JPS58144179A - Permanent water repellent fabric and production thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-repellent portion of a textile product and a method for manufacturing the same. More specifically, the present invention relates to a durable water-repellent fabric that has a soft feel and is extremely durable when washed, and a method for producing the same.

It is widely known that water repellency has been imparted to textile products using silicone resins or fluorine resins. However, it is well known that the water-repellent effect of all these products deteriorates significantly when washed with water or with dry cleaning, resulting in loss of their original performance. The primary reason for this is that the water repellent agent falls off during washing. In addition, some fluororesins have a water repellent whose molecular arrangement is disturbed by washing, resulting in a further deterioration in performance. For this reason, some products can recover some of their performance by ironing or heat treatment after washing, but they require an additional step of heat treatment after washing, and many secondary products used by consumers do not require physical heat treatment. There were many things that could not be done, which caused problems. Also,
Products that are water repellent and have excellent wash resistance against either the water washing method or the dry cleaning method are actually used. However, in neither the water washing method nor the dry cleaning method, a product with excellent water repellency and washing resistance has not been used.

On the other hand, in order to impart water repellency and flexibility to fiber fabrics, various organopolysiloxas/organosilanes, processing agents made of compositions thereof, and processing methods using them have been provided or proposed.

For example, dimethylpolysiloxane oil and its emulsion are used to impart flexibility, and in order to impart durable water repellency and flexibility,
In Japanese Patent Publication No. 9957 and Japanese Patent Publication No. 46-18269, a treatment agent consisting of methylhydrogenpolysiloxane, dimethylpolysiloxane endblocked with hydroxyl groups at both ends, and a catalyst for condensation reaction is described in Japanese Patent Publication No. 51-9440, a treatment agent consisting of methylhydrogenpolysiloxane, A treatment agent comprising a vinyl group-containing diorganopolysiloxane and an addition reaction catalyst has been proposed. In Japanese Patent Publication No. 4B-17514, in order to impart flexibility to organic synthetic fibers, a treatment agent consisting of an epoxy group-containing organopolysiloxane and an amino group-containing organopolysiloxane is used.
A treatment agent comprising a diorganopolysiloxane blocked with hydroxyl groups at both ends, an aminoalkylalkoxysilane, and/or a partial hydrolyzate or condensate thereof is disclosed in Japanese Patent Publication No. 55-19.
In Japanese Patent Publication No. 715 and Japanese Patent Publication No. 19716/1983, a treatment agent consisting of an aminoalkyltrialkoxysilane and an epoxy group-containing organopolysiloxane is disclosed in Japanese Patent Publication No. 55-19716.
3-98499 discloses an aminoalkyl group-containing diorganopolysiloxane with one triorganosilyl group blocked at both ends, and JP-A-55-152864 discloses a diorganopolysiloxane containing one amino group bonded to a silicon atom via a hydrocarbon group. A fiber treatment agent consisting of a diorganopolysiloxane having at least two in its molecule and a diorganopolysiloxane having at least two carboxyl groups or carboxylic acid ester groups in each molecule bonded to a silicon atom via a hydrocarbon group. is proposed.

However, these conventionally known treatments and treatments have some drawbacks. For example, a treatment agent based on dimethylpolysiloxane oil or diorganopolysiloxane containing a minoalkyl group and having triorganosilyl groups blocked at both ends has the drawback of lacking durability in water repellency and flexibility. Washing with water or dry cleaning, especially the latter, can significantly reduce water repellency and flexibility.

Processing agents containing methylhydrogen polysiloxane as an essential component have the drawback that they do not cure sufficiently unless a catalyst is used, and the use of a catalyst shortens the life of the processing bath too much.

Additionally, the fabric becomes stiffer. Chalk marks occur (
There are also disadvantages such as whitening of the creases) and lack of durability in the resulting water repellency.

A processing agent containing an epoxy group-containing organopolysiloxane as an essential component has the disadvantage that water repellency and durability of flexibility cannot be obtained unless sufficient heat treatment is performed. A treatment agent consisting of a diorganopolysiloxane with hydroxyl groups blocked at both ends and an aminoalkyl alkoxysilane or its hydrolyzate has the disadvantage that it does not provide durable water repellency, and its water repellency tends to decrease during dry cleaning or washing with water. There is.

The fiber treatment agent proposed in JP-A-55-152864 has no silicon-bonded alkoxy groups or silanol groups in any of the diorganopolysiloxanes, so dry cleaning was repeated at least 6 times at 5 degrees. The disadvantage is that the water repellency is not sufficient.

As a result of intensive studies to resolve the drawbacks of conventionally known fiber fabric treatment agents and treatment methods as described above, the inventors of the present invention have discovered a method that does not deteriorate the flexibility of fiber fabrics by drying at room temperature or by mild heat treatment. To achieve this invention by discovering that it is possible to easily produce a highly durable durable water-repellent fabric that does not cause chalk marks and does not lose its water repellency even after being washed with water or dry-cleaned more than 10 times.

That is, one aspect of the present invention is that the silicone water repellent attached to the fiber fabric is 6% by weight or less based on the weight of the raw fabric, and the water repellent does not form a film that binds the fibers together. The present invention also provides a durable water-repellent fabric having a water repellency of 70 points or more after being washed at least 15 times.

Furthermore, in the present invention, the fiber fabric is treated with (a) an amino group-containing organodialkoxysilane, an amino group-containing organotrikoxysilane, or a partial hydrolyzate or hydrolyzate thereof, and then (b) one molecule of A method for producing a durable water-repellent fabric, characterized in that it is treated with a substantially linear organopolysiloxane having at least two silicon-bonded organic groups containing a carboxyl group or a carboxylic acid ester group.

The base material, which is the fiber base material of the durable water-repellent fabric according to the present invention, is wool, silk, linen, cotton, natural fibers such as asbestos, rayon, cupro, and soft cloth.

Regenerated fibers such as acetate, organic synthetic fibers such as polyamide, polyester, polyester ether, polyacrylonitrile, vinylon, polyvinylidene chloride, polyvinyl chloride, polyethylene, polypropylene, spandex, and glass fibers.

It may be any inorganic synthetic fiber such as carbon fiber or silicon carbide fiber, and the fabric may be in any form such as a woven fabric, a nonwoven fabric, a resin-treated fabric, or a sewn product.

The durable water-repellent fabric according to the present invention is obtained as a synergistic effect of a special combination of an initial processing agent and a subsequent processing agent.

Next, a method for producing a durable water-repellent fabric according to the present invention will be explained.

The fiber fabric is first treated with component (a), an amine group-containing organodialkoxysilane, an amino group-containing organotrialkoxysilane, or a partially hydrolyzed product thereof.

Here, the amine group-containing organodialkoxysilane refers to a silane compound in which an organic group that does not have an amine group, an organic group that has at least one amino group, and two alkoxy groups are bonded to a silicon atom. . The organic group not having an amine group is bonded to the silicon atom through an 0-8i bond, and examples thereof include an alkyl group, a haloalkyl group, a Schiff-prokyl group, and an aryol group. The organic group having at least one amine group is bonded to the silicon atom through an 0-8i bond, and the amine group may be present at any position of the organic group, and the number of amine groups It is sufficient that the number is at least one, but if it is too large, it causes yellowing, so it is preferably 10 or less, particularly 2 or less.

This amino group may be primary, secondary, or 6th class, but
From the viewpoint of reactivity with the carboxyl group and carboxylic acid ester group of component (b), primary and secondary ones are preferred. 2
As class amino groups, alkylamino group, arylamino group, synroalkylamino group, poly(alkylamino)
The group is shown as IZIJ. A dialkylamino group as the 6th-class amine 7 group.

Alkylarylamino group, diarylamino group.

Examples include an alkylcycloalkylamino group and a dicycloalkylamino group. Examples of the organic group to which the amino group is bonded include an alkylene group, an arylene group, an alkylenearylene group, and an alkyleneoxyalkylene group.

The alkoxy group is bonded to the silicon atom through a 0-8i bond, and examples thereof include an unsubstituted alkoxy group, a substituted alkoxy group, and a cycloalkoxy group.

An amino group-containing organotrialcoquine silane is a silane compound in which an organic group having at least one amine group and six alkoxy groups are bonded to a silicon atom. The organic group, amino group, and alkoxy group having at least one amino group are as described above.

Typical examples of such amine group-containing organodialkoxysilanes and amino group-containing organotrialkoxysilanes include the general formula [wherein R is a monovalent hydrocarbon group R1 is a divalent hydrocarbon group R
2 is a hydrogen atom or a monovalent hydrocarbon group, R' is an alkyl group, a is an integer from 0 to 9, and b is 0 or 1.

Those with b=1 correspond to amine group-containing organodialkokidinolanes, and those with b=0 correspond to amino group-containing organotrialkoxysilanes.

R is a monovalent hydrocarbon group, such as an alkyl group such as a methyl group, a globyl group, or a hexyl group, an aryl group such as a phenyl group or a naphthyl group, a cycloalkyl group such as a cyclohexyl group, a 3-chloropropyl group, Examples include haloalkyl groups such as 3,3.3-)lifluoropropyl groups. From the viewpoint of ease of synthesis, methyl group and phenyl group are preferred, particularly methyl group.

R1 is a divalent hydrocarbon group, and includes an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a 2-)propylene group, an arylene group such as a phenylene group, and an alkylene group such as an ethylene phenylene group. An example is an arylene group.

From the viewpoint of ease of synthesis, an alkylene group is preferred.

In particular, it is a propylene group.

R' is a hydrogen atom or a monovalent hydrocarbon group, and even if both are hydrogen atoms, one is a hydrogen atom and the other is a monovalent hydrocarbon group, or both are monovalent hydrocarbon groups good.

Examples of the -monovalent hydrocarbon group include those exemplified for R. In view of the reactivity of the carboxyl group and carboxylic acid ester group of component (b), R1 preferably has two hydrogen atoms or one of which is a hydrogen atom.

R1 is an alkyl group, such as a methyl group or an ethyl group.

Examples include unsubstituted alkyl groups such as propyl, substituted alkyl groups such as 6-chloropropyl and methoxyethyl, and cycloalkyl groups such as cyclohexyl and cycloheptyl. Unsubstituted alkyl groups and alkoxyalkyl groups due to hydrolyzability, volatility and odor of by-products during hydrolysis, etc.

Particularly preferred is an unsubstituted alkyl group having 1 to 2 carbon atoms.

a is an integer from 0 to 9, but preferably 0 or 1 from the viewpoint of yellowing.

The amino group-containing organodialkoxysilane and the ami7-containing organotrialkoxysilane may be used alone, two or more types may be used in combination, or both may be used in combination. The amino group-containing organodialkoxysilane and the amino group-containing organotrialkoxysilane may be used in the form of a partially hydrolyzed product or a hydrolyzate.

The partial hydrolyzate mentioned here is one in which part of the alkoxy group has been changed to a silanol group, or one in which the silanol groups are condensed with each other to form an oligomer.

All of the alkoxy groups become silanol groups, and some of them are condensed to form oligomers. Moreover, a hydrolyzate is a product in which all or most of the alkoxy groups become silanol groups, and these groups are condensed to form a polymer.

Partial hydrolysates and hydrolyzates can be prepared by adding water to amino group-containing organodialkoxysilane or amine group-containing diorganotrialkoxysilane and stirring, or by adding these alkoxysilanes to water or a mixture of water and an organic solution. It can be easily manufactured by adding and stirring.

If the molar ratio of the alkoxysilane and water is increased or the stirring time is shortened, there is a greater tendency for zero-partial hydrolyzate to be produced; conversely, if the molar ratio of the alkoxysilane and water is decreased or the stirring time is If the time is increased or the mixture is heated and stirred, hydrolyzates tend to form. Amino group-containing organodialkoxysilane is a partial hydrolyzate.

Favorable treatment results can be obtained using any form of hydrolyzate; however, organotrialkoxysilane containing amine groups tends to turn into a resin and solidify when completely hydrolyzed, so it may be used as is or as a partially hydrolyzate. It is preferable to use it in the form of

When producing partial hydrolysates and hydrolysates of amino group-containing organodialkoxy 7ranes or amino group-containing trialkoxysilanes, only one type of alkoxysilane may be used as a raw material, or two or more types may be used as raw materials. , both may be used as raw materials. Additionally, other organoalkoxysilanes.

For example, it may be co-hydrolyzed and bonded with dimethyldimethoxysilane, dimethyljethoxysilane, methyltriethoxysilane, vinyltrimethoxyfuran, methylphenyldiethoxysilane, organoalkoxysiloxane, and diorganopolysiloxane blocked with hydroxyl groups at both terminals. However, as the proportion of other organoalkoxysilanes, organoalkoxysiloxanes, etc. increases, the treatment effect decreases, so it is preferable to keep the proportions of other organoalkoxysilanes, organoalkoxysiloxanes, etc. within a small range.

Amino group-containing organodialkoxy h for treatment of fiber fabrics
≦When using its partial hydrolyzate or hydrolyzate, a more flexible finish is possible.

When using an amino group-containing organotrialkoxysilane, its partial hydrolyzate, or hydrolyzate, flexibility cannot be achieved with the former, so if an intermediate texture is desired, mix the former in an appropriate ratio. It is preferable to do so, and it may also be used in the form of a cohydrolyzate with other diorganodialkoxysilanes or diorganopolysiloxanes with both terminals capped with hydroxyl groups.

This component adheres to the surface of the fiber fabric, fills the voids thereof, penetrates into the gaps between the fibers, or penetrates into the interior of the fibers. Since this component contains a silicon atom-bonded alkoxy group or a silanol group, it condenses and polymerizes on or within the fiber fabric due to the catalytic action of the amino group, thereby firmly adhering to or bonding to the fiber. In addition, fiber fabrics having negative groups such as carboxyl groups and sulfonic acid groups 9 such as nylon 6 and nylon 6.6
．． Polyester, silk, wool, and certain acrylic fibers tend to have higher durability because the amine groups of one component are chemically bonded. After the fiber fabric is treated with component (a), it is treated with component (b).

Component (b) is a substantially linear organopolysiloxane having at least two organic groups containing a carboxyl group or a carboxylic acid ester group in one molecule, and this organic group is 0-8i. It is bonded to the organopolysiloxane by a bond.

Substantially linear means completely linear or slightly branched. The degree of polymerization may be 2 or more, but preferably 10 to 1000. This is because if the degree of polymerization is too low, the flexibility imparting effect will not be sufficient, and if the degree of polymerization is too high, emulsification may become difficult.
□ At least 2 carboxyl groups or carboxylic acid ester group-containing organic groups are present in one organopolysiloxane molecule.
There is no particular upper limit, but from the viewpoint of ease of synthesis, viscosity, water repellency imparting effect, etc., it is less than 50 molar proportion of all organic groups.

In particular, 20 molti or less is preferable.

The carboxyl group or carboxylic acid ester group-containing organic group may be present only in the side chain of the organopolysiloxane, only at the end of the molecular chain, or at both the side chain and the end of the molecular chain. It's okay. Furthermore, both a carboxyl group-containing organic group and a carboxylic acid ester group-containing organic group may be present in one molecule of the organopolysiloxane, or both a carboxyl group and a carboxylic acid ester group may be bonded to one organic group. You may do so.

As an ester of this carboxylic acid ester group.

From the viewpoint of alcohol ester and cycloalkanol ester properties, alcohol esters, particularly alcohol esters having 1 to 2 carbon atoms, are preferred.

The organic group to which a carboxyl group or carboxylic acid ester group is bonded is an alkylene group.

Examples include an alkylene okylene alkylene group, an alkylenethioalkylene group, an arylene group, and an alkylene arylene group, but an alkylene group is preferred from the viewpoint of ease of synthesis.

Examples of organic groups to which neither carboxyl group nor carboxylic acid ester group is bonded are alkyl groups and haloalkyl groups. Cyanoalkyl group, cycloalkyl group.

Examples include an aryl group and an aralkyl group.

In addition to organic groups, a small number of reactive functional groups such as alkoxy groups, hydroxyl groups, and hydrogen atoms may be bonded to the silicon atoms in this organopolysiloxane. A typical example of component (b) is a compound of the general formula [wherein R'' is a monovalent hydrocarbon group having 1 to 20 carbon atoms.

RS is a hydrogen atom or a monovalent hydrocarbon group, A is an R" or -Q-00OR" group, and Q is a divalent hydrocarbon group.

k is a positive integer, l is an integer greater than or equal to 0, 'l(4
1 is at least 10. of all silicon-bonded organic groups
-Q -00OR'' group ratio is 0.2 to 50 mole], and is a diorganopolysiloxane having at least two -Q-CO○R8 groups in one molecule.

R" is a monovalent hydrocarbon group having 1 to 20 carbon atoms.

Methyl group, ethyl group, propyl group, octyl group.

Alkyl groups such as dodecyl groups, haloalkyl groups such as 5-chloropropyl groups, 3,3.3-trifluoropropyl groups, cyanoalkyl groups such as 3-cyanopropyl groups, phenyl groups, yoonaaryl groups such as naphthyl groups ,2
-Phenylethyl group, aralkyl group such as 1-phenylether group, and cycloalkyl group such as cyclohexyl group are exemplified. R" may be of the same type present in one molecule, or different types may be mixed, but at least 50 moles of R" are methyl groups, at least 50 moles of R" are methyl groups, Generally, the remainder is an alkyl group other than a methyl group, a phenyl group, or a 3,3,5-trifluoroalkyl group.

R6 is preferably a hydrogen atom, and examples of the monovalent hydrocarbon group include the same monovalent hydrocarbon groups as R4. Among these, alkyl groups, particularly alkyl groups having 1 to 2 carbon atoms, are preferred from the viewpoint of odor and volatility of reaction by-products that are reactive with amine groups.

Q is a divalent hydrocarbon group, such as a methylene group, an ethylene group,
Examples include an alkylene group such as a propylene group, a 2-methylpropylene group, an arylene group such as a phenylene group, and an arylene group such as an ethylenephenylene group. From the viewpoint of ease of synthesis, alkylene groups, particularly those having 2 to 4 carbon atoms, are preferred.

A is R" or -Q-00OR" group, and since at least two -Q-00OR" groups are required in one molecule, when l=0, both A is -Q-00OR" When 1=1, at least one of the 9 A's can be a -Q-00OR' group, and when 1-2, both A's can be R''.

-Q-000R' in one molecule of organonas siloxane
The reason why at least two groups are required is that if only one group is used, the durability of water repellency will be insufficient, probably because the amino group of component (a) will not be crosslinked.

The ratio of -Q-00OR' groups in all organic groups is 0.2 to 5.
The reason why this ratio is set to 0 molt is because if this ratio is too small, the durability of the water repellency will be insufficient, and if this ratio is too large, the water repellency will not be sufficient.

k+t is set to at least 10 by adding an unsaturated carboxylic acid or an unsaturated carboxylic acid ester depending on the degree of polymerization;

It can be easily synthesized by cohydrolytic condensation of an organoalkoxysilane containing a carboxyl group or a carboxylic acid ester group and another diorganodialkoxysilane.

To treat textile materials with component (a), they can be treated as is or dissolved in water or organic solvents.

It may be processed in an emulsified or dispersed form. The emulsifier for emulsifying this component may be appropriately selected from nonionic, cationic, or amphoteric emulsifiers.

Examples of organic solutions for dissolving this component include alcohol, toluene, kiln, verchlorethylene, and trichlorethylene.

In order to attach or absorb component (A) onto the fiber fabric, component (A) itself, its aqueous solution, its organic solvent solution, its emulsified layer, or its dispersion (hereinafter referred to as "component (A), etc.") are required.
After immersing the fiber fabric in the solution, dry it as it is or after squeezing it with a roll or mangle, or by spraying or coating the fiber fabric with component (a), etc., and then drying it. good.

When immersing in component (a), etc., it is done under heat.

The pH may be adjusted to be weakly acidic or slightly alkaline. Also, when drying, you can air dry at room temperature,
It may be dried with hot air. Its temperature.

Regarding the time, conditions may be appropriately selected so as not to damage the fiber fabric.

Component (a) is preferably attached or adsorbed to the fiber fabric in an amount of 0.001 to 6% by weight, particularly 0.01 to 2.0% by weight. If there is too little water repellency, the water repellency will be insufficient, and if there is too much water, the yellowed texture will be too rough and hard.

In order to treat the fiber fabric treated with component 0) with component (b), it may be treated with component (b) itself, or it can be treated in the form of its emulsion, its organic solvent solution, or its dispersion. It's okay.

Anionic emulsifiers such as higher alcohol sulfate ester salts and alkylbenzene sulfonates are used as emulsifiers to create the emulsified liquid of component (2).

Higher fatty acid polyoxyalkylene ester, higher alcohol polyoxyalkylene ether, alkylphenol polyoxyalkylene ether.

Non-ionic products such as higher fatty acid Rubitan ester.

Examples include emulsifiers such as emulsifiers and various other emulsifiers used for emulsifying silicone oil.

Also, an organic substance used to make a solution of component (b).

Examples of the solvent include those similar to the organic solvent for component C).

In order to make component (B) adhere to or adsorb onto the fiber fabric treated with component (A), component (B) itself and its emulsion must be used.

After immersing the fibers/fiber fabrics treated with component (A) in the dispersion or its solution (hereinafter referred to as "component (B), etc."), dry it as it is or after squeezing it with a roll or mangle, or The ingredients (
(b) etc. may be sprayed or applied and then dried.

The immersion in component (b) etc. may be carried out under heating or by adjusting the pH to be weakly acidic or weakly alkaline. Also, when drying, you can air dry at room temperature, hot air dry,
Promotion means such as heating roller treatment may also be applied. The temperature and time may be appropriately selected so as not to damage the fiber fabric.

Both treatment with component (a) and treatment with component (b) can achieve the desired durable water repellency with only room temperature or mild heat treatment.However, in order to increase treatment efficiency and production efficiency, It is also possible to adopt suitable heat/□ treatment.

Component (B) is 0.0% added to the fiber fabric treated with component (A).
It is preferable to attach or adsorb 0.05 to 3% by weight, particularly 0.05 to 2% by weight. If there is too little, you will not be able to obtain the water repellency of 9 wins and the durability when repeatedly dry-cleaned and washed with water, and if there is too much, the uneven adhesion will look like uneven staining, and it may be uneconomical. , it is a force that actually spoils the texture.

In addition, the total of component (a) and component (b) is 0 for fiber fabric.
．． 0.06 to 6% by weight, particularly 0.06 to 4% by weight, is preferably attached or adsorbed. This is due to the same reasons as above.

Furthermore, the ratio of the amount of component (B) attached to the amount of component (A) attached is, if component 0) is 1, component (B) is 0.
A range of 1 to 50 is preferred. By treating the fiber fabric with component (a) and component (b), the fiber fabric is given excellent water repellency, and even after repeated dry cleaning and water washing, and even after long-term use outdoors, the fiber fabric remains water repellent. It almost never decreases. The reason for this is that the component (a) attached, adsorbed, or chemically bonded to the fiber fabric condenses and becomes partial, and the carboxyl group of component (b) forms an ionic bond or even an amide bond with the amino group. It is assumed that this is because it is in a cross-linked form.

As shown in the scanning electron micrograph in Figure 1, the durable water-repellent fabric of the present invention does not form a film that binds the fibers, so the flexibility, air permeability, and moisture permeability of the fabric before treatment are hardly changed. I won't let you.

As is clear from the manufacturing method, the durable water-repellent fabric of the present invention has extremely excellent water repellency and durability against washing with water and dry cleaning, has excellent flexibility, and does not cause chalk marks or the like. We don't have any, so bring raincoat or other rain clothing.

Sportswear such as golf wear and ski wear.

It is extremely useful for making umbrellas, tents, tarpaulins, etc.

Note that the washing test method and water repellency evaluation method employed in the present invention were as follows.

Washing conditions J Engineering S L-0217 (10
3) Water repellency J-K5L-1092 (spray test)
Next, we will discuss examples and comparative examples.

In the comparative examples, 0 part or 0 means part by weight or % by weight, and the viscosity is the value at 25°C.

Example 1 2 NH, (OH,), NH (OH,), 5i (oc
'H, ), 0.3 parts of aminosilane represented by
Snow wear fabric (outer material for quilting) made of 100% nylon filament taffeta was immersed in the treatment liquid (liquid A) made of 100% nylon filament taffeta for 1 minute, then pulled out and squeezed with a squeezing roller to a squeezing rate of 50 mm. After drying (aminosilane adhesion amount: 0.15%), it was heat-treated at 150°C for 5 minutes.

Then, it is expressed as 1 equation, ? After immersing for 1 minute in a treatment solution (solution B) in which 1.5 parts of carboxyl group-containing organopolysiloxane having a viscosity of 1100 cst was dissolved in 98.5 parts of toluene, it was pulled up and squeezed with a squeezing roller to a squeezing rate of 100 inches. After squeezing and drying (carboxyl group-containing organopolysiloxane adhesion amount: 1.5%), it was heat-treated at 150° C. for 5 minutes.

Here, the total amount of water repellent attached is 1.65%.

For comparison, the following three types of treated fabrics were produced using the above nylon taffeta.

+11 After being immersed in liquid B for 1 minute, pulled up, squeezed with a squeezing roller to a squeezing rate of 100% and dried (carboxyl group-containing organopolysiloxane adhesion amount: 1.5%).

Heat treatment was performed at 150°C for 5 minutes.

+21 (The fabric treated in step 11 was immersed in liquid A for 1 minute, pulled up, squeezed with a squeezing roller to a squeezing rate of 50 inches, and dried (
After aminosila/adhesion amount of 0.15 cm), heat treatment was performed at 150° C. for 5 minutes.

(3) 1.6 parts of a water repellent consisting of 90 parts of methylhydrogen polysiloxane endblocked with trimethylsilyl groups at both ends and 10 parts of dimethylpolysiloxane oil endblocked with trimethylsilyl groups at both ends, which is the most typical water repellent agent, and 0 parts of diptyltin diacetate catalyst. Nylon taffeta was immersed in a treatment solution (liquid C) in which 0.05 parts of nylon taffeta was dissolved for 1 minute.
After squeezing to zero and drying, it was heat-treated at 150° C. for 5 minutes.

The water repellency and wash resistance of each treated nylon taffeta mentioned above are as shown in Table 1.9 The water repellency of the treated fabric according to the present invention is washable with water or dry clean.

It was extremely durable, maintaining a score of 80 even after blowfishing was repeated 60 times. Moreover, the texture was very flexible and no chalk marks were generated.

Example 2 r″ 2 NH, (OH,), NH (OH,), 5i (cH
A Tetron/cotton blend (65/65) raincoat fabric was immersed in a treatment solution (solution D) in which 0.5 parts of aminosilane represented by , The mixture was squeezed to a ratio of 100 degrees and hung to dry at room temperature for 24 hours (amino silica/coating amount: 0.5-%). Next, it was immersed for 1 minute in a treatment solution (solution F) in which 1.5 parts of a carboxyl group-containing organopolysiloxane having a viscosity of 304 D cst, expressed by formula 1, was dissolved in 98.5 parts of toluene, and then raised and squeezed with a squeezing roller. Squeeze to a ratio of 100% and dry (carboxyl group-containing organopolysiloxane adhesion amount 1)
．． 5%) and then heat-treated at 150°C for 5 minutes. Here, the total amount of water repellent applied is 2 cm.O For comparison, the same raincoat fabric was used and treated in the same manner with liquid C of Example 1.OAs shown in Table 2, the present invention The treated fabric had a water repellency of 70 degrees or more even after being washed 15 times, and had a soft feel.

Table 2 1 Water repellency after washing with water Table 2 2 Water repellency after dry cleaning Example 6 100 parts of Aminosila used in Example 2 and 50 parts of water were placed in a 6-ton flask. A cooling tube was attached and hydrolysis was carried out at 80 to 85°C for 5 hours to produce a low-degree condensate.

A condensate of cst was obtained. A jumper fill fabric made of nylon filament yarn was immersed for 1 minute in a treatment solution (solution F) in which 0.4 parts of this condensate was dissolved in 996 parts of water, and after pulling it up, it was pulled up with a squeezing roller at a squeezing rate of 50 inches (aminosilane condensation After drying at 105°C for 10 minutes, the film was heat-treated at 140°C for 7 minutes.

Next, 735 parts of a carboxyl group-containing organopolysiloxane represented by formula 1 and having a viscosity of 1400 cat, 5 parts of water, and three types of polyoxyethylene nonylphenol ether (ethylene oxide - 2 mol, 5 mol, and 25 mol addition) were added. Pour 3 parts of the mixed system (adjusted to p#HLB 11.5) into a container.

After stirring using a stirrer, the mixture was passed through a colloid mill emulsifier, and then 45 parts of water was added and mixed to prepare an emulsion.

After immersing a nylon film fabric previously treated with F solution in a treatment solution prepared by dissolving 100 parts of this emulsion in 6400 parts of water and pulling it up, the squeezing rate was 100% (carboxyl group-containing organopolysiloxane adhesion amount) using a squeezing roller. After drying, the mixture was heated at 160° C. for 5 minutes. .

Here, the total amount of water repellent applied is 1.2 inches. 2 treated cloths
Divide into pieces, wash each piece with water and repeat 15 times.

The remaining one sheet was dry cleaned 15 times.

The water repellency of each was investigated. As a result, the water repellency was maintained at 80 points in all cases.

Example 4 Formula NH, OH, OH, OH, 5i (QC2H,).

Aminosilane o, 4 parts t-toluene 996
Tetron/cotton blend (6
5/Ro5) After soaking the raincoat fabric for 2 minutes.

It was pulled up, squeezed with a squeezing roller to a squeezing rate of 100%, and then hung to dry at room temperature for 24 hours (aminosilane adhesion amount was 069%).

Next, 1% of the treatment solution (H solution) was dissolved in 98.5 parts of trichlorethylene in 71.5 parts of a carboxylic acid ethyl ester group-containing organosiloxane expressed as 0 formula % and having a viscosity of 2910 cst. After soaking for a minute, it was pulled up and squeezed with a squeezing roller to a squeezing rate of 100 inches, and after air-drying, it was treated with hot air at 150°C for 10 minutes (carboxylic acid ethyl ester group-containing organopolysiloxane attached - Jil, 5 inches). Here, the total amount of water repellent applied was 1.89%.

This treated cloth was washed with water or dry cleaned 15 times, and its water repellency and flexibility were examined before and after washing. The initial water repellency was 90 to 100 points, and the water repellency after washing with water or dry cleaning 15 times was 80 points.

Flexibility is initial, wash with water or dry clean 15
Both results were excellent after multiple repetitions.

Example 5 Tetron long fiber fabrics, acrylic short fiber fabrics, silk fabrics, and wool fabrics were treated with the aminosilane aqueous solution used in Example 1 under the conditions shown in Table 3, and then the carboxyl group-containing organopolymer used in Example 1 was treated with the aminosilane aqueous solution used in Example 1. Siloxane was treated under the conditions shown in Table 4 using perchloromethane as a solvent. Here, the total amount of water repellent applied to each fabric is 0.26% for the Tetron long fiber fabric, 2.01% for the acrylic short fiber fabric, 1.17% for the silk fabric, and 1.65% for the wool fabric. The water repellency and wash resistance of each are shown in Table 5. All of them were extremely durable, maintaining a water repellency of 70 points or higher even after being washed 15 times. Moreover, the texture was similar to that of unprocessed cloth.

Table 6 Aminosilane treatment conditions Table 4 Carboxyl group-containing organopolysiloxane treatment conditions Example 6 Nylon taffeta (warp and weft both 70 denier,
The aminosilane aqueous solution used in Example 1 was treated with the aminosilane aqueous solution used in Example 1 under each condition in Table 6 to obtain a single yarn of 68 yarns, a warp yarn density of 118 yarns/2.54, and a weft yarn density of 92 yarns/2.54 an.
The carboxyl group-containing organopolysiloxane used in Example 1 was then treated with perchloromethane as a solvent under the conditions shown in Table 7 to prepare samples with different amounts of adhesion.

Table 6 Aminosilane treatment conditions Table 7 Carboxyl group-containing organopolysiloxane treatment conditions Each treated fabric was washed with water or dry cleaned 15 times, and the water repellency before and after was examined. The water repellency after repeated water washing or dry cleaning 15 times was 70 to 80 points.

On the other hand, the flexibility of the texture, the degree of film formation of the water repellent agent between single yarns, and the degree of uneven dyeing defects due to uneven adhesion of the water repellent agent were investigated for each treated fabric, and the results are shown in Table 8. Ta.

[Note]

(1) Flexibility A. Measured with a texture meter manufactured by Uenoyama Kiko ■.

B・Sample size 18cnx18■, slit width 1m□ C0 Fabric surface vertically, horizontally, fabric layer vertically.

Total value of measurements from four locations in the horizontal direction.

D. Flexibility of untreated fabric 35 g.

(2) Degree of film formation of water repellent agent They were ranked as follows based on microscopic observation.

No water repellent film is observed between the single woven yarns ○
Half-stackiness is observed Δ The spaces between the single yarns of the woven yarn are completely covered with the water repellent film ×
(3) Uneven adhesion of water repellent in the form of uneven dyeing The appearance of the fabric was evaluated with the naked eye and ranked as follows.

Absolutely no uneven dyeing observed ○ Slightly observed △ Significantly observed On the other hand, as film formation progresses, air permeability and moisture permeability also decrease. If the amount of silane deposited is 6 or less, no such film will be formed and the flexibility of the fabric will not be significantly impaired.

Next, as the amount of the carboxyl group-containing organopolysiloxane increases, the uneven adhesion of the treatment agent becomes noticeable in the form of uneven staining. If the amount of polysiloxane deposited is 3 or less, such uneven staining due to uneven deposition will not occur.

Therefore, it is desirable that the total amount of water repellent applied is 6 inches or less.

[Brief explanation of drawings]

FIG. 1 is a scanning electron micrograph of the surface of a fabric according to an embodiment of the present invention.

Claims (1)

[Claims] (ll til! The amount of silicone water repellent attached to the textile fabric is 6% or less based on the weight of the original fabric, and the water repellency after washing at least 15 times is 70 points or higher. A durable water-repellent fabric characterized by: (2) The durable water-repellent fabric according to claim 1, wherein the water-repellent agent attached to the fiber fabric does not form a film that binds fibers together. (3) Fibers Claim 1, wherein the amount of silicone water repellent attached to the fabric is 4% by weight or less based on the weight of the raw fabric.
The durable water-repellent fabric according to items 1 to 2. (4) The fiber fabric is treated with (a) an amino group-containing organodialkoxysilane, an amino group-containing organotrialkoxysilane, or a partially hydrolyzed moiety or hydrolyzate thereof, and then (b) in one molecule. A method for producing a durable water-repellent fabric, characterized in that it is treated with a substantially linear organopolysiloxane having at least two silicon-bonded organic groups containing a carboxyl group or a carboxylic acid ester group. (5) The amino group-containing organodialkoxysilane or amino-containing organotrialkoxysilane of the component (a) has the general formula [wherein R is a monovalent hydrocarbon group, Ro is a divalent hydrocarbon group,
The durable repellent according to claim 4, wherein R2 is a hydrogen atom or a monovalent hydrocarbon group, R1 is an alkyl group, a is an integer of 0 to 9, and b is 0 or 1. Method for manufacturing water-based fabric. (6) The durable water-repellent fabric according to claim 5, wherein R in component (a) is a methyl group, R1 is an alkylene group, Ro is a hydrogen atom, and a is O or 1. manufacturing method. (7) (a) Component Ro is a propylene group p,
7. The method for producing a durable water-repellent fabric according to claim 6, wherein Rg is a methyl group or an ethyl group. (8) The component (b) has the general formula [wherein R" is a monovalent hydrocarbon group having 1 to 20 carbon atoms. Rs is a hydrogen atom or a monovalent hydrocarbon group, and A is R" or -Q-COOR] group, Q is a divalent hydrocarbon group, is a positive integer, l is D or an integer of 1 or more, k+t is at least 10. -Q-00OR' among all silicon-bonded organic groups
The ratio of groups is 0.2 to 50 molti],
-Q-(1! A method for producing a durable water-repellent fabric according to claim 4, which is a diorganopolysiloxane having at least two OOR' groups in one molecule. (9) Ro of component (b) is an alkyl group having 1 to 20 carbon atoms, R5 is a hydrogen atom or an alkyl group, and A is an alkyl group having 1 to 20 carbon atoms, or -Q, -00O
9. The method for producing a durable water-repellent fabric according to claim 8, wherein R' is an alkylene group. Q (1 (b) component Ro is a methyl group, Ro is a hydrogen atom, Q is a propylene group, and A is a methyl group or -OH, OR, OH, -COOR group) The method for producing a durable water-repellent fabric according to item 9. The patent claim in which the component (a) is deposited on the αυ fiber fabric in an amount of o, ooi to filtration weight percent, and the component (b) is deposited in an amount of 0.005 to !1 percent by weight. A method for manufacturing a durable water-repellent fabric according to items 4 to 10. α2 Component (a) is applied in the form of an aqueous solution, emulsion/or organic solvent solution, and dried, and then component (b) is applied as an emulsion or organic solvent solution. A process for producing a durable water-repellent fabric according to claims 4 to 11, which comprises applying in the form of a solvent solution and drying.