Method for producing polysiloxane-containing composite body and polysiloxane-containing composite body

Abstract

To provide a method for producing a polysiloxane-containing composite body which can make hydrogen polysiloxane recyclable as a polysiloxane-containing composite body, while safely and efficiently treating the hydrogen polysiloxane.SOLUTION: A method for producing a polysiloxane-containing composite body includes a contact step of bringing hydrogen polysiloxane having an Si-H bond and a hypochlorite on the surface of a base material in the presence of water into contact with each other, and producing polysiloxane having an Si-OH bond or its condensate. The hypochlorite is preferably sodium hypochlorite. The blended amount of the hypochlorite is preferably 0.1 mol or more and 2 mol or less with respect to 1 mol of the Si-H bond possessed by the hydrogen polysiloxane.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for producing a polysiloxane-containing composite and a polysiloxane-containing composite.

Background Art

[0002] Organic polysiloxanes into which various organic groups have been introduced are widely used in fields such as paints, molding materials, medical materials, various coating materials, cosmetics, personal care compositions, home care compositions, release agents, and fiber treatment agents. Hydrogen polysiloxane, which is a polysiloxane having an Si-H bond, is useful as a precursor for such organic polysiloxanes.

[0003] On the other hand, when hydrogen polysiloxane comes into contact with a substance having active hydrogen such as water, dehydrogenation may occur between adjacent hydrogen atoms under certain conditions, generating hydrogen gas. Hydrogen gas is dangerous in terms of ignition and explosion and must be handled with care. In recent years, from the viewpoints of safety in the working environment and reduction of environmental load, the use of hydrogen polysiloxane in the form of an aqueous emulsion has been increasing, and the frequency of the generation of the hydrogen gas tends to increase. Therefore, a technique for treating excess hydrogen polysiloxane to a safe state is required.

[0004] As the treatment technique, a technique of blowing ethylene gas into hydrogen polysiloxane (Patent Document 1) and a technique of generating a cross-linked product of a vinyl group-containing polysiloxane and hydrogen polysiloxane in the presence of a catalyst (Patent Document 2) have been proposed.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, among the above-mentioned treatment techniques, in the former technique, the reaction occurs at the gas-liquid interface, resulting in poor reaction efficiency and difficulty in pressure and temperature control. In the latter technique, a large amount of vinyl group-containing polysiloxane is required, and the reaction may be difficult to proceed due to steric hindrance, leaving room for improvement. Separating hydrogen polysiloxane from water is also not easy from the same perspective.

[0007] Furthermore, from the perspectives of the environment and sustainability, the demand for reusing the products after treatment is increasing.

[0008] An object of the present invention is to provide a method for producing a polysiloxane-containing composite that can safely and efficiently treat hydrogen polysiloxane and make it reusable as a polysiloxane-containing composite, and the polysiloxane-containing composite.

Means for Solving the Problems

[0009] The inventors of the present invention conducted intensive studies to solve the above problems. Surprisingly, they found that by treating hydrogen polysiloxane with hypochlorite on the surface of a substrate, it is possible to safely and efficiently make it reusable as a polysiloxane-containing composite. The present invention has been completed based on such new findings.

[0010] In one embodiment, the present invention a contacting step of contacting hydrogen polysiloxane having an Si-H bond with hypochlorite on the surface of a substrate in the presence of water to produce polysiloxane having an Si-OH bond or a condensate thereof relates to a method for producing a polysiloxane-containing composite, which includes the above step.

[0011] According to the method for producing the polysiloxane-containing composite, in the presence of water, by bringing a hydrogen polysiloxane having an Si-H bond into contact with a hypochlorite on the surface of a substrate, a polysiloxane having an Si-OH bond or a condensate thereof (hereinafter, also collectively referred to as "polysiloxane derivative") can be safely and efficiently produced on the substrate surface. The polysiloxane derivative is a reusable and highly functional polysiloxane compound. The polysiloxane derivative can be used as it is, or the hydroxy groups of the polysiloxane derivative can be modified with other substituents to enhance its functionality. Through the method for producing the polysiloxane-containing composite, safe and efficient conversion of hydrogen polysiloxane into a polysiloxane derivative and reuse as a polysiloxane-containing composite can be achieved, which can greatly contribute to environmental protection and sustainable development.

[0012] As used herein, "polysiloxane" means a compound containing a siloxane bond (-Si-O-Si-).

[0013] In one embodiment, the hypochlorite is preferably sodium hypochlorite in terms of reaction efficiency.

[0014] In one embodiment, the amount of the hypochlorite is preferably 0.1 mol or more and 2 mol or less per 1 mol of the Si-H bond of the hydrogen polysiloxane. By setting the amount of the hypochlorite within the above range, a polysiloxane derivative can be efficiently produced from the hydrogen polysiloxane.

[0015] In one embodiment, it is preferable to allow an acid to coexist in the contact step. In one embodiment, it is more preferable that the acid is an organic acid. In one embodiment, it is even more preferable that the acid is acetic acid or lactic acid. Since the hypochlorite acts as an oxidizing agent with respect to the hydrogen polysiloxane, by allowing such an acid to coexist, the action of the hypochlorite as an oxidizing agent is enhanced, and the conversion efficiency of the hydrogen polysiloxane into a polysiloxane derivative can be further improved.

[0016] In one embodiment, in the presence of the acid, it is preferable that the pH of the water be 7 or more and 11 or less 3 hours after the start of the contact step. By reacting under mild conditions, decomposition of the hypochlorite can be suppressed, and hydrogen polysiloxane can be more efficiently converted into a polysiloxane derivative.

[0017] In one embodiment, the hydrogen polysiloxane may be present in the form of an emulsion with the water. Even for an aqueous emulsion of hydrogen polysiloxane, which has conventionally been difficult to make safe and reusable, it can be safely converted into a useful polysiloxane derivative simply by contacting it with hypochlorite if it is a method for producing the polysiloxane-containing composite. As a result, it can also contribute to measures in terms of the environment and sustainability.

[0018] In one embodiment, it is preferable that the surface of the base material has a hydroxy group. A covalent bond can be formed by condensation with the Si-OH bond of the produced polysiloxane derivative, and the polysiloxane derivative can be firmly fixed to the surface of the base material.

[0019] The base material may be any of cloth, paper, wood, a porous material, or inorganic particles. According to the method for producing the polysiloxane-containing composite, a polysiloxane-containing composite having a polysiloxane derivative on the surface of the base material can be widely formed regardless of the properties and structure of the base material.

[0020] In other embodiments of the present invention, a base material, a polysiloxane having an Si-OH bond or a condensate thereof, formed on the surface of the base material, and relate to a polysiloxane-containing composite.

[0021] Since the polysiloxane-containing composite has a highly functional polysiloxane derivative on the surface of the base material, it can be applied to various uses.

Embodiments for Carrying Out the Invention

[0022] A method for producing a polysiloxane-containing composite and the polysiloxane-containing composite according to an embodiment of the present invention will be described below. The present invention is not limited to these embodiments. Combinations of preferred embodiments are also preferred.

[0023] 《Method for Producing Polysiloxane-Containing Composite》 The method for producing a polysiloxane-containing composite according to this embodiment includes a contacting step of contacting a hydrogen polysiloxane having an Si-H bond with a hypochlorite on the surface of a substrate in the presence of water to form a polysiloxane having an Si-OH bond or a condensate thereof.

[0024] The water is not particularly limited, and pure water, ultrapure water, purified water, ion-exchanged water (deionized water), distilled water, etc. can be used.

[0025] The type of the substrate is not particularly limited, and various substrates can be adopted according to the application. Examples of the substrate include cloth, paper, wood, porous materials, inorganic particles, steel plates, aluminum foils, glass, gypsum, resin substrates, etc. Examples of the cloth include woven cloth, knitted cloth, non-woven cloth, etc. Examples of the paper include synthetic paper, natural paper, etc. The wood may be in any form such as chips, boards, square timbers, etc. Examples of the porous material include activated carbon, zeolite, silica gel, diatomaceous earth, pumice, metal porous materials, glass porous materials, etc. Examples of the inorganic particles include aluminum hydroxide particles, titanium oxide particles, silica particles, etc.

[0026] The surface of the substrate preferably has a hydroxy group. A covalent bond can be formed by condensation with the Si-OH bond of the produced polysiloxane derivative, and the polysiloxane derivative can be firmly fixed to the substrate surface. A hydroxy group may be introduced by performing plasma treatment or the like on the substrate surface.

[0027] Note that the surface of the substrate is a concept that includes the range where water or a mixture of water and hydrogen polysiloxane (hereinafter also referred to as "water etc.") can penetrate from the outermost surface of the substrate. Therefore, for example, as the surface of the cloth, it includes not only the apparent surface of the cloth but also the surface of the fibers constituting the cloth within the range where water etc. can penetrate.

[0028] Hydrogen polysiloxane is a polysiloxane having an Si-H bond. Hydrogen polysiloxane preferably has a polymer form. A "polymer" refers to a compound having two or more structural units. When two or more identical structural units are consecutive in a polymer, this structural unit is also referred to as a "repeating unit". Hydrogen polysiloxane preferably has a structural unit (α) represented by the following formula (1-1). Hydrogen polysiloxane may have one or more kinds of structural units (α).

[0029] [Chemical formula]

[0030] In formula (1-1), a is an integer from 1 to 3. R 1 is a monovalent organic group having 1 to 20 carbon atoms or a halogen atom. b is an integer from 0 to 2. When b is 2, the two Rs 1 are the same as or different from each other. However, a + b is 3 or less.

[0031] In this specification, an "organic group" means a group containing at least one carbon atom.

[0032] In the above formula (1-1), as the monovalent organic group having 1 to 20 carbon atoms represented by R 1 , for example a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group containing a divalent heteroatom-containing linking group between carbon-carbon bonds of the above hydrocarbon group or at the terminal of the above hydrocarbon group (hereinafter also referred to as "group (α)"), a group in which some or all of the hydrogen atoms of the above hydrocarbon group or the above group (α) are substituted with a monovalent heteroatom-containing substituent (hereinafter also referred to as "group (β)"), A group formed by combining at least two of the above hydrocarbon group, the above group (α), and the above group (β) (hereinafter, also referred to as "group (γ)"). etc. can be mentioned.

[0033] Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0034] Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms include a monovalent chain aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms and a monovalent chain aliphatic unsaturated hydrocarbon group having 1 to 20 carbon atoms. Examples of the monovalent chain aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, and tert-butyl group. Examples of the monovalent chain aliphatic unsaturated hydrocarbon group having 1 to 20 carbon atoms include alkenyl groups such as ethenyl group, propenyl group, and butenyl group; and alkynyl groups such as ethynyl group, propynyl group, and butynyl group.

[0035] Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic alicyclic saturated hydrocarbon groups such as cyclopentyl group and cyclohexyl group; polycyclic alicyclic saturated hydrocarbon groups such as norbornyl group, adamantyl group, tricyclodecyl group, and tetracyclododecyl group; monocyclic alicyclic unsaturated hydrocarbon groups such as cyclopentenyl group and cyclohexenyl group; and polycyclic alicyclic unsaturated hydrocarbon groups such as norbornenyl group, tricyclodecenyl group, and tetracyclododecenyl group.

[0036] Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group, and anthryl group, and aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group, and anthrylmethyl group.

[0037] Examples of the heteroatoms constituting the divalent heteroatom-containing linking group and the monovalent heteroatom-containing substituent include, for example, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a halogen atom, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom (in this specification, unless otherwise specified, these atoms are included as the "halogen atom").

[0038] Examples of the divalent heteroatom-containing linking group include, for example, -O-, -C(=O)-, -S-, -C(=S)-, -NR’-, -SO2-, and groups formed by combining two or more of these. R’ is a hydrogen atom or a monovalent hydrocarbon group.

[0039] Examples of the monovalent heteroatom-containing substituent include, for example, a halogen atom, a hydroxy group, a carboxy group, a cyano group, an amino group, a sulfanyl group, etc.

[0040] R 1 The number of carbon atoms of the monovalent organic group represented by is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4.

[0041] R 1 As the halogen atom represented by, a chlorine atom is preferred.

[0042] R 1 is preferably a monovalent chain hydrocarbon group, a monovalent aromatic hydrocarbon group, or a monovalent group in which some or all of the hydrogen atoms of a monovalent hydrocarbon group are substituted with a monovalent heteroatom-containing group, more preferably an alkyl group or an aryl group, even more preferably a methyl group, an ethyl group, or a phenyl group, and particularly preferably a methyl group.

[0043] In the above formula (1-1), a is preferably 1 or 2, and more preferably 1. In the above formula (1-1), b is preferably 0 or 1, and more preferably 1.

[0044] (Structural unit (β)) The hydrogen polysiloxane may have a structural unit (β) represented by the following formula (2-1). The hydrogen polysiloxane may have one or more kinds of the structural unit (β).

[0045] [Chemical formula] (In the above formula (2-1), R 12 is a monovalent organic group having 1 to 20 carbon atoms or a halogen atom. e is an integer from 0 to 3. When e is 2 or more, a plurality of R 12 are the same or different.)

[0046] As the monovalent organic group having 1 to 20 carbon atoms represented by R 12 , the monovalent organic group having 1 to 20 carbon atoms represented by R 1 in the above formula (1-1) can be preferably adopted.

[0047] As R 12 , it is preferably a substituted or unsubstituted monovalent alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

[0048] Specific examples of the monovalent alkoxy group having 1 to 20 carbon atoms include alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, and isopropoxy group.

[0049] Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, naphthyl group, and anthracenyl group.

[0050] Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and t-butyl group.

[0051] When the above-mentioned alkoxy group, aryl group and alkyl group have substituents, the monovalent heteroatom-containing substituents can be preferably adopted as the substituents. Further, as the substituents of the aryl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, an acyl group, an acyloxy group, or a group in which a hydrogen atom of these groups is substituted with a halogen atom, etc. can be mentioned.

[0052] e is preferably an integer of 0 to 2, more preferably 1 or 2, and still more preferably 2.

[0053] The above-mentioned hydrogen polysiloxane can be produced by a known method. Specific structures of the hydrogen polysiloxane include methylhydrogen polysiloxane, dimethylsiloxane·methylhydrogen siloxane copolymer, methylphenylsiloxane·methylhydrogen siloxane copolymer, etc. The hydrogen polysiloxane may be cyclic or chain-like. The chain-like may be either linear or branched. In the contacting step, the hydrogen polysiloxane may be used alone or a plurality of types may be mixed and used. The hydrogen atoms in the hydrogen polysiloxane may be bonded only to the silicon atoms at the (both) ends of the molecular chain of the hydrogen polysiloxane (hereinafter, also referred to as "terminal hydrogen polysiloxane"), may not be bonded to the silicon atoms at the (both) ends of the molecular chain, and may be bonded only to the silicon atoms as side chains of the molecular chain (hereinafter, also referred to as "side-chain hydrogen polysiloxane"), or may be bonded to the silicon atoms at the (both) ends of the molecular chain and to the silicon atoms as side chains of the molecular chain (hereinafter, also referred to as "both-type hydrogen polysiloxane").

[0054] Although the content of hydrogen atoms in the hydrogen polysiloxane (the ratio of the total atomic weight of hydrogen atoms in the molecular weight of the hydrogen polysiloxane) is not particularly limited, the lower limit of the content may be 0.005%, may be 0.01%, or may be 0.02%. The upper limit of the content may be 3%, may be 2%, or may be 1.8%.

[0055] The hydrogen polysiloxane according to this embodiment exists in the form of an emulsion with the water. As the form of the emulsion, it may be an oil-in-water (o / w) emulsion or a water-in-oil (w / o) emulsion. From the viewpoint of the contact efficiency with the hypochlorite, it is preferable that the hydrogen polysiloxane exists as an oil-in-water emulsion.

[0056] The method for forming the emulsion is not particularly limited, and known methods such as the liquid crystal emulsification method, the mechanical emulsification method, the phase inversion emulsification method, the phase inversion temperature emulsification method, and the D-phase emulsification method can be adopted.

[0057] The concentration of the hydrogen polysiloxane in water is not particularly limited and can be appropriately set in consideration of the contact efficiency and reaction efficiency with the hypochlorite, workability, etc. For example, when the hydrogen polysiloxane is in an emulsion state, the lower limit of the concentration may be 0.5% by mass, 1% by mass, 2% by mass, or 3% by mass. The upper limit of the concentration may be 70% by mass, 60% by mass, or 50% by mass.

[0058] When forming the emulsion of the hydrogen polysiloxane, optional components such as a surfactant, a stabilizer, and a preservative may be added, for example.

[0059] The hypochlorite is a salt of hypochlorous acid and functions as an oxidizing agent for the hydrogen polysiloxane. As the salt, an alkali metal salt such as sodium or potassium, or an alkaline earth metal salt such as magnesium, calcium, or barium is preferable. The hypochlorite is preferably an alkali metal salt of hypochlorous acid, and more preferably sodium hypochlorite.

[0060] By bringing the hydrogen polysiloxane having an Si-H bond into contact with the hypochlorite, a polysiloxane having an Si-OH bond or a condensate thereof can be produced safely and efficiently. Although this reaction mechanism is not clear, for example, when using sodium hypochlorite, it is presumed to proceed by the following reaction scheme.

[0061]

Chem.

[0062] In the above scheme, each R is independently a monovalent organic group or a halogen atom.

[0063] The -O of sodium hypochlorite - Na + attacks the silicon atom of the Si-H bond, and as a transition state, Si-O - Na + bond is formed. Along with this, the hydrogen atom of the Si-H bond desorbs to generate hydrogen chloride. Finally, the sodium of the Si-O - Na + bond and the hydrogen atom are exchanged to produce a polysiloxane having a Si-OH bond. In this scheme, hydrogen gas is not generated at any stage of the reaction, and the final by-product is sodium chloride, which is highly safe.

[0064] The generated polysiloxane having a Si-OH bond may condense between the Si-OH bonds to form a cross-linked product. According to the method for producing the polysiloxane compound, a polysiloxane having a Si-OH bond and its condensate can be safely and efficiently produced as a polysiloxane derivative.

[0065] In addition, the polysiloxane having a Si-O - Na + bond purified in the transition state may be contained as the final product while maintaining its original form.

[0066] The lower limit of the amount of hypochlorite may be 0.1 mol, 0.5 mol, or 0.8 mol per 1 mol of Si-H bond in the hydrogen polysiloxane. The upper limit of the amount may be 2 mol, 1.5 mol, or 1.2 mol per 1 mol of Si-H bond in the hydrogen polysiloxane. The amount of hypochlorite can be appropriately set in consideration of the conversion degree of Si-H bond in the hydrogen polysiloxane to Si-OH bond, reaction efficiency, and the like.

[0067] The mode of contact between the hydrogen polysiloxane and the hypochlorite on the surface of the substrate in the presence of water is not particularly limited, and an appropriate method can be adopted according to the type of the substrate. Specific examples of the contact method include preparing a mixture of water and hydrogen polysiloxane (preferably an emulsion), immersing the substrate in this mixture, taking it out and removing (drying) the excess water, and then putting this into an aqueous solution of hypochlorite; preparing a mixture of water and hydrogen polysiloxane (preferably an emulsion), immersing the substrate in this mixture, taking it out and removing (drying) the excess water, and then spraying an aqueous solution of hypochlorite thereon; preparing a mixture of water and hydrogen polysiloxane (preferably an emulsion), immersing the substrate in this mixture, and further adding hypochlorite or an aqueous solution of hypochlorite; applying a mixture of water and hydrogen polysiloxane to the substrate, and further applying an aqueous solution of hypochlorite, and the like.

[0068] When preparing an aqueous solution of hypochlorite, the concentration of hypochlorite in the aqueous solution is not particularly limited and can be appropriately set in consideration of the reaction efficiency and workability. The lower limit of the concentration of hypochlorite is preferably 0.1% by mass, preferably 0.5% by mass, preferably 0.8% by mass. The upper limit of the concentration of hypochlorite is preferably 10% by mass, preferably 5% by mass, preferably 3% by mass. The amount of the aqueous solution of hypochlorite can be appropriately set so as to obtain the amount of hypochlorite compounded with respect to the hydrogen polysiloxane. In addition, depending on the solubility of hypochlorite, a mixture with water may be prepared in the form of a suspension instead of an aqueous solution.

[0069] In the contacting step, it is preferable to coexist an acid. The acid may be either an organic acid or an inorganic acid. Examples of the organic acid include carboxylic acids and sulfonic acids. Examples of the carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, and propionic acid; dicarboxylic acids such as oxalic acid, malonic acid, and succinic acid; and hydroxy acids such as lactic acid, malic acid, tartaric acid, and citric acid. Examples of the sulfonic acid include methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid. Examples of the inorganic acid include hydrochloric acid, nitric acid, and sulfuric acid. Among them, as the acid, an organic acid is preferable, and acetic acid or lactic acid is more preferable.

[0070] The lower limit of the blending amount of the acid is preferably 0.01 mol, more preferably 0.05 mol, and even more preferably 0.1 mol with respect to 1 mol of the hypochlorite. The upper limit of the blending amount is preferably 0.5 mol, more preferably 0.3 mol with respect to 1 mol of the hypochlorite. By setting the blending amount of the acid within the above range, the activity of the hypochlorite can be improved, and the decomposition of the hypochlorite to generate chlorine gas can be suppressed.

[0071] When coexisting an acid in the contacting step, it may be coexisted from the initial stage of the contact between the hydrogen polysiloxane and the hypochlorite, or the acid may be added and coexisted after a predetermined time has elapsed from the contact between the hydrogen polysiloxane and the hypochlorite. Further, the addition of the acid may be carried out at once, continuously over time, or stepwise at intervals. Due to the coexistence of the acid, in the above reaction scheme, the attack of the Si-H bond of the -O - Na + portion of sodium hypochlorite on the silicon atom is promoted, while the decomposition of sodium hypochlorite may be induced. The timing of the addition of the acid may be appropriately set in consideration of these points. As a result, the conversion to the Si-OH bond can proceed more efficiently. When coexisting the acid, it is preferable to add it in the form of an aqueous solution of the acid. The concentration of the acid in the aqueous solution can be appropriately set within the range of 0.1% by mass or more and 5% by mass or less.

[0072] In the contacting step, the reaction time and reaction temperature can be appropriately set so that the degree of conversion of the target hydrogen polysiloxane to the polysiloxane derivative can be obtained. The lower limit of the reaction time is preferably 5 minutes, more preferably 10 minutes, and even more preferably 15 minutes. The upper limit of the reaction time is preferably 80 minutes, more preferably 60 minutes, and even more preferably 40 minutes. In the method for producing the polysiloxane compound, since the conversion with the hypochlorite is achieved, the reaction can proceed at room temperature (20 °C) without heating. The lower limit of the reaction temperature may be 10 °C, may be 15 °C, or may be 20 °C. The upper limit of the reaction temperature may be 60 °C, may be 50 °C, or may be 40 °C.

[0073] When an acid is added after a predetermined time has elapsed since the contact between the hydrogen polysiloxane and the hypochlorite, the lower limit of the elapsed time since the contact is preferably 5 minutes later, more preferably 10 minutes later, and even more preferably 15 minutes later. The upper limit of the elapsed time is preferably 80 minutes later, more preferably 60 minutes later, and even more preferably 40 minutes later.

[0074] When the acid is added, in the case of an aqueous solution of the acid, it may be added all at once or may be added over a certain period of time. From the viewpoint of allowing the reaction to proceed gently and suppressing undesirable side reactions, it is preferable to add the aqueous solution of the acid over a certain period of time. The addition over a certain period of time may be carried out continuously or discontinuously (for example, by dropping). The lower limit of the addition time from the start to the end of the addition is preferably 5 minutes, more preferably 10 minutes, and even more preferably 15 minutes. The upper limit of the addition time is preferably 40 minutes, more preferably 30 minutes, and even more preferably 25 minutes.

[0075] When the acid does not coexist, it is preferable to make the reaction time in the contact step longer and the reaction temperature higher. When the acid does not coexist, the lower limit of the reaction time is preferably 40 minutes, more preferably 80 minutes, and even more preferably 120 minutes. The upper limit of the reaction time is preferably 900 minutes, more preferably 600 minutes, and even more preferably 300 minutes. When the acid does not coexist, the lower limit of the reaction temperature is preferably 20 °C, more preferably 30 °C, and even more preferably 40 °C. The upper limit of the reaction temperature is preferably 80 °C, more preferably 70 °C, and even more preferably 60 °C.

[0076] After the contact step, washing, drying, etc. of the polysiloxane-containing composite may be carried out as necessary. Washing can be carried out using the water. The lower limit of the drying temperature is preferably 40 °C, more preferably 50 °C. The upper limit of the drying temperature is preferably 100 °C, more preferably 80 °C. The drying time is not particularly limited, and the lower limit may be 1 minute, may be 3 minutes, or may be 6 minutes. The upper limit of the drying time may be 120 minutes, may be 60 minutes, or may be 30 minutes. When the moisture content in the substrate is high, the moisture content in the substrate may be reduced by pressing with a roller or the like before drying.

[0077] Thereby, the target polysiloxane-containing composite can be produced.

[0078] 《Polysiloxane-containing composite》 The polysiloxane-containing composite includes a substrate and a polysiloxane having Si-OH bonds or a condensate thereof formed on the surface of the substrate. Since it has a highly functional polysiloxane derivative on the surface of the substrate, it can be applied to various uses such as imparting water absorption flexibility that combines water absorption and flexibility to fibers, cloth, sheets, etc., or imparting hydrophobicity by further treatment using a silane coupling agent. The polysiloxane-containing composite can be preferably produced by the method for producing the polysiloxane-containing composite.

Examples

[0079] Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to the following examples as long as it does not exceed the gist thereof.

[0080] <Preparation of Oil-in-Water Emulsion of Hydrogen Polysiloxane> [Preparation Example 1] In a 200 mL beaker, 40 parts by mass of a side-chain hydrogen siloxane (dimethylsiloxane·methylhydrogen siloxane copolymer) having a viscosity of 50 mPa·s and a hydrogen content (H%) of 0.73%, 1.0 part by mass of polyoxyethylene tridecyl ether having an ethylene oxide addition mole number of 10 as a surfactant, and purified water were added to make a total of 100 parts by mass and mixed. This mixture was stirred at 3000 rpm for 20 minutes at room temperature using a homogenizer (manufactured by IKA, "Ultra Turrax T50 Basic Shaft Generator G45G") to obtain Oil-in-Water Emulsion 1. The particle size of the emulsion measured by a laser diffraction particle size analyzer (manufactured by Malvern, "MASTERSIZER 3000") was 0.5 μm. Hereinafter, the particle size of the emulsion was measured by the same apparatus.

[0081] [Preparation Example 2] Oil-in-Water Emulsion 2 was obtained by diluting Oil-in-Water Emulsion 1 10-fold with purified water (diluting 5 mL of Oil-in-Water Emulsion 1 to 50 mL with purified water).

[0082] [Preparation Example 3] Oil-in-Water Emulsion 3 was obtained in the same manner as in Preparation Example 1 except that the blending amount of polyoxyethylene tridecyl ether as a surfactant was 3.0 parts by mass. The particle size of the emulsion was 0.2 μm.

[0083] [Preparation Example 4] Oil-in-Water Emulsion 4 was obtained in the same manner as in Preparation Example 1 except that a side-chain hydrogen siloxane (dimethylsiloxane·methylhydrogen siloxane copolymer) having a viscosity of 50 mPa·s and a hydrogen content (H%) of 1.60% was used as the hydrogen siloxane. The particle size of the emulsion was 15 μm.

[0084] [Preparation Example 5] As the hydrogen siloxane, an amphoteric hydrogen siloxane (a compound in which both ends of a dimethylsiloxane·methylhydrogen siloxane copolymer are hydrogen atoms) having a viscosity of 1000 mPa·s and a hydrogen content (H%) of 0.012% was used, and an oil-in-water emulsion 5 was obtained in the same manner as in Preparation Example 1 except for this. The particle size of the emulsion was 10 μm.

[0085] <Treatment of hydrogen polysiloxane on the substrate surface with hypochlorite> [Example 1] A 10 cm × 10 cm cotton cloth was immersed in 50 mL of the oil-in-water emulsion 1 for 5 minutes. Then the cloth was pulled up, excess emulsion was removed with a rubber roller, and then dried at 60°C for 10 minutes. The mass after drying was measured, and the pre-treatment adhesion rate (%) of the active ingredient (hydrogen polysiloxane) of the emulsion to the dried cloth was calculated based on the following formula. The results are shown in Table 2 below. Pre-treatment adhesion rate (%) = 100 × {(mass of the dried cloth (g) - initial mass of the cloth (g)) / initial mass of the cloth (g)}

[0086] The dried cloth was immersed in 50 mL of an aqueous sodium hypochlorite solution adjusted to a concentration of 1.1% by mass. Then, 0.2 mL of an aqueous acetic acid solution with a concentration of 1.0% by mass was dropped, and the operation of gently stirring for 5 minutes was repeated 5 times until the total amount of the acetic acid aqueous solution added reached 1 mL. Then, the cloth was taken out, gently rinsed with 50 mL of 0.2% acetic acid water for 1 minute, and then rinsed again with 50 mL of deionized water. After removing the moisture of the cloth with a roller, it was dried at 60°C for 10 minutes. The post-treatment adhesion rate (%) of the active ingredient (polysiloxane derivative) of the emulsion to the dried cloth was calculated based on the following formula. The results are shown in Table 2 below. Post-treatment adhesion rate (%) = 100 × {(mass of the cloth after treatment and drying (g) - initial mass of the cloth (g)) / initial mass of the cloth (g)}

[0087] [Example 2] The cloth was treated in the same manner as in Example 1, except that the water-in-oil emulsion 2 was used. The results of the adhesion rate before treatment (%) and the adhesion rate after treatment (%) are shown in Table 2 below.

[0088] [Example 3] The cloth was treated in the same manner as in Example 1, except that the water-in-oil emulsion 3 was used. The results of the adhesion rate before treatment (%) and the adhesion rate after treatment (%) are shown in Table 2 below.

[0089] [Example 4] The cloth was treated in the same manner as in Example 1, except that the water-in-oil emulsion 4 was used. The results of the adhesion rate before treatment (%) and the adhesion rate after treatment (%) are shown in Table 2 below.

[0090] [Example 5] The cloth was treated in the same manner as in Example 1, except that the water-in-oil emulsion 5 was used. The results of the adhesion rate before treatment (%) and the adhesion rate after treatment (%) are shown in Table 2 below.

[0091] [Comparative Example 1] The cloth was treated in the same manner as in Example 1, except that 0.2 mL of acetic acid aqueous solution was not added and stirring was carried out for 5 minutes. The results of the adhesion rate before treatment (%) and the adhesion rate after treatment (%) are shown in Table 2 below.

[0092] [Confirmation of the formation of polysiloxane derivative by IR]< The formation of the polysiloxane derivative was confirmed by IR measurement according to the following procedure. The results are shown in Table 1.

[0093] In Example 1, polysiloxane was obtained at each stage before immersion in the aqueous sodium hypochlorite solution, before addition of the aqueous acid solution (total amount), and after addition of the aqueous acid solution (total amount). When water was present, water was evaporated by heating. For this dried product, using a Fourier transform infrared spectrophotometer (manufactured by ThermoFisher SCIENTIFIC, NICOLET iS 10), Si-O-Si groups (around 1100 cm -1 ), CH3 groups (around 3000 cm -1The absorption intensity near -1 and the absorption intensity near the Si-OH group (3300 cm

[0094] were measured. When the absorption intensity of the CH3 group was set to 10, the absorption intensity of the Si-OH group was 2.8 before the addition of the sodium hypochlorite aqueous solution, 3.4 before the first addition of the acid aqueous solution, and 4.6 after the first addition of the acid aqueous solution. Therefore, as the reaction proceeded, the intensity of the Si-OH peak increased, and the formation of the polysiloxane derivative was confirmed.

[0095]

Table 1

[0096] <Confirmation of the disappearance of the Si-H bond of hydrogen polysiloxane> For the dried product after treatment with hypochlorite, using a Fourier transform infrared spectrophotometer (manufactured by ThermoFisher SCIENTIFIC, NICOLET iS 10), the absorption intensity of the Si-H group (2200 cm -1 ) specific to hydrogen polysiloxane was measured. The results are shown in Table 2 below.

[0097]

Table 2

[0098] In the examples, the peak of the Si-H bond of hydrogen polysiloxane disappeared in comparison with the comparative examples. From this result and the above IR measurement results, it can be seen that the Si-H bond of hydrogen polysiloxane was converted to the Si-OH bond by contact with hypochlorite.

Claims

1. A contacting step of bringing a hydrogen polysiloxane having an Si—H bond into contact with a hypochlorite on the surface of a substrate in the presence of water to produce a polysiloxane having an Si—OH bond or a condensate thereof A method for producing a polysiloxane-containing composite, comprising:

2. The method for producing a polysiloxane-containing composite according to claim 1, wherein the hypochlorite is sodium hypochlorite.

3. The method for producing a polysiloxane-containing composite according to claim 1, wherein the blending amount of the hypochlorite is 0.1 mol or more and 2 mol or less per 1 mol of the Si—H bond of the hydrogen polysiloxane.

4. The method for producing a polysiloxane-containing composite according to any one of claims 1 to 3, wherein an acid coexists in the contacting step.

5. The method for producing a polysiloxane-containing composite according to claim 4, wherein the acid is an organic acid.

6. The method for producing a polysiloxane-containing composite according to claim 4, wherein the acid is acetic acid or lactic acid.

7. The method for producing a polysiloxane-containing composite according to any one of claims 1 to 3, wherein the hydrogen polysiloxane exists in the form of an emulsion with the water.

8. The method for producing a polysiloxane-containing composite according to any one of claims 1 to 3, wherein the surface of the substrate has a hydroxy group.

9. The method for producing a polysiloxane-containing composite according to any one of claims 1 to 3, wherein the substrate is cloth, paper, wood, a porous material or inorganic particles.

10. A substrate, A polysiloxane having an Si—OH bond or a condensate thereof formed on the surface of the substrate A polysiloxane-containing composite comprising:

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