JP2010058494A - Silicone emulsion composition, two-pack wood treatment agent, and wood treatment method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone emulsion composition for coloring wood which prevents leaching by water without losing woody feeling and taked consideration to environment, and to provide a two-pack wood treatment agent, and a wood treatment method using them. <P>SOLUTION: The silicone emulsion is obtained by emulsifying and dispersing in water, the components composed of (A) organopolysiloxane having at least two hydroxy groups bound to a silicon atom in one molecule, (B) a reaction product of an amino group-containing organoxysilane with an acid anhydride, and further if necessary, (C) an epoxy group-containing organoxysilane and/or a partial hydrolyzate thereof, (D) colloidal silica and/or polysilsesquioxane and (E) a curing catalyst. The silicone emulsion composition is obtained by adding and mixing an aqueous solution (II) in which (F) a boron compound and (G) pigment are dispersed with the silicone emulsion (I) in an amount of 0.1 to 300 pts.mass of solid content based on 100 pts.mass of the solid content in the silicone emulsion. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention can be colored without losing the wood texture, can be added to wood with good water repellency, water absorption prevention, dimensional stability, antiseptic, anti-ant, and antiseptic / anticidal properties. Silicone emulsion composition, two-part wood treating agent useful as wood colorant that can improve the leaching property of pigments and pigments with water, and is suitable for a wide variety of people's taste, and wood treatment method using them About.

Wood, which is widely used as a material for building materials and crafts, has been conventionally colored in order to enhance the appearance and design.
For example, JP-A-61-261001 (Patent Document 1) describes a method of injecting and curing a resin liquid composition containing ultrafine particles of hollow particles made of a synthetic resin. However, a polymerizable monomer is used, which is a problem in terms of environment.

JP-A-1-299905 (Patent Document 2) and JP-A-2-220804 (Patent Document 3) describe a method of impregnating or applying a dye and a water-soluble resin to wood and solidifying the resin. Are listed. It can be said that it is environmentally friendly because it uses water-soluble resin. However, since water-soluble resin is used, it is not enough to prevent leaching with rainwater after the resin is solidified. It was not suitable for use.
In addition, these colored pigments have the disadvantage of hiding the grain and losing the essential wood texture.

  In JP-A-6-271805 (Patent Document 4), a method of applying a mixture of an ultraviolet curable prepolymer, a colorant, and a solvent as a binder to wood, further applying an ultraviolet curable coating, and irradiating with ultraviolet rays, Japanese Patent Application Laid-Open No. 8-66903 (Patent Document 5) describes a method in which an adhesive is applied to a colored sheet and pressure-bonded to wood. In either case, the problem of leaching can be prevented to some extent, but the process is complicated and not economical, and further, JP-A-6-271805 uses a solvent, which causes a problem in terms of environment.

  Japanese Patent Application Laid-Open No. 2007-51236 (Patent Document 6) describes a method in which a boron-based compound is added to and mixed with a silicone emulsion, and surface treatment, immersion treatment, decompression or pressure injection treatment is performed on wood. However, these buildings and crafts are often required to have various colors, that is, design, and have not yet been able to meet the tastes of a wide variety of people.

  Accordingly, there has been a demand for a composition for coloring wood that prevents leaching by water without losing the wood texture and is environmentally friendly.

JP 61-261001 A JP-A-1-299005 JP-A-2-220804 JP-A-6-271805 JP-A-8-66903 JP 2007-51236 A

  The present invention was made in view of the above circumstances, and without losing the wood texture, prevents leaching with water, and is environmentally friendly silicone emulsion composition for coloring wood, a two-part wood treating agent and these It aims at providing the used wood processing method.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors obtained the following components (A) and (B) and, if necessary, the components (C) to (E) by emulsifying and dispersing them in water. A silicone emulsion that forms a rubbery film and an aqueous solution in which (F) a boron-based compound and (G) pigment for imparting antiseptic and ant-repellent properties are dispersed in a solid content. When wood is used at a ratio of 0.1 to 300 parts by weight with respect to parts by weight, it can be colored without losing the wood texture, and further has good water repellency, water absorption prevention, dimensional stability, It has been found that it is possible to impart antiseptic properties, ant-repellent properties, and weather resistance, and further improve the leaching property of the antiseptic / anticidal properties-imparting agent and pigment with water.

Accordingly, the present invention provides the following silicone emulsion composition, two-part wood treating agent and wood treating method.
[Claim 1]
(A) Organopolysiloxane containing at least two hydroxyl groups bonded to silicon atoms in one molecule: 100 parts by mass
(B) Reaction product of amino group-containing organoxysilane and acid anhydride: 0.5 to 20 parts by mass,
(C) Epoxy group-containing organoxysilane and / or partial hydrolyzate thereof: 0 to 20 parts by mass,
(D) Colloidal silica and / or polysilsesquioxane: 0 to 50 parts by mass, and (E) Curing catalyst: 0 to 10 parts by mass of silicone emulsion (I) emulsified and dispersed in water, (F) boron An aqueous solution (II) in which a system compound and (G) pigment are dispersed is added and mixed at a solid content of 0.1 to 300 parts by mass with respect to 100 parts by mass of the solid content of the silicone emulsion. A silicone emulsion composition.
[Claim 2]
The silicone emulsion composition according to claim 1, wherein the pigment (G) is bengara and / or carbon black.
[Claim 3]
(A) Organopolysiloxane containing at least two hydroxyl groups bonded to silicon atoms in one molecule: 100 parts by mass
(B) Reaction product of amino group-containing organoxysilane and acid anhydride: 0.5 to 20 parts by mass,
(C) Epoxy group-containing organoxysilane and / or partial hydrolyzate thereof: 0 to 20 parts by mass,
(D) colloidal silica and / or polysilsesquioxane: 0 to 50 parts by mass, and (E) curing catalyst: silicone emulsion (I) in which 0 to 10 parts by mass are emulsified and dispersed in water;
(F) A boron compound and (G) an aqueous solution (II) in which a pigment is dispersed, and the amount of the aqueous solution (II) used is 0.1% by solid content with respect to 100 parts by mass of the solid content of the silicone emulsion. A two-part wood treating agent characterized by having a ratio of 1 to 300 parts by mass.
[Claim 4]
The two-part wood treating agent according to claim 3, wherein the pigment (G) is Bengala and / or carbon black.
[Claim 5]
A wood treatment method using the silicone emulsion composition according to claim 1 or 2, wherein the silicone emulsion (I) and the aqueous solution (II) in the silicone emulsion composition are mixed and applied to wood immediately before use. A wood treatment method characterized by impregnating.
[Claim 6]
A wood treatment method using the two-part wood treating agent according to claim 3 or 4, wherein an aqueous solution (II) in which the components (F) and (G) in the two-part wood treating agent are dispersed is applied to wood. Alternatively, the wood treatment method is characterized by impregnating and immediately applying or impregnating the wood with the silicone emulsion (I) in the two-part wood treating agent.

According to the present invention, by treating wood with a specific silicone emulsion composition or a two-part wood treating agent, it is possible to color without losing the wood texture, and even better water repellency, water absorption prevention, dimensional stability. , Antiseptic and ant-proofing wood can be added. In addition, the leaching property of the antiseptic / anticidal properties-imparting agent and the pigment with water can be improved, and it has the effect of adapting to the tastes of a wide variety of people.
Furthermore, the silicone emulsion composition and the two-part wood treating agent of the present invention use an emulsion, and use a Bengala (red iron oxide) and carbon black, which have been used for a long time in pigments. It is also environmentally friendly.

The silicone emulsion composition and the two-part wood treating agent of the present invention are
(A) an organopolysiloxane containing at least two hydroxyl groups bonded to silicon atoms in one molecule;
(B) a reaction product of an amino group-containing organoxysilane and an acid anhydride,
Preferably further
(C) an epoxy group-containing organoxysilane and / or a partial hydrolyzate thereof,
(D) colloidal silica and / or polysilsesquioxane, and (E) a silicone emulsion (I) in which a curing catalyst is emulsified and dispersed in water;
(F) A boron compound and (G) an aqueous solution (II) in which a pigment is dispersed.

［ここで、Ｒは同一又は異種の炭素数１〜２０のアルキル基又は炭素数６〜２０のアリール基、Ｘは同一又は異種の炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシ基又はヒドロキシル基、ＹはＸ又は−［Ｏ−Ｓｉ（Ｘ）₂］_c−Ｘで示される同一又は異種の基で、Ｘ及びＹ中の少なくとも２個はヒドロキシル基である。ａは０〜１，０００の正数、ｂは１００〜１０，０００の正数、ｃは１〜１，０００の正数である。］ The organopolysiloxane of component (A) contains at least two hydroxyl groups bonded to silicon atoms in one molecule, and those represented by the following general formula are preferred.

[Wherein R is the same or different alkyl group having 1 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms, X is the same or different alkyl group having 1 to 20 carbon atoms, and aryl having 6 to 20 carbon atoms. Group, an alkoxy group having 1 to 20 carbon atoms or a hydroxyl group, Y is the same or different group represented by X or — [O—Si (X) ₂ ] _c —X, and at least two of X and Y are It is a hydroxyl group. a is a positive number from 0 to 1,000, b is a positive number from 100 to 10,000, and c is a positive number from 1 to 1,000. ]

Here, R is the same or different alkyl group having 1 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms, specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl. , Decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, tolyl, naphthyl group, and the like, and a methyl group is preferable.
X is the same or different alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, or hydroxyl group. Specifically, in addition to the hydroxyl group, methyl, Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl, tolyl, naphthyl, methoxy, ethoxy, propoxy, butoxy, hexyloxy, Examples include heptyloxy, octyloxy, decyloxy, and tetradecyloxy groups.
Y is the same or different group represented by X or — [O—Si (X) ₂ ] _c —X, and when a is greater than 1,000, the strength of the resulting film becomes insufficient. A positive number of 1,000, preferably a positive number of 0 to 200, and b is less than 100 if the film has poor flexibility, and if it exceeds 10,000, the tear strength decreases. A positive number of 000, preferably a positive number of 1,000 to 5,000, and c is a positive number of 1 to 1,000.
Moreover, it is necessary to have at least 2, preferably 2 to 4 hydroxyl groups in one molecule from the viewpoint of crosslinkability.

（上記式中、ａ、ｂ、ｃは上記と同じである。） Specific examples of such organopolysiloxanes include the following.

(In the above formula, a, b and c are the same as above.)

  Such an organopolysiloxane can be synthesized by a known method. For example, it can be obtained by carrying out an equilibration reaction between a cyclic siloxane such as octamethylcyclotetrasiloxane and an α, ω-dihydroxysiloxane oligomer in the presence of a catalyst such as a metal hydroxide. In addition, since the component (A) is preferably used in the form of an emulsion, it may be converted into an emulsion by a known emulsion polymerization method. Accordingly, this may be a cyclic siloxane or α, ω-dihydroxysiloxane oligomer, After emulsifying and dispersing α, ω-dialkoxysiloxane oligomer, alkoxysilane, etc. in water using an anionic surfactant or cationic surfactant, a catalyst such as an acid or alkaline substance is added as necessary. It can be easily synthesized by carrying out a polymerization reaction.

  Here, the anionic surfactant or the cationic surfactant is not particularly limited, but alkyl sulfate, alkyl benzene sulfonate, alkyl phosphate, polyoxyethylene alkyl sulfate, alkyl amine hydrochloride, Examples include alkylamine acetate. As this usage-amount, it is about 0.1-20 mass% of the amount of siloxane.

  Examples of the catalyst for acid, alkaline substance and the like include sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, formic acid, lactic acid, trifluoroacetic acid, potassium hydroxide, sodium hydroxide, ammonia and the like. it can. When an acidic substance such as alkylbenzene sulfonic acid, alkyl sulfuric acid, or alkyl phosphoric acid is used as the surfactant, it is not necessary to use a catalyst.

  The reaction product of the (B) component amino group-containing organoxysilane and the acid anhydride is a component for improving the adhesion between the silicone film and the base wood, and the amino group-containing alkoxysilane and It is preferable to react with a dicarboxylic acid anhydride.

Here, the amino group-containing alkoxysilane as a raw material has the following general formula:
A (R) _g Si (OR) _3-g
[Wherein, R is the same as defined above, A is the formula —R ¹ (NHR ¹ ) _h NHR ² (wherein R ¹ is the same or different divalent hydrocarbon group having 1 to 6 carbon atoms, R ² is R Or a hydrogen atom, h is an integer of 0 to 6.), and g is 0, 1 or 2. ]
The thing represented by these can be used, and the following are mentioned specifically.
(C ₂ H ₅ O) ₃ SiC ₃ H ₆ NH ₂ , (C ₂ H ₅ O) ₂ (CH ₃ ) SiC ₃ H ₆ NH ₂
(CH ₃ O) ₃ SiC ₃ H ₆ NH ₂ , (CH ₃ O) ₂ (CH ₃ ) SiC ₃ H ₆ NH ₂
(CH ₃ O) ₃ SiC ₃ H ₆ NHC ₂ H ₄ NH ₂ ,
(CH ₃ O) ₂ (CH ₃ ) SiC ₃ H ₆ NHC ₂ H ₄ NH ₂

  Examples of the dicarboxylic acid anhydride for reacting with the amino group-containing organoxysilane include maleic acid anhydride, phthalic acid anhydride, succinic acid anhydride, methyl succinic acid anhydride, glutaric acid anhydride, itaconic acid anhydride. Etc. Of these, maleic anhydride is preferred.

  The reaction between the amino group-containing organoxysilane and the acid anhydride depends on the mixing ratio of the above two so that the amino group / acid anhydride (molar ratio) is 0.5 to 2, particularly 0.8 to 1.5. If necessary, it can be easily carried out by mixing in a hydrophilic organic solvent at room temperature or under heating. Examples of the hydrophilic organic solvent at this time include alcohols such as methanol, ethanol, isopropanol and butanol, ketones such as acetone and methyl ethyl ketone, acetonitrile and tetrahydrofuran. Moreover, as the usage-amount of a hydrophilic organic solvent, it is about 0-100 mass% of the amount of reaction products.

  (B) The compounding quantity of a component is 0.5-20 mass parts with respect to 100 mass parts of (A) component, and when it is less than 0.5 mass part, the adhesive effect with wood will become weak, When the amount is more than 20 parts by mass, the film is hard and brittle. More preferably, it is 1-10 mass parts.

  As described above, when a reaction between an amino group-containing organoxysilane and an acid anhydride is performed using a hydrophilic organic solvent, the component (B) may be used as it is, or a solvent may be used. You may use after removing.

  The (C) component epoxy group-containing organoxysilane and / or its partial hydrolyzate is a component for improving the adhesion between the silicone film and the substrate. Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethoxy Examples include methylsilane.

  (C) The compounding quantity of component is 0-20 mass parts with respect to 100 mass parts of (A) component, and when more than 20 mass parts, a film | membrane will become hard and brittle. Preferably it is 0-10 mass parts. When mix | blending, it is preferable that it is 1 mass part or more.

  The (D) component colloidal silica and / or polysilsesquioxane is added as a film reinforcing agent, specifically, polymethylsil which is a hydrolysis condensate of colloidal silica and trimethoxymethylsilane. Examples include sesquioxane.

  As the colloidal silica, commercially available ones can be used, and there is no limitation on the kind thereof. For example, the average particle diameter may be 5 to 50 nm and may be stabilized with sodium, ammonium, aluminum, etc. Snowtex (manufactured by Nissan Chemical Industries, Ltd.), Ludox (manufactured by DuPont), silica doll (manufactured by Nippon Chemical Industry Co., Ltd.), Adelite AT (manufactured by Asahi Denka Kogyo Co., Ltd.), Cataloid S (manufactured by Catalyst Chemical Industries, Ltd.) Commercial products.

  As polymethylsilsesquioxane, an acid such as sulfuric acid or an alkali compound such as potassium hydroxide is added as a condensation catalyst to an aqueous surfactant solution, and trimethoxymethylsilane is further added dropwise and stirred. An emulsion containing methylsilsesquioxane can be used. At this time, alkoxytrialkylsilane, dialkoxydialkylsilane, tetraalkoxysilane or the like may be added to adjust the degree of crosslinking of the polysilsesquioxane. Also, vinyl silane, epoxy silane, acryl silane, methacryl silane or the like may be added to increase the reactivity of polysilsesquioxane.

  In addition, the compounding quantity of (D) component is 0-50 mass parts with respect to 100 mass parts of (A) component, and when more than 50 mass parts, a silicone membrane | film | coat will become a hard and brittle thing. Preferably it is 0-30 mass parts, and when mix | blending, it is preferable to set it as 10 mass parts or more.

  The average particle size of the component (D) is preferably 2 to 200 nm, particularly 5 to 100 nm. In the present invention, the average particle diameter is a value measured by the BET method.

  The curing catalyst as component (E) is blended in order to rapidly crosslink and cure the components of the composition of the present invention by a condensation reaction, and specifically, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dilaurate. , Dioctyltin diversate, dioctyltin diacetate, dibutyltin bisoleyl malate, tin octylate, zinc stearate, zinc octylate, zinc acetate, iron octylate and other organic acid metal salts, n-hexylamine, guanidine, etc. The amine compound can be mentioned.

  These curing catalysts are preferably in the form of an emulsion emulsified and dispersed in water using a surfactant in advance, except when water-soluble.

  The blending amount of the component (E) is 0 to 10 parts by mass with respect to 100 parts by mass of the component (A). . A preferable range is 0 to 5 parts by mass, and when blended, 0.5 parts by mass or more is preferable.

  In order to further improve the properties of the coating film of the emulsion composition of the present invention, the silicone resin emulsion (I) contains a silane coupling agent, a silicone resin, a silicone oil, a silicone resin powder and the like without departing from the scope of the present invention. Addition and blending are optional. Examples of the silane coupling agent include various types containing an acryloxy group, a methacryloxy group, a mercapto group, a carboxyl group, a cyano group, and the like. Examples of the silicone resin include trialkylsiloxypolysilicate. Α, ω-dihydroxyalkylpolysiloxane, alkylpolysiloxane, and the like. Examples of the silicone resin powder include silicone resin powder and silicone rubber powder.

The method for preparing (emulsifying and dispersing) the silicone emulsion (I) is not particularly limited, but the components (B), (C), (D), and (E) are added under stirring of the component (A), and 30 minutes to Continue stirring for 1 hour.
The solid content in the obtained silicone emulsion (I) is preferably 35 to 60% by mass, particularly 40 to 55% by mass.

Next, the boron-based compound as the component (F) is a component that imparts antiseptic and ant-repellent properties to wood. Examples of the boron-based compound include boric acid, borax, and disodium octaborate tetrahydrate ( Na ₂ B ₈ O ₁₃ · 4H ₂ O), trialkyl borate, triethyl borate, trialkyl borate such as tripropyl borate, tributyl borate, etc., borax, disodium octaborate tetrahydrate An alkali metal borate such as a product is preferred.

  (G) The pigment which is a component is a component which provides designability. Examples of the pigment include bengara (red iron oxide), carbon black, cadmium red, vermilion, aniline black, mars black, and the like, and one or more of these can be used. Among these, Bengala and carbon black, which have been used for a long time, are preferred in consideration of the environment.

  Component (G) is preferably blended in an amount of 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight per 100 parts by weight of component (F). If the amount is less than 0.1 parts by mass, the coloring effect may be lowered, and if it exceeds 100 parts by mass, the dispersibility may be deteriorated.

  The aqueous solution (II) can be prepared by dispersing the components (F) and (G) in water. In this case, the active ingredient (component (F) and component (G) (solid content)) of the aqueous dispersion is preferably 5 to 20% by mass, particularly preferably 10 to 15% by mass.

  In the present invention, an aqueous solution (II) in which the components (F) and (G) are dispersed is added to and mixed with the silicone emulsion (I) to obtain a silicone emulsion composition. In the present invention, it can also be used as a two-part wood treating agent comprising the silicone emulsion (I) and the aqueous solution (II).

  As the wood treating agent, the component (F) alone has a problem of leaching, and the component (G) alone has a problem of insufficient permeation into wood, but by containing both the component (F) and the component (G), Both components F) and (G) efficiently penetrate into the wood, and are less likely to leach out. This effect is more remarkably exhibited by adding the silicone emulsion (I). Further, when only the component (G) is added to the silicone emulsion (I), aggregates are generated. Aggregate generation can be prevented by adding the aqueous solution (II) in which the components (F) and (G) are dispersed to the silicone emulsion (I).

  In the silicone emulsion composition of the present invention, the aqueous dispersion (II) of (F) boron compound and (G) pigment is solid with respect to 100 parts by mass of the solid content of the silicone emulsion (I) obtained above. Add 0.1 to 300 parts by weight, preferably 10 to 250 parts by weight per minute. When the amount is less than 0.1 parts by mass, water absorption and weather resistance (antiseptic and ant repellency) are deteriorated. Moreover, when it exceeds 300 mass parts, miscibility with the said silicone emulsion (I) will worsen.

  Moreover, when it is set as a two-component wood treating agent, the use ratio of the aqueous dispersion (II) of the components (F) and (G) and the silicone emulsion (I) is the same as in the preparation of the silicone emulsion composition. The solid content of the aqueous dispersion (II) is 0.1 to 300 parts by mass, preferably 10 to 250 parts by mass with respect to 100 parts by mass of the solid content of the silicone emulsion (I). If the proportion of the aqueous dispersion (II) used is too small, the water absorption and weather resistance (antiseptic and ant repellency) deteriorate. Moreover, when there are too many usage rates of aqueous dispersion liquid (II), drying time will also become extremely long and will become inefficient.

  In addition, various thickeners, penetrants, antistatic agents, antifoaming agents, flame retardants, antibacterial agents, water repellents, and the like are appropriately added to the silicone emulsion composition or two-part wood treating agent of the present invention. Is optional.

  The wood that can be treated with the silicone emulsion composition or the two-part wood treating agent of the present invention is not particularly limited, and various kinds of wood such as solid wood, plywood, veneer laminate, LVL, particle board, and the like.

As the wood treatment method using the silicone emulsion composition of the present invention, the silicone emulsion (I) obtained above and the aqueous dispersion (II) of the components (F) and (G) are immediately before wood treatment. Mix to prepare a silicone emulsion composition and apply or impregnate the composition to wood. Time of immersion is preferably 5 minutes to 1 hour, amount of processing 2~60kg / m ³ on a dry weight, and particularly preferably to 10 to 30 kg / m ^3.

Further, in the two-part wood treating agent of the present invention, the aqueous dispersion (II) of the components (F) and (G) is applied or impregnated on wood, and immediately thereafter (immediately to 1 hour), the silicone emulsion ( I) is applied or impregnated on the wood. Incidentally, (F), (G) component of the aqueous dispersion treatment of (II) is, by dry weight 0.5~30kg / m ^3, preferably in particular 2 to 10 kg / m ^3, a silicone emulsion ( The treatment amount of I) is preferably 1 to ³⁰ kg / m ³ , particularly 5 to 20 kg / m ³ in terms of dry mass.

  Of the silicone emulsion composition of the present invention, the silicone emulsion and the boron-based compound have high penetrability into wood, and therefore the pigment penetrates into wood efficiently. The same can be said when an aqueous dispersion of a boron compound and a pigment is applied to wood immediately before use, and then a silicone emulsion is applied. The reason why the silicone emulsion and the components (F) and (G) are mixed immediately before use is that the pot life of the present silicone emulsion composition is about 24 hours.

  Furthermore, since the silicone emulsion film of the present invention is water-absorbing and rubbery, it has good followability to the base material, so cracks are unlikely to occur, and antiseptic / anti-white ant agents and pigments by water such as rainwater It is possible to impart a leaching prevention effect.

  Also, there is no particular limitation on the method for applying the silicone emulsion composition and the two-part wood treating agent, such as surface treatment such as brush coating, roll coating, spray coating, immersion treatment, decompression / pressure injection treatment, etc. It can be performed by a known method. In particular, it is a particularly excellent point of the present invention that even when applied with a brush, it is possible to impart an antiseptic / anticidal agent and a pigment leaching preventing effect by water such as rainwater. Thereafter, a cured film is formed by drying at room temperature. Curing is accelerated by heating at 50 to 150 ° C., and the processing time is shortened. The cured film is rubbery.

  EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part and% show a mass part and the mass%, respectively.

[Production Example 1]
498 g of octamethylcyclotetrasiloxane, 2 g of triethoxyphenylsilane, 50 g of 10% aqueous sodium lauryl sulfate solution and 50 g of 10% aqueous solution of dodecylbenzenesulfonic acid were charged in a 2 liter polyethylene beaker and uniformly emulsified with a homomixer. The mixture was gradually added for dilution, and passed twice through a high-pressure homogenizer at a pressure of 300 kgf / cm ² to obtain a uniform white emulsion. This emulsion was transferred to a 2 liter glass flask equipped with a stirrer, thermometer and reflux condenser, subjected to a polymerization reaction at 50 ° C. for 24 hours, aged at 10 ° C. for 24 hours and then 12 g of 10% aqueous sodium carbonate solution. Neutralized to pH 6.2. This emulsion has a non-volatile content of 45.4% after drying at 105 ° C. for 3 hours, the organopolysiloxane in the emulsion is a non-flowable soft gel, and the average composition is [(CH ₃ ) ₂ SiO _{2. / 2} ] / [(C ₆ H ₅ ) SiO _3/2 ] = 100 / 0.1 (molar ratio). In this way, emulsion [A-1] containing 44.4% of component (A) was obtained.

[Production Example 2]
Charge 500 g of octamethylcyclotetrasiloxane, 50 g of 10% aqueous sodium lauryl sulfate solution and 50 g of 10% aqueous solution of dodecylbenzenesulfonic acid into a 2 liter polyethylene beaker, uniformly emulsify with a homomixer, and gradually add 400 g of water to dilute. And passed through a high-pressure homogenizer at a pressure of 300 kgf / cm ² twice to obtain a uniform white emulsion. This emulsion was transferred to a 2 liter glass flask equipped with a stirrer, thermometer and reflux condenser, subjected to a polymerization reaction at 50 ° C. for 24 hours, aged at 10 ° C. for 24 hours and then 12 g of 10% aqueous sodium carbonate solution. Neutralized to pH 6.2. This emulsion has a non-volatile content of 45.5% after drying at 105 ° C. for 3 hours. The organopolysiloxane in the emulsion is represented by HO — [(CH ₃ ) ₂ SiO] _n —H, and has a viscosity of 1,000 Pa · s. It was the above raw rubber-like thing. In this way, an emulsion [A-2] containing 44.5% of the component (A) was obtained.

[Production Example 3]
After 154 g of maleic anhydride was dissolved in 500 g of ethanol, 346 g of 3-aminopropyltriethoxysilane was added dropwise at room temperature over 1 hour, and further reacted at 80 ° C. under reflux of ethanol for 24 hours. B) A solution [B-1] containing 50% of the component was obtained. This solution had a non-volatile content of 45.1% after drying at 105 ° C. for 3 hours, and the reaction product in the solution was subjected to instrumental analysis such as IR, GC, NMR, GCMS, etc. And the remaining approximately 40% were oligomers derived from them.
_{(C 2 H 5 O) 3} SiC 3 H 6 -NHCO-CH = CHCOOH
_{(C 2 H 5 O) 3} SiC 3 H 6 -NH 3 + -OCOCH = CHCOOC 2 H 5

[Production Example 4]
After adding 300 g of dioctyltin dilaurate and 50 g of polyoxyethylene nonylphenyl ether (EO 10 mol adduct) into a 2 liter polyethylene beaker, uniformly mixing with a homomixer, 650 g of water was gradually added and emulsified and dispersed in water. An emulsion [E-1] containing 30% of component (E) was obtained by passing twice through a high-pressure homogenizer at a pressure of 300 kgf / cm ² .

[Comparative Production Example 1]
To a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser and a dropping funnel, 2.0 g of a reactive emulsifier (Adekaria soap SE-10N, manufactured by Asahi Denka Kogyo Co., Ltd.) and 342.1 g of water are added, and the temperature is adjusted. The temperature was raised to 75 ° C. On the other hand, to 244.5 g of water, 2.0 g of a reactive emulsifier (Adekaria Soap SE-10N) was added and dissolved, and 230 g of 2-ethylhexyl acrylate, 230 g of styrene, 19 g of glycidyl methacrylate and 12.5 g of methacrylic acid were dissolved therein. The unsaturated monomer mixture was added and stirred, emulsified well, and then placed in a dropping funnel. Next, 5% of this monomer mixture is transferred to a reaction vessel, 0.5 g of potassium persulfate is added as a polymerization initiator, the temperature is raised to 80 ° C. and held for 10 minutes, and then the remaining monomer mixture emulsion And 50.0 g of a 3% potassium persulfate aqueous solution were uniformly added dropwise to the reaction vessel over 3 hours. After completion of the dropwise addition, a ripening reaction was carried out at 80 ° C. for 1 hour, and then the mixture was cooled to room temperature and neutralized by adding 3.5 g of ammonia water to obtain an emulsion [A-3] having a solid content concentration of 45%.

  In the pure composition shown in Table 1, γ-glycidoxypropyltrimethoxysilane [C-1] as component (C), colloidal silica as component (D) (Snowtex C manufactured by Nissan Chemical Industries, Ltd .: active ingredient 20) %) [D-1] was used to obtain each silicone emulsion.

[Production Example 5] (mixture of (F) and (G) 1) [FG-1]
U. S. Borax Inc. borate compounds called Timbor of _{(Na 2 B 8 O 13 ·} 4H 2 O) was used as a 10% aqueous solution with ion exchange water, EMF-BLACK HK (Toyo Ink Mfg. Co., Ltd. Carbon black in its 10% aqueous solution 87g ) Was added and mixed, and further 10% aqueous solution FG-1 was dispersed by adding ion-exchanged water. The solid content ratio of the borate compound and EMF-BLACK HK is 100 parts: 12 parts.

[Production Example 6] (mixture 2 of (F) and (G) 2) [FG-2]
U. S. Borax Inc. borate compounds called Timbor of _{(Na 2 B 8 O 13 ·} 4H 2 O) was used as a 10% aqueous solution with ion-exchanged water, the EMF-BLACK HK its 10% aqueous solution 85g 1g, EMF-BROWN HR ( 4 g of Toyo Ink Manufactured Bengala (red iron oxide) was added and mixed, and ion-exchanged water was further added to form a 10% aqueous solution FG-2.
The solid content ratio of the borate compound, EMF-BLACK HK, and EMF-BROWN HR is 100 parts: 4 parts: 31 parts.

[Production Example 7] (mixture 3 of (F) and (G)) [FG-3]
U. S. Borax Inc. borate compounds called Timbor of _{(Na 2 B 8 O 13 ·} 4H 2 O) was used as a 10% aqueous solution with deionized water, and mixed 6g added EMF-BROWN HR to the 10% aqueous solution 84 g, further ions A 10% aqueous solution FG-3 in which exchange water was added and dispersed was used.
The solid content ratio of the borate compound and EMF-BROWN HR is 100 parts: 46 parts.

<Test piece preparation>
[Examples 1 to 9]
To the silicone emulsion obtained in Table 1, an aqueous dispersion of components (F) and (G) was added and mixed with the formulation shown in Table 2 to prepare a silicone emulsion composition of the present invention. The final solid content in each example was adjusted to 10%. The composition is composed of 3 pieces of cedar wood of 1.4 cm × 3 cm × 3 cm (1.4 cm × 3 cm of the end of the mouth) and 9 pieces of cedar wood of 2 cm × 2 cm × 1 cm (2 cm × 2 cm of the end of the mouth) of room temperature Immersion treatment was carried out for 10 minutes under normal pressure and dried at 25 ° C. for 7 days to obtain modified wood. Three 1.4 cm × 3 cm × 3 cm cedar woods were used for the water absorption confirmation test, and 9 cm 2 cm × 2 cm × 1 cm cedar wood timbers were used for measuring the residual rate of boric acid. Each test method is shown below, and each test result is shown in Table 2.

[Example 10]
As shown in Table 2, FG-1 (10% aqueous dispersion) is 1.4 cm × 3 cm × 3 cm (the front end is 1.4 cm × 3 cm), 3 cedar woods and 2 cm × 2 cm × 1 cm (the front end is 2 cm). × 2 cm) cedar wood was dipped in 9 pieces each to a dry mass of 5.6 kg / m ³ , and then EM-1 was dipped to a dry mass of 11 kg / m ³ at 25 ° C. The modified wood was obtained by drying for 7 days. The test was carried out in the same manner as in Examples 1-9. The test results are shown in Table 2.

[Comparative Example 1]
The test was performed using three untreated cedar woods having the same dimensions as in the example. The results are shown in Table 3.

[Comparative Example 2]
Using FG-1 (10% aqueous dispersion), test pieces were prepared and tested in the same manner as in Examples 1-9. The results are shown in Table 3.

[Comparative Example 3]
U. S. Borax Inc. borate compounds called Timbor of _{(Na 2 B 8 O 13 ·} 4H 2 O) was used as a 10% water dispersion with deionized water, the test piece in the same manner as in Example 1-9 using this Were made and tested. The results are shown in Table 3.

[Comparative Example 4]
1 g of EMF-BLACK HK (manufactured by Toyo Ink Mfg. Co., Ltd.) and 4 g of EMF-BROWN HR (manufactured by Toyo Ink Mfg. Co., Ltd.) were added and mixed, and then 10% aqueous dispersion was used. A test piece was prepared and tested in the same manner as described above. The results are shown in Table 3.

[Comparative Examples 5 and 6]
With the formulation shown in Table 2, silicone emulsion compositions were prepared in the same manner as in Examples 1 to 9, and test pieces were prepared by the same method and tested. The results are shown in Table 3. In Comparative Example 6, since aggregates were generated, the subsequent test could not be performed.

[Comparative Example 7]
The emulsion EM-6 in Table 1 was added and mixed with the FG-1 aqueous dispersion to adjust the final solid content to about 10%, and test pieces were prepared and tested in the same manner as in Examples 1-9. The results are shown in Table 3.

[Comparative Example 8]
Although the FG-1 aqueous dispersion was added to and mixed with the emulsion EM-7 in Table 1, agglomerates were generated, and subsequent tests could not be performed.

<Mixability>
Each component was put into a 500 ml stainless steel container, and then stirred and mixed with a three-blade propeller at 200 rpm for 5 minutes using a three-one motor.
○: No foreign matter was generated and mixing was successful. Δ: Aggregates were generated after 2 to 3 minutes of mixing. X: Aggregates were generated immediately after mixing.

<Water absorption test>
The obtained 1.4 cm × 3 cm × 3 cm test piece (with a front end of 1.4 cm × 3 cm) was fully immersed in water, taken out after 24 hours, and measured for water absorption by the following formula (1). The average value of the test pieces was taken as the water absorption rate.
Water absorption rate = (W−W0) / W0 × 100 (%) (1)
W0: Weight of test specimen before water immersion (g)
W: Weight of test specimen immediately after completion of water immersion (g)

<Leaching test>
Using the test pieces of 2 cm × 2 cm × 1 cm (the end face is 2 cm × 2 cm) obtained in Examples 1 to 10 and Comparative Examples 2, 3, 5 and 7, the remaining amount of borate as shown below Was measured.
Method for measuring the amount of remaining borate (B amount) in a test piece A set of 9 test pieces is put in a 500 ml beaker, deionized water is added 10 times the volume of the test piece, and the test piece is placed below the surface of the water. Sink. Using a magnetic stirrer, the rotor is rotated at 400 to 450 revolutions per minute at a temperature of 25 ° C., stirred for 8 hours, and leached, and immediately the surface of the specimen is lightly drained. Subsequently, the volatile matter is volatilized by standing in a circulating dryer at a temperature of 60 ° C. for 16 hours. The above operation is repeated 10 times alternately.
Put a wood test piece in a Teflon beaker, add 50 ml of 3% nitric acid, and heat on a hot plate (200 ° C.) for 2 hours. After cooling, add water and dissolve to 50 ml. This operation is repeated 5 times, and the amount of each B is measured with an ICP analyzer, and the total amount is defined as the remaining amount of borate in the wood. The average value of nine samples is taken as the remaining amount.

<Weather resistance>
Ultraviolet irradiation was performed at 63 ° C. for 100 hours using ATLAS UV2000.
○: Almost no deterioration due to ultraviolet rays Δ: Although there is almost no color change due to ultraviolet rays, fine cracks occurred ×: Progression of deterioration on all or part of wood pieces

<Color fading>
Using a gauze soaked in water, the test piece was reciprocated 10 times, and the subsequent state was visually confirmed.
○: Color transfer to gauze is not observed ×: Color transfer to gauze is observed

Claims (6)

(A) Organopolysiloxane containing at least two hydroxyl groups bonded to silicon atoms in one molecule: 100 parts by mass
(B) Reaction product of amino group-containing organoxysilane and acid anhydride: 0.5 to 20 parts by mass,
(C) Epoxy group-containing organoxysilane and / or partial hydrolyzate thereof: 0 to 20 parts by mass,
(D) Colloidal silica and / or polysilsesquioxane: 0 to 50 parts by mass, and (E) Curing catalyst: 0 to 10 parts by mass of silicone emulsion (I) emulsified and dispersed in water, (F) boron An aqueous solution (II) in which a system compound and (G) pigment are dispersed is added and mixed at a solid content of 0.1 to 300 parts by mass with respect to 100 parts by mass of the solid content of the silicone emulsion. A silicone emulsion composition.   The silicone emulsion composition according to claim 1, wherein the pigment (G) is bengara and / or carbon black. (A) Organopolysiloxane containing at least two hydroxyl groups bonded to silicon atoms in one molecule: 100 parts by mass
(B) Reaction product of amino group-containing organoxysilane and acid anhydride: 0.5 to 20 parts by mass,
(C) Epoxy group-containing organoxysilane and / or partial hydrolyzate thereof: 0 to 20 parts by mass,
(D) colloidal silica and / or polysilsesquioxane: 0 to 50 parts by mass, and (E) curing catalyst: silicone emulsion (I) in which 0 to 10 parts by mass are emulsified and dispersed in water;
(F) A boron compound and (G) an aqueous solution (II) in which a pigment is dispersed, and the amount of the aqueous solution (II) used is 0.1% by solid content with respect to 100 parts by mass of the solid content of the silicone emulsion. A two-part wood treating agent characterized by having a ratio of 1 to 300 parts by mass.   The two-part wood treating agent according to claim 3, wherein the pigment (G) is Bengala and / or carbon black.   A wood treatment method using the silicone emulsion composition according to claim 1 or 2, wherein the silicone emulsion (I) and the aqueous solution (II) in the silicone emulsion composition are mixed and applied to wood immediately before use. A wood treatment method characterized by impregnating.   A wood treatment method using the two-part wood treating agent according to claim 3 or 4, wherein an aqueous solution (II) in which the components (F) and (G) in the two-part wood treating agent are dispersed is applied to wood. Alternatively, the wood treatment method is characterized by impregnating and immediately applying or impregnating the wood with the silicone emulsion (I) in the two-part wood treating agent.