JP3120719B2 - Fiber treatment composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a fiber treatment composition which can impart excellent flexibility and water absorbency to fibers and is less yellowed by heat and ultraviolet rays.

[0002]

2. Description of the Related Art
Various organopolysiloxanes such as dimethylpolysiloxane, epoxy-containing polysiloxane, and aminoalkyl-containing polysiloxane are widely used as treatment agents for imparting flexibility and smoothness to various fiber products. Aminoalkyl group-containing polysiloxane is most often used because it can provide particularly good flexibility.

[0003] However, the fiber treating agent containing an aminoalkyl group-containing polysiloxane as a main component has a serious disadvantage that the color tone of the treated product changes to yellow because the aminoalkyl group is oxidized by heat or ultraviolet rays. doing.

As measures for remedying the above-mentioned drawbacks, for example, with respect to yellowing, aminoalkyl group-containing polysiloxanes and organic acid anhydrides or chlorides (JP-A-57-101076) and epoxy compounds (JP-A-59-179988). Japanese Patent Application Publication), higher fatty acids (Japanese Patent Application Laid-Open No. 1-306683),
It has been proposed to modify an aminoalkyl group by reacting with carbonate (JP-A-2-47371) or the like.

[0005] In general, a treated product with an aminoalkyl group-containing polysiloxane is water-repellent, and therefore, even if the fiber originally has water absorbency, it shows hydrophobicity after being treated. There was also a disadvantage that it was almost lost. Regarding the provision of water absorption, a combination of an aminoalkyl group-containing polysiloxane and a polyether-containing carboxylic acid is disclosed in Japanese Patent Application Laid-Open No. 1-606682.
Japanese Patent Application Laid-Open No. S59-5959), an aminoalkyl group and a polyoxyalkylene group are contained in the same polysiloxane molecule.
Japanese Patent Publication No. 179887), and the reaction of an aminoalkyl group-containing polysiloxane with a polyoxyalkylene glycidyl ether compound (Japanese Patent Publication No. 64-1588).

[0006] However, although the above-mentioned measures for improving yellowing have an improvement in discoloration as compared with the aminoalkyl group-containing polysiloxane before modification, the effect is still insufficient and the treated fiber has a smoothness. There is a drawback that the inherent properties of the aminoalkyl group-containing polysiloxane, which imparts the same, are impaired.

[0007] In addition, although the improvement of the water absorption described later improves the water absorption, it has a drawback that the flexibility, smoothness and the like are greatly reduced. Furthermore, when the polyoxyalkylene group is increased in order to make the obtained polyoxyalkylene group-containing organopolysiloxane an aqueous solution, the water absorption becomes good, but the flexibility becomes insufficient, and conversely, the polyoxyalkylene group is reduced. With respect to (1), an emulsifier is required, and in that case, flexibility is insufficient, and at present, both characteristics have not been satisfied.

[0008] Accordingly, there is a demand for the development of a fiber treating agent composition which has good effects on imparting flexibility and water absorption to treated fibers and low yellowing.

The present invention has been made in view of the above circumstances,
In addition to giving the treated fiber excellent flexibility and water absorption,
It is an object of the present invention to provide a fiber treatment composition which has very little yellowing due to heat, ultraviolet light, or the like.

[0010]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that an aminoalkyl group-containing polysiloxane represented by the following general formula (1) and By compounding in combination with an amide group-containing ether carboxylic acid having a limited structure represented by the formula (2), there is almost no yellowing due to heat, ultraviolet rays, etc., and the treated fiber is not yellowed. The present inventors have found that a fiber treatment composition capable of simultaneously imparting excellent flexibility and water absorbability to fibers can be obtained, and the present invention has been accomplished.

Accordingly, the present invention provides (1) an aminoalkyl group-containing organopolysiloxane represented by the following general formula (1): (2) an amide group-containing ether carboxylic acid compound represented by the following general formula (2): A fiber treatment composition characterized by comprising:

[0012]

Embedded image Wherein R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, A
Is -R ^1- (NR ² CH ₂ CH ₂ ) _a NR ³ R ⁴ (R ¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms, R ² , R ³ , and R ⁴ are each a hydrogen atom and 1 carbon atom. 8 is a monovalent hydrocarbon group or an acyl group, a is a number from 0-4.) in the group represented, X is R, a or -OR ⁵ (R ⁵ is 1 to hydrogen atom or a carbon atoms 8 is a monovalent hydrocarbon group). m is 5
Is a positive number of ２０００2000, n is a positive number of 0-100, and n =
In the case of 0, at least one of X is A. ]

[0013]

Embedded image (Where R ⁶ is a monovalent hydrocarbon group having 6 to 24 carbon atoms,
R ⁷ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, B is an alkylene group having 2 to 4 carbon atoms, and p is an integer of 0 to 20. )

Now, the present invention will be described in further detail. The first component of the fiber treatment composition of the present invention is an aminoalkyl group-containing organopolysiloxane represented by the following general formula (1).

[0015]

Embedded image Wherein R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, A
Is -R ^1- (NR ² CH ₂ CH ₂ ) _a NR ³ R ⁴ (R ¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms, R ² , R ³ , and R ⁴ are each a hydrogen atom and 1 carbon atom. 8 is a monovalent hydrocarbon group or an acyl group, a is a number from 0-4.) in the group represented, X is R, a or -OR ⁵ (R ⁵ is 1 to hydrogen atom or a carbon atoms 8 is a monovalent hydrocarbon group). m is 5
Is a positive number of ２０００2000, n is a positive number of 0-100, and n =
In the case of 0, at least one of X is A. ]

In the above formula (1), R is a group having 1 to 2 carbon atoms.
0, preferably 1 to 6 monovalent hydrocarbon groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl,
Dodecyl group, tetradecyl group, alkyl group such as octadecyl group, vinyl group, alkenyl group such as allyl group, cyclopentyl group, cycloalkyl group such as cyclohexyl group,
Aryl groups such as phenyl, tolyl, and naphthyl;
-Phenylethyl group, aralkyl groups such as 2-phenylpropyl group and the like, and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms or any organic groups can be mentioned, among which alkyl groups, An alkenyl group and an aryl group are preferred, and a methyl group is particularly preferred. R in one molecule may be the same or different.

A is -R ^1- (NR ² CH ₂ CH ₂ ) _a
NR ³ R ⁴ (R ¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms, R ² ,
R ³ and R ⁴ are each a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms or an acyl group, and a is a number of 0 to 4. )
Is a group represented by Here, as the divalent hydrocarbon group having 1 to 8 carbon atoms for R ¹ , for example, an alkylene group such as a methylene group, a dimethylene group, a trimethylene group, and a tetramethylene group is preferable, and a trimethylene group is particularly preferable. R ² ,
R ³ and R ⁴ are each a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms or an acyl group, for example, a hydrogen atom, an alkyl group such as a methyl group, an ethyl group or a propyl group, or an aryl group such as a phenyl group; , A cycloalkyl group such as a cyclohexyl group, and an acyl group such as an acetyl group and a benzoyl group. a is a number from 0 to 4.

[0018] X is a group represented by R, A or -OR ^5. R ⁵ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, for example, a hydrogen atom, a methyl group, an ethyl group, an alkyl group such as butyl group, and an aryl group such as a phenyl group.

In the above equation (2), when n = 0, at least one of X must be A.

M is 5 to 2000, preferably 10 to 50
When it is less than 5, the effect of imparting flexibility and smoothness becomes insufficient, and when it is more than 2,000, the effect of imparting water absorbency becomes insufficient and emulsification becomes difficult. n is 0 to 10
0, preferably a positive number from 0.5 to 10, and n is 100
If it is larger, the effect of imparting flexibility becomes insufficient.

The amine equivalent of the organopolysiloxane of the above formula (1) is 500 to 10000 g / mol, particularly 1
000-5000 g / mol is preferable, and 1000 g / mol
If it is less than mol, yellowing is apt to occur and it becomes 5000 g / m.
If it exceeds ol, the flexibility is reduced.

The viscosity at 25 ° C. is 500 to 5
000 cs (centistokes).

Next, the second component is an amide group-containing ether carboxylic acid compound represented by the following general formula (2).

[0024]

Embedded image (Where R ⁶ is a monovalent hydrocarbon group having 6 to 24 carbon atoms,
R ⁷ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, B is an alkylene group having 2 to 4 carbon atoms, and p is an integer of 0 to 20. )

In the above formula (2), R ⁶ has 6 to 24 carbon atoms;
Preferably a monovalent hydrocarbon group of 8 to 18, for example, hexyl group, pentyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group , Octadecyl group and the like, and R ⁶ CO is an oleic acid residue, a renoleic acid residue, a renolenic acid residue, or the like;
Palm oil fatty acid residues, palm oil fatty acid residues, tallow fatty acid residues, and the like, which are mixed groups thereof, can also be used.
Among these, a nonyl group, an undecyl group, and a coconut oil fatty acid residue or a palm oil fatty acid residue as R ⁶ CO are preferable.

R ⁷ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and specific examples include a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group.
A methyl group is preferred.

B is an alkylene group having 2 to 4 carbon atoms,
Specific examples include an ethylene group, a propylene group, a 1,2-butylene group, and a 1,4-butylene group.

In the above formula (2), (BO) _p represents that p mole of alkylene oxide having 2 to 4 carbon atoms is added. The alkylene oxide may be used in combination of two or more (random addition or block addition), but is preferably ethylene oxide. Here, p is an integer of 0 to 20, preferably 0 to 10.

In the present invention, the mixing ratio of the aminoalkyl group-containing organopolysiloxane of the above formula (1) and the amide group-containing ether carboxylic acid compound of the above formula (2) is determined based on the formula (1). The amide group-containing ether carboxylic acid of the above formula (2) is used in an amount of 0.1 to 10 mol, especially 0.2 to 5 mol, per 1 mol of the primary or secondary amino group of the aminoalkyl group in the organopolysiloxane. It is preferable to add an acid compound. If the amount is less than 0.1 mol, the effect of preventing yellowing and the effect of imparting water absorption may be lost. If the amount exceeds 10 mol, flexibility and texture may be deteriorated.

The fiber treatment composition of the present invention may be added with other fiber agents, for example, a wrinkle-preventing agent, a flame retardant, an antistatic agent, a heat-resistant agent, etc., as long as the properties are not impaired. Absent. In addition, the addition amount of these optional components can be a usual amount as long as the effect of the present invention is not hindered.

The fiber treatment composition of the present invention comprises the first
Two components are essential components.When treating various fiber products using this fiber treatment agent composition, adjust to the desired concentration by diluting in a solvent or diluting with water, dipping, spraying, roll coating It is preferable that the composition of the present invention is used by dissolving the composition in an organic solvent or by adding a cationic or nonionic surfactant to emulsify in water. Is preferred.

In this case, examples of the organic solvent include toluene, xylene, n-hexane, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, and mineral terpene.

Examples of the cationic surfactant include octyltrimethylammonium hydroxide,
No.4 such as dodecyltrimethylammonium hydroxide
Examples include quaternary ammonium hydroxide and salts thereof. Specific examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene phenol ether, and polyoxyalkylene sorbitan alkyl ester.

The amount of the surfactant to be used is preferably 5 to 50 parts, more preferably 10 to 30 parts, per 100 parts (parts by weight, hereinafter the same) of the first component organopolysiloxane. The amount of water used may be any amount, but generally, the concentration of the organopolysiloxane is 5 to 60% by weight, particularly 10% by weight.
Preferred is an amount that results in ４０40% by weight.

As the emulsifying method, a usual method can be adopted. For example, the first and two components are mixed with an emulsifier and water, and the mixture is emulsified by an emulsifying machine such as a homogenizer, a colloid mill, and a line mixer. .

When various fiber products are treated with the composition of the present invention as described above, the amount of adhesion varies depending on the fiber product and is not particularly limited. It is generally in the range of from 0.01 to 10% by weight. After adhering to the treated cloth, it may be dried by blowing with hot air, heating or the like.
Hot air blowing or heat treatment at 00 to 150 ° C. for 2 to 4 minutes is suitable.

Further, the fiber treatment composition of the present invention is not particularly limited to the fiber or fiber product to be treated.
It is effective for natural fibers such as silk, hemp, wool, angora, mohair, etc., as well as synthetic fibers such as polyester, nylon, acryl, spandex, and fiber products using these.

[0038]

Industrial Applicability The fiber treating composition of the present invention can impart excellent flexibility and water absorption to treated fibers and can prevent yellowing of treated fibers.
It can be widely used for processing natural fibers such as silk, hemp, wool, angora and mohair, synthetic fibers such as polyester, nylon, acrylic and spandex, and fiber products using these.

[0039]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. All parts in each example are parts by weight, and the viscosity is a value at 25 ° C.

Example 1 1 part of an amino group-containing organopolysiloxane (viscosity: 750 cs, amine equivalent: 1900 g / mol) represented by the following formula (3) and an amide group-containing ether carboxylic acid represented by the following formula (4) A treatment bath was prepared by blending 1.7 parts (5 times mol based on the total NH) and 97.3 parts of toluene.

[0041]

Embedded image

After immersing T / C broad, polyester knit cloth and fluorescent-treated cotton broad in the obtained treatment bath, squeezing using a roll at a squeezing rate of 100%, and then at 100 ° C. for 2 minutes. Further, heat treatment was performed at 150 ° C. for 2 minutes.

The flexibility of the T / C broad cloth after the treatment was evaluated by touch according to the following criteria. ：: Extremely flexible texture with slimy feeling. Δ: The texture is slightly coarse and hard with a slimy feeling and the core remains. ×: A texture with coarse hardness and no flexibility at all.

Next, a water drop of about 50 μl was placed on the treated polyester knit cloth with a dropper, and the time until the water drop was absorbed by the cloth was evaluated to evaluate the water absorption. The time required to complete the process was 0.5 seconds or less, demonstrating that the water absorption was extremely good.

For cotton broad, color difference meter
The measured value was -8.5. The substance itself was subjected to a heat treatment at 180 ° C. for 5 minutes, and the B value was measured. As a result, it was −6.3, and almost no yellowing was observed.

Example 2 1 part of an amino group-containing organopolysiloxane (viscosity 30 cs, amine equivalent 1000 g / mol) represented by the following formula (5) and an amide group-containing ether carboxylic acid represented by the above formula (4) 0.7 parts (all N
H (1 mol per mol of H) and 98.3 parts of toluene to prepare a treatment bath.

[0047]

Embedded image

Example 3 1 part of an amino group-containing organopolysiloxane (viscosity: 850 cs, amine equivalent: 1500 g / mol) represented by the following formula (6) and an amide group-containing ether carboxylic acid represented by the above formula (4) A treatment bath was prepared by blending 1.3 parts (3 times mol based on the total NH) and 97.7 parts of toluene.

[0049]

Embedded image

Comparative Example 1 One part of an amino group-containing organopolysiloxane represented by the above formula (3) and the following formula (7)
Was mixed with 1.7 parts of ether carboxylic acid represented by the formula (5 moles to the total NH) and 97.3 parts of toluene to prepare a treatment bath.

[0051]

Embedded image

Comparative Example 2 One part of the amino group-containing organopolysiloxane represented by the above formula (3) was added to the following formula (8)
And 1.4 parts of polyoxyalkylene glycidyl ether represented by
A treatment bath was prepared by mixing 7.6 parts.

[0053]

Embedded image

Comparative Example 3 One part of an amino group-containing organopolysiloxane represented by the above formula (3) and the following formula (9)
Was mixed with 1 part of glycidyl alcohol (15 moles based on the total NH) and 98 parts of toluene to prepare a treatment bath.

[0055]

Embedded image

Comparative Example 4 A treatment bath was prepared by mixing 1 part of the organopolysiloxane represented by the above formula (5) and 99 parts of toluene.

The obtained treatment bath was measured for flexibility, water absorption and yellowing in the same manner as in Example 1. Table 1 shows the results.

From the results shown in Table 1, it was found that when treated with the fiber treating agent composition of the present invention, a cloth which was excellent in flexibility and water absorption and hardly yellowed was obtained.

[0059]

[Table 1]

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-1-306682 (JP, A) JP-A-4-327269 (JP, A) JP-A-61-296184 (JP, A) JP-A-1-306682 306683 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D06M 13/00-13/535 D06M 15/00-15/715

Claims (2)

(57) [Claims] (1) An aminoalkyl group-containing organopolysiloxane represented by the following general formula (1): Wherein R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, A
Is -R ^1- (NR ² CH ₂ CH ₂ ) _a NR ³ R ⁴ (R ¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms, R ² , R ³ , and R ⁴ are each a hydrogen atom and 1 carbon atom. 8 is a monovalent hydrocarbon group or an acyl group, a is a number of 0-4. group represented by), X is the R, a or -OR ⁵ (R ⁵ is 1 number hydrogen or C ~ 8
Is a monovalent hydrocarbon group. ). m is a positive number from 5 to 2000, and n is a positive number from 0 to 100. When n = 0, at least one of X is A. (2) Amide group-containing ether carboxylic acid compound represented by the following general formula (2): (Where R ⁶ is a monovalent hydrocarbon group having 6 to 24 carbon atoms,
R ⁷ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, B is an alkylene group having 2 to 4 carbon atoms, and p is an integer of 0 to 20. ). A fiber treatment composition comprising: 2. The amide group-containing ether carboxylic acid compound of the above formula (2) is added to the aminoalkyl group-containing organopolysiloxane of the above formula (1) with respect to 1 mol of the primary or secondary amino group of the aminoalkyl group. The fiber treating agent composition according to claim 1, which is incorporated in an amount of 0.1 to 10 mol.