JPH0351375A - Treating of fibrous material - Google Patents

Abstract

PURPOSE: To impart yellowing resistance, softness, water repellency, slipperiness and the like to synthetic fibers or the like by treating them with an amino- containing organosiloxane consisting of the reaction product of an organopolysiloxane having a specific unit with a monoepoxide. CONSTITUTION: A composition applicable to a fiber material consisting of an emulsion of an amine-containing organosilicone is obtained by reacting an organopolysiloxane having units expressed by formula I or II [X is a <=8C monovalent hydrocarbon; R is a divalent alkylene, R<1> is H or a group of the formula; RZ (Z is NHX, NH2 , NHRNH2 or the like): a=1, 2; b=2, 3], especially a linear polydiorganosiloxane containing 100-500 siloxane units in which 80% of the X groups are methyl, and 1-10 mol% of the siloxane units are formula III with a monoepoxide of formula IV (n=0-8). When synthetic or natural fibers are treated with the composition, yellowing resistance, softness, water repellency, slipperiness, wrinkle resistance and the like are imparted to them.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for treating fibrous materials, and more specifically to a method for treating textile materials.

When we say textile materials, we mean synthetic fibers or naturally occurring fibers, such as wool, cotton,
Polyester, carbon and mixtures thereof.

The present invention relates not only to the treatment of the fiber type itself, but also to the treatment of fabrics or textiles to which the fiber type has been added.

[Prior Art and Problems] It is known to treat textile materials with compositions containing amine-containing silicone compounds in order to impart desired properties, such as flexibility, water repellency, slipperiness and wrinkle resistance. For example, GB 1.491.747 provides a composition comprising 1 part of certain aminosilanes and 1 to 20 parts of certain epoxysiloxanes for the treatment of synthetic fibers. There is. British patent cylinder 1,296,
No. 136, the process consists of treatment with a composition comprising: a) a mixture of an aminosiloxane and a polyepoxide, b) a mixture of a liquid epoxysiloxane and a polyamine, or C) a mixture of a liquid epoxysiloxane and an aminosiloxane. , provides a method for treating organic synthetic textile fibers. However, these materials tend to impart some yellowing to the treated fibers. U.S. Pat. No. 4,757,121 discloses that when treating synthetic fibers made with cotton wadding, 5-95% by weight of an amino-substituted organopolysiloxane and 95-5% by weight of another amine-substituted organopolysiloxane are used. It is proposed that the problem of yellowing can be solved by using a composition comprising 100 parts by weight of a combination of two organopolysiloxanes consisting of %. The composition is the reaction product of a liquid amino-substituted organopolysiloxane and a liquid organic epoxy compound, 1 to 50 parts by weight of an epoxy-containing alkoxysilane and 1 to 50 parts by weight of a monoepoxy compound.

By limiting the amine-containing organosiloxane to those pre-reacted with a monoepoxide, the inventors achieved the following:
It has been found that improved treatment compositions are obtained.

Means for Solving the Problems] Accordingly, the present invention provides, as a single amine-containing organosilicone compound, at least one unit of the formula -m, and a compound of the general formula 04--Si
A method for treating textile materials comprising applying to textile raw materials a composition containing a reaction product of an organopolysiloxane having at least one unit of Xb = 1- and one or more monoepoxides. [wherein, X
is a monovalent carbon having up to 8 carbon atoms [wherein, X represents a divalent alkylene group, and R' is a hydrogen atom or a formula R-2
(In the formula, Zl, tNHX, Nl2, N)IRN) represents a group of 1m or 1m represents NHRNHX, and a is 1 or 2
, and b has a value of 2 or 3.

The organopolysiloxane used in the preparation of the reaction product is a siloxane polymer having at least one unit of the general formula % and at least one unit having the general formula Although small amounts of units resulting in branching of the siloxane may be used, preferably substantially linear polydiorganosiloxane polymers, this should not be present in excess of 5% of the total amount of units. Such a unit has the -shell structure 03 SiX 7- , in which the substituent X can be any hydrocarbon group having up to 8 carbon atoms, such as an alkyl, aryl, alkenyl, alkylaryl and arylalkyl group. Preferred X groups are lower alkyl groups. Preferably at least 80%, optimally substantially all, of the X groups are methyl groups.However, small amounts of other substituents such as hydroxyl or alkoxy groups are It can be present in contact with a silicon atom. The R group is a divalent alkylene group, preferably having up to 8 carbon atoms, optimally 3 to 8 carbon atoms. An example of a base is
Includes dimethylene, propylene, isobutylene and hexylene. The R' group is hydrogen or has the formula RZ, where Z
may represent a primary or secondary amine group or a diamine of the formula NIIRNH2 or NHRNIIX), the fact that a has a value of 1 or 2 means that the unit can be placed in a siloxane chain; Or it means that it can be a terminal unit of a siloxane chain. Examples of amine-containing substituents include 0Si(CHs)(CHz
)JHz,0Si(CHs)CHzCH(CI,)CI
28Hz, 0Si(CH3)CHzCH(CHi)CH
2NH (CHi) JHt, O Engineering Sr (CL) 2cLc
)I (C11,)CHzNH(CHzC113), 0
Engineering 5i (CH,)2 (CB2), NH (CH,), NH
(C) 12>, NH.

It is. The other units of the organopolysiloxane are of the general formula % where b has a value of 2 or 3 and X has the same meaning as defined above. This means that the units can be present in the siloxane chain or as end groups of the chain. Preferably, the polydiorganosiloxane has from 10 to 1000 siloxane units, in particular from 100 to 500 units, optimally around 400 units may be used; the viscosity of the polydiorganosiloxane imparts to the treated material tends to determine flexibility;
The higher the viscosity, the more flexible the finished product will be. However, for practical reasons it is preferred to use materials that are liquid at room temperature. Also, all siloxane units are 0
．． It is preferable that 1 to 20 mol % is a unit of formula %, more preferably 1 to 10 mol %
%, optimally from 1 to 4%, a particularly advantageous amount is 2%. Amounts exceeding 10% cannot be expected to have any further beneficial effects on the treated material. Organopolysiloxanes suitable for the preparation of the reaction products used in the process of the invention are known in the art. and many are commercially available. These are obtained by methods known in the art, for example by condensation of amino-functional silanes or their hydrolysates with cyclic siloxanes in the presence of end-stopping units such as those obtained with hexamethyldisiloxanes. can be manufactured.

The monoepoxide used to prepare the reaction product is an organic compound with one epoxy group.

The term epoxy refers to a group consisting of an oxirane oxygen bonded to two adjacent carbon atoms. Monoepoxides suitable for use in the present invention are those in which the substituents on the adjacent carbon atoms described above are It is a hydrocarbon group containing hydrogen, a hydrocarbon group, an ether group, or an ester group. Preferably, one carbon atom has only hydrogen atoms.

Other carbon atoms are attached to alkyl groups ranging from methyl to straight chain alkyl groups having 21 carbon atoms.

Optimally, the alkyl group has 1 to 10 carbon atoms, especially 1 to 4 carbon atoms.

Examples of suitable monoepoxides include ethylene oxide, propylene oxide, butadiene monoxide, 2,3-epoxycyclopentane, 'Il-substituted olefin oxides such as 2,3-epoxypropylbenzene, epoxy alcohols such as glycidol,
2.3-epoxycyclopentanol, 3.4-epoxy-6-methylcyclo-\xylmethane, glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether or glycidyl esters such as glycidyl acetate. Preferably, the general formula (wherein n is 0 to 20, preferably 0 to 8, optimally O
A monoepoxide with a value of ~3) is preferred.

The reaction products used in the process of the invention can be prepared by known methods, for example by reacting the two reagents together in the presence of a low molecular weight aliphatic alcohol or in the presence of a catalytic amount of water. I can do it. The reaction can be carried out in the presence of such a catalyst at room temperature, but is preferably carried out at elevated temperatures, such as 50°C or higher.

To make the reaction easier to handle, it can be carried out in the presence of a solvent. This solvent may be an alcohol as mentioned above or other suitable solvent. The amount of monoepoxide used in the reaction should be such that no more than 10% of all amine groups of the polyorganosiloxane are present in the reaction product as non-reactants.

Where primary amine groups are present in the organopolysiloxane, two monoepoxide molecules can react with the amine. Although it is preferred that the majority of the amino groups in the reaction product be tertiary amine groups, the presence of enough secondary amine groups to exclude tertiary amines is also suitable. The amine groups of the reaction product are thus tertiary, secondary,
It can be a mixture of these or one or both of these with up to 10% of the primary amine groups.

What is important is that the reaction product used in the process of the invention is not simply a mixture of the polydiorganosiloxane and the monoepoxide. Mere mixtures containing polydiorganosiloxanes with a relatively large amount of primary amine groups are undesirable since they will still exhibit yellowing of the treated material, and the use of these two in the presence of water, e.g. using emulsions, is Even in mixtures of two components, the absence of primary amines in the reaction product is undesirable since the yellowing caused by treatment with such mixtures or emulsions is a worse result than with the treatment of the process of the invention. suitable. Optimally, secondary amines are also absent from the reaction product.

The method of the invention comprises the application to textile materials of a composition comprising the reaction product described above as the sole amine-containing compound. This application can be done in any convenient manner. Suitable methods of application include bagging, dipping and spraying the composition containing the reaction product. The composition used may be in any form, such as a solution, dispersion or emulsion. Although the dispersion can be an aqueous or solvent-based material, it is preferred that the emulsion is an oil-in-water emulsion. Particularly preferred are emulsions, in particular the microemulsions (+1c
Compositions useful in the method of the present invention may contain other ingredients useful in fibrous material treatment compositions, such as fatty acid softeners. Other ingredients in the emulsion such as surfactants are also useful.

However, preferably the composition does not contain any amine-containing compounds other than the reaction product.

Operation The method of the invention is suitable for treating both naturally occurring and synthetic fibers, such as carbon fibers, polyester fibers, cotton fibers and mixtures of cotton and polyester fibers. This application can be carried out during the fiber production stage, the fabric production stage or after the special treatment stage N, for example during the washing of the woven fabric.

This application can be done after drying at room temperature or at elevated temperatures. It is preferred that the drying step is followed by a further heat treatment of the fibrous material; this latter is particularly useful when the woven fabric is treated during its manufacture. The presence of small amounts of primary amines in the reaction product increases the durability of the final textile materials, especially when they are subjected to washing operations. Textile materials and fabrics treated by the method of the invention have a yellowish color due to the treatment. It has improved softening and skewering properties, comfortable feel and handling without exacerbating spoilage.

A further aspect of the invention is that a fibrous material treated by the method of the invention is provided.

Also included are fabrics or fabrics to which fibers have been added when treated in the method of the invention.

[Example] In the following, the invention will be illustrated by means of a number of examples.

All parts are by weight unless otherwise stated.

In the presence of 95 parts of methanol, 3 parts of isopropanol and 2 parts of water, at a temperature of 50 °C, the average formula % formula %) (wherein R is -CH2CII(CHz)) CH2NIIC
1 molar part of a polydiorganosiloxane compound of the average formula (representing tl-CHs) where n is 0.1.3.7 and 9 for Examples 1.2.3.4 and 5, respectively ) was reacted with 2 molar parts of monoepoxide.

This gives the average formula (% formula %) where R' is -CH, C11C112NCR2CII
(CH2)nCH.

C1l, CIIl, CH.

) was obtained.

A bath was prepared with a 2,77% perchloroethylene solution of the reaction products prepared in Examples 1-5 and polyester-cotton (6
5/35) was treated by padding. After treatment, the piece was heated to 110°C for 1 minute, followed by 180°C for 2 minutes. The piece was impregnated with 0.5% by weight of the reaction product.

In the presence of 95 parts of methanol, 3 parts of isopropanol and 2 parts of water, at a temperature of 50 °C, the average formula % formula %) )CH,NHC
1 molar part of a polydiorganosiloxane compound of the average formula (representing H2Cl-12NH2) where n is 0.1.3.7 and 9 for Examples 6.7.8.9 and 10, respectively. was reacted with 6 molar parts of a monoepoxide containing

This gives an average formula% formula%) (where R' is CH CHzCHC112N(CIl2)2N[CIIzCt
l(CHz)ncll*)]2CH,CH2Cl(CI
□)ncI'! .

CH ) was obtained.

A bath was prepared with a 2.77% perchloroethylene solution of the reaction products prepared in Examples 6-10, and polyester-cotton (
65/35) pieces were treated by padding. After treatment, the piece was heated to 110°C for 1 minute, followed by 180°C.
Heat at ℃ for 2 minutes. The piece was impregnated with 0.5% by weight of the reaction product.

11-15 In the presence of 95 parts of methanol, 3 parts of isopropanol and 2 parts of water, at a temperature of 50 °C, the average formula % formula % () (where R is -CH2C11(CH,)C112N) I
1 mole part of a polydiorganosiloxane compound of the average formula (where n is Example 11.12.13.14 and 15)
Oll, 3.7 and 9 respectively). This gave a reaction product which appeared to have an average formula (% formula %) (where R' represents 0H CH ).

A bath was prepared with a 2.77% perchlorethylene solution of the reaction products prepared in Examples 11-15 and a piece of polyester-cotton (65/35) was treated by padding. After treatment, the pieces were heated at 110°C for 1 minute and then at 18°C.
Heat at 0°C for 2 minutes. The piece was impregnated with 0.5% by weight of the reaction product.

16-20 in the presence of 95 parts of methanol, 3 parts of isopropanol and 2 parts of water at a temperature of 50 °C, with the average formula % formula % (wherein R is -(C112)lNltcH2cH2NH
1 molar part of a polydiorganosiloxane compound of the average formula (where n is Example 16.17.18.19 and 20
0, 1, 3, 7 and 9 respectively). This gives the average formula % formula %) (where R' is CH CI+2CHzCHJ(C1t2)2N[cllzcl
I(CH2)ncH3)]zCH2C8(C112)n
CH.

CH ) was obtained.

A bath was prepared with a 2.77% perchlorethylene solution of the reaction products prepared in Examples 16-20 and a piece of polyester-cotton (65/35) was treated by padding. After treatment, the pieces were heated at 110°C for 1 minute, followed by heating at 18°C.
Heat at 0°C for 2 minutes. The piece contains 0.5 of the reaction product.
Impregnated by weight%.

21-22 In the presence of 95 parts of methanol, 3 parts of isopropanol and 2 parts of water, at a temperature of 50 °C, the average formula % formula % (wherein R is -(CH2Cl(CB,)CH2)NHC
One mole part of a polydiorganosiloxane compound (representing H, CH2NH2) was reacted with 24 mole parts of a monoepoxide having the formula. This gives the average formula% formula%): (where R' is 11 CH2C11(CHff)CH3S(CI+2>2N[
CH2Cl1CH2C113]2CI12CHCH,C
H.

CH A reaction product believed to have the following formula was obtained.

A bath was prepared with a microemulsion containing 1.4% of the reaction product prepared in Example 21 and a piece of polyester-cotton (65/35) was treated by padding. After treatment, the pieces were heated to 110"C for 90 seconds, followed by 180"C for Examples 21 and 22, respectively.
Heat at 150°C for 2 minutes and 150°C for 5 minutes. The piece is
1% and 0.5% by weight of the reaction product were impregnated, respectively.

Fire "1 special λ" CH, O), 5i (CHi) C) I2CH (CL) C
1 mole of H2NH (C1, >2NH2 and methanol was added to the reaction vessel. 1.2 mole of 1,2 butylene oxide was added to the reaction vessel.
1 mole was added through the addition funnel and the mixture was heated at 50° C. maintained under a nitrogen blanket for 1 hour. This product was stripped on a rotary evaporator under reduced pressure. 1 mole of this product was mixed with 3 moles of water and heated at 110°C to cause condensation of the silane. After purification,
Hexamethyldisiloxane and cyclic dimethylsiloxane were added along with an alkaline catalyst.

This mixture was heated at 140°C for 5 hours, followed by neutralization. The reaction product after p filtration has the formula %formula%) (wherein R' is HCl12CI(CH,)CH2NHCI1.C)lcH
2c11°). This reaction product was added to a piece of polyester-cotton according to the method described in Example 22.

Ratio 11K''2: Top Blade - Prepare a bath with a 2.77% perchloroethylene solution of only the amine-containing polydiorganosiloxane used in Examples 11-15 and pad a piece of polyester-cotton (85/35). It was processed by The piece was impregnated with 0.5% by weight of siloxane. (Comparative Example 1) Comparative Example 1 was carried out in the same manner as in Comparative Example 1 except that a mixture of 1 mole part of the polyorganosiloxane of Comparative Example 1 and 2 mole parts of propylene oxide was used, but no reaction occurred. (Comparative Example 2) Comparative Example 3 was the untreated polyester-cotton (blank) piece used in Examples 11 to 15.

A bath was prepared with only the 2.77% perchlorethylene solution of the amine-containing polydiorganosiloxane used in Examples 16-20, and a piece of polyester-cotton (65/35) was treated by padding. The piece is made of siloxane.
It was impregnated with 5% by weight. (Comparative Example 4) Comparative PA5 was the untreated polyester-cotton (85/35) piece used in Examples 16-20.

Comparative Example 6 was a microemulsion consisting of a mixture of the two reactants of Example 21 in the same proportions and concentrations, and a piece of polyester-cotton (65/35) was treated by padding. The piece was impregnated with 1% by weight of siloxane.

Comparison fP47 was a microemulsion of only the amine-containing polydiorganosiloxane of Example 21 at the same concentration, and a piece of polyester-cotton (65/35) was treated by padding. The piece was impregnated with 1% by weight of siloxane.

Comparative Example 8 was the untreated polyester-cotton (blank) piece used in Example 21.

Comparative Example 9 was the untreated polyester-cotton (blank) piece used in Examples 22 and 23.

Comparative Example 10 is a microemulsion containing only the amino-containing polyorganosiloxane of Example 22 at the same concentration,
A piece of polyester-cotton (65/35) was treated by padding. The piece was impregnated with 0.5% by weight of siloxane.

11 pieces of treated polyester-cotton for all comparative examples.
Heated at 0°C for 1 minute, followed by 2 minutes at 180°C for Comparative Examples 1-8 and 5 minutes at 150°C for Comparative Examples 9 and 10. The treated pieces of polyester-cotton from Examples 1 to 23 were compared for their softness and effect on yellowing. Increasing the molecular weight of the siloxane polymer used also increased the softness of the treated material. Within each series of similar molecules, the highest softness was obtained by materials with values of n=o, 1 or 3.

The whiteness index of Examples 16-20 was measured using Hunterlab Optical Sensor Model D25M (Hunterlab Optical Sensor Model D25M).
optical 5sensor D25M) and compared with Comparative Examples 4 and 5. The following results were obtained.

17 71.618
74.819
74.020 73.
3 Comparative Example 4 62.5 Comparative Example 5 75.7 The whiteness index of Example 11 is Hunterlab optical sensor model D25M () Hunterlab optical 5enso
r 025M) and compared with Comparative Examples 1.2 and 3. The following results were obtained for the whiteness index of Example 21 using the Hunter Lab Optical Sensor. Model D25M (Hunterlab optical 5ensor
025M) and compared with Comparative Examples 6.7 and 8. The following results were obtained Knee Maru 1 Ken - pressure chromatography [2172,6 Comparative Example 6 65.1 Comparative Example 7 58.0 Comparative Example 8 76.4 A. The whiteness index of Examples 22 and 23 was determined by Hunter Love optical sensor model D25M (Hunterlab
optical 5sensor 025M) and compared with Comparative Examples 9 and 10. The following results were obtained. It can be seen that a treated material is obtained which has almost no yellowing when compared to the material treated by and has a whiteness very close to that of the untreated material.

Claims (1)

[Claims] 1. The single amine-containing organosilicone compound in the composition contains at least one unit of the general formula O_3_-_a_/_2SiXa-R-NH-R' and the general formula O_4_-_b_/_
2Si-Xb [wherein, X represents a monovalent hydrocarbon having up to 8 carbon atoms, R represents a divalent alkylene group, and R' is a hydrogen atom or ,NH_2,NHR
NH_2 or NHRNHX), a has a value of 1 or 2, and b has a value of 2 or 3]; 1. A method for treating textile materials, comprising applying to the textile materials a composition consisting of an amine-containing organosilicone compound, characterized in that it is a reaction product with a monoepoxide. 2. In the organopolysiloxane, at least 80% of all X groups are methyl groups, and 1 to 10 mol% of all siloxane units
is the formula O_3_-_a_/_2SiXa-R-NH-R
' is a substantially linear polydiorganosiloxane containing 100 to 500 siloxane units, and the monoepoxide has a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, n is 0 8. Method according to claim 1, characterized in that the method has a value of .about.8. 3. Most of the amine groups in the reaction product are tertiary amine groups, and the primary amine groups present in this reaction product are 10
3. A method according to claim 1 or 2, characterized in that the method does not exceed %. 4. The method according to any one of claims 1 to 3, characterized in that the composition is in the form of an emulsion. 5. Fabrics loaded with fibers, characterized in that the fibers have been treated by the method according to any one of claims 1 to 4.