KR101693722B1 - Complexing-dying auxiliary for dyeing fiber having enhancing Light fastness, non-flame and water-repellency, Complexing-dying auxiliary using the same and Manufacturing method of the same - Google Patents

Abstract

The present invention relates to a complex dyeing agent composition for dyeing fibers, a composite dyeing agent for dyeing fibers using the same, and a production method thereof. The complex dyeing agent is produced by co-polymerizing a special monomer having light fastness, a monomer having water repellency, a specific monomer having flame retardancy, and other specific monomers in an optimum composition and optimum conditions, and thus has excellent light fastness, flame retardancy and water repellency.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a composite dyeing composition for dyeing fibers having excellent light, flame retardancy, and water-repellency tomorrow, a composite dyeing aid for dyeing fibers using the dyeing composition, and a method for producing the dyeing auxiliary dyeing fiber for enhancing light fastness, non- Complexing-dying auxiliary using the same and manufacturing method of the same}

The present invention relates to a composite dyeing aid capable of simultaneously realizing the photostability, the flame retardancy and the water-repellency, and a composition for use in the preparation thereof and a method for preparing the composite dyeing aid using the same.

It is well known that the development of high value-added products is urgent as the existing textile-related industries move to China, Indonesia, etc. where wages are relatively low in Korea. As a result, attempts have been made to enhance the competitiveness of products through special processing that gives differentiated functions. In particular, textile water-repellent processing is required not only in outdoor and sportswear but also in industrial fabrics. As outdoor activities such as camping and glamping become active, tomorrow's daylight on ultraviolet rays, which can be easily exposed outside, becomes an important topic have.

Currently, the method of imparting light / flame retardancy to tomorrow proceeds mainly by mixing a photo-stabilizer (light-emitting agent) and a flame retardant agent tomorrow during the dyeing process. However, when the water-repellent agent is processed in the post-process, flame retardancy is poor. To solve this problem, when a water repellent agent and a flame retardant are mixed and processed with a post-treatment, it is difficult to satisfy both water repellency and flame retardancy, and there is a problem that compatibility between two products must be considered.

Therefore, in order to satisfy all of the above three properties simultaneously, it is necessary to develop a single compound preparation considering both water repellency, light resistance and flame retardancy.

Korean Patent Registration No. 10-0178403 (Apr. 1, 1999) Korean Patent Publication No. 10-2010-026090 (2010.03.10.) Japanese Unexamined Patent Application Publication No. 2004-360137 (2004.12.24.)

SUMMARY OF THE INVENTION The present invention has been conceived to solve the problems as described above, and it is an object of the present invention to provide a method for producing a thermosetting resin composition, which can cope with a good tomorrow's weather, weatherability, and flame retardancy by copolymerizing a special monomer, Flame retardancy and water repellency, and thus the present invention has been completed.

The present invention relates to a composite dyeing and curing composition for dyeing fibers, which comprises a fluorine-containing acrylic monomer represented by the following formula (1); Light-resistant acrylic monomers; A flame-retardant acrylic monomer represented by the following formula (5); Acrylic monomers; Initiator; Emulsifiers; And a compatibilizing agent, wherein the light-resistant acrylic monomer comprises at least one selected from the group consisting of compounds represented by the following general formulas (2), (3) and (4)

[Chemical Formula 1]

또는

이며, R²는 C1 ~ C5의 알킬기이고, B는 수소원자 또는 할로겐원자이며, k는 0 또는 1이고, m은 0 ~ 6의 정수이며, n은 3 ~ 21의 정수이고, x는 0 또는 1이다.In Formula (1), R ¹ is a hydrogen atom, a straight-chain alkyl group having from ¹ to 5 carbon atoms, or a branched alkyl group having from 3 to 5 carbon atoms, and A is

or

And, R ² is an alkyl group of C1 ~ C5, B is a hydrogen atom or a halogen atom, and k is 0 or 1, m is an integer of 0 ~ 6, n is an integer from 3 ~ 21, x is 0 or 1.

(2)

(3)

[Chemical Formula 4]

,

또는

이며, R³, R⁴ 및 R⁵ 서로 같거나 다른 것으로서, R³, R⁴ 및 R⁵는 독립적으로, 수소원자, 탄소수 1 ~ 5의 직쇄형 알킬기, 탄소수 3 ~ 5의 분쇄형 알킬기, 페닐기, 하이드록시기, 설폰기, 알콕시기 또는 아민기이고,Y is an integer of 0 or 1, R ¹ is a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms, or a branched alkyl group having 3 to 5 carbon atoms, and R ² is

,

or

R ³ , R ⁴ and R ⁵ are the same or different from each other and each of R ³ , R ⁴ and R ⁵ independently represents a hydrogen atom, a straight chain alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, , A hydroxy group, a sulfonic group, an alkoxy group or an amine group,

[Chemical Formula 5]

,

또는

이고, n은 1 ~ 100의 정수이다.In Formula 5, R ¹ is an alkylene group having 1 to 3 carbon atoms, R ² is a linear alkyl group having 1 to 5 carbon atoms, and R ³ is

,

or

And n is an integer of 1 to 100.

The present invention also provides a composite dyeing assistant for dyed fibers prepared from the composition, wherein the fluorine-containing acrylic monomer represented by Formula 1; The light-resistant acrylic monomer; A flame-retardant acrylic monomer represented by the following formula (5); And an acrylic monomer; and a copolymer.

The present invention also provides a method for producing the composite dyeing auxiliary for dyeing fibers using the composition.

The present invention solves the problem of deterioration in the photostability in the absence of a water-repellent agent after the mixing treatment of the photostabilizer in the past in the conventional dyeing process. Therefore, it is possible to omit the process of pre-treating the photochemical preparation tomorrow, so that the dyeing process can be simplified, and it is possible to provide dyeing fibers and dyeing fabrics excellent in both light resistance and water repellency as well as flame retardancy.

Fig. 1 shows the water repellency measurement tool and the discrimination criteria conducted in Experimental Example 1. Fig.
2 is a photograph of a gray scale measurement measured in Experimental Example 2. Fig.
3 is a photograph showing a CCM device and a color coordinate system used in Experimental Example 2. FIG.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a composite dyeing and curing composition capable of improving the durability, flame retardancy and water repellency of dyed fibers, wherein the composite dyeing and curing composition of the present invention comprises a specific fluorine-containing acrylic monomer; Specific light-resistant acrylic monomers; Specific flame retardant acrylic monomers; Acrylic monomers; Initiator; Emulsifiers; And a compatibilizer.

In the composition of the present invention, the fluorine-based acrylic monomer may include a fluorine-based acrylic monomer represented by the following general formula (1).

[Chemical Formula 1]

또는

이며, 바람직하게는

이다. 그리고, 상기 R²는 C1 ~ C5의 알킬기, 바람직하게는 C1 ~ C2의 알킬기이다. 그리고, 화학식 1의 상기 m은 0 ~ 6의 정수, 바람직하게는 1 ~ 3이고, 더구 바람직하게는 2이다. 그리고, n은 3 ~ 21의 정수, 바람직하게는 4 ~ 15의 정수이고, 더욱 바람직하게는 5 ~ 10의 정수이다. 또한, x는 0 또는 1이며, x가 1일 때, 상기 B는 수소원자 또는 할로겐원자이며, 바람직하게는 수소원자 또는 염소원자이다.R ¹ is a hydrogen atom, a straight-chain alkyl group having ¹ to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms, preferably R ¹ is a straight-chain alkyl group having ¹ to 3 carbon atoms, more preferably a methyl group. And k is 0 or 1, preferably 0, and when k is 1, A is

or

, And preferably

to be. And R ² is a C 1 to C 5 alkyl group, preferably a C 1 to C 2 alkyl group. M is an integer of 0 to 6, preferably 1 to 3, and more preferably 2. And n is an integer of 3 to 21, preferably an integer of 4 to 15, more preferably an integer of 5 to 10. X is 0 or 1, and when x is 1, B is a hydrogen atom or a halogen atom, preferably a hydrogen atom or a chlorine atom.

In the composition of the present invention, the content of the fluorine-based acrylic monomer may be 2 to 25% by weight, preferably 5 to 20% by weight, based on the total weight of the composition. If the content of the fluorine- The water solubility can not be ensured. If it is used in an amount of more than 25% by weight, the content of the other acrylic monomer may be decreased, so that flame retardancy and / or weather resistance may not be secured.

In the composition of the present invention, the light-resistant acrylic monomer includes at least one selected from compounds represented by the following general formulas (2), (3) and (4)

(2)

(3)

[Chemical Formula 4]

,

또는

이며, 바람직하게는

또는

, 더욱 바람직하게는

이다. 그리고, R³, R⁴ 및 R⁵ 서로 같거나 다른 것으로서, R³, R⁴ 및/또는 R⁵는 독립적으로, 수소원자, 탄소수 1 ~ 5의 직쇄형 알킬기, 탄소수 3 ~ 5의 분쇄형 알킬기, 페닐기, 하이드록시기, 설폰기, 알콕시기 또는 아민기이고, 바람직하게는 R³, R⁴ 및/또는 R⁵ 각각은 수소원자, 탄소수 1 ~ 3의 직쇄형 알킬기 또는 탄소수 3 ~ 5의 분쇄형 알킬기이다.In the general formulas (2) to (4), y is an integer of 0 or 1, preferably 1. R ¹ is a hydrogen atom, a straight-chain alkyl group having 1 to 5 carbon atoms, or a branched alkyl group having 3 to 5 carbon atoms, preferably a straight-chain alkyl group having 1 to 3 carbon atoms. Also, R < ² >

,

or

, And preferably

or

, More preferably

to be. R ³ , R ⁴ and R ⁵ are the same or different from each other and each of R ³ , R ⁴ and / or R ⁵ independently represents a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms , A phenyl group, a hydroxyl group, a sulfonic group, an alkoxy group or an amine group, and preferably each of R ³ , R ⁴ and / or R ⁵ is a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms, Lt; / RTI >

이고, R³ 및 R⁴는 수소원자 또는 메틸기일 수 있다.Preferably, the light-resistant acrylic monomer may include one or two selected from the compounds represented by Chemical Formula 2 and Chemical Formula 3, wherein y in Chemical Formula 2 is 0, R ¹ is C1- C 2 linear alkyl group, and R ³ and R ⁴ may be a hydrogen atom or a methyl group. In formula (3), y is 1, R ¹ is a straight-chain alkyl group having ¹ to ² carbon atoms, and R ² is

And R ³ and R ⁴ may be a hydrogen atom or a methyl group.

In the composition of the present invention, the content of the light-resistant acrylic monomer may be 1 to 15% by weight, preferably 3 to 10% by weight, based on the total weight of the composition, and if the content of the acrylic acid monomer is less than 1% If it is used in an amount exceeding 15% by weight, the content of the other acrylic monomer may be decreased and the flame retardancy and / or water-repellent ability may not be ensured.

The flame retardant acrylic monomer as one of the composition components of the present invention may include a compound represented by the following general formula (5).

[Chemical Formula 5]

,

또는

이고, 바람직하게는

또는

이며, 더욱 바람직하게는

이다. 그리고, n은 1 ~ 100의 정수이며, 바람직하게는 5 ~ 20의 정수이다.In Formula 5, R ¹ is an alkylene group having 1 to 3 carbon atoms, preferably an alkylene group having 1 to 2 carbon atoms, more preferably a methylene group. R ² is a straight-chain alkyl group having 1 to 5 carbon atoms, preferably a straight-chain alkyl group having 1 to 3 carbon atoms. Also, R < ³ >

,

or

, And preferably

or

, And more preferably

to be. And n is an integer of 1 to 100, preferably an integer of 5 to 20.

In the composition of the present invention, the content of the flame-retardant acrylic monomer may be 2 to 25% by weight, preferably 5 to 20% by weight based on the total weight of the composition. If the flame-retardant acrylic monomer content is less than 2% And if it is used in an amount of more than 25% by weight, the content of the other acrylic monomer may be relatively small, so that the photocatalytic and / or water-repellent ability may not be secured tomorrow.

In addition, the acrylic monomer may be selected from the group consisting of methyl acrylate, methyl methacrylate, styrene, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate ethyl Hexyl acrylate, hexyl acrylate, ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, styrene, benzyl acrylate and benzyl Methacrylate, and the like.

In the composition of the present invention, the content of the acrylic monomer may be 1 to 20% by weight, preferably 2 to 7% by weight based on the total weight of the composition. If the content of the flame-retardant acrylic monomer is less than 1% There may be a problem that the water content may be lowered, and when it is used in an amount exceeding 20% by weight, the fluorine-based acrylic monomer may be relatively small and the water-repellency may decrease.

The initiator, which is one of the composition components of the present invention, serves to accelerate and initiate the copolymerization reaction. The content thereof is 0.05 to 1% by weight, preferably 0.1 to 0.8% by weight, more preferably 0.05 to 1% 0.1 to 0.5 parts by weight may be used. When the amount is less than 0.05% by weight, the amount of the copolymer is too small and the copolymerization reaction time may take too long. As a result, the copolymerization may be poor. When the amount is more than 1% by weight, the degree of polymerization of the copolymer becomes too large, The processability and handling property may be deteriorated. Therefore, it is preferable to use within the above range. As the initiator, an initiator for polymerization of an acrylic component generally used in the art may be used, and preferably benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3 -Carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine-dibasic acid salt, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, t- Selected from the group consisting of butyl hydroperoxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, potassium peroxide, ammonium peroxide and diisopropyl peroxydicarbonate. Species or two or more species, preferably selected from lauryl peroxide, cumene hydroperoxide and t-butyl peroxypivalate Or one or more selected from the group consisting of cumene hydroperoxide and t-butyl peroxy pivalate is more preferable.

In the composition of the present invention, the emulsifier serves to uniformly disperse hydrophobic monomer particles, and the content thereof is 0.5 to 5% by weight, preferably 1 to 4% by weight, It is preferable to use 1.5 to 3.5% by weight. If the amount is less than 0.5% by weight, the amount of the emulsifier to be used is too small, and the dispersion stability of the monomer component deteriorates, so that the degree of polymerization of the copolymer may deteriorate. If the amount is more than 5% by weight, It is recommended to use it within the above range as there is a problem to be removed. As the emulsifier, at least one selected from the group consisting of an ether emulsifier, a chloride emulsifier and a sulfonate emulsifier may be used, and preferably at least one selected from the group consisting of polyoxyethylene tridecyl ether, polyoxyethylene lauryl ether, polyoxyethylene dodecyl Ether emulsifiers containing at least one selected from the group consisting of ether, polyoxyethylene trimethylnonyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; A chloride-based emulsifier containing at least one selected from the group consisting of lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, cetyl dimethyl benzyl ammonium chloride and stearyl dimethyl benzyl ammonium chloride; And dibutyl sulfonate, lauryl benzene sodium sulfonate, cetylbenzene sodium sulfonate, stearyl benzene sodium sulfonate, lauryl sodium sulfonate, cetyl sodium sulfonate, stearyl sodium sulfonate, polyoxyethylene lauryl ether sodium A sulfonate emulsifier containing at least one selected from the group consisting of sulfonate, peroxyethylene cetyl ether sodium sulfonate and polyoxyethylene stearyl ether sodium sulfonate; Can be used alone or in admixture of two or more. Among them, it is possible to use a mixture of a chloride-based emulsifier selected from lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride and lauryldimethylbenzylammonium chloride It is preferable to use one selected species alone or a mixture of two or more species.

In the composition of the present invention, the compatibilizing agent serves to facilitate the emulsification of the monomers. The content of the compatibilizing agent is preferably 5 to 30% by weight, more preferably 10 to 30% by weight, 15 to 28% by weight can be used. If the amount of the compatibilizing agent is less than 5% by weight, the emulsifying power may be poor and the storage stability may be deteriorated. If the amount of the compatibilizing agent is more than 30% by weight, the particles may become too small and the water- The compatibilizing agent may be selected from the group consisting of methanol, ethanol, isopropyl alcohol, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol, diethylene glycol, ethyl cellosolve, butyl cellosolve, ethyl acetate, And preferably at least one selected from propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol, and diethylene glycol may be used singly or in combination.

After mixing the above-described composition of the present invention, the mixture is put into a high-pressure homogenizer, the monomer is sufficiently dispersed, and then the copolymerization reaction is carried out to prepare the complex dyeing assistant of the present invention. To 90 ° C for 4 to 7 hours, preferably at 65 to 75 ° C. If the temperature is lower than 65 deg. C, the reaction yield may be lowered. If the temperature is higher than 90 deg. C, the reaction rate may be excessively high and an unwanted copolymer may be generated.

In the composition of the present invention, the solvent commonly used in the art can be used, and water can be preferably used.

Through the above-described composition and process of the present invention, the fluorine-containing acrylic monomer represented by Formula 1 is obtained. At least one selected from the compounds represented by Chemical Formulas (2), (3) and (4) is used as a light-resistant acrylic monomer; A flame-retardant acrylic monomer represented by the following formula (5); And an acrylic monomer can be obtained as a composite dyeing auxiliary.

The composite dyeing auxiliary of the present invention is excellent in both water repellency and antistatic property. The composite dyeing auxiliary of the present invention is produced by padding a polyester fabric (length x length, 20 x 20 cm) with the above- When the cured fabric is measured according to an ISO 4920 spray test, the water content may be 95 or more, preferably 95 to 100, more preferably 97 to 100 have.

The composite dyeing assistant of the present invention can be produced by padding a polyester fabric (length x length, 20 x 20 cm) with the above-mentioned composite dyeing aid, curing the fabric, and then fusing the fabric with 0.55 W / After exposure to a light source intensity and 80 DEG C for 20 hours, the gray scale rating may be 3.5 or higher, preferably 3.5 to 4.5.

The composite dyeing assistant of the present invention can be obtained by padding polyester fabric (length x length, 20 x 20 cm) with the above-mentioned composite dyeing aid, and then curing the fabric with 0.55 W / The DL ^* value was 0.01 to 0.50 L, the Da ^* value was 1.00 to 10.00 R, and the Db (value) was measured at the light source intensity and 80 ° C for 20 hours. ^{* May} range from 5.00 to 20.00 Y, preferably a DL ^* value of 0.01 to 0.20 L, a Da ^* value of 1.00 to 6.00 R, and a Db ^* value of 5.00 to 15.00 Y.

The composite dyeing assistant of the present invention can be used in a post-treatment process during the dyeing process of various kinds of fibers to improve the light resistance, flame retardancy and water repellency of the fibers. Examples of the fibers include cotton fibers, nylon fibers And polyester fibers. Such dyed fibers can be applied to various textile products. Examples of textile products include sheets such as automobile sheets, furniture sheets, etc., but the present invention is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

[Example]

Example 1

10 weight% of a fluorine-containing acrylic monomer represented by the following formula 1-1, 5 weight% of a light-resistant acrylic monomer represented by the following formula 3-1, 10 weight% of a flame-retardant acrylic monomer represented by the following formula 5-1, 3 weight of stearyl methacrylate , 0.2% by weight of azobisisobutylamidine-dihydrochloride as an initiator, 2% by weight of stearyltrimethylammonium chloride as an emulsifier and 2% by weight of polyoxyethylene lauryl ether were mixed together and 20% by weight of tripropylene glycol as a compatibilizer By weight, and 46.8% by weight of water as a solvent.

Next, a composite dyeing auxiliary was prepared by dispersing the composition using a high-pressure homogenizer and performing a copolymerization reaction at 70 DEG C for 5 hours.

[Formula 1-1]

In formula (1-1), R ¹ is a methyl group, m is 2, k is 0, x is 0, and n is 6.

[Formula 3-1]

이며, R³ 및 R⁴는 수소원자이다.In Formula (3-1), R ¹ is a methyl group, y is 2, and R ² is

And R ³ and R ⁴ are hydrogen atoms.

[Formula 5-1]

이고, n은 10이다.In formula (5-1), R ¹ is a methylene group, R ² is a methyl group, and R ³ is

And n is 10.

Example 2

A composite dyeing auxiliary was prepared by the same composition, compositional ratio and method as in Example 1 except that a light-resistant acrylic monomer represented by the following Chemical Formula 2-1 was used as a light-resistant acrylic monomer instead of the Chemical Formula 3-1.

[Formula 2-1]

In formula (2-1), R ¹ is a methyl group, y is 2, and R ³ and R ⁴ are each a hydrogen atom.

Examples 3 to 6 and Comparative Examples 1 to 4

Composite dyeing auxiliaries were prepared by the same compositions and methods as those of Example 1, and composite dyeing auxiliaries were prepared with the composition and composition ratios shown in Table 1 below, and Examples 3 to 6 and Comparative Examples 1 to 4 were carried out.

[Formula 1-2]

이고, R²는 메틸기이며, x는 0이며, n은 8이다.In formula 1-2, R ¹ is a methyl group, m is 2, k is 1, A is

, R ² is a methyl group, x is 0, and n is 8.

Classification (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Fluorine-based acrylic monomer (1-1) (1-1) (1-1) (1-1) (1-1) 10 wt% 10 wt% 18 wt% 18 wt% 8 wt% Light-resistant acrylic monomer 3-1 2-1 3-1 2-1 3-1 5 wt% 5 wt% 5 wt% 5 wt% 7 wt% Flame retardant acrylic monomer 5-1 5-1 5-1 5-1 5-1 10 wt% 10 wt% 10 wt% 10 wt% 18 wt% Acrylic
Monomer Stearyl methacrylate 3 wt% 3 wt% 3 wt% 3 wt% 3 wt% Initiator 0.2 wt% 0.2 wt% 0.2 wt% 0.2 wt% 0.2 wt% Emulsifier 4 wt% 4 wt% 4 wt% 4 wt% 4 wt% Compatibilizer 20 wt% 20 wt% 20 wt% 20 wt% 20 wt% water Remaining balance Remaining balance Remaining balance Remaining balance Remaining balance

Classification (parts by weight) Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Fluorine-based acrylic monomer 1-2 (1-1) (1-1) (1-1) (1-1) 10 wt% 12 wt% 10 wt% 1 wt% 10 wt% Light-resistant acrylic monomer 3-1 3-1 3-1 3-1 3-1 5 wt% 7 wt% 5 wt% 10 wt% 18 wt% Flame retardant acrylic monomer 5-1 5-1 5-1 5-1 5-1 10 wt% 0.7 wt% 10 wt% 12 wt% 10 wt% Acrylic
Monomer Stearyl methacrylate 3 wt% 3 wt% 0.5 wt% 3 wt% 3 wt% Initiator 0.2 wt% 0.2 wt% 0.2 wt% 0.2 wt% 0.2 wt% Emulsifier 4 wt% 4 wt% 4 wt% 4 wt% 4 wt% Compatibilizer 20 wt% 20 wt% 20 wt% 20 wt% 20 wt% water Remaining balance Remaining balance Remaining balance Remaining balance Remaining balance

Production Example 1

A polyester fiber fabric (light blue fabric) which had been dyed and washed was prepared.

Then, the complex dyeing auxiliary of Example 1 was diluted with pure water to a concentration of 5% by volume to prepare 500 g of a test liquid. After dipping the polyester fiber fabric in the test liquid for 10 seconds, padding was performed using mangles, The padded fabric was cured using a tenter.

At this time, the mangling speed was 10 m / min, and the temperature of the tenter and the treatment time of the tenter were 160 ° C. and 1 minute.

Production Example 2 to Production Example 6

The fabric was cured in the same manner as in Preparation Example 1, except that the fabric dyes prepared in Examples 2 to 6 were used instead of the dye-containing fabric in Example 1, and the fabric was patched and cured.

Comparative Production Examples 1 to 4

Comparative Preparation Example 2 and Comparative Production Example 3 were carried out in the same manner as in Comparative Production Example 1 except that no preparation was conducted and the water repellent agent (trade name: BENESOL FR-6100, manufacturer: ICEI allergy) and the tomorrow light agent (trade name: BENESOL UVA-WS , Manufacturer: ICEI Woobang). Comparative Production Example 4 was treated only with a flame retardant (trade name: BENESOL UVA-WS, manufactured by ICEI, Ltd.).

Comparative Production Example 5 to Comparative Production Example 8

The fabric was cured in the same manner as in Preparation Example 1 except that each of the composite dyeing preparations prepared in Comparative Examples 1 to 4 was used instead of the dyeing composition of Example 1 to prepare a fiber cloth Were patched and cured.

Classification (% by volume) Water repellent agent My Magnifier Flame retardant Compound dyeing preparation Comparative Preparation Example 1 - - - - Comparative Preparation Example 2 5% - - - Comparative Production Example 3 - 2% - - Comparative Production Example 4 - - 5% - Comparative Preparation Example 5 5% 2% 5% - Comparative Preparation Example 6 - - - 5% Comparative Preparation Example 7 - - - 5% Comparative Preparation Example 8 - - - 5% Production Example 1 - - - 5% Production Example 2 - - - 5% Production Example 3 - - - 5% Production Example 4 - - - 5% Production Example 5 - - - 5% Production Example 6 - - - 5%

Experimental Example 1: Measurement of water repellency

The fabric prepared in Production Examples 1 to 6 and Comparative Production Examples 1 to 8 was prepared as a test piece with a size of 20 × 20 cm and then a fabric was attached to a spray tester according to an ISO 4920 spray test method, Respectively. The spray tester device used in the experiment is shown in Fig. 1, and the results are shown in Table 4 below.

division Water repellency Comparative Preparation Example 1 0 Comparative Preparation Example 2 95 Comparative Production Example 3 0 Comparative Production Example 4 0 Comparative Preparation Example 5 70 Comparative Preparation Example 6 100 Comparative Preparation Example 7 90 Comparative Preparation Example 8 55 Production Example 1 100 Production Example 2 100 Production Example 3 100 Production Example 4 100 Production Example 5 80 Production Example 6 80

Referring to Table 4 and FIG. 2, in Comparative Production Example 1 and Comparative Production Example 3, there was almost no water repellency, and in Comparative Production Example 4, water repellency was inferior. However, in the case of Production Examples 1 to 6, the water content was 70 or more and excellent results were obtained.

Experimental Example 2: Measurement of light resistance

(1) Measurement of light fastness

The fabrics prepared in Preparation Examples 1 to 6 and Comparative Production Examples 1 to 8 were subjected to a rapid exposure test using a UV-2000 tester of ATLAS at 80 ° C and 0.55 w / m ² for 20 hours, respectively, Gray scale, and the results are shown in Table 5 and FIG. 2 below.

division Grayscale rating Comparative Preparation Example 1 1.5 Comparative Preparation Example 2 3.0 Comparative Production Example 3 4.0 Comparative Production Example 4 3.0 Comparative Preparation Example 5 3.5 Comparative Preparation Example 6 4.0 Comparative Preparation Example 7 4.0 Comparative Preparation Example 8 4.0 Production Example 1 4.5 Production Example 2 4.0 Production Example 3 4.0 Production Example 4 3.5 Production Example 5 4.0 Production Example 6 4.0

As shown in Table 5 and FIG. 3, in Comparative Production Examples 1 and 2 and Comparative Production Example 4, the gray scale rating was less than 3.5, which is low. However, in Examples 1 to 6, the gray scale rating was higher than 3.5, showing excellent light fastness values.

(2) Measurement of depth and color of fabric - Computer color matching (CCM) measurement

In order to observe the color change of the fabric before and after exposure to daylight (0.55 W / m ² , 20 hours exposure to 80 ° C.) prepared in Preparation Examples 1 to 6, a CCM apparatus (color i5, x-rite) And the results are shown in Table 5 below.

As shown in the lower part of FIG. 4, the L * value represents the absolute depth value of the sample and the DL * value represents the depth value of the fabric before exposure to sunlight. The a * value is the absolute value of the red-green tone as shown in the color coordinate system, and Da * represents the relative value to the fabric before exposure to daylight. The b * value represents the absolute value of the yellow-blue tone. Similarly, Db * represents the relative value to the fabric before exposure to sunlight. The DE * value means the color change relative to the fabric before exposure to sunlight.

division Before / after daylight exposure L * a * b * DL * Da * Db * DE * Production Example 1 I'm 55.63 -24.02 -23.91 - - - - after 55.73 -18.74 -11.65 0.10 L 5.28 R 12.26 Y 13.35 Production Example 2 I'm 55.27 -23.89 -24.02 - - - - after 55.46 -18.33 -11.59 0.19 L 5.56 R 12.43 Y 13.62 Production Example 3 I'm 55.71 -23.94 -23.73 - - - - after 55.75 -18.12 -11.44 0.04 L 5.82 R 12.29 Y 13.60 Production Example 4 I'm 55.42 -24.32 -24.24 - - - - after 55.62 -18.32 -11.69 0.20 L 6.00 R 12.55 Y 13.91 Production Example 5 I'm 55.14 -24.13 -23.96 - - - - after 55.30 -18.20 -11.60 0.16 L 5.93 R 12.36 Y 13.71 Production Example 6 I'm 55.89 -24.07 -24.04 - - - - after 56.06 -18.44 -11.56 0.17 L 5.63 R 12.48 Y 13.69

Table 6 shows that the composite dyeing auxiliary prepared in Example 1 was treated (Production Example 1), and almost the same result as that in the case where only the light-absorbing agent was treated (Comparative Production Example 3) was obtained. When the composite dyeing aid was treated, the light resistance was slightly lower than that in the case where only the light-absorbing agent was treated (Comparative Preparation Example 3), but the light resistance was greatly improved as compared with the case where the water- Respectively.

Experimental Example 3: Flame retardance measurement experiment

The flame retardancy test was carried out according to the MS 300-08 horizontal method test method using AM-500H possessed by Daichek Research Institute, and the results are shown in Table 7 below.

division Flammability Comparative Production Example 4 SE Production Example 1 SE Production Example 2 SE Production Example 3 SE Production Example 4 SE Production Example 5 SE Production Example 6 SE

As a result of the flame retardancy test, when the synthesized composite formulation (Example 1) was treated, good results were obtained as compared with the case where the water repellent agent, the anti-light agent and the flame retardant agent were treated together (Comparative Example 5).

Through the above Examples and Experimental Examples, it was confirmed that the dyed fibers produced using the composite dyeing aid of the present invention had both excellent water repellency and anti-flammability as well as flame retardancy.

Claims (17)

A fluorine-containing acrylic monomer represented by the following formula (1); Light-resistant acrylic monomers; A flame-retardant acrylic monomer represented by the following formula (5); Acrylic monomers; Initiator; Emulsifiers; Compatibilizers; And a solvent,
Wherein the light-resistant acrylic monomer comprises at least one selected from the group consisting of compounds represented by the following general formulas (2), (3) and (4);
[Chemical Formula 1]

In Formula (1), R ¹ is a hydrogen atom, a straight-chain alkyl group having from ¹ to 5 carbon atoms, or a branched alkyl group having from 3 to 5 carbon atoms, and A is

or

And, R ² is an alkyl group of C1 ~ C5, B is a hydrogen atom or a halogen atom, and k is 0 or 1, m is an integer of 0 ~ 6, n is an integer from 3 ~ 21, x is 0 or 1.
(2)

(3)

[Chemical Formula 4]

Y is an integer of 0 or 1, R ¹ is a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms, or a branched alkyl group having 3 to 5 carbon atoms, and R ² is

,

or

R ³ , R ⁴ and R ⁵ are the same or different from each other and each of R ³ , R ⁴ and R ⁵ independently represents a hydrogen atom, a straight chain alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, , A hydroxy group, a sulfonic group, an alkoxy group or an amine group,
[Chemical Formula 5]

In Formula 5, R ¹ is an alkylene group having 1 to 3 carbon atoms, R ² is a linear alkyl group having 1 to 5 carbon atoms, and R ³ is

,

or

And n is an integer of 1 to 100. The compound according to claim 1, wherein R ¹ in the formula (1) is a linear alkyl group having 1 to 3 carbon atoms, k is 0, m is 1 to 3, n is an integer of 4 to 15, Which is excellent in lightness, flame retardancy and water solubility. The method of claim 1, wherein y in the formula 2 to formula 4 is 1, R ¹ is a straight-chain alkyl group of C1 ~ C3, R ² is

or

And R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a linear alkyl group having 1 to 3 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms. The dyed fiber having excellent antistatic properties, ≪ / RTI > The photosensitive resin composition according to claim 1, wherein the light-resistant acrylic monomer comprises one or two compounds selected from the group consisting of compounds represented by formulas (2) and (3)
Y in the general formula (2) is 0, R ¹ is a linear alkyl group having ¹ to 2 carbon atoms, R ³ and R ⁴ are each a hydrogen atom or a methyl group,
Y in formula (3) is 1, R ¹ is a straight-chain alkyl group having ¹ to ² carbon atoms, and R ² is

And R ³ and R ⁴ are a hydrogen atom or a methyl group. The acrylic resin composition according to claim 1, wherein the acrylic monomer is at least one selected from the group consisting of methyl acrylate, methyl methacrylate, styrene, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate ethyl Hexyl acrylate, hexyl acrylate, ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, styrene, benzyl acrylate and benzyl Methacrylic acid, and methacrylic acid. The photosensitive resin composition according to claim 1, which comprises 10 to 30% by weight of the fluorinated acrylic monomer, 2 to 15% by weight of the light resistant acrylic monomer, 2 to 25% by weight of the flame retardant acrylic monomer, 5 to 20% by weight of the acrylic monomer, %, An emulsifier of 0.5 to 5 wt.%, A compatibilizer of 5 to 30 wt.%, And a residual amount of a solvent. The composite dyeing preparations composition for dyeing fibers is excellent in resistance to sunlight, flame retardancy and water repellency. 3. The composition of claim 1, wherein the initiator is selected from the group consisting of benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine- Butyl peroxide, di-t-butyl peroxide, di-t-butyl peroxide, di-t-butyl peroxide, di-t-butyl peroxide, Characterized in that it comprises at least one member selected from the group consisting of titanium oxide, titanium oxide, iron oxide, cumene hydroperoxide, t-butyl peroxypivalate, potassium peroxide, ammonium peroxide and diisopropyl peroxydicarbonate. A composition for dyeing a complex for excellent dyed fibers. The composition of claim 1, wherein the emulsifier is selected from the group consisting of polyoxyethylene tridecyl ether, polyoxyethylene lauryl ether, polyoxyethylene dodecyl ether, polyoxyethylene trimethylnonyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, An ether emulsifier containing at least one selected from polyoxyethylene oleyl ether;
A chloride-based emulsifier containing at least one selected from the group consisting of lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, cetyl dimethyl benzyl ammonium chloride and stearyl dimethyl benzyl ammonium chloride; And
Dibutyl sulfonate, lauryl benzene sodium sulfonate, cetylbenzene sodium sulfonate, stearyl benzene sodium sulfonate, lauryl sodium sulfonate, cetyl sodium sulfonate, stearyl sodium sulfonate, polyoxyethylene lauryl ether sodium sulfoxide Sulfonate emulsifiers containing at least one member selected from the group consisting of polyoxyethylene cetyl ether sodium sulfonate and polyoxyethylene stearyl ether sodium sulfonate;
Wherein the composition further comprises at least one selected from the group consisting of a dyed fiber, The method of claim 1, wherein the compatibilizer is selected from the group consisting of methanol, ethanol, isopropyl alcohol, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol, diethylene glycol, ethyl cellosolve, butyl cellosolve, ethyl acetate, Acetate, which is excellent in resistance to sunlight, flame retardancy and water repellency. A process for producing a composite dyeing auxiliary for dyeing fibers excellent in resistance to sunlight, flame retardancy, and water-repellency, which comprises preparing a composite dyeing auxiliary composition according to any one of claims 1 to 9 and then carrying out a copolymerization reaction . [Claim 11] The method according to claim 10, wherein the copolymerization is carried out at 65 to 90 DEG C for 4 to 7 hours, wherein the copolymerization reaction is excellent in resistance to sunlight, flame retardancy and water repellency. A fluorine-containing acrylic monomer represented by the following formula (1); At least one compound selected from the group consisting of compounds represented by the following formulas (2), (3) and (4) is referred to as a light-resistant acrylic monomer; A flame-retardant acrylic monomer represented by the following formula (5); And an acrylic monomer;
The acrylic monomer may be selected from the group consisting of methyl acrylate, methyl methacrylate, styrene, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate ethylhexyl acrylate, Selected from among methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, styrene, benzyl acrylate and benzyl methacrylate A composite dyeing preparation for dyeing fibers having excellent photostability, flame retardancy, and water repellency;
[Chemical Formula 1]

In Formula (1), R ¹ is a hydrogen atom, a straight-chain alkyl group having from ¹ to 5 carbon atoms, or a branched alkyl group having from 3 to 5 carbon atoms, and A is

or

And, R ² is an alkyl group of C1 ~ C5, B is a hydrogen atom or a halogen atom, and k is 0 or 1, m is an integer of 0 ~ 6, n is an integer from 3 ~ 21, x is 0 or 1,
(2)

(3)

[Chemical Formula 4]

Y is an integer of 0 or 1, R ¹ is a hydrogen atom, a linear alkyl group having 1 to 5 carbon atoms, or a branched alkyl group having 3 to 5 carbon atoms, and R ² is

,

or

R ³ , R ⁴ and R ⁵ are the same or different from each other and each of R ³ , R ⁴ and R ⁵ independently represents a hydrogen atom, a straight chain alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, , A hydroxy group, a sulfonic group, an alkoxy group or an amine group,
[Chemical Formula 5]

In Formula 5, R ¹ is an alkylene group having 1 to 3 carbon atoms, R ² is a linear alkyl group having 1 to 5 carbon atoms, and R ³ is

,

or

And n is an integer of 1 to 100. The method according to claim 12, wherein the polyester fabric (length x length, 20 x 20 cm) is padded with the composite dyeing aid, and the cured fabric is subjected to an ISO 4920 spray teat, And a water repellency of 95 or more when measured according to the method of the present invention is excellent in fire resistance, flame retardancy and water repellency. The method according to claim 12, wherein the polyester fabric (length x length, 20 x 20 cm) is padded with the composite dyeing aid, then the cured fiber is irradiated with a light source intensity of 0.55 W / After 20 hours of exposure at 80 DEG C, the gray scale rating was 3.5 to 4.5,
The DL ^* value was 0.01 to 0.50 L, and the Da ^* value (d ^* ) was measured during CCM (computer color matching) measurement after the cured material was exposed to a light source intensity of 0.55 W / Is in the range of 1.00 to 10.00R and the Db ^* value is in the range of 5.00 to 20.00 Y. A composite dyeing preparation for dyeing fibers excellent in light resistance, flame retardancy and water repellency. A dyed fiber treated with the composite dyeing auxiliary for dyeing fibers according to any one of claims 12 to 14. 16. The dyed fiber according to claim 15, wherein the dyed fiber comprises at least one selected from cotton fibers, nylon fibers and polyester fibers. A fabric article comprising the dyed fibers of claim 15.

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