JPH1180277A - Reactive silyl-containing copolymer and method for treating with same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart water repellency, stainproofness, wrinkle resistance and sizableness to a substrate by coating the substrate with a copolymer containing as the constituent monomers a trifunctionalsilyl-containing acrylic ester (A), an alkyl acrylate (B) and a siloxane-containing acrylic ester (C) and crosslinking the copolymer by hydrolysis. SOLUTION: Component A is a monomer represented by formula I (wherein R1 is H or methyl; R2 is a 1-6C alkylene; and R3 to R5 are each a reactive functional group). Component B is a monomer represented by formula II (wherein R6 is H or methyl; and R7 is a 1-18C alkyl). Component C is a monomer represented by formula III [wherein R8 is H or methyl; R9 is a 1-6C alkylene; and X is formula IV (wherein R10 is a 1-6C alkyl), formula V (wherein R11 is a 1-6C alkyl; and x1 is a positive integer) or formula VI (wherein R12 is a 1-6C alkyl; and x2 is a positive integer)]. It is desirable that the copolymer has a monomer ratio A/B/C of (25-85 wt.%)/(5 wt.% or above)/(1 wt.% or above).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel reactive silyl group-containing copolymer, particularly to a material to be treated, which imparts excellent water repellency and antifouling property, and provides a fiber material with an adhesive property and an antifouling property. The present invention relates to a copolymer which can impart wrinkle properties and a good feeling in use, and is excellent in durability of the effect, and a method for treating the copolymer.

[0002]

2. Description of the Related Art As a method for imparting water repellency and antifouling property to a certain material, a method of treating a resin, a silicone compound or the like is known. In particular, fiber materials are of course not only water-repellent, but are also repeatedly washed and folded, so higher durability is required than other materials. Feeling is also very important. Also, in addition to water repellency and antifouling properties, it is often desired for clothing such as shirts to have an effect of gluing, removing wrinkles, and extending wrinkles. In response to these needs, a water repellent, a sizing agent, a wrinkle remover (iron smoother) and the like have been conventionally marketed.

[0003]

However, there have not been obtained satisfactory water repellency and antifouling properties, effects such as wrinkle removal and gluing, durability and feeling of use. There has been a demand for a fiber treatment agent that can easily provide the effect with a single treatment. The present invention has been made in view of such problems of the prior art, and an object of the present invention is to provide a fiber material with water repellency, antifouling property, wrinkle resistance, and sizing property in a simple manner. Another object of the present invention is to provide a substance having a good feeling and durability of these effects and a method for treating the same.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, (A) an acrylic ester having a trifunctional silyl group, and (B) an acrylic acid ester Excellent water repellency by applying a copolymer containing an alkyl ester and (C) a siloxane-containing acrylic acid-based ester to a material to be treated, such as a fiber material, and then hydrolyzing to crosslink the copolymer. , Antifouling,
It has been found that wrinkle-preventing properties, gluing properties and a feeling of use are imparted, the durability of these effects is extremely high, and that flaking does not occur, and the present invention has been completed.

That is, a copolymer according to the present invention comprises a monomer (A) represented by the following general formula (I) and a monomer represented by the following general formula (I):
It has a monomer (B) represented by (II) and a monomer (C) represented by the following general formula (III) as constituent monomers.

[0006]

Embedded image (In the general formula (I), R ₁ is a hydrogen atom or a methyl group, R ₂
Represents an alkylene group having 1 to 6 carbon atoms, and R ₃ , R ₄ and R ₅ each represent a reactive functional group capable of crosslinking between the copolymer molecules by being hydrolyzed. )

Embedded image (In the general formula (II), R ₆ represents a hydrogen atom or a methyl group, R ₇
Represents an alkyl group having 1 to 18 carbon atoms. )

Embedded image (In the general formula (III), R ₈ represents a hydrogen atom or a methyl group;
₉ means an alkylene group having 1 to 6 carbon atoms. X means a group represented by any of the following formulas (IV) to (VI). )

[0007]

Embedded image (In the general formula (IV), R ₁₀ means an alkyl group having 1 to 6 carbon atoms.)

Embedded image (In the general formula (V), R ₁₁ is an alkyl group having 1 to 6 carbon atoms, x ₁
Means a positive integer. )

Embedded image (In the general formula (VI), R ₈ and R ₉ are as defined above.
₁₂ is an alkyl group having 1 to 6 carbon atoms, x ₂ denotes a positive integer. )

In the copolymer of the present invention, the proportion of the monomer (A) is preferably 25 to 85% by weight in the copolymer. Further, in the copolymer of the present invention,
It is preferable that the ratio of the monomer (B) is 5% by weight or more in the copolymer, and the ratio of the monomer (C) is 1% by weight or more in the copolymer.

The copolymer of the present invention may further comprise a monomer (D) represented by the following general formula (VII) as a constituent monomer.

Embedded image (In the general formula (VII), R ₁₃ is a hydrogen atom or a methyl group,
R ₁₄ represents an alkylene group having 1 to 6 carbon atoms. Y is-
A group represented by N ⁺ (R ₁₅ ) ₃ or —N (R ₁₅ ) ₂ ;
R ₁₅ represents an alkyl group having 1 to 6 carbon atoms. The proportion of the monomer (D) is preferably in the range of 1 to 100% by weight based on the total weight of the monomers (A), (B) and (C) in the copolymer. .

Further, in the copolymer of the present invention, R ₃ ,
R ₄ and R ₅ are preferably an alkoxy group having 1 to 6 carbon atoms. The fiber treating agent according to the present invention is characterized by comprising the above-mentioned copolymer. Further, the water repellent according to the present invention is characterized by comprising the copolymer. The method for treating a copolymer according to the present invention is characterized in that after applying the copolymer to a material to be treated, the copolymer is hydrolyzed to crosslink the copolymer molecules.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The monomer (A) represented by the general formula (I) is an ester of acrylic acid or methacrylic acid containing a trifunctional silyl group -SiR ₃ R ₄ R ₅ . In the general formula (I), R ₁ is a hydrogen atom or a methyl group. R ₂ represents an alkylene group having 1 to 6 carbon atoms, and is preferably a propylene group. R ₃ , R ₄ , R
₅ is a siloxane-bonded Si-
O-Si is a reactive functional group capable of forming a cross-link between the copolymer molecules of the present invention, for example, a hydrogen atom,
Examples thereof include an alkoxy group, a halogen atom, an acyloxy group, and an amino group, and are preferably carbon in view of stability of a copolymer, safety of a by-product generated by hydrolysis, reactivity of a crosslinking reaction described later, and the like. It is an alkoxy group having the number of 1 to 6, particularly preferably a methoxy group or an ethoxy group. Note that R ₃ , R ₄ , and R ₅ may be the same or different. In the copolymer of the present invention, one or more of the above monomers (A) can be used as constituent monomers.

The monomer (B) is an alkyl ester of acrylic acid or methacrylic acid. In the general formula (II), R ₆ is a hydrogen atom or a methyl group, and R ₇ is a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, and preferably has 1 carbon atom. To 6 alkyl groups, and particularly preferably a methyl group. In the copolymer of the present invention, one or more of the above monomers (B) may be used as constituent monomers.

The monomer (C) is siloxane-containing (meth)
Acrylic ester. In the general formula (III), R ₈
Is a hydrogen atom or a methyl group. R ₉ is an alkylene group having 1 to 6 carbon atoms, preferably an ethylene group, a propylene group or a 2-hydroxypropylene group. X means a siloxane represented by any of the above general formulas (IV) to (VI). In the general formulas (IV) to (VI), R ₁₀ , R ₁₁ ,
R ₁₁ ′ and R ₁₂ represent a linear or branched alkyl group having 1 to 6 carbon atoms, or a phenyl group. It should be noted that a plurality of R ₁₀ , R ₁₁ and R ₁₂ are present in each of the general formulas, but these may be the same or different. R ₁₀ , R ₁₁ and R ₁₂ are preferably a methyl group. R ₁₁ ′ is preferably a butyl group. When X is the general formula (V) or the general formula (VI), the molecular weight of the monomer (C) is 1,000 to 100,
000, preferably 2,000 to 20,000.
In the copolymer of the present invention, the monomer (C)
One or more of these may be used as a constituent monomer.

The copolymer of the present invention may further comprise, as a constituent monomer, an amine-containing (meth) acrylate monomer (D) represented by the general formula (VII). In the general formula (VII), R ₁₃ is a hydrogen atom or a methyl group. R ₁₄ represents an alkylene group having 1 to 6 carbon atoms, preferably an ethylene group or a propylene group. Y is a group represented by -N ⁺ (R _{15) 3} or _{-N (R 15) 2, R} 15 denotes an alkyl group having 1 to 6 carbon atoms. In the case of -N ⁺ (R ₁₅ ) _3, a salt having a counter ion such as a halogen or an organic acid may be used.

Incidentally, as long as the effects of the present invention are not impaired, a monomer (E) other than the above-mentioned monomers (A) to (D) may be contained as a constituent monomer of the copolymer of the present invention. The copolymer according to the present invention can be obtained by polymerizing the above monomers using a known polymerization method, and for example, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, or the like can be used. For example, in the case of the solution polymerization method, the copolymer of the present invention can be obtained by dissolving each monomer in a solvent with a desired monomer composition, adding a radical polymerization initiator under a nitrogen atmosphere, and heating and stirring. it can.

As a solvent used in the polymerization, any solvent can be used as long as it can dissolve or suspend a monomer and is an organic solvent containing no water. For example, methanol, ethanol, and the like can be used. Alcohol solvents such as propyl alcohol, isopropyl alcohol and butyl alcohol, hexane, heptane, octane,
Hydrocarbon solvents such as isooctane, decane and liquid paraffin; ether solvents such as dimethyl ether, diethyl ether and tetrahydrofuran; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; methylene chloride Dimethylformamide, diethylformamide, dimethylsulfoxide, dioxane, and the like, in addition to chloride solvents such as chloroform, carbon tetrachloride and the like. These solvents may be used as a mixture of two or more kinds. Usually, it is preferable to select a solvent having a boiling point higher than the starting temperature of the polymerization initiator to be used.

The polymerization initiator is not particularly limited as long as it has the ability to initiate radical polymerization. For example, peroxides such as benzoyl peroxide, azobisisobutyronitrile, 2,2'-azobis (Isobutyric acid) In addition to azo compounds such as dimethyl, persulfate polymerization initiators such as potassium persulfate and ammonium persulfate are exemplified. In addition, polymerization can be performed by photochemical reaction, irradiation of radiation, or the like, without using these polymerization initiators. The polymerization temperature is equal to or higher than the polymerization initiation temperature of each polymerization initiator. For example, in the case of a peroxide-based polymerization initiator, the temperature may be usually about 70 ° C.

Although the polymerization time is not particularly limited, it is usually 2 to 2.
24 hours. When it is desired to obtain a polymer having a relatively high molecular weight, the reaction is desirably performed for about one day. If the reaction time is too short, unreacted monomers may remain and the molecular weight may be relatively small. The average molecular weight of the copolymer of the present invention is not particularly limited, and the desired effect can be exhibited as long as the copolymer has a degree of polymerization equal to or higher than the oligomer. However, when the degree of polymerization is reduced, the speed of a crosslinking reaction described below is reduced, and
If the degree of polymerization is too high, the viscosity becomes high and the coatability and workability are poor, so the average molecular weight is 2,000.
It is preferably about 150,000.

The copolymer of the present invention thus obtained has a functional silyl group derived from the monomer (A). For this reason, by hydrolyzing it, the copolymer molecules of the present invention crosslink with each other to form a crosslinked body. By performing such a cross-linking reaction on the material to be treated, a cross-linked film of the copolymer is firmly formed on the surface of the material, thereby exhibiting high durability and high water repellency and antifouling properties. it can. Further, the crosslinked film of the copolymer of the present invention has a feature that it exerts a gluing property, a wrinkle elongation and a wrinkle-preventing effect on the fibrous material, and is also excellent in the usability. Therefore, it is suitable for applications in which these effects are to be provided at once.

As the monomer composition of the copolymer of the present invention, the proportion of the monomer (A) in the copolymer is preferably 25 to 85% by weight, more preferably 40 to 75% by weight. If the amount of the monomer (A) is too small, the number of crosslinking reaction sites is small, and the effects such as water repellency and washing resistance are not sufficiently exhibited. On the other hand, when the proportion of the monomer (A) is too large,
Water repellency and washing resistance tend to decrease. This is presumably because the cross-linking reaction sites are too many and dense, so that the cross-linking reaction does not proceed cleanly and a large amount of unreacted sites remain on the cross-linked body. Also, the feeling of use is bad,
Flaking may occur.

The monomer (B) contributes to the water repellency of the crosslinked film, suppresses flaking, suppresses the stickiness of the monomer (C), and adjusts the properties of the crosslinked film. The ratio of the monomer (B) is 5% in the copolymer.
% By weight or more, preferably 10% by weight or more. When the proportion of the monomer (B) increases, the proportion of other monomers decreases, and the copolymer becomes hardly soluble in alcoholic solvents. Therefore, the proportion of the monomer (B) is at most 74% by weight or less, preferably 60% by weight. It is as follows. The monomer (C) has a siloxane portion, whereby the water repellency of the crosslinked body film is remarkably increased, and the fiber can be given a smoothness to give a good finish. It also suppresses flaking. In the copolymer of the present invention, the monomer (C) is 1% by weight.
As described above, the content is preferably 5% by weight or more. However, if the proportion of the monomer (C) is too large, the proportion of other monomers tends to be relatively low and the washing resistance tends to be inferior.
It is at most 70% by weight, preferably at most 60% by weight.

When a copolymer having the monomer (D) as a constituent monomer is further treated together with the monomers (A) to (C), the fiber is given a smooth and slimy feeling and is moist. Sensation is obtained. However, when the proportion of the monomer (D) is too large, the amine portion of the monomer (D) increases the hydrophilicity of the coating, resulting in poor water repellency, washing resistance and the like. As the ratio of the monomer (D), the monomer (A)
1 to 100% by weight, preferably 5 to 50% by weight, based on the total weight of (C).

Preferred examples of the copolymer of the present invention include, for example, a copolymer represented by the general formula (VIII) and a copolymer represented by the general formula (IX).

Embedded image

Embedded image In the general formulas (VIII) and (IX), R ₁ , R ₂ ,
R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₃ , R ₁₄ ,
X and Y are as defined above. n, m, l, and p represent the molar ratio of monomer (A), monomer (B), monomer (C), and monomer (D), respectively.

The method of treating a copolymer according to the present invention is characterized in that after applying the copolymer of the present invention to a material to be treated, it is hydrolyzed to crosslink the copolymer molecules. Examples of the crosslinking method include a reaction with water, an acid, an alkali and a reaction with heat. Specifically, there is a method in which, after the copolymer of the present invention is applied, the applied portion is brought into contact with water (or water vapor or the like), an acid, or an alkali, or is hydrolyzed or crosslinked by heating. Alternatively, the copolymer may be applied to a material to be treated which has been previously treated with water, an acid or an alkali, and then subjected to hydrolysis and crosslinking. Further, a method of mixing the copolymer of the present invention with water, an acid or an alkali and immediately applying the mixture is also conceivable. In the case of a reaction with water, an acid or an alkali, heating may be performed, but treatment at room temperature is usually sufficient. When the progress of the cross-linking reaction may be slow, it is also possible to perform natural cross-linking with atmospheric moisture without contact with such acids, alkalis and water.

An acid used in the treatment method according to the present invention,
The alkali is not particularly limited as long as it can hydrolyze the copolymer to cause a crosslinking reaction, and organic and inorganic acids and alkalis can be used. Of course, one or more of these acids and alkalis can be used, and a mixture with water may be used. The copolymer of the present invention can be used in the form of a solution, a dispersion or an emulsion of an appropriate solvent. Among them, one of the preferred embodiments is a non-aqueous composition containing the copolymer.

Examples of the non-aqueous composition include those obtained by dissolving or dispersing the copolymer in an organic solvent. Examples of such organic solvents include aliphatic hydrocarbons, aromatic hydrocarbons, chlorine compound hydrocarbons, ether solvents, alcohol solvents, aliphatic C1-4 alcohols having 1 to 4 carbon atoms, ethyl cellosolve, and butyl cellosolve. Cellosolve solvents, dioxane, methyl acetate, diformamide and the like can be mentioned. Among these, aliphatic and dihydric alcohols are preferable from the viewpoint of toxicity and safety, and examples thereof include methanol, ethanol, isopropanol and propylene glycol. Particularly, from the viewpoint of safety, ethanol and isopropanol are preferable. .

When the copolymer according to the present invention is used as a water-containing composition, a cross-linking reaction occurs in the product, so that it is preferable to appropriately prepare the composition at the time of application. In addition, such a water-containing composition is also included in the scope of the present invention. In the composition containing the copolymer of the present invention, the concentration of the copolymer is not particularly limited, but is preferably 0.1 to 10% by weight, and particularly preferably 1 to 5% by weight. If the amount is too small, sufficient effects may not be obtained in a single treatment. If the amount is too large, coating properties, extensibility, feeling of use, etc. may be poor, or flaking may occur.

The processing composition according to the present invention may contain other components as long as the effects of the present invention are not impaired. For example, surfactants, UV protection agents,
Examples include a pH adjuster, a preservative, an antioxidant, a chelating agent, a thickener, a film forming agent, an oily component, a polymer compound, and a propellant. It is preferable that water, acid, and alkali are separately prepared from the copolymer, but if appropriately prepared at the time of coating, water, acid, and alkali are mixed in the composition together with the copolymer of the present invention as described above. It is also possible. Also,
If a coloring material such as a pigment or a pigment is blended, a water-resistant colored film can be formed, and if a UV absorber is blended, fading of the material to be treated can be prevented.

The materials to be treated in the present invention include:
Fiber materials in any form of single fibers, spun yarns, random fibers, fabrics and finished products are suitable. Such end products include, for example, shoes, umbrellas, hats, ski wear, shirts, carpets, and the like. In the present invention, the fibrous material also includes other fibrous materials such as leather, paper fibers, and paper products, and products thereof. In addition to fiber materials,
It is also possible to treat other materials requiring water repellency and antifouling properties, such as glass plates and glass products, metal plates and metal products.

As means for applying the copolymer of the present invention, conventionally known means such as a dipping method, a roll coating method and a spray method may be used. Needless to say, tools such as a brush and a comb can be used as needed. One of the simplest treatment methods in the present invention is, for example, a method in which the copolymer solution of the present invention is immersed or sprayed in the material to be treated, optionally squeezed, and naturally dried or heated. For clothing such as shirts, it is also preferable to spray the copolymer solution before ironing, and then iron or steam iron.

By subjecting the copolymer of the present invention to a crosslinking treatment on a material to be treated, a crosslinked coating film having excellent water repellency and antifouling properties is formed. In addition, this coating allows you to
Anti-wrinkle properties, gluing properties, etc. can also be imparted. And, since the film is very difficult to remove even with water or detergent, these effects are continuously exhibited. In addition, since this crosslinked film has no flaking and has an excellent feeling in use when applied to a fiber material, it is particularly suitable as a fiber treatment agent, a sizing agent for fibers, and an anti-wrinkle agent. Further, it can be used as a water repellent and an antifouling agent for various materials.

The mechanism by which such an effect appears is considered as follows. FIG. 1 schematically shows an example of a crosslinking reaction of the copolymer according to the present invention. That is, the copolymer according to the present invention has a trifunctional silyl group -SiR ₃ R ₄ R ₅ derived from the monomer (A). This trifunctional silyl group is easily hydrolyzed with water, an acid, an alkali, or the like, to give a trihydroxysilyl group —Si (OH) ₃ . This trihydroxysilyl group reacts with another trihydroxysilyl group to form a stable siloxane-bonded Si-O-Si, and as a result, a cross-linked copolymer in which copolymer molecules are cross-linked in a three-dimensional network. (In the present invention, it may be referred to as a crosslinked body). Therefore, after the copolymer is applied, by hydrolyzing, cross-linking occurs in the applied portion, and the cross-linked body coats the material to be treated firmly and uniformly in a mesh form, and forms a film having excellent water repellency and washing resistance. It is presumed to form.

Even if the crosslinked product is synthesized in advance and is to be applied, it is very difficult to apply the crosslinked product because the crosslinked product becomes a gel or a plastic. Hereinafter, the present invention will be described in more detail with reference to specific examples. First, the test method used in the present invention will be described.

A 5% ethanol solution of each of the water-repellent copolymers was sprayed on a cotton shirt and air-dried. Several drops of water were dropped on the shirt, and the water repellency was visually evaluated. Further, this shirt was repeatedly washed with a commercially available household detergent in a washing machine and naturally dried 10 times, and the water repellency thereafter was similarly evaluated. Evaluation criteria A: extremely good. ：: good. Δ: Somewhat poor. X: Poor.

[0035] One cotton fabric of a 5% ethanol solution 2g of smoothness each copolymer (1
0 g) and air-dried. The smoothness of this cloth was sensory-evaluated by hand with 20 specialized panels. Evaluation criteria A: 15 or more respondents answered that they were good. ：: 10 to 14 persons answered that it was good. Δ: 5 to 9 persons answered that they were good. X: Four or less responded that it was good.

Gluing A 5% ethanol solution of the test copolymer was sprayed onto a cotton shirt and cured by applying a steam iron. The state immediately after the ironing was evaluated organoleptically by touch. Furthermore, the gluing property after washing and drying 10 times was also evaluated in the same manner as in the water repellency test. Evaluation criteria A: extremely good. ：: good. Δ: Somewhat poor. X: Poor.

[0037] in the same manner as in the wrinkles stretch, wrinkle resistant the gluing test, to determine the wrinkles of the state after the ironing and after 10 times washing and drying in a vision, were evaluated wrinkles stretched and anti-wrinkle properties. Evaluation criteria A: extremely good. ：: good. Δ: Somewhat poor. X: Poor.

Antifouling properties One drop of coffee liquid was dropped on a shirt treated in the same manner as in the above water repellency test, and the stain adhesion after wiping off with another cloth was visually judged to evaluate the antifouling properties. Evaluation criteria A: extremely good. ：: good. Δ: Somewhat poor. X: Poor.

Smoothness 2 g of a 5% ethanol solution of each copolymer was applied to one cotton cloth (1
0 g) and air-dried. The slimyness of the cloth was evaluated by hand by 20 sensory professional panels. Evaluation criteria A: 15 or more respondents answered that they were good. ：: 10 to 14 persons answered that it was good. Δ: 5 to 9 persons answered that they were good. X: Four or less responded that it was good.

The structures of the respective monomers used below are as follows. Monomer A1:

Embedded image Monomer B1:

Embedded image Monomer C1 (molecular weight 422):

Embedded image Monomer C2 (average molecular weight 12,000):

[0041]

Embedded image Monomer C3 (average molecular weight 5,000):

Embedded image Monomer C4:

Embedded image Monomer D1:

Embedded image

[0042]

[Table 1] 共 Copolymer monomer [parts by weight] Water repellency Antifouling Smoothness A1 B1 C2 Immediately after treatment After washing ──────────────────────────────────── 1 10 40 50 ○ × ○ ◎ 2 20 40 40 ○ × ◎ ◎ 3 45 50 5 ◎ ◎ ◎ ◎ ◎ 4 50 25 25 ◎ ◎ ◎ ◎ ◎ 5 50 10 40 ◎ ◎ ◎ ◎ ◎ 6 55.6 33.3 11.1 ◎ ◎ ◎ ◎ ◎ ◎ 7 60 35 5 ◎ ◎ ◎ ◎ 8 71.4 14.3 14.3 ◎ ◎ ◎ ◎ 9 85 10 5 ○ △ ○ ◎ ────────────────────────────── Ａ a 100--△ × △ × b 50 50-○ ○ ○ △ c 50-50 − * − * − * − * ──────────────── ──────────────────── * not tested

As can be seen from Table 1, the copolymer a comprising only the monomer (A) has low water repellency and antifouling property, and has a poor feeling upon use. Flaking also occurs. On the other hand, the copolymer b comprising the monomer (A) and the monomer (B) improves these effects, but is not sufficient. On the other hand, the copolymer composed of the monomers (A) to (C) can exhibit extremely excellent water repellency and antifouling property, and has a very good feeling of use without any stickiness. Was. In addition,
If the proportion of the monomer (A) in the copolymer is too small or too large, the water repellency and the washing resistance tend to decrease.
It is preferably 85% by weight, more preferably 40-75% by weight.

The water repellency of the monomer (C) can be remarkably increased, and a smooth feel can be given to the fiber. In order to obtain such an effect, the proportion of the monomer (C) in the copolymer is as follows:
It is at least 1% by weight, preferably at least 5% by weight. In addition,
As for the monomer (B), the copolymer c composed of the monomer (A) and the monomer (C) was extremely sticky and was extremely difficult to use, so the presence of the monomer (B) was C) to reduce stickiness,
It was suggested that appropriate coating properties were given. In the copolymer, the proportion of the monomer (B) is at least 5% by weight, preferably at least 10% by weight.

[0045]

[Table 2] ──────────────────────────────────── Copolymer monomer [parts by weight] Water repellency Antifouling Smoothness A1 B1 C * Immediately after treatment After washing ──────────────────────────────────── 10 50 10 40 (C1) ◎ ◎ ◎ ◎ 11 60 35 5 (C3) ◎ ◎ ◎ ◎ 12 60 35 5 (C4) ◎ ◎ ◎ ◎ 13 50 25 25 (C4) ◎ ○ ◎ ◎ ─────── ─────── ───────────────────────────── * () shows the used monomer. As can be seen from Table 2, monomer (C) is monomer C1,
In the case of a copolymer which is C3 or C4, the monomer C
The same effect as in the case of the copolymer No. 2 was obtained.

[0046]

[Table 3] ──────────────────────────────────── Copolymer monomer [parts by weight] Water repellency A1 B1 C3 C4 D1 Immediately after treatment After washing ──────────────────────────────────── 11 60 35 5--◎ ◎ △ 12 60 35-5-◎ ◎ △ ─────────────────────────────────── ─ 14 60 35 5-10 ◎ ◎ ◎ 15 60 35-5 10 ◎ ○ ◎ 16 60 35-5 20 ◎ ○ ◎ 17 60 35-5 50 ○ ○ ◎ 18 60 35-5 100 △ × ◎ ──── ────────────────────────────────

As can be seen from Table 3, the monomers (A) to
The copolymer composed of (D) gives the fiber a slimy feeling and a moist touch. When the proportion of the monomer (D) is increased, the hydrophilicity of the crosslinked body coating is increased, and the water repellency and the washing resistance tend to be reduced. Therefore, the ratio of the monomer (D) is 1 to 1 with respect to the total weight of the monomers (A) to (C) in the copolymer.
00% by weight, preferably 5 to 50% by weight.

[0048]

[Table 4] 処理 Untreated copolymer 4 10 11 13 15 ┌─────────────────────────────────── Gluing property (immediately after processing) ◎ ◎ ◎ ◎ ◎ × (Washing After) ◎ ◎ ◎ ○ ○ × ┌─────────────────────────────────── Wrinkle straightening (immediately after ironing) ◎ ◎ ◎ ◎ ◎ × ・ Wrinkle resistance (after washing) ◎ ○ ◎ ○ ○ × ┌─────────────────────────────わ か る As can be seen from Table 4, the copolymer according to the present invention exerts excellent effects on the sizing property to the fiber, the wrinkle elongation and the anti-wrinkle property.

[0049]

[Table 5] 処理 Untreated copolymer 4 10 11 13 15水性 Water repellency (immediately after treatment) ◎ ◎ ◎ ◎ ◎ × ┌─汚 Antifouling property ◎ ◎ ◎ ◎ ◎ × ┌────── ───────────────────────────── Table 5 shows the water repellency test and stain resistance using paper instead of cotton shirt. This is the result of the test. From this, it is understood that high water repellency and antifouling property can be obtained even when the copolymer of the present invention is treated on paper.

[0050]

[Table 6] 未 Untreated copolymer 4 10 11 13 15接触 Contact angle 96.0 96.4 92.0 97.0 94.6 9.7 ┌─────傾斜 Inclination angle 13.0 11.0 14.2 15.0 13.8-* ┌────────── ───────────────────────── * Water droplets remain and measurement is not possible.

Table 6 shows the results obtained by using a glass plate in place of the cotton shirt and treating the glass in the same manner as in the water repellency test to examine the degree of hydrophobicity of the glass. The degree of hydrophobicity was evaluated based on the contact angle with water and the inclination angle. As for the contact angle, one drop of water was dropped on glass, and the contact angle was measured. In addition, the inclination angle was set at an angle to the glass little by little, and the angle at which the water droplet began to move was measured. The greater the contact angle and the smaller the inclination angle, the greater the degree of hydrophobicity. As a result, the glass sheet treated with the copolymer according to the present invention has a very large contact angle with water, while the inclination angle is very small, as compared with the untreated glass sheet. This indicates that the copolymer according to the present invention can impart a very high hydrophobicity even to a glass plate.

[0052]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited thereto. Synthesis Examples 1 to 24 The monomer mixture was mixed with ethanol 1 at each charge so that the monomers (A) to (D) had the ratios shown in Table 7, respectively.
After dissolving in 100 ml, and heating and stirring at 70 ° C. for 1 hour under a nitrogen stream, 0.05 g of potassium persulfate was added and reacted overnight to complete the copolymerization reaction. The reaction was cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in ethanol (10 ml) and added to n-hexane (500 ml). The precipitate was collected to obtain the desired copolymer.

[0053]

[Table 7] 合成 Synthesis example Monomer [parts by weight] Rate A1 B1 C1 C2 C3 C4 D1 (g) (%) ──────────────────────────────────── 15 14----20 97.5 25 1 2----16 96.9 35 1-4---20 98.5 4.5 1-1---14 100.0 55 3-1---18 98.9 6 12 7-1---20 97.5 7 9 10-1---20 92.5 8 2 1-1---20 98.5 9 5 1--4--20 99.0 10 12 7--1--20 97.0 11 9 10--1--20 95.0 12 5 1---4-20 99.0 13 5 3---1-20 97.5 14 12 7---1-20 98.5 15 9 10---1-20 94.5 16 2 1---1-20 97.5 17 12 7--1 2-20 97.0 18 12 7---1 2 20 99.5 19 12 7---1 4 22 90.9 20 12 2---6 2 22 91.4 21 12 2---6 4 24 96.7 22 12 4---4 2 22 90.0 23 12 4---4 4 24 91.3 24 4 8-8---20 91.0 ───────── ─────── ───────────────────

FIGS. 2 to 5 show Synthesis Examples 6, 10 and 10, respectively.
13 shows NMR spectrum data of the copolymers obtained in Nos. 12 and 18. Each of these copolymers has its NMR
Spectral data (solvent CDCl ₃ or DMSO-d ₆ )
No peak of CH ₂ ＣC hydrogen atoms derived from the raw material monomer, which was observed in the vicinity of 6 to 7 ppm, was observed, and this confirmed the formation of the copolymer. It should be noted that formation of the copolymer was similarly confirmed for other copolymers.

[0055]

By applying the copolymer according to the present invention to the material to be treated and then hydrolyzing it, a strong crosslinked product film is formed on the surface, and excellent water repellency, antifouling property, sizing property, Wrinkle resistance, good feeling of use, and the like can be imparted. In addition, these effects are not reduced by water or a detergent, and exhibit high durability.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a crosslinking reaction of a copolymer according to the present invention.

FIG. 2 is an NMR spectrum diagram of a copolymer according to one example of the present invention.

FIG. 3 is an NMR spectrum diagram of a copolymer according to one example of the present invention.

FIG. 4 is an NMR spectrum diagram of a copolymer according to one example of the present invention.

FIG. 5 is an NMR spectrum diagram of a copolymer according to one example of the present invention.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09K 3/18 104 C09K 3/18 104 D06M 15/643 D06M 15/643

Claims (9)

[Claims] 1. A monomer (A) represented by the following general formula (I), a monomer (B) represented by the following general formula (II), and a monomer (C) represented by the following general formula (III) A copolymer having as a constituent monomer. Embedded image (In the general formula (I), R ₁ is a hydrogen atom or a methyl group, R ₂
Represents an alkylene group having 1 to 6 carbon atoms, and R ₃ , R ₄ and R ₅ each represent a reactive functional group capable of crosslinking between the copolymer molecules by being hydrolyzed. ) (In the general formula (II), R ₆ represents a hydrogen atom or a methyl group, R ₇
Represents an alkyl group having 1 to 18 carbon atoms. ) (In the general formula (III), R ₈ represents a hydrogen atom or a methyl group;
₉ means an alkylene group having 1 to 6 carbon atoms. X means a group represented by any of the following formulas (IV) to (VI). ) (In the general formula (IV), R ₁₀ represents an alkyl group having 1 to 6 carbon atoms.) (In the general formula (V), R ₁₁ is an alkyl group having 1 to 6 carbon atoms, x ₁
Means a positive integer. ) (In the general formula (VI), R ₈ and R ₉ are as defined above.
₁₂ is an alkyl group having 1 to 6 carbon atoms, x ₂ denotes a positive integer. ) 2. The copolymer according to claim 1, wherein the proportion of the monomer (A) is 25 to 85% by weight in the copolymer. 3. The copolymer according to claim 1, wherein the proportion of the monomer (B) is at least 5% by weight in the copolymer.
A copolymer, wherein the proportion of the monomer (C) is 1% by weight or more in the copolymer. 4. The copolymer according to claim 1, further comprising a monomer (D) represented by the following general formula (VII) as a constituent monomer. Embedded image (In the general formula (VII), R ₁₃ is a hydrogen atom or a methyl group,
R ₁₄ represents an alkylene group having 1 to 6 carbon atoms. Y is-
A group represented by N ⁺ (R ₁₅ ) ₃ or —N (R ₁₅ ) ₂ ;
R ₁₅ represents an alkyl group having 1 to 6 carbon atoms. ) 5. The copolymer according to claim 4, wherein the proportion of the monomer (D) is 1 to the total weight of the monomers (A), (B) and (C) in the copolymer. 1
A copolymer characterized by being in the range of 00% by weight. 6. The copolymer according to claim 1, wherein R ₃ , R ₄ and R ₅ are an alkoxy group having 1 to 6 carbon atoms. 7. A fiber treating agent comprising the copolymer according to claim 1. 8. A water repellent comprising the copolymer according to claim 1. 9. The copolymer according to claim 1, wherein the copolymer according to any one of claims 1 to 5 is applied to a material to be treated, then hydrolyzed to crosslink the copolymer molecules. Processing method.