JP2008196082A - Fiber-treating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber-treating agent consisting of an emulsion of organopolysiloxane containing an amino group but not containing an acidic substance as a main agent, which is excellent in dilution stability, preservation stability and mechanical stability, and also capable of imparting excellent flexibility, smoothness, water repellency, deep-coloring property, etc., to various fibers. <P>SOLUTION: This fiber-treating agent consisting of an oil-in-water emulsion of organopolysiloxane containing an amino group, as main components, which contains the following components (A), (B) and (C): (A) the organopolysiloxane containing the amino group having a dynamic viscosity at 25°C of 100 to 1,000,000 mm<SP>2</SP>/s, and an amine equivalent of 1,000 to 100,000 g/mol, (B) a polyoxyalkylene-branched alkyl ether, and (C) water, does not contain the acidic substance, and contains 10 to 50 mass% of the component (B) based on the mass of the component (A), and 30 to 90 mass% of the component (C) based on the total mass of the components (A), (B), and (C). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a fiber treatment agent that imparts excellent flexibility, smoothness, water repellency, and darkness to natural fibers, synthetic fibers, and the like, and more particularly, stability of emulsions of amino-functional organopolysiloxanes. The present invention relates to a fiber treatment agent mainly composed of an emulsion of an amino-functional organopolysiloxane which is excellent in dilution stability, storage stability and mechanical stability even though it does not contain an acidic substance which is an agent.

As a fiber treatment agent for imparting flexibility, smoothness, etc. to various fibers and fiber products, various organopolysiloxanes such as dimethylpolysiloxane, epoxy group-containing organopolysiloxane, amino group-containing organopolysiloxane, etc. Emulsions are widely used, and emulsions of amino group-containing organopolysiloxanes that give particularly good flexibility are most often used.
In particular, an emulsion of an amino group-containing organopolysiloxane having a 3-aminopropyl group or an N- (2-aminoethyl) -3-aminopropyl group as an amino group is common, and particularly N- (2-aminoethyl). ) An emulsion of an amino group-containing organopolysiloxane having a 3-aminopropyl group is an important material for a fiber treatment agent because of its superior performance and cost (see Patent Documents 1 to 4).

As a conventional method for producing an amino group-containing organopolysiloxane microemulsion or a reduced particle size emulsion, a nonionic surfactant or a nonionic surfactant and an anionic surfactant are used in combination with an amino group-containing organopolysiloxane. A general method is to mix, mechanically emulsify, and mix and neutralize an acidic substance, particularly acetic acid, which is a carboxylic acid. Also, the emulsion can be produced by emulsifying cyclic dimethylsiloxane with a cationic emulsifier and emulsion polymerization with an alkali catalyst, and in this case, an acidic substance is used.
On the other hand, the median diameter of the above emulsion when not containing an acidic substance was as large as 0.3 μm or more, and had the disadvantage of being poor in dilution stability, storage stability, and mechanical stability.
In this way, the stability and transparency of the emulsion can be obtained by using an acidic substance when producing a microemulsion of an amino group-containing organopolysiloxane or an emulsion having a reduced particle size. The material is very effective in improving the properties of the emulsion. Conventional techniques relating to microemulsification of amino group-containing organopolysiloxane using an acidic substance are disclosed in, for example, Patent Documents 5 to 10.

Patent Document 5 discloses a technique in which, in the production of a fine particle emulsion of aminosilicone and epoxy-modified aminosilicone, an acidic substance (formic acid, acetic acid) of 0.1 molar equivalent or more relative to the nitrogen atom of aminosilicone is added, followed by heat aging. is doing. Patent Document 6 discloses a technique in which acetic acid, propionic acid, and fatty acid, which are monovalent carboxylic acids, are used in combination for the purpose of promoting a reduction in particle size when producing a microemulsion containing linear polyorganosiloxane. Yes. Patent Document 7 discloses a technique of blending glycolic acid, aspartic acid or the like when producing an amino group-containing organopolysiloxane microemulsion. Patent Document 8 discloses a technique of using hypophosphorous acid, nitric acid, hydrochloric acid, lactic acid, glycolic acid, propionic acid, formic acid, and acetic acid as acids when producing an amino group-containing organopolysiloxane microemulsion. ing. In Patent Document 9, when a fiber treatment agent having good flexibility is produced by improving dilution stability and mechanical stability, carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, and inorganic acids are used as acids. A technique using an acid as a neutralizing agent is disclosed. Patent Document 10 discloses a technique in which a saturated aliphatic carboxylic acid, an unsaturated aliphatic carboxylic acid, a carbocyclic carboxylic acid, acetic anhydride, or the like is used as a carboxylic acid.
Japanese Patent Publication No. 48-1480 Japanese Examined Patent Publication No. 54-43617 Japanese Examined Patent Publication No. 57-43673 Japanese Patent Publication No. 60-185879 JP-A-2-284959 JP 2002-80603 A JP-A-8-73748 Japanese Examined Patent Publication No. 7-30182 Japanese Patent Laid-Open No. 9-53016 JP 2002-194675 A

  As described above, the conventional methods for producing a microemulsion of an amino group-containing organopolysiloxane or an emulsion having a reduced particle size are all made by using various acidic substances, thereby producing an amino group-containing organopolysiloxane. This improves the stability of the emulsion and makes it a microemulsion or a small particle size. Thus, in producing the emulsion of amino group-containing organopolysiloxane, an acidic substance is an essential component, and in particular, acetic acid is generally used as the acidic substance. By using an acidic substance, an amino group-containing organopolysiloxane emulsion having a median diameter of 0.3 μm or less can be obtained.

  In contrast, an amino group-containing organopolysiloxane emulsion that does not contain an acidic substance has a median diameter of 0.3 μm or more, as described above, in terms of dilution stability, storage stability, and mechanical stability. Inferior. In particular, the mechanical stability is greatly lowered, and when used in an actual machine, the stability against mechanical shearing force is insufficient, so that the emulsion is broken and oil spots are generated on the fiber product surface. .

  Also, in amino group-containing organopolysiloxane emulsions using acidic substances, when used as a fiber treatment agent, amino groups react with acidic substances to form quaternary salts, whereby cotton cloth and polyester / cotton cloth There was a decrease in the performance of various fibers, such as flexibility, smoothness, water repellency, and darkness, which was thought to be due to a decrease in the adsorptivity of the above-mentioned organopolysiloxane to the cellulose surface. .

  The present invention has been made in view of the above circumstances, and its purpose is excellent in dilution stability, storage stability, mechanical stability, and excellent flexibility, smoothness, water repellency, darkness for various fibers. It is an object of the present invention to provide a fiber treatment agent mainly containing an emulsion of an amino group-containing organopolysiloxane that does not contain an acidic substance and can impart color and the like.

［式中、Rは炭素数１〜８の１価炭化水素基であり、Ａは−R¹（ＮR²CH₂CH₂）_aNR³R⁴（R¹は炭素数１〜８の２価炭化水素基であり、R²、R³、R⁴は水素原子、炭素数１〜４の１価炭化水素基又は−CH₂CH（OH）CH₂OHであり、ａは０〜４の整数である。）で示される１価の基であり、XはR、A又は−OR⁵（R⁵は水素原子又は炭素数１〜８の１価炭化水素基である。）で示される１価の基であり、ｍ及びｎは平均重合度を示し、上記動粘度及びアミン当量の数値範囲を満たす数である。但し、ｎ＝０の場合、Xの少なくとも１個はAである。］
（Ｂ）ポリオキシアルキレン分岐アルキルエーテル
（Ｃ）水
を含有し、酸性物質を含有せず、（Ｂ）成分の含有量は、（Ａ）成分の質量に対して10〜50質量％であり、（Ｃ）成分の含有量は、（Ａ）成分と（Ｂ）成分と（Ｃ）成分の合計質量に対して30〜90質量％である水中油型アミノ基含有オルガノポリシロキサンのエマルジョンを主剤とする繊維処理剤である。 As a result of intensive studies to solve the above-mentioned problems, the present inventor uses a polyoxyalkylene branched alkyl ether which is a nonionic surfactant as a surfactant used in the production of an emulsion of an amino group-containing organopolysiloxane. As a result, even without the use of acidic substances, it has excellent dilution stability, storage stability and mechanical stability, and gives excellent flexibility, smoothness, water repellency, and darkness to various fibers. An emulsion that can be obtained is obtained, and it has been found that the above object can be achieved, and the present invention has been completed.
That is, the present invention includes the following components (A), (B) and (C):
(A) An amino group-containing organopolysiloxane represented by the general formula (1) having a kinematic viscosity at 25 ° C. of 100 to 1,000,000 mm ² / s and an amine equivalent of 1,000 to 100,000 g / mol.

[In the formula, R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, A is -R ¹ (NR ² CH ₂ CH ₂ ) _a NR ³ R ^{4, where} R ¹ is a divalent hydrocarbon having 1 to 8 carbon atoms. A hydrocarbon group, R ² , R ³ and R ⁴ are hydrogen atoms, monovalent hydrocarbon groups having 1 to 4 carbon atoms or —CH ₂ CH (OH) CH ₂ OH, and a is an integer of 0 to 4 X is R, A or —OR ⁵ (R ⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms). Where m and n are average numbers of polymerization and satisfy the above numerical ranges of kinematic viscosity and amine equivalent. However, when n = 0, at least one of X is A. ]
(B) Polyoxyalkylene branched alkyl ether
(C) It contains water, does not contain an acidic substance, the content of the component (B) is 10 to 50% by mass with respect to the mass of the component (A), and the content of the component (C) is: It is a fiber treatment agent mainly composed of an emulsion of an oil-in-water amino group-containing organopolysiloxane that is 30 to 90% by mass relative to the total mass of the component (A), the component (B), and the component (C).

  According to the present invention, although it does not contain an acidic substance, it has excellent dilution stability, storage stability and mechanical stability, and has excellent flexibility, smoothness, water repellency, dark color for various fibers. Provided is a fiber treatment agent mainly composed of an emulsion of an amino group-containing organopolysiloxane capable of imparting properties such as properties.

［式中、Rは炭素数１〜８の１価炭化水素基であり、Ａは−R¹（ＮR²CH₂CH₂）_aNR³R⁴（R¹は炭素数１〜８の２価炭化水素基であり、R²、R³、R⁴は水素原子、炭素数１〜４の１価炭化水素基又は−CH₂CH（OH）CH₂OHであり、ａは０〜４の整数である。）で示される１価の基であり、XはR、A又は−OR⁵（R⁵は水素原子又は炭素数１〜８の１価炭化水素基である。）で示される１価の基であり、ｍ及びｎは平均重合度を示し、上記動粘度及びアミン当量の数値範囲を満たす数である。但し、ｎ＝０の場合、Xの少なくとも１個はAである。］ Hereinafter, the present invention will be described in more detail. As described above, the fiber treatment agent of the present invention is based on a water-in-oil emulsion of an amino group-containing organopolysiloxane, and the emulsion comprises the components (A), (B) and (C). It is an essential component and does not contain acidic substances.
The component (A) constituting the present invention is an amino group-containing organopolysiloxane represented by the general formula (1).

[In the formula, R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, A is -R ¹ (NR ² CH ₂ CH ₂ ) _a NR ³ R ^{4, where} R ¹ is a divalent hydrocarbon having 1 to 8 carbon atoms. A hydrocarbon group, R ² , R ³ and R ⁴ are hydrogen atoms, monovalent hydrocarbon groups having 1 to 4 carbon atoms or —CH ₂ CH (OH) CH ₂ OH, and a is an integer of 0 to 4 X is R, A or —OR ⁵ (R ⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms). Where m and n are average numbers of polymerization and satisfy the above numerical ranges of kinematic viscosity and amine equivalent. However, when n = 0, at least one of X is A. ]

  Specific examples of R in the general formula (1) include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, and other alkyl groups; vinyl groups, Alkenyl groups such as allyl group, propenyl group and butenyl group; cycloalkyl groups such as cyclobutyl group, cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group and phenethyl group; Or the group in which the hydrogen atom couple | bonded with the carbon atom of these groups was partially substituted by the halogen atom can be mentioned. Among these, a methyl group is particularly preferable from the viewpoints of water repellency, smoothness and flexibility.

A in the general formula (1) is a monovalent group represented by —R ¹ (NR ² CH ₂ CH ₂ ) _a NR ³ R ⁴ , and R ¹ has 1 to 8 carbon atoms, preferably 2 to 2 carbon atoms. 4, a alkylene group such as a methylene group, a dimethylene group, a trimethylene group, or a tetramethylene group is preferable, and a trimethylene group is particularly preferable. Moreover, a is an integer of 0-4. R ² , R ³ and R ⁴ are a hydrogen atom, a monovalent hydrocarbon group having 1 to 4 carbon atoms, or —CH ₂ CH (OH) CH ₂ OH.

Specifically, examples of A which is an amino group include the following.
-C ₃ H ₆ NH ₂
-C ₃ H ₆ NHC ₂ H ₄ NH ₂
-C ₃ H ₆ NHC ₂ H ₄ NHC ₂ H ₄ NH ₂
-CH ₂ CH (CH ₃ ) CH ₂ NHC ₂ H ₄ NH _{2
-C 3 H 6 N (CH 2} CH (OH) CH 2 OH) C 2 H 4 NH (CH 2 CH (OH) CH 2 OH)
Among these is the -C ₃ H ₆ NH ₂ 3- aminopropyl group, -C ₃ H ₆ is _{NHC 2 H 4 NH 2 N- (} 2- aminoethyl) -3-aminopropyl group, fiber In view of the reason that good flexibility is obtained, it is most preferable.

The amino group-containing organopolysiloxane (A) has a kinematic viscosity at 25 ° C. of 100 to 1,000,000 mm ² / s, preferably 1,000 to 100,000 mm ² / s. When the kinematic viscosity at 25 ° C. is less than 100 mm ² / s, becomes insufficient flexibility to be imparted to the fibers, the kinematic viscosity at 25 ° C. greater than 1,000,000 mm ² / s, it is difficult to emulsify .
The amino group-containing organopolysiloxane (A) has an amine equivalent of 1,000 to 100,000 g / mol, preferably 1,500 to 50,000 g / mol, and most preferably 2,000 to 20,000 g / mol. When the amine equivalent is less than 1,000 g / mol, the flexibility imparted to the fiber is lowered, and when it exceeds 100,000 g / mol, the flexibility imparted to the fiber is insufficient. The amine equivalent is the average molecular weight per nitrogen atom.

X in the general formula (1) is a monovalent group represented by R, A or —OR ⁵ (R ⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms). Here, specific examples of the monovalent hydrocarbon group represented by R ⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a phenyl group.

The amino group-containing organopolysiloxane as component (A) can be easily obtained by a known synthesis method. For example, in the presence of a catalyst such as alkali metal hydroxide or tetramethylammonium hydroxide, cyclic siloxane such as octamethylcyclotetrasiloxane and 3-aminopropyldiethoxysilane or N- (2-aminoethyl) -3-amino It can be obtained by carrying out an equilibration reaction of propylmethyldimethoxysilane or a hydrolyzate thereof and a compound selected from hexamethyldisiloxane and the like as other raw materials.
A branch unit may be introduced into the amino group-containing organopolysiloxane skeleton. It is also possible to use reaction products with organic acid anhydrides, carbonates, epoxy compounds and the like.

  In the component (B) constituting the present invention, a polyoxyalkylene branched alkyl ether is used as a nonionic surfactant. The polyoxyalkylene moiety in this polyoxyalkylene branched alkyl ether is usually composed of an oxyalkylene unit having 2 to 4 carbon atoms, that is, an adduct of alkylene oxide having 2 to 4 carbon atoms, and the average of the alkylene oxides. The added mole number is 2 to 105.

Moreover, as a branched alkyl part in polyoxyalkylene branched alkyl ether, a C8-C24 branched alkyl group which has 1-3 alkyl groups as a side chain is preferable. When the alkyl group is not branched, it is difficult to obtain good emulsion stability (dilution stability, storage stability, mechanical stability) as shown in Comparative Example 5 described later. .
In particular, polyoxyalkylene branched decyl ethers in which the branched alkyl moiety is a branched decyl group such as an isodecyl group, ethyl octyl group, butylhexyl group, etc., are equivalent to the dilution stability, storage stability and mechanical properties of emulsions containing acidic substances. This is preferable in that stability is obtained.

上記式（２）中、Ｒ⁶は炭素数が４〜６のアルキル基、Ｒ⁷は炭素数が２〜４のアルキル基を示し、−（ＡＯ）−は炭素数が３及び／又は４のオキシアルキレンユニット、−（ＥＯ）−は炭素数が２のオキシエチレンユニットを示す。また、ｎ及びｍは、それぞれアルキレンオキサイド、エチレンオキサイドの平均付加モル数を示し、ｎが１〜５、ｍが１〜100である。
上記式（２）で示されるポリオキシアルキレン分岐アルキルエーテルのうち、特に好ましいものは、酸性物質を配合したエマルジョンと同等の希釈安定性、保存安定性及び機械的安定性を得る点で、ポリオキシエチレンポリオキシプロピレン分岐デシルエーテルである。 The (B) component polyoxyalkylene branched alkyl ether has a carbon number of 10 to 11, particularly in terms of reducing ecotoxicity (aquatic biotoxicity), wide emulsification performance, and good viscous behavior of the resulting emulsion. Nonionic surfactants derived from 2-alkyl-1-alkanol type saturated primary alcohols and having the structure of the following general formula (2) are preferred.

In the above formula (2), R ⁶ represents an alkyl group having 4 to 6 carbon atoms, R ⁷ represents an alkyl group having 2 to 4 carbon atoms, and — (AO) — represents 3 and / or 4 carbon atoms. An oxyalkylene unit,-(EO)-, represents an oxyethylene unit having 2 carbon atoms. Moreover, n and m show the average addition mole number of alkylene oxide and ethylene oxide, respectively, n is 1-5 and m is 1-100.
Among the polyoxyalkylene branched alkyl ethers represented by the above formula (2), particularly preferred are polyoxyalkylene branched alkyl ethers in that the polyoxyalkylene branched alkyl ether has the same dilution stability, storage stability and mechanical stability as an emulsion containing an acidic substance. Ethylene polyoxypropylene branched decyl ether.

  In addition, as the polyoxyalkylene branched alkyl ether of component (B), its HLB value (defined by the Griffin method) is 12 to 16, so that the dilution stability equivalent to an emulsion containing an acidic substance is obtained. This is preferable in that storage stability and mechanical stability can be obtained.

The component (B) may be composed of one kind of polyoxyalkylene branched alkyl ether, but is preferably composed of a mixture of two or more kinds of polyoxyalkylene branched alkyl ethers having different HLB values. In that case, it is possible to select the polyoxyalkylene branched alkyl ether so that the HLB value of the mixture of the polyoxyalkylene branched alkyl ether is 12 to 16, so that the dilution stability and storage stability equivalent to the emulsion containing an acidic substance are obtained. And preferable in terms of obtaining mechanical stability. For example, as two types of polyoxyethylene polyoxypropylene branched decyl ether, polyoxyethylene having an average addition mole number of EO (ethylene oxide) of 4 moles and an average addition mole number of PO (propylene oxide) of 2 moles. (4) Polyoxypropylene (2) Branched decyl ether and polyoxyethylene (40) polyoxypropylene (2) branched with an average added mole number of EO of 40 moles and an average added mole number of PO of 2 moles When using together with decyl ether, those mass ratios are polyoxyethylene (4) polyoxypropylene (2) branched decyl ether / polyoxyethylene (40) polyoxypropylene (2) branched decyl ether = 1 / 0.2. ˜1 / 3, preferably in the range of 1 / 0.5 to ½.
Moreover, when using together 2 or more types of polyoxyalkylene branched alkyl ether, you may employ | adopt what a HLB value is outside the said range, However, It is preferable that the HLB value of those mixtures exists in the said range. The HLB value of a mixture of polyoxyalkylene branched alkyl ethers is a weighted average of the HLB values of each component.

  (B) As for the compounding quantity of a component, 10-50 mass% is preferable with respect to the mass of (A) component, More preferably, it is 20-40 mass%. If it is less than 10% by mass, the median diameter of the obtained emulsion does not become 0.3 μm or less, and the stability is lowered. If it is 50% by mass or more, the component (B) inhibits the properties of the amino group-containing organopolysiloxane of the component (A), and it is not advantageous in terms of cost.

  The amount of water as component (C) is preferably 30 to 90% by mass, particularly 45 to 70% by mass, based on the total mass of component (A), component (B) and component (C).

The oil-in-water amino group-containing organopolysiloxane emulsion, which is the main component of the present invention, contains the components (A), (B) and (C), and can be produced by a conventionally known formulation. That is, if the amino group-containing organopolysiloxane (A) and the polyoxyalkylene branched alkyl ether (B) are mixed, they are emulsified with an emulsifier such as a homomixer, homogenizer, colloid mill, or line mixer. Good. Thereby, an oil-in-water amino group-containing organopolysiloxane emulsion excellent in stability can be obtained. In the fiber treatment agent of the present invention, the median diameter of the emulsion is preferably 0.3 μm or less, and particularly preferably in the range of 0.05 to 0.25 μm from the viewpoint of emulsion stability. This median diameter is measured by a laser diffraction / scattering particle size distribution measuring apparatus.
By the way, in general emulsification of amino group-containing organopolysiloxane, acidic substances such as formic acid, acetic acid, propionic acid, lauric acid, stearic acid, glutamic acid, aspartic acid, oxyglutamic acid, butyric acid, glycolic acid, etc. are used in the final step. It is essential to add a carboxylic acid or an inorganic acid such as phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, etc., thereby forming a quaternary salt in a part of the amino group and imparting stability to the emulsion.
However, unlike the prior art, the present invention is characterized in that it does not use the acidic substance as described above, which is essential for the stability of an amino group-containing organopolysiloxane emulsion. The emulsion of the amino group-containing organopolysiloxane, which is the main component of the present invention, contains at least two types of polyoxyethylene polyoxypropylene branched decyl ethers having different component (B), particularly HLB values, even without containing an acidic substance. By using this, it is possible to obtain dilution stability, storage stability and mechanical stability equivalent to those of an emulsion containing an acidic substance. On the contrary, when an acidic substance is blended, as shown in Comparative Examples 1 to 4 described later, the flexibility imparted to the fiber and the adsorptivity to the fiber are lowered.

The fiber treatment agent of the present invention is an additive of the above oil-in-water amino group-containing organopolysiloxane, which is the main agent, as long as it does not impair the properties, for example, a wrinkle preventive agent, a flame retardant, An antistatic agent, an antioxidant, an antiseptic, a rust inhibitor, etc. may be added.
When various fibers or fiber products are treated using the fiber treatment agent of the present invention, the fiber treatment agent is prepared to a predetermined concentration and adhered to the fiber by dipping, spraying, roll coating or the like. The amount of adhesion varies depending on the type of fiber and is not particularly limited. However, the amount of adsorbed organopolysiloxane is generally in the range of 0.01 to 10% by mass of the fiber mass. Then, it may be dried by hot air blowing, a heating furnace or the like. Although it depends on the type of fiber, drying may be performed at 100 to 150 ° C. for 2 to 5 minutes.

The fiber treated with the fiber treatment agent of the present invention is more flexible, smooth and water repellent than the fiber treated with a fiber treatment agent containing an amino group-containing organopolysiloxane emulsion containing an acidic substance. In addition, the darkness is good. This is because the amino group-containing organopolysiloxane which is the component (A) constituting the present invention is the same treatment as the amino group-containing organopolysiloxane in which a part of the amino group forms a quaternary salt by an acidic substance. Under certain conditions, the adsorptivity to cotton or polyester / cotton fabric is high, and a larger amount of amino group-containing organopolysiloxane is adsorbed on the fiber surface.
Conventionally, the amount of organopolysiloxane adsorbed on the fiber surface has been quantified by fluorescent X-ray analysis, but the fluorescent X-ray analysis has been an analysis method lacking quantitativeness in terms of accuracy. In the present invention, as shown in the examples described below, the treatment cloth with the fiber treatment agent is heat-treated in the presence of tetraethoxysilane and KOH, thereby converting the organopolysiloxane to ethoxysilane and quantifying it by gas chromatography. Then, by converting the quantitative value into the adsorption amount of the amino group-containing organopolysiloxane, the adsorption amount of the organopolysiloxane on the fiber surface was determined. As can be seen from the results of the examples, according to this analysis method, the results of the quantitative determination of the organopolysiloxane adsorption amount were obtained.

The fiber or fiber product that can be treated with the fiber treatment agent of the present invention is not particularly limited. For natural fibers such as cotton, silk, hemp, wool, angora, and mohair, and synthetic fibers such as polyester, nylon, acrylic, and spandex. But all are valid.
Further, the shape and shape are not limited, and the present invention includes not only raw material shapes such as staples, filaments, tows, yarns, etc., but also textile products in various processed forms such as woven fabrics, knitted fabrics, stuffed cotton, and non-woven fabrics. It becomes the object which can be processed with the fiber treatment agent.

  The fiber treated with the fiber treatment agent of the present invention is more flexible, smooth and water repellent than the fiber treated with a fiber treatment agent containing an amino group-containing organopolysiloxane emulsion containing an acidic substance. Moreover, it has good dark color properties and can be used widely as a treatment agent for various fibers.

  Specific embodiments of the present invention will be described below in more detail with reference to examples, but the present invention is not limited to the following examples. In the following examples, the viscosity is a value measured at 25 ° C. measured with a BH viscometer (manufactured by Tokyo Keiki Co., Ltd.), and the median diameter is measured with a laser diffraction / scattering type particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.). Indicates the measured value.

[Example 1]
300 g of amino group-containing organopolysiloxane represented by the following formula (3) (kinematic viscosity: 1,200 mm ² / s, amine equivalent: 1,690 g / mol), polyoxyethylene (4) polyoxypropylene (2) branched decyl ether (Neugen XL-40: HLB value 10.5, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name) 40 g and polyoxyethylene (40) polyoxypropylene (2) branched decyl ether (Neugen XL-400D (65% aqueous solution): HLB value 18.4, made by Daiichi Kogyo Seiyaku Co., Ltd., trade name) 62g was charged into a 2 liter poly mug, mixed thoroughly at high speed using a homomixer, added with 100g of phase inversion water, kneaded, and ion exchange 498 g of water was added and mixed with a homomixer at 2,500 rpm for 20 minutes to obtain an oil-in-water emulsion (A) having an amino group-containing organopolysiloxane concentration of 30%. This emulsion (A) is a pale white liquid, has a median diameter of 0.17 μm, a pH of 9.8, a viscosity of 30 mP · s (25 ° C.), and a non-volatile content after 3 hours at 105 ° C. of 35.7% by mass. It was.
For this emulsion (A), the following “softness”, “adsorption amount of amino group-containing organopolysiloxane to cotton broad cloth”, “dilution stability”, “storage stability” and “mechanical stability” The properties were evaluated and the results are shown in Table 1.

[Comparative Example 1]
To 200 g of the emulsion (A) obtained in Example 1, 0.02 g of acetic acid (purity 99%) (0.01 molar equivalent with respect to the nitrogen atom of the amino group-containing organopolysiloxane) was added, and 10 minutes at 2,500 rpm with a homomixer. After mixing for minutes, the mixture was heated at 80 ° C. for 4 hours to obtain an oil-in-water emulsion (B). This emulsion (B) is a pale white liquid, has a median diameter of 0.12 μm, a pH of 9.5, a viscosity of 20 mP · s (25 ° C.), and a non-volatile content of 35.7 mass% after 3 hours at 105 ° C. It was.
For this emulsion (B), the following “softness”, “adsorption amount of amino group-containing organopolysiloxane on cotton broad cloth”, “dilution stability”, “storage stability” and “mechanical stability” The properties were evaluated and the results are shown in Table 1.

[Comparative Example 2]
In Example 1, 0.54 g of acetic acid (purity 99%) was added to 200 g of the obtained emulsion (A) (0.25 molar equivalent with respect to the nitrogen atom of the amino group-containing organopolysiloxane) at 2,500 rpm with a homomixer. After mixing for 10 minutes, the mixture was heated at 80 ° C. for 4 hours to obtain an oil-in-water emulsion (C). This emulsion (C) is a pale white translucent liquid, has a median diameter of 0.10 μm, pH of 7.3, viscosity of 750 mP · s (25 ° C.), and a non-volatile content of 35.1 mass after 3 hours at 105 ° C. %Met.
For this emulsion (C), the following “softness”, “adsorption amount of amino group-containing organopolysiloxane on cotton broad cloth”, “dilution stability”, “storage stability” and “mechanical stability” The properties were evaluated and the results are shown in Table 1.

[Comparative Example 3]
In Example 1, 1.08 g of acetic acid (purity 99%) was added to 200 g of the obtained emulsion (A) (0.5 molar equivalent to the nitrogen atom of the amino group-containing organopolysiloxane) at 2,500 rpm with a homomixer. After mixing for 10 minutes, the mixture was heated at 80 ° C. for 4 hours to obtain an oil-in-water emulsion (D). This emulsion (D) is a pale white translucent liquid, has a median diameter of 0.11 μm, a pH of 6.5, a viscosity of 3,900 mP · s (25 ° C.), and a non-volatile content after 3 hours at 105 ° C. of 34.7 It was mass%.
For this emulsion (D), “flexibility”, “adsorption amount of amino group-containing organopolysiloxane on cotton broad cloth”, “dilution stability”, “storage stability” and “mechanical stability” described below. The properties were evaluated and the results are shown in Table 1.

[Comparative Example 4]
In Example 1, 2.14 g of acetic acid (purity 99%) was added to 200 g of the obtained emulsion (A) (1 molar equivalent with respect to the nitrogen atom of the amino group-containing organopolysiloxane) at 2,500 rpm with a homomixer. After mixing for 10 minutes, the mixture was heated at 80 ° C. for 4 hours to obtain an oil-in-water emulsion (E). This emulsion (E) is a pale white translucent liquid, has a median diameter of 0.12 μm, a pH of 5.1, a viscosity of 21,000 mP · s (25 ° C.) and a non-volatile content of 33.8 at 105 ° C. after 3 hours. It was mass%.
For this emulsion (E), the following “flexibility”, “adsorption amount of amino group-containing organopolysiloxane on cotton broad cloth”, “dilution stability”, “storage stability” and “mechanical stability” The properties were evaluated and the results are shown in Table 1.

[Example 2]
The ratio of the two types of polyoxyethylene polyoxypropylene branched decyl ether emulsifiers used in Example 1 was changed. That is, 300 g of amino group-containing organopolysiloxane (kinematic viscosity: 1,200 mm ² / s, amine equivalent: 1,690 g / mol) and polyoxyethylene (4) polyoxypropylene (2) branched decyl ether (Neugen XL-40: Daiichi Kogyo Seiyaku Co., Ltd., trade name) 30 g and polyoxyethylene (40) polyoxypropylene (2) branched decyl ether (Neugen XL-400D (65% aqueous solution): Daiichi Kogyo Seiyaku Co., Ltd., trade name) 77 g Into a 2 liter poly mug, mix well at high speed using a homomixer, add 100 g of phase inversion water, knead, add 493 g of ion exchange water, and mix for 20 minutes at 2,500 rpm with a homomixer. Thus, a water-in-oil emulsion (F) having an amino group-containing organopolysiloxane concentration of 30% was obtained. This emulsion (F) is a pale white liquid, has a median diameter of 0.11 μm, a pH of 9.6, a viscosity of 35 mP · s (25 ° C.), and a non-volatile content of 35.9% by mass after 3 hours at 105 ° C. It was.
For this emulsion (F), the following “softness”, “adsorption amount of amino group-containing organopolysiloxane on cotton broad cloth”, “dilution stability”, “storage stability” and “mechanical stability” The properties were evaluated and the results are shown in Table 1.

[Example 3]
The ratio of the two types of polyoxyethylene polyoxypropylene branched decyl ether emulsifiers used in Example 1 was changed. That is, 300 g of amino group-containing organopolysiloxane (kinematic viscosity: 1,200 mm ² / s, amine equivalent: 1,690 g / mol) and polyoxyethylene (4) polyoxypropylene (2) branched decyl ether (Neugen XL-40: Daiichi Kogyo Seiyaku Co., Ltd., trade name) 60 g and polyoxypropylene polyoxyethylene (40) polyoxypropylene (2) branched decyl ether (Neugen XL-400D (65% aqueous solution): Daiichi Kogyo Seiyaku Co., Ltd., trade name ) Add 31g to a 2 liter poly mug, mix well at high speed using a homomixer, add 100g of phase-inverted water, knead, add 493g of ion-exchanged water, and 2,500rpm with a homomixer. By mixing for 20 minutes, a water-in-oil emulsion (G) having an amino group-containing organopolysiloxane concentration of 30% was obtained. This emulsion (G) is a pale white liquid, has a median diameter of 0.12 μm, a pH of 9.9, a viscosity of 30 mP · s (25 ° C.), and a non-volatile content of 35.8 mass% after 3 hours at 105 ° C. It was.
For this emulsion (G), the following “flexibility”, “adsorption amount of amino group-containing organopolysiloxane on cotton broad cloth”, “dilution stability”, “storage stability” and “mechanical stability” The properties were evaluated and the results are shown in Table 1.

[Comparative Example 5]
The polyoxyethylene polyoxypropylene branched decyl ether emulsifier used in Example 1 was changed. That is, 300 g of amino group-containing organopolysiloxane (kinematic viscosity: 1,200 mm ² / s, amine equivalent: 1,690 g / mol) and polyoxyethylene (10) tridecyl ether (Neugen TDS-100: HLB value 13.8, first 80 g of Kogyo Seiyaku Co., Ltd. (trade name) was charged into a 2 liter poly mug, mixed well at high speed using a homomixer, added with 100 g of phase inversion water, kneaded, and then added 520 g of ion-exchanged water. The mixture was mixed with a homomixer at 2,500 rpm for 20 minutes to obtain an emulsion (H) having an amino group-containing organopolysiloxane concentration of 30%. This emulsion (H) was a milky white liquid, had a median diameter of 0.59 μm, a pH of 10.0, a viscosity of 960 mP · s (25 ° C.), and a non-volatile content after 3 hours at 105 ° C. of 36.6% by mass. .
For this emulsion (H), the following “softness”, “adsorption amount of amino group-containing organopolysiloxane on cotton broad cloth”, “dilution stability”, “storage stability” and “mechanical stability” The properties were evaluated and the results are shown in Table 1.

[Evaluation]
(Flexibility)
Ion exchange water was added to each of the emulsions obtained in Examples 1 to 3 and Comparative Examples 1 to 5, and diluted to a solid content of 0.5% by mass to prepare a test solution. A polyester / cotton broad cloth (65 % / 35%; manufactured by Tanigami Shoten Co., Ltd.) for 1 minute, squeezed with a roll under the condition of 100% squeezing rate, dried at 100 ° C. for 2 minutes, and then heat-treated at 150 ° C. for 2 minutes for flexibility. A treatment cloth for evaluation was produced. The flexibility of the treated fabric was evaluated by the three panelists according to the following criteria.
Evaluation criteria A: Very good.
○: Good.
X: It is bad.

(Adsorption amount of amino group-containing organopolysiloxane on cotton broad cloth)
In the treatment cloth for flexibility evaluation, the polyester / cotton broad cloth was replaced with cotton broad cloth (100%: manufactured by Tanigami Shoten Co., Ltd.), and a treatment cloth was produced by the same operation as the treatment cloth for flexibility evaluation. 40 cm ^{2 of} this treated cloth (0.47 to 0.49 g) is collected in a glass container, tetraethoxysilane and KOH powder are added to this, and the organopolysiloxane is ethoxylated by heat treatment and quantified by gas chromatography. The quantitative value was converted to the adsorption amount of the amino group-containing organopolysiloxane.

(Dilution stability)
Each emulsion obtained in Examples 1 to 3 and Comparative Examples 1 to 5 was diluted to 2% by mass with ion-exchanged water, and the surface state after 24 hours was visually observed. Evaluated.
Evaluation criteria ○: No oil floating, interference film or the like is observed.
Δ: Interference film is observed.
X: Oil float is recognized.

(Storage stability)
After taking 100 g of each emulsion obtained in Examples 1 to 3 and Comparative Examples 1 to 5 in a glass bottle and standing still in a thermostatic bath at 50 ° C. for 30 days, the appearance and non-volatile content of the upper and lower layers are visually observed and measured. The storage stability was evaluated according to the following criteria.
Evaluation criteria ○: No light / dark separation is observed.
Δ: Slight density separation is confirmed in the upper and lower layers.
X: Separated into two layers.

(Mechanical stability)
Each emulsion obtained in Examples 1 to 3 and Comparative Examples 1 to 5 was diluted to 2% by mass with ion-exchanged water, and the surface state after stirring at 5,000 rpm for 10 minutes was visually observed using a homomixer. The mechanical stability was evaluated according to the following criteria.
Evaluation criteria ○: No oil floating, interference film or the like is observed.
Δ: Interference film is observed.
X: Oil float is recognized.

(Evaluation results)
As is clear from Table 1, in Examples 1 to 3, in the evaluation of “adsorption amount of amino group-containing organopolysiloxane on cotton broad cloth”, the adsorption amount of amino group-containing organopolysiloxane was large, In the evaluation of “flexibility”, very good results were obtained, so that the emulsions of amino group-containing organopolysiloxanes of Examples 1 to 3 were excellent in flexibility as a fiber treatment agent, It can be understood that smoothness, water repellency and dark color are imparted.
Further, it was confirmed that the emulsions of Examples 1 to 3 were excellent in all points of dilution stability, storage stability, and mechanical stability.
On the other hand, in Comparative Examples 1 to 3 to which acetic acid was added, flexibility and a decrease in the adsorption amount of the amino group-containing organopolysiloxane were observed. Moreover, in Comparative Example 5 using polyoxyethylene (10) tridecyl ether in which the alkyl part is not branched, it was confirmed that the dilution stability, storage stability and mechanical stability were poor.

Claims (5)

The following (A), (B) and (C) components:
(A) An amino group-containing organopolysiloxane represented by the general formula (1) having a kinematic viscosity at 25 ° C. of 100 to 1,000,000 mm ² / s and an amine equivalent of 1,000 to 100,000 g / mol.

[In the formula, R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, A is -R ¹ (NR ² CH ₂ CH ₂ ) _a NR ³ R ^{4, where} R ¹ is a divalent hydrocarbon having 1 to 8 carbon atoms. A hydrocarbon group, R ² , R ³ and R ⁴ are hydrogen atoms, monovalent hydrocarbon groups having 1 to 4 carbon atoms or —CH ₂ CH (OH) CH ₂ OH, and a is an integer of 0 to 4 X is R, A or —OR ⁵ (R ⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms). Where m and n are average numbers of polymerization and satisfy the above numerical ranges of kinematic viscosity and amine equivalent. However, when n = 0, at least one of X is A. ]
(B) Polyoxyalkylene branched alkyl ether
(C) It contains water, does not contain an acidic substance, the content of the component (B) is 10 to 50% by mass with respect to the mass of the component (A), and the content of the component (C) is: A fiber treatment agent mainly composed of an emulsion of an oil-in-water amino group-containing organopolysiloxane that is 30 to 90% by mass relative to the total mass of the component (A), the component (B), and the component (C).   The fiber treatment agent according to claim 1, wherein the polyoxyalkylene branched alkyl ether of component (B) is a polyoxyalkylene branched decyl ether.   The fiber treatment agent according to claim 1, wherein the polyoxyalkylene branched alkyl ether of component (B) is a polyoxyethylene polyoxypropylene branched decyl ether.   The component (B) is composed of two or more types of polyoxyalkylene branched alkyl ethers having different HLB values, and the mixture of the polyoxyalkylene branched alkyl ethers has an HLB value of 12 to 16. The fiber treatment agent according to item.   The fiber treatment agent according to any one of claims 1 to 4, wherein the emulsion of the oil-in-water amino group-containing organopolysiloxane has a median diameter of 0.3 µm or less.