JPH1180711A - Water repellent and treatment thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water repellent, capable of manifesting excellent water repellency or the like and excellent even in durability by using a copolymer containing a trifunctional silyl group-containing acrylic ester and an acrylic acid-based alkyl ester as constituent monomers. SOLUTION: This water repellent comprises a copolymer containing (A) a monomer represented by formula I (R1 is H or the like; R2 is a 1-6C alkylene; R3 to R5 are each a reactive functional group) and (B) a monomer represented by formula II (R6 is H or the like; R7 is a 1-18C alkyl) as constituent monomers. A material to be treated is coated with the water repellent and the functional silyl groups are then hydrolyzed to cross-link the copolymer. Thereby, excellent water repellency and anti-fouling properties are imparted to the material to be treated. The copolymer preferably has (C) a monomer represented by formula III [R8 is H or the like; R9 is a 1-6C alkylene; X is a group represented by formula IV (R10 is a 1-6C alkyl) or the like] as a constituent monomer. The amounts of the components in the water repellent are preferably 25-85 wt.% component A, >=5 wt.% component B and >=1 wt.% component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel reactive silyl group-containing copolymer, particularly a copolymer which imparts excellent water repellency and antifouling property to a material to be treated, and also has excellent durability. The present invention relates to coalescence and a processing method thereof.

[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.

[0003]

However, there has not yet been obtained any satisfactory water repellency, stain resistance and durability. In addition, although the degree of water repellency is of course, especially for textile materials, since it is repeatedly washed and folded, it is required to have higher durability than other materials, and it does not cause flaking and its use. Feeling is also very important. The present invention has been made in view of such problems of the related art, and an object thereof is to easily impart durable water repellency and antifouling property to a material to be treated, and to a fiber material. Another object of the present invention is to provide a substance capable of giving a good feeling of use and a method for treating the substance.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, (A) an acrylic acid ester having a trifunctional silyl group; and (B)
Good water repellency and antifouling properties are imparted by applying a copolymer having an acrylic acid alkyl ester as a constituent monomer to the material to be treated, and then hydrolyzing the copolymer to crosslink the copolymer. The inventors have found that the durability is high and no flaking occurs, and the present invention has been completed.

That is, the water repellent 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 is characterized by comprising a copolymer having the monomer (B) represented by I) 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. )

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. )

In the present invention, it is preferable that the copolymer has a monomer (C) represented by the following general formula (III) as a constituent monomer.

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). )

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 water repellent of the present invention, the proportion of the monomer (A) is preferably 25 to 85% by weight in the copolymer. In the water repellent of the present invention, the proportion of the monomer (B) is preferably 5% by weight or more in the copolymer, and the proportion of the monomer (C) is preferably 1% by weight or more in the copolymer. In the water repellent of the present invention, the copolymer may further have 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 determined based on the ratio of the monomers (A), (B) and (C) in the copolymer.
Is preferably in the range of 1 to 100% by weight based on the total weight of Further, in the water repellent of the present invention, R ₃ , R ₄
And R ₅ is preferably an alkoxy group having 1 to 6 carbon atoms. The water repellent treatment method of the present invention is characterized in that after applying the water repellent to a material to be treated, the material is hydrolyzed to crosslink the copolymer molecules.

[0009]

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.

In the copolymer of the present invention, in order to enhance the effect, it is preferable that the monomer (C) be a constituent monomer in addition to the monomers (A) and (B). The monomer (C) is a siloxane-containing (meth) acrylate. 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,
-A hydroxypropylene group. X represents the above-mentioned general formula (I
It means a siloxane represented by any of V) 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 above 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.

The monomer (E) other than the above-mentioned monomers (A) to (D) can be contained as a constituent monomer of the copolymer of the present invention as long as the effects of the present invention are not impaired. 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 the solvent used in the polymerization, any solvent can be used as long as it can dissolve or suspend the monomer, and can be any organic solvent containing no water, such as methanol, ethanol, and the like. 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 from 2 to
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 thus obtained copolymer of the present invention 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. The monomer composition of the copolymer of the present invention is such that the proportion of the monomer (A) in the copolymer is 2%.
It is preferably from 5 to 85% by weight, more preferably from 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, the water repellency and the washing resistance also 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. Further, the feeling of use may be poor or flaking may occur.

The monomer (B) contributes to the water repellency of the crosslinked film, and suppresses the flaking and the stickiness of the monomer (C) to adjust the properties of the crosslinked film. The proportion of the monomer (B) is at least 5% by weight, preferably at least 10% by weight in the copolymer. 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 75% by weight or less, preferably 60% by weight. It is as follows.

The monomer (C) has a siloxane moiety,
As a result, the water repellency of the crosslinked film can be remarkably increased, and the fiber can be given a smooth finish to achieve a good finish. It also suppresses flaking. In the copolymer of the present invention, the content of the monomer (C) is at least 1% by weight, preferably at least 5% by weight. However, when the proportion of the monomer (C) is too large, the proportion of other monomers becomes relatively low. The content is at most 70% by weight or less, preferably 60% by weight or less, since the washing resistance tends to be poor.

Further, when a copolymer having the monomer (A) as a constituent monomer is further treated together with the above monomers (A) to (C), the fiber has 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 treatment 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.

The copolymer of the present invention forms a crosslinked film excellent in water repellency and antifouling property by performing a crosslinking treatment on the material to be treated. The coating is very hard to remove even with water or a detergent, so that these effects are continuously exhibited. Therefore, the coating can be used as a water repellent and an antifouling agent for various materials. In addition, since this crosslinked film has no flaking and has an excellent feeling in use when applied to a fiber material, it is also suitable as a fiber treatment agent.

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).

Accordingly, the copolymer is coated and then hydrolyzed to cause cross-linking at the coated portion, whereby the cross-linked body covers the material to be treated firmly and uniformly in a mesh-like manner, and has a water-repellent property and washing resistance. It is assumed that an excellent film is formed. In addition,
Even if you synthesize this crosslinked product in advance and try to apply it,
It is very difficult to apply the crosslinked product because it 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 allowed to air dry. 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.

[0033] 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.

Antifouling property One drop of coffee liquid was dropped on a shirt treated in the same manner as in the water repellency test, and the degree of adhesion of the stain after wiping with a separate cloth was visually judged to evaluate the antifouling property. 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):

[0037]

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

Embedded image Monomer C4:

Embedded image Monomer D1:

Embedded image

2.0 g of the monomer A1 (3-methacryloxypropyltrimethoxysilane) and 8.0 g of the monomer B1 (methyl methacrylate) of the copolymers 1 to 6 were dissolved in 100 ml of ethanol.
After 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 10 ml of ethanol, and n-hexane 500
ml. The precipitate was separated and copolymer 1 was obtained. Copolymers 2 to 6 were prepared in the same manner as copolymer 1 except that the ratio of monomer A1 and monomer B1 was as shown in Table 1.
I got

Test results

[Table 1] 共 Copolymer monomer [parts by weight] Water repellency Antifouling Smoothness A1 B1 Immediately after treatment After washing １ 1 20 80 ○ × ○ △ 233 67 ○ ○ ○ △ 3 50 50 ○ ○ ○ △ 4 67 33 ○ ○ ○ △ 5 83 17 ○ △ ○ △ 6 100 0 △ × △ × ─────────── ───────────────────────── Unprocessed − − × × × × ───────────────── ───────────────────

As can be seen from Table 1, a copolymer comprising the monomer (A) and the monomer (B) can impart good water repellency and antifouling property. When the proportion of the monomer (A) in the copolymer is too small, sufficient washing resistance cannot be obtained, and the durability of the effect is poor. On the other hand, when the monomer (A) is 100%, water repellency, washing resistance, and antifouling properties tend to decrease. In this case, the feeling of use was poor and flaking occurred. Therefore, the proportion of the monomer (A) is 25 to 85% by weight in the copolymer,
More preferably, it is in the range of 40 to 75% by weight. Next, a test was conducted on a copolymer having the monomers (C) and (D) together with the monomers (A) and (B).

[0041]

[Table 2] ──────────────────────────────────── Copolymer monomer [parts by weight] Water repellency Antifouling Smoothness A1 B1 C2 Immediately after treatment After washing ７ 7 10 40 50 ○ × ○ ◎ 8 20 40 40 ○ × ◎ ◎ 9 45 50 5 ◎ ◎ ◎ ◎ ◎ 10 50 25 25 ◎ ◎ ◎ ◎ ◎ 11 50 10 40 ◎ ◎ ◎ ◎ 12 55.6 33.3 11.1 ◎ ◎ ◎ ◎ ◎ 13 60 35 5 ◎ ◎ ◎ ◎ 14 71.4 14.3 14.3 ◎ ◎ ◎ ◎ 15 85 10 5 ○ △ ○ ◎ ────────────────────────────── ────── 16 50-50 − * − * − *-* ──────────────────────────────── ──── * not tested

As can be seen from Tables 1 and 2, when the copolymer comprising the monomers (A) to (C) was treated,
Compared to the case of only monomer (A) and monomer (B),
Water repellency, washing resistance, and antifouling properties can be significantly improved. The finished shirt was also very smooth and extremely good. In order to obtain such effects, the proportion of the monomer (C) in the copolymer is at least 1% by weight, preferably at least 5% by weight. As for the monomer (B), in the case of the copolymer 15 composed of the monomer (A) and the monomer (C), the stickiness was remarkable and the use was very difficult. Reduces stickiness due to monomer (C),
It was suggested that appropriate coating properties were given. The proportion of the monomer (B) in the copolymer is at least 5% by weight, preferably at least 10% by weight.

[0043]

[Table 3] ──────────────────────────────────── Copolymer monomer [parts by weight] Water repellency Antifouling Smoothness A1 B1 C * Immediately after treatment After washing ──────────────────────────────────── 17 50 10 40 (C1) ◎ ◎ ◎ ◎ 18 60 35 5 (C3) ◎ ◎ ◎ ◎ 19 60 35 5 (C4) ◎ ◎ ◎ ◎ 20 50 25 25 (C4) ◎ ○ ◎ ◎ ─────── ─────── ───────────────────────────── * () shows the used monomer. As can be seen from Table 3, 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.

[0044]

[Table 4] ──────────────────────────────────── Copolymer monomer [parts by weight] Water repellency A1 B1 C3 C4 D1 Immediately after treatment After washing ──────────────────────────────────── 18 60 35 5--◎ ◎ △ 19 60 35-5-◎ ◎ △ ─────────────────────────────────── ─ 21 60 35 5-10 ◎ ◎ ◎ 22 60 35-5 10 ◎ ○ ◎ 23 60 35-5 20 ◎ ○ ◎ 24 60 35-5 50 ○ ○ ◎ 25 60 35-5 100 △ × ◎ ──── ────────────────────────────────

As can be seen from Table 4, 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.

[0046]

[Table 5] 未 Copolymer untreated 3 5 10 17 18 20 22 水性 Water repellency (immediately after treatment) ○ ○ ◎ ◎ ◎ ◎ ◎ × ┌─────────────────────────────────── Antifouling property ○ ○ ◎ ◎ ◎ ◎ ◎ × ┌ ─────────────────────────────────── Table 5 shows the similar repellency using paper instead of cotton shirt. It is a result of performing an aqueous test and an antifouling 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.

[0047]

[Table 6] 未 Copolymer untreated 3 5 10 17 18 20 22 ┌─────────────────────────────────── Contact angle 96.0 94.5 96.0 96.4 92.0 97.0 94.6 9.7 ┌─傾斜 Inclination angle 14.8 15.5 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 instead of a cotton shirt and treating the glass in the same manner as in the above-mentioned 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 plate treated with the copolymer according to the present invention has a very large contact angle with water and a very small inclination angle as compared with the untreated glass plate. This indicates that the copolymer according to the present invention can impart a very high hydrophobicity even to a glass plate.

[0050]

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.

[0051]

[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 the synthesis examples 6 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. In the present invention, the formation of the copolymer was similarly confirmed for other copolymers.

Synthesis Example 25 Monomer A1 10.00 g, Monomer B1 2.02 g
Was dissolved in 100 ml of ethanol, and heated to 70 ° C under a nitrogen stream.
After heating and stirring for 1 hour, 0.05 g of dimethyl 2,2-azobis (isobutyrate) was added, and the mixture was heated and stirred at 70 ° C. for 24 hours to complete the copolymerization reaction. Cool the reaction to room temperature,
It was concentrated under reduced pressure. The residue is dissolved in 10 ml of ethanol, and n
-Added in 500 ml of hexane. Collect the sediment,
11.50 g (yield 95.7%) of the desired copolymer was obtained.

Synthesis Example 26 3-Methacryloxypropyltriethoxysilane
00 g and 5.00 g of ethyl methacrylate in ethanol 1
After stirring under heating in a nitrogen stream at 70 ° C. for 1 hour, 2,2-azobisisobutyronitrile 0.05 g
Was added and stirred at 70 ° C. for 24 hours to complete the copolymerization reaction. The reaction was cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in 10 ml of ethanol, and n-hexane 500
ml. The precipitate was collected to obtain 14.20 g (yield 94.7%) of the desired copolymer. Synthesis Example 27 Monomer A1 10.00 g, Monomer B1 10.00
g and the intended copolymer 1 in the same manner as in Synthesis Example 3
8.95 g (94.8% yield) was obtained.

[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 of the material, resulting in excellent water repellency, antifouling properties, feeling of use, etc. Can be provided. 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 code FI C08G 77/442 C08G 77/442 C08J 3/24 CEY C08J 3/24 CEYZ D06M 15/263 D06M 15/263

Claims (8)

[Claims] 1. A water repellent comprising a copolymer having, as constituent monomers, a monomer (A) represented by the following general formula (I) and a monomer (B) represented by the following general formula (II). 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. ) 2. The water repellent according to claim 1, wherein the copolymer further comprises a monomer (C) represented by the following general formula (III) as a constituent monomer. 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). ) (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. ) 3. The water repellent according to claim 1 or 2,
The proportion of the monomer (A) is 25 to 85% by weight in the copolymer.
A water repellent, characterized in that: 4. The water repellent according to claim 2, wherein
A water repellent, wherein the proportion of the monomer (B) is 5% by weight or more in the copolymer, and the proportion of the monomer (C) is 1% by weight or more in the copolymer. 5. The water repellent according to claim 1, wherein the copolymer further comprises a monomer (D) represented by the following general formula (VII) as a constituent monomer. Water repellent. 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. ) 6. The water repellent according to claim 5, wherein the proportion of the monomer (D) is 1 to 1 based on the total weight of the monomers (A), (B) and (C) in the copolymer. 10
A water repellent characterized by being in the range of 0% by weight. 7. The water repellent according to claim 1, wherein R ₃ , R ₄ and R ₅ are an alkoxy group having 1 to 6 carbon atoms. 8. A water-repellent treatment method comprising applying the water-repellent agent according to claim 1 to a material to be treated, hydrolyzing the material, and crosslinking the copolymer molecules.