JP3124527B2 - Fiber treatment agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a fiber treating agent comprising a fluorosilicone copolymer oil.

[0002]

2. Description of the Related Art Conventionally, dimethyl silicone oil has been used as a synthetic oil having excellent heat and cold resistance, and a methyl group bonded to a silicon atom has been developed as a grade having improved oil and solvent resistance .
Fluorosilicone oils having one trifluoropropyl group are known. On the other hand , as the field of use of silicone oils in the industry has expanded in recent years, various properties of the oils (refractive index, surface tension, solubility in organic solvents, etc.)
Need to be strictly controlled over a wide range to respond to individual applications.

[0003] The existing oil was bought essentially et response for a homopolymer such demands Lena. Copolymer oils composed of dimethylsiloxane units and trifluoropropylmethylsiloxane units are also known,
Since the physical properties of the trifluoropropyl group itself were insufficient, the range in which the oil physical properties could be changed was small.

Japanese Patent Application Laid-Open No. 59-189933 discloses a defoaming effect when a copolymer comprising dimethylsiloxane units and long-chain perfluoroalkylethylmethylsiloxane units is used in combination with an organopolysiloxane having an oxyalkylene group and a perfluoroalkyl group. It is described that it has excellent self-emulsifying property, but there is no description about evaluation as a copolymer alone.

[0005]

In recent years, as the field of use of silicone oils in the industry has expanded, it has become necessary to strictly control the properties of the oils over a wide range and to respond to individual uses. An object of the present invention is to meet the above-mentioned demand by providing a fiber treating agent comprising a copolymerized oil comprising a dimethylsiloxane unit and a long-chain perfluoroalkylethylmethylsiloxane unit.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has a fiber treating agent comprising a fluorosilicone copolymer oil represented by the following formula (1). provide.

In the formula 1, R ^f is a perfluoroalkyl group having 4 to 9 carbon atoms, and R ^F is CH ₃ or R ^f CH ₂ CH
₂ , n ≧ 1, m ≧ 1 and (CH ₃ ) ₂ S in the formula
(R ^f C ₂ H ₄ ) (CH ₃ ) based on the total weight of iO _2/2 units
The ratio of the total weight of SiO _2/2 units is 50/50 to 10/90
It is.

[0008]

Embedded image

In the present invention, R ^f in the formula 1 represents 4 carbon atoms.
-9, and R ^F is CH ₃ or R ^f CH ₂ CH ₂ . Such long-chain perfluoroalkyl group containing fluorosilicone copolymer oil, passing <br/> normal, R ^F (CH ₃₎ a chain transfer agent ₂ SiOSi (C
In the presence of _{^{H 3) 2 R F, [}} (R f CH 2 CH 2) (CH 3)
SiO] ₃ and _{[(CH 3) 2 SiO]} p (p is 3 or 4) is produced by ring-opening polymerization using an appropriate catalyst.

As R ^f becomes longer, [(R ^f CH ₂ C
A preferable R ^f is a perfluorobutyl group because production of H ₂ ) (CH ₃ ) SiO] ₃ becomes difficult. On the other hand , R ^F is particularly preferably a methyl group because of availability of raw materials. n, m
Is that n ≧ 1, m ≧ 1 and (CH ₃ ) ₂ S in the formula
(R ^f C ₂ H ₄ ) (CH ₃ ) based on the total weight of iO _2/2 units
The ratio of the total weight of SiO _2/2 units is 50/50 to 10/90
It is.

[0011] oils of this invention, by varying the copolymerization <br/> sets formed as shown later, can be changed accurately physical properties such as surface tension, refractive index. Therefore, to manufacture a fluorosilicone oil having various physical properties corresponding to the Field of subdivided silicone oil,
It can be used as a fiber treatment agent without any particular limitation on its use conditions.

That is, a fiber treatment agent such as a raw material for a softening agent, a raw material for a water repellent agent, a deep-color processing agent, a lubricating agent for a sewing thread, etc. utilizing water repellency, oil repellency, low reflection, flexibility, lubricity and the like. It can be used <br/> as.

The kinematic viscosity of the fluorosilicone copolymer oil of the present invention is preferably about 10,000 cSt or less. If the kinematic viscosity is too high, fluidity,
Particularly, the fluidity at a low temperature is unfavorably reduced.

[0014]

In the present invention, the long-chain perfluoroalkyl group imparts various properties (oil resistance / solvent resistance, low surface tension, low refractive index) derived from fluorine to oil. Then (R ^f C
H ₂ CH ₂ ) (CH ₃ ) SiO _2/2 and (CH ₃ ) ₂ SiO _2/2
By changing the copolymerization ratio of the oil, various properties of the oil can be strictly controlled over a wide range, and the oil can be used in various applications.

[0015]

EXAMPLES (Production Example 1) A four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer was purged with argon, and [(C ₄ F ₉ C ₂ H ₄ ) (C
15 g of [H ₃ ) SiO] ₃ and 1 of [(CH ₃ ) ₂ SiO] ₃
5 g and 1 g of (CH ₃ ) ₃ SiOSi (CH ₃ ) ₃ were charged. The internal temperature was raised to 75 ° C., and 48 mg of trifluoromethanesulfonic acid was introduced into the flask with a microsyringe.

After 6 hours, it was confirmed that the monomer was completely consumed. After the product was washed successively with 5% aqueous sodium bicarbonate solution and water, to remove low boiling components at 200 ° C., a kinematic viscosity 11
27.9 g ( yield 90%) of a 2 cSt fluorosilicone oil was obtained. This oil has ¹ H-NMR and IR
Has confirmed that it has the following structure.

[0017]

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[0018] (Preparation Example _{2) [(C 4 F 9} C 2 H 4) (CH 3) SiO] 3 to 6.1 g,
[(CH ₃ ) ₂ SiO] ₃ in 14.1 g and (CH ₃ ) ₃ S
iOSi the (CH _{3) 3} to 0.85 g, except for changing the trifluoromethanesulfonic acid 26mg in the Production Example 1 and <br/> Similarly, fluorosilicone oil 18.7 g (yield of kinematic viscosity 104cSt 88.9%). The oil was confirmed to have the following structure by ¹ H-NMR and IR.

[0019]

Embedded image

The oil of the present invention is (R ^f CH ₂ CH ₂ ) (C
By changing the copolymerization ratio of H ₃ ) SiO _2/2 and (CH ₃ ) ₂ SiO _2/2 , various physical properties of the oil can be controlled over a wide range. Table 1 shows the relationship between the copolymer composition and the physical properties when R ^f is C ₄ F ₉ .

[0021]

[Table 1]

[0022]

[0023]

[0024]

[0025]

<Application Example> An emulsion for fiber treatment having the following composition was prepared. (1) 30 parts of oil consisting of (C ₄ F ₉ C ₂ H ₄ ) (CH ₃ ) SiO _2/2 / (CH ₃ ) ₂ SiO _2/2 = _10/90 ( weight / weight ); (2) 3 parts of polyoxyethylene nonylphenyl ether, (3) 67 parts of water.

Next , 3 parts of this emulsion was mixed with 2000 parts of water.
And the mixture was diluted to give a fiber treatment solution. The polyester fiber is immersed in this treatment liquid for 120 minutes, squeezed, and then
Dried for minutes. As a comparative example, the same operation was carried out for the case where (1) was changed to trifluoropropyl fluorosilicone oil (Comparative Example 1) and dimethyl silicone oil (Comparative Example 2), and the water repellency of the treated cloth was evaluated by shower water repellency. The results shown in Table 2 were obtained.

[0028]

[Table 2]

[0029]

[Effect of the Invention] oil of the present invention is superior in present in by profit slipping like perfluoroalkyl group. By further adjusting the copolymerization ratio of dimethyl silicone, effect that can properties of the oil controls also observed.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 77/24 D06M 15/643-15/657

Claims (3)

(57) [Claims] 1. A fiber treating agent comprising a fluorosilicone copolymer oil represented by the following formula 1. However, in the formula 1, R ^f is a perfluoroalkyl group having 4 to 9 carbon atoms, R ^F is CH ₃ or R ^f CH ₂ CH ₂ , n ≧ 1, m
Is ≧ 1, _{and, (CH 3) 2 SiO 2} /2 (R f C 2 H 4) relative to the total weight of the unit (CH ₃₎ total weight ratio of SiO _2/2 units in the formula is 50/50 〜１０10 / 90. Embedded image 2. The fiber treating agent according to claim 1, wherein R ^F is CH ₃ . 3. The fiber treating agent according to claim 1, wherein R ^f is a perfluorobutyl group.