b) of the glycerin derivative is a partially fatty acid esterified product of the glycerin derivative, and examples of the glycerin derivative include polyglycerin obtained by polymerizing glycerin and glycerin. On the other hand, examples of fatty acids used for esterification include stearic acid, palmitic acid, myristic acid, oleic acid, lauric acid, behenic acid, erucic acid, and the like. These may be used alone or in combination of two or more. be able to.

  Specific examples of such fatty acid esters (b) include glycerin monofatty acid esters such as glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, and glycerin monooleate; Glycerin dilaurate, glyceryl dimyristate, glycerin dipalmitate, glycerin distearate, glycerin dibehenate, glycerin dilate, and other glycerin difatty acid esters; diglycerin monolaurate, diglycerin monomyristylate, diglycerin mono Diglycerin monofatty acid esters such as palmitate, diglycerin monostearate, diglycerin monobehenate, diglycerin monooleate; Germany or in combination of two or more can be used.

  In this invention, it is suitable from the point of the storage stability of a processing agent that the said fatty acid ester (b) contains the partial fatty acid ester of polyglycerol as a part of the component.

  In the present invention, the biodegradable resin (a) and the fatty acid ester (b) of the glycerin derivative are characterized in that the total amount thereof is 60% by mass or more in the solid content of the treatment agent.

  When the total amount of the biodegradable resin (a) and the fatty acid ester (b) of the glycerin derivative is less than 60% by mass, the finish of the treated film applied to a substrate such as a wooden substrate, the water resistance of the treated film, etc. Since the protective function for the base material is impaired, it is not preferable.

  The total amount of the biodegradable resin (a) and the fatty acid ester (b) of the glycerin derivative is more preferably in the range of 75 to 90% by mass in the treatment agent solid content.

  Moreover, as a use rate of the said biodegradable resin (a) and the fatty acid ester (b) of a glycerol derivative, the storage stability of a processing agent, the permeability | transmittance with respect to base materials, such as a wooden base material, and the raw material feeling after application | coating stand out. From the point of view, it is suitable that the biodegradable resin (a) / glycerin derivative fatty acid ester (b) has a mass ratio of 99/1 to 80/20, preferably 98/2 to 90/10. Yes.

An anionic surfactant (c) having a polyoxyethylene group;
In the present invention, the treatment agent may further contain an anionic surfactant (c) having a polyoxyethylene group for the purpose of improving the dispersibility of the biodegradable resin (a).

  Examples of the anionic surfactant (c) having a polyoxyethylene group include polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, and polyoxyethylene. An alkyl ether phosphate, a polyoxyethylene alkyl phenyl ether phosphate, etc. can be mentioned, These can be used individually or in combination of 2 or more types.

  As a counter ion forming a salt with such an anionic surfactant, inorganic ions such as potassium, sodium and ammonium, and organic amines such as monoethanolamine, diethanolamine and triethanolamine are preferable.

  The content of the anionic surfactant (c) having a polyoxyethylene group is 0.01 to 15% by mass, preferably 1 to 10% by mass, based on the mass of the biodegradable resin (a). It is suitable from the point of the water dispersion stability of biodegradable resin (a) and the water resistance of the process film | membrane after application | coating that it exists in the range.

Fats and oils and / or fatty acids (d);
Moreover, the said processing agent can further contain fats and oils and / or a fatty acid (d) in order to improve the drying property of a process film. Specific examples of such fats and oils include soybean oil, safflower oil, linseed oil, tall oil, palm oil, palm kernel oil, castor oil, dehydrated castor oil, fish oil, and tung oil. As fats and oils, dry oil or semi-dry oil having an iodine value of 100 or more is preferable, and soybean oil, safflower oil, linseed oil, and the like are particularly preferable. Examples of fatty acids include soybean oil fatty acid, safflower oil fatty acid, linseed oil fatty acid, tall oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, castor oil fatty acid, dehydrated castor oil fatty acid, fish oil fatty acid, and tung oil fatty acid. Can be mentioned. As the fatty acid, a dry oil fatty acid or semi-dry oil fatty acid having an iodine value of 100 or more is preferable, and soybean oil fatty acid, safflower oil fatty acid, linseed oil fatty acid and the like are particularly preferable.

  As content of these fats and oils and / or fatty acid (d), it is 0.5-20 mass% on the basis of the mass of biodegradable resin (a), Preferably it exists in the range of 1-15 mass%. This is preferable from the viewpoint of the drying property of the treated film.

  When these fats and / or fatty acids (d) are used, the drying properties of the treated film can be further improved by using a metal dryer such as cobalt naphthenate, zirconium naphthenate, calcium naphthenate and the like. The amount of such a metal dryer is suitably 0.1 to 7% by mass, particularly 0.5 to 5% by mass based on the mass of the oil and / or fatty acid (d).

Plasticizer (e);
In the present invention, the treating agent may further contain a plasticizer (e) for the purpose of improving the film forming property. Specific examples of the plasticizer (e) include, for example, citric acid derivatives such as triethyl citrate, tributyl citrate, triethyl citrate, tributyl acetyl citrate; diethylene glycol diacetate, triethylene glycol diacetate, triethylene glycol Ether ester derivatives such as dipropionate; glycerin derivatives such as glycerin triacetate, glycerin tripropionate and glycerin tributyrate; adipic acid derivatives such as a condensate of adipic acid and 1,4-butanediol; polycaprolactone, polypropio Examples thereof include polyhydroxycarboxylic acids such as lactones, and these can be used alone or in combination of two or more.

  When blending the plasticizer (e), the blending amount may be adjusted within the range of 1 to 30% by weight, particularly 3 to 20% by weight, based on the weight of the biodegradable resin (a). desirable.

Surface treatment agent;
You may mix | blend an insect repellent with the said processing agent of this invention as needed. As such insect repellents, conventionally known ones can be used without limitation. Specific examples thereof include fenitrothion, diazinon, dichlorvos, fenthion, trichlorfone, propetanephos, prothiophos, pyridafenthion, oxime, and other organophosphorus insecticides, fenocarb, carbaryl Carbamate insecticides such as methomyl, phenothrin, permethrin, pyrethroid insecticides such as allethrin, phthalthrin, praretrin, bifenthrin, imiprotolin, ciphenothrin, etofenprox; imidacloprid, acetamiprid, clothianidin, thianicotinoid, etc. Examples include natural pyrethrin, fipronil, chlorophenapyl, and the like, and these can be used alone or in combination of two or more.

  The amount of the insect repellent used can be in the range of 0.1 to 5 mass%, particularly 0.1 to 3 mass%, based on the mass of the biodegradable resin (a).

  In addition, the treatment agent is an organic resin, an organic solvent, a pigment, a pigment dispersant, a matting agent, a surface conditioner, an antisettling agent, an antistatic agent, a crosslinking agent, and an antibacterial agent as long as the effects of the present invention are not impaired. Additives such as perfumes, UV absorbers, UV stabilizers, curing catalysts, antifoaming agents, thickeners, film-forming aids, antiseptics, fungicides, algaeproofing agents, antifreezing agents, pH adjusters, etc. It can be appropriately selected and combined.

  The solid concentration of the treatment agent is desirably adjusted within a range of 5 to 50%, particularly 5 to 40% from the viewpoints of coating workability and storage stability of the treatment agent.

  In the present specification, the solid content concentration is a percentage by weight expressed as a percentage of the amount of the remaining substance after weighing about 2 g of a sample in a tin plate and drying at 105 ° C. for 3 hours.

  The treatment agent of the present invention is produced, for example, by simultaneously charging a biodegradable resin (a), a fatty acid ester (b) of a glycerin derivative and water in a sealed container having a stirrer, and pressurizing while heating and stirring. Method: A method of adding and stirring a melt containing a biodegradable resin (a) and a fatty acid ester (b) of a glycerin derivative in hot water maintained at normal pressure or under pressure; biodegradable resin A method for producing by gradually adding water to a solution containing the organic solvent solution (a) and the fatty acid ester (b) of the glycerin derivative (b) while stirring and dispersing, and then removing the organic solvent; biodegradable resin It can be obtained by a method in which (a) is heated and melted, an aqueous solution containing the fatty acid ester (b) of a glycerin derivative is added thereto and dispersed in water, and then produced. In production, a dispersing device such as a high-pressure emulsifying device may be used in combination as necessary.

  In addition, the average particle diameter of the treatment agent is in the range of 50 to 1000 nm, particularly 50 to 500 nm, from the viewpoint of storage stability of the treatment agent and permeability to a substrate such as a woody substrate of the treatment agent. Is suitable.

  In this specification, the average particle diameter is a value measured by a light scattering method using a submicron particle analyzer manufactured by Beckman Coulter.

  In the surface treatment method of the present invention, a treatment agent obtained as described above is applied to a substrate.

  The substrate applied to the surface treatment method of the present invention is not particularly limited, but a permeable substrate, particularly a wood substrate, is suitable.

  Examples of such a wooden base material include a wooden base material used for a wall surface in a building, a door, a window frame, a ceiling, a beam, a pillar, a woodwork product, and the like. For example, beech, cypress, too much, Wood materials such as teak and lawan; laminates made from these wood materials, ordinary plywood, wood fiberboard, particle board and the like.

  The coating means can be performed using a coating means known per se. For example, a roller, an air spray, an airless spray, a ricin gun, a universal gun, a brush, a trowel, a roll coater, and the like are appropriately selected. Can do.

Although it can change according to the kind of base material etc. which are coated, etc., it can usually be in the range of 50-500 g / m < ² >, preferably 80-200 g / m < ² > per application. Moreover, you may apply repeatedly several times in the range which does not impair the coating-film external appearance.

  The treatment film to be formed can be dried at room temperature, but heat drying or forced drying may be performed as necessary.

  According to the surface treatment method of the present invention, it is possible to obtain an appearance that makes use of the material feeling of a base material such as a wooden base material. However, if necessary, after applying a treatment agent, a top coat may be applied. Absent.

  Hereinafter, the present invention will be described in more detail with reference to examples. “Part” and “%” indicate “part by mass” and “% by mass”, respectively.

Production Example 1 of Surface Treatment Agent
The following components were placed in a 2 L inner surface coated can and stirred with a disper until uniform. Then, 500 parts of deionized water was gradually added while fixing the number of revolutions of the disper at 2000 rpm, and after phase inversion emulsification, toluene was removed under reduced pressure to obtain a surface treating agent (A-1). The average particle diameter of the surface treatment agent (A-1) was 430 nm.
20% modified starch (Note 1) 500 parts "Poem DL-100" (Note 2) 5 parts (Note 1) 20% modified starch: "Corn Pole CP-5" (trade name, manufactured by Nippon Cornstarch Co., Ltd., esterified starch ) It was manufactured by adding 400 parts of toluene to 100 parts and stirring with a disper until uniform.
(Note 2) “Poem DL-100”: trade name, manufactured by Riken Vitamin Co., Ltd., diglycerin monolaurate.

Examples 2-5 and Comparative Examples 1-2
Surface treatment agents (A-2) to (A-5) and (A-7) to (A-8) are the same as in Production Example 1 except that the formulation composition in Production Example 1 is changed as shown in Table 1. Got.

(Note 3) “Poem O-80”: trade name, manufactured by Riken Vitamin Co., sorbitan fatty acid ester,
(Note 4) “Emar 20T”: trade name, manufactured by Kao Corporation, polyoxyethylene alkyl ether sulfate, active ingredient 40%.

Example 6
20L modified starch (Note 1) 500 parts, "Poem DL-100" (Note 2) 5 parts, "Emar 20T" (Note 4) 10 parts, flaxseed oil 5 parts, tributyl acetylcitrate 10 parts and 1 part of permethrin were added and stirred with a disper until uniform. Thereafter, while fixing the number of revolutions of the disper at 2000 rpm, 500 parts of deionized water was gradually added to effect phase inversion emulsification, and then the treatment was performed by a high pressure emulsifying apparatus that applied high pressure energy to collide fluids. Thereafter, toluene was removed under reduced pressure to obtain a surface treating agent (A-6). The average particle diameter of the surface treatment agent (A-6) was 210 nm.
(* 1) Storage stability 500 parts of the surface treatment agents (A-1) to (A-8) shown in Table 1 were put into an inner surface coated can with a capacity of 1 L and stored in a constant temperature room at 40 ° C. for 14 days. . Then, it returned to room temperature, the state in a container was observed visually, and the following reference | standard evaluated.
○: Separation is not allowed,
Δ: Soft caking and separation are observed, but uniform by stirring.
X: Hard caking and separation are recognized, and it does not become uniform by stirring.

Examples 7-12 and Comparative Examples 3-4
Each component shown in Table 2 is sequentially added to the surface treatment agents (A-1) to (A-8) produced in Examples 1 to 6 and Comparative Examples 1 to 2, and stirred with a disper until uniform. The surface treatment agents (B-1) to (B-8) for coating were prepared by the above. The surface treatment agents (B-1) to (B-8) were evaluated according to the following criteria. The results are also shown in Table 2.

(Note 5) "Sura-off 72N": trade name, manufactured by Takeda Pharmaceutical Company Limited, antiseptic,
(Note 6) “SN deformer 380”: trade name, manufactured by San Nopco, antifoaming agent,
(Note 7) “DICnate 3111”: trade name, manufactured by Dainippon Ink & Chemicals, Ltd., dryer, Co content 3%.

Evaluation test (* 2) Finishing property Each treatment agent (B-1) to (B-8) was applied to Lauan material with a brush so that the coating amount as a treatment agent was 150 g / m ² , and the temperature was 20 ° C. Each test coated plate was obtained by drying for 24 hours under conditions of a relative humidity of 60%. Thereafter, the finish was visually evaluated.
○: Good with no suction unevenness,
Δ: Suction unevenness is observed,
X: Coating film defects such as cracks and cracks are observed.
(* 3) Dryability The dryness to touch of each test coated plate obtained in the same manner as (* 2) above was evaluated according to the following criteria.
◎: No fingerprints at all
○: Fingerprint is attached, but after a while, it returns to the original.
Δ: Fingerprint is attached and does not return.
X: A coating film adheres to a finger.
(* 4) Permeability After 1% of phthalocyanine blue was added to each treatment agent (B-1) to (B-8) shown in Table 2, each treatment agent (B-1) to (B-8) was added to the lauan material. ) Was applied with a brush so that the coating amount as a treating agent was 150 g / m ^2, and dried for 24 hours under conditions of an air temperature of 20 ° C. and a relative humidity of 60% to obtain each test coated plate. Then, the test coating board was cut | disconnected and the cross section was evaluated visually.
(Double-circle): Blue coloring is recognized to the depth of 7 mm or more from the surface,
○: Blue coloring is recognized from the surface to a depth of 4 or more and less than 7 mm,
Δ: Blue coloring is recognized from the surface to a depth of 1 or more and less than 4 mm,
X: Blue coloring is recognized from the surface to a depth of 0 or more and less than 1 mm.

Claims (7)

A biodegradable resin (a), a polyglycerin partial fatty acid ester (b ) and a composition containing oil and fat and / or fatty acid (d) are dispersed in water, and the biodegradable resin (a) and the polyglycerin part the total amount of der entire solid content 60% by mass or more of the treatment agent fatty acid ester (b) is, and the fats and / or fatty acid (d) is an iodine value of 100 or more, drying oils, semi-drying oil, drying oil A room-temperature drying type surface treatment agent characterized by being selected from fatty acids and semi-drying oil fatty acids . The surface treating agent according to claim 1, wherein the biodegradable resin (a) is a modified starch. The ratio of biodegradable resin (a) and partial fatty acid esters of polyglycerol (b) is a biodegradable resin (a) / poly partial fatty acid esters of glycerol (b) weight ratio of 99/1 to 80/20 The surface treatment agent according to claim 1 or 2, which is within a range. The surface treating agent according to any one of claims 1 to 3, further comprising an anionic surfactant (c) having a polyoxyethylene group. The surface treating agent according to any one of claims 1 to 4, further comprising a metal dryer. The surface treating agent according to any one of claims 1 to 5, further comprising a plasticizer (e) (excluding a partial fatty acid ester (b) of polyglycerol ). The surface treatment method formed by apply | coating the surface treating agent of any one of Claim 1 thru | or 6 to a base-material surface.