KR101339752B1 - Synthesis of Fluoro type Durable water repellent Composition with internal Crosslinking Agent - Google Patents

Abstract

상기 화학식 1에서,
R은 탄소수 1 ~ 6의 알킬렌 또는 사이클로 알킬렌 중 단독 또는 이들의 혼합물이며, 분자 내의 이소시아네이트 갯수는 2개 또는 3개를 가질 수 있다.Durable fluorine water repellent composition and a method for synthesizing the crosslinking agent according to the present invention is characterized in that the monomer synthesized acrylate having a block isocyanate represented by the following formula (1) is emulsified with the fluorine water repellent monomer and then polymerized by a catalyst. It is done.
[Chemical Formula]

In Formula 1,
R is solely or a mixture of alkylenes or cycloalkylenes having 1 to 6 carbon atoms, and the number of isocyanates in a molecule may have two or three.

Description

Durable fluorine water repellent composition incorporating polyfunctional isocyanate that acts as a crosslinking agent and a method for synthesizing it {Synthesis of Fluoro type Durable water repellent Composition with internal Crosslinking Agent}

The present invention relates to a durable fluorine water repellent composition having a crosslinking agent and a method for synthesizing the same, and more particularly, to a blocky isocyanate derivative containing a crosslinking agent component in a molecular chain, which is synthesized by forcibly emulsifying a fluorinated acrylic resin to form a separate crosslinking agent. It relates to a durable fluorine water repellent composition for one-component fibers and a method of synthesizing which do not need to be added.

For many years, the public has become accustomed to purchasing fabrics or garments made from natural cellulose fibers such as cotton or cotton blends with various protective additives, resilience enhancement additives and / or softening additives to improve the properties of the garment. come. However, these additives can also impart undesirable properties to the fibers. As a result, it has become common practice to add one or more complementary materials to compensate for the deficiencies of various additives.

For example, fusiform resins, all or part of which are added to fabrics made of cellulose fibers, have been found to improve appearance and minimize ironing, while at the same time making the fabrics more susceptible to contamination, especially oily contamination. It has been found very difficult to remove these contaminations during washing, especially during washing. This tendency can be alleviated by adding textile finishes with polymers containing aliphatic fluorides. This gives the fabric a high oil and water repellency and reduces the tendency of the fabric to accept contamination. Further improvements can be made by adding constituents containing hydroxyl groups or other hydrophilic groups to the fluoropolymer to help remove dirt during washing.

Water repellents generally used for textiles include wax-based, higher alcohol-based, silicone-based and fluorine-based water repellents. Among these, fluorine-based water repellents are most usefully used because of their excellent water repellency and oil repellency due to the basic physical properties of fluorine. However, due to the characteristics applied to the fiber is exposed to various contaminants during use, and also through the repeated washing process is inevitable degradation of the water repellent performance. Usually, after 10 times of washing process, only water repellency of less than 50% of the initial water repellency is shown.

In order to improve this problem, a crosslinking agent is used in combination with a water repellent to improve water repellency and laundry durability. Durable water repellent is a crosslinking agent for achieving the purpose that there should be no decrease in water repellency in spite of the change of environment such as weather, degree of pollution according to the use condition, washing temperature, detergent amount and washing method according to the type of washing machine. It is necessary to use.

The crosslinking agent for a fluorine-repellent agent may include a blocked isocyanate compound, a melamine resin compound, a glyoxal resin compound, a urea resin compound, a polymer (acrylic acid ester copolymer) consisting of a crosslinkable monomer, and the like. .

 Blocked isocyanates are also usefully used in various fields for home and industrial use, including the use of adhesives, coupling agents, crosslinking agents and the like. Therefore, the demand for such blocked isocyanates continues to be demanded, and there is always a demand for a product having a new function and a complex function without deteriorating physical properties of the base.

Blocked isocyanates dissociate at high temperatures and isocyanates act as crosslinkers to the adhesive, improving the bond between the fluorine water repellent and the fiber, and also forming a three-dimensional network to improve durability.

However, the conventional blocked isocyanate is a hydrophobic material, so it cannot be used in combination with a fluorine water repellent used in water because it is not soluble in water. Therefore, the liquid is prepared through a forced emulsification process using a conventional surfactant. In this case, since the compatibility with the fluorine water repellent does not come out, it has a disadvantage in that each of the two water repellents and block crosslinking agent to be prepared separately after treatment to the fabric.

In addition, these blocked isocyanates are usually low in stability enough to generate precipitates within a period of about one week, and since the conventional fluorine water repellents are water repellent, only a very small amount of emulsifier is used to prepare the water repellents. When the mixture is mixed with each other, emulsification breakdown occurs, so that it cannot be used as a water repellent, or even when used, it does not have a water repellency.

The present invention for solving the above problems is synthesized so that the cross-linking agent component is forcibly introduced into the fluorine water repellent resin used to impart a water repellency having a durability to the textile fabric durability to realize water repellency and durability at the same time only one treatment It is an object to provide a composition of a fluorine water repellent agent.

In addition, the copolymerization of these two components requires forced emulsification using a mechanical homogenizer, and at the same time, a surfactant component designed to maintain a separate hydrophilic-lipophilic balance for a high emulsification process is required. The purpose is to provide an optimum durable water repellent composition and its synthesis method.

In order to achieve the above object, the present invention provides a durable fluorine water repellent composition in which a crosslinking agent is polymerized through a catalyst after emulsifying a monomer obtained by synthesizing an acrylate having a block isocyanate represented by Formula 1 with a fluorine water repellent monomer. .

[Formula 1]

In Formula 1,

R is solely or a mixture of alkylenes or cycloalkylenes having 1 to 6 carbon atoms, and the number of isocyanates in a molecule may have two or three.

In addition, R in the general formula (1) is more specifically alkylene, including methylene, butylene and hexamethylene having 1 to 6 carbon atoms, or R is cyclohexane, dicyclohexyl methane, phenylene, tolylene, xylene, Diphenylmethane, isopropylidene-bis (4-phenylene), naphthalene and isophorone.

In addition, the fluorine water repellent monomer is one selected from monomers having the following chemical formula structure.

(A)

Fluoroacrylate

R = -H or -CH ₃

l, m = 1 to 20

[Formula b]

Special reactive acrylates

R = -H or -CH ₃

R ₂ = -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH _3, -CH ₂ CH ₂ CH ₂ CH ₃

q = 1 to 20

(C)

Alkyl acrylate

R = -H or -CH ₃

 o = 1 to 22

[Chemical formula d]

Vinyl halogen compounds

R = -H or -CH ₃

 X = Halogen compound (ex. -F, -Br, -Cl)

In addition, the fluorine water repellent composition includes a reactive surfactant having the following chemical formula structure.

(E)

n = 1 to 50, m = 1 to 50

[Formula f]

l = 1 to 50,

R = -CH ₃ , -CH ₂ (CH ₂ ) sCH ₃ (S = 1-20), -Phenyl,

                -Octylphenyl,-Nonylphenyl

[Formula g]

o = 1 to 10, p = 1 to 50, q = 1 to 50

In another embodiment of the present invention for achieving the above object, by synthesizing the acrylate having a block isocyanate by synthesizing a polyfunctional isocyanate, a reactive monomer and a blocking agent represented by Scheme 1 below the synthesized monomer is a fluorine water repellent It is characterized by polymerizing with a catalyst after emulsifying with a monomer for the.

[Reaction Scheme 1]

The blocking agent is one selected from the group consisting of 2-butanone oxime, cyclohexanone oxime, malonic acid diethyl ester, 3-methylpyrazole, 3,5-dimethylpyrazole or a mixture thereof. Corresponds to

The present invention constituted and functioned as described above does not cause changes in emulsification fracture or sedimentation, which is a problem when using a conventional water repellent, when the water repellent agent and the crosslinking agent coexist in a single molecule, even when stored at a high temperature of 80 ° C. Improves the performance of more than 30%, and even after more than 20 washing process has a great effect that can maintain more than 80 water repellency.

Hereinafter, with reference to the accompanying drawings will be described in detail a preferred embodiment of the durable fluorine water repellent composition and a method for the synthesis of the cross-linking agent is introduced according to the present invention.

Durable fluorine water repellent composition and a method for synthesizing the crosslinking agent according to the present invention is characterized in that the monomer synthesized acrylate having a block isocyanate represented by the following formula (1) is emulsified with the fluorine water repellent monomer and then polymerized by a catalyst. It is done.

In Formula 1,

R is solely or a mixture of alkylenes or cycloalkylenes having 1 to 6 carbon atoms, and the number of isocyanates in a molecule may have two or three.

The fluorine water repellent composition in which the crosslinking agent is introduced according to the present invention is a fluorine water repellent composition for fibers containing a crosslinking agent component in a molecular chain. A one-component fluorine water repellent composition is described.

As shown in Formula 1 above, the polyfunctional isocyanate and the reactive monomer and the blocking are first synthesized to synthesize an acrylate having a block isocyanate. This monomer is forcibly emulsified together with a conventional fluorine-repellent monomer and then polymerized using a catalyst to finally synthesize a durable fluorine-repellent composition containing a crosslinking agent component.

The compound may be synthesized through the following reaction.

[Response]

In Formula 1, R is more specifically alkylene including methylene, butylene and hexamethylene having 1 to 6 carbon atoms, or R is cyclohexane, dicyclohexylmethane, phenylene, tolylene, xylene, di Phenylmethane, isopropylidene-bis (4-phenylene), naphthalene and isophorone.

In addition, the blowing agent is one selected from the group consisting of 2-butanone oxime, cyclohexanone oxime, malonic acid diethyl ester, 3-methylpyrazole, 3,5-dimethylpyrazole and mixtures thereof.

The durable water repellent may be synthesized by mixing the material of Formula 1 with the monomer for fluorine water repellent forcibly emulsifying.

Conventional fluorine water repellent monomers have the following types.

R = -H or -CH ₃

 l, m = 1 to 20

Fluoroacrylate

R = -H or -CH ₃

R ₂ = -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH _3, -CH ₂ CH ₂ CH ₂ CH ₃

 q = 1 to 20

Special reactive acrylates

R = -H or -CH ₃

 o = 1 to 22

Alkyl acrylate

R = -H or -CH ₃

 X = Halogen compound (ex. -F, -Br, -Cl)

Vinyl halogen compounds

In addition, the synthesis of the fluorine water repellent requires a reactive surfactant component whose molecular structure is designed to maintain a separate hydrophilic-lipophilic balance. Conventional water repellent surfactants are nonionic surfactants or cationic surfactants. Typically, the emulsifying nonionic surfactant is a polyoxyalkylene monoalkyl ether, polyoxyalkylene monoalkenyl ether, polyoxyethylene mono (substituted phenyl) ether, polyol fatty acid ester, polyoxyalkylene polyoxypropylene co It was selected from the group consisting of polymers (Co-Polymer) and mixtures thereof, and also cationic surfactants are typically substituted ammonium salt type surfactants, specifically monooctadecyltrimethylammonium chloride, monohexyltrimethylammonium chloride, mono HeC22 decyltrimethylammonium chloride dimethylmonoethylammoniumethylsulfate, monooctadecylmonomethyldipolyethyleneglycolammonium chloride, dialkyldimethylammonium chloride, dimethylmonlaurylamineacetic acid salt and mixtures thereof have been mainly used.

However, in the present reaction, since the crosslinking agent component is very poor in water stability, it is not possible to prepare a stable emulsion by using a conventional surfactant.

In addition, when the amount of the surfactant is increased to increase the stability, it inevitably leads to a drop in water repellency.

Therefore, in order to solve this problem, it is necessary to design so that the water repellent resin itself has emulsification when the water repellent is synthesized as follows. In combination with existing surfactants, this problem could be solved by introducing a reactive surfactant into the resin molecule.

Reactive surfactants that can be used have the following structure.

(E)

n = 1 to 50, m = 1 to 50

Formula f]

l = 1 to 50,

R = -CH ₃ , -CH ₂ (CH ₂ ) sCH ₃ (S = 1-20), -Phenyl,

                -Octylphenyl,-Nonylphenyl

[Formula g]

o = 1 to 10, p = 1 to 50, q = 1 to 50

The deepening agent manufacturing method of the present invention will be described through the following examples.

Example 1

Prepare a reactor equipped with a nitrogen introduction tube, an addition funnel, a reflux cooler, a thermometer, a stirring device, and a vacuum pump. Subsequently, after the moisture is completely removed under vacuum, nitrogen is replaced into the reactor, and 500 parts of polyfunctional isocyanate (TKA, AsahiKasei) is prepared. After adding 300 parts of N-methylpyrrolidone and methoxy-propyl acetate (50:50) as a solvent, the mixture was heated up and stirred, and 230 parts of hydroxyethyl acrylate (HEA) was added at 70-80 ° C. to give NCO concentration ( When the%) is in the range of 6.0 to 8.0, the reaction solution is cooled to 50 degrees, and 97 parts of 3,5-dimethylpyrazole is added to proceed with the reaction for 3 hours. After confirming that there is no NCO group by disappearing the peak of 2350cm ^-1 {cyanate group} by FT-IR, dilute 6 parts of glacial acetic acid in 100 parts of water, add the temperature again at 80 ℃, and mature for 1 hour, and then cool. Terminate the reaction. Since the reactivity is excellent, the yield is converted to 100%.

[Example 2]

After preparing a reactor equipped with an addition funnel, reflux condenser, thermometer, and stirring device, 100 parts of a synthetic product synthesized in Example 1, 100 parts of fluorine acrylate (FLUOWET AC812, Clariant), 100 parts of bihenyl acrylate, 150 parts of lauryl acrylate, 50 parts of vinyl chloride, 20 parts of polyoxyalkylene polyoxypropylene copolymer (PE-74, KPX), 20 parts of reactive emulsifier (Emulsogen RAL 208, Clariant). 10 parts of dialkyldimethylammonium chloride was added, the temperature was raised to 80 degrees, and completely emulsified. The emulsion is separated when stirring stops. The emulsion is prepared through a forced emulsification process three times at a pressure of 600Bar using a high pressure homogenizer to prepare a stable emulsion.

The synthesis is carried out at 80 ° C. for about 3 hours using an organic catalyst (AIBN) diluted in a hydrophilic solvent in a separate catalyst input tube.

Dipropylene glycol is added in about 5% of solids for emulsion stability. Dilute 5 parts of glacial acetic acid, add to mature for 1 hour, and then add water to obtain about 1,000 parts of a pale yellow-light yellow semi-transparent dispersion having a solid content of 30%.

[Example 3]

A copolymer-type reactive emulsifier (Emulsogen R208, Clariant) was used instead of the reactive emulsifier in Example 2, and the same method as in Example 2 was carried out.

Example 4

Except for using a reactive emulsifier (ADEKAREASOAP ER, ADEKA) instead of the reactive emulsifier in Example 2 was carried out in the same manner as in Example 2.

Comparative Example 1

Example 2 was carried out in the same manner as in Example 2, except for the synthesis of Example 1.

Comparative Example 2

The solution synthesized in Comparative Example 1 was compared by mixing 30% concentration of BN-69 manufactured by Daichi Kokyo Co., Ltd., compared to the resin solids.

All the synthesized liquids were prepared to compare the stability and durability of water repellency in Table 1 below.

No
division
stability
(40 ℃ * 1 month)

Durable water repellency ¹⁾

HL = 0
HL = 20
One
Comparative Example 1
stability
100
50
2
Comparative Example 2
Precipitation occurs
100
80
3
Example 2
stability
100
70
4
Example 3
stability
100
80
5
Example 4
stability
100
80

1) The fabric was immersed in 30g / l liquid based on water repellent using 40'S of 100% polyester fabric, and then padded by pick-up 80% by passing through mangle, and dried and cured (170 ℃ * 1min). After that, the water repellency was measured according to the AATCC 22 method (spray method). The washing method of the fabric was tested according to KS K 0432 method.

In addition, the fluorine water repellent composition according to the present invention may use an additive in a range that does not interfere with the effect. The additive may be a preservative, antioxidant, antifoaming agent, pH adjuster and the like. The additive may be added in an appropriate amount within a range that does not affect product stability.

While the invention has been described and illustrated in connection with a preferred embodiment for illustrating the principles of the invention, the invention is not limited to the construction and operation as shown and described. Rather, those skilled in the art will appreciate that many modifications and variations of the present invention are possible without departing from the spirit and scope of the appended claims. And all such modifications and changes as fall within the scope of the present invention are therefore to be regarded as being within the scope of the present invention.

Claims (6)

The acrylate monomer having a block isocyanate represented by Formula 1 is emulsified with a fluorine water repellent monomer and then polymerized through a catalyst.
[Chemical Formula 1]

The fluorine water repellent monomer,
Durable fluorine water repellent composition is a polyfunctional isocyanate is introduced to serve as a crosslinking agent is one selected from monomers having the formula structure.

(A)
Fluoroacrylate

R = -H or -CH ₃
l, m = 1 ~ 20

[Formula b]
Special reactive acrylates

R = -H or -CH ₃
R ₂ = -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH _3, -CH ₂ CH ₂ CH ₂ CH ₃
q = 1-20

(C)
Alkyl acrylate

R = -H or -CH ₃
o = 1 to 22

[Chemical formula d]
Vinyl halide compounds

R = -H or -CH ₃
X = Halogen compound (ex. -F, -Br, -Cl)

In Formula 1,
R is singly or a mixture of alkylene or cycloalkylene having 1 to 6 carbon atoms,
The number of isocyanates in a molecule can have two or three. The method of claim 1,
R of Formula 1 is alkylene, cyclohexane, dicyclohexyl methane, phenylene, tolylene, xylene, diphenylmethane, isopropylidene-bis (4-phenylene), naphthalene and iso A durable fluorine water repellent composition incorporating a polyfunctional isocyanate that acts as a crosslinking agent comprising poron. delete The method of claim 1, wherein the fluorine water repellent composition,
Durable fluorine water repellent composition is a polyfunctional isocyanate is introduced to serve as a crosslinking agent further comprising a reactive surfactant having a chemical formula below.

(E)

n = 1 to 50, m = 1 to 50

[Formula f]

l = 1 to 50,
R = -CH ₃ , -CH ₂ (CH ₂ ) sCH ₃ (S = 1-20), -Phenyl,
-Octylphenyl,-Nonylphenyl
[Formula g]

o = 1 to 10, p = 1 to 50, q = 1 to 50 Synthesizing the acrylate having a block isocyanate by synthesizing a polyfunctional isocyanate, a reactive monomer and a blocking agent represented by the following scheme, and then emulsifies the synthesized monomer with a monomer for fluorine water repellent and then polymerizes with a catalyst. A method for synthesizing a durable fluorine water repellent composition in which functional isocyanate is introduced.

[Scheme]

Wherein R is alkylene, cyclohexane, dicyclohexylmethane, phenylene, tolylene, xylene, diphenylmethane, isopropylidene-bis (4-phenylene), naphthalene and isophorone Polyfunctional isocyanate comprising, BH (blocking agent) is composed of one or a mixture of 2-butanone oxime, cyclohexanone oxime, malonic acid diethyl ester, 3-methylpyrazole, 3,5-dimethylpyrazole 1 species selected from the group.) delete