JP2007126807A - Fiber-treating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber-treating agent which maintains the original water-absorbing property of fibers and can simultaneously impart quick dryability, flexibility and toughness to the fibers. <P>SOLUTION: This fiber-treating agent is characterized by comprising an alkoxysilane (a), an organic acid (b), and water (c), wherein ≥50 wt.% of the component (c) is an alkoxysilane represented by general formula (1): R<SP>1</SP><SB>p</SB>Si(OR<SP>2</SP>)<SB>4-p</SB>(1) [R<SP>1</SP>is a 1 to 6C alkyl, phenyl or a 2 to 6C alkenyl; R<SP>2</SP>is a 1 to 6C alkyl; (p) is an integer of 1 to 3]; the amount of the component (c) is three times mole or more that of the component (a); pH at 20°C is 2 to 5. A method for treating the fibers with the fiber-treating agent is also provided. And the fibers treated with the method. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fiber treatment agent, a production method thereof, a treatment method of fibers using the same, and a fiber treated by the method.

  For the purpose of imparting water repellency, toughness, and flame retardancy to fibers, it has been practiced to treat the fibers with a silicon compound. For example, by imparting water repellency to the fibers, the moisture content of the fibers can be reduced, and quick drying properties can be imparted to the fibers and clothes. That is, drying after washing is a time-consuming process, and shortening the drying time has been a problem that has been pursued conventionally. Especially in the rainy season and in winter, there are many cases of indoor drying, and the situation in which laundry cannot be dried outdoors to prevent hay fever is increasing. Under these circumstances, there is a strong demand for shortening the drying time.

  In order to achieve this purpose, methods have been studied to reduce the water content by hydrophobizing the fiber. Patent Document 1 discloses a cellulose fiber processing method in which cellulose fibers are treated with an alkali metal hydroxide, washed with water, and then treated with a hydrophobic processing agent such as a resin processing agent, a hydrophobizing cross-linking agent, or a hydrophobizing agent. Yes.

  Further, from the viewpoint of pursuing quick drying and water absorption, Patent Document 2 discloses a water-absorbing quick-drying imparting composition containing a copolymer comprising a specific monomer including a silicone-containing monomer and an organic solvent. A method of treating a fiber by spraying a copolymer containing the polymer onto a target fiber and volatilizing a solvent is disclosed.

  On the other hand, in Patent Document 3, as a method for imparting toughness to a fiber, a silane-based coating liquid containing an alkoxysilane condensate as a main component is applied to a fiber material such as paper or cloth and cured and solidified by the action of a catalyst. Thus, a method for coating a surface-forming fiber is disclosed.

In addition, as an agent for imparting water repellency and oil repellency to fibers, Patent Document 4 discloses cohydrolysis of fluorinated alkyl group-containing alkoxysilanes, alkyl group-containing alkoxysilanes, amino group-containing alkoxysilanes, and epoxy group-containing alkoxysilanes. A fiber treatment agent obtained by dissolving a reaction product obtained by condensation in water is disclosed, and Patent Document 5 discloses a modifier mainly composed of an organosilane compound.
JP 2003-342875 A JP 2005-89882 A JP 2002-61094 A Japanese Patent Laid-Open No. 9-249748 JP 2001-181599 A

  In the method described in Patent Document 1, due to the pursuit of hydrophobicity, a decrease in water absorption occurs, the texture inherent to the fiber deteriorates, and comfort during use or use is impaired. In addition, since it is necessary to treat the fiber with an alkali metal hydroxide, the fiber is altered or damaged, and it is difficult to maintain the original properties of the fiber.

  There is a description that when the composition of Patent Document 2 is applied to the fiber, the texture when worn is improved, but since the silicone copolymer adheres to the fiber surface, water repellency is imparted to the fiber, and water absorption The performance has not yet been satisfactory for both dryness and quick-drying.

  The method of Patent Document 3 is a method of coating a silicon compound on the fiber surface, and the resulting fiber is solidified with a silicon compound, and does not maintain the texture and softness inherent to the fiber.

  In the methods of Patent Document 4 and Patent Document 5, since a silicon compound having a water-repellent functional group is applied on the surface, a natural texture is not obtained.

  Thus, a method for treating fibers while maintaining the properties inherent to the fibers has not been known so far.

  The subject of this invention is providing the novel fiber processing agent which can provide quick-drying property, a softness | flexibility, and / or toughness to a fiber.

  The present inventors can control the polymerization rate of a silanol compound produced by hydrolysis of an alkoxysilane to an appropriate rate by a fiber treatment agent composed of a specific alkoxysilane, an organic acid, and water, and its As a result, the silanol compound is allowed to penetrate into the single fiber and polymerized inside the single fiber, so that the polymer of the silanol compound does not fill the void of the single fiber with the polymer of the silanol compound. It was found that can be contained.

That is, the present invention is composed of alkoxysilane (a), organic acid (b), and water (c), and 50% by weight or more in component (a) is represented by the general formula (1).
R ¹ _p Si (OR ² ) _4-p (1)
Wherein, R ¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched alkenyl group having a phenyl group, or 2 to 6 carbon atoms, R ² is 1 to the number of carbon atoms 6 linear or branched alkyl groups, p R ¹ and (4-p) R ² may be the same or different. p shows the integer of 1-3. ]
A fiber treating agent, alkoxysilane (a), organic acid, wherein the amount of component (c) is at least 3 times the amount of component (a) It is obtained by mixing (b) and water (c), and 50% by weight or more in component (a) is alkoxysilane (1), and the amount of component (c) is 3 of the amount of component (a). A fiber treatment agent having a pH of 2 to 5 at 20 ° C., a production method thereof, a general formula (4) produced by hydrolysis of alkoxysilane (1) by contacting the fiber treatment agent with fibers.

[Wherein, X represents a group represented by R ¹ , OR ² or OH, t represents an integer of 0 to 2, and (2t + 4) X may be the same or different, and at least one of these is OH. R ¹ and R ² have the above meanings. ]
A method for treating fibers, and a method for polymerizing the silanol compound (4), and a method for treating the fiber, including the step (i) of allowing the silanol compound (hereinafter referred to as silanol compound (4)) to penetrate into the single fiber To provide a treated fiber.

  Moreover, this invention provides the fiber which contains more polymer of a silanol compound (4) in the inside of a single fiber than a single fiber surface layer.

  According to the present invention, quick drying, flexibility and / or toughness can be imparted to the fiber while maintaining the properties inherent to the fiber.

[(A) component]
The alkoxysilane which is the component (a) of the present invention is preferably 50% by weight or more of alkoxysilane (1), 60% by weight or more of alkoxysilane (1), and 80% by weight or more of alkoxysilane. (1) is more preferable, and 100% by weight is most preferably alkoxysilane (1).

In the alkoxysilane (1), the alkyl group represented by R ¹ and R ^2, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a t- butyl group and the like can be mentioned, with R ¹ Examples of the alkenyl group shown include a vinyl group and an allyl group, and R ¹ also includes a phenyl group. R ¹ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms, from the viewpoint of penetration into the single fiber. R ² is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, from the viewpoints of safety of by-products generated by hydrolysis, reactivity of the hydrolysis reaction, and the like. As for p, 1-2 are preferable.

  As the component (a), the trialkoxysilane (a1) represented by the general formula (2) and the dialkoxysilane (a2) represented by the general formula (3) may be used alone, respectively, From the viewpoint of not only imparting quick drying properties but also maintaining water absorption and improving the feel in use, it is more preferable to include both trialkoxysilane (a1) and dialkoxysilane (a2).

R ¹ Si (OR ² ) ₃ (2)
R ¹ ₂ Si (OR ² ) ₂ (3)
[Wherein, R ¹ and R ² have the above-mentioned meanings. ]
As the trialkoxysilane (a1), alkyl (1 to 6 carbon atoms) trimethoxysilane and alkyl (1 to 6 carbon atoms) triethoxysilane are preferable, and methyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane are particularly preferable. Is more preferable. As the dialkoxysilane (a2), dialkyl (C1-6) dimethoxysilane, dialkyl (C1-6) diethoxysilane and the like are preferable, and dimethyldimethoxysilane and diethyldiethoxysilane are more preferable.

  The weight ratio of the trialoxysilane (a1) and the dialkoxysilane (a2) is preferably 9/1 to 1/9, more preferably 9/1 to 3/7, and still more preferably 8/2 to 4/6. 7/3 to 5/5 is particularly preferable.

[Component (b)]
As the organic acid which is the component (b) of the present invention, oxalic acid (pKa = 1.04, 3.82), maleic acid (pKa = 1.75, 5.83), tartaric acid (pKa = 2.82, 3.96), fumaric acid (pKa = 2.85, 4.10), citric acid (pKa = 2.90, 4.34), malic acid (pKa = 3.24, 4.71), succinic acid ( pKa = 4.00, 5.24), formic acid (pKa = 3.55), lactic acid (pKa = 3.66), adipic acid (pKa = 4.26, 5.03), acetic acid (pKa = 4.56) ), Propionic acid (pKa = 4.67) and the like, but from the viewpoint of easy pH adjustment, an organic acid having a first dissociation (pKa1) in the range of 2.9 to 5.0 is preferable. More preferred are organic acids in the range of 3.5 to 5.0. Among these, adipic acid, malic acid, acetic acid and propionic acid, which can easily control the hydrolysis reaction and polymerization reaction of alkoxysilane (1), are preferred, and adipic acid with little odor is particularly preferred.

[Fiber treatment agent]
The fiber treatment agent of the present invention is obtained by mixing alkoxysilane (a), organic acid (b), and water (c). Further, the fiber treatment agent of the present invention is composed of alkoxysilane (a), organic acid (b), and water (c) before hydrolysis, and after hydrolysis, hydrolysis of alkoxysilane (1). The silanol compound (4) produced | generated in (4), the organic acid (b), and water (c) are contained. Moreover, when the fiber treatment agent of this invention is a two-component type, it is comprised from the 1st agent containing an alkoxysilane (a), and the 2nd agent containing an organic acid (b) and water (c).

  The amount of the alkoxysilane (a) in the fiber treatment agent of the present invention is the same as that in the fiber treatment agent of the present invention ("in the fiber treatment agent" means that the first agent and the second agent are combined in the case of a two-component system. In addition, it is preferably 0.1% by weight or more, particularly 2% by weight or more, more preferably 82% by weight or less, and particularly preferably 58% by weight or less. Further, the content of the alkoxysilane (a) in the first agent is preferably 70 to 100% by weight, more preferably 80 to 100% by weight, and particularly preferably 90 to 100% by weight from the viewpoint of storage stability.

  The amount of the organic acid (b) in the fiber treatment agent of the present invention is preferably 0.001 to 5% by weight, more preferably 0.001 to 1% by weight, from the viewpoint of suppressing the polymerization reaction. When the fiber treatment agent of the present invention is a two-component type, the organic acid (b) is preferably blended only in the second agent and not in the first agent from the viewpoint of solubility and storage stability.

  The amount of water (c) in the fiber treatment agent of the present invention is sufficient to swell the single fiber sufficiently to allow the silanol compound (4) produced by hydrolysis of the alkoxysilane (1) to sufficiently penetrate into the single fiber. It is preferably 30% by weight or more, more preferably 50% by weight or more, and particularly preferably 70% by weight or more. The upper limit is preferably 99.9% by weight or less, more preferably 95% by weight or less, and particularly preferably 85% by weight or less.

  Moreover, the ratio of alkoxysilane (a) and water (c) is the amount of alkoxysilane (a) from the viewpoint of allowing the silanol compound (4) produced by hydrolysis of alkoxysilane (1) to sufficiently penetrate into the single fiber. 3 times mole or more, 10-1000 times mole is preferable, and 25-600 times mole is more preferable.

  When the fiber treatment agent of the present invention is a two-component type, the water in the fiber treatment agent of the present invention is preferably blended only in the second agent and not in the first agent.

  The fiber treatment agent of the present invention preferably contains a surfactant (d) in order to improve the dispersion of the alkoxysilane (a) in the aqueous phase and promote the hydrolysis reaction. As the surfactant, any of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used.

  Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester, higher fatty acid mono- or diethanolamide, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid Examples thereof include esters, polyoxyethylene sorbite fatty acid esters, alkyl saccharide surfactants, alkyl amine oxides, and alkyl amido amine oxides. Of these, polyoxyalkylene alkyl ether and polyoxyethylene hydrogenated castor oil are preferable, and polyoxyethylene alkyl ether is particularly preferable.

  Anionic surfactants include alkyl benzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, Examples include α-sulfone fatty acid salts, N-acyl amino acid type surfactants, phosphate mono- or diester type surfactants, and sulfosuccinate esters. As counter ions of the anionic surfactant, alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; 1 to 3 alkanol groups having 2 or 3 carbon atoms Examples thereof include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine.

  Examples of the cationic surfactant include a quaternary ammonium salt represented by the general formula (5).

[In the formula, R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 28 carbon atoms or a benzyl group, and simultaneously become a hydrogen atom or a benzyl group; Except when it is a lower alkyl group. An ⁻ represents an anion. ]
In the general formula (5), one of R ³ and R ⁴ is preferably an alkyl group having 16 to 24 carbon atoms, more preferably 22 alkyl groups, particularly a linear alkyl group, and the other one having 1 to 3 carbon atoms. A lower alkyl group, particularly a methyl group is preferred. Examples of the anion An ⁻ include halide ions such as chloride ion, bromide ion and iodide ion; organic anions such as methyl sulfate ion, ethyl sulfate ion, methyl carbonate ion and saccharinate ion. In particular, chloride ions are preferred.

  As the cationic surfactant, mono long-chain alkyl quaternary ammonium salts are preferable, and specific examples include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, aralkyltrimethylammonium chloride, and behenyltrimethylammonium chloride. Stearyl trimethyl ammonium and behenyl trimethyl ammonium chloride are preferable.

  Examples of amphoteric surfactants include imidazoline series, carbobetaine series, amide betaine series, sulfobetaine series, hydroxysulfobetaine series, and amide sulfobetaine series.

  Among these surfactants (d), from the viewpoint of emulsifying ability (miscibility of alkoxysilane (a), organic acid (b), water (c) and surfactant (d)), HLB 9-15, especially 11-14 nonionic surfactants are preferred. In addition, HLB here shows the calculated value by the Griffin method.

  Surfactants can also be used in combination of two or more, and the content of the surfactant in the fiber treatment agent of the present invention is 0.1 to 0.1 from the viewpoint of emulsification and hydrolysis during mixing. 20 weight% is preferable, 0.5-15 weight% is more preferable, 1-10 weight% is still more preferable.

The fiber treatment agent of the present invention is for the purpose of dissolving the silanol compound (4) produced by hydrolysis of the alkoxysilane (1), and has 1 to 3 carbon atoms such as methanol and ethanol, lower monohydric alcohols such as methanol and ethanol, and glycerin. A water-soluble organic solvent such as 2 to 4 polyhydric alcohols can also be contained. The content of the water-soluble organic solvent in the fiber treatment agent of the present invention is 35% by weight or less, particularly 20% by weight, from the viewpoint of sufficiently swelling the single fiber and allowing the silanol compound (4) to sufficiently penetrate into the single fiber. The following is preferable. In addition to this, the fiber treatment agent after hydrolysis of the alkoxysilane (1) contains R ² OH (R ² has the above meaning) as a by-product.

  In addition, the fiber treatment agent of the present invention is for pH adjusters, oil agents, silicone derivatives, cationic polymers, moisturizers, viscosity modifiers, fragrances, dyes, ultraviolet absorbers, antioxidants, antibacterial agents, etc. It can mix | blend suitably according to it.

  The fiber treatment agent of the present invention is required to hydrolyze the alkoxysilane (1) to form the silanol compound (4), and to allow the silanol compound (4) to penetrate into the single fiber to cause a polymerization reaction in the single fiber. In order to do so, it is necessary to delay the polymerization reaction. For this purpose, the pH at 20 ° C. is adjusted to 2 to 5, with 2 to 4 being preferred. In the case of the two-agent type, the pH of the second agent at 20 ° C. is adjusted to the above range.

  The form of the fiber treatment agent of the present invention contains alkoxysilane (a) from the viewpoint of ensuring long-term stability, and 50% by weight or more in component (a) is alkoxysilane (1). A two-component system comprising an agent, a second agent containing an organic acid (b) and water (c) and having a pH of 2 to 5 at 20 ° C is preferred. In the context of the present invention, the “two-component formula” means that the alkoxysilane (a) in the first agent is in a form separated from the organic acid (b) and water (c) in the second agent. In any of the first agent and the second agent, individual components (for example, trialkoxysilane (a1) and dialkoxysilane (a2) described later) may be provided in a state of being further separated from each other.

  Moreover, it is prepared by mixing the alkoxysilane (a), organic acid (b), water (c), surfactant (d) or other optional components as necessary, and adjusting the pH to 2-5 immediately before use. It may be what was done.

  When the fiber treatment agent of the present invention is a two-component type, the surfactant (d) is preferably contained in the second agent, but when the first agent does not contain moisture, it may be contained in the first agent. it can. Moreover, although it is preferable to contain other arbitrary components in the 2nd agent, if it is a non-aqueous liquid component and a solid component, it can also mix | blend in a 1st agent.

  The fiber treatment agent of the present invention is useful as a quick-drying imparting agent, a flexibility imparting agent, and / or a toughness imparting agent to fibers. Here, toughness can be evaluated as wear resistance or fluff prevention.

[Method for producing fiber treatment agent]
When preparing the fiber treatment agent of the present invention by mixing alkoxysilane (a), organic acid (b), and water (c), if necessary, surfactant (d), or other optional components immediately before use. The order of mixing is not particularly limited, but in order to delay the polymerization of the silanol compound (4) produced by hydrolysis of the alkoxysilane (1) and to sufficiently penetrate the single fiber, the organic acid ( It is preferable to mix alkoxysilane (a) after mixing b), water (c) and, if necessary, surfactant (d).

  Furthermore, when using both trialkoxysilane (a1) and dialkoxysilane (a2) as alkoxysilane (a), first, trialkoxysilane (a1), organic acid (b), and water (c) were mixed. Thereafter, it is more preferable to mix the dialkoxysilane (a2). After mixing the trialkoxysilane (a1), the organic acid (b), and the water (c), before mixing the dialkoxysilane (a2), at least a part of the trialkoxysilane (a1) is hydrolyzed. Is preferred. The progress of hydrolysis can be judged by the increase in the transparency of the liquid.

  By mixing the alkoxysilane (a), the organic acid (b), and the water (c), if necessary, the surfactant (d), or other optional components, the alkoxysilane (1) is converted into a silanol compound ( 4), and penetration into single fibers becomes possible.

[Fiber treatment method and treated fiber]
The fiber treatment method of the present invention is a step (i) in which the fiber treatment agent according to the present invention is brought into contact with the fiber to allow the silanol compound (4) produced by hydrolysis of the alkoxysilane (1) to penetrate into the single fiber. And a step (ii) of polymerizing the silanol compound (4).

  The silanol compound (4) preferably has at least one OH among (2t + 4) Xs and (t + 2) or more OHs from the viewpoint of physical properties and permeability into single fibers. . t represents an integer of 0 to 2, and t = 0 is preferable from the viewpoint of permeability into a single fiber.

  The molecular weight of the silanol compound (4) is preferably 300 or less, more preferably 200 or less, and more preferably 90 or more, from the viewpoint of easy penetration into single fibers.

  The content of the silanol compound (4) in the fiber treatment agent of the present invention after hydrolysis is preferably 0.1% by weight or more, more preferably 2% by weight or more, preferably 69% by weight or less, and 49% by weight or less. Is more preferable.

  Examples of fibers suitable for treatment in the present invention include plant fibers such as cotton and hemp; animal fibers such as wool and silk; regenerated fibers or semi-synthetic fibers such as rayon and acetate; pulp, cocoons, cocoons, kenaf, and cotton linters. The papermaking fiber is mentioned.

  In step (i), in order to bring the fiber treatment agent of the present invention into contact with the fiber, alkoxysilane (a), organic acid (b), and water (c), surfactant (d), or any other optional agent After mixing the components before use, the mixture is preferably stirred and mixed by means such as shaking, and after confirming that the mixed solution has become clear visually, the resulting mixture is preferably brought into contact with the fibers.

  In the case of the two-component type, the mixing ratio of the first agent and the second agent (weight ratio of the first agent / second agent) is preferably 80/20 to 1/99, more preferably 60/40 to 20/80. It is. Immediately after mixing, the mixture is in a white turbid emulsified state or partially emulsified state, but becomes transparent as it is left standing or stirred as necessary, whereby the alkoxysilane (1) is hydrolyzed and the silanol compound (4). Can be confirmed.

  If the resulting mixture is allowed to stand, the polymerization reaction of the silanol compound (4) proceeds, so within 24 hours, preferably within 12 hours, more preferably within 3 hours, particularly preferably within 1 hour. It is preferred to contact the fiber. Thereby, a silanol compound (4) can be osmose | permeated in a single fiber. Examples of the method of bringing the treating agent into contact with the fiber include a method of immersing the fiber in the treating agent, a method of spraying the treating agent on the fiber, and a method of applying the treating agent to the fiber. The fibers to be contacted may be wet or dry.

  The silanol compound (4) sufficiently penetrates into the single fiber by contact for several seconds, but may be left for 1 minute to 2 hours in order to penetrate more uniformly.

  In step (ii), the silanol compound (4) is sufficiently infiltrated into the single fiber, and then the silanol compound (4) inside the single fiber is polymerized.

  The polymerization can be promoted by heating, preferably at 60 ° C. or higher, and more preferably at 80 to 200 ° C. Polymerization proceeds in a shorter time as the temperature increases. Specifically, warm air drying and press heating are exemplified.

  Further, the polymerization can be promoted by adjusting the pH of the treatment agent to 0 to 2 or 5 to 12.5 without drying the fibers. The pH can be adjusted using an acid or a base while the fiber is immersed in the treatment agent or after removing excess liquid.

  After the polymerization step, excess polymer is removed by further washing with water, and the natural fiber texture can be maintained.

  Moreover, it is preferable to have the process (iii) which wash | cleans a fiber further between process (i) and process (ii). By performing the step (iii), the excess silanol compound (4) on the fiber surface can be removed, and the texture inherent to the fiber can be maintained.

  The fiber treated by the fiber treatment method of the present invention can contain more polymer of the silanol compound (4) inside the single fiber than the single fiber surface layer. The distribution of the polymer of the silanol compound (4) can be measured by an energy dispersive X-ray analyzer (EDS) described later. According to the fiber treatment method of the present invention, the inside of a single fiber can be modified, and the treated fiber is excellent in quick drying property, flexibility, toughness and the like.

  In the following examples,% is% by weight unless otherwise specified.

Preparation Example of Catalyst Solution Adipic acid, water and, if necessary, polyoxyethylene lauryl ether (Emulgen 108 manufactured by Kao Corporation) are mixed to prepare catalyst solutions B1 to B4 (second agent) having the composition shown in Table 1. did.

Example 1
(1) Synthesis of treatment liquid C1 1.37 g of methyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., LS-1890, the same shall apply hereinafter) is added to 4.11 g of catalyst solution B1, and the cloudy suspension becomes transparent. The solution was stirred for 10 minutes until a treatment liquid C1 was obtained. Table 2 shows the composition of the treatment liquid obtained (referred to as the composition before hydrolysis; the same applies hereinafter).

²⁹ Si NMR (UNITY INOVA 300, manufactured by Varian) was measured immediately after preparation, after 0 to 1 hour, after 4 to 5 hours, and after 1 day in order to confirm the formation of silanol in the obtained treatment liquid. The result is shown in FIG.

In ²⁹ Si NMR, a peak appears in the vicinity of 37 ppm for Si in the trihydroxyalkylsilane, in the vicinity of 46 ppm for Si in the dihydroxyalkylsiloxy group, and in the vicinity of 56 ppm for Si in the monohydroxyalkylsiloxy group. The presence of the alkylsilanol monomer can be confirmed from the amount of Si in the trihydroxyalkylsilane.

The distribution 0 to 1 hour after preparation was 64% for the monomer, 33% for the dimer, and 3% for the trimer or higher. The distribution after 4 to 5 hours of preparation was 48% for the monomer, 43% for the dimer, and 7% for the trimer or more. The distribution one day after preparation was 28% for the monomer, 41% for the dimer, and 31% for the trimer or more.
In the following fiber treatment, the treatment liquid immediately after preparation was used.

(2) Treatment to cotton broad cloth 5.48 g of treatment liquid C1 was applied to 5.48 g of cotton broad cloth pretreated by the following method, left still at room temperature for 60 minutes, and further dried at 80 ° C. for 2 hours. . The amount of alkoxysilane relative to the fabric was 25% by weight. Wash the dried fabric with a detergent for clothes (liquid attack, manufactured by Kao Corporation) (washing conditions; use of 30 g of detergent, 45 L of tap water, 5 minutes of washing-one rinse with water-3 minutes of dehydration), indoors To obtain a treated cloth. The weight increase rate of the cloth after the treatment was 5.5%.

<Pretreatment method of cotton broad cloth>
A cotton broad cloth (manufactured by Tanigami Shoten) was washed 10 times with a commercial detergent (Kao Co., Ltd. Attack) using a two-tank washing machine (Toshiba model: VH-360S1) (detergent concentration 0.0667% by mass, Tap water 40L, water temperature 20 ° C., washing for 10 minutes, rinsing with running water for 15 minutes, dehydration for 5 minutes), and air drying. This cloth was cut into 15 cm × 25 cm to obtain a pretreated cloth.

(3) SEM observation After the treatment cloth was embedded in an epoxy resin and cured, a cross-section was cut out with a microtome (manufactured by ULTRACUT UTR LEICA), and a conductive treatment was performed by Pt-Pd vapor deposition. This fiber cross section was observed with a field emission scanning electron microscope (FE-SEM: S4800 model, manufactured by Hitachi, Ltd., acceleration voltage 15 kV, probe current High, focus mode HR, condenser lens 5, diaphragm 1). The result is shown in FIG. In addition, silicon surface analysis was performed with an energy dispersive X-ray analyzer (EDS) (EMAX ENERGY EX-350, manufactured by Horiba, mapping measurement time 1500 s, process time 5). The result is shown in FIG. 3, and the enlarged view is shown in FIG.

  From the SEM image of FIG. 2, a cross section of the cotton single fiber is observed. From the Si mapping image of FIG. 3, it was observed that silicon was mainly distributed inside the single fiber of cotton and hardly existed in the gap between the fiber and the fiber. In the Si mapping enlarged view of FIG. 4, the profile of the silicon concentration is shown. It was observed that the silicon concentration was high inside the single fiber and hardly existed in the gap between the fibers.

Example 2
(1) Synthesis of treatment liquid C2 1.00 g of methyltriethoxysilane was added to 4.28 g of catalyst solution B3 and stirred for 20 minutes until the cloudy suspension became colorless and transparent. Furthermore, 0.43 g of dimethyldiethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., LS-1370, hereinafter the same) was added, and the mixture was stirred again for 3 minutes until the suspension became transparent to obtain a treatment liquid C2. The composition of the treatment liquid obtained is shown in Table 2.

(2) Treatment to cotton broad cloth 5.71 g of treatment liquid C2 was immersed in 5.71 g of cotton broad cloth pretreated in the same manner as in Example 1, and then allowed to stand at room temperature for 60 minutes, and further at 80 ° C. for 2 hours. Dried. The amount of alkoxysilane relative to the fabric was 25% by weight. The dried cloth was washed with a detergent for clothing (liquid attack, manufactured by Kao Corporation) and naturally dried indoors to obtain a treated cloth. The weight increase rate of the cloth after the treatment was 2.1%.

(3) SEM observation The treated cloth was embedded in an epoxy resin, and the fiber cross section was observed with a scanning electron microscope in the same manner as in Example 1. From the SEM image of FIG. 5 and the Si mapping image of FIG. 6, it was observed that silicon was mainly distributed inside the single fiber of cotton and hardly existed in the gap between the fibers.

Example 3
(1) Synthesis of treatment liquid C3 3.11 g of methyltriethoxysilane was added to 9.33 g of catalyst solution B1, and stirred for 10 minutes until the cloudy suspension became transparent to obtain treatment liquid C3. The composition of the treatment liquid obtained is shown in Table 2.

(2) Treatment to wool jersey After applying 12.44 g of treatment liquid C3 to 12.44 g of wool jersey (wool jersey knit cloth (manufactured by Tanigami Shoten) cut to 2.0 cm × 2.0 cm) at room temperature It was dried for 60 minutes and further dried at 80 ° C. for 2 hours. The amount of alkoxysilane relative to the fabric was 25% by weight. The dried cloth was washed with a detergent for clothing (liquid attack, manufactured by Kao Corporation) and naturally dried indoors to obtain a treated cloth. The weight increase rate of the cloth after the treatment was 8.4%.

(3) SEM observation The treated cloth was embedded in an epoxy resin, and the fiber cross section was observed with a scanning electron microscope in the same manner as in Example 1. From the SEM image in FIG. 7 and the Si mapping image in FIG. 8, it was observed that silicon was mainly distributed inside the wool single fiber and hardly existed in the gap between the fiber and the fiber.

Example 4
(1) Synthesis of treatment liquid C4 1.89 g of methyltriethoxysilane was added to 8.09 g of catalyst solution B3 and stirred for 20 minutes until the cloudy suspension became colorless and transparent. Further, 0.81 g of dimethyldiethoxysilane was added, and the mixture was stirred again for 3 minutes until the suspension became transparent to obtain a treatment liquid C4. The composition of the treatment liquid obtained is shown in Table 2.

(2) Treatment to Wool Jersey After applying 10.79 g of the treatment liquid C4 to the same wool jersey as in Example 3, it was dried at room temperature for 60 minutes and further dried at 80 ° C. for 2 hours. The amount of alkoxysilane relative to the fabric was 25% by weight. The dried cloth was washed with a detergent for clothing (liquid attack, manufactured by Kao Corporation) and naturally dried indoors to obtain a treated cloth. The weight increase rate of the cloth after the treatment was 11.7%.

(3) SEM observation The treated cloth was embedded in an epoxy resin, and the fiber cross section was observed with a scanning electron microscope in the same manner as in Example 1. From the SEM image of FIG. 9 and the Si mapping image of FIG. 10, it was observed that silicon was mainly distributed inside the wool single fiber and hardly existed in the gap between the fiber and the fiber.

Comparative Example 1
(1) Synthesis of coating liquid CC1 181 g of methyltrimethoxysilane, 50 g of methanol, and 18 g of water were added and stirred. Further, stirring was continued at 80 ° C. for 3 hours while adding 2 g of 61% nitric acid. Thereafter, the inside of the container was depressurized to remove methanol, and a methyltrimethoxysilane oligomer was produced. The degree of condensation is estimated to be 3 to 4 mer.
To 19 g of the obtained methyltrimethoxysilane oligomer, 0.8 g of dibutyltin acetate and 20 g of isopropyl alcohol were added and mixed well to prepare a coating liquid CC1.

(2) Treatment to cotton broad cloth After applying 3.0 g of coating liquid CC1 to 5.7 g of cotton broad cloth pretreated in the same manner as in Example 1, it was allowed to stand at room temperature for 10 minutes, and further at 130 ° C. for 2 hours. Dried. The dried cloth was washed with a detergent for clothing (liquid attack, manufactured by Kao Corporation) and naturally dried indoors to obtain a treated cloth. The weight increase rate of the cloth after the treatment was 11.3%.

(3) SEM observation The treated cloth was embedded in an epoxy resin, and the fiber cross section was observed with a scanning electron microscope in the same manner as in Example 1. From the SEM image in FIG. 11, a cross section of the cotton single fiber is observed. A filler seen as polysiloxane is observed in the gap between the single fibers, and the Si mapping image in FIG. 12 shows that silicon is present in the gap between the single fibers and binds the fibers in the form of a binder. On the other hand, silicon is not observed inside the cotton single fiber, indicating that the polysiloxane does not penetrate into the cotton single fiber. A silicon concentration profile is shown in the enlarged Si mapping in FIG. 13, and it is observed that the silicon concentration hardly exists inside the single fiber and exists at a higher concentration due to the gap between the fibers.
In addition, the part seen in the fiber center part of an enlarged view is the space | gap part called a lumen | rumen, and this part is not considered the inside of a single fiber.

Example 5
(1) Synthesis of treatment liquid C5 10 g of methyltriethoxysilane was added to 20 g of the catalyst solution B1 and stirred for 10 minutes until the cloudy suspension became transparent to obtain a treatment liquid C5. The composition of the treatment liquid obtained is shown in Table 2.

(2) Treatment to paper After 5.3 g of paper obtained by the following method was immersed in 30 g of treatment liquid C5, the paper was pulled up after 30 seconds, air-dried at room temperature for 10 minutes, and further dried at 80 ° C. for 2 hours. The weight increase rate of the paper after the treatment was 38.7%.

<Paper preparation method>
Hardwood bleached pulp (Laubholz Bleached Kraft Pulp, hereinafter abbreviated as LBKP) was disaggregated and beaten with a beater at room temperature to give 2.2% LBKP slurry. The Canadian standard freeness of the slurry was 420 ml. The 2.2% LBKP slurry was weighed so that the basis weight of the sheet after paper making was 85 g / m ² when it was absolutely dry. Thereafter, the mixture was diluted with water so that the pulp concentration was 0.5%, and after stirring, the paper was made with a 150-mesh wire with a square tapi paper machine and coached to obtain a wet paper. The wet paper after paper making was pressed with a press at 3.5 kg / cm ² for 5 minutes and dried at 105 ° C. for 2 minutes using a drum dryer. The dried paper was conditioned for 1 day at 23 ° C. and 50% humidity.

(3) SEM observation The treated paper was embedded in an epoxy resin, and the fiber cross section was observed with a scanning electron microscope in the same manner as in Example 1. From the SEM image in FIG. 14 and the Si mapping image in FIG. 15, it was observed that silicon was mainly distributed inside the pulp single fiber and hardly existed in the gap between the fibers. In the Si mapping enlarged view of FIG. 16, the silicon concentration profile is shown. It was observed that the silicon concentration was high inside the single fiber and hardly existed in the gap between the fibers.

Comparative Example 2
(1) Synthesis of coating liquid CC2 9.5 g of the methyltrimethoxysilane oligomer obtained in Comparative Example 1 was added to a mixed liquid of 0.4 g of dibutyltin acetate and 10 g of isopropyl alcohol, and mixed well to prepare a coating liquid CC2. .

(2) Treatment on paper After immersing 5.3 g of the same paper as in Example 5 in 9.9 g of the coating liquid CC2, it was pulled up after 30 seconds, air-dried at room temperature for 10 minutes, and further dried at 130 ° C. for 60 minutes. . The weight increase rate of the treated paper was 60.4%.

(3) SEM observation The treated paper was embedded in an epoxy resin, and the fiber cross section was observed with a scanning electron microscope in the same manner as in Example 1. From the SEM image in FIG. 17 and the Si mapping image in FIG. 18, it can be seen that silicon is present in the gaps between the pulp single fibers and the fibers are bound in a binder form. On the other hand, silicon is not observed inside the pulp single fiber, indicating that the polysiloxane does not penetrate into the pulp single fiber. In the Si mapping enlarged view of FIG. 19, the profile of silicon concentration is shown. It was observed that the silicon concentration hardly exists inside the single fiber and exists at a higher concentration due to the gap between the fibers.

  Table 2 summarizes the results of Examples 1 to 5 and Comparative Examples 1 and 2.

Examples 6-11
Treatment liquids C6 to C11 having the compositions described in Table 3 were prepared. The treatment liquid having a methyltriethoxysilane / dimethyldiethoxysilane ratio of 10/0 is the same as the preparation method of Example 1, and the treatment liquid having a methyltriethoxysilane / dimethyldiethoxysilane ratio of 7/3 is that of Example 2. Prepared in the same manner as the preparation method.

  A cotton towel pretreated by the following method is immersed in the obtained treatment solution for 60 minutes, and then dried at 80 ° C. for 12 hours, so that the treatment amount of alkoxysilane with respect to the towel varies in the range of 2.5 to 25% by weight. An evaluation towel was produced. About the obtained towel, quick-drying property and water absorption were evaluated by the following method. The results are shown in Table 3.

<Pretreatment method of cotton towel>
Cotton towel (T.W220 manufactured by Takei Towel Co., Ltd., white) using a commercially available laundry detergent (Kao Corporation Liquid Attack) in a fully automatic washing machine (Hitachi Fully Automatic Washing Machine KW-5026 before Shizugo) 10 times Laundry was repeated (37 g of detergent, 57 L of tap water was used, 5 minutes for washing-one rinse with water-3 minutes for dehydration). After dehydration of the last treatment round was completed, pretreatment was carried out by hanging and drying indoors. The weight of one pretreated towel is 70 g.

<Quick-drying evaluation method>
Wash the evaluation towel in a fully automatic washing machine (Hitachi fully automatic washing machine KW-5026 before static control) (30g of detergent, 45L of tap water, 5 minutes of washing-1 rinse of water-3 minutes of dehydration), 20 It air-dried until it became constant weight by hanging and drying by the constant temperature and humidity of (degreeC-65% RH). The moisture content (%) over time was determined by the following calculation formula (I). The time from the start of drying until the moisture content reached 10% was used as an index for quick drying.

  Moisture content (%) = {towel weight immediately after dehydration (g) −towel weight reaching constant weight (g)} / towel weight reaching constant weight (g) × 100 (I)

<Water absorption evaluation method (Bairec method)>
The plain weave portion of the towel is cut into a 2 cm × 25 cm strip, the upper end of the strip fabric is fixed and hung in the vertical direction, and the time after the lower end 1 cm portion is immersed in 20 ° C. water (1 minute, 3 minutes, 5 minutes) The water absorption height was visually observed and recorded in mm. The measurement was performed in a constant temperature and humidity chamber at 20 ° C.-65% RH.

Examples 12 and 13
A cotton towel pretreated in the same manner as in Example 6 was immersed in the same treatment liquid C10 or C11 as in Examples 10 and 11 for 60 minutes, and then dried at 80 ° C. for 12 hours. Further, washing, dehydration, and drying were performed under the same washing conditions as in the quick drying property evaluation method. This dipping / washing / drying treatment was repeated 10 times to produce an evaluation towel subjected to cumulative treatment. The amount of alkoxysilane treated on the towel was 2.5% by weight per treatment. The obtained towel was evaluated for quick drying and water absorption in the same manner as in Example 6. The results are shown in Table 3.

Examples 14 and 15
Using the catalyst solution B2 or B4 not containing a nonionic surfactant, treatment liquids C12 and C13 having the compositions shown in Table 3 were prepared. A cotton towel pretreated in the same manner as in Example 6 was immersed in this treatment solution for 60 minutes, and then dried at 80 ° C. for 12 hours to produce an evaluation towel having an alkoxysilane treatment amount of 25 wt% with respect to the towel. . The obtained towel was evaluated for quick drying and water absorption in the same manner as in Example 6. The results are shown in Table 3.

Comparative Example 3
A quick-drying property and a water-absorbing property were evaluated in the same manner as in Example 6 using a towel pretreated as in Example 6 and not subjected to the treatment with the treatment liquid of the present invention as an evaluation towel. The results are shown in Table 3.

  As is apparent from Table 3, the moisture content of the towel treated with the treatment liquid of the present invention was reduced when it was dehydrated after washing, and the time required for drying to 10% was shortened. In addition, when both alkyltrialkoxysilane and dialkyldialkoxysilane were used in combination, the water absorption was as high as that of the untreated towel, indicating that the water absorption was excellent. Further, the use of a nonionic surfactant when preparing the treatment liquid has improved water absorption and quick drying properties.

Examples 16-18
The same treatment liquids C7, C13, and C11 as in Examples 7, 15, and 11 were prepared, and a cotton towel pretreated in the same manner as in Example 6 was soaked for 60 minutes, and then dried at 80 ° C. for 12 hours and treated. Towels were manufactured. The amount of alkoxysilane treated on the towel was 25% by weight in Examples 16 and 17 and 2.5% by weight in Example 18.

  The obtained towel was evaluated for flexibility by the following method, and water absorption was evaluated by the same method as in Example 6. The results are shown in Table 4.

<Flexibility evaluation method>
Towels were washed once using a commercially available laundry detergent (liquid attack manufactured by Kao Corporation) in a fully automatic washing machine (Hitachi fully automatic washing machine KW-5026 before static control) (use 37g of detergent, 57L of tap water, washing) 5 minutes-1 rinse with water-3 minutes of dehydration). The washed towel was naturally dried indoors, and then allowed to stand in a constant temperature and humidity room at 20 ° C./65% RH for one day. Then, about the softness of a touch, five panelists performed sensory evaluation 3 times according to the following references | standards, respectively, and made the average value those softness | flexibility. The untreated towel is an evaluation towel of Comparative Example 4 below.

-3 points: treated towels are clearly harder than untreated towels -2 points: treated towels are slightly harder than untreated towels -1 points: treated towels are slightly harder than untreated towels When it becomes hard 0 points: When there is no difference between treated towels and untreated towels 1 point: When treated towels are slightly softer than untreated towels 2 points: When treated towels are slightly softer than untreated towels 3 points: The treated towel is clearly softer than the untreated towel.

Comparative Example 4
Flexibility and water absorption were evaluated in the same manner as in Example 16 using a towel pretreated as in Example 6 and not treated with the treatment liquid of the present invention as an evaluation towel. The results are shown in Table 4.

  As is apparent from Table 4, the towel treated with the treatment liquid of the present invention was soft to the touch so as to be sufficiently recognized as compared with the untreated one. Further, the water absorption was equivalent to that of the untreated towel, and the fiber could be given flexibility while maintaining the texture.

Examples 19-23
According to the treatment liquid preparation method of Example 2, treatment liquids C7 and C14 to C16 having the compositions shown in Table 5 were prepared. Instead of cotton towel, wool sweater (lamcrew neck sweater, gray, made by UNIQLO)), silk, rayon tow, hemp, acetate tow (all are commercially available), and the treatment amount of alkoxysilane to the fiber is 25% by weight The fibers were soaked for 60 minutes and then dried at 80 ° C. for 12 hours to produce treated fibers. The obtained fiber was evaluated for flexibility in the same manner as in Example 16. The results are shown in Table 5.

  As is clear from Table 5, the hand became soft enough to be sufficiently recognized as compared with the untreated fibers.

Examples 24-27
Using the same treatment liquid C6-9 as in Examples 6-9, a cotton towel pretreated in the same manner as in Example 6 was soaked for 60 minutes and then dried at 80 ° C. for 12 hours to produce a treated towel for evaluation. The amount of alkoxysilane treated on the towel was 25% by weight or 6% by weight. About the obtained processing towel, the fluff fall-out prevention property was evaluated by the following method. The results are shown in Table 6.

<Evaluation method for prevention of fluff loss>
Five towels were dried with a tumbler dryer (dehumidification type electric clothes dryer NH-D502, manufactured by Matsushita Electric Co., Ltd.) for 3 hours, and this was repeated 10 times. From the amount of fluff remaining on the filter of the dryer, the fluff loss rate was determined by the following formula.

Fluff loss rate (%) =
The amount of fluff remaining on the filter of the dryer / the towel weight before drying × 100

Comparative Example 5
As in Example 6, pre-treatment and a towel not subjected to treatment with the treatment liquid of the present invention was used as an evaluation towel, and evaluation of fuzz removal was performed in the same manner as in Example 24. The results are shown in Table 6.

Examples 28 and 29
The same wool jersey as in Example 3 was immersed in the same treatment liquids C3 and C4 as in Examples 3 and 4 for 60 minutes, and then dried at 80 ° C. for 12 hours to produce an evaluation wool jersey. The amount of alkoxysilane treated relative to the wool jersey was 25% by weight. The treated wool jersey was evaluated for wear resistance by the following method. The results are shown in Table 7.

<Abrasion resistance evaluation method>
Wool jersey cut to a width of 1.3 cm and a length of 19.5 cm is wrapped around the rotating part of an Akron abrasion tester (for JIS tire rubber), weight 4.5 kg, bevel 5 degrees, wear wheel A36-P5-V, 3000 The abrasion test was performed at a rotation speed of 75 rpm, and the damage of the cloth in contact with the grindstone was visually evaluated according to the following criteria.
A: Fraying (fiber cutting) is less than 10% B: Fraying (fiber cutting) is 10% or more and less than 50% X: Fraying (fiber cutting) is 50% or more

Comparative Example 6
Abrasion resistance was evaluated in the same manner as in Example 28, using the same wool jersey as in Example 3 that was not treated with the treatment liquid of the present invention as an evaluation wool jersey. The results are shown in Table 7.

  As is apparent from the results in Tables 6 and 7, the fiber treated with the treatment liquid of the present invention has less fuzz generation in the treatment with the dryer than the untreated fiber, and the abrasion resistance by the grindstone is low. It was improved and the toughness was shown to increase.

It is a ²⁹ Si NMR spectrum immediately after preparation of the treatment liquid obtained in Example 1, 0 to 1 hour later, 4 to 5 hours later, and 1 day later. 1 is an SEM diagram of a treated cloth obtained in Example 1. FIG. 3 is a silicon mapping diagram of the treated cloth obtained in Example 1. FIG. FIG. 3 is an enlarged view of silicon mapping of the treated cloth obtained in Example 1. 3 is a SEM diagram of the treated cloth obtained in Example 2. FIG. 6 is a silicon mapping diagram of the treated cloth obtained in Example 2. FIG. 6 is a SEM diagram of the treated cloth obtained in Example 3. FIG. FIG. 6 is a silicon mapping diagram of the treated cloth obtained in Example 3. 6 is an SEM diagram of the treated cloth obtained in Example 4. FIG. It is a silicon mapping figure of the process cloth obtained in Example 4. FIG. 4 is a SEM diagram of the treated cloth obtained in Comparative Example 1. FIG. 5 is a silicon mapping diagram of the treated cloth obtained in Comparative Example 1. FIG. It is a silicon mapping enlarged view of the treated cloth obtained in Comparative Example 1. FIG. 6 is an SEM view of the treated paper obtained in Example 5. 6 is a silicon mapping diagram of the treated paper obtained in Example 5. FIG. It is a silicon mapping enlarged view of the treated paper obtained in Example 5. 6 is a SEM view of the treated paper obtained in Comparative Example 2. FIG. 5 is a silicon mapping diagram of the treated paper obtained in Comparative Example 2. FIG. It is a silicon mapping enlarged view of the treated paper obtained in Comparative Example 2.

Claims (17)

It is composed of alkoxysilane (a), organic acid (b), and water (c), and 50% by weight or more in component (a) is represented by the general formula (1)
R ¹ _p Si (OR ² ) _4-p (1)
Wherein, R ¹ represents a linear or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched alkenyl group having a phenyl group, or 2 to 6 carbon atoms, R ² is 1 to the number of carbon atoms 6 linear or branched alkyl groups, p R ¹ and (4-p) R ² may be the same or different. p shows the integer of 1-3. ]
A fiber treatment agent wherein the amount of component (c) is at least 3 times the amount of component (a).   A first agent containing alkoxysilane (a), wherein 50% by weight or more of component (a) is alkoxysilane (1), an organic acid (b) and water (c), and a pH at 20 ° C. The fiber treatment agent of Claim 1 comprised from the 2nd agent which is 2-5.   It is obtained by mixing alkoxysilane (a), organic acid (b), and water (c), and 50% by weight or more in component (a) is alkoxysilane (1) according to claim 1, wherein (c) ) A fiber treatment agent having a pH of 2 to 5 at 20 ° C., wherein the amount of the component is at least 3 times the amount of the component (a). Formula (4) generated by hydrolysis of alkoxysilane (1)
[Wherein, X represents a group represented by R ¹ , OR ² or OH, t represents an integer of 0 to 2, and (2t + 4) X may be the same or different, and at least one of these is OH. R ¹ and R ² have the same meaning as in claim 1. ]
The fiber processing agent of Claim 3 containing the silanol compound (henceforth a silanol compound (4)) represented by these, organic acid (b), and water (c).   The fiber processing agent in any one of Claims 1-4 whose quantity of (c) component in a fiber processing agent is 30-99.9 weight%.   Furthermore, the fiber treatment agent in any one of Claims 1-5 containing surfactant (d). The component (a) contains a trialkoxysilane (a1) represented by the general formula (2) and a dialkoxysilane (a2) represented by the general formula (3). Fiber treatment agent.
R ¹ Si (OR ² ) ₃ (2)
R ¹ ₂ Si (OR ² ) ₂ (3)
[Wherein, R ¹ and R ² have the same meaning as in claim 1. ]   The fiber treatment agent according to claim 7, wherein a weight ratio of the trialoxysilane (a1) and the dialkoxysilane (a2) is 9/1 to 1/9.   It is a quick-drying imparting agent, The fiber treatment agent in any one of Claims 1-8.   It is a softness | flexibility imparting agent, The fiber processing agent in any one of Claims 1-8.   It is a toughness imparting agent, The fiber processing agent in any one of Claims 1-8.   The method for producing a fiber treatment agent according to claim 7 or 8, wherein the trialkoxysilane (a1), the organic acid (b) and the water (c) are mixed, and then the dialkoxysilane (a2) is mixed.   A step (i) of bringing the silanol compound (4) produced by hydrolysis of the alkoxysilane (1) into contact with the fiber by bringing the fiber treatment agent according to any one of claims 3 to 11 into contact with the fiber, and the silanol compound A method for treating a fiber, comprising the step (ii) of polymerizing (4).   The fiber processing method according to claim 13, wherein the step (ii) is performed by heating to 60 ° C. or higher.   The method for treating a fiber according to claim 13 or 14, further comprising a step (iii) of washing the fiber with water between the step (i) and the step (ii).   The fiber processed by the method in any one of Claims 13-15.   The fiber which contains more polymer of the silanol compound (4) represented by General formula (4) of Claim 4 inside a single fiber than a single fiber surface layer.