JPS6029778B2 - Composition for fiber treatment - Google Patents

Description

[Detailed description of the invention] FIELD OF THE INVENTION The present invention relates to a composition for treating fibers.

More specifically, the present invention relates to a polysiloxane composition that can impart water repellency and oil repellency to fiber materials. Conventionally, it has been widely practiced to use methylhydrogenpolysiloxane or dimethylpolysiloxane as they are, or to use them together with a curing catalyst in the form of an emulsion or organic solvent solution, and heat-treat them to impart water repellency to fiber materials. There is.

In this case, the treated fiber material exhibits practically effective water repellency, but has the disadvantage of poor oil repellency.
Therefore, in general, in order to impart twill properties to textile materials,
Usually, a special fiber treatment agent containing fluorinated hydrocarbons as a main component is used, but in this case, the treatment agent is expensive, the dilution solvent is limited, the treatment process is difficult, and the treatment process is difficult. However, the unavoidable drawback is that it imparts an unfavorable tactile feel to textile materials, especially rope fabrics for clothing.

On the other hand, in Samurai Kaisho 50-140388, a partially hydrolyzed condensate of perfluoroalkyl alkoxysilane, alkyl alkoxysilane, and diorganopolysiloxane having PH groups at both ends was used to prevent stains on inorganic materials such as slate boards and tiles. However, it is practically difficult to apply such a coating agent to textile materials, and it is also completely different from the present invention in terms of chemical composition. It is.

Furthermore, Japanese Patent Publication No. 47-38505 proposes treating an inorganic fiber cloth with an organopolysiloxane containing a trifluoro-substituted aromatic group to provide a filter cloth with good twist resistance and lubricity. in this case,
Because it is non-curing, it lacks washing resistance and hot water resistance.

In addition, Japanese Patent Publication No. 42-2637 proposes a method of making fibrous organic substances water repellent using the vapor of silane containing a perfluoroalkyl group, but even with this method, it is still difficult to control the treatment process. However, there remains the drawback that the treatment effect is not long lasting or durable.

The present inventors have conducted extensive research into a polysiloxane composition for fiber treatment that improves the drawbacks of the prior art as described above, imparts water repellency and oil repellency to fiber materials at the same time, and has a wider range of practical performance. , arrived at the present invention.

That is, the present invention provides a substantially bran-like organopolysiloxane having at least 5 mol% of A(a) units and at least three elementary-bonded hydrogen atoms in one molecule. , R is an unsubstituted hydrocarbon group having 1 to 6 carbon atoms,
[Q is a fluorinated hydrocarbon group] or {〇) {1) A substantially straight line consisting of 5 to 100 mol% units and 95 to 0 mol% units, with a poppy and a hydroxyl group bonded to an elementary atom at each end organopolysiloxane [wherein R and Q are monovalent unsubstituted hydrocarbon groups as described above], and
■ Organohydrodiene polysiloxane containing at least three elementary-bonded hydrogen atoms in one molecule
Here, the organic group is a monovalent unsubstituted hydrocarbon group] and B a catalyst for dehydrogenation condensation between poppy and elementary atom-bonded hydrogen atoms or between a silicon atom-bonded hydrogen atom and a poppy or elementary atom-bonded hydroxyl group. The present invention relates to a fiber treatment composition characterized by comprising:

In the composition of the present invention, component A is catalyzed by component B.
It dehydrogenates and crosslinks to form a durable, oil- and water-repellent cured film on the fiber. Ingredient A is ingredient
It may be used alone or in combination of component (o) (1-) and component {rho {2).Here, the component... is a component that exhibits oil repellency and water repellency, and Since it has at least three atomically bonded hydrogen atoms in one molecule,
The catalytic action of component B causes dehydrogenation and crosslinking to form a cured film on the fiber surface. Silicon-bonded hydrogen atoms usually exist in the form of stop units in the primary mirror, but they can also exist in the form of units at the ends of molecular chains.

units in the molecular chain, In addition to the unit, other diorganosyloxy Sun units may also be present.

Oil repellency is insufficient unless the unit is present in an amount of at least 5 mol % in one molecule.

When the polysiloxane is substantially linear, it is meant that it may be completely linear or slightly branched linear.

This component is usually liquid at room temperature, and preferably has a viscosity of 20 to 100,00 St at 25°C.

This component is usually used alone, but it is a diorganopolymer that has poppy and elementary atom-bonded hydroxyl groups at both ends. It may be used in combination with xane etc. This diorganopolysiloxane has
It should be noted that the organopolysiloxane of component 1} is also included. Examples of R in the unit include methyl group, ethyl group, propyl group, vinyl group, and phenyl group.

Q is CF3CH2CH2-. C2F5CQCH
2-, CF3C ratio CH2CH2-, C2F5CH2CH
2CH2-, is exemplified.

This polysiloxane is, for example, and and By co-hydrolysis of It can be easily manufactured.

Component 'o' is a component that exhibits oil repellency and water repellency like component [i], and because there is a hydroxyl group bonded to an elementary atom at the end of the molecular chain, the catalytic action of component B causes the component'
o} ■ to form a cured film on the fiber by dehydrogenation condensation and crosslinking.

The present organopolysiloxane is also substantially linear, the meaning of which has been previously described.

This component may be in a fluid state or in the form of raw rubber at room temperature.

If the unit is not present at 5 mol% or more, the oiliness will be insufficient, so it should be more than 5 mol% and at most 10
It may be 0 mol%.

R' and R'' in the unit include alkyl groups such as methyl, ethyl and octyl groups, alkenyl groups such as vinyl groups, aryl groups such as phenyl groups, 8
-Aralkyl groups such as phenylethyl group are exemplified, and R
' and R'' may be the same or different.

Ingredient 'o}■ is an ingredient'.

X1} is a crosslinking agent, organohydrogenpolysiloxane whose both ends are blocked with organic groups, diorganosiloxane/organohydrogensiloxane copolymer whose both ends are blocked with organic groups, poppy at both ends, There are organohydrogenpolysiloxanes and organohydrogencyclics that have hydrogen atoms bonded to elementary atoms, and the organic groups include methyl groups, phenyl groups,
Vinyl groups are common, and they are usually liquid at room temperature.
Ingredients【〇}【2''Usually Ingredients'Rho {1-Poppy seeds in an amount equal to or greater than the number of moles of elementary-bonded hydroxyl groups, and a sufficient amount to provide the number of moles of elementary-bonded hydrogen atoms. It is preferable.

Component B is a component necessary for the crosslinking reaction between component A and component A, and contains tin, lead, zirconium, zinc, iron, and manganese. Examples include heavy metal salts such as carboxylates, titanate esters, and platinum salts.

Specific examples include dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, tin octylate, tin dioctylate, mercaptoacetate diisooctylate, tin octylate, zinc octylate, zirconium naphthenate, manganese naphthenate, naphthene. These include iron acid, tetrabutylorthotitanate, and chloroplatinic acid. Component B is usually used in an amount of 0.1 to 2 parts by weight based on the weight of component AIO, but it can be selected as appropriate depending on its type, content of functional groups in component A, curing conditions, especially temperature. good. The fiber treatment composition of the present invention comprises component A in component A and component B, or component A in component A.

}[1], component [beating 2] and component B are easily produced by simply mixing. When treating textile materials with the compositions of the invention, suitable diluents such as acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl ketone, cyclohexanone, acetylacetone, tetrahydrofuran, dioxane, ethyl acetate, propyl acetate, butyl acetate, It is convenient to form a solution using amyl acetate, methyl propionate, ethyl propionate, dimethylformamide, dimethylacetamide, methyl selonorub acetate, etc. Depending on the situation, in addition to the above solvents, an appropriate amount of toluene may be added. It is also possible to use a mixture of commonly used solvents for organopolysiloxanes, such as xylene, inpropyl alcohol, and hexane.

Furthermore, suitable surfactants such as higher alcohol sulfate ester salts, alkylbenzene sulfonates, higher alcohol polyoxyalkylene adducts, higher fatty acid polyoxyalkylene adducts, alkylphenol polyoxyalkylene adducts, fatty acid ester polyoxyalkylene It is preferable to select an adduct and apply the composition of the present invention as an emulsion to the fiber material.

To treat the fiber material with the composition of the present invention or its diluted solution in an organic solvent or emulsifier as described above, methods used in conventional fiber treatment processes, such as bonding, loaf coating, or spraying, can be applied. If necessary, it can be heated to impart durable water and oil repellency to the surface of the fibrous material or to the inner layer of the fibrous material.

In addition, it is also possible to impart patternability and flexibility to the fiber material as other effects.

The fiber materials mentioned here include natural fibers such as wool, silk, cotton, hemp, and asbestos, recycled fibers such as rayon and acetate, and synthetic fibers such as polyester, polyamide, polypinyl alcohol, polyacrylic, and polyolefin. , and other glass fibers, and the composition of the present invention can be applied to these in any form such as fibers, filaments, knitted fabrics, woven fabrics, and non-woven fabrics, but preferably in the form of continuous sheets such as knitted fabrics and non-woven fabrics. It is efficient to process Particularly in non-woven fabrics, other binders such as styrene butadiene rubber latex,
It can also be used in combination with nitrile rubber latex.
The present invention will be explained below with reference to Examples.

In the examples, parts mean parts by weight. In the structural formula of organopolysiloxane, Me means a methyl group. Example 1 Two parts of an organopolysiloxane represented by the following structural formula having a viscosity of 2yC and 3.50 ratio St were dissolved in 97.8 parts of methyl ethyl ketone.

Next, 0.2 part of dibutyltin dilaurate was added and uniformly dissolved to prepare a treatment liquid of the present invention. (Treatment Solution A) For comparison, a similar treatment solution was prepared by dissolving dimethyl/methylhydrogen polysiloxane having the same degree of polymerization as the polysiloxane of the present invention of the above formula in toluene and adding a catalyst. (Treatment solution B) Next, 10 x 10 pieces of Tetron taffeta (plain woven fabric) made of 50 denier, which had been cleaned and refined, were immersed in each treatment solution, and then mangled so that the amount of silicone adhesion was 2% by weight. Squeezed dry with a roller.

Next, heat treatment was performed at 15,000 for 5 minutes to cause crosslinking by dehydrogenation and condensation reaction.

Tilt this treated fabric at a 45 degree angle and attach it using ASTMM. 2 oil and water were added dropwise. As shown in Table 1, the cloth treated with the composition of the present invention had good water repellency and oil repellency.

Organopolysiloxane 10 base having the structure of Table 1 Comparative Example 2 of twill water and twill oil, with a molar ratio of X:Y:Z of 10:3:87 and a viscosity of 3,000,00 ratio St. , 5 parts of methylhydrogenpolysiloxane having a viscosity of 3% St, capped at both ends with trimethylsilyl groups, was melted in 30 parts of methyl isobutyl ketone, and then 3 parts of dibutyltin diacetate was dissolved. was added to prepare a treatment solution.

(Treatment Solution C) Two asbestos plates measuring 10 ribs in length, 5 ribs in width, and 3 ribs in thickness were immersed in the treatment solution for 1 minute. The solution was pulled up from the treatment solution C to evaporate the solvent, and then put into a 150 oo hot air dryer and cured for 1 hour. A hard, glossy protective film was formed on the surface of the asbestos board. A commercially available adhesive tape for packaging was pasted on top of this treated board, a load of 20 days/ground was placed on it, and the tape was left at room temperature for 2 hours, but it did not adhere at all. In addition, another processed sheet was given ASTM No. After immersing the bond in 1 oil for 5 weeks, it was cut and observed for blackening of the cut surface due to oil penetration, but no oil penetration was observed.

Example 3 Tetron taffeta was treated with treatment liquid C under the same conditions as in Example 1, resulting in excellent twill oiliness and oiliness as shown in Table 1.
Water repellency was obtained.

Example 4 When a glass fiber fabric was treated with treatment liquid A under the same conditions as in Example 1, excellent oil and water repellency was obtained.

Claims (1)

[Scope of Claims] 1 A (a) ▲ Includes mathematical formulas, chemical formulas, tables, etc. Linear organopolysiloxane [where R is an unsubstituted hydrocarbon group having 1 to 6 carbon atoms, Q
is a fluorinated hydrocarbon group. ] Or (b) (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Units are 5 to 100 mol %, ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ Consisting of units 95 to 0 mol %, with a key at each end. a substantially linear organopolysiloxane having an elementary atom-bonded hydroxyl group [wherein R and Q are as described above, and R' and R'' are monovalent unsubstituted hydrocarbon groups]; and (2) a silicon atom bond. Organohydrodiene polysiloxane having at least three hydrogen atoms in one molecule [wherein the organic group is a monovalent unsubstituted hydrocarbon group], and B between silicon-bonded hydrogen atoms or between silicon-bonded hydrogen atoms A fiber treatment composition comprising a catalyst for dehydrogenation condensation between an atom and a silicon atom-bonded hydroxyl group.