JP2021024868A - Water-repellent agent composition and method of treating fiber product - Google Patents

Abstract

To provide a water-repellent agent composition capable of imparting water repellency excellent in removability of water droplets to a material to be treated without impairing the texture.SOLUTION: The water-repellent agent composition contains (X) a silicone-containing block copolymer and (Y) an alcohol. The mass ratio of (X) is 0.1 to 10 pts.mass and the mass ratio of (Y) is 90 to 99.9 pts.mass when the total content of (X) and (Y) is 100 pts.mass. The (X) is composed of (A) a silicone segment and (B) a non-silicone segment. The mass ratio ((A)/(B)) of the silicone segment (A) to the non-silicone segment (B) is 30/70 to 70/30. The alcohol (Y) is one or more kinds of alcohols selected from the group consisting of a 2-4C monohydric alcohol and a 2-4C dihydric alcohol.SELECTED DRAWING: None

Description

The present invention relates to a water repellent composition capable of imparting excellent water repellency to an object to be treated.

In recent years, there has been an increasing demand for non-fluorine-based water repellents that do not contain fluorine compounds as water repellents for treating products such as textiles, clothing, and leather. As an alternative to the fluorine-based water repellent, a water repellent composition containing a silicone resin as a main component is used. However, in general, from the viewpoint of solubility, an organic solvent such as ketones, esters, aliphatic or aromatic hydrocarbons is used for the silicone resin. Therefore, a solvent having high safety is required.

On the other hand, regarding water repellency, when rainwater adheres to textile products in daily life or during sports, not only is it difficult for water droplets to penetrate (large contact angle), but it is also easy to roll off from the surface (water droplets). (Highly removable) is required.

Under such circumstances, for example, Patent Document 1 discloses a water-repellent treatment agent using an acrylic-silicone-based graft copolymer using alcohol as a main solvent. This acrylic-silicone graft copolymer is a copolymer of a silicone-containing monomer and a (meth) acrylic acid alkyl ester monomer.

Further, Patent Document 2 discloses a water repellent treatment agent using a highly safe acrylic-silicone copolymer using only alcohol as a solvent.

JP-A-7-97770 JP-A-2004-210962

However, although the water repellent treatment agent disclosed in Patent Document 1 exhibits water repellency comparable to that of a fluorine-based water repellent, it is necessary to contain an organic solvent such as toluene in order to dissolve the graft copolymer in an alcohol solvent. Yes, it lacks safety.

Further, in the water repellent treatment agent described in Patent Document 2, although the static contact angle of water shows a large value, since the copolymer contains a hydrophilic monomer, it interacts with water and water droplets adhere to it. It tends to be easy and difficult to roll off.

The present invention has been made in view of the above problems, and an object of the present invention is that it can be applied to a highly safe alcohol solvent, does not impair the texture of the object to be treated, and has excellent water droplet repellent properties. An object of the present invention is to provide a water repellent composition capable of imparting water content.

As a result of diligent studies to achieve the above-mentioned problems, a silicone-containing block copolymer containing a structural unit derived from a specific (meth) acrylic acid alkyl ester monomer is soluble in alcohol, and further, the silicone-containing block copolymer It has been found that by treating an object to be treated such as a textile product with a composition in which a polymer is dissolved in alcohol, water repellency having excellent water droplet removability can be imparted, and the present invention has been completed.

（式（１）において、nは５〜５００の整数を表す。）

（式（２）において、
Ｒ^１は水素原子またはメチル基を示し、
Ｒ^２は炭素数２〜４の直鎖状の脂肪族炭化水素基を表す。）

（式（３）において、
Ｒ^３は水素原子またはメチル基を示し、
Ｒ^４は炭素数４の分岐状の脂肪族炭化水素基を表す。 Therefore, the present invention relates to (1) and (2).
(1) A water repellent composition containing (X) a silicone block copolymer and (Y) an alcohol.
When the total content of the (X) -containing silicone block copolymer and the (Y) alcohol is 100 parts by mass, the mass ratio of the (X) -containing silicone block copolymer is 0.1 to 10 parts by mass. (Y) The mass ratio of alcohol is 90 to 99.9 parts by mass.
The (X) -containing silicone block copolymer is composed of (A) silicone segment and (B) non-silicone segment.
When (A) the total content of the silicone segments is 100 parts by mass, (a) the mass ratio of the constituent units represented by the following formula (1) is 50 to 90 parts by mass, and (b) the following formula (2). The mass ratio of the structural unit represented by) is 0 to 25 parts by mass, and (c) the mass ratio of the structural unit represented by the following formula (3) is 10 to 50 parts by mass.
When (B) the total content of the non-silicone segment is 100 parts by mass, (b) the mass ratio of the structural unit represented by the following formula (2) is 0 to 50 parts by mass, and (c) the following formula (c) The mass ratio of the structural unit represented by 3) is 50 to 100 parts by mass.
The mass ratio ((A) / (B)) of the (A) silicone segment to the (B) non-silicone segment is 30/70 to 70/30.
(Y) A water repellent composition, wherein the alcohol is one or more alcohols selected from the group consisting of monohydric alcohols having 2 to 4 carbon atoms and dihydric alcohols having 2 to 4 carbon atoms.

(In equation (1), n represents an integer of 5 to 500.)

(In equation (2)
R ¹ represents a hydrogen atom or a methyl group
R ² represents a linear aliphatic hydrocarbon group having 2 to 4 carbon atoms. )

(In equation (3)
R ³ represents a hydrogen atom or a methyl group
R ⁴ represents a branched aliphatic hydrocarbon group having 4 carbon atoms.

(2) A method for treating a textile product, which comprises treating the textile product with the water-repellent composition of (1).

According to the present invention, it is possible to provide a water repellent composition capable of imparting water repellency having excellent water droplet removability to an object to be treated without using a harmful organic solvent without impairing the texture. it can.

In the water-repellent treatment agent of the present invention, the silicone-containing block copolymer is patented in that it also uses a (meth) acrylic acid alkyl ester monomer having a branched aliphatic hydrocarbon group having 4 carbon atoms. Unlike Document 1, this provides a water repellent composition that does not contain harmful organic solvents such as toluene.
Further, in the water repellent treatment agent of the present invention, the silicone-containing block copolymer is different from Patent Document 2 in that it does not contain a monomer having a tertiary amino group or a quaternary ammonium group, whereby water droplets slide off. A water repellent composition having a small angle value is obtained.

The water repellent agent according to this embodiment contains (X) a silicone block copolymer and (Y) alcohol.

[(X) -containing silicone block copolymer]
The (X) -containing silicone block copolymer according to the present embodiment has (A) a silicone segment and (B) a non-silicone segment.

<(A) Silicone segment>
The components of the silicone segment (A) are a structural unit derived from a silicone-containing monomer represented by the formula (a) (1) and an aliphatic group having 2 to 4 carbon atoms represented by the formula (b) (2). A structural unit derived from a (meth) acrylic acid alkyl ester monomer having a hydrocarbon group, (meth) acrylic acid having a branched aliphatic hydrocarbon group having 4 carbon atoms represented by the formula (3) (c). Contains structural units derived from alkyl ester monomers.

(A) In the formula (1), n represents an integer of 5 to 500. From the viewpoint of the present invention, n is preferably 50 to 300, and particularly preferably 50 to 200. The silicone-containing monomers may be used alone or in combination of two or more. The silicone-containing monomer (a) is available as a commercially available product, and is, for example, Cyraplane FM-0711 (in formula (1), n = 10) (manufactured by JNC Corporation), Cyraplane FM0721 (formula (1)). Among them, n = 64) (manufactured by JNC Corporation), silaplane FM0725 (in formula (1), n = 131) (manufactured by JNC Corporation) and the like, but are not limited thereto.

In formula (b) (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a linear aliphatic hydrocarbon group having 2 to 4 carbon atoms. The aliphatic hydrocarbon group is preferably an alkyl group or an alkenyl group, and examples thereof include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Be done. Preferably, it is an ethyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

The (meth) acrylic acid alkyl ester monomer having an aliphatic hydrocarbon group having 2 to 4 carbon atoms represented by the formula (2) may be used alone or in combination of two or more kinds.

In formula (c) (3), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a branched aliphatic hydrocarbon group having 4 carbon atoms. R ⁴ is branched alkyl group having 4 carbon atoms is preferably an alkenyl group, for example, isobutyl group, sec- butyl group, and a tert- butyl group, an isobutyl group, a tert- butyl group are preferred, A tert-butyl group is more preferred. As the (meth) acrylic acid alkyl ester monomer having a branched aliphatic hydrocarbon group having 4 carbon atoms represented by the formula (3), one kind or a combination of two or more kinds of monomers is used. Also, tert-butyl methacrylate is particularly preferable.

<(B) Non-silicone segment>
The (B) non-silicone segment includes (b) a structural unit derived from a (meth) acrylic acid alkyl ester monomer having an aliphatic hydrocarbon group having 2 to 4 carbon atoms represented by the following formula (2), and (c). ) Contains a structural unit derived from a (meth) acrylic acid alkyl ester monomer having a branched aliphatic hydrocarbon group having 4 carbon atoms represented by the formula (3). The non-silicone segment does not contain silicon atoms.

(B) In the formula (2), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a linear aliphatic hydrocarbon group having 2 to 4 carbon atoms. The aliphatic hydrocarbon group is preferably an alkyl group or an alkenyl group, and examples thereof include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Be done. Preferably, it is an ethyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.
The (meth) acrylic acid alkyl ester monomer having an aliphatic hydrocarbon group having 2 to 4 carbon atoms represented by the formula (2) may be used alone or in combination of two or more kinds.

In formula (c) (3), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a branched aliphatic hydrocarbon group having 4 carbon atoms and a branched aliphatic hydrocarbon group having 4 carbon atoms. R ⁴ is branched alkyl group having 4 carbon atoms is preferably an alkenyl group, for example, isobutyl group, sec- butyl group, and a tert- butyl group, an isobutyl group, a tert- butyl group are preferred, A tert-butyl group is more preferred. As the (meth) acrylic acid alkyl ester monomer having a branched aliphatic hydrocarbon group having 4 carbon atoms represented by the formula (3), one kind or a combination of two or more kinds of monomers is used. Also, tert-butyl methacrylate is particularly preferable.

<Polymerization method of silicone-containing block copolymer>
The silicone-containing block copolymer can be produced by a known method, but it can also be produced by a production method including the following first step and second step.
The first step is a step of polymerizing the monomer forming the (A) -containing silicone segment using the polymer peroxide as a polymerization initiator to obtain a peroxy bond-containing polymer.
The second step is a step of polymerizing the monomer forming the (B) non-silicone segment using the obtained peroxy bond-containing polymer as a polymerization initiator.

A polymer peroxide is a compound having two or more peroxy bonds in one molecule. As the polymer peroxide, for example, one represented by the following formula (4) or (5) can be used.

（式（４）中、ｍは２〜２０の整数を表す。）

(In equation (4), m represents an integer of 2 to 20.)

（式（５）中、ｌは２〜２０の整数を表す。）

(In equation (5), l represents an integer of 2 to 20.)

The polymer peroxides may be used alone or in combination of two or more.

The (X) -containing silicone block copolymer can be obtained by a solution polymerization method, a massive polymerization method, a suspension polymerization method, or an emulsion polymerization method using the polymer peroxide.

<(Y) alcohol>
The (Y) alcohol used as a solvent in the water repellent treatment agent of the present invention is one or more alcohols selected from the group consisting of monohydric alcohols having 2 to 4 carbon atoms and dihydric alcohols having 2 to 4 carbon atoms. (Y) The alcohol may be one kind, and two or more kinds may be mixed.

Examples of the (Y) alcohol include ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, ethylene glycol and the like. Of these alcohols, ethanol, n-propanol, and isopropyl alcohol are preferable from the viewpoint of safety, odor, and dryness.

<Composition ratio>
In the water repellent composition of the present invention, when the total content of (X) and (Y) is 100 parts by mass, the (X) -containing silicone block copolymer and (Y) alcohol are (X) -containing silicone. The block copolymer is contained in an amount of 0.1 to 10 parts by mass and (Y) alcohol is contained in an amount of 90 to 99.9 parts by mass, but the (X) -containing silicone block copolymer is preferably contained in an amount of 0.5 to 3. 0 parts by mass and (Y) alcohol are 97 to 99.5 parts by mass. When the content of the (X) -containing silicone block copolymer is smaller than 0.1 parts by mass in the range, the removability of water droplets tends to be low. On the other hand, when the content of the (X) -containing silicone block copolymer is larger than 10 parts by mass in the range, the texture of the object to be treated tends to decrease.

In the (X) silicone-containing block copolymer, when the mass ratio of the (A) silicone segment and the (B) non-silicone segment is (A) / (B), it is 30/70 to 70/30. Preferably, it is 40/60 to 60/40. When the mass ratio of the (A) silicone segment is smaller than 30/70 in the range, the removability of water droplets tends to be low. On the other hand, when the mass ratio of the (A) silicone segment is larger than 70/30, the solubility in alcohol tends to decrease.

When the total content of the (a) -containing silicone monomer and the (b) and (c) (meth) acrylic acid alkyl ester monomers in the (A) silicone segment is 100 parts by mass. The component (a) is contained in an amount of 50 to 90 parts by mass, the component (b) is contained in an amount of 0 to 25 parts by mass, and the component (c) is contained in an amount of 10 to 50 parts by mass. Preferably, the component (a) is 50 to 80 parts by mass, the component (b) is 10 to 25 parts by mass, and the component (c) is 20 to 50 parts by mass.
It is preferable that (A) is substantially composed of the components (a), (b) and (c), but the components other than (a) to (c) are 5 parts by mass or less within a range that does not adversely affect the present invention. It may be included.

When the total content of the (b) and (c) (meth) acrylic acid alkyl ester monomers in the (B) non-silicone segment is 100 parts by mass, the component (b) is 0 to 50 parts by mass. The component (c) is contained in an amount of 50 to 100 parts by mass, preferably the component (b) is contained in an amount of 10 to 50 parts by mass and the component (c) is preferably contained in an amount of 50 to 90 parts by mass.
It is preferable that (B) is substantially composed of the components (b) and (c), but the components other than (b) and (c) are contained in an amount of 5 parts by mass or less within a range that does not adversely affect the present invention. May be good.

Although the detailed factors have not been clarified, the (X) -containing silicone block copolymer contains the (meth) acrylic acid alkyl ester monomers of (b) and (c) in the above range. By doing so, it is considered that the (X) -containing silicone block copolymer takes a special dispersed state in alcohol and becomes soluble in alcohol. Furthermore, the branched butyl groups derived from the (c) (meth) acrylic acid alkyl ester monomer are thought to prevent interaction with water molecules and contribute to the formation of a surface on which water droplets can easily roll.

The water repellent composition of the present invention can be applied to an object to be treated by a conventionally known method. As a conventionally known method, for example, a method of applying a water repellent composition to the surface of an object to be treated by a dip coat, a spray coat, a roll coat or the like and drying it can be mentioned. Further, the water repellent composition of the present invention may be used in combination with additives such as an antibacterial agent, a moisturizer, an antistatic agent, a wrinkle preventive agent and a softener as long as the effects of the present invention are not impaired. is there.

Examples of the object to be treated with the water repellent composition of the present invention include textile products, leather, glass, plastic, paper and the like. Among them, it is possible to impart particularly excellent water repellency to textile products. Examples of textile products include synthetic fibers such as polyester, polyamide, polyvinyl chloride and polyacrylonitrile, animal natural fibers such as cotton, hemp and silk, semi-synthetic fibers such as rayon and acetate, and inorganic fibers such as glass fiber and carbon fiber. Fibers or mixed fibers thereof can be mentioned.

Hereinafter, specific examples of the present invention will be described.
(Example 1)
760 g of isopropyl alcohol (hereinafter, also referred to as IPA) was charged into a 5-liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, and heated to 70 ° C. while blowing nitrogen gas. Then, 180 g of n-butyl methacrylate (hereinafter, also referred to as BMA), 180 g of tert-butyl methacrylate (hereinafter, also referred to as tBMA), and silaplane FM0725 (manufactured by JNC) as a polysiloxane group-containing monomer were placed in the flask. Both the mixed solution consisting of 360 g and 250 g of IPA and the mixed solution consisting of 500 g of IPA and 180 g of the polymeric peroxide (l is 5) of the formula (5) were simultaneously added dropwise over 1 hour, and a polymerization reaction was further carried out for 3 hours to carry out a peroxy bond. A dispersion solution of a copolymer having a containing silicone segment was obtained.

Subsequently, a mixed solution consisting of 1101 g of IPA, 240 g of BMA, and 240 g of tBMA was added dropwise to the dispersion solution of the copolymer having the above-mentioned peroxy bond-containing silicone segment over 30 minutes, and a polymerization reaction was further carried out for 3 hours. Then, the temperature was raised to 80 ° C. and a polymerization reaction was carried out for 2 hours to obtain a solution containing (X) a silicone block copolymer having (A) a silicone segment and (B) a non-silicone segment.

As shown in Table 2, the composition ratios (A) / (B) of the (A) silicone segment and the (B) non-silicone segment in the (X) fluorine-containing block copolymer obtained in Example 1 are It is 60/40, and the ratio of the (a) -containing silicone monomer in the (A) silicone segment to the (b) and (c) (meth) acrylic acid alkyl ester monomers ((a) / (b) / (C)) is 50/25/25, and the ratio of (b) and (c) (meth) acrylic acid alkyl ester monomers in the (B) non-silicone segment is (((b) / (c)). It is 50/50.

(Examples 2 to 4)
In Examples 2 to 4, the monomers were produced in the same manner as in Example 1 except that the monomers were changed to the types or amounts shown in Table 2.

Next, a production example of the silicone-containing block copolymer according to Comparative Examples 1 to 4 will be described.

(Comparative Examples 1 to 4)
Comparative Examples 1 to 4 were produced in the same manner as in Example 1 except that the polymerization solvent or monomer was changed to the type or amount shown in Table 3.

The weight average molecular weight of the silicone-containing block copolymers obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was measured. Specifically, TOSOH HLC-8320 GPC was used as the GPC system, two TOSOH TSKgel Super Multipore HZ-M and one TOSOH TSKgel Super H-RC were continuously mounted as columns, and the column temperature was set to 40 ° C. as a reference. The substance was polystyrene, the developing solvent was tetrahydrofuran, the developing solvent was flowed at a flow rate of 1 mL / min, 0.1 mL of a sample solution having a sample concentration of 0.1% by weight was injected, and an EcoSEC-WorkStation GPC calculation program was used. It was measured.

In Tables 2 and 3, the parts by mass of each monomer are represented by values obtained by converting the total of the monomer components used in the above Examples and Comparative Examples into 100 parts by mass.

(Creation of test piece)
The dispersion solution of the silicone-containing block copolymer obtained above was diluted with IPA to prepare a solution having a concentration of 3% by mass. As a test piece, nylon taffeta (nylon 6, manufactured by Texwipe) was used. Nylon taffeta was applied by immersing it in each solution, after which excess treatment agent was removed and dried at 130 ° C. for 3 minutes.

(Water repellency test)
The water repellency of each test piece was evaluated by the static contact angle and the removability of water droplets. In general, the removability of water droplets can be evaluated by tilting the test piece on which the droplets are landed and measuring the sliding angle of the droplets.

The details of each evaluation method are as follows.
"Measurement of static contact angle"
The static contact angle was measured based on JIS R 3257. An automatic contact angle meter DropMaster500 (manufactured by Kyowa Interface Science Co., Ltd.) was used for the measurement. 6.0 μL of ion-exchanged water was dropped onto the prepared test piece, and the contact angle (θ _S ) (unit: °) of the water was measured.

"Measurement of sliding angle"
DMo-501 (manufactured by Kyowa Interface Science Co., Ltd.) was used for the measurement. 25 μL of ion-exchanged water was added dropwise, and the stage angle was slowly changed. The angle at which the droplet starts to fall is defined as the sliding angle (θ _T ) (unit: °), and the advance angle (θ _A ), receding angle (θ _R ), and contact angle hysteresis (cos θ = cos θ) are determined from the shape of the droplet at that time. _A −cosθ _R ) was determined.

(Evaluation of texture of test piece)
The texture of each test piece was evaluated according to the five-step criteria shown in Table 1.

[Evaluation results]
Table 2 shows the evaluation results of Examples 1 to 4, and Table 3 shows the evaluation results of Comparative Examples 1 to 4.

The raw materials used in Tables 2 and 3 are shown below.
FM0725: JNC siler plane FM0725 (Structure of equation (1): n = 131)
EMA: Ethyl methacrylate BMA: n-Butyl methacrylate iBMA: Isobutyl methacrylate tBMA: tert-Butyl methacrylate MMA: Methyl methacrylate MAA: IPA methacrylate: Isopropyl alcohol

As is clear from the results in Table 2, all of Examples 1 to 4 were soluble in IPA and were excellent in static contact angle, sliding angle, and texture.

On the other hand, as is clear from the results in Table 3, in Comparative Examples 1 to 4, the balance of these performances was insufficient.

Specifically, in Comparative Examples 1 and 2, the component (c) was not contained in the (A) silicone segment and the (B) non-silicone segment in the (X) -containing silicone block copolymer, and the carbon number was 1 ( The polymer solution was not soluble in IPA due to the inclusion of building blocks derived from the meta) acrylic acid alkyl ester monomer (MMA).

In Comparative Example 3, since the structural unit derived from the (meth) acrylic acid alkyl ester monomer having a branched aliphatic hydrocarbon group having 4 carbon atoms in the formula (c) (3) is not included, the sliding angle is large. The value is shown. In addition, the treated nylon taffeta was sticky, and a decrease in texture was observed.

In Comparative Example 4, since the (B) silicone segment in the (X) -containing silicone block copolymer contained a structural unit derived from the hydrophilic monomer (MAA), the sliding angle showed a large value. In addition, the treated nylon taffeta tended to become hard.

Claims (2)

A water repellent composition containing (X) a silicone block copolymer and (Y) an alcohol.
When the total content of the (X) -containing silicone block copolymer and the (Y) alcohol is 100 parts by mass, the mass ratio of the (X) -containing silicone block copolymer is 0.1 to 10 parts by mass. (Y) The mass ratio of alcohol is 90 to 99.9 parts by mass.
The (X) -containing silicone block copolymer is composed of (A) silicone segment and (B) non-silicone segment.
When (A) the total content of the silicone segments is 100 parts by mass, (a) the mass ratio of the constituent units represented by the following formula (1) is 50 to 90 parts by mass, and (b) the following formula (2). The mass ratio of the structural unit represented by) is 0 to 25 parts by mass, and (c) the mass ratio of the structural unit represented by the following formula (3) is 10 to 50 parts by mass.
When (B) the total content of the non-silicone segment is 100 parts by mass, (b) the mass ratio of the structural unit represented by the following formula (2) is 0 to 50 parts by mass, and (c) the following formula (c) The mass ratio of the structural unit represented by 3) is 50 to 100 parts by mass.
The mass ratio ((A) / (B)) of the (A) silicone segment to the (B) non-silicone segment is 30/70 to 70/30.
(Y) A water repellent composition, wherein the alcohol is one or more alcohols selected from the group consisting of monohydric alcohols having 2 to 4 carbon atoms and dihydric alcohols having 2 to 4 carbon atoms.

(In equation (1), n represents an integer of 5 to 500.)

(In equation (2)
R ¹ represents a hydrogen atom or a methyl group
R ² represents a linear aliphatic hydrocarbon group having 2 to 4 carbon atoms. )

(In equation (3)
R ³ represents a hydrogen atom or a methyl group
R ⁴ represents a branched aliphatic hydrocarbon group having 4 carbon atoms. A method for treating a textile product, which comprises treating the textile product with the water repellent composition according to claim 1.