JP3283277B2 - Organopolysiloxane composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organopolysiloxane composition, and more particularly to an antistatic property at low humidity when used as an oil agent for treating fibers.
The present invention relates to an organopolysiloxane composition which is excellent in card passing property and bundle property of fiber bundles, has no roller wrapping, and can be easily washed off.

[0002]

BACKGROUND OF THE INVENTION Natural and synthetic fibers themselves have many desirable properties, but are often subjected to further treatments to impart more desirable properties. Depending on the type of natural and synthetic fibers and the type of treatment, the lubricity, feel or other chemical or physical properties of the fibers can be improved. Various treatment agents and treatment methods have been proposed to obtain fibers having better properties.

[0003] Oil treatments containing a wide variety of silicone treatment agents are currently widely used for fiber treatment. However, these fiber treatment oil treatments have insufficient antistatic properties at low humidity to generate static electricity or polyester. In the case of fiber, etc., the cylinder wraps around the card, the doffer rolls up,
Coil tube clogging occurs. In addition, due to the insufficient bundle property of the fiber bundle, there is a drawback in the carding process or the drawing process that the amount of sliver stored in the can is small and the work efficiency is reduced.

[0004] In order to prevent static electricity at low humidity, it is considered effective to increase the phosphoric acid value and the monoester ratio of the alkyl phosphate ester and to use a cationic surfactant or an amphoteric surfactant. However, these surfactants have a very high hygroscopicity, and have a drawback that they cause roller wrapping and rust on metal parts of the spinning machine. The bundle quality of the fiber bundle can be enhanced by using a nonionic surfactant which is an animal or vegetable oil, a fatty acid ester, a fatty acid soap, or a higher alcohol or an ethylene oxide adduct of a fatty acid. When used in a large amount, for example, 80% by weight or more in the oil component, deterioration of card passing property, occurrence of roller wrapping due to high tackiness of the oil agent, and further decrease in antistatic ability occur. There is a limit on usage.

Further, the above-mentioned alkyl phosphates, cationic surfactants, amphoteric surfactants, animal and vegetable oils,
Both fatty acid esters and nonionic surfactants have serious drawbacks such as incompatibility with silicone in a transparent manner, lack of performance such as antistatic ability, and lack of stability. It is also possible to use various silicone-based surfactants, but none of them is transparently compatible with silicone, and the disadvantages have not been solved.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks, and has as its object to provide a composition of silicone and a compounding agent which is transparently compatible with the silicone. Another object of the present invention is to provide a fiber treatment oil agent which has excellent antistatic properties at low humidity, card passing properties and fiber bundle convergence properties, does not wrap around a roller, and can be more easily washed off. I do.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that when a linear polysiloxane-polyoxyalkylene block copolymer having a specific molecular structure is blended with an organopolysiloxane as a silicone, a compatibility is obtained. The present inventors have found that these compositions exhibit excellent performance as an oil agent for fiber treatment, and have completed the present invention.

That is, the present invention relates to 100 parts by weight of an organopolysiloxane and the following formula 1: [-(R ₂ SiO) _a R ₂ SiYO (C _n H _{2 n} O) _b Y-] _c (1) , R represents a monovalent hydrocarbon group containing no aliphatic unsaturation, Y represents a divalent organic group having one end bonded to a silicon atom and the other end bonded to an oxygen atom, and a represents an integer of 6 or more. Represent
b represents an integer of 4 or more; c represents an integer of 2 or more;
Represents an integer of 2, 3 or 4, each siloxane block has an average molecular weight of 400 to 10000, and each polyoxyalkylene block has an average molecular weight of 200 to 1000.
0, containing at least 5% by weight of ethylene oxide, and the siloxane block is 25 to 95% by weight of the whole block copolymer.
Configure and block copolymer linear polysiloxane represented by having) an average molecular weight of 1200 or more - polyoxyalkylene block copolymer 0.5 to 100-fold
About organopolysiloxane composition characterized by comprising a quantity unit.

The organopolysiloxane used in the present invention may be any of linear, branched, cyclic, network, and three-dimensional networks, but linear and cyclic ones are preferred. The degree of polymerization of the organopolysiloxane is not particularly limited, but is preferably 1,000 or less. A particularly desirable organopolysiloxane is dimethylpolysiloxane.

The linear polysiloxane-polyoxyalkylene block copolymer used in the present invention is represented by the above formula (1), wherein each group (R and Y) in the formula is
Will be described below.

Examples of the group R include alkyl groups (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group,
A dodecyl group, an octadecyl group, an eicosyl group, etc., an aryl group (eg, phenyl group, naphthyl group, etc.), an aralkyl group (eg, benzyl group, phenylethyl group, etc.), a tolyl group, a xylyl group, a cyclohexyl group. .

The group Y is a divalent organic group having one end bonded to a silicon atom and the other end bonded to an oxygen atom, ie, a silicon-bonded bond to an adjacent silicon atom, and a polyoxy group bonded through an adjacent oxygen atom. A divalent organic group bonded to the alkylene block, for example, the following formula: -R'-, -R'-CO-, -R'-NHCO-,-
R'-NHCONH-R "-NHCO- or -R'-
OOCNH-R "-NHCO- (wherein R 'represents a divalent alkylene group such as an ethylene group, propylene group, butylene group, particularly preferably a phenylene group, and R" represents a divalent alkylene group such as R exemplified group or a divalent arylene group with respect to ', for example _{-C 6 H 4 -, - C} 6 H 4 -C 6 H 4 -, - C 6 H
_{4 -CH 2 -C 6 H 4 -} , - C 6 H 4 -CH (CH 3)
—C ₆ H ₄ —).

Preferred examples of group Y are: -CH ₂ CH _2- , -CH ₂ CH ₂ CH _2- , -CH _{2
CH (CH 3) CH 2 -} , - CH 2 CH 2 CH 2 CH 2
_{-, - (CH 2) 2} CO -, - (CH 2) 3 NHCO
_{-, - (CH 2) 3} NHCONHC 6 H 4 NHCO- or _{- (CH 2) 3 OOCNC 6} H 4 NHCO-.

The most preferred radical Y is a divalent alkylene radical, in particular -CH ₂ CH ₂ CH ₂ -or -CH ₂ CH (C
H ₃₎ CH ₂ - is.

The linear polysiloxane-polyoxyalkylene block copolymer is obtained by reacting a polyoxyalkylene compound having a reactive terminal group with a dihydrocarbylsiloxane having a terminal group which reacts with the reactive terminal group of the compound. It can be manufactured by doing.

The linear polysiloxane-polyoxyalkylene block copolymer used in the present invention is represented by the above formula 1, wherein R, Y, a, b, c
And n and the molecular weight of each block and the copolymer as a whole represent those in the range defined above, but if it is out of this range, the compatibility with the organopolysiloxane decreases,
It becomes a cloudy dispersion or a phase separation state, which is not desirable. Further, unless each polyoxyalkylene block in the formula 1 contains 5% by weight or more of ethylene oxide, excellent antistatic properties cannot be obtained.

[0017] The organopolysiloxane composition of the present invention is represented by the formula (1) based on 100 parts by weight of the organopolysiloxane.
Is preferably in the range of 0.5 to 100 parts by weight.

Further, the oil agent for treating fibers containing the organopolysiloxane composition of the present invention is excellent in antistatic property, card passing property and fiber bundle convergence property at low humidity, and has no roll wrapping, and is easier to use. Can be washed off. Accordingly, the present invention relates to an oil agent for treating fibers containing the organopolysiloxane composition of the present invention.

In addition to the composition of the present invention, such fiber treatment oils may contain conventional additives such as surfactants, combustion inhibitors, coloring agents, antistatic agents, lubricants, water repellents, and softeners. Agent,
Hand improver, durable press resin
) Can be added.

The linear polysiloxane-polyoxyalkylene block copolymer used in the present invention imparts new desirable properties such as antistatic properties without impairing the excellent properties inherent to organopolysiloxanes. In addition, since the compound is transparently compatible with the organopolysiloxane, the performance is imparted to the organopolysiloxane with high stability and uniformity. Therefore, the organopolysiloxane composition of the present invention is a cosmetic, a release agent, an antifoaming agent, a foam stabilizer for urethane foam, a fiber treatment agent,
It can be used as an adhesive, a pressure-sensitive adhesive, an antifogging agent, a glazing agent, a water repellent, a paint / resin additive, a heating medium, and the like, or by being blended therein.

[0021]

EXAMPLES Next, the present invention will be described based on examples, but the present invention is not limited by these examples. In the following examples, a methyl group may be referred to as Me. Synthesis Example of Linear Polysiloxane-Polyoxyalkylene Block Copolymer Synthesis Example 1 In a 500 ml three-necked flask equipped with a mechanical stirrer, condenser, thermometer and nitrogen inlet, dimethallyl polyether [CH ₂ ＣC (CH ₃ ) CH ₂ O (C ₂ H
₄ O) ₁₈ (C ₃ H ₆ O) ₃₃ CH ₂ C (CH ₃ ) = C
H ₂ ], 100 g of toluene, 350 g of toluene, and chloroplatinic acid so that the platinum content was 20 ppm. The mixture is treated with dihydropolydimethylsiloxane [HMe ₂ SiO (Me
₂ SiO) ₄₀ SiMe ₂ H] 103 g was gradually added. The end of this reaction was determined by the negative value of the AgNO ₃ test for SiH. The reaction mixture is then washed with NaHCO
Neutralize with ₃ , filter, and 5 with a rotary evaporator
Removal of the solvent at 0 ° C./1 mmHg yields the following formula: [-(Me ₂ SiO) ₄₁ Me ₂ SiCH ₂ CH (C
H ₃ ) CH ₂ O (C ₂ H ₄ O) ₁₈ (C ₃ H ₆ O) ₃₃ CH
193 g of a linear polysiloxane-polyoxyalkylene block copolymer having a molecular weight of 95,000 represented by ₂ CH (CH ₃ ) CH ₂ —] _16.1 was obtained.

Synthesis Example 2 Dimethallyl polyether [CH ₂ ＣC (CH ₃ ) CH
₂ O (C ₂ H ₄ O) ₂₀ (C ₃ H ₆ O) ₂₉ CH ₂ C (CH
₃ ) = CH ₂ ] 70 g, dihydropolydimethylsiloxane [HMe ₂ SiO (Me ₂ SiO) ₃₀ SiMe ₂ H]
43 g, 350 g toluene, and 20 pp platinum content
m and the same operation as in Synthesis Example 1 using a platinum-based addition catalyst, the following formula: [-(Me ₂ SiO) ₃₁ Me ₂ SiCH ₂ CH (C
H ₃ ) CH ₂ O (C ₂ H ₄ O) ₂₀ (C ₃ H ₆ O) ₂₉ CH
_{2 CH (CH 3) CH 2} - linear polysiloxane having a molecular weight of 67000, represented by] _13.3 - polyoxyalkylene block copolymer 106g was obtained.

Synthesis Example 3 Dimethallyl polyether [CH ₂ ＣC (CH ₃ ) CH
₂ O (C ₂ H ₄ O) ₂ (C ₃ H ₆ O) ₂₅ CH ₂ C (CH
₃ ) = CH ₂ ] 150 g, dihydropolydimethylsiloxane [HMe ₂ SiO (Me ₂ SiO) ₈ SiMe
₂ H] 61 g, toluene 350 g, and a platinum content of 2
Synthesis example 1 using a platinum-based addition catalyst so as to be 0 ppm
By performing the same operation as described above, the following formula: [− (Me ₂ SiO) ₉ Me ₂ SiCH ₂ CH (C
H ₃ ) CH ₂ O (C ₂ H ₄ O) ₂ (C ₃ H ₆ O) ₂₅ CH
₂ CH (CH ₃ ) CH ₂ —] 203 g of a linear polysiloxane-polyoxyalkylene block copolymer represented by _13.3 and having a molecular weight of 32,000 was obtained.

Synthesis Example 4 Dimethallyl polyether [CH ₂ ＣC (CH ₃ ) CH
₂ O (C ₂ H ₄ O) ₁₈ (C ₃ H ₆ O) ₂₀ CH ₂ C (CH
₃ ) = CH ₂ ] 120 g, dihydropolydimethylsiloxane [HMe ₂ SiO (Me ₂ SiO) ₁₅ SiMe
₂ H] 68 g, toluene 330 g, and a platinum content of 2
Synthesis example 1 using a platinum-based addition catalyst so as to be 0 ppm
By performing the same operation as described above, the following formula: [− (Me ₂ SiO) ₁₆ Me ₂ SiCH ₂ CH (C
H ₃ ) CH ₂ O (C ₂ H ₄ O) ₁₈ (C ₃ H ₆ O) ₂₀ CH
174 g of a linear polysiloxane-polyoxyalkylene block copolymer having a molecular weight of 71,000 represented by ₂ CH (CH ₃ ) CH ₂ —] _21.5 was obtained.

Synthesis Example 5 Dimethallyl polyether [CH ₂ ＣC (CH ₃ ) CH
₂ O (C ₂ H ₄ O) ₃ (C ₃ H ₆ O) ₃ CH ₂ C (CH
₃ ) = CH ₂ ] 45 g, dihydropolydimethylsiloxane [HMe ₂ SiO (Me ₂ SiO) ₂₀ SiMe ₂ H]
154 g, toluene 330 g, and a platinum content of 20 p
pm and the same operation as in Synthesis Example 1 using a platinum-based addition catalyst, the following formula: [-(Me ₂ SiO) ₂₁ Me ₂ SiCH ₂ CH (C
_{H 3) CH 2 O (C} 2 H 4 O) 3 (C 3 H 6 O) 3 CH
_{2 CH (CH 3) CH 2} - linear polysiloxane having a molecular weight of 21000, represented by] _10.5 - polyoxyalkylene block copolymer 186g was obtained.

Synthesis Example 6 (for Comparative Example) Hydrosilyl group-containing dimethylpolysiloxane [Me ₃
SiO (Me ₂ SiO) ₁₀₀ (MeHSiO) ₁₃ SiM
e ₃ ] 27 g, allyl polyether [CH ₂ ＣＨCHCH
_{2 O (C 2 H 4 O} ) 18 (C 3 H 6 O) 20 CH 3 ] 94
g, 330 g of toluene, and the same operation as in Synthesis Example 1 using a platinum-based addition catalyst so that the platinum content becomes 20 ppm, the following formula: 111 g of a polysiloxane-polyoxyalkylene copolymer having a molecular weight of 35,000 was obtained.

Synthesis Example 7 (for Comparative Example) Dihydropolydimethylsiloxane [HMe ₂ SiO (M
e ₂ SiO) ₂₀₀ SiMe ₂ H] 97 g, allyl polyether [CH ₂ ＣＨCHCH ₂ O (C ₂ H ₄ O) ₂₇ (C ₃
H ₆ O) ₃₀ CH ₃ ] 43 g, toluene 320 g, and the same operation as in Synthesis Example 1 using a platinum-based addition catalyst such that the platinum content becomes 20 ppm, the following formula: CH ₃ (C ₃ H ₆₎ O) ₃₀ (C ₂ H ₄ O) ₂₇ OC ₃ H
₆ (Me ₂ SiO) ₂₀₁ SiMe ₂ C ₃ H ₆ O (C ₂ H
_{4 O) 27 (C 3 H} 6 O) 30 polysiloxane having a molecular weight of 21000, represented by CH ₃ - polyoxyalkylene copolymer 133g was obtained.

Synthesis Example 8 (for Comparative Example) Dimethallyl polyether [CH ₂ ＣC (CH ₃ ) CH
₂ O (C ₂ H ₄ O) ₂₀ (C ₃ H ₆ O) ₂₉ CH ₂ C (CH
₃ ) = CH ₂ ] 150 g, dihydropolydimethylsiloxane [HMe ₂ SiO (Me ₂ SiO) ₈ SiMe
₂ H] 38 g, toluene 350 g, and a platinum content of 2
Synthesis example 1 using a platinum-based addition catalyst so as to be 0 ppm
By performing the same operation as described above, the following formula: [− (Me ₂ SiO) ₉ Me ₂ SiCH ₂ CH (C
H ₃ ) CH ₂ O (C ₂ H ₄ O) ₂₀ (C ₃ H ₆ O) ₂₉ CH
_{2 CH (CH 3) CH 2} - linear polysiloxane having a molecular weight of 62000, represented by] _18.3 - polyoxyalkylene block copolymer 176g was obtained.

Example 1 In a 500 ml beaker equipped with a mechanical stirrer, 200 g of dimethylpolysiloxane (100 cst) was placed.
When 50 g of the linear polysiloxane-polyoxyalkylene block copolymer obtained in Synthesis Example 1 was gradually added, a transparent solution was obtained.

Examples 2 to 5 The same procedure as in Example 1 was repeated, except that the linear polysiloxane-polyoxyalkylene block copolymer produced in Synthesis Example 1 was replaced with those obtained in Synthesis Examples 2 to 5. Was performed, and clear solutions were obtained in all cases.

Examples 6 to 10 Cyclic dimethylpolysiloxane (mixture of polymerization degree 4 and 5)
Then, the same operation as in Example 1 was performed using the linear polysiloxane-polyoxyalkylene block copolymer obtained in Synthesis Examples 1 to 5, and a transparent solution was obtained.

Example 11 The same operation as in Example 1 was carried out using the linear polysiloxane-polyoxyalkylene block copolymer obtained in Synthesis Example 3 for dimethylpolysiloxane (5000 cst). A solution was obtained.

Comparative Examples 1 to 3 Synthesis Example 6 with dimethylpolysiloxane (100 cst)
Using the polysiloxane-polyoxyalkylene copolymer obtained in and 7 and the linear polysiloxane-polyoxyalkylene block copolymer obtained in Synthesis Example 8, the same operation as in Example 1 was performed. Neither of them was dissolved, the particles were in a cloudy dispersion state, and no transparent solution was obtained.

Example 12 Polyester staples (1.5 d, 38 mm) were immersed in the following spinning oil by the immersion oiling method.
% Or 80% for a day and night to obtain an equilibrium moisture content, and then a spinning test (card test, drawing test) was performed. The test conditions and results are summarized in Tables 1 and 2. Oils A to E (invention) and F to H (control) PEG-300 monopalmitate 50 parts by weight Lauryl phosphate potassium salt 30 parts by weight Organopolysiloxane composition (Examples 1 to 5 and Comparative Examples 1 to 3) 20 parts by weight

[0035]

[Table 1] Card test conditions A small flat card was used and measured under the following conditions (temperature: 20 ° C., humidity: 40%).・ Spinning speed: 7 m / min ・ Amount of cotton: 30 g was spun, and the amount of charge generated on the web and the winding around the cylinder were measured. -Generated charge amount: The generated charge amount of the web at the time of spinning was measured by a current collecting potential difference meter. Cylinder winding: The winding width around the cylinder when 30 g of cotton was spun out was measured.

[Table 2] Drawing test conditions-Spinning speed: 43 m / min-Roller winding: The number of windings on the rubber roller of a petri dish-type drawing machine was measured through a 1500 m sliver with the clearer removed (temperature 30 ° C, 30 ° C).
Humidity 80%). Convergence of sliver Strength: The sliver strength after drawing was measured using a U gauge (the larger the value, the better). Bulkiness: 20 g of test cotton is spun with a flat card, and the spun web is metal roller (diameter 6 cm, length 30 c)
m) Wrap in a wrap shape and cut, 15cm x 80c
After forming a sheet shape of m, a load of 0.2 g was applied per cm, and the height of the cross section was measured (the smaller the value, the better the convergence).

The following can be understood from these results. First, the oils F to H using the preparations according to the comparative examples are inferior in antistatic properties, are likely to be related thereto, are often wound around rollers under high temperature and high humidity, and are inferior in card passability. It can be a mixture of an organopolysiloxane and a polysiloxane-polyoxyalkylene copolymer, or a linear polysiloxane.
This is considered to be caused by non-uniformity due to phase separation due to poor compatibility with the polyoxyalkylene block copolymer. On the other hand, the oils A to E using the preparations according to the examples of the present invention are excellent in all of the antistatic properties, card passing properties, roller winding prevention properties, and sliver convergence properties.

[0037]

As described in detail above, the present invention provides
It was found for the first time that 0.5 to 100 parts by weight of a linear polysiloxane having a specific molecular structure-polyoxyalkylene block copolymer was blended with 100 parts by weight of an organopolysiloxane, and that they were compatible with each other transparently. This makes it possible to uniformly and stably impart properties such as antistatic properties to the organopolysiloxane by the copolymer. Therefore, the oil agent for treating fibers containing the organopolysiloxane composition of the present invention has excellent antistatic properties at low humidity, excellent card passing properties and fiber bundle convergence properties, and has no roller wrapping, which is relatively easy. It has the advantage that it can be washed off.

Further, the organopolysiloxane composition of the present invention can be used as a cosmetic, a release agent, an antifoaming agent, a foam stabilizer for urethane foam, a fiber treatment agent, an adhesive, a pressure-sensitive adhesive, an anti-fogging agent, a glazing agent, It can be suitably used as a water repellent, a paint / resin additive, a heat medium, or the like, or by being blended therein.

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 83/12 C08L 83/04 C08G 77/46

Claims (3)

(57) [Claims] 1. 100 parts by weight of an organopolysiloxane
When the following formula 1: _{[- (R 2 SiO) a R} 2 SiYO (C n H 2n O) b Y- ] _c (1) (wherein, R is a monovalent hydrocarbon free of aliphatic unsaturation Y represents a divalent organic group having one end bonded to a silicon atom and the other end bonded to an oxygen atom, a represents an integer of 6 or more,
b represents an integer of 4 or more; c represents an integer of 2 or more;
Represents an integer of 2, 3 or 4, each siloxane block has an average molecular weight of 400 to 10000, and each polyoxyalkylene block has an average molecular weight of 200 to 1000.
0, containing at least 5% by weight of ethylene oxide, and the siloxane block is 25 to 95% by weight of the whole block copolymer.
Configure and block copolymer linear polysiloxane represented by having) an average molecular weight of 1200 or more - polyoxyalkylene block copolymer 0.5 to 100-fold
Organopolysiloxane composition characterized by comprising a quantity unit. 2. The organopolysiloxane composition according to claim 1, wherein the organopolysiloxane is dimethylpolysiloxane. 3. An oil agent for treating fibers containing the organopolysiloxane composition according to claim 1 .