JP2709370B2 - Fiber treatment composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a fiber treatment composition, and particularly to a fiber product which has been subjected to a flame retardant treatment, without reducing the flame retardancy, without reducing the smoothness, The present invention relates to a fiber treatment composition capable of improving flexibility and giving a good texture.

[Conventional technology]

BACKGROUND ART Conventionally, silicone-based fiber treatment agents have been widely used for treating fiber products made of various natural fibers and synthetic fibers to improve their properties, for example, smoothness and flexibility, and to impart good texture. . Examples of the silicone fiber treating agent include those containing dimethylpolysiloxane as a main component, those containing amino group-modified organopolysiloxane as a main component (Japanese Patent Publication No. 59-26707), and those for softening polyester wadding. As a treating agent, an amino group-modified organopolysiloxane and an epoxy compound as essential components (Japanese Patent Publication No. 48-17514), high-molecular-weight dimethylpolysiloxane blocked with a silanol group at the end, alkoxysilane and condensation A catalyst comprising a reaction catalyst (JP-B-51-37996) is known. However, when a fiber product subjected to recent flame retarding treatment with these conventional fiber treating agents is treated, the flame retardancy may be reduced. Accordingly, as a fiber treatment agent which does not relatively reduce flame retardancy, those comprising amino group-modified organopolysiloxane having a relatively low viscosity (Japanese Patent Publication No. 57-43673) and those comprising phosphate ester-modified organopolysiloxane ( Japanese Patent Publication No. 62-61219) is known.

[Problems to be solved by the invention]

However, when treated with a fiber treating agent comprising the above-mentioned low-viscosity amino group-modified organopolysiloxane or phosphate ester-modified organopolysiloxane, the texture or the like is reduced to some extent without reducing the flame retardancy of the flame-retarded fiber. Although it could be improved, the improvement of the feeling was not yet sufficient.

Accordingly, an object of the present invention is to provide a good texture without reducing the flame retardancy of the flame-retarded fiber in response to the recent progress of the advanced flame retardant treatment of the fiber. It is to provide a fiber treatment composition.

[Means for solving the problem]

Means for Solving the Problems The present invention provides a composition I: (A) (A) an average composition formula (I): Wherein R ¹ represents a monovalent aliphatic unsaturated hydrocarbon group, R ² represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group or a lower alkoxy group; 0 <a <3, b is a number of 0 <b <3, provided that 1 <a + b <3], and the aliphatic unsaturated hydrocarbon group represented by R ¹ in one molecule is represented by the following formula: A room temperature liquid organopolysiloxane containing at least one and (B) an average composition formula (II): [Wherein, R ³ is the same as R ² , and Z is a group represented by the following formula (II
I): —R ⁴ NH—R ⁵ _n NR ⁶ R ⁷ (III) (where R ⁴ and R ⁵ may be the same or different and are a divalent hydrocarbon group having 1 to 8 carbon atoms) , R ⁶ and R ⁷ may be the same or different and each have a hydrogen atom or 1 to carbon atoms.
20 is a monovalent hydrocarbon group, n is an integer of 0 to 3), c is a number satisfying 0 <c ≦ 1, and d is 0
<D <3, where 1 <c + d <3], wherein at least one organic group represented by Z is contained in one molecule and the organopolysiloxane is a liquid at room temperature. The present invention provides a fiber treatment composition comprising 100 parts by weight of at least one selected liquid organopolysiloxane, (b) a platinum compound, and 0.0001 to 1.0 parts by weight of platinum, and (c) an organic solvent alone.

Further, as another composition for solving the above-mentioned problem, the composition II: (a) the same organopolysiloxane (A) and organopolysiloxane (B) as in the composition I described above.
100 parts by weight of at least one liquid organopolysiloxane selected from the group consisting of: (b) the same platinum compound as in the case of the composition I, 0.0001 to 1.0 part by weight as platinum, (d) water and (e) only an emulsifier It is intended to provide a fiber treatment composition comprising an emulsion.

The organopolysiloxane (A) used as the liquid organopolysiloxane which is the component (A) of the composition of the present invention is represented by the general formula (I).
In the formula, R ¹ is an aliphatic unsaturated hydrocarbon group, and examples thereof include a vinyl group and an allyl group. At least one aliphatic unsaturated hydrocarbon group is contained in one molecule of the organopolysiloxane (A), and 10% or less of all the substituents in the organopolysiloxane (A) are aliphatically unsaturated. It is preferably a hydrocarbon group. R ² represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group or a lower alkoxy group. Examples of the substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group,
Alkyl groups such as dodecyl group; aromatic hydrocarbon groups such as phenyl group and tolyl group; or part or all of the hydrogen atoms contained in these hydrocarbon groups are substituted with halogen atoms such as fluorine or cyano groups. And the like. Examples of the lower alkoxy group include a methoxy group and an ethoxy group. According to the composition of the present invention, in order to treat the fiber and obtain a soft texture,
90% of the substituent R ² possessed by the organopolysiloxane (A)
% Or more is preferably a methyl group.

These organopolysiloxanes (A) represented by the formula (I) may be used alone or in combination of two or more.

The organopolysiloxane (A) may be a liquid at room temperature, but when used in the form of an emulsion, it has a viscosity of 50 to 50 at 25 ° C. because it can be easily emulsified.
Those with 0000 cSt are preferred.

The production of the organopolysiloxane (A) can be carried out according to a method known in the art. For example, the reaction can be carried out by reacting an organopolysiloxane compound containing no aliphatic unsaturated hydrocarbon group and an organopolysiloxane compound containing an aliphatic unsaturated hydrocarbon group using a catalyst.

Examples of the organosiloxane compound containing no aliphatic unsaturated hydrocarbon group include, for example, octamethylcyclotetrasiloxane and the like. Examples of the organosiloxane compound containing an aliphatic unsaturated hydrocarbon group include, for example, the following formula: And the like.

As the catalyst used, for example, an alkaline substance,
Examples include an acidic substance, tetramethylammonium hydroxide, tetrabutylphosphonium hydroxide, and the like.

When an alkaline substance is used as a catalyst, the reaction mixture may be heated to about 120 to 160 ° C. while stirring to react, and after the reaction, the alkaline substance may be neutralized with an acidic substance. Examples of the alkaline substance used as the catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide and the like. Examples of the acidic substance used for neutralization include formic acid, acetic acid, hydrochloric acid, sulfuric acid, and ethylene chlorohydrin.

When the reaction is carried out using an acidic substance as a catalyst, the reaction mixture may be heated at room temperature while stirring, and after the reaction, the acidic substance may be neutralized with an alkaline substance. Examples of the acidic substance used as the catalyst include sulfuric acid, fuming sulfuric acid, methsulfonic acid, trifluoromethanesulfonic acid, and trifluoroacetic acid. Examples of the alkaline substance used for neutralization include sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide and the like.

When tetramethylammonium hydroxide or tetrabutylphosphonium hydroxide is used as a catalyst, the reaction mixture is heated to about 100 to 120 ° C. while stirring to cause a reaction.
The catalyst component may be decomposed and deactivated at 0 to 160 ° C.

Specific examples of the organopolysiloxane (A) include, for example, the following formula: And the like.

The organopolysiloxane (B) used as the liquid organopolysiloxane which is the component (A) of the composition of the present invention is represented by the general formula (II).
In the formula, R ³ is the same as the above ² , and Z is the following formula (II
I): —R ⁴ NH—R ⁵ _n NR ⁶ R ⁷ (III) (where R ⁴ and R ⁵ may be the same or different and are a divalent hydrocarbon group having 1 to 8 carbon atoms) Examples thereof include an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, and a hexamethylene group; an arylene group such as a phenylene group, etc. R ⁶ and R ⁷ may be the same or different; It is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include the same substituted or unsubstituted hydrocarbon groups as those exemplified for R ² , and a cycloalkyl group such as a cyclohexyl group.
Is an integer of 0 to 3). c is a number satisfying 0 <c ≦ 1, d is 0
<D <3, where 1 <c + d <3.

These organopolysiloxanes (B) represented by the formula (II) may be used alone or in combination of two or more.

In order to treat the fibers with the composition of the present invention and obtain a soft texture, it is preferable that 90 mol% or more of all the substituents of the organopolysiloxane (B) are methyl groups.

The organopolysiloxane (B) may be liquid at room temperature, but when used in the form of an emulsion, it has a viscosity at 25 ° C of 10 to facilitate emulsification.
Those having 0 to 500,000 cSt are preferred.

Further, at least one organic group represented by the formula (III) is contained in one molecule of the organopolysiloxane (B), and the fiber is treated with the composition of the present invention to improve the texture. In order to obtain a good composition, 5 mol% or less of the total organic groups contained in the organopolysiloxane (B) is represented by the formula (II)
It is preferably an organic group represented by I).

The production of the organopolysiloxane (B) can be carried out according to a method known in the art similar to the production of the organopolysiloxane (A). For example,
The reaction is carried out by reacting an organosiloxane compound having an organic group or an aralkoxysilane compound represented by the formula (III) with an organosiloxane compound having no organic group at a predetermined ratio using a catalyst. Can be.

Examples of the organosiloxane compound having an organic group represented by the formula (III) used include, for example, the following formula: And the like. Examples of the alkoxysilane compound include, for example, And the like.

Examples of the organopolysiloxane compound having no organic group represented by the formula (III) include, for example, octamethylcyclotetrasiloxane, and hexamethylditetrasiloxane as an organosiloxane compound at the molecular chain end of the obtained organopolysiloxane. Siloxane and the like.

As the catalyst to be used, for example, the same alkaline substance, tetramethylammonium hydroxide, tetrabutylphosphonium hydroxide and the like as those used for the production of the organopolysiloxane (A) can be mentioned.

The reaction temperature is about 120 to 160 ° C, and the reaction time is about 4 to 8 hours. After completion of the reaction, the catalyst may be neutralized with the above-mentioned acidic substance or may be thermally decomposed.

Specific examples of the organopolysiloxane (B) include, for example, the following formula: And the like.

The production of the organopolysiloxanes of the above (A) and (B) is carried out according to the above-mentioned aliphatic unsaturated hydrocarbon group and formula (III).
And a cyclic siloxane such as octamethylcyclotetrasiloxane, a compound having an organic group represented by the formula (V
Organopolysiloxane represented by I) or the like or a formula: [Where q is a positive integer] is prepared by emulsifying in water using an emulsifier and then reacting with dimethylpolysiloxane represented by the following formula. It can also be used as the liquid organopolysiloxane of component (a). When the organopolysiloxane of (A) is produced by this method, it can be carried out by emulsion polymerization using an anionic emulsifier or a cationic emulsifier described below, and the production of the organopolysiloxane of (B) is as follows.
It can be carried out by emulsion polymerization using a cationic emulsifier described below. As the catalyst used, sodium hydroxide,
Strongly alkaline substances such as potassium hydroxide, rubidium hydroxide, and tetraalkylammonium hydroxide are exemplified.

In the case where the organopolysiloxane (A) or (B) is produced by this method, the sulfate of the anionic emulsifier in the emulsion is converted to the acid form by using an acid-functional ion exchange resin as required. Or emulsified with sulfuric acid,
Add an acidic substance such as hydrochloric acid, for example, 40-80 ° C. 12-48
After the reaction for a time, the organopolysiloxane (A) or (B) can be prepared as an emulsion polymerization latex by neutralizing with the above-mentioned alkaline substance. The obtained emulsion polymerization latex can be used as it is or as a liquid organopolysiloxane (a) by mixing it with another organopolysiloxane (A) and / or (B).

Examples of the platinum compound that is the component (b) of the composition of the present invention include chloroplatinic acid, alcohol-modified chloroplatinic acid obtained by modifying chloroplatinic acid with alcohol, and chloroplatinic acid together with a vinyl group-containing low-molecular siloxane. Platinum-vinylsiloxane complexes, platinum black, complexes of chloroplatinic acid and olefins or aldehydes, etc. obtained by heat treatment can be exemplified.

Examples of the alcohol used for preparing the alcohol-modified chloroplatinic acid include ethanol, propanol, butanol, octanol and the like.

The mixing ratio of the platinum compound of the component (b) in the composition of the present invention is 0.0001 to 1 part by weight, preferably 0.001 to 0.05 part by weight of platinum based on 100 parts by weight of the component (a).

In order to use the composition of the present invention for the treatment of textiles, the components (a) and (ii) are each diluted with an organic solvent (c) to an appropriate concentration to prepare a solution, May be used as a mixture at the time of treatment, or an emulsion obtained by emulsifying component (a) and component (b) in water, which is component (d), using a suitable emulsifier (e). They may be mixed and used when processing fiber products in the form.

The emulsifier used is not particularly limited, and examples thereof include nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, and glycerin fatty acid ester;
Anionic emulsifiers such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and sodium polyoxyethylene ether carboxylate; and cationic emulsifiers such as quaternary ammonium salts.

The treatment of the fiber product with the fiber treatment composition of the present invention is performed by attaching the composition of the present invention to the fiber product by a method such as dipping, padding or spraying, and then using a mangle, a centrifugal separator, or the like to use an excess treatment liquid. Is removed, the amount of the composition to be applied is adjusted, and drying or heating is performed. The heating temperature may be usually about 100 to 180 ° C, and the heating time may be about 2 to 30 minutes.

Further, the composition of the present invention is a component that suppresses the activity of the platinum compound, for example, in order to suppress an undesirable reaction such as a reaction in which the platinum compound of the component (b) is oxidized during storage or processing of a textile product. , An amine compound, a phosphorus compound, a sulfur compound, an ethynyl group-containing compound, or the like may be added in trace amounts.

The fiber treatment composition of the present invention can improve the smoothness, flexibility, etc., of any fiber product, and can impart a good texture. In the treatment, a good texture can be imparted without reducing the flame retardancy of the textile product. For example,
The present invention can be applied to various types of fiber products such as wadding made of polyester fiber containing a flame retardant component in a molecular structure, wadding made of allyl fiber or nylon fiber, and natural fiber such as cotton fiber and wool fiber product. In addition, these fiber products can be applied in any form such as a filament, a thread, a cloth, a knitted fabric manufactured using these fibers, and the like. Further, the present invention can be applied to inorganic fibers such as glass fibers, carbon fibers, and aramid fibers. In addition to textile products, it can be used as a surface treatment agent for flame-retarded paper products and synthetic resin molded products.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples.

Preparation Example 1 1,3-Divinyl-1,1,
18.6 g of 1,3,3-tetramethyldisiloxane, 129 g of 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane and octamethylcyclotetrasiloxane
After charging 2094 g, 0.2 g of potassium hydroxide was charged and heated at 150 ° C. for 4 hours with stirring under a nitrogen atmosphere to cause a reaction. Next, after adding 1.2 g of ethylene chlorohydrin to neutralize potassium hydroxide in the reaction mixture, the reaction mixture was heated under reduced pressure at 140 ° C./10 mmHg to remove low molecular weight substances, and the viscosity at 25 ° C. Is 950 cSt, the following average composition formula: A vinyl group-containing organopolysiloxane represented by the following formula was obtained.

To 30 parts by weight of the obtained vinyl group-containing organopolysiloxane, 5 parts by weight of polyoxyethylene nonylphenyl ether and 65 parts by weight of water were added, emulsified and dispersed using a homomixer, and then 200 kg / cm ² using a homogenizer. To obtain an emulsion (a).

Preparation Example 2 General formula in a reactor with an internal volume of 3 having a stirrer: Amino group-containing cyclic organopolysiloxane 3 represented by
After charging 2.0 g, 16.2 g of hexamethyldisiloxane and 2190 g of octamethylcyclotetrasiloxane, 0.17 g of potassium hydroxide was charged, and the mixture was stirred for 1 hour in a nitrogen stream.
The reaction was carried out by heating at 40 ° C. for 6 hours. Next, after adding 1.2 g of ethylene chlorohydrin and stirring for 1 hour to neutralize potassium hydroxide in the reaction mixture, the mixture was heated under reduced pressure at 140 ° C./10 mmHg for 2 hours to remove low molecular weight substances. And the following formula: And an amino group-containing organopolysiloxane having a viscosity at 25 ° C. of 1200 cSt was obtained.

To 30 parts by weight of the obtained amino group-containing organopolysiloxane, 5 parts by weight of polyoxyethylene nonylphenyl ether and 65 parts by weight of water were added, emulsified and dispersed using a homomixer, and then 200 kg / cm ² using a homogenizer. To obtain an emulsion (b).

Comparative Preparation Example 1 5 parts by weight of polyoxyethylene nonylphenyl ether and 65 parts by weight of water were added to 30 parts by weight of methyl hydrogen polysiloxane represented by the following formula, and the mixture was emulsified and dispersed using a homomixer, and then 200 kg / cm ² using a homogenizer. To obtain an emulsion (c).

Comparative Preparation Example 2 After adding 30 parts by weight of the isocyanurate compound represented by 5 parts by weight of polyoxyethylene nonylphenyl ether and 65 parts by weight of water, and emulsifying and dispersing using a homomixer,
Using a homogenizer, the mixture was uniformly dispersed at a pressure of 200 kg / cm ² to obtain an emulsion (d).

Examples 1 to 3 and Comparative Examples 1 to 5 In each example, the above Preparation Examples 1 to 2 and Comparative Preparation Example 1
Emulsions (a), (b), (c) obtained in
(D) and 10 parts by weight of a 2% butanol solution of chloroplatinic acid were mixed with an emulsifier polyoxyethylene nonylphenyl ether 90
A self-emulsifiable composition containing 0.0753% by weight as a platinum component, which was prepared by dissolving it in parts by weight, and dimethyl poly having a molecular chain end blocked by a hydroxyl group and having a viscosity of 10,000 cSt at 25 ° C. Emulsion (e) prepared from 30 parts by weight of siloxane, 5 parts by weight of polyoxyethylene noniphenyl ether and 5 parts by weight of water was blended as shown in Table 1 to obtain a treatment liquid comprising a liquid composition.

Examples 1 to 3 and Comparative Examples 1 and 4 were added to the obtained processing solutions.
In ~ 5, polyester wadding treated with flame retardant by kneading the flame retardant was immersed for 10 seconds, and the excess treatment liquid was removed using a centrifugal separator.
For 20 minutes to obtain a treated polyester wadding.

The flexibility of the treated polyester wadding was evaluated by the following method, and the flame retardancy was evaluated by the following method. In Comparative Example 2, the flexibility and the flame retardancy were evaluated without treating the stuffed cotton subjected to the flame retarding treatment and the stuffing cotton not subjected to the flame retarding treatment in Comparative Example 3 with the composition. The results are shown in Tables 1 and 2.

Flexibility The cotton wadding after the treatment was touched by hand, and the flexibility was evaluated based on the following criteria.

A: extremely soft and smooth B: soft and smooth C: slightly soft D: rough and hard E: extremely rough and hard flame retardant After unraveling evenly using a loading device, filling in a wire mesh box with dimensions of 10 × 15 × 1.5 cm, then place the wire mesh box in the horizontal direction.
Tilt to a 45 ° angle, 1.5 cm at 2 cm from the bottom of the box
The tip of the flame of a propane-Bunsen burner adjusted to a length of cm was applied, and (i) the time until the cotton melted and a through hole was formed in the thickness direction; and (ii) the through hole was formed. At that time, the size (length × width) of the through hole after removing the burner was measured.

[Effects of the Invention] The fiber treatment composition of the present invention can be used to treat a fiber product to improve its smoothness and flexibility, thereby imparting a texture. In particular, by treating a fiber product that has been subjected to flame retardancy, it is possible to impart a texture by improving smoothness, flexibility, etc. without reducing the flame retardancy, and to add value to the fiber product. Can be increased.

Continuation of front page (56) References JP-A-52-63961 (JP, A) JP-B-57-43673 (JP, B2) JP-B-59-26707 (JP, B2) JP-B-1-14345 (JP, A) , B2) Jikku Sho 61-46588 (JP, Y2)

Claims (2)

(57) [Claims] (1) (A) (A) Average composition formula (I): Wherein R ¹ represents a monovalent aliphatic unsaturated hydrocarbon group, R ² represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group or a lower alkoxy group; 0 <a <3, b is a number of 0 <b <3, provided that 1 <a + b <3], and the aliphatic unsaturated hydrocarbon group represented by R ¹ in one molecule is represented by the following formula: A room temperature liquid organopolysiloxane containing at least one and (B) an average composition formula (II): [Wherein, R ³ is the same as R ² , and Z is a group represented by the following formula (II
I): —R ⁴ NH—R ⁵ _n NR ⁶ R ⁷ (III) (where R ⁴ and R ⁵ may be the same or different and are a divalent hydrocarbon group having 1 to 8 carbon atoms) , R ⁶ and R ⁷ may be the same or different and each have a hydrogen atom or 1 to carbon atoms.
20 is a monovalent hydrocarbon group, n is an integer of 0 to 3), c is a number satisfying 0 <c ≦ 1, and d is 0
<D <3, where 1 <c + d <3], wherein at least one organic group represented by Z is contained in one molecule and the organopolysiloxane is a liquid at room temperature. 100 parts by weight of at least one selected liquid organopolysiloxane, (b) a platinum compound, 0.0001 to 1.0 parts by weight of platinum, and (c) a fiber treatment composition comprising only an organic solvent. (A) (A) Average composition formula (I): Wherein R ¹ represents a monovalent aliphatic unsaturated hydrocarbon group, R ² represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydroxyl group or a lower alkoxy group; 0 <a <3, b is a number of 0 <b <3, provided that 1 <a + b <3], and the aliphatic unsaturated hydrocarbon group represented by R ¹ in one molecule is represented by the following formula: A room temperature liquid organopolysiloxane containing at least one and (B) an average composition formula (II): [Wherein, R ³ is the same as R ² , and Z is a group represented by the following formula (II
I): —R ⁴ NH—R ⁵ _n NR ⁶ R ⁷ (III) (where R ⁴ and R ⁵ may be the same or different and are a divalent hydrocarbon group having 1 to 8 carbon atoms) , R ⁶ and R ⁷ may be the same or different and each have a hydrogen atom or 1 to carbon atoms.
20 is a monovalent hydrocarbon group, n is an integer of 0 to 3), c is a number satisfying 0 <c ≦ 1, and d is 0
<D <3, where 1 <c + d <3], wherein at least one organic group represented by Z is contained in one molecule and the organopolysiloxane is a liquid at room temperature. 100 parts by weight of at least one selected liquid organopolysiloxane, (b) platinum compound 0.0001 to 1.0 part by weight as platinum (d) water and (e) a fiber treatment composition comprising an emulsion comprising only an emulsifier.