JPS6146588B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to improvements in silicone-based fiber treatment agents, and particularly to a fiber treatment agent composition that can be applied to various fibers to process fibers with markedly improved durability. When silicone-based fiber treatment agents are applied to fibers, they give the fibers a unique and desirable texture, as well as flexibility and water repellency, so they are applied to various fibers as fiber treatment agents and are used in a wide range of fields. It is widely used. However, this silicone-based fiber treatment agent has the disadvantage that it easily falls off from the fiber surface due to washing or friction, and has poor durability in fiber processing. This fact confirms that the silicone-based fiber treatment agent is not strongly adhered or bonded to the fiber surface, but is merely physically weakly attached or adsorbed. Therefore, research to improve silicone-based fiber treatment agents has mainly focused on overcoming these drawbacks, and attempts have been made to fix them using resin treatment agents such as melamine-based resins and glyoxal-based resins. In some cases, the expected durability was not obtained, or the texture, flexibility, water repellency, etc. were impaired, and the treatment effect of the silicone-based fiber treatment agent was significantly reduced. It's not working. The present inventors have developed a method to provide durability, such as improved resistance to washing and dry cleaning, by firmly bonding the silicone component to the fiber surface without impairing the inherent excellent properties of the silicone fiber treatment agent. As a result of numerous experimental studies, we have learned that the objective can be effectively achieved by combining a silicone-based fiber treatment agent and an isocyanurate-based compound. That is, the present invention provides (a) an average composition formula A _a (CH ₃ ) _b SiO [wherein A is an amino group-containing or substituted amino group-containing hydrocarbon group, an epoxy group-containing compound residue, a hydroxycarbonyl group-containing compound residue, quaternary ammonium salt-containing compound residue, polyether-containing compound residue, hydrogen atom, hydroxyl group, hydrolyzable group, or saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, a is 0 <a1.00, and (a+b) is within the range of 1.90 to 2.10] 100 parts by weight of an organopolysiloxane represented by (b) general formula [Wherein, X is a hydroxyl group, an epoxy group, or R _1o Y _3-o Si—
group (where R ¹ is a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, Y is a hydrolyzable group,
n is 0, 1 or 2) and m is 2, 3 or 4] 0.1 to 2.0 parts by weight of an isocyanurate compound, and (iii) tin, platinum, zinc, titanium, zirconium, aluminum. , a metal compound such as manganese, an organic acid salt, and an organic metal salt. The first component (a) used in the composition of the present invention is:
It is an organopolysiloxane represented by the above average composition formula, and is a silicone fiber treatment agent component known as a treatment agent suitable for imparting various functions to fibers, such as flexibility, water repellency, and water absorption. be. A in the above compositional formula is a hydrogen atom, a hydroxyl group,
Groups that can be easily hydrolyzed by contact with water, such as hydrolyzable groups such as methoxy, ethoxy, acetoxy, and isopropenoxy groups, and carbon atoms of 1 to 6 such as vinyl, allyl, or phenyl groups.
can be a saturated or unsaturated hydrocarbon group,
It may also be a compound residue containing an amino group, an epoxy group, a hydroxycarbonyl group, a quaternary ammonium salt, a polyether, or the like. Such residues include, for example, H ₂ NCH ₂ −CH ₂ −CH ₂ −
group, _H2N - _CH2 - _CH2 -NH- _CH2 - _CH2 - _CH2-
basis,

[Formula] Amino such as a group or a substituted amino group-containing hydrocarbon residue,

[Formula] Group

[Formula] Epoxy group-containing compound residue such as group, HO-CO-CH ₂ -S-CH ₂ -CH ₂ - group,

[Formula] Residue of a compound containing a hydroxycarbonyl group such as a group, CN(CH ₃ −) ₃ −CH ₂ −CH ₂ −CH ₂ −
basis, Quaternary ammonium group-containing compound residues such as _CH3 -O-( _CH2 -CH2 _- O) ¹⁰ - _CH2 - _CH2-
CH ₂ − group, Examples include residues of polyether-containing compounds such as. Further, a in the formula satisfies O<a1.00 and satisfies the range of a+b=1.90 to 2.10. As the organopolysiloxane of component (a), those having a viscosity at 25° C. ranging from a few centitokes to several tens of millions of centitokes can be used. Further, in the organopolysiloxane of component (a), A in the above average composition formula may be a single type, or may be a mixture of two or more types. Furthermore, the chemical structure of the organopolysiloxane may be linear, branched, or three-dimensional network. Component (b) used in the present invention is an isocyanurate compound given by the above general formula, where X is a hydroxyl group, an epoxy group, a vinyl group, or
It is a silyl group represented by R _1o Y _3-o Si-. R ¹ in the silyl group is a saturated or unsaturated monovalent hydrocarbon group having 1 to 6 carbon atoms, and specific examples include methyl group, ethyl group, propyl group,
Examples include vinyl group, allyl group, phenyl group, and cyclohexyl group. Further, Y is a hydrolyzable group, and examples thereof include alkoxy groups such as methoxy, ethoxy, and phenoxy groups, acyloxy groups such as acetoxy, oxime groups such as acetoxime and butanoxime, and substituted vinyloxy groups such as isopropenoxy. can do. n is 0,
1 or 2, preferably 0 or 1.
Further, m is 2, 3, or 4. A specific example of a silyl group is

【formula】

【formula】

[Formula] can indicate a group, etc. These silyl group-containing isocyanurate compounds can be produced by conventionally known methods. That is, it can be prepared by carrying out an addition reaction between a silane compound having a ≡Si-H bond and an isocyanurate compound containing an unsaturated bond. Note that even if some unreacted substances are present during production, the effects of the present invention are not impaired in any way. Typical compounds included in component (b) include, for example: etc. can be mentioned. In addition, the substance (c) used in the present invention is a curing catalyst for silicone fiber treatment agents, and is particularly a metal compound such as tin, platinum, zinc, titanium, zirconium, aluminum, manganese, etc. Included are organic acid salts and organometallic salts.
Examples of curing catalysts containing these metals include diptyltine dilaurate, dioctyltin dioctoate, chloroplatinic acid, tetrabutyl titanate, zirconium naphthenate, and manganese naphthenate. The composition of the present invention is a combination of component (a) and component (b), or a combination of components (a), (b), and (c), and the proportions of these components are such that silicone of component (a) The isocyanurate compound (component (b)) is used in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the fiber treatment agent. The amount of isocyanurate used in combination is 0.1% by weight
If it is less than 20% by weight, the effect of improving the durability of the treatment agent will be insufficient, and if it exceeds 20% by weight, the treatment agent's inherent effect of imparting texture, flexibility, etc. to the fibers will be reduced, which is not preferable. A preferred amount range is from 0.1 to 20 parts by weight, particularly preferably from 0.1 to 10 parts by weight. In addition, the metal-containing curing catalyst of component (c) does not have to be used in combination, but it is preferable to use them together because it enhances the treatment effect of the silicone fiber treatment agent of component (a). Amounts of up to about 20 parts by weight per 100 parts by weight are advantageously used. If the amount exceeds 20 parts by weight, the curing speed of the silicone-based treatment agent will be too fast and the properties of the fiber treatment agent will be impaired, which is not preferable. A preferred combination amount is 0.1 to 10 parts by weight. When the composition of the present invention is applied to textile products, it is used in the form of an organic solvent solution, a dispersion of this solution in another organic solvent, or an aqueous emulsion. As the solvent for the above-mentioned organic solvent solution, any organic solvent that can simultaneously dissolve all the components in combination, such as aromatic, halogenated hydrocarbon, ketone, alcohol, or ether, can be used. Further, in the preparation of an aqueous emulsion, a nonionic, cationic or anionic surfactant is used, and the emulsion can be easily prepared by a commonly known emulsion method. The fiber treatment composition of the present invention, which is a combination of the above-mentioned components (a) and (b) or (a), (b), and (c), is usually prepared into a liquid mixture containing these predetermined combined components. is,
The fibers are conveniently treated with the preparation. However, in the composition of the present invention, it is not necessary to apply each of these components to fiber treatment using the same composition liquid; for example, a single component liquid for each component is prepared separately, and a predetermined amount of each is used to sequentially treat fibers. can do. For example, after first treating the fibers with a preparation containing component (b),
The liquid containing component (a) and the liquid containing component (c) may be treated sequentially in predetermined amounts, or a liquid containing predetermined amounts of each component may be mixed in advance, or a predetermined amount of each of component (i) and (c) may be treated. It can also be treated with a concentration preparation solution. Or ingredients
After treating the fibers with a mixed solution to which predetermined amounts of each of (a) and component (b) have been added, or a portion of both of these components or a reaction solution in which a sufficient condensation reaction has taken place, the fibers are treated with a prepared solution of component (c). Multi-stage processing methods such as processing can be advantageously employed. Since the effects of the present invention can be similarly obtained by any of these fiber treatment methods, the treatment composition of the present invention also includes such treatment methods. As a treatment means for applying the combined fiber treatment agent of the present invention to fibers, any means applicable to ordinary fiber processing, such as padding method, roll coating method, spray method, knife coating method, etc., can be used. In addition, more desirable results can often be obtained if heat treatment is performed after the treatment, and the temperature of the heat treatment is 50℃ to 180℃.
A range of is advantageously employed. The composition of the present invention can be applied to various fiber materials such as cotton,
Natural fibers such as wool, silk, linen, polyester,
Excellent effects can be obtained when applied to synthetic fibers such as nylon, polyamide, and acrylic, recycled fibers such as rayon and acetate, inorganic fibers such as glass fiber and carbon fiber, and blends thereof. The improving effect of the composition of the present invention can be obtained by combining a silicone-based fiber treatment agent and an isocyanurate-based compound, and in this combination, the compound of component (b) It strengthens the bond with the processing agent and significantly improves the durability of fiber processing, and in that case,
Silicone-based fiber processing agents are highly desirable agents because their processing effects, such as flexibility, antistatic properties, and water repellency, are not substantially reduced. The composition of the present invention is not only easy to apply to fibers, but also effectively eliminates the drawbacks of conventional silicone-based fiber treatment agents and has excellent resistance to normal washing and dry cleaning. This is extremely desirable in practice since the treatment effect is maintained over a long period of time. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 Average composition formula 30 parts by weight of methylhydrodiene polysiloxane, 2 parts by weight of a cationic surfactant, acetic acid
A mixture consisting of 0.2 parts by weight and 65.8 parts by weight of water was emulsified using a colloid mill to prepare Base-1. Next, 30 parts by weight of Zn(OAc) ₂ , 3 parts by weight of the same cationic surfactant used in the emulsion preparation of Base-1, and 67 parts by weight of water were mixed and emulsified using a colloid mill. 2 was prepared. Also, the expression 30 parts by weight of an isocyanurate compound represented by
3 parts by weight of the cationic surfactant used in the preparation of Base-1 and 67 parts by weight of water were mixed and emulsified in the same manner using a colloid mill to prepare Base-3. Using the single-component emulsified dispersion base liquid thus prepared, two types of fiber treatment agent compositions were prepared in the following weight proportions. Mixed components Fiber treatment agent composition Base-1 5 5 Base-2 2 2 Base-3 1 - Water 92 93 Each of the prepared treatment agent compositions was used as a treatment bath for fiber treatment, and a fiber treatment test was conducted in the following manner. I did it. That is, a polyester/cotton blend broadcloth (blend ratio 65/35) is immersed in a bath, and the squeezing rate is 80.
Squeeze using a roll to make 100%
After pre-drying at 150°C for 2 minutes, it was heat-treated at 150°C for 2 minutes. Next, the heat-treated cloth was subjected to a washing test based on JIS-103 method. Further, the water repellency of the test cloth washed in this way was measured according to JISL-1079. The relationship between the number of washings and water repellency is shown in the following table, comparing the treatment composition of the present invention and a comparative composition.

[Table] As is clear from the results in the table above, it can be seen that silylated isocyanurate compounds contribute to significantly improving the adhesion durability of silicone fiber treatment agents. Example 2 Formula Amino silicone and formula represented by Using an isocyanurate compound represented by and toluene as a dissolving solvent, a treatment agent composition () with the following weight ratio was prepared, and for comparison, a composition () to which no isocyanurate compound was added was prepared. A comparative test was conducted.

[Table] Broad cotton cloth was soaked in each of these treatment solutions, squeezed with a mangle roll to a squeezing rate of 100%, and dried by heating at 130°C for 2 minutes. Each of the treated fabrics obtained by treatment with the treatment agent was washed 10 times and the decrease in softness was measured. Their flexibility was measured using a Uenoyama type texture meter manufactured by Uenoyama Kiko Co., Ltd. The results are shown below.

[Table] As shown above, it can be seen that there is a significant difference in durability. Example 3 Average composition formula Organopolysiloxane with unterminated OH represented by
20 parts by weight, average composition formula A base consisting of 3 parts by weight of methylhydrodiene polysiloxane and 77 parts by weight of toluene was prepared. This base, dioctyltin dilaurate as a curing catalyst, and the formula A treatment solution was prepared by blending the isocyanurate compound represented by the following composition, and this was coated with a knife on Tetron taffeta cloth so that the coating amount was 5 g/ ^m2 , and preheated at 100℃ for 2 minutes. After drying, it was further heat-treated at 150°C for 2 minutes. After this, normal washing was performed. When the water pressure resistance of the cloth thus treated was measured according to JISL-1079, the following results were obtained.

【table】

[Table] As shown above, it can be seen that the isocyanurate compound contributes not only to improving durability but also to significantly improving the initial water pressure resistance value.

Claims (1)

[Claims] 1(a) Average compositional formula A _a (CH ₃ ) _b SiO〓〓〓〓 [In the formula, A is an amino group-containing or substituted amino group-containing carbohydrate hydrogen group, an epoxy group-containing compound residue, A hydroxycarbonyl group-containing compound residue, a quaternary ammonium salt-containing compound residue, a polyether-containing compound residue, a hydrogen atom, a hydroxyl group, a hydrolyzable group, or a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms. and a is 0<a1.00,
and (a+b) is within the range of 1.90 to 2.10] 100 parts by weight of an organopolysiloxane represented by (b) General formula [Wherein, X is a hydroxyl group, an epoxy group, a vinyl group, or
R _1o Y _3-o Si- group (however, R ¹ has 1 to 6 carbon atoms
saturated or unsaturated hydrocarbon group, Y represents a hydrolyzable group, n is 0, 1 or 2), m
is 2, 3 or 4] and (c) tin, platinum, zinc, titanium, zirconium,
A fiber treatment composition comprising 0 to 20 parts by weight of a curing catalyst selected from the group consisting of metal compounds such as aluminum and manganese, organic acid salts, and organic metal salts.