JP2020062752A - Composite material comprising base material and layer of lacquer and organoalkoxysilane based material - Google Patents

Abstract

To provide a structure capable of protecting a lacquer material, inexpensive, and easy to be produced.SOLUTION: A composite material comprises: a base material 11; and a solidified layer 16 of a mixed liquid agent including a lacquer liquid agent and an organoalkoxysilane based liquid agent on the surface of the base material 11.SELECTED DRAWING: Figure 1

Description

The present invention relates to a composite material containing a lacquer and an organoalkoxysilane-based material having functions such as weather resistance on a substrate.

Lacquer is a natural resin paint whose main component is urushiol obtained by processing sap collected from Japanese lacquer tree (lacquer tree), and is used for paints and adhesives. As a lacquer used as a paint, for example, black lacquer is a traditional craft that has been evaluated for its unique beauty and texture, and is used for tableware, high-end furniture, musical instruments and the like. Lacquer has been used since the Jomon period since ancient times and is widely distributed in various parts of Japan as a craft product made by craftsmen and other experts, and there is a demand for the general public to make lacquerware that is lacquered. However, since lacquer can collect only about 200 g of sap from a single Japanese cypress, it is expensive and it causes a rash. As a working condition of lacquer coating, for example, the drying is performed in a normal temperature and high humidity drying chamber (called a room (muro)) where the humidity is kept at 75% to 85% and the temperature is kept at 20 ° C to 30 ° C. As described above, the drying conditions are special, and it is necessary to dry for a long time (10 days for a long one). Also, in order to obtain a beautiful lacquer coating, it is necessary to use craftsmanship that requires a high level of skill using various tools such as a lacquer brush and a spatula. In order to solve these problems, in Patent Document 1, a protein-related substance consisting of a protein hydrolyzate containing 0.05 to 25% by weight of a protein and an amino acid is added to lacquer, and the mixture is cured and dried at a lacquer rash and low temperature and low humidity. An improved lacquer is disclosed.

JP-A-10-73618 JP, 2016-056469, A

The improved lacquer disclosed in Patent Document 1 cannot be reduced in price because the amount of lacquer is 99.95 to 75% by weight. This improved lacquer application method has a problem that the original beauty of lacquer cannot be obtained unless it is applied by conventional lacquer application, the skill of a craftsman is still required, and that it is difficult for ordinary people to work easily. The protein-related substances added have low strength, so they do not serve as materials for protecting lacquer. Also, in the case of a single layer of lacquer, the lacquer coated product will be dried for the first time under a narrow special condition where the humidity is 75% to 85% and the temperature is 20 ° C to 30 ° C, and the drying time also requires 10 days. In some cases, productivity and efficiency are not good. When the temperature and humidity are high, the surface dries rapidly and the surface becomes dull and cloudy.When the humidity is too high, the components harden rapidly and the applied surface shrinks. It is also difficult to shorten the time and improve productivity and efficiency. The lacquer ware produced by drying under normal conditions is stable after 90 days to several months, but the lacquer layer is relatively soft until then, and there is a problem that it is easily damaged. Moreover, the degree of perfection of products from lacquer application to drying treatment depends on many years of experience of craftsmen, and it is difficult for ordinary people to make lacquer products.

The present invention is excellent in water repellency, strength, weather resistance, etc., strengthens the lacquer layer with a mixed lacquer agent of an easy-to-handle organoalkoxysilane-based material and lacquer, and prevents damage to the lacquer layer to prevent lacquer layers from the environment. Provide a structure that is protected and has a long life. Further, the present invention also provides a technique whereby even an ordinary person (amateur) can easily produce a lacquered product at low cost. Specifically, it has the following features.
(1) The present invention is a base material, a composite material having a solidified layer of a mixed liquid agent containing a lacquer liquid agent and an organoalkoxysilane-based liquid agent on the surface of the base material, or a base material, an organo-organic material on the surface of the base material. A first layer which is a solidified layer of an alkoxysilane liquid agent, and a second layer which is a solidified layer of a mixed liquid agent containing a lacquer liquid agent and an organoalkoxysilane liquid agent on the first layer, or a lacquer liquid agent on the first layer. Is a composite material having a second layer which is a solidified layer, and is characterized in that a solidified layer of an organoalkoxysilane-based liquid agent is provided on the solidified layer.

(2) The present invention is, in addition to (1), a solidified layer of a mixed liquid agent or a solidified layer of a lacquer liquid agent containing a lacquer liquid agent and an organoalkoxysilane-based liquid agent, and a plurality of solidified layers of the lacquer liquid agent. The solidified layer of the lacquer liquid agent is disposed between the solidified layers of No. 1, and the ratio of the lacquer liquid agent to the (organoalkoxysilane-based liquid agent + lacquer liquid agent) in the mixed liquid agent is 5 to 95% by weight. To do.
(3) In the invention, in addition to (1) and (2), the solidified layer of the organoalkoxysilane-based liquid agent or the mixed liquid agent has a siloxane bond, and the organoalkoxysilane-based liquid agent is an organoalkoxysilane, The organoalkoxysilane comprises R1 Si (OR2) 3 (wherein R1 is an organic group having 1 to 8 carbon atoms, and R2 is R2). Are the same or different and each represents an alkyl group having 1 to 4 carbon atoms and / or an alkenyl group having 5 to 7 carbon atoms), and the organoalkoxysilane further includes R12Si ( OR2) 2 (in the formula, R1 is the same or different, an organic group having 1 to 8 carbon atoms, R2 is the same or different, an alkyl group having 1 to 4 carbon atoms and / or a carbon atom) It is characterized by containing a diorganodialkoxysilane represented by an alkenyl group or a phenyl group of the formulas 1-8.

(4) In the present invention, in addition to (1) to (3), the organoalkoxysilane-based liquid agent is a liquid agent containing a curing and solidifying catalyst, and the catalyst is a hydrolyzable organometallic compound. The organometallic compound is an organometallic compound containing at least one metal selected from the group consisting of titanium, zirconium, aluminum, and tin, and the base material is an organic material, an inorganic material, or a mixed material thereof. The organic material is paper, wood, veneer, corrugated board, cloth, non-woven fabric, leather, plastic, polymer material, or a mixed material thereof, and the inorganic material is metal, ceramic, stone, concrete. , An insulator, a semiconductor, or a mixed material thereof, and the substrate is an embossed, shaped, or bent processed product, or Embossing timber after forming, shaping and bending, a processed product that various modifications, further the substrate is characterized by a piano, musical instrument, that is the external base portion of audio products.

In a composite material that has a mixed layer that is solidified by laminating a mixture of lacquer liquid and organoalkoxysilane-based liquid on the base material, lacquer is fused with the organoalkoxysilane-based liquid even in the mixed liquid state, and further heat treatment・ By a drying treatment, the lacquer is polycondensed with an organoalkoxysilane-based liquid agent, and the lacquer is in a state of being covered with glass films having a siloxane-containing side chain that cannot hydrolyze (siloxane bond). In addition, since the organoalkoxysilane-based liquid agent has a very high permeability, when the organoalkoxysilane-based liquid agent is mixed with the lacquer solution, the lacquer is uniformly dispersed by entering the lacquer solution and the lacquer has excellent homogeneity. + Glass mixed liquid agent can be made. When this mixed liquid agent is applied to a substrate, the mixed liquid agent spreads and coats on the surface of the substrate. A siloxane bond is also formed with the base material to firmly attach them. This is because lacquer has a stronger chemical bond than physically attached to the substrate by itself, and is also resistant to external force and environmental changes. Furthermore, it is possible to control the thickness of the coating of the mixed liquid agent, and it is possible to obtain the decorativeness and the high-class feeling of lacquer. Since the solidified layer is vitrified after coating, the coating layer is very stable. The time required for vitrification of the solidified layer is shorter than the conventional coating of lacquer alone, and the production time can be shortened.

Since the siloxane-bonded glass film has excellent weather resistance and heat resistance, wind and rain, moisture in the air, and tableware, etc., were coated with the (siloxane-bonded) glass film even if they were exposed to hot water such as washing water in a dishwasher. It has almost no effect on the layer containing lacquer. Further, since the (siloxane bond) glass film has a siloxane bond (Si-O-Si bond), it has a high mechanical strength and has strength superior to that of lacquer alone against external impact and external force and protects the substrate. In addition, the (siloxane-bonded) glass film has water repellency and can prevent cracking and peeling caused by the function of only the lacquer layer due to water or the like. The glass coating film on the base material has strength due to the chemical bond with the OH group in the base material, and also prevents the coating film from cracking or peeling due to a large change in environmental temperature that is impossible with the lacquer layer alone. It is possible and has excellent storability. Thus, in the composite material of the present invention, the lacquer is protected mechanically and environmentally, and the life of the product is extended. The (siloxane-bonded) glass film has flame resistance (basically does not burn) and heat resistance, so even if the base material is easily burnable (for example, wood, cloth, paper), the heat resistance is increased. Moreover, it protects the product from fading due to heat. Although this lacquer is a rare and expensive material, the amount of lacquer can be reduced, so the product price can be reduced. Also, because the lacquer layer is reaction-protected by (siloxane-bonded) glass coatings, or because the lacquer liquid is a mixed liquid of organoalkoxysilane-based liquids, it is difficult for the lacquer to rash and ordinary people can use lacquer materials with peace of mind. Can handle. The coating layer using a lacquer solution and an organoalkoxysilane-based solution has a large degree of freedom as a base material and can be applied to various base materials, and the texture of lacquer can be easily utilized. Furthermore, the coating using the lacquer solution and the organoalkoxysilane-based solution is highly resistant to dryness, ultraviolet rays, and changes in temperature due to the siloxane bond to the glassy substrate while maintaining the texture of the lacquer. It is strong, does not peel or crack the lacquer layer or mixed layer, and is resistant to drying, so it can be used in protection of cultural assets and in the harsh environmental conditions of the Middle East, desert areas such as the United States and Africa. Further, since the product can be easily washed with water and has moisture resistance, for example, the product is less contaminated, and even if it is contaminated, the product can be kept clean by washing with water.

FIG. 1 is a diagram showing a composite material having a solidified layer of a mixed liquid agent containing a lacquer liquid agent and an organoalkoxysilane-based liquid agent on a base material. FIG. 2 shows a first layer which is a solidified layer of an organoalkoxysilane-based liquid agent on a substrate, and a second layer which is a solidified layer of a mixed liquid agent containing a lacquer liquid agent and an organoalkoxysilane-based liquid agent on the first layer. It is a figure which shows the composite material which has. FIG. 3 is a diagram showing a composite material having a solidified layer of an organoalkoxysilane-based liquid agent as the uppermost layer.

The present inventor has arrived at the present invention by discovering that a glass film produced from an organoalkoxysilane (a loxane bond produced by mixing lacquer into a functional group side chain) has a large strength and a film protective function. The present invention solves the problems of lacquer while maintaining the goodness of lacquer. FIG. 1 is a view showing an embodiment of the present invention, in which a first surface and / or a second surface of a base material 11 having a first surface (also described as a front surface or an upper surface) and a second surface (also described as a back surface or a lower surface) A layer consisting of a liquid agent (also referred to as a mixed liquid agent or a mixed lacquer paint) in which a silane-based coating liquid agent (hereinafter, referred to as an organoalkoxysilane-based liquid agent) such as a lacquer liquid agent and an organoalkoxysilane-based liquid agent (including a liquid agent) is mixed on the surface. 16 (also referred to as a mixed layer) is laminated. That is, a mixed liquid agent (mixed lacquer paint) of a lacquer liquid agent and an organoalkoxysilane-based liquid agent is prepared, and the mixed lacquer paint is laminated (applied) on the surface of the base material 11 by various application means, and lacquer (liquid agent) ) And an organoalkoxysilane-based liquid agent are mixed to form a layer 16 (mixed liquid agent or mixed lacquer paint), and the layers 16 can be applied in layers if necessary. The base material 11 may be heat-treated or dried before applying the mixed liquid agent. For example, it is dried at 40 to 60 ° C. in a dry atmosphere for 2 to 10 hours in an inert gas (for example, N 2, rare gas). After the layer 16 made of the mixed liquid agent (mixed liquid agent or mixed lacquer paint) is applied and laminated, an appropriate heat treatment is performed to form the solidified layer 16 of the layer made of the mixed liquid agent (mixed liquid agent or mixed lacquer paint). In the case of recoating, a solidified layer may be formed between them by heat treatment or drying. In the present invention, the structural material of the base material 11 and the solidified layer 16 is called a composite material. (Note that in the case shown in FIGS. 2 and 3, a base material described in this specification in which a plurality of solidified layers are formed and a structural material including these solidified layers are also referred to as a composite material.)

The base material 11 is an organic material, an inorganic material, or a mixed material thereof. The organic material is a material mainly composed of an organic material, and is, for example, a polymer material, plastic, resin, rubber, leather, leather, cloth / woven fabric / knitted fabric, woven fabric, non-woven fabric, paper (Japanese paper, Western paper). , Functional papers, general papers, etc.), cellulosic materials such as wood, veneer, corrugated cardboard, cork, and other various fibers, and mixed materials thereof. Here, the mixed material refers to a material in which these materials are laminated, a material in which these materials are mixed in a mosaic shape, or a material in which these materials are mixed and mixed and integrated. The inorganic material is a material mainly composed of an inorganic material, and examples thereof include metals, semiconductors, insulators other than organic materials, stones, rocks, glass, concrete, ceramics, inorganic fibers, and the like, and mixed materials thereof. Alternatively, a mixed material of an organic material and an inorganic material may be used. Moreover, a porous body of these organic materials or inorganic materials may be used. Examples of the shape of the base material 11 include a plate shape, a square shape, a rod shape, a bowl shape, a conical shape, a spherical shape, an elliptical shape, and other various curved shape bodies, a sheet shape, a film shape, etc. Includes those that cannot be deformed and those that can be deformed.

An example of a deformable material is a material such as a sheet of paper or cloth, which can be bent or rolled, such as a film. For example, the substrate may be a stamped, shaped, or bent processed product. Alternatively, it may be a naturally curved body. For example, it may be a tree (including a broken tree and a dead tree), a plant (including a dead one and a fallen one), an animal (including a carcass, a skin, and a bone), and a fossil. Alternatively, it may be a building, various structures, their broken pieces, or ruins. Alternatively, a processed product obtained by performing various kinds of processing after forming the composite material can be used. For example, a processed product in which the composite material is embossed, shaped, bent, or otherwise deformed after the composite material is manufactured may be used. The thickness of the substrate is not particularly limited, but is 5 μm to 5 mm in the case of a sheet or film, and 50 μm to 50 mm in the case of a plate. Further, the area of the first surface / second surface of the base material is not particularly limited, and any size can be selected. The present invention is also a substitute for a conventional lacquer ware using lacquer alone, and thus can be applied to a material used for a conventional lacquer ware. For example, wood, bamboo, cloth, leather, paper, synthetic resin, glass, ceramics, plastic and the like can be mentioned. The base material 11 may be heat-treated or dried before applying the mixed liquid agent or the like. For example, it may be dried at 40 to 60 ° C. in a dry atmosphere and in an inert gas (for example, N 2, rare gas) for 2 to 10 hours.

The lacquer (liquid agent) used in the present invention will be described. For example, sap is collected from sumacaceae (lacquer tree) and black tree of the family Rhus. Make a notch on the surface of these trunks and store the exuding sap in a container. This sap is called "arami". The best time to collect the sap is from May to November when the sap is actively released. Although the amount of sap that can be taken depends on the thickness of the trunk, about 200 g of sap can be taken from one tree. The bark and dust are mixed in the radish, so heat it a little to increase the fluidity before filtering. The filtered sap is called "Kirushi". Next, raw lacquer is refined. The refining process of raw lacquer is divided into two processes, "nayashi" and "kurome". Nayashi is a process in which a stirrer is rubbed well to make a uniform state so that the coating film is dense and smooth, and has gloss or matte. Krome is a process of heating at 40 to 45 ° C. to remove excess water from coconut lacquer and stirring for 3 to 4 hours to make residual water content of, for example, 2 to 3%. In these processes, additives such as oil and iron are added according to the application and quality to produce refined lacquer. As the lacquer (liquid agent) used in the present invention, for example, refined lacquer that has undergone these two steps is used.

The one to which iron is added at the time of refining is called black lacquer (black lacquer), and a black color can be produced by a chemical reaction with urushiol. What is not added at the time of refining is lacquer lacquer (suki-urushi), which is a light-colored refined lacquer. Pigments (for example, vermilion (cinnabar sand), titanium oxide pigments (lake pigment)) are added to this lacquer lacquer as needed. ) Can be added to add color. As the lacquer (liquid agent) used in the present invention, various lacquer liquid agents such as black lacquer (black lacquer), transparent lacquer (sukiurushi), pigmented transparent lacquer are used. There are two types of refined lacquer, an oil-based system to which oil (for example, natural drying oil and rosin) is added and an oil-free system to which oil is not added. Generally, oil-based paints have good color and luster and are used for decoration and top coating. Oil-free type is suitable for polishing (such as sharpening and waxy finish). The lacquer (liquid agent) used in the present invention is both oil-based and oil-free.

Next, the organoalkoxysilane-based liquid agent used in the present invention will be described. The organoalkoxysilane-based liquid agent contains (a) at least one selected from the group of organoalkoxysilanes, hydrolysates thereof, and polycondensates thereof as a main component. Examples of the (a) organoalkoxysilanes include those represented by the formula (1); R1 Si (OR2) 3 (wherein R1 is an organic group having 1 to 8 carbon atoms, R2 is the same or different and is an alkyl group having 1 to 5 carbon atoms). And / or an organoalkoxysilane represented by an acyl group having 1 to 4 carbon atoms and / or an alkenyl group having 5 to 7 carbon atoms (hereinafter also referred to as "organoalkoxysilane (1)"), a hydrolyzate thereof. Or a polycondensate thereof. The component (a) may be an emulsion (including colloidal form) or a solvent type. The organoalkoxysilanes (a) have the formula (2); R12 Si (OR2) 2 (wherein R1 is the same or different, an organic group having 1 to 8 carbon atoms, R2 is the same or different, and the carbon number is An organoalkoxysilane represented by an alkyl group having 1 to 5 and / or an acyl group having 1 to 4 carbon atoms and / or an alkenyl group having 1 to 8 carbon atoms or a phenyl group (hereinafter referred to as “organoalkoxysilane (2)”). "), Its hydrolyzate, or its polycondensate in component (a) can be used in an amount of about 50% by weight or less.

Organoalkoxylanes are those which undergo hydrolysis and polycondensation in the presence or absence of an acid or alkali in the presence of water to give a high molecular weight, and the coating film cures or solidifies under heating or at room temperature. . Examples of the acid serving as the hydrolysis catalyst for the organoalkoxysilanes include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid and the like. Examples of the base serving as the hydrolysis catalyst include ammonia, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, ethanolamine, diethanolamine, triethanolamine and the like. When using these ordinary catalysts, water of reaction is allowed to coexist during hydrolysis. As described above, the silane-based coating liquid such as the organoalkoxylane-based liquid agent contains the catalyst and the reaction water. However, there is no particular problem in normal use, but when it is stored for a long period of time, there is a problem that the coating liquid is easily gelated by the reaction water. In order to solve this, it is preferable to use a hydrolyzable organometallic compound as a catalyst instead of the above-mentioned usual catalyst. When a hydrolyzable organometallic compound is used, it is not necessary to allow reaction water to coexist, and long-term storage stability is improved. Examples of the organometallic compound also include those containing titanium, zirconium, aluminum, or tin, and those containing two or more of these metals.

In the organoalkoxysilane (1), R1 in the above formula is an organic group having 1 to 8 carbon atoms, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, a .gamma.-chloropropyl group, a vinyl group, 3 , 3,3-trifluoropropyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, phenyl group, 3,4-epoxycyclohexylethyl group, γ-aminopropyl group, etc. R2 in the formula are the same or different, and are an alkyl group having 1 to 5 carbon atoms and / or an acyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and n. An organic silane compound such as -butyl group, sec-butyl group, t-butyl group, acetyl group, epoxy group, glycidyl group.

Specific examples of these organoalkoxysilanes (1) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyl. Trimethoxysilane, i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-Trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxy Ropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethylmethoxysilane, 3,4-epoxycyclohexylethylethoxy Examples thereof include silane, γ-aminopropylmethoxysilane and γ-aminopropylethoxysilane.

These organoalkoxysilanes (1) may be used alone or in combination of two or more. Preferably, methyltrimethoxysilane and / or methyltriethoxysilane are used. Further, as the component (a), a hydrolyzate obtained by previously hydrolyzing the organoalkoxysilane in the presence or absence of an acid or an alkali, and a polycondensate obtained by further aging the hydrolyzate and polycondensing It can also be used. Examples of the degree of polycondensation include polycondensates of about 2 to 10 molecules.

Specific examples of the organoalkoxysilane (2) constituting the component (a) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and methylvinyldimethoxysilane. , Methylvinyldiethoxysilane and the like, and polycondensates of about 2 to 10 molecules of these compounds can be exemplified. The amount of the organoalkoxysilane (2) used is about 50% by weight or less in the component (a), and if it exceeds 50% by weight, a siloxane bond is not formed well with the organoalkoxysilane (1), which is not preferable. The amount of the organoalkoxysilane (2) used in the component (a) is 50% by weight or less, preferably 5 to 40% by weight, more preferably 10 to 30% by weight. When the organoalkoxysilane (2) is used in combination with the component (a), flexibility can be imparted to the obtained coating film.

The component (a) of the present invention is obtained by subjecting an organoalkoxysilane to hydrolysis and polycondensation using an acid or a base as a hydrolysis catalyst in the presence of water. It is a mixture system of an alkoxysilane, a hydrolyzate thereof, and a polycondensate thereof, which is a mixture system of reaction water and generated alcohols, and its form is a solvent system, an emulsion, or a colloidal form. The component (a) of the present invention is obtained by subjecting an organoalkoxysilane to hydrolysis and polycondensation using an acid or a base as a hydrolysis catalyst in the presence of water. It is a mixture system of an alkoxysilane, a hydrolyzate thereof, and a polycondensate thereof, which is a mixture system of reaction water and generated alcohols, and its form is a solvent system, an emulsion, or a colloidal form.

An organometallic compound may be used as a catalyst for the hydrolysis and polycondensation of the component (a). Examples of this are, for example, titanium, zirconium, aluminum or tin complex, tetrapropoxy titanium, tetrabutoxy titanate, tetrapropoxy zirconate, tetrabutoxy zirconate, tripropoxyaluminate, aluminum acetylacetonate, dibutyltin diacetate, Examples thereof include dibutyltin dilaurate.

The organoalkoxysilane-based liquid agent may contain a hydrophilic organic solvent, and this hydrophilic organic solvent is used as a hydrolysis modifier of (a) the organoalkoxysilane. The hydrophilic organic solvent here also includes an alcohol produced by hydrolysis of the organoalkoxysilane constituting the component (a). The hydrophilic organic solvent used in the present invention is alcohols, glycols, esters, ethers, ketones and the like. Examples of the alcohols include aliphatic alcohols having 1 to 8 carbon atoms, such as methanol, ethanol, n-propanol, i-propanol, n-butanol, sec-butanol, t-butanol, n-pentanol, n-hexanol, 4 -Methyl-2-pentanol, 4-methyl-n-pentanol and the like can be mentioned. Examples of glycols include ethylene glycol and propylene glycol. Examples of the esters include esters of the alcohols and glycols such as formic acid, acetic acid and propionic acid, specifically, methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, ethyl propionate and the like. it can.

As the ethers, alkyl ethers of alcohols and glycols, such as dimethyl ether, diethyl ether, dibutyl ether, methyl ethyl ether, ethyl butyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether. Examples include ether. Examples of the ketones include acetone, diethyl ketone, methyl ethyl ketone, acetophenone and the like.

The mixing ratio of the hydrophilic organic solvent in the organoalkoxysilane-based liquid agent is, for example, 10 to 60% by weight, preferably 10 to 50% by weight. When the blending ratio of the organic solvent is less than 10% by weight, the viscosity of the liquid is excessively increased and the storage stability is lowered, while when it exceeds 60% by weight, the storage stability is improved, but the solid content concentration in the coating liquid is This is not preferred because the drying rate and the hydrolysis rate of the resulting coating film becomes smaller and the curing takes a long time.

The organoalkoxysilane-based liquid agent contains water (H2O) as a hydrolyzing agent for (a) the organoalkoxysilane. As this water, tap water, distilled water, ion-exchanged water, or an OH group component of water content in the substrate can be used. It also includes (a) water produced by hydrolysis of the alkylalkoxysilane. In addition, the water in the air may be used. The mixing ratio of water in the organoalkoxysilane-based liquid agent is, for example, 2 to 50% by weight, preferably 5 to 20% by weight. When the content of water is less than 2% by weight, (a) the organoalkoxysilane is not easily hydrolyzed, while when it exceeds 50% by weight, the stability of the coating solution is decreased and the drying speed of the coating film is also decreased. Is reduced, which is not preferable.

Further, the organoalkoxysilane-based liquid agent may be blended with other fillers. As these other fillers, for example, water-insoluble general pigments such as organic pigments or inorganic pigments, or particulate or fibrous metals and alloys other than pigments and oxides, hydroxides, and carbides thereof, One or more of nitrides and sulfides. Specifically, iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite. , Zircon (zirconium silicate), aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, molybdenum disulfide, zinc oxide, cobalt oxide, copper oxide, nickel oxide, tin oxide, cerium oxide, barium oxide, Examples thereof include antimony oxide, chromium hydroxide, molybdenum red, molybdenum white, manganese violet, azure blue, emerald green, and tungsten, but are not limited thereto.

Further, it is preferable to add an acid to the organoalkoxysilane-based liquid agent of the present invention as described above. The acid adjusts the pH of the coating liquid to an acidic region of less than 7, accelerates hydrolysis of the component (a), and accelerates curing of the coating film after coating. Examples of this type of acid include inorganic acids such as nitric acid and hydrochloric acid, acetic acid, formic acid, propionic acid, maleic acid, chloroacetic acid, citric acid, benzoic acid, dimethylmalonic acid, glutaric acid, glycolic acid, malonic acid, and toluenesulfonic acid. And organic acids such as oxalic acid. Of these acids, acetic acid is particularly preferable. These acids can be used alone or in combination of two or more. The mixing ratio of the acid in the composition is, for example, about 0.1 to 3% by weight with respect to the organoalkoxysilane constituting the component (a) in the organoalkoxysilane-based liquid agent. This makes it possible to adjust the pH of the coating liquid to less than 7, preferably 3.5 to 5.5. When the content of the acid is less than 0.1% by weight, (a) the hydrolysis of the organoalkoxysilane and the curing of the coating film after coating become insufficient, while when it exceeds 3% by weight, the residual acid when the coating film is formed is obtained. It is not preferable because it increases.

Furthermore, the organoalkoxysilane-based liquid agent of the present invention includes various surfactants, silane coupling agents, titanium coupling agents, metal acetylacetonates, naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, carbonic acid, etc. It is also possible to add other conventionally known additives such as a stabilizer such as an alkali metal salt of, and Tinuvin (manufactured by Ciba Specialty Chemicals). In addition, a deodorant that alleviates the peculiar odor of wood vinegar oil or a fragrance that produces a pleasant odor and masks the peculiar odor of wood vinegar oil can be added. An emulsion or colloidal liquid composition containing the above components and, if necessary, an additive such as an acid and having a solid content concentration of 10 to 40% by weight, preferably 10 to 30% by weight in an acidic region of less than pH 7. is there. If the solid content is less than 10% by weight, a coating film having a sufficient thickness cannot be obtained by one application, resulting in poor workability or too low coating strength. On the other hand, if it exceeds 40% by weight, gelation occurs. It is not preferable because the viscosity is easily increased, the adhesion is deteriorated, and it is difficult to obtain a coating film having a uniform film thickness. The organoalkoxysilane-based liquid agent of the present invention includes, for example, a solution-based or emulsion-based or colloidal component (a) (including a hydrophilic organic solvent and water), if necessary, with an acid component and other fillers added. It can be prepared by sufficiently dispersing using a roll mill, ball mill, stirrer, etc., but the preparation method is not limited.

The ratio in the mixed liquid of the lacquer liquid and the organoalkoxysilane-based liquid may be appropriately selected by a combination that optimizes the effect and life of the lacquer according to the purpose of use, but the weight% (lacquer liquid / (organoalkoxysilane It is preferably 5% to 95% in a system liquid agent + lacquer liquid agent)). If it is less than 5%, the effects such as the texture of lacquer will be weakened, and if it exceeds 95%, the effect of the organoalkoxysilane-based liquid agent will not be exhibited. However, if the effect of lacquer or the effect of the organoalkoxysilane-based liquid agent is not required so much, a composition outside these ranges may be used. A lacquer solution and an organoalkoxysilane-based solution are put into an appropriate amount in a container, stirred automatically or manually, and sufficiently mixed to prepare a mixed solution. At this time, another solvent such as alcohol or ether, or a diluting solution of a lacquer solution (for example, turpentine oil, one brain oil, camphor) may be added. For the laminated coating of the mixed liquid agent on the surface of the substrate, coating means such as spin coating, brush coating, spraying, spraying, spraying, dipping, roll coating, printing and squeegee can be used. As described above, in the case of the mixed lacquer paint, various means can be used as the application method, so that not only craftsmen but also ordinary people can easily apply it, and productivity and efficiency can be easily increased. Moreover, since the amount of lacquer, which is an expensive material, can be reduced, the material price and the product price can be reduced. Of course, a conventional method of applying a lacquer liquid agent can also be used. For example, a spatula, a brush, a spray or the like is used for undercoating, intermediate coating, and topcoating to form the mixed liquid agent layer. It is also possible to add sharpening or polishing before or after these steps, or to add other methods (for example, applying metal powder for lacquer work, attaching gold foil, etc.).

These steps may be repeated, and if necessary, several mixed liquid agent layers may be laminated and laminated. After the laminated coating, a heat treatment and / or a drying treatment and / or a humidity adjusting treatment are performed to solidify or cure the mixed liquid agent layer. When a mixed liquid agent layer having a predetermined amount or a predetermined thickness cannot be formed by one-time application, application or lamination may be performed a plurality of times, and in that case, the above-mentioned application methods may be used in combination. In the case of recoating, heat treatment and / or drying treatment and / or humidity adjustment treatment may be performed once or plural times. In this case, the mixed layer is a group of a plurality of mixed layers (a laminated body of mixed layers). The heat treatment is preferably carried out in an inert gas (for example, nitrogen, argon, etc.) or air atmosphere under reduced pressure / pressurization / normal pressure at 50 ° C. to 200 ° C. for about 5 minutes to 120 minutes. When dried at room temperature, it may be left for about half a day to 6 days. In the intermediate heat treatment / intermediate drying treatment in the case of recoating, the mixed liquid agent layer may not be sufficiently solidified but may be sufficiently dried and solidified in the final heat treatment. Even if the final heat treatment does not sufficiently solidify, the mixed liquid agent layer can be sufficiently solidified by leaving it to stand. In some cases, the mixed liquid agent layer may not be sufficiently solidified depending on the use. Further, the heat treatment and / or the drying treatment and / or the humidity adjusting treatment and the like can be appropriately changed depending on the state (thickness, amount, solidification or liquefaction degree) of the mixed liquid agent layer 16 or manufacturing conditions or working conditions. . In this way, when the mixed liquid agent layer is subjected to heat treatment, drying treatment, etc., the layer containing the organoalkoxysilane-based liquid agent undergoes a siloxane reaction ((3-step reaction formula (i) Si-OR + H ₂ O → Si-OH + ROH, ( ii) Si-OH + HO- Si → Si-O-Si + H 2 O, (iii) Si-OH + RO-Si → Si-O-Si + ROH) solidified, siloxane bond is produced which is the basic skeleton of glass, (i.e., a siloxane A network polymer is formed) and a cured layer is formed. (Patent Document 2) By the siloxane bond reaction of the alkoxysilane, a siloxane bond is formed by reacting with the OH group of the base material or with the OH group in the air, and the lacquer is bonded to the base material and the siloxane, that is, Lacquer is considered to be incorporated into the siloxane network polymer, and the mixed (coating) layer 16 is formed. In other words, the mixed (coating) layer is siloxane-bonded to the base material and firmly adheres to it, and is stronger than the case where lacquer is physically attached to the base material alone, so it is strong against external force and environmental changes. .

The layered application of the mixed liquid agent on the surface of the base material may be carried out by using the conventional method of lacquering. For example, using a spatula, a brush, a spray or the like, undercoating, intermediate coating, and topcoating are performed to form the mixed liquid agent layer 16. Before and after these steps, polishing, polishing, heat treatment, drying treatment, or the like can be added, or other methods (for example, applying metal powder for lacquer work or attaching gold foil) can be added. Furthermore, coloring can be performed by mixing a lacquer liquid containing pigment or mixed rust, and conventional techniques used in various lacquer techniques may be adopted. These steps may be repeated, and if necessary, several layers of these layers may be stacked and laminated (mixed layer laminate). Also, a single layer or a plurality of lacquer liquid agent layers may be inserted between these mixed liquid agent layers (or solidified layers thereof). It is also possible to add the component contained in the organoalkoxysilane-based liquid agent after mixing the component (a) in the organoalkoxysilane-based liquid agent with the lacquer liquid agent. Alternatively, the mixed liquid agent layer can be applied using another method (for example, dipping (dipping), screen printing, spin coater). After this, heat treatment and drying are performed to solidify the applied lacquer layer. For example, the drying conditions are 15 ° C. to 30 ° C., the humidity is 20% to 85% (the atmosphere is the humidity in the air), and the drying time is 1 to 10 days. It is also possible to change the conditions as appropriate by checking the dryness. In the case of overcoating, heat treatment, drying treatment or the like may be performed each time. The mixed liquid agent layer 16 (solidified layer thereof) shown in FIG. 1 is a layer obtained through these steps.

The thickness of the mixed liquid agent layer (solidified layer or mixed layer) 16 is, for example, 5 μm to 5 mm, depending on the thickness of the base material, but depending on the application and the position of the base material, the thickness is appropriately set. You can change it. When the coating layer 16 having a predetermined amount or a predetermined thickness cannot be formed by one coating, the coating layer 16 can be formed by stacking the coating layer in multiple times, and heating / drying treatment / humidity adjustment during and / or at the end thereof. You may perform a process etc. The heat treatment (which becomes a laminate of mixed layers in this case) is, for example, 20 ° C. to 100 ° C., the humidity is 30% to 90%, the atmosphere is nitrogen, an inert gas, and air, and the pressure is pressurization, normal pressure, depressurization. The time can be 10 minutes to 1 day. Suitable heat treatment conditions with the siloxane bond mixed liquid agent are 30 ° C to 80 ° C, humidity 40 to 80%, time is 30 minutes to 5 hours, optimally 40 ° C to 60 ° C, humidity 50 to 70%, time is 90. Minutes to 3 hours. After coating, vitrification of the mixed layer stabilizes the coating in the mixed layer, and the time required for vitrification is 1/2 to 1/10, which is much shorter than that of conventional lacquer alone. The time is greatly reduced. Multiple coatings can be applied if necessary, but to obtain the same effect, it is possible to make it thinner than in the case of using lacquer alone, and the number of repeated coatings can be reduced. The degree of freedom in heat treatment and drying conditions is greater than in the case of using the lacquer liquid layer alone, and the processing time is short, so productivity is high and efficiency is good. In the intermediate heat treatment in the case of multiple coating, the coating layer may be solidified (cured), or the solidification may be slightly insufficient. Further, natural drying for 1 day to 1 week can be performed. When the deformation temperature of the substrate is high, the temperature can be higher than the above temperature, and the treatment can be performed for a short time. It is desirable that the mixed layer is sufficiently solidified by the final heat treatment and the final treatment, but the solidification may not be sufficient depending on the use. The reaction curing is completed over time by leaving it to stand for a while. In this way, by forming the mixed lacquer paint layer on the substrate using the mixed lacquer paint, the degree of freedom of heat treatment conditions is greater than when lacquer alone, and the mixed lacquer paint layer is cured by heat treatment for a short time. be able to. Therefore, not only craftsmen but also ordinary persons can easily heat-treat to produce products, and productivity and efficiency can be easily improved.

In these mixed liquid agents, it is considered that the lacquer liquid agent is covered with the organoalkoxysilane-based liquid agent in the mixed liquid agent state, that is, in a microscopic state. That is, since the organoalkoxysilane-based liquid has a very high permeability, in the mixed liquid mixed with the lacquer liquid, the organoalkoxysilane-based liquid gets into the lacquer liquid, so that the lacquer is uniformly dispersed in the mixed liquid and is homogeneous. A liquid mixture of lacquer and glass liquid with excellent properties can be made. When this mixed liquid agent is applied to the substrate, the mixed liquid agent spreads and coats on the surface of the substrate. By heat treatment or drying, the siloxane bond reaction of the alkoxysilane reacts with the OH group of the base material or with the OH group in the air to form a siloxane bond, and it is thought that lacquer is bonded to the base material and its siloxane. The mixed coating film 16 is produced. That is, the mixed coating film is siloxane-bonded to the base material and firmly adheres to it, and since the lacquer has a stronger chemical bond than the case where the lacquer is physically attached to the base material alone, it is strong against external force and environmental changes. Since the thickness of the mixed coating film can be controlled appropriately, the decorativeness, high-class feeling, and texture of lacquer can be obtained. When the base material 11 is a porous fiber or the like, a part of the mixed liquid agent permeates the inside of the fiber 11 through the pores and solidifies. (Indicated by the broken line arrow 18 in FIG. 1B.) Therefore, the solidified layer (cured layer) 16 formed by the mixed liquid agent is formed inside the base material 11 and on the surface of the base material 11. Therefore, the solidified layer 16 formed on the surface of the base material 11 by the mixed liquid has particularly good adhesion to the base material 11. In addition, the (siloxane-bonded) glass film has flame resistance (basically does not burn) and heat resistance, so even if the base material is easily burnable (for example, wood (woodenware)), Protect the product from. Also, for lacquer rashes, since the lacquer liquid is in a state of being covered with the organoalkoxysilane-based liquid, and because the ratio of lacquer to the organoalkoxysilane-based liquid is low, it is difficult for the lacquer to rash and the general public feels comfortable with the mixed liquid formulation. Can handle.

Since the organopolysiloxane in which the organoalkoxysilanes are solidified (cured) is a strong film, the solidified layer (cured layer) 16 formed by the mixed layer is also strong and is strong against external impact and the like and is not easily scratched. Furthermore, since the organopolysiloxane layer is resistant to acids, alkalis, moisture, etc., it has excellent environmental resistance. As described above, by using the mixed lacquer paint, anyone can easily apply the lacquer layer to the base material and cure it, and it is inexpensive. The product can also be used in a dishwasher or dryer, and will not deteriorate or crack even if the product placed in the product is heated in a microwave oven (within 2 minutes if the base material is cellulosic). Even if a high temperature object is placed on the mixed layer on the substrate, the mixed layer does not discolor, and since the mixed layer has high film strength, it is not damaged even when the products are stacked. Furthermore, the coating film does not peel due to environmental changes, and it has antibacterial and antifungal properties. In this way, it is possible to perform a treatment that cannot be performed with a conventional lacquer single layer. Since the mixed layer has a high adhesion due to the siloxane bond with the base material, a mixed liquid agent is applied and solidified to form a mixed layer on a base material that cannot be conventionally applied, for example, a concrete wall portion such as a castle wall or a building. The effect of lacquer can be demonstrated. INDUSTRIAL APPLICABILITY The present invention can be applied to exteriors of pianos and audio products, interior products and interiors and exteriors of automobiles, and can increase the added value by exerting effects such as protection of cultural properties and the beauty and luxury of lacquer. For example, as a coating film for an exterior base material such as a lid of a piano, the coating film of the present invention is used in place of the coating material (for example, urethane coating material or polyester coating material) used for conventional piano black coating. It is also possible to produce effects such as texture and a sense of quality.

FIG. 2 is a view showing another embodiment of the present invention, in which a part or all of the surface of the substrate 11 is a first layer 22 which is a solidified layer of an organoalkoxysilane-based liquid agent, and the first layer 22. 2 shows a composite material having a second layer 23 which is a solidified layer of a mixed liquid agent containing a lacquer liquid agent and an organoalkoxysilane-based liquid agent in a part or all of the above. The composition, materials, etc. of the base material 11, the organoalkoxysilane-based liquid agent, and the lacquer liquid agent are the same as those described in FIG. Depending on the type of base material, the adhesion between the base material and the lacquer solution may not be very good, or, if the ratio of the lacquer solution among the mixed solution becomes high, the mixture solution containing the lacquer solution and the organoalkoxysilane-based solution There is a possibility that the solidified layer 16 may be peeled off the base material 11 or the like. On the other hand, the organoalkoxysilane-based liquid agent has good adhesiveness regardless of the type of the base material (that is, siloxane bond to the base material and firmly adheres to the base material). A solidified layer 22 is formed, and then a solidified layer (mixed layer) 23 of a mixed liquid agent containing a lacquer liquid agent and an organoalkoxysilane-based liquid agent is formed. Since the first layer and the second layer are also siloxane-bonded and firmly adhered, a stable texture of lacquer can be maintained for a long time regardless of the type of the base material 11. As described in FIG. 1, the mixed layer may be a laminated body of mixed layers.

On the surface of the base material 11 (after the base material 11 is subjected to a pretreatment such as a drying treatment, a heat treatment, or a humidity adjusting treatment, if necessary), an organoalkoxysilane-based liquid agent (including a liquid agent) such as a silane-based coating liquid agent (hereinafter , An organoalkoxysilane-based liquid agent). Even if the thickness of the solidified layer 22 of the organoalkoxysilane-based liquid agent is considerably thin, the adhesion of the solidified layer 23 of the mixed liquid agent thereon can be improved. However, considering the cost of the liquid agent, it is preferably about 5 μm to 10 mm. Is 100 μm to 5 mm. The layer containing the organoalkoxysilane-based liquid agent can be laminated by using coating means such as spin coating, brush coating, spraying, spraying, spraying, dipping, roll coating, printing, and squeegee. When it is not possible to form a layer containing a predetermined amount or a predetermined thickness of the organoalkoxysilane-based liquid agent by a single coating, a plurality of coatings or laminations may be performed. In that case, the above coating methods may be used in combination. it can. In the case of recoating, the heat treatment and / or the drying treatment and / or the humidity adjusting treatment may be performed once or plural times. In this case, the layer containing the organoalkoxysilane-based liquid agent is a laminate of layers containing the organoalkoxysilane-based liquid agent (including its solidified layer) in which a plurality of layers containing the organoalkoxysilane-based liquid agent are stacked. The heat treatment is preferably carried out in an inert gas (for example, nitrogen, argon, etc.) or air atmosphere under reduced pressure / pressurization / normal pressure at 50 ° C. to 200 ° C. for about 5 minutes to 120 minutes, and also at room temperature. In this case, it may be left for 1 to 6 days. The layer containing the organoalkoxysilane-based liquid agent does not have to be sufficiently solidified in the intermediate heat treatment, the intermediate drying treatment, the humidity adjustment treatment, and the like in the case of recoating, and may be sufficiently solidified in the final heat treatment. Even if the solidification is not sufficient even by the final heat treatment, the layer containing the organoalkoxysilane-based liquid agent can be sufficiently solidified by leaving it to stand. Further, depending on the application, the layer containing the organoalkoxysilane-based liquid agent may not be required to be sufficiently solidified. Thus, when the layer containing the organoalkoxysilane-based liquid agent is subjected to heat treatment, drying treatment, etc., it undergoes a siloxane reaction (three-step reaction formula (i) Si-OR + H2O → Si-OH + ROH, (ii) Si-OH + HO-Si). → Si-O-Si + H2O, (iii) Si-OH + RO-Si → Si-O-Si + ROH) Solidify to form a siloxane bond, which is the basic skeleton of glass (that is, a siloxane network polymer is formed), and a cured layer 22 is formed. (Patent Document 2)

Then, a mixed liquid agent containing a lacquer liquid agent and an organoalkoxysilane liquid agent is laminated on the solidified layer (first layer) 22 of the organoalkoxysilane liquid agent, and heat treatment is performed to solidify the mixed liquid agent (second layer). 23 is formed. This condition may be the same as that described in FIG. As described in the description of FIG. 1, a plurality of lacquer single layers may be included between the solidified layers of the mixed liquid agent. The same material as the organoalkoxysilane-based liquid agent is used for the first layer and the second layer, and since the first layer and the second layer have many strong siloxane bonds and are firmly adhered to each other, the thickness of the second layer is Compared with the case shown in FIG. 1, the thickness can be reduced for the same characteristics (for example, texture as lacquer). Therefore, since the amount of (expensive) lacquer can be reduced as compared with the case where only the solidified layer of the mixed liquid agent shown in FIG. 1 is used, the material cost of the lacquer liquid agent can be reduced. Alternatively, the second layer 23 may be a liquid layer containing no organoalkoxysilane-based liquid material, that is, a solidified layer containing only a lacquer liquid material. Since lacquer has a high viscosity, it can be diluted with a diluting solution (for example, turpentine oil, cerebrum oil, camphor) for easy application if necessary. A lacquer layer is formed by using a spatula, a brush, a spray or the like to apply a base coat, a middle coat, and a top coat. It is also possible to add sharpening or polishing before or after these steps, or to add other methods (for example, applying metal powder for makie). These steps may be repeated, and if necessary, several lacquer layers may be stacked and laminated. Adhesion and wettability of the solidified layer of the first layer organoalkoxysilane-based liquid agent and lacquer are good, and after the lacquer layer is solidified, the lacquer layer and the solidified layer of the underlying organoalkoxysilane-based liquid agent are firmly bonded by siloxane bonds. Since it is adhered to, it is possible to thin the conventional lacquer layer only. For example, the amount of expensive lacquer can be reduced by reducing the amount to less than half that of the conventional lacquer layer. Also, even if the conventional lacquer alone is overcoated, less than half of it can be overcoated. Alternatively, the lacquer layer 23 can be applied using another method (for example, dipping (dipping), screen printing, spin coater). After this, heat treatment and drying are performed to solidify the applied lacquer layer. For example, the drying conditions are 15 ° C. to 30 ° C., the humidity is 75% to 85% (atmosphere is air), and the drying time is 1 to 10 days. It is also possible to change the conditions as appropriate, depending on the dryness. In the case of overcoating, heat treatment, drying treatment or humidity adjustment treatment may be performed each time. The lacquer layer 23 shown in FIG. 2 is a layer of lacquer which has undergone these steps. The lacquer layer 23 has a thickness of, for example, 5 μm to 5 mm, and the thickness may be changed depending on the application and the position of the base material.

FIG. 3 is a view showing another embodiment, showing a composite material having a solidified layer of an organoalkoxysilane-based liquid agent as the uppermost layer. FIG. 3A shows the structure shown in FIG. 1, that is, the composite material in which the solidified layer 16 of the mixed liquid agent containing the lacquer liquid agent and the organoalkoxysilane liquid agent is formed on the base material 11 and further the solidification of the organoalkoxysilane liquid agent. It is a figure which shows the composite material which formed the layer (mixed layer) 24. FIG. 3B is a structure shown in FIG. 2, that is, a solidified layer of a mixed liquid agent containing a first layer 22 on the base material 11 and a lacquer liquid agent and an organoalkoxysilane-based liquid agent on the first layer 22. It is a figure which shows the composite material which further formed the solidification layer 25 of the organoalkoxysilane type liquid agent in the composite material which formed the layer 23. The contents such as the composition and forming conditions of the organoalkoxysilane-based liquid agent for the solidified layers 24 and 25 are the same as those described above. Alternatively, even when the second layer 23 is a lacquer layer, a solidified layer 25 of an organoalkoxysilane-based liquid agent can be further formed on this composite material. In the structure shown in FIG. 3A, the first layer may be the lacquer layer and the second layer (the uppermost layer) may be the solidified layer 25 of the organoalkoxysilane-based liquid agent. The formation of the first lacquer layer is the same as that described above, and it is also possible to use overcoating (laminate of lacquer layer) such as undercoating, intermediate coating, and topcoating. In this case, the second layer is then covered with the first layer by a solid layer (cured layer) obtained by reacting and solidifying the organoalkoxysilane liquid agent to protect the first lacquer layer. The first layer of can be thinned. For example, the amount of the expensive lacquer layer can be reduced by reducing the amount of the lacquer layer to less than half that of the conventional lacquer layer. Further, even if the conventional coating is repeated, less than half of the coating is required. A heat treatment or a drying treatment for applying a lacquer layer (first layer) of a predetermined amount or a predetermined thickness (the thickness may be different depending on the location of the base material) on the base material 11 and curing the lacquer layer (first layer). Or a humidity control treatment to cure the lacquer layer (first layer), and then a silane-based coating liquid agent (such as a liquid agent containing an organoalkoxysilane-based liquid agent) on the lacquer layer (first layer) (this specification). Then, an organoalkoxysilane-based liquid agent is also described) is laminated (coated) to form a second layer (a layer containing the organoalkoxysilane-based liquid agent) 13. Next, heat treatment, drying treatment, etc. are performed to solidify the layer of the silane-based coating liquid agent. In the case of repeated coating (multilayer coating), heat treatment, drying treatment or the like may be performed each time.

After heat-treating or drying the layer containing the organoalkoxysilane-based liquid agent, the layer containing the organoalkoxysilane-based liquid agent is solidified so as to cover the solidified layer (mixed layer) of the mixed solution of the lacquer solution and the organoalkoxysilane-based liquid agent. . When a layer containing an organoalkoxysilane-based liquid agent is laminated and heat-treated and dried without sufficient solidification of the mixed layer, the mixed layer may also penetrate into the layer containing the organoalkoxysilane-based liquid agent and become mixed together. is there. For example, the mixed layer penetrates into the pores formed in the layer containing the organoalkoxysilane liquid agent and solidifies. In the heat treatment / drying step after stacking the layers containing the organoalkoxysilane-based liquid agent, the mixed layer in which the highly-permeable organoalkoxysilane-based liquid agent has permeated to form a thin film. That is, the mixed layer permeated inside the siloxane-bonded glass thin film formed by polycondensation of the organoalkoxysilane-based liquid is retained. As described above, the layer containing the organoalkoxysilane-based liquid agent (the liquid portion almost disappears after the heat treatment or after the drying, but is described with the same name for convenience) not only covers the base mixed layers 16 and 23 but also penetrates. The mixed layer is also osmotically coated. Therefore, the underlying mixed layer and the uppermost layer are firmly bonded by a siloxane bond. In addition, the composite material in which a layer containing an organoalkoxysilane-based liquid agent is formed on the lacquer layer is also covered with a glassy thin film formed by siloxane-bonding the lacquer layer by heat treatment, drying treatment, humidity adjustment treatment, etc. Is. Since the organoalkoxysilane-based liquid agent layer is siloxane-bonded to the OH groups of the lacquer layer, the adhesion between the lacquer layer (solidified layer) and the organoalkoxysilane-based liquid agent layer (solidified layer) is extremely good.

The hardness of the hardened lacquer layer is 3 to 4 in Mohs' hardness, which is relatively hard, but it may be damaged by nails as well as knives. Although the mixed layer is harder than the lacquer single layer, it is softer than the solidified layer (6 to 7 in Mohs hardness) of the organoalkoxysilane-based liquid agent, and the lower the mixing ratio of the lacquer liquid agent, the lower the hardness of the mixed layer. Therefore, the composite material with the mixed layer on top should be treated carefully to avoid damage. However, since the layers 24 and 25 containing the organoalkoxysilane-based liquid agent have a vitreous siloxane bond after being solidified (cured), they are strong and have high heat resistance, abrasion resistance, strength and hardness, and thus are strong. If the structure, that is, the mixed layer is covered with a siloxane-bonded glass layer obtained by solidifying an organoalkoxysilane-based liquid agent, it can be prevented from being damaged by a large external pressure. In addition, since the layers 24 and 25 containing the organoalkoxysilane-based liquid agent have a vitreous siloxane bond after solidification, they have environmental resistance (light resistance, heat resistance, flame retardancy, water repellency, water resistance, acid resistance, oxidation resistance). Etc.) are also excellent. Further, since the vitreous material after the solidification of the layers 24 and 25 containing the organoalkoxysilane liquid agent is transparent to visible light, it does not affect the texture of the underlying mixed layer 12. The thickness of the mixed layer as the uppermost layer is effective if it exists, but it is preferably 100 μm to 5 mm. The same applies when the lower layers of the layers 24 and 25 containing the organoalkoxysilane-based liquid agent, which are the uppermost layers, are lacquer layers. In particular, in the case of the lacquer layer alone, the layer is softer than the mixed layer and is therefore easily scratched. However, by covering the upper layer with a layer containing an organoalkoxysilane-based liquid agent as in the present invention, damage is less likely to occur.

Therefore, by using the solidified layer of the organoalkoxysilane-based liquid agent as the uppermost layer of the present invention, the composite material can be protected so as not to damage the lacquer material such as the lacquer ware for a long period of time while maintaining a bewitching beauty. Moreover, when the mixed layer or the like is the uppermost layer, the thickness of the mixed layer needs to be increased to some extent in order to maintain the strength, but in the present invention, the thickness of the mixed layer or the like is thin, for example, the mixed layer or the like is about half the thickness of the uppermost layer. Since it can be applied, the material cost of the expensive lacquer layer can be reduced. The structure of the present invention can also be applied to lacquer work / gold leaf, which is one of the lacquer craft techniques. Maki-e is a technique in which a lacquer (mixed layer) is used to draw pictures, patterns, letters, etc. on the surface of the lacquerware, and before it dries, the metal powder such as gold or silver is “sown” to be fixed on the surface of the lacquerware. Then, an organoalkoxysilane-based liquid agent, which is the uppermost layer, is applied on this makie and heat-treated or dried to solidify the layer of the organoalkoxysilane-based liquid agent. As a result, the lacquer work and the gold foil can be protected by the vitreous layer having a siloxane bond so as not to be easily scratched, and the deterioration of the product is small even after long-term use, and the life of the product can be extended. Further, since the uppermost glassy layer having a siloxane bond has flame retardancy and heat resistance, the risk of fire is small.

As explained in detail above, a mixed layer of a lacquer solution and an organoalkoxysilane-based solution is formed on the base material to form a mixed layer on the base material, or a solidified layer of the organoalkoxysilane-based solution is formed on the base material. After that, by forming a mixed layer, etc., or by forming a solidified layer of an organoalkoxysilane-based liquid agent as the uppermost layer of these composite materials, the problem of the lacquer single layer applied and laminated on the substrate is solved. can do. In addition, a solid glass of siloxane bond generated from the inside of the base material by polycondensation reaction with the OH groups in the base material or in the air due to the permeation of the mixed liquid agent of the lacquer liquid agent and the organoalkoxysilane-based liquid agent or the organoalkoxysilane-based liquid agent Due to the scientific effect of quality, the base material and the mixed layer or the solidified layer of the organoalkoxysilane liquid agent firmly adheres to the base material. Lacquer is a natural product that exists in the natural world, and siloxanes (general formula: R3SiO- (R2SiO) n-SiR3) obtained by heat-treating an organoalkoxysilane-based liquid agent are also harmless, thus affecting the global environment and the human body. Therefore, the material used in the present invention is a material that is kind to the earth and can be used with peace of mind. No harmful gas is generated during combustion.
In addition, the base material and the like having the layer and the like containing lacquer and alkoxysilane shown so far are referred to as a composite material in the present invention because it has a plurality of layers including the base material. In the present specification, the fact that the contents described and described in a certain part of the specification but not described can be applied to other parts without contradiction, needless to say, the contents can be applied to the other parts. Further, it goes without saying that the above embodiment is an example, and various modifications can be made without departing from the scope of the invention, and the scope of rights of the present invention is not limited to the above embodiment. Needless to say, the lacquer and organoalkoxysilane-based substances and compositions used in the present invention also include the contents described in other documents.

The present invention can be applied to all products using lacquer.

11 ... Substrate, 16, 23 ... Layer made of material containing lacquer liquid and organoalkoxysilane liquid or its solidified layer (mixed layer), 18 ... Penetration, 22, 24, 25 ... A layer made of a material containing an organoalkoxysilane-based liquid agent or a solidified layer thereof

Claims (14)

A composite material having a base material and a solidified layer of a mixed liquid agent containing a lacquer liquid agent and an organoalkoxysilane-based liquid agent on the surface of the base material. A base material, a first layer which is a solidified layer of an organoalkoxysilane-based liquid agent on the surface of the base material, and a second layer which is a solidified layer of a mixed liquid agent containing a lacquer solution and an organoalkoxysilane-based liquid agent on the first layer. Alternatively, a composite material having a second layer which is a solidified layer of a lacquer liquid agent on the first layer. The composite material according to claim 1 or 2, further comprising a solidified layer of an organoalkoxysilane-based liquid agent on the solidified layer. The solidified layer of the mixed liquid agent containing the lacquer liquid agent and the organoalkoxysilane-based liquid agent, or the solidified layer of the lacquer liquid agent is a plurality of laminated layers, the method according to any one of claims 1 to 3. Composite material. The composite material according to claim 4, wherein a solidified layer of the lacquer liquid agent is arranged between the solidified layers of the mixed liquid agent of the plurality of layers. In the mixed liquid agent, the ratio of the lacquer liquid agent to the (organoalkoxysilane-based liquid agent + lacquer liquid agent) is 5 to 95% by weight, and the composite material according to any one of claims 1 to 5. . The composite material according to any one of claims 1 to 6, wherein a solidified layer of the organoalkoxysilane-based liquid agent or the mixed liquid agent has a siloxane bond. 8. The organoalkoxysilane-based liquid agent comprises at least one selected from the group of organoalkoxysilanes, hydrolysates thereof, and polycondensates thereof, according to claim 1. The described composite material. The organoalkoxysilane has R1 Si (OR2) 3 (wherein R1 is an organic group having 1 to 8 carbon atoms, R2 is the same or different, and an alkyl group having 1 or 4 carbon atoms and / or 5 carbon atoms). The composite material according to claim 8, wherein the composite material is a siloxane bond represented by ??? The organoalkoxysilane further includes R12Si (OR2) 2 (wherein R1 is the same or different, an organic group having 1 to 8 carbon atoms, R2 is the same or different, an alkyl group having 1 to 4 carbon atoms and / or a carbon group). The composite material according to claim 8 or 9, comprising a diorganodialkoxysilane represented by an alkenyl group or a phenyl group of the numbers 1 to 8. The organoalkoxysilane-based liquid agent is a liquid agent containing a catalyst for curing and solidification, the catalyst is a hydrolyzable organometallic compound, the organometallic compound from the group consisting of titanium, zirconium, aluminum, and tin. The composite material according to any one of claims 1 to 10, which is an organometallic compound containing one or more selected metals. The base material is an organic material, an inorganic material, or a mixed material thereof, and the organic material is paper, wood, veneer, corrugated cardboard, cloth, non-woven fabric, leather, plastic, polymer material, or a mixed material thereof. And
The composite material according to claim 1, wherein the inorganic material is a metal, a ceramic, a stone, a concrete, an insulator, a semiconductor, or a mixed material thereof. The base material is a processed product that is embossed, shaped, or bent, or is a processed product that is embossed, shaped, bent, or variously deformed after the composite material is formed. Item 13. The composite material according to item 12. The composite material according to any one of claims 1 to 12, wherein the base material is an exterior base material for pianos, musical instruments, and audio products.