Silane-based coating liquid composition

Abstract

To provide a silane-based coating liquid composition capable of imparting various functionalities.SOLUTION: A silane-based coating liquid composition of the present invention comprises, as main components, a compound represented by the following chemical formula, a catalyst, a solvent, an adjusting agent, and an organic solvent.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a silane-based coating liquid composition, particularly a silane-based coating liquid composition that can be used as a coating agent.

Background Art

[0002] Conventionally, various coating liquids have been developed to impart various functions. For example, coating liquids for improving the properties of paper materials and coating liquids for the purpose of radiation shielding have been developed. Paper materials, except for paraffin paper, cellophane paper, etc., are weak against water because they are paper. That is, the known papers generally have poor water repellency. Although there are materials having light transmittance and water repellency, not limited to paper, these are, for example, those produced by stretching plastic materials or vinyl materials into sheets. In addition, paper materials are also widely used for residential buildings. For example, for shoji doors used as partitions for opening and closing in Japanese-style rooms, shoji Japanese paper, rayon shoji paper produced by blending rayon, polypropylene, etc. with pulp at a predetermined ratio, shoji paper obtained by laminating a plastic film on this rayon shoji paper, and shoji paper obtained by laminating an acrylic material or a vinyl chloride material on the surface of Japanese paper are used.

[0003] As an attempt to further improve while making use of the inherent characteristics of these original materials, for example, as an inexpensive impregnated paper with high liquid stability during processing, an impregnated paper in which a silane coupling agent or a composition containing a silane coupling agent and one or more kinds of agents for modifying paper are dispersed in the paper and do not lose water resistance even when boiled in hot water is known (Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, including the above patent documents, in the prior art, although the base material is imparted with liquid stability, water resistance, etc., the development of a more functional liquid agent has been desired. If it is a stable liquid agent, it is also possible to cure and solidify it at the desired time of use to impart the desired use to the base material or the like. Further, for example, if various functions can be imparted to the base material according to the application, from those having rigidity to those having flexibility, it is also possible to provide a material with high industrial utility value. However, such a coating liquid composition has not been known so far.

[0006] Therefore, an object of the present invention is to provide a silane-based coating liquid composition capable of imparting various functions.

Means for Solving the Problems

[0007] In order to achieve the above problems, the present inventor has intensively studied a modifier for a silane-based coating liquid composition, and as a result, has found the present invention.

[0008] That is, the silane-based coating liquid composition of the present invention has, as a main component, the following chemical formula [Chemical Formula 1]:

Chemical Formula

[0009] Further, in a preferred embodiment of the silane-based coating liquid composition of the present invention, the regulator is at least one of hydrogen peroxide, acetic acid, and ammonia.

[0010] In a preferred embodiment of the silane-based coating liquid composition of the present invention, the catalyst is an organometallic compound.

[0011] In a preferred embodiment of the silane-based coating liquid composition of the present invention, in addition to the main component, a compound represented by the following chemical formula [Chemical Formula 2] having three hydrolyzable substituents and one non-hydrolyzable substituent:

Chemical Formula

[0012] In a preferred embodiment of the silane-based coating liquid composition of the present invention, in addition to the main component, a compound represented by the following chemical formula [Chemical Formula 3] having two hydrolyzable substituents and two non-hydrolyzable substituents:

Chemical Formula

[0013] In a preferred embodiment of the silane-based coating liquid composition of the present invention, it further contains an acrylic resin.

[0014] In a preferred embodiment of the silane-based coating liquid composition of the present invention, the composition is characterized by having a decomposition function, an antibacterial function, or an adsorption function.

[0015] The method for producing a functional material of the present invention comprises a step of applying the silane-based coating liquid composition of the present invention to a substrate, and a step of drying the substrate coated with the coating composition.

[0016] The coating material of the present invention is characterized by being formed by applying the silane-based coating liquid composition of the present invention to a substrate.

[0017] The solidified body of the present invention is characterized by being formed by solidifying the silane-based coating liquid composition of the present invention.

Advantages of the Invention

[0018] In the present invention, among the four substituents of the silicon atom, one is a substituent R that cannot be hydrolyzed and does not participate in the polycondensation of compounds. 4 According to the embodiment in the case of using a condensate substituted with it, it is possible to coat a fiber material and impart appropriate strength, good light transmittance, good water repellency and flexibility, and furthermore, wear resistance and flame retardancy (heat resistance), etc., which has an advantageous effect.

[0019] Also, according to the present invention, as is clear from the description of the examples described later, by taking advantage of the property of having flexibility of fiber materials such as Japanese paper, Western paper, and cloth that are present nearby, it is possible to provide a coating material having various characteristics as described above, which has an advantageous effect. Moreover, various characteristics imparted to these coating materials can be relatively freely adjusted by the implementer by arbitrarily selecting and adjusting, for example, the selection and usage amount of the organometallic catalyst used as a catalyst, the selection and usage amount of the compounds of [Chemical Formula 2] and / or [Chemical Formula 3], the coating amount of the coating liquid composition, etc., which also has an advantageous effect.

[0020] Moreover, in the present invention, unlike materials that could not be manufactured without factory production, for a base material such as ordinary paper material that is readily available and easily obtainable, while taking advantage of its flexibility, advantageous effects can be achieved such as imparting strength, light transmittance, water repellency, flame retardancy, and abrasion resistance. Further, according to the present invention, there is an advantageous effect that it is possible to optimize the exertion of the target function by adjusting the ratios of the main agent, catalyst, and regulator.

[0021] Also, according to the manufacturing method of the functional material of the present invention, not only the degree of various properties imparted by the coating film, but also the thickness of the coating film can be arbitrarily adjusted. Therefore, for example, when used for products used in places exposed to outdoor wind and rain, or when used for interior decoration such as wallpaper, etc., it is possible to adjust the types and amounts of each compound as needed, and there is an advantageous effect that an optimal coating material can be manufactured and provided. Furthermore, according to the present invention, a coating liquid with ultraviolet resistance characteristics can also be manufactured, and it is possible to maintain durability by using it for outdoor benches, piles, etc.

Brief Description of the Drawings

[0022]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Embodiments for Carrying Out the Invention

[0023] The silane-based coating liquid composition of the present invention contains, as main components, the following chemical formula [Chemical Formula 1]:

Chemical Formula

[0024] Examples of the trifunctional silane that serves as the main agent in [Chemical Formula 1], taking alkoxysilane as an example, are as follows. Examples of trifunctional silanes include, for example, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, methyltripropoxysilane, ethyltripropoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, y-(methacryloxypropyl)trimethoxysilane, y-glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, y-(methacryloxypropyl)triethoxysilane, y-glycidoxypropyltriethoxysilane, aminopropyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, etc., and polymers of about 2 to 10 molecules of these can be cited. Note that these polymers may be polymers of only one type of monomer, or may be polymers of two or more types of monomers.

[0025] Also, examples of tetrafunctional silanes include polymers such as tetramethoxysilane, tetraethoxysilane, tetrapoloboxysilane, tetrabutoxysilane, etc. Note that these polymers may be polymers of only one type of monomer or polymers of two or more types. Tetrafunctional silanes may be single or a mixture of two or more types.

[0026] Also, R in [Chemical Formula 1] 1 , R 2 , R 3 and R 4It is hydrogen or an alkyl group having 1 to 4 carbon atoms, which may be the same or different, from the viewpoint that a trifunctional silane and a hydrolyzable organometallic compound react in an organic solvent. Also, n is 2 to 10. In [Chemical Formula 1], the reason why the main-chain repetition is n = 2 to 10 is that when n = 1, that is, when using a monomer, it takes a long time for polymerization and it becomes difficult to produce a coat film having sufficient strength in a short time. However, when n is 11 or more, conversely, when applied to a fiber material, the number of alkoxy groups etc. for polymerization on the fiber material becomes insufficient and it becomes difficult to produce a coat film having sufficient strength. Therefore, in the present invention, condensates with n = 2 to 10, especially n = 2 to 8, are preferred.

[0027] In general, when synthesizing a condensate such as [Chemical Formula 1] from a monomer, it is technically almost impossible to accurately control its degree of polymerization. Therefore, the meaning of using those with n = 2 to 10, preferably n = 2 to 8 in the present invention is nothing other than using a coating liquid mainly containing those with n = 2 to 10, preferably mainly 2 to 8 in terms of the degree of polymerization distribution. Even if a compound with n being 11 or more is contained, for example, it does not matter. Such a compound can be obtained by condensing a monomer (for example, methyltrimethoxysilane).

[0028] As described above, the raw material (monomer) for obtaining the compound of [Chemical Formula 1] can be purchased at about the same price as that of tetraalkoxysilane which is inexpensive but has strong inorganic properties. Therefore, by using the compound of [Chemical Formula 1], it is possible to produce a coating material having a film with sufficient organic properties and sufficient strength without using a so-called expensive silane coupling agent together.

[0029] Examples of the compound shown in Chemical Formula 1 specifically include condensates such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, methyltripropoxysilane, and ethyltripropoxysilane. Note that the compound of Chemical Formula 1 may be a condensate of only one of such monomers or a condensate of two or more of the above-exemplified monomers.

[0030] Note that the primary role of the non-hydrolyzable substituent (R 4 ) in the compound of Chemical Formula 1 is to impart flexibility to the coating film. However, if water repellency is to be imparted to the coating film at the same time, R 4 shall be an alkyl group. Generally, the greater the number of carbon atoms in an organic substituent, the greater the organicity, i.e., the greater the water repellency. However, if the number of carbon atoms becomes too large, strain will occur in the coating film due to steric hindrance, causing a decrease in the film strength. Therefore, it is preferable to determine the number of carbon atoms in the alkyl group and the type and amount of each monomer constituting the compound (condensate) of Chemical Formula 1 by conducting preliminary production tests while referring to the examples in this specification, etc. However, since the imparting of water repellency to the coating film can also be achieved by adding the compound of Chemical Formula 2 or Chemical Formula 3 described later, it is not necessarily essential for R 4 in the compound of Chemical Formula 1 to be an alkyl group.

[0031] Also, in the present invention, the content of the compound shown in Chemical Formula 1 is not particularly limited, but the content of the compound shown in Chemical Formula 1 can preferably be 20 to 70% by weight, more preferably 30 to 50% by weight, in terms of organoalkoxysilane. If it is 10% by weight or less, there is a risk of reducing the effect as a binder. Note that if no other additives are considered, it may be 50% by weight or more.

[0032] In the present invention, the catalyst is not particularly limited. Since both the element of the main agent and the element of the catalyst cause a sol-gel reaction, ultimately, the element of the main agent (Si (silicon)) can successfully support the element of the catalyst, and from the perspective of enabling the catalyst to exert its function without directly affecting the substrate coated with the catalyst element, for example, organometallic compounds can be cited as the catalyst.

[0033] When an organometallic compound is mixed with the compound of Chemical Formula 1 to form a coating liquid composition and this is applied to a fibrous material such as paper, the paper absorbs moisture in the paper or moisture (humidity) in the air, and the organometallic compound undergoes self-hydrolysis. At this time, it forms a network with the compound of Chemical Formula 1, and the compound of Chemical Formula 1 can be cured and solidified. Examples of the organometallic compound preferably used in the present invention include those containing titanium, zirconium, aluminum, or tin. More specifically, tetrapropoxytitanate, tetrabutoxytitanate, tetrapropoxyzirconate, tetrabutoxyzirconate, tripropoxyaluminate, aluminum acetylacetonate, dibutyltin diacetate, or dibutyltin dilaurate, etc. can be cited.

[0034] In the present invention, the content of the catalyst is not particularly limited either. However, from the perspective of enabling hydrolysis and polycondensation reactions to occur in order to cure and solidify the silane-based coating liquid as the main agent, the content of the catalyst is preferably 1 to 10% by weight, more preferably 3 to 7% by weight.

[0035] As the catalyst for curing and solidifying the compound represented by Chemical Formula 1, commonly used catalysts can be used without special restrictions. For example, if it is an acid catalyst, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, or acetic acid, etc. can be cited. If it is a base catalyst, ammonia, tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, ethanolamine, diethanolamine, or triethanolamine, etc. can be cited. When using these ordinary catalysts, in order to cure and solidify the compound of Formula 1, water of reaction is made to coexist.

[0036] Thus, the coating liquid composition provided by the present invention can contain the compound of Chemical Formula 1, a catalyst, and water of reaction. Although there are usually no problems when it is used, when it is stored for a long time, there is a problem that the coating liquid is likely to gel due to the water of reaction. In order to solve this problem, it is preferable to use a hydrolyzable organometallic compound as the catalyst instead of the normal catalyst as described above. By using a hydrolyzable organometallic compound, it becomes unnecessary to coexist the water of reaction, and long-term storage stability is achieved, which is preferable.

[0037] In addition, in the coating liquid composition of the present invention, a solvent can be added in order to uniformly mix the compound of Chemical Formula 1, the catalyst, and, if necessary, the water of reaction. Examples of the solvent used for this purpose, for example, as the organic solvent, alcohols can be exemplified. More specifically, methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, etc. can be exemplified. Further, by controlling the addition amount, it is also possible to adjust the viscosity and drying rate of the coating liquid.

[0038] For the purpose of such adjustment, in particular, for example, glycols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, etc., cellosolves such as methoxyethanol, propoxyethanol, butoxyethanol, methoxypropanol, ethoxypropanol, propoxypropanol, or butoxypropanol, etc., organic solvents having a high viscosity and boiling point are preferably used alone or in a mixture of two or more. Of course, the above alcohols may be added simultaneously with one or more of the above organic solvents having a high viscosity and boiling point. When the purpose is to adjust the viscosity and drying rate of the coating liquid, not only the above organic solvent but also a surfactant can achieve the same effect.

[0039] In particular, since the above-mentioned glycols and cellosolves have hydroxyl groups in their molecules, they may be introduced into the network of siloxane bonds formed by the condensation reaction of the compound of Formula 1. Since glycols and cellosolves have organic properties, the introduction thereof increases the organic properties of the resulting coating film, that is, the organic properties of the coating material.

[0040] In the present invention, the content of the solvent is not particularly limited either. However, from the viewpoints of the substrate, function, and appropriate concentration, the content of the solvent is preferably 2 to 95% by weight, more preferably 25 to 50% by weight.

[0041] In a preferred embodiment of the silane-based coating liquid composition of the present invention, from the viewpoint that the functions originally possessed by the compounds constituting the main agent and the catalyst can be effectively imparted, the conditioner is characterized by being hydrogen peroxide and / or acetic acid. As the conditioner, a weakly acidic or basic catalyst can be used, and for example, it can be at least one of acetic acid, hydrogen peroxide, and ammonia. Although this conditioner can also be said to be a second catalyst, the inventors have found that by adding this, it is possible to create a new function as if a new element sequence has occurred. This conditioner is completely different from the action and function of strong acids and a large amount of water (H 2 O) used in the sol-gel method of the conventional process.

[0042] That is, although most matters remain unresolved, surprisingly, the inventors have found that by adding a conditioner such as these acid groups, it is possible to efficiently express the functions originally possessed by the compound constituting the added metal catalyst. Specifically, for example, as will be apparent in the examples described later, when an organometallic compound, for example, tetrabutoxytitanium, is used as a catalyst, due to the action of the conditioner, the synthesis of titanium oxide having an adsorption / decomposition function possessed by the compound constituting the catalyst is successful, and a composition capable of containing the functional component in a liquid state has been found.

[0043] In the present invention, the content of the regulator is not particularly limited, but from the viewpoint of secondary function expression, the content of the regulator is preferably 0.5 to 5% by weight, more preferably 1 to 2% by weight.

[0044] Further, in a preferred embodiment of the silane-based coating liquid composition of the present invention, in addition to the main component, a compound represented by the following chemical formula [Chemical Formula 2] having three hydrolyzable substituents and one non-hydrolyzable substituent:

Chemical Formula

[0045] In the present invention, by using a coating liquid containing the compound of Chemical Formula 2 in addition to the compound of Chemical Formula 1, compared with a coating material produced without using this, it is possible to newly impart properties such as organic properties possessed by the compound of Chemical Formula 2, or to increase properties such as organic properties. The compound of Chemical Formula 2 added for such a purpose is a compound in which three of the four substituents are hydrolyzable substituents and the remaining one is composed of a non-hydrolyzable substituent.

[0046] In Chemical Formula 2, R 5 , R 6 and R 7 may be the same or different from each other and are monomers composed of hydrogen or an alkyl group or an alkenyl group having 1 to 10 carbon atoms, and R 5 O, R 6 O and R 7The bond between O and Si is an oligomer composed of siloxane bonds, and R 8 is an alkyl group, alkenyl group or phenyl group having 1 to 10 carbon atoms, which may contain an epoxy group or glycidyl group in its molecule.

[0047] In the present invention, specific examples of the compound represented by Chemical Formula 2 include vinyltrimethoxysilane, phenyltrimethoxysilane, γ-(methacryloxypropyl)trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, aminopropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, γ-(methacryloxypropyl)triethoxysilane, γ-glycidoxypropyltriethoxysilane, aminopropyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, etc., and condensates of about 2 to 10 molecules of these can be exemplified.

[0048] Note that the compound of Chemical Formula 2 may be two or more of such monomers. When a condensate of two or more molecules is used as the compound of Formula 2, it may be a condensate of two or more of such monomers.

[0049] Further, in a preferred embodiment of the silane-based coating liquid composition of the present invention, in addition to the main component, a compound represented by the following chemical formula [Chemical Formula 3] having two hydrolyzable substituents and two non-hydrolyzable substituents:

Chemical Formula

[0050] In the present invention, in addition to the coating liquid composition containing the compound of Chemical Formula 1, or in addition to the coating liquid composition containing both the compound of Chemical Formula 1 and the compound of Chemical Formula 2, by using a coating liquid composition further added with the compound of Chemical Formula 3, compared with a coating material produced without using this, it is possible to newly impart properties such as organic properties possessed by the compound of Chemical Formula 3, or to increase properties such as organic properties.

[0051] Among the four substituents of the compound of Chemical Formula 3, two are hydrolyzable substituents and the other two are non-hydrolyzable substituents. In Chemical Formula 3, R 9 and R 11 may be the same or different from each other and are monomers composed of hydrogen or an alkyl group or alkenyl group having 1 to 10 carbon atoms, and R 9 and R 11 The bond between and Si is an oligomer composed of a siloxane bond, and R 10 and R 12 is an alkyl group, alkenyl group or phenyl group having 1 to 10 carbon atoms which may contain an epoxy group or glycidyl group in its molecule.

[0052] Specific examples of the compound represented by Chemical Formula 3 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, etc., and condensates of about 2 to 10 molecules of these can be exemplified. Note that the compound of Formula 3 may be two or more of such monomers, and even when using a condensate of two or more molecules, it may be a condensate of two or more of such monomers.

[0053] By adding either the compound of Chemical Formula 2 or the compound of Chemical Formula 3 as described above to the coating liquid composition, the organic property of the coating film can be increased. However, if both the compounds of Chemical Formula 2 and Chemical Formula 3 are added to the coating liquid composition, the organic property of the coating film can be further improved, and as a result, the water repellency of the coating material and the like can be further improved.

[0054] The compound of Chemical Formula 2 and / or the compound of Chemical Formula 3 is preferably added to the coating liquid composition generally in a total amount not exceeding 50% with respect to the compound represented by Chemical Formula 1 which is the main component of the coating liquid composition. If the total addition amount of both exceeds this range, when the coating liquid composition is applied to the fiber material, it may not bond well with the compound of Chemical Formula 1 which is the main component, and the strength of the coating film may become insufficient. Therefore, when actually adding the compound of Chemical Formula 2 and / or the compound of Chemical Formula 3, assuming that the strength of the coating film decreases depending on the addition amount, referring to the examples in this specification, conducting preliminary production tests, etc., and clarifying the range of the addition amount that can achieve the purpose, it is preferable to minimize the addition.

[0055] In addition, the primary role of the non-hydrolyzable substituents (R 8 , R 10 , R 12 ) in the compounds of Chemical Formula 2 and Chemical Formula 3 is to impart flexibility to the coating film. However, since these are organic substituents such as alkyl groups, they also play a role of imparting water repellency to the coating film at the same time. Generally, the greater the number of carbon atoms of the organic substituent, the greater the organic property, that is, the water repellency. However, if the number of carbon atoms becomes too large, strain occurs in the coating film due to steric hindrance, causing a decrease in the film strength. Therefore, it is preferable to determine the number of carbon atoms of the organic substituent and the types and amounts of each monomer constituting the compounds (condensates) of Chemical Formula 2 and / or Chemical Formula 3 by conducting preliminary production tests, etc., referring to the examples in this specification.

[0056] The siloxane bond with strong heat resistance and abrasion resistance is also a so-called "hard" bond. Due to this "hardness", when applied to fibrous materials such as paper, the material can be imparted with abrasion resistance. However, fibrous materials such as paper are characterized by having flexibility, and the coating material is sometimes required to have the same flexibility as the paper or the like that is the material.

[0057] Conventionally, the generally used sol-gel coating solution uses tetraalkoxysilane (Si(OR) 4 ) or its oligomer as the starting material. When this is completely hydrolyzed (steps (1) to (3) in Reaction Formula 1 described later) to form a coating film, all four bonds of the silicon atom form a network of hard siloxane bonds, which is as hard as a ceramic, but becomes a brittle film lacking flexibility. Therefore, it was practically impossible to produce a coating material that makes use of the flexibility of paper or the like.

[0058] However, the present invention solves this problem by using, as the main component of the coating liquid composition, a compound of Chemical Formula 1 in which one of the four substituents of the silicon atom is not hydrolyzed. Further, in the present invention, by adding a compound of Chemical Formula 2 and a compound of Chemical Formula 3 each having one or two non-hydrolyzable substituents to the coating liquid composition, it becomes possible to further increase flexibility and the like.

[0059] Further, in a preferred embodiment of the silane-based coating liquid composition of the present invention, it is further characterized by containing an acrylic resin.

[0060] In the present invention, the acrylic resin is not particularly limited, and for example, those obtained by radical copolymerization of an acrylic monomer and another monomer copolymerizable with the acrylic monomer can be used.

[0061] Among these, the acrylic monomer is not particularly limited. For example, it may be an alkyl group-containing (meth)acrylic monomer such as methyl (meth)acrylate (indicating either methyl acrylate or methyl methacrylate; the same applies hereinafter), ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate; a hydroxyl group-containing (meth)acrylic monomer such as 2-hydroxyethyl (meth)acrylate; an ethylenically unsaturated carboxylic acid such as (meth)acrylic acid; an amino group-containing (meth)acrylic monomer such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate; an amide-containing (meth)acrylic monomer such as (meth)acrylamide, ethyl (meth)acrylamide; a nitrile group-containing (meth)acrylic monomer such as acrylonitrile; an epoxy group-containing (meth)acrylic monomer such as glycidyl (meth)acrylate, etc.

[0062] Examples of other monomers copolymerizable with the acrylic monomer include aromatic hydrocarbon vinyl monomers such as styrene, methylstyrene, chlorostyrene, vinyltoluene; ethylenically unsaturated carboxylic acids such as maleic acid, itaconic acid, crotonic acid, fumaric acid, citraconic acid; sulfonic acid-containing vinyl monomers such as styrenesulfonic acid, vinylsulfonic acid; acid anhydrides such as maleic anhydride, itaconic anhydride; chlorine-containing monomers such as vinyl chloride, vinylidene chloride, chloroprene; hydroxyl group-containing alkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether; alkylene glycol monoallyl ethers such as ethylene glycol monoallyl ether, propylene glycol monoallyl ether, diethylene glycol monoallyl ether; α-olefins such as ethylene, propylene, isobutylene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether; allyl ethers such as ethyl allyl ether, butyl allyl ether, etc.

[0063] The above acrylic resin is obtained, for example, by an emulsion polymerization method. There is no particular limitation on the emulsion polymerization method, and in a dispersion system having, as basic composition components, the above monomers, chain transfer agents, surfactants, radical polymerization initiators, and other additive components used as necessary in an aqueous medium, in a conventionally known method, the monomers can be polymerized to produce an acrylic resin emulsion.

[0064] In the present invention, the acrylic resin is 10 to 30% by weight, preferably 25 to 30% by weight, in terms of solid content, based on the total amount of the composition of the present invention. If it is less than 10% by weight, the resulting coating film tends to become hard and brittle, while if it exceeds 30% by weight, the coating film is soft, but when adding components having functionality, the addition amount thereof decreases, and there is a risk that the functionality of the component decreases.

[0065] Further, in a preferred embodiment of the silane-based coating liquid composition of the present invention, the composition is characterized by having a decomposition function, an antibacterial function, or an adsorption function.

[0066] The silane-based coating liquid composition of the present invention can be safely stored by low-temperature storage or the like in a sealed state. That is, even in a state containing the compound of Chemical Formula 1, a catalyst, an adjusting agent, etc., a stable liquid composition can be obtained. It is possible to carry out a reaction and a polycondensation reaction by OH groups (moisture / water) in the air or OH groups (intrinsic moisture) of the substrate when coating. That the coating liquid composition is stable is also one of the features of the present invention.

[0067] A major difference from the conventional glass production method by the sol-gel method is that neither a large amount of water nor the addition of acid catalysts such as sulfuric acid, nitric acid, phosphoric acid, and hydrochloric acid is required, and it is not essential. The glass of sol-gel is strongly alkaline, but the glasses of Coating Agents Nos. 1 to 17 in the examples as described later are weakly acidic to neutral, so it is possible to produce safe glasses that do not impose a burden on the human body or the environment.

[0068] Thus, an important feature of the coating liquid composition of the present invention is that it does not cure or solidify unless it comes into contact with moisture in the air or reacts with the moisture of the substrate, even when a catalyst is added. If it is sealed, it can be a coating liquid composition that can be easily applied at any time and is also inexpensive. That is, because the liquid agent of the present invention has good wettability, it is possible to form a film by coating even the details in a complex shape and exhibit the intended function.

[0069] Note that the coating liquid composition of the present invention may be used after being solidified as it is, or may be applied to a substrate and used as described later.

[0070] Further, the method for producing a functional material of the present invention is characterized by comprising a step of applying the silane-based coating liquid composition of the present invention to a substrate and a step of drying the substrate to which the coating composition has been applied. Regarding the silane-based coating liquid composition, the description of the silane-based coating liquid composition of the present invention described above can be directly applied to the method for producing a functional material.

[0071] In the present invention, the substrate to be coated is not particularly limited. For example, fabrics such as knitted fabrics, woven fabrics, non-woven fabrics, and paper, and films, sheets, etc. can be mentioned. Specifically, in addition to fabrics and films made of polyamide fibers, polyester fibers, rayon fibers, cotton, pulp, etc., Japanese paper, copy paper, Tyvek (a non-woven fabric made of polyethylene manufactured by DuPont), wallpaper, fusuma paper, shoji paper, ceiling paper, tablecloth, curtain, mat, rubber sheet, etc. can be mentioned. Further, in addition to the above papers, etc., trees, wooden products, and buildings can be mentioned as substrates. Furthermore, since a siloxane bond is also possible for inorganic substances, metals, concrete, carbon compounds, glass, and their products can also be exemplified as substrates.

[0072] For coating the substrate with the composition of the present invention, coating means such as brush coating, spraying, dipping, roll coating, printing, etc. can be used. A coating film with the desired dry film thickness can be formed in one coating, and it can also be applied in about 2 to 5 layers. Further, in the case of overcoating, heating and drying treatments may be performed each time.

[0073] When the composition of the present invention is coated on a substrate, at a temperature from room temperature to 60 °C, (a) a hydrolysis and polycondensation reaction occurs simultaneously with the hydrolysis of the organoalkoxysilane to generate a sol, and further the reaction proceeds to form a gel, that is, an organopolysiloxane. By leaving this at room temperature for 1 to 6 days or heating it at 80 to 150 °C for 10 to 60 minutes, the organopolysiloxane and optionally the acrylic resin co-condense with the volatilization of the solvent, and when a component having functionality is further included, a cured coating film composite of the component can be formed. However, the reaction temperature and the standing or heating time vary depending on the types and blending ratios of the respective components used, and thus are not limited to the above.

[0074] In the method for producing a functional material according to the present invention, first, an arbitrary fiber material can be cut and processed into an arbitrary size and shape, and the coat liquid composition of the present invention described above can be applied thereto. The specific coating method is not particularly limited, and for example, it can be carried out by immersing the fiber material in the coat liquid, applying the coat liquid to the fiber material, or spraying the coat liquid onto the fiber material. Further, as the coating method, for example, brush-in, brush coating, roller method, spraying method, dipping method, gravure printing machine coating method, absolute drying method, etc. can be used.

[0075] Also, the drying process is not particularly limited. For example, the liquid agents up to No. 1 to 17 in the examples described later can basically be cured and solidified by natural drying (at environmental temperature and environmental humidity). When accelerating the reaction quickly in terms of time and promoting the formation of a cured and solidified film, heating is effective.

[0076] In the present invention, for example, materials such as fibers obtained by draining and drying bark, high-quality Japanese handmade paper, machine-made ordinary Japanese paper, Western paper, or Japanese paper, fibers using a non-woven fabric, ordinary cloth, etc. are used as fiber materials, and functional materials such as coating materials can be manufactured. Note that for the fiber material, prior to applying the coating liquid composition, by performing a predetermined pretreatment, the bond between the surface of the fiber material and the coating film can be strengthened compared to those without the pretreatment.

[0077] As an example of this pretreatment, for example, a substrate such as a fiber material is immersed in high-purity isopropyl alcohol of about 98% for about 30 minutes, then left at a high temperature of about 100 °C, completely dried, and then irradiated with ultraviolet rays for about 30 minutes. As described above, when the coating liquid composition is applied to a substrate such as a fiber material that has been subjected to a predetermined pretreatment or not, the compound of Chemical Formula 1 is hydrolyzed, and through the reactions shown in (1) to (3) of Reaction Formula 1 below, a siloxane bond (Si-O-Si) is formed.

[0078] Reaction Formula 1: (1) Si-OR + H 2 O → Si-OH + ROH (2) Si-OH + HO-Si → Si-O-Si + H 2 O (3) Si-OH + RO-Si → Si-O-Si + ROH

[0079] The bond energy of Si-O in the siloxane bond (Si-O-Si) thus formed is 106 kcal / mol. On the other hand, the bond energy of a typical C-C bond in an organic compound is 82.6 kcal / mol. Therefore, it can be seen that the glassy coating film having a siloxane bond formed by the hydrolysis of the compound of Chemical Formula 1 has a much more thermally stable bond than an organic compound. Due to this thermally stable bond, the coating film formed according to the present invention is excellent in heat resistance and abrasion resistance, and as a result, it becomes possible to manufacture a coating material excellent in heat resistance and abrasion resistance.

[0080] In addition, when the coating liquid composition of the present invention contains the above-described organometallic compound (e.g., tetrabutoxytitanium, etc.) as a catalyst, even if the reaction water is not contained in the coating liquid, the reactions (1) to (3) in the above reaction formula 1 proceed. In this case, the reactions are specifically as shown in (4) and (5) in the following reaction formula 2.

[0081] Reaction formula 2: (4)Ti-OR + H 2 O → Ti-OH + ROH (5)Ti-OH + RO-Si → Ti-O-Si

[0082] As described above, by introducing the Ti-O bond into the coating film, the heat resistance and wear resistance can be further improved as compared with the coating film having only a siloxane bond. Thus, when an organometallic compound is used as a catalyst, not only is it unnecessary to coexist with reaction water, but also the heat resistance and wear resistance of the coating film can be further improved, and as a result, the heat resistance and wear resistance of the coating material can be made even stronger.

[0083] In the present invention, further, the above-described regulator is included. As described above, the present invention is not a sol-gel method in which a general large amount of water, acid, or base is added, but a sol-gel reaction of both the main agent and the catalyst can be utilized by adding a regulator as needed. Thus, contrary to the common technical knowledge in the prior art, the inventors have found that a novel functional material capable of stably exhibiting the original functions of the elements of the main agent and the catalyst can be provided.

[0084] In addition, the coating material of the present invention is characterized by applying the silane-based coating liquid composition of the present invention to a substrate. Further, the solidified body of the present invention is characterized by solidifying the silane-based coating liquid composition of the present invention. Regarding the silane-based coating liquid composition of the present invention, the substrate, the coating method, the solidification method, etc., the description of the silane-based coating liquid composition of the present invention or the manufacturing method of the functional material described above can be directly referred to.

Examples

[0085] Hereinafter, the present invention will be described in more detail based on examples. However, the examples are merely examples, and the present invention is not to be construed as being limited to these examples. Needless to say, it can be appropriately changed without departing from the gist of the present invention.

[0086] Examples 1 - 16 Production of alkoxysilane condensate A methyltrimethoxysilane condensate was synthesized as follows.

[0087] 181 g of methyltrimethoxysilane, 50 g of methanol, and 18 g of pure water were added to a 500 ml three-necked flask and stirred well. Further, 2 g of 61% nitric acid was added and heated under reflux for 3 hours while stirring. After the reaction was completed, the inside of the reaction vessel was depressurized while heating to remove methanol. The methyltrimethoxysilane thus obtained was centered around trimers and tetramers by gas chromatography analysis.

[0088] Next, the coating liquid composition was prepared and the functional material (coating material) was produced. Using the alkoxysilane condensate synthesized as described above, 16 types of the functional materials of the present invention shown in Table 1 containing these as main components were prepared (the unit of the mixing weight is g). In Table 1, specifically for the main compounding agent A, Nos. 1 - 7, 11 - 14 are methyltrimethoxysilane (trifunctional), and Nos. 8 - 10 are tetraethoxysilane oligomer (tetrafunctional). For compounding agents B and C, specifically, Nos. 5 - 7 are tetraethoxysilane oligomer (tetrafunctional), and Nos. 12, 15, and 16 are polyalkylalkoxysilane (trifunctional) (in No. 15, Ti powder is used as a modifier to improve adhesiveness). For the organic solvent, specifically, Nos. 1 - 11 and 14 - 16 are isopropyl alcohol, and Nos. 12 and 13 are ethyl acetate. For the reaction accelerator (catalyst), specifically, Nos. 1 - 16 are tetrabutoxytitanium. Function 1 represents water repellency, function 2 represents flame retardancy, function 3 represents light transmissibility, function 4 represents decomposition, antibacterial, antifouling, adsorption, and function 5 represents adhesion, respectively. The sources of the components used are as follows. · Acrylic acid ester polymer (Toagosei Co., Ltd.) · Tetraethoxysilane oligomer (Tama Chemical Industry Co., Ltd.) · Polymethylphenylsiloxane (Shin-Etsu Chemical Co., Ltd.) · Tetramethoxysilane oligomer (Mitsubishi Chemical Corporation) · Acrylic acid ester copolymer (Toagosei Co., Ltd.) · Polyalkylalkoxysilane (Shin-Etsu Chemical Co., Ltd.) · Polymethylhydrogensiloxane (Merck) · Isopropyl alcohol (Sankyo Chemical Industry Co., Ltd.) · Ethyl acetate (Showa Denko K.K.) · Tetrabutoxytitanium (Nippon Soda Co., Ltd.)

[0089]

Table 1

[0090] Manufacture of Functional Material (Coating Material) In the applicant's laboratory (room temperature 25°C, humidity 70%), coating liquid compositions No. 1 to 16 were applied to a cellulose fiber material to manufacture a functional material. First, a plurality of Japanese papers were prepared as the fiber material, and this Japanese paper was immersed in each coating liquid composition for 30 seconds. Then, in order to prevent the Japanese paper from being thermally deformed, drying was started at 60°C first, the temperature was gradually increased, and finally, the temperature was raised to 100°C to completely dry the Japanese paper, thereby manufacturing the functional material (Japanese paper) of the present invention.

[0091] Note that, for example, in the examples, the No. 1 liquid agent can be dried at room temperature (5°C to 40°C) after coating the substrate (wood). After the surface is dry, it can be put into a dryer at 80°C to 140°C for 1 hour. The No. 2 liquid agent can be dried at 120°C for 60 minutes after being immersed in the substrate (glass fiber) and dried for 10 minutes. The No. 3 to No. 10 liquid agents are the same process as No. 1 after coating the substrate, but depending on the type of substrate, it may be raised to 80°C to 400°C. The No. 11, No. 15, and No. 16 liquid agents are coating agents for multi-purpose substrates using acrylic ester polymers, so it is appropriate to dry at 5°C to 140°C for about 1 hour. It can be determined according to the substrate. Also, the No. 12 to 14 liquid agents are liquid agents that generate a glassy film and impart water repellency (without using fluorine) so as not to impair the characteristics of the flexible substrate, and drying at room temperature to about 120°C is appropriate.

[0092] Next, regarding the manufactured functional materials, the following evaluation experiments on water repellency, flame retardancy, light transmittance, antibacterial and antifouling, air purification, and adhesiveness were conducted. In Table 1, considering each evaluation result comprehensively, the results are shown with double circles, single circles, and triangles. The double circles indicate that it was very excellent, the single circles indicate that it was excellent, and the triangles indicate that it was slightly inferior.

[0093] (1) Evaluation of light transmittance When evaluating light transmittance, in addition to Japanese paper, rubbed paper obtained by rubbing Japanese paper, water-drop paper obtained by dropping water droplets on Japanese paper to create a pattern, wood-chip paper made by collecting wood chips and making them into paper, and cardboard made of cardboard were used to manufacture coating materials (functional materials) for evaluation.

[0094] The evaluation was carried out by illuminating each manufactured coating material from below with a light box and observing it with the naked eye to evaluate gloss, color development, transparency, etc. As a result, since the coating liquid itself of the coating material manufactured from Japanese paper with this coating liquid composition is colorless and transparent, the surface is shiny and translucent, the color of the Japanese paper as the material becomes darker, and the white part of the Japanese paper remains white and shows shiny translucency. On the other hand, in the comparative coating liquid, since the coating liquid itself showed yellow, the white part of the Japanese paper was shiny and translucent with a slight yellowish tint.

[0095] (2) For the coated material made from crepe paper on which the evaluation of mechanical strength and light transmittance was conducted, when this was folded by hand, it was visually observed whether or not peeling of the coating film occurred, and the hardness (mechanical strength) of each coating film was evaluated. In the case of the coated material manufactured using this coating liquid composition, even when the paper was folded, the situation where the surface peeled off did not occur. Also, all the Japanese paper airplanes coated with the coating liquid were found to be able to withstand the wind speed of Mach 7 in the 200-degree high-temperature wind tunnel experiment device of JAXA within the Kashiwa Campus of the University of Tokyo.

[0096] The above results mean that in the coating film formed by this coating liquid composition, the flexibility is large and the overall mechanical strength is increased. This is because the main component contained in the coating liquid (the compound of Chemical Formula 1), the added silane compound (the compound of Chemical Formula 2 and / or Chemical Formula 3), the catalyst, etc. hydrolyze and polycondense on the crepe paper and polymerize to form a coating film. During this process, they enter into the fine parts of the crepe paper, physically bond with the paper fibers and mechanically intertwine, or hydrophobically bond between the organic parts. Also, it is presumed that the mechanical strength has increased because the hydroxyl group of cellulose, which is the main component of the paper, and the silane compound are chemically bonded.

[0097] Furthermore, at the Tokyo Metropolitan Industrial Technology Research Center, the liquid agent tensile hardness and tear strength obtained for hand-made Japanese paper were measured. As the test method, for the tensile strength test, a constant speed elongation type tensile test (RTF-1250 manufactured by A&D Co., Ltd.) was used (width of test piece: 25 mm, tensile speed: 50 mm / min, grip interval: 100 mm, number of measurements: 3 times). For the tear strength test, an Elmendorf type tear tester (No. 445 manufactured by Yasuda Seiki Seisakusho Co., Ltd.) was used (number of measurements: 5 times).

[0098] As a result, for the base paper, the tensile strength was improved by more than 2.24 times for Glass Coating Liquid No. 2 for base paper sheets, 2.25 times for No. 3 for semiconductors, 2.18 times for No. 5, and 2.4 times for No. 7 that exhibits the titanium oxide function. The sheets of the No. 7 liquid had the best numerical values both longitudinally and transversely. It was clearly found that while having the optical functional liquid function, the organic matter was not destroyed, the paper did not become shredded, and each fiber was firmly protected by the siloxane bond film. Note that the tear strength is inversely proportional to the tensile strength because the flexibility of the uncoated paper is impaired by the hardening and solidification of the liquid.

[0099] Figure 1 shows the SEM photographs of No. 2, 3, 5, and 7. Figure 1(a) shows the SEM photograph of the base paper, (b) shows No. 2, (c) shows No. 3, (d) shows No. 5, and (e) shows No. 7. The white part between the fibers is the glassy substance in the space that generates the adhesion function.

[0100] (3) Evaluation of water repellency The evaluation of water repellency was carried out based on the "Water Repellency Test Method for Paper and Paperboard (JIS-P8137)". First, a test piece with a length of 300 mm or more and a width of 200 mm without folds, wrinkles, or unevenness was taken from the coated material made from Japanese paper according to JIS P8110 (Test Paper Sampling Method), and this was pretreated according to the conditions shown in JIS P8111 (Pretreatment of Test Paper).

[0101] (4) Regarding the evaluation of flame retardancy, the coated material manufactured according to the present invention has uses as building materials such as coverings, shades, outer wall protection materials, wallpapers for interior decoration, shoji papers, etc. for stained glass, electric stands, etc. Therefore, an evaluation was made as to whether it has the flame retardancy required for building materials. In this flame retardancy evaluation, based on the UL standard (a standard specification regarding fire prevention, electrical safety, theft prevention, etc. established by Underwriter’s Laboratories, an insurance testing laboratory operated by the National Fire Protection Association in the United States, and a UL approval label is given to products that conform to this UL standard), the horizontal combustion test and the vertical combustion test were carried out by the following methods.

[0102] In conducting this combustion test, in the method shown in the above embodiments, 7.5 g of each coating liquid per 1 m of Japanese paper was immersed to produce " 2 7.5 g / m 2 ", and 15 g of each coating liquid per 1 m of Japanese paper was immersed to produce " 2 15 g / m 2 ". These were cut into test pieces with a length of 125 ± 5 mm, a width of 13.0 ± 0.3 mm, and a thickness of approximately 0.18 mm. Also, Japanese paper that had not been immersed in any of the coating liquids was cut to the same dimensions to produce a "blank" test piece. Then, each test piece was left standing for 48 hours at a temperature of 23 ± 2°C and a humidity of 50 ± 5% or less as a pretreatment.

[0103] An airtight chamber, enclosure, laboratory hood, and a burner with a length of 100 ± 10 mm and an inner diameter of 9.5 ± 0.3 mm were prepared, and industrial-grade methanol gas (minimum purity 98%) was supplied to the burner. A regulator and a flow meter were provided to enable supply, and a clock device (accuracy 1 second), a manometer with an accuracy up to 0.01 mm, and a ring stand with a clamp for supporting the test piece were also prepared. In the horizontal combustion test (conforming to UL standard 94HB), first, lines were drawn at positions 25 mm and 100 mm respectively from the ignition end of each prepared test piece.

[0104] Next, a 20-mesh wire mesh with a size of 125 mm × 125 mm was placed horizontally at a predetermined height position on the ring stand, and the other end of the long-side ignition end of the test piece was supported by a clamp at a height position with a predetermined interval above this wire mesh. The burner was ignited at a position away from the test piece, and after adjusting the gas flow rate and other parameters so that there was no yellow flame and the flame height was 20 ± 1 mm, the burner flame was made to touch the test piece for 30 seconds so that the position of the burner flame reached a position 6 ± 1 mm from one end of the test piece. If the combustion of the test piece reached the line at the 25-mm position within 30 seconds, the burner was moved away, and when it continued to burn, the horizontal combustion time from the line at the 25-mm position to the line at the 100-mm position of the test piece was measured three times.

[0105] When the flame retardancy was evaluated as described above, the coated materials produced using this coating liquid composition showed good results in the horizontal combustion test.

[0106] Also, in the vertical burning test (conforming to UL standard 94V-0), the test pieces used in the horizontal burning test were used. First, a "7.5 g / m 2 " test piece coated with a non-combustible material and a "15 g / m 2 " test piece coated with a non-combustible material were prepared. With the long direction of the test piece vertical, the upper end thereof was supported by the clamp of the ring stand. After adjusting the burner so that the flame height was 20 ± 1 mm, the tip of the flame was placed 10 mm below the center of the edge of the lower end of the test piece and indirect burning was carried out for 10 seconds. Thereafter, the burner was moved at least 150 mm away from the test piece and the first afterflame time measurement was performed. After the afterflame stopped, the burner was placed again at a position 10 mm below the center of the edge of the lower end, indirect burning was carried out for 10 seconds, the burner was moved at least 150 mm away from the test piece, the second afterflame time measurement was performed, and the after-smoke time at this time was measured.

[0107] Summarizing the above, it is as follows. No.1 can be mainly used as an impregnating agent for wood. It is a trifunctional type with high water repellency and can form a fine surface bonding film on wood. When applied to paper, etc., the strength such as tensile strength and tear strength of the paper is improved by a fine reaction. No.2 can be mainly used as a liquid agent for glass fiber. It is a modified reaction type liquid agent with trifunctional, water repellency and extensibility, and can form a porous film. No.3 can be used for semiconductor, metal surface coating, non-porous film, wood finishing agent, water and oil resistant paper, etc. It has high water repellency, oil repellency and strong film strength, and can form a flat glass cured and solidified film on the substrate. The light transmittance becomes high depending on the substrate. No.4 can be used as an antibacterial agent. It is obtained by adding a base modifier to the No.2 liquid agent for modification. It is a trifunctional functional generating type liquid agent, and by increasing the amount of the polyorganosiloxane composition, a new antibacterial function is generated in the glass coating film. The light transmittance is very high. No.5 is a tetrafunctional + trifunctional addition type liquid agent, which is a liquid agent that imparts freedom to the cured film in the strong glassification reaction of the tetrafunctional type. It has high water repellency and good abrasion resistance. It also has good adhesion to the film. The glass cured and solidified film has rigidity. It has good reactivity with nylon, polyester, urethane and generates adhesion. Also, it can prevent the migration of dyes such as polyester fibers. No.6 is a tetrafunctional + trifunctional + acid group modifier addition type liquid agent. It is a liquid agent that exhibits a strong and flat reaction film layer for the glass cured film. The film has rigidity and very high light transmittance. No.7 is a liquid agent with an adsorption and decomposition function. It is a liquid agent obtained by adding tetrafunctional + trifunctional + an additive and a small amount of acetic acid. The glass cured film is strong, but the reaction film has weak light transmittance.

[0108] No.8 is a tetrafunctional type liquid agent, and the porous reaction film is a strong and hard glass film. Coating on PVC can also form a reaction film without a primer. By adding a small amount of acetic acid to the No.8 liquid, the reaction bond becomes denser and the surface strength is improved. Therefore, an improvement in the strength of synthetic fibers can also be expected. Although not shown, in No.1, 2, 5, 11 - 14 in Table 1 above, compared with those without an adjusting agent such as acetic acid, the same effect of improving strength was confirmed for those with an adjusting agent. No.9 is a tetrafunctional type liquid agent. In the No.8 liquid agent, H2 O 2 By adding it, a hard film layer is formed, but the surface film layer forms a smooth crystal structure. No. 10 is a tetrafunctional liquid. By adding CH 3 COOH at 0.5 - 2.0% of the total weight, the function of titanium dioxide synthesized by reacting with organometallic titanium as a catalyst is retained in the solidified coating film. It is also expressed in bulk flakes. (Photocatalytic titanium dioxide function expression) The hardness of the coated and solidified film is maximized. No. 11 is a trifunctional application-type liquid. By adding an acrylate copolymer to the side chain, the surface coating film of the liquid becomes smooth, imparting waterproof performance and barrier properties. It is also effective as an anchor agent. Since the reaction film layer is flexible, it can be used to make paper that can be sewn with a sewing machine for coating on paper. It is also effective as a paper dust inhibitor. A liquid mixed with an ultraviolet inhibitor is expected to be a wood outdoor deterioration inhibitor. No. 12 is a trifunctional + bifunctional addition-type liquid. By changing the solvent and adding a functional agent to the side chain functional group, the glass solidified body has appropriate hardness and softness, and is a liquid that exhibits water repellency, slipperiness, and oil repellency. It is a liquid that uses a platinum compound catalyst in addition to the organometallic titanium catalyst. It is expected to be used for woodwork, paper products, etc. No. 13 is a trifunctional + bifunctional type liquid. By changing the mixing ratio of No. 12, it exhibits oil resistance, peelability, and super water repellency. It is non-fluorinated and environmentally friendly. No. 14 is a trifunctional, solvent-modified liquid. The film layer has flexibility and strong water repellency. It is non-fluorinated and is an environmentally friendly water repellent functional agent. No. 15 is a liquid composed of a trifunctional addition type + acrylate polymer + titanium powder. No. 16 is a liquid of trifunctional + acrylate polymer + benzenepropanoic acid + titanium powder. It is a liquid that can realize a radiation shielding sheet. It is a liquid that can react with the OH groups on the surface of the metal powder to form a porous and soft coating film. In addition, as examples expected to have the same effect as No. 7 liquid, it is considered that the organometallic catalyst is doubled in amount and depends on the addition of acetic acid, and the possible liquids are expected to be two types of liquids, No. 2 and No. 10.

[0109] Example 17 Next, regarding No. 7, the coating liquid composition of the present invention was cured and solidified to obtain a solid. For the solid, the effect of the functional material was examined. Specifically, the data showing the progress of putting the solid into a methylene blue solution is presented. Data showing the situation of applying the liquid agent to paper with a brush, cutting the paper into pieces, and putting them into a methylene blue solution is also presented. As a result, it was possible to confirm the decomposition of the methylene blue dye for both the glass flakes and the coated sheet.

[0110] Figure 2 is a diagram showing the functionality of the solid in one embodiment of the present invention. Figure 2(a) shows a photograph of the solid (glass flakes) of the present invention. Figure 2(b) shows the state of immersing 3 g of the solid of the present invention in 0.00375 g of methylene blue / 100 g of water (September 27th). Figure 2(c) shows the subsequent progress of Figure 2(b) (October 3rd). The left one (with a white lid) was placed by the window, and the right one (with a yellow lid) was stored in a locker. Figure 2(d) shows the subsequent progress of Figure 2(b) (October 9th). It can be seen that for the one on the left, due to the influence of sunlight, the color of the solution and the lower solid has decolorized and become transparent. Figure 2(f) is the one irradiated with sunlight together with the specimen of the repeated test. Figure 2(g) shows that the one on the left has become transparent and the one on the right has not changed. From these, it can be seen that it is possible to further promote the reaction and express functionality by irradiation with visible light or the like. The one on the left has reached transparency and has been further decomposed after adsorption (expression of titanium oxide), while the one on the right is adsorbed on the solid but shows a blue color, so it is judged as adsorption. It is expected that the one on the right will also exhibit a decomposition function by further light irradiation ((expression of titanium oxide)). Note that the repeated test used the glass solid of No. 7, and in the repeated repeated test, the paper obtained by applying the No. 7 liquid agent to Japanese paper and drying it was cut into 5×20 cm pieces and put into a methylene blue solution, and it was found that the decomposition of the titanium oxide function was expressed.

[0111] In one embodiment of the present invention, an example of No. 7 liquid agent has a structure such as [Chemical Formula 1] and [Chemical Formula 2], and uses trifunctional silanes and tetrafunctional silanes of organoalkoxysilanes. By coating the mixed liquid agent, first, a reaction occurs in which a glassy thin film is first formed on the substrate by the reaction of [Chemical Formula 1]. Thereafter, it is presumed that the polycondensation reaction of [Chemical Formula 2] occurs. At this time, by the action of the regulator CH 3 COOH etc., TiO 2 is generated in the liquid agent. However, the liquid agent maintains transparency and has a low viscosity (2 cP to 500 cP, and No. 7 liquid agent is 2 cP to 30 cP). It has new photocatalytic titanium oxide functions such as decomposability, adsorbability, and antibacterial property, is stable and easy to use, and does not require high-temperature firing like conventional photocatalytic titanium oxide powder. It can also contribute to the reduction of CO 2 and can provide a coating agent that can greatly contribute to a stable, safe, and inexpensive environment. In fact, 1) Methylene blue experiment diagram (decomposition function). 2) Coating experiment diagram on the deterioration film for tents (decomposition function) (Figure 3) 3) Adsorption data of KSP, 4) Antibacterial test data on the paper coated with No. 7 liquid agent (at the Antibacterial Test Laboratory of the Photocatalyst Group, Antibacterial and Antiviral Research Group, Research and Development Department, Tachimachi Branch, Kanagawa Prefectural Institute of Industrial Technology. According to the test result report of [Antibacterial Performance Evaluation Test Using Bacteria], the evaluation of "having antibacterial effect"). When the effects were confirmed, it was found that all of them exhibited good functions, namely, decomposition function, adsorption function, and antibacterial function, etc.

[0112] Note that FIG. 3 is a diagram showing an example of the present invention in one embodiment of the present invention when applied to a resin for a tent of a building. Specifically, it is a diagram showing the sunlight effect when the coating liquid composition of the present invention is coated. FIG. 3(a) is described as light, and it is a photograph showing that the brown coating film decolorizes to white by visible light projection one week after coating. FIG. 3(b) is described as dark, and it is a photograph showing that the color of the brown film remains brown even after one week in a dark room with light blocked. That is, it can be seen that it decolorizes to white by one week of sunlight, but the one with light blocked remains unchanged. Although not shown, when coated on the resin film of the tent, it was confirmed by a high-magnification electron micrograph that the defective parts of the resin were also filled to form a complete coating film. Therefore, it can be seen that the contaminants stay on the surface and are removed by the photocatalytic reaction. In general photocatalysts, titanium oxide particles are supported and coated so as not to directly touch the resin, so defects are formed in the titanium layer. The contaminants in the defective parts accumulate without being removed, so the dirt spreads and the photocatalytic function itself is also lost, but according to the present invention, such problems can be solved.

[0113] In addition, a recovery function was also observed in which the soiled ones were also recovered. That is, the composition of the present invention was coated on a tent piece that had been discolored to brown due to long-term use and deterioration, and as a result of exposing it to sunlight for one week, it regained its original white color, filled in the minute cracks in the test piece, and it was found that there was a complete catalytic effect on the entire surface, covering the surface beautifully.

[0114] Example 18 Next, a liquid agent was prepared by adding a Pt catalyst at a total weight ratio of 0.0013% to the above-described (coating liquid (liquid agent) of No. 7) (coating liquid No. 17 (= coating liquid No. 7 + Pt catalyst)). For the coating liquid No. 17, the weights of the mixed components were the same as those of the coating liquid No. 7 except that a Pt catalyst was used. Using the composition of the coating liquid No. 17, the effects of the functional material were examined for the solidified body obtained by curing and solidifying (FIGS. 4 to 6).

[0115] <Test piece production> The abrasive glass (50 - 100 mm) was coated with the No. 17 liquid agent and dried at 120 °C for 1 h. As the coating method, the abrasive glass was immersed in a petri dish containing the liquid agent No. 17 and immediately taken out and dried.

[0116] Next, the decomposition performance of the solidified body manufactured using No. 17 was examined. As the test method, the measurement of wet decomposition performance of JIS R1703 - 2 was carried out. According to the standard, the measurement after 3 h of light irradiation was performed, and then, in order to confirm the change over a longer period of time, the measurement after 24 h was also carried out. Subsequently, it was extended and carried out according to the results. When ultraviolet rays hit a photocatalyst, it generates a strong oxidizing power and has the property of decomposing the touched organic substances into carbon dioxide and water. In the photocatalyst JIS test using methylene blue, water in which an organic dye (methylene blue) was dissolved was brought into contact with a test piece coated with the photocatalyst, and the initial absorbance (the degree to which light is absorbed) was measured with a spectrophotometer. The performance of the photocatalyst can be indicated by the amount of change. The "light" in this case refers to the situation where ultraviolet rays are irradiated from the ultraviolet irradiation reaction system. Also, the ultraviolet illuminance on the catalyst surface at this time is 10 W / m 2 is set. At this time, since the test body receives not only ultraviolet rays but also visible light, the decomposition of methylene blue occurs by both types of light, and the amount thereof is designated as A. Since it is necessary to see the influence of only ultraviolet rays, a dark condition is also required. "Dark" means a situation where the ultraviolet rays are not irradiated, and the photocatalytic action works by visible light, and methylene blue is decomposed. The amount thereof is designated as B. Then, by taking the difference between the two (A - B), the decomposition amount due to the photocatalytic action by ultraviolet rays can be measured. The "light" of the blank refers to the situation where ultraviolet rays are irradiated to a sample without the photocatalyst agent applied to the test body. This measures the decomposition amount of methylene blue by ultraviolet rays themselves, and the decomposition amount is designated as C. Eventually, the net decomposition amount by the photocatalyst agent under ultraviolet irradiation is the result of subtracting C from A - B above, but in reality, the amount of C is small, so it can be evaluated by A - B.

[0117] As samples, (1) ground glass coated with Liquid Agent No. 17 under light conditions 1 and 2 (light conditions 1 and 2 respectively indicate Test Specimens 1 and 2 under light conditions), (2) ground glass coated with Liquid Agent No. 17 under dark conditions 1 and 2 (dark conditions 1 and 2 respectively indicate Test Specimens 1 and 2 under dark conditions), and (3) ground glass under light conditions (Blanks 1 and 2 in Fig. 4 (Test Specimens 1 and 2 in the blank)) were used.

[0118] If there is a difference between (1) and (2) above, the effect of light irradiation can be confirmed. Also, it was confirmed whether there was any change in methylene blue after long-term UV irradiation in (3).

[0119] As a result, although a slight decrease in the concentration of methylene blue was observed even under dark conditions, for the solidified body using No. 17, a significant decrease in the concentration of methylene blue was found under any light conditions, and the state of decomposition was confirmed. Thus, it was found that even in the solidified body using Liquid Agent No. 17 obtained by adding a Pt catalyst to Liquid Agent No. 7 at a weight ratio of 0.0013%, the effect of an excellent functional material was exhibited.

[0120] Example 19 In addition, an adsorption performance test of the glass flakes obtained using No. 7 described above was conducted. Since methylene blue can be decomposed by a photocatalyst, the photocatalytic performance can be evaluated by measuring the decomposition rate under ultraviolet irradiation. The performance is represented by the decomposition activity index R. If the index is 5 or more, it is determined that there is photocatalytic activity.

[0121] This time, at the Kanagawa Science Park (KSP), the sample and methylene blue concentration test conditions were made equivalent to those of a normal photocatalytic decomposition test, and the change in the concentration of methylene blue was measured in the dark instead of under light irradiation. That is, glass flakes made from the No. 7 liquid agent were added to a methylene blue solution of a certain concentration, and the change in the concentration of methylene blue was measured in the dark. In this experiment, the methylene blue in the solution was adsorbed by the glass flakes, and the concentration of methylene blue in the solution decreased. The concentration change is as shown in Figure 8. As a result of evaluating the decomposition activity index from the concentration change, a high decomposition activity index of 15.3 nmol / L / min was obtained. It can be said that this high decomposition index indicates the adsorption performance of the glass flakes. As a result of this experiment, the solution became transparent and the glass flakes turned blue.

[0122] Furthermore, regarding the solid obtained using the No. 7 liquid agent according to the above manufacturing method, an observation was made using a transmission electron microscope at the Institute of Physical and Chemical Research, Kashiwa Campus, The University of Tokyo, to determine what substances the above photocatalytic properties are derived from. Figure 7 is a diagram showing a micrograph of the solid (No. 7) in one embodiment of the present invention. K indicates magnification by a factor of 1000. For example, 300K indicates magnification by a factor of 300,000. As a result of these observations, nanoparticle dispersion was seen in the micrograph of the solid obtained using the No. 7 liquid agent of the present invention that exhibited a photocatalytic function, and substances that were recognized as anatase-type titanium oxide crystals were confirmed. Although it cannot be determined with certainty that it is 100%, it is highly likely to be titanium oxide, and it can be inferred that the photocatalytic effect was thereby exhibited.

[0123] The drawbacks of conventional titanium dioxide (photocatalyst) alone are described below (it is in powder form). 1) It has no effect without sunlight (natural) light (ultraviolet light). 2) When directly applied to an organic substance, it decomposes the substrate (base layer), so a primer is required, and it has to be applied repeatedly such as in a two-coat process, which is time-consuming and costly. 3) When blended with an organic substance, it decomposes the organic substance, so direct blending of the powder is not possible. 4) It cannot decompose unless it is in contact with the powder surface for a certain period of time, and only has a partial effect on the surface.

[0124] Regarding the above (1), it has been found that the functional material (No.7) of the present invention has the characteristics that adsorption and decomposition by liquid coating are effective even under visible light and it has an adsorption function even in the dark. Regarding the above (2), it has been found that for the functional material (No.7) of the present invention, the organic decomposition of the liquid special base material is protected by the siloxane bonding film on the base material, and the photocatalytic function is sufficiently expressed by a single surface coating, so the cost can be low. Regarding the above (3), it has been found that for the functional material (No.7) of the present invention, the liquid is composed of side chain functional groups 3 and 4 functional groups, and even if a functional agent is incorporated into one opening part of the 3 functional groups, it will not be decomposed by the tetrafunctional bonding film, so it has no influence on organic functional substances and can be blended. Regarding the above (4), it has been found that the functional material (No.7) of the present invention is transparent, has low viscosity, good permeability, and good drying property. It has been found that the effect is high because it forms a penetrating coating film not only on the surface but also in the Z direction. Also, with this liquid, it is possible to create a bulk glass from a very thin film. It is a transparent glass solidified body.

[0125] Note that although not all aspects of the discovery of the liquid titanium oxide of the present invention have been elucidated yet, unlike conventional photocatalytic titanium oxide, it is not a "particle body", can be coated anywhere, has the same decomposition performance as titanium oxide, and is a liquid that can be synthesized as a three-dimensional structure like plastic, and it can be seen that it is very useful.

[0126] That is, the functional material of the present invention, taking titanium as an example, for example, is different from conventional powdered photocatalytic titanium oxide. There is no need to paste the powder on the surface with an adhesive, and there is no need to devise an adsorbent below. It can be said to be a coating liquid having a transparent photocatalytic / titanium oxide function that can exhibit both "decomposition performance" and "adsorption performance". Titanium oxide powder is usually a "white powder", and it is a photocatalytic titanium oxide that cannot exhibit its function unless it is scattered on the surface. On the other hand, the functional material of the present invention is a liquid that can be coated by a siloxane bonding reaction group anywhere and can exhibit its function, so it is significant in that it can greatly expand the existing application areas of titanium oxide.

Industrial Applicability

[0127] Since the silane-based coating liquid composition of the present invention can provide materials having various functions at low cost, it is expected to make a great contribution to industrial development in a wide range of fields.

Claims

1. The main component is the following chemical formula (1): 【Chemistry 1】 (However, R １ , R ２ , R ３ and R ４ a catalyst comprising a hydrolyzable organometallic compound, a regulator comprising a weakly acidic catalyst or a basic catalyst, and an organic solvent, wherein the compound is a polycondensate of a monomer represented by chemical formula (1) where n is 1, and the solvent used in polycondensation of the monomer has been removed from the silane-based coating liquid composition.

2. 2. The silane-based coating composition according to claim 1, which does not contain reaction water for polycondensing the compound.

3. 3. The silane-based coating composition according to claim 1, wherein the regulator is at least one of acetic acid, hydrogen peroxide, and ammonia.

4. 4. The silane-based coating composition according to claim 1, wherein the content of the regulator is 0.5 to 5% by weight.

5. The silane-based coating liquid composition according to any one of claims 1 to 4, characterized in that, during use, the compound is polycondensed via a catalyst made of the hydrolyzable organometallic compound by moisture in the air and / or a hydroxyl group or moisture contained in a substrate to which the coating composition is applied.

6. The silane-based coating liquid composition according to claim 5, characterized in that the catalyst consisting of the hydrolyzable organometallic compound polycondenses the compound, and also generates a metal oxide dispersed in the polycondensate of the compound by hydrolysis of the organometallic compound, thereby expressing a function due to the metal oxide.

7. The silane-based coating liquid composition according to claim 5 or 6, characterized in that the catalyst consisting of the hydrolyzable organometallic compound is an organotitanium compound, and the compound is polycondensed, and at the same time, titanium oxide, which is a metal oxide dispersed in the polycondensate of the compound, is generated by hydrolysis of the organotitanium compound, and at least one of antibacterial function, decomposition function and adsorption function due to the titanium oxide is exhibited.

8. 8. The silane-based coating liquid composition according to claim 6, wherein the regulator is involved in the reaction in which the metal oxide is produced from the organometallic compound.

9. A compound having three hydrolyzable substituents and one non-hydrolyzable substituent in addition to the main component, and represented by the following chemical formula (2): 【Chemistry 2】 (However, R ５ , R ６ and R ７ may be the same or different and are monomers consisting of hydrogen, alkyl groups or alkenyl groups; R ５ O, R ６ O and R ７ The bond between O and Si is an oligomer consisting of a siloxane bond, and R ８ The silane-based coating liquid composition according to any one of claims 1 to 8, characterized in that it contains:

10. A compound having two hydrolyzable substituents and two non-hydrolyzable substituents in addition to the main component, and represented by the following chemical formula (3): 【Chemistry 3】 (However, R ９ and R １１ may be the same or different and are monomers consisting of hydrogen, alkyl groups or alkenyl groups; R ９ O and R １１ The bond between O and Si is an oligomer consisting of a siloxane bond, and R １０ and R １２ is an alkyl group, an alkenyl group or a phenyl group which may contain an epoxy group or a glycidyl group in its molecule.

11. The silane-based coating liquid composition according to any one of claims 1 to 10, further comprising an acrylic resin.

12. The main component is the following chemical formula (1): 【Chemistry 4】 (However, R １ , R ２ , R ３ and R ４ a catalyst comprising a hydrolyzable organometallic compound, a regulator comprising a weak acid catalyst or a basic catalyst, and an organic solvent, A method for producing a silane-based coating liquid composition, comprising polycondensing a monomer represented by the above chemical formula (1) in which n is 1 in the presence of a solvent, removing the solvent used in the polycondensation of the monomer from the obtained polycondensate by heating under reduced pressure, and mixing the obtained compound with the catalyst consisting of the hydrolyzable organometallic compound, the regulator, and the organic solvent.

13. The method for producing a silane-based coating liquid composition according to claim 12, characterized in that no reaction water that hydrolyzes the compound is present.

14. 14. The method for producing a silane-based coating liquid composition according to claim 12, wherein the regulator is at least one of acetic acid, hydrogen peroxide, and ammonia.

15. The method for producing a silane-based coating liquid composition according to any one of claims 12 to 14, wherein the catalyst made of a hydrolyzable organometallic compound is an organotitanium compound.

16. A functional material obtained by applying the silane-based coating liquid composition according to any one of claims 1 to 11 to a substrate and solidifying it.

17. The functional material according to claim 16, characterized in that it is produced by hydrolysis of a catalyst consisting of a hydrolyzable organometallic compound, contains a metal oxide dispersed in a polycondensate of the compound, and has a function due to the metal oxide.

18. The functional material according to claim 16 or 17, characterized in that the catalyst consisting of the hydrolyzable organometallic compound is an organotitanium compound, contains titanium oxide produced by hydrolysis of the organotitanium compound and dispersed in a polycondensate of the compound, and has at least one of an antibacterial function, a decomposition function, and an adsorption function due to the titanium oxide.

19. A method for producing a functional material, comprising the steps of: applying the silane-based coating liquid composition according to any one of claims 1 to 11 to a substrate; polycondensing the compound by the moisture in the air and / or a hydroxyl group or moisture contained in the substrate via a catalyst made of the hydrolyzable organometallic compound; and drying the substrate to which the coating composition has been applied.

20. 20. The method for producing a functional material according to claim 19, characterized in that the compound is polycondensed by a catalyst made of the hydrolyzable organometallic compound, and a metal oxide dispersed in the polycondensate of the compound is generated by hydrolysis of the organometallic compound, thereby expressing a function due to the metal oxide.

21. 21. The method for producing a functional material according to claim 19 or 20, characterized in that the catalyst consisting of the hydrolyzable organometallic compound is an organotitanium compound, and the compound is polycondensed, and at the same time, titanium oxide, which is a metal oxide dispersed in the polycondensate of the compound, is generated by hydrolysis of the organotitanium compound, and at least one of antibacterial function, decomposition function and adsorption function due to the titanium oxide is exhibited.

22. A coated material obtained by applying the silane-based coating liquid composition according to any one of claims 1 to 11 to a substrate.

23. A solidified body obtained by solidifying the silane-based coating liquid composition according to any one of claims 1 to 11.

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