JPH0247371A - Silicone-based softening agent composition for textile - Google Patents

Abstract

PURPOSE:To obtain the subject composition to be applied to a textile product to impart said textile with excellent softness and stretchability without causing the yellowing and discoloration of the fiber by using a specific silicone oil as a main component. CONSTITUTION:The objective softening agent composition composed of a re-modified silicone oil can be produced by reacting an amino-modified silicone oil of formula [m and l are >=1; n is 0 or >=1; R is CH3 or OCH3; X is (CH2)3NH (CH2)2NH2 or (CH2)3NH2; Y is (CH2)3N(Z)(CH2)2NHZ, (CH2)3NH(CH2)2NHZ or (CH2)3NHZ; Z is COOCH(R')CH2OH (R' is H or CH3)] with ethylene carbonate and/or propylene carbonate. The composition exhibits excellent softness and stretchability and low thermal yellowing tendency compared with conventional softening agent.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silicone-based softener composition for textiles, and particularly to a silicone-based softener composition for textiles that does not cause yellowing or discoloration of textile products. .

[Conventional technology]

Silicone-based compositions have been widely used as fiber treatment agents to impart good flexibility, smoothness, and other textures to textile products, as well as water repellency. Compositions based on so-called silicone oils, such as dimethylpolysiloxane or methylhydrogenpolysiloxane, have been used.

In recent years, the demands on the texture of textile products have diversified, and there has been differentiation such as ultra-soft processing, gloss processing, deep color processing, water absorption processing, etc.
Demand for high added value is increasing, and for this reason, compositions whose main component is modified silicone oil modified with dimethylpolysiloxane have come to be used.

There are various types of such modified silicone oils, but among them, compositions whose main component is organopolysiloxane modified with a 7-minoalkyl group, that is, amino-modified silicone oil, are as follows:
Since it imparts excellent flexibility, smoothness, and stretch back properties to fibers, its usage has been increasing significantly in the field of soft processing of textile products.

[Problem d that the invention seeks to solve]

However, the above-mentioned amino-modified silicone oil has the disadvantage that the 7-mino group is oxidized and yellows when exposed to ultraviolet rays during heating during the dry lamp treatment process of textile products or during use and storage of textile products. This has the problem of causing yellowing or discoloration in white or light-colored textile products, which impairs their commercial value.

For this reason, oil-based softener compositions and dimethylpolysiloxane-based softener compositions have conventionally been used for white or light-colored textile products. However, these softener compositions have a disadvantage in that their softening effect is inferior to the above-mentioned TRT compositions containing amine-modified silicone oil as a main component.

Therefore, an object of the present invention is to provide a silicone-based softener composition for textiles that eliminates the above-mentioned drawbacks of conventional 7-mino-modified silicone oils and provides excellent flexibility and stretch-back properties. be.

[Means to solve the problem]

As a result of extensive research to achieve the above object, the present inventors have discovered that by reacting some or all of the amino groups of amino-modified silicone oil with ethylene carbonate and/or propylene carbonate to further modify the amino groups, The present invention was completed based on the discovery that it is possible to prevent yellowing and discoloration without impairing the excellent properties such as flexibility and stretch-back properties unique to modified silicone oils.

That is, the present invention is directed to the general formula (where m and l are integers of 1 or more, m is O or an integer of 1 or more, and R is 10H, a group, or -I-QC).

represents a group, and X is -(CH,), NH(CH,), NH
, group or -(CH,), NH, group, and Y represents -(C
HI)IN (ZXCH,), NH2 group or bar (CH,)
, NH(CH,), NHz group or -(CH,), NH2
represents a group, 2 is -COOCI((R')CH,O)1
This is a silicone softener composition for fibers, the main component of which is a silicone oil represented by the group R' is H or -CH, and R' represents a group.

The silicone oil represented by the general formula (1) used in the silicone softener composition for textiles according to the present invention is as described above. It is obtained by reaction with ethylene carbonate and/or propylene carbonate, ie, by carbamate formation.

Amino-modified silicone oil, which is a raw material for making the silicone oil of general formula (1), has been well known and contains -(CH,), NH(CH,), and N in the molecule.
) 11 or -(CH,), NH, or an organopolysiloxane in which both of these are randomly contained,
The amine value is usually in the range of 15 to 40, and the viscosity of this silicone oil at 25°C is usually in the range of 100 to 1000.
A range of 00 cs is preferred.

The reaction between amino-modified silicone O()V and ethylene carbonate and/or propylene carbonate is carried out by mixing the two at room temperature and then heating to raise the temperature. The reaction temperature is 100
The temperature may be lower than or equal to 40°C, and preferably 40 to 80°C. Although the reaction time varies depending on the reaction temperature, 1 to 4 hours is usually sufficient.

At this time, no particular catalyst is required.

The ratio of amino-modified silicone oil to ethylene carbonate and/or propylene carbonate is based on the reactive amino 2 content in the amino-modified silicone oil.
It is preferable to use the carbonate in a proportion of 0.5 to 1 mole per 1 mole of Ir.

The decrease in the content of amino groups contained in the amino-modified silicone oil due to the above-mentioned reaction can be confirmed by measuring the total amine value and determining the ft of the amino groups to which the reaction progresses.

The degree of the above reaction, that is, the degree of carbamate formation, can be arbitrarily changed depending on the texture of the textile product provided by the desired softener composition, but if the degree of carbamate formation is low, the effect of preventing yellowing will be poor. Undesirable. Therefore, it is usually preferable to carry out carbamate conversion to such an extent that the amine value becomes 1/2 or less of the amine value of the starting amino-modified silicone oil.

The silicone softener composition for textiles according to the present invention contains a silicone oil represented by the general formula (1) as a main component, but the composition contains a small amount of, for example, 30% by weight.
Other silicone oils can be added in the following cases. These silicone oils that can be added in small amounts include dimethyl silicone oil, α,ω-dihydroxydimethyl silicone oil, epoxy-modified silicone oil, and polyalkylene oil. Examples include oxide-modified silicone oil, carboxyl-modified silicone oil, and alcohol-modified silicone oil.

By using the silicone softener composition for fibers of the present invention,
& Products can be processed using conventionally known methods, such as emulsifying and dispersing the silicone oil in water using a suitable emulsifier, or diluting it with an appropriate organic solvent, and then padding method,
It may be applied to the paper fiber product by a known method such as a coating method or a spray method and then dried, and this drying treatment may be carried out at a temperature of 70 to 170° C. within a range that does not deteriorate the fiber product.

Examples of emulsifiers that can be used in the emulsification described above include nonionic emulsifiers such as polyoxyethylene full ether and polyoxyethylene alkyl phenyl ether, quaternary ammonium salts, and ethylene oxide addition of quaternary ammonium salts. Examples include cationic emulsifiers such as

Further, as the organic solvent, the above-mentioned formula (1) according to the present invention is used.
Aromatic solvents such as benzene, toluene and xylene, which are highly compatible with silicone oil, petroleum solvents such as industrial gasoline and kerosene, chlorinated solvents such as trichlorethylene, tetrachloroethylene and trichloroethane, and Examples include various fluorinated solvents.

[Effect]

The silicone softener composition for textiles according to the present invention is obtained by carbamateing the 7-mino group of the conventional 7-mino-modified silicone oil with ethylene carbonate and/or brobylene carbonate, so the total amine value is reduced to 0 to 15. Therefore, without impairing the flexibility and stretch back properties obtained with conventional amine-modified silicone oils,
Prevents yellowing or discoloration.

〔Example〕

Examples of the present invention will be described below. The middle part of the example shows parts by weight, and the viscosity is the value at 25°C.

Example 1 In a reaction vessel, the viscosity was 1200 cs, the molecule contained -(Cl,)INH, group, and the amine value was -16.
200 g of 7-mino-modified silicone oil terminal-terminated with trimethylsiloxy units (0) and ethylene carbonate.
After mixing 1.7fi of carbonate and 2 g of propylene carbonate at room temperature, the mixture was heated to 8°C, reacted at this temperature for 2 hours, and then cooled. The amine value of the reaction product at this time was determined to be 5.2.

100 parts of the above reaction product and 77/l of polyoxyethylene
Nucor 1305 (kill ether type emulsifier)
Product name, manufactured by Nippon Nyukazai Co., Ltd.) 11 parts and New Boo 71z
14 parts of 1310 (trade name, manufactured by Nippon Nyukazai Co., Ltd.) were uniformly mixed, and 375 parts of water was gradually added dropwise to the mixture while stirring to obtain a stable emulsion (referred to as composition A).
.

Example 2 In the reaction vessel, the viscosity was 300 cs, and -
(CH,), NH (C1,),? 200 g of amino-modified silicone oil containing IH* groups and terminated with dimethoxymethylsiloxy units with an amine value of 29.5
A reaction was carried out in the same manner as in Example 1 using 3.5 g of 3JF and ethylene carbonate) and 3.5 g of propylene carbonate. The amine value of this reaction product was 10.4. This product was emulsified in the same manner as in Example 1 to obtain a stable emulsion (referred to as Composition B).

Example 3 In the reaction vessel, the viscosity was 1400 cs, and -
(CH,) JR (CH,), 200 g of amino-modified silicone oil terminal-terminated with trinothi-siloxy units containing NH* groups and having an amine value of 33.0, 3 g of ethylene carbonate, and 3.51 g of propylene carbonate.
1 was used, and the reaction was carried out in the same manner as in Example 1. The amine value of this reaction product was 14.0. This product was emulsified in the same manner as in Example 1 to obtain a stable emulsion (referred to as Composition C).

Comparative Example 1 The trimethylsiloxy-terminated amino-modified silicone oil used in Example 1 was directly emulsified in the same manner as in Example 1 to obtain a stable emulsion (referred to as Comparative Composition X).

Comparative Example 2 An emulsion containing 20% by weight of dimethylpolysiloxane with a viscosity of 10,000 cs was prepared (referred to as comparative composition Y).
.

Comparative Test ■ Composition A% B% C and comparative composition X% Y were used to compare flexibility, stretch back properties, and compressive elasticity.

(Preparation of test cloth Sample cloth: 40g of cotton broadcloth Polyester/cotton (65/35) Broad cotton mercerized knit dyed cloth Processing conditions: Dipping 1 dip, 1 nip squeezing Heavy line broadcloth 80% Polyester/cotton broadcloth 0% Cotton knit 100% Pre-dried broad 105℃ x 3 minutes Knit 105℃ x 5 minutes Heat treatment 150℃ x 3 minutes Bath concentration Silicone emulsion 3% solution (3)
The fruits are shown in Table 1.

(2) Evaluation method I) Flexibility Judgment was made using the handling method.

◎: Extremely flexible O: Good flexibility △: Slight flexibility ×: No flexibility 11) Stretch back property According to JIS L-1018, the stretching force and The elongation recovery rate during constant elongation was measured.

Test piece size (width x length): 2.5cRX 20
Distance between tym grips: ENG Oc! IL Elongation rate: 50% 1i1) Compression elasticity The compression rate and compression elastic modulus of the cotton knit were measured according to JIS r, -1018.

As described above, compositions A and B%C of the present invention exhibited stretch back properties and compressive elasticity equal to or better than comparative composition X.

Comparative Test (1) Thermal yellowing was compared using Compositions A, B, C, Comparative Compositions X and Y, and the optical brightener Hatsucol BY Conc (trade name, manufactured by Showa Kagaku Kogyo Co., Ltd.).

(1) Preparation of sample fabric Cotton broadcloth 40s was treated under the following conditions.

Soaking 1 dip, 1 nip Aperture rate: 80% Dry at 110℃ x 3 minutes Bath concentration: Fluorescent brightener 0.2% solution (2) Preparation of test cloth The sample fabric was treated under the following conditions.

Immersion 1 dip, 1 nip squeezing rate 80% Drying 110°C x 3 minutes Bath concentration Silicone emulsion 3% solution (3) Evaluation method The test fabric was heat treated at 180°C for 3 minutes, and the mask MS20
20 (Macbeth Co., Ltd. color measuring machine) was used to measure the Ll@
[Value, -value and b0 value were measured.

(4) Results It is shown in Table 2 and Table 3.

Table 2 Table 3 *- value is brightness, - value and ♂ value are red (G) - green H, respectively.
The hue change of %m-ff1 is shown.

As mentioned above, it can be seen that the composition A181C of the present invention has an extremely low degree of yellowing compared to the comparative composition X.

〔Effect of the invention〕

As is clear from the above data, the fabric softener composition according to the present invention has the same or better stretch-back properties and compressive elasticity than conventional fabric softener compositions, and has an excellent effect with an extremely low degree of yellowing. has.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, m and l are integers of 1 or more, n is 0 or an integer of 1 or more, and R is a -CH_2 group or -OCH_3 group, X is -(CH_2)_2NH(CH_2)_
2NH group or -(CH_2)_2NH_2 group,
Y is -(CH_2)_3N(Z)(CH_2)_2NH
Z group or -(CH_2)_3NH(CH_2)_2NH
Represents a Z group or a -(CH_2)_3NHZ group, where Z is -
A silicone softener composition for textiles, the main component of which is a silicone oil represented by COOCH (R') CH_2OH group, where R' represents H or -CH_3 group.