JPH08109580A - Fiber treatment composition - Google Patents

Abstract

(57) [Summary] (Modified) [Objective] The present invention can impart good water repellency, oil repellency, flexibility and smoothness to various fibers when various fiber products are treated therewith. Furthermore, this treated cloth has heat,
It is an object of the present invention to provide a fiber treatment composition which can be prevented from yellowing even when left standing for a long time. The composition for fiber treatment of the present invention comprises (A) the general formula 1 An amino group-containing polysiloxane represented by the formula (B) and a fluorine compound represented by the general formula (2), (3) Rf-COOR (2) Rf-R'-OCOC (R ") = CH ₂ (3) It is characterized by containing a reaction product obtained by reacting a modified carboxylic acid alkyl ester compound and / or a (meth) acrylic acid fluorinated alkyl ester compound as a main component.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention imparts good water repellency, oil repellency, flexibility and smoothness to a fiber treatment composition, especially various fibers, and improves the yellowing of treated fabrics due to heat and aging. The present invention relates to a fiber treatment composition that can be used.

[0002]

2. Description of the Related Art As a fiber treatment agent for imparting water repellency and oil repellency to a textile product, a silicone water repellent agent such as methylhydrogenpolysiloxane, a perfluoroalkyl acrylate copolymer, a perfluoroalkyl urethane polymer is used. Fluorine-based water repellents composed of coalesce and the like are known (see JP-A-54-74000, JP-A-56-131687, JP-A-57-39285). However, although this silicone water repellent imparts good water repellency and flexibility to the treated cloth, it is difficult to impart oil repellency, and the fluorine water repellent imparts excellent water repellency and oil repellency to the treated cloth. However, this has a problem in that the flexibility of the treated cloth is impaired.

[0003]

Further, as a treating agent for imparting flexibility and smoothness to various fibers, in addition to the above-mentioned methyl hydrogen polysiloxane, dimethyl polysiloxane, epoxy group-containing polysiloxane, Amino group-containing polysiloxanes and the like are known (see JP-B-48-1480, JP-B-54-43617 and JP-B-59-26707), among which amino group-containing polysiloxanes have particularly excellent flexibility. It is widely used because it can be added.

Therefore, it has been proposed to blend the above-mentioned fluorine-based water repellent with the amino group-containing polysiloxane to improve its flexibility (see JP-A-60-81278). Although the flexibility is certainly improved, this has the disadvantage that the water repellency and oil repellency are reduced, and when this amino group-containing polysiloxane is used, the treated cloth will turn yellow due to heat or aging. There was a big drawback to do. Therefore, there is a demand for a fiber treatment composition which can impart excellent water repellency, oil repellency, flexibility and smoothness as described above and does not yellow even when heated or aged.

[0005]

The present invention relates to a fiber treatment composition which can solve the above disadvantages and problems and can meet the above-mentioned needs, and it relates to (A) general formula (1).

Embedded image [Wherein R ¹ is the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and Z is a formula -R ² (NR ³ R ⁴ ) _a NHR
⁵ (In the formula, R ² and R ⁴ are each an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ and R ⁵ are each a hydrogen atom and / or an unsubstituted or substituted one having 1 to 20 carbon atoms. A monovalent hydrocarbon group, a is an aminoalkyl group represented by 0 to 5), Y is R ¹ , Z or a formula —OR ⁶ (in the formula, R ⁶ is a hydrogen atom and / or a carbon number of 1 to 20). A group selected from the groups represented by unsubstituted or substituted monovalent hydrocarbon groups), m
Is a positive number from 1 to 10,000, n is a positive number from 0 to 100, where n = 0
And at least one of Y is Z], and (B) a general formula (2),
(3) Rf-COOR ... ( 2) Rf-R'-OCOC (R ") = CH 2 ... (3) [ wherein, Rf is a monovalent perfluoroalkyl group and / or a monovalent 3 to 15 carbon atoms Perfluoropolyether group,
R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms,
R'is an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms, R "is a hydrogen atom or a methyl group] and / or a (meth) acrylic acid alkyl fluoride compound A compound with respect to the hydrogen atom of the nitrogen bond in the component (A) (B)
It is characterized in that it contains as a main component a reaction product obtained by reacting the components in an amount 0.2 times to equimolar.

That is, as a result of various investigations by the present inventors to develop a novel fiber treating composition which can meet the above-mentioned demands, the present fiber treating composition is represented by the above general formula (1). Reaction product obtained by reacting the amino group-containing polysiloxane described above with a fluorinated carboxylic acid alkyl ester compound and / or a (meth) acrylic acid fluorinated alkyl ester compound represented by the general formulas (2) and (3). It has been found that a composition containing as a main component is an excellent fiber-treating agent, and treating the fiber with this imparts good water repellency, oil repellency, flexibility and smoothness to this treated cloth. The present invention was completed by confirming that yellowing did not occur due to heat and aging. This will be described in more detail below.

[0007]

The fiber treating composition of the present invention comprises an amino group-containing polysiloxane represented by the general formula (1), a fluorinated carboxylic acid alkyl ester compound represented by the general formulas (2) and (3), and / or Alternatively, it is mainly composed of a reaction product with a (meth) acrylic acid fluorinated alkyl ester compound, but when a textile product is treated with this, the treated cloth has excellent water repellency, oil repellency, flexibility, It provides smoothness and the advantage that it does not yellow with heat and aging.

The amino group-containing polysiloxane as the component (A) forming the fiber treatment composition of the present invention is represented by the above-mentioned general formula (1). In this formula, R ¹ is a methyl group. , Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tetradecyl group, alkyl group such as octadecyl group, alkenyl group such as vinyl group and allyl group, phenyl group , Aryl group such as tolyl group and naphthyl group, cycloalkyl group such as cyclopentyl group and cyclohexyl group, and substitution of some or all of hydrogen atoms bonded to carbon atoms of these groups with halogen atom, cyano group, etc. C1-C20 unsubstituted or substituted monovalent carbon selected from chloromethyl group, trifluoropropyl group, cyanoethyl group, etc. It is a hydrogenated group.

Further, Z in the general formula (1) is expressed by the formula −
R ² (NR ³ R ⁴ ) _a NHR ⁵ and R ² and R ⁴ in the formula are each an unsubstituted or substituted divalent group having 1 to 10 carbon atoms, which is exemplified by an alkylene group, an arylene group, an alkenylene group and the like. Hydrocarbon group, R
³ , R ⁵ is a hydrogen atom or has the same carbon number of 1 to 20 as R ¹ above.
An unsubstituted or substituted monovalent hydrocarbon group, a is an aminoalkyl group which is an integer of 0 to 5, and Y is R ¹ described above,
Z or the formula -OR ⁶ , wherein R ⁶ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms which is the same as R ^1, and m is larger than 10,000. In that case, the flexibility becomes insufficient, so that an integer of 1 to 10,000, preferably 10 to 1,000, and when n is 100 or more, the smoothness becomes insufficient, an integer of 0 to 100, preferably 0 to 10 is obtained. It is an integer.

The amino group-containing polysiloxane is basically of a linear structure and may have some branching, and the following are exemplified.

Embedded image

Next, the fluorinated carboxylic acid alkyl ester compound and the (meth) acrylic acid fluorinated alkyl ester compound as the component (B) forming the fiber treatment composition of the present invention are represented by the general formulas (2) and (3). ) Rf-COOR (2) Rf-R'-OCOC (R ") = CH ₂ ... (3), wherein Rf is a monovalent perfluoroalkyl group having 3 to 15 carbon atoms or a monovalent perfluoropoly With an ether group,
This may be linear or branched, for example
_{CF 3 (CF 2) 3 -} , CF 3 (CF 2) 7 -, CF 3 (CF 2) 12 -, (CF 3) 2 CFCF
_2- , CF ₃ (CF ₂ ) ₂ OC (CF ₃ ) F-,

[Chemical 4] What is shown by is illustrated.

R in the above formula (2) is the same as R ¹ described above, which is unsubstituted or substituted 1 to 20 carbon atoms.
A valent hydrocarbon group, R ′ in the formula (3) is the above R
² , similar to R ^{4 but} not substituted or substituted with 1 to 10 carbon atoms
The valent hydrocarbon group, R ″, is a hydrogen atom or a methyl group, and is a fluorinated carboxylic acid alkyl ester compound or a (meth) acrylic acid fluorinated alkyl ester compound represented by the formulas (2) and (3). The following are exemplified as CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ OCOCH = CH ₂ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) OCOCH = CH ₂ ,, C
F ₃ (CF ₂ ) ₁₂ (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ ,

Embedded image

[Chemical 6]

The fiber-treating composition of the present invention comprises this (A)
The main component is a reaction product of an amino group-containing polysiloxane as a component and a fluorinated carboxylic acid alkyl ester compound or a (meth) acrylic acid fluorinated alkyl ester compound as the component (B). Is usually the component (A) and the component (B) at room temperature to 150 ℃ 1
The reaction may be performed for ~ 10 hours, which is shown by the following formula. -N (R ⁵ ) H + ROCO-Rf → -N (R ⁵ ) -CO-Rf + ROH, -N (R ⁵ ) H + CH ₂ = C (R ")-COO-R'-Rf →- N (R ⁵ ) -CH ₂ -C (R ") HC
OO-R'-Rf

In this case, the component (A) and the component (B)
When the component (B) is less than 0.2 times the molar amount of the nitrogen-bonded hydrogen atoms in the component (A), the reaction product has poor yellowing resistance, water repellency, and oil repellency. If the amount exceeds the equimolar amount, the reaction product becomes poor in flexibility and smoothness. Therefore, the amount of the component (B) is 0.2 times the molar amount of the nitrogen-bonded hydrogen atom in the component (A). A molar range is required.

As described above, the fiber treatment composition of the present invention comprises an amino group-containing polysiloxane as the component (A) and a fluorinated carboxylic acid alkyl ester compound and / or a (meth) acrylic acid fluoride as the component (B). The main component is a reaction product with a modified alkyl ester compound, but the fiber to be treated with this is not particularly limited. Therefore, this is a natural fiber such as cotton, wool, hemp, silk, polyester, nylon and the like. It is effective for all kinds of fibers including synthetic fibers such as acrylic, but other fiber agents such as anti-wrinkle agents, flame retardants, antistatic agents, etc. are added to the extent that the characteristics are not impaired. That is optional.

When various fibers are treated with the composition for treating fibers of the present invention, the composition is diluted with a suitable solvent to adjust the concentration to a desired level, or this is diluted with a surfactant in water. After emulsifying and dispersing in to form an emulsion, dilute with water to adjust to the desired concentration, dip the fiber in it, or attach it to the fiber by means such as spraying or roll coating, and if necessary, After drying at 80 to 120 ° C for 1 to 10 minutes, heat treatment at 140 to 180 ° C for 1 to 10 minutes may be performed. In this case, the amount of the composition deposited is not particularly limited. However, it may be about 0.5 to 5% by weight.

The surfactant used when emulsifying the composition as described above is an anionic surfactant such as sodium alkylsulfate or sodium alkylbenzenesulfonate, polyoxyethylene alkylphenyl ether, polyoxy Nonionic surfactants such as ethylene alkyl ether and sorbitan fatty acid ester, and cationic surfactants such as quaternary ammonium salts may be used.

[0018]

EXAMPLES Next, synthesis examples of the fiber treating composition of the present invention and the fiber treating composition as a comparative example, and examples and comparative examples of the present invention using the reaction product prepared in this synthetic example The viscosity of the reaction product in the examples, the refractive index shows the measured value of 25 ℃, this Example,
The evaluation methods for water repellency, oil repellency, flexibility, smoothness, and yellowing of the fibers obtained in Comparative Examples were as follows. (Water repellency) It was evaluated by the spray method of JIS L-1092.

(Oil repellency) The oil repellency was evaluated by sequentially depositing droplets of the following mixture on the treated cloth and confirming the liquid composition capable of holding for 3 minutes or more.

[Table 1]

(Flexibility / Smoothness) Evaluation was performed by touch. ◯ ... The texture was extremely flexible and smooth. Δ: The texture was slightly rough and hard, and had less flexibility and smoothness. X: Coarse and hard, and had no softness or smoothness. (Yellowness) After the treated cloth was further heated at 180 ° C. for 5 minutes, the degree of yellowing was visually evaluated. 〇… It did not turn yellow at all. Δ: Yellowed a little. X: Yellowing was extremely strong.

Synthesis Example 1 A flask having a capacity of 500 ml equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introducing tube was charged with the compound of the formula (I).

[Chemical 7] 115.0 g of an amino group-containing polysiloxane represented by is charged, and the temperature is raised to 100 ° C.

Embedded image Fluorinated carboxylic acid alkyl ester compound 22
3.2 g (0.67 times mol relative to hydrogen atoms of nitrogen bond in amino group-containing polysiloxane) was added dropwise with stirring for 1 hour while introducing nitrogen gas, and after completion of the reaction, the mixture was further reacted at 100 ° C. for 6 hours. The reaction product is depressurized to 100 mmHg at 100 ℃.
After removing the low boiling fraction for 2 hours,
A reaction product-1 having a refractive index of 1.259 was obtained at 610 cS, and it was found by instrumental analysis such as GPC, IR, and NMR that this product had the following formula.

[Chemical 9]

Synthetic Example 2 Instead of the fluorinated carboxylic acid alkyl ester compound in Synthetic Example 1, acrylic acid represented by the formula (III) CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ OCOCH = CH ₂ ... (III) Fluorinated alkyl ester compound 17
1.1g (for nitrogen bond in polysiloxane containing amino group)
The reaction product-2 represented by the following formula having a viscosity of 1,130 cS and a refractive index of 1.292 was obtained by treating in the same manner as in Synthesis Example 1 except that (0.67 times mol) was used.

[Chemical 10]

Synthetic Examples 3 to 4 The amount of the fluorocarboxylic acid alkyl ester added in Synthetic Example 1 was 109.9 g (0.33 times moles with respect to hydrogen atoms of nitrogen bonds in the amino group-containing polysiloxane) and 333.2 g (containing amino group). The reaction was carried out in the same manner as in Synthesis Example 1 except that the hydrogen atom of the nitrogen bond in the polysiloxane was changed to equimolar), and the viscosity was 220 cS, the refractive index was 1.367, and the reaction product-3 represented by the following formula,

[Chemical 11] A reaction product-4 represented by the following formula was obtained with a viscosity of 1,850 cS and a refractive index of 1.217.

[Chemical 12]

Synthesis Example 5 Formula (IV)

[Chemical 13] 228.4 g of the amino group-containing polysiloxane represented by 61.0 g of the fluorocarboxylic acid alkyl ester compound of the formula (II) used in Synthesis Example 1 (equivalent to the hydrogen atom of the nitrogen bond in the amino group-containing polysiloxane). When the same treatment as in Synthesis Example 1 was carried out except that a molar amount) was added, a viscosity of 4,6
40cS, refractive index 1.274 and reaction composition represented by the following formula-5
was gotten.

Embedded image

Comparative Synthetic Example 1 In the same flask used in Synthetic Example 1, 24.0 g of the fluorinated acrylic acid alkyl ester compound of the formula (III) used in Synthetic Example 2 and the formula C ₄ H ₉ OCOCH = CH _When 6.0 g of an acrylic acid alkyl ester compound represented by ₂ and 270.0 g of meta-xylene hexafluoride and 1.0 g of azobisisobityronitrile were charged, a co-polymerization reaction was carried out at 60 ° C. for 3 hours while introducing nitrogen gas, A reaction product-6 represented by the following formula was obtained as a solution containing 10% of a perfluoroalkyl acrylate copolymer.

[Chemical 15]

Examples 1 to 5 The reaction products 1 to 5 obtained in Synthesis Examples 1 to 5 were diluted with meta-xylene hexafluoride to 1.0% by weight, and a cotton broad cloth was dipped in this, and then squeezed with a roll. The treated cloth was prepared by squeezing it to 100% and then heat treating it at 100 ° C. for 2 minutes and then at 150 ° C. for 2 minutes. The physical properties of the obtained treated cloth were examined, and as shown in Table 2 below. Results were obtained.

Comparative Example 1 The perfluoroalkyl acrylate copolymer in the reaction product-6 obtained in Comparative Synthesis Example 1 was diluted with meta-xylene hexafluoride to a concentration of 1.0% by weight, and this was used. A treated cloth was prepared in the same manner as in the example, and the physical properties of the treated cloth thus obtained were examined. The results shown in Table 2 below were obtained.

Comparative Example 2 The perfluoroalkyl acrylate copolymer in the reaction product-6 obtained in Comparative Synthesis Example 1 was diluted with meta-xylene hexafluoride so that the concentration was 1.0% by weight. The amino group-containing polysiloxane (I) used in 1 to 4 was diluted with metaxylene hexafluoride so that the concentration of the polysiloxane (I) was 0.3% by weight, and using this, a treated cloth was prepared in the same manner as in the example. When the physical properties of the treated cloth thus obtained were examined, the results shown in Table 2 below were obtained.

[0029]

[Table 2]

[0030]

The present invention relates to a fiber treating composition of the present invention, which comprises (A) an amino group-containing polysiloxane represented by the general formula (1) and (B) a general formula (2) as described above. The fluorinated carboxylic acid alkyl ester compound or (meth) acrylic acid fluorinated alkyl ester compound represented by (3) is added to the component (A) in an amount 0.2 times the molar amount of the component (B) with respect to the nitrogen-bonded hydrogen atom in the component (A). ~ It is characterized by containing a reaction product obtained by reacting an equimolar amount as a main component, but when various fiber products are treated with this composition for fiber treatment, this treated cloth is excellent. Water repellency, oil repellency, flexibility, and smoothness are imparted, and further, it has an advantage that yellowing is extremely reduced even when it is heated or left to stand with time.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yasushi Yamamoto 1 Hitomi, Osamu Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (1)

[Claims] (A) General formula (1) [Wherein, R ¹ is the same or different and is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, Z is a formula —R ² (NR ³ R ⁴ ) _a NHR ⁵ (wherein R ² , R ^{2 4} is an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms, R ³ and R ⁵ are each a hydrogen atom and / or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms,
a is an integer of 0-5), an aminoalkyl group represented by Y,
Is a group selected from R ¹ , Z or a group represented by formula —OR ⁶ (wherein R ⁶ is a hydrogen atom and / or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms), and m is 1 to
Positive number of 10,000, n is a positive number of 0 to 100, when n = 0,
At least one of Y is Z], and (B) a general formula (2), (3) Rf-COOR (2) Rf-R'-OCOC (R ") = CH ₂ (3) [wherein, Rf is a monovalent perfluoroalkyl group and / or monovalent perfluoropolyether group having 3 to 15 carbon atoms,
R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms,
R'is an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms, R "is a hydrogen atom or a methyl group] and / or a (meth) acrylic acid alkyl fluoride compound A compound as a main component, which is obtained by reacting a compound with a hydrogen atom of a nitrogen bond in the component (A) in an amount 0.2 to equimolar to the component (B). A composition for treating fibers.