KR101406880B1 - Light fastness enhancer and dying auxiliary having that - Google Patents

Abstract

The present invention relates to a light fastness enhancer and a dye assistant including the same. To explain more specifically, the present invention relates to the novel light fastness enhancer and the novel dye assistant including the same which minimize a decrease in the light fastness before and after sunlight exposure. According to the present invention, the light fastness enhancer includes an emulsifier containing one or more selected from anionic emulsifiers and nonionic emulsifiers.

Description

[0001] The present invention relates to a light fastness enhancer and a dyeing auxiliary containing the same,

The present invention relates to a novel light fastness enhancer for suppressing the phenomenon of discoloration due to decomposition of a dye after exposure to sunlight for a long period of time, such as automobile fibers and fabrics, a dyeing aid containing the same, and a product using the same.

Physical, functional, and aesthetic performance of automotive sheet fibers is required. The improvement of the light fastness that suppresses the dyeing fading of the sheet fabric caused by exposure to sunlight for a long time is one of the most difficult problems with flame retardancy. Further, in the case of sheet fibers for automobiles due to various needs of consumers, various fibers are required to be used, changes in blend and weaving structure, various designs, and the like, and the factors of deterioration of daylight fastness also increase.

For example, in the case of using microfibers, the increase of the surface area increases the contact of daylight, and therefore, the light fastness of the fabric is remarkably lower than that of the fabric of normal fineness. At the present dyeing site, a high performance light fastness improving agent is used 2 to 3 times as much as a fabric of general fineness, but there is a problem that the fastness is lowered. Another example is that the raw materials of the light fastness enhancer are sublimated while undergoing a heat-set process such as printing or coating in order to enhance the aesthetic effect, and the fastness of the light in the final product tends to be lower than the fastness before dyeing It is showing. Also, the raw materials of the sublimed sunlight fastness enhancer accumulate in the processing equipment as well as in the factory to cause secondary pollution to the processed products, and the production cost is increased due to the time and cost used for treating such pollutants. Of course, it is a homework that must be solved as a harmful factor to the health of workers.

Therefore, the development of a light fastness improving agent corresponding to process and diversification is already required in the market, and the process and diversification are expected to be continuously changed, so that the growth potential of the market is expected to continue.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a novel light fastness improving agent capable of minimizing sublimation and / It is an object of the present invention to provide an enhancer.

Disclosure of the Invention In order to solve the above-described problems, the present invention relates to a novel light fastness improving agent. And an emulsifier containing at least one selected from anionic emulsifiers and nonionic emulsifiers.

[Chemical Formula 1]

Wherein R 1 is a hydrogen atom, -OH, a C 1 to C 5 alkyl group or a C 1 to C 5 alkoxy group, and each of R 2 and R 3 independently represents a hydrogen atom, a C 1 to C 5 alkyl group or a C 2 to C 5 alkylene group to be.

Another aspect of the present invention relates to a dyeing auxiliary, and can be characterized by including the above-described light fastness improving agent.

Another aspect of the present invention relates to a fiber, and may be characterized in that it comprises the dyeing auxiliary.

Another aspect of the present invention relates to a cover for a sheet and / or a sheet, characterized in that it comprises and / or is woven of said fibers.

The light fastness enhancer of the present invention is not sublimated in the processing step after the dyeing process, minimizes sublimation, and has excellent absorption ability of sunlight to minimize the destruction of the dye before and after exposure to sunlight, thereby reducing the decrease in light fastness to light. , A fabric, and a sheet (or a cover for a sheet) using the same. In particular, it is possible to provide a dye combination of a beige system, a fiber produced using the same, and an application product thereof, Do.

Fig. 1 is a photograph of a UV-2000 light fastness test of a PET fabric dyed in beige dyes in Experimental Example 2. Fig.
Fig. 2 is a photograph of the UV-2000 light fastness test of the gray dyed PET fabric conducted in Experimental Example 3. Fig.
FIG. 3 is a photograph of the light-fastness test of the PET fabric dyed in beige in Example 2 with a Fade-O-Meter.

The term C1 to C5 as used in the present invention means 1 to 5 carbon atoms.

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

The light fastness improving agent of the present invention may include a compound represented by the following formula (1), preferably a compound represented by the following formula (1-1).

[Chemical Formula 1]

[Formula 1-1]

In the above formula (I) and / or formula 1-1, R ¹ is a hydrogen atom, -OH, an alkoxy group of C1 ~ C5 alkyl group or a C1 ~ C5, preferably R ¹ is a hydrogen atom, -OH, C1 ~ C5 alkoxy group, more preferably a C1-C3 alkoxy group.

Further, in the formula I and / or formula 1-1, R ² and R ³ are each independently a hydrogen atom, an alkyl group of C1 ~ C5 alkyl group or a C2 ~ C5, preferably R ² and R ³ are each Independently, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably R ² and R ³ are each a hydrogen atom.

The present invention may include an emulsifier in addition to the compounds represented by the above-mentioned formulas (1) and / or (1-1). The emulsifier may be selected from the group consisting of an anionic emulsifier and a nonionic emulsifier, or a mixture thereof. Preferably, an anionic emulsifier and a nonionic emulsifier are used in combination.

The emulsifier may be used in an amount of 10 to 50 parts by weight, preferably 20 to 40 parts by weight, based on 100 parts by weight of the compound represented by Formula 1 and / or Formula 1-1, If the amount of the emulsifier is less than 10 parts by weight, the emulsification and dispersing properties are poor. When the amount of the emulsifying agent is more than 50 parts by weight, problems such as bubbles and color difference may occur during dyeing.

As the anionic emulsifier, it is preferable to use at least one selected from sodium lignin sulfonate and formaldehyde-2-naphthalenesulfonic acid copolymer sodium salt.

As the nonionic emulsifier, it is preferable to use at least one selected from polyoxyethylene alkyl ether and polyoxyethylene glycol mono (tristyrylphenyl) ether .

When the anionic emulsifier and the nonionic emulsifier are mixed, the anionic emulsifier and the nonionic emulsifier are used at a weight ratio of 1: 0.1 to 30, preferably 1: 5 to 20, If the ratio is less than 1: 0.1, the effect of mixing is hardly obtained. If the weight ratio is more than 1: 30, the emulsification and dispersing properties are deteriorated. As a result, It is preferable to use it within the above range.

The light fastness enhancer of the present invention may further comprise at least one compound selected from the group consisting of antifoaming agents and thickeners in addition to the compounds represented by the above-mentioned formula (1) and emulsifiers.

The antifoaming agent may be one generally used in the art, but preferably one or more selected from a silicone antifoaming agent, a mineral oil antifoaming agent and a self-emulsifying silicone antifoaming agent may be used. It is preferable to use 0.1 to 1.0 part by weight based on 100 parts by weight of the compound to be used.

The agglomerant may be one generally used in the art, but preferably one or more selected from the group consisting of a cellulose-based thickener, an acrylic thickener, and a urethane-based thickener may be used. It is preferable to use 0.1 to 1.0 part by weight based on 100 parts by weight of the compound.

The light fastness enhancer of the present invention is a yellowish liquid phase, and the proportion of particles having an average particle diameter of 1 탆 or less may be 70% or more, preferably 75% or more.

The light fastness enhancer of the present invention has a pH of 6.2 to 6.8 when diluted to a concentration of 10 vol% (vol%) in distilled water and a solid content of 22 to 27 wt% when dried at 105 ° C for 40 minutes. Lt; / RTI >

Such a light fastness enhancer of the present invention can be used as a dyeing auxiliary additive to minimize and / or prevent the decrease of light fastness before and after exposure to sunlight, and is more effective than dyeing fabrics of beige color system in particular.

In addition, when a product using fibers dyed with such a dyeing aid, preferably an automobile sheet, is applied, an automobile sheet having excellent light fastness to light can be produced. Further, since the sunlight fastness enhancer of the present invention is minimized and / or scarcely minimized in the processing step after the dyeing operation, it is accumulated in the factory as well as the processing equipment to cause secondary contamination to the processed product, It is effective to increase the production cost due to the manufacturing time and cost, and it is possible to minimize or prevent the problem of harming the health of the worker due to the sublimation component like the existing daylight fastness enhancer.

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]

Preparation Example: Preparation of a compound represented by the formula (1)

(1) A 1-liter flask was charged with magnesium particles and tetrohydrofuran (THF) at 25 ° C and nitrogen gas, equipped with a stirrer, dropping funnel, condenser and thermometer.

Then, the mixture was heated to reflux at 62 ° C. Next, a small amount of iodine and bromobenzene was added and the reaction was started. Then, a chlorobenzene solution dissolved in THF was slowly dropped at 78 ° C for 2 hours. Thereafter, the mixture was stirred at the same temperature for 2.5 hours, and then cooled to 5 DEG C to prepare a Grinard solution.

Next, a 2 liter flask was equipped with a stirrer, a dropping funnel, a condenser and a thermometer, and cyanuric chloride and THF were added. After stirring, the mixture was cooled to 0 ° C, and 2.5 The Grignard solution synthesized for a period of time was added dropwise.

Thereafter, the same temperature was maintained for 30 minutes, the ice-bath was removed, and the mixture was stirred for 4 hours while maintaining the temperature at 25 ° C. Then, the temperature was raised to 90 ° C to remove THF by about 30% did. Then, an aqueous 5 wt% HCl solution was dropped thereon, cooled to 20 DEG C, filtered, washed with distilled water, and then dried to prepare a first-stage compound.

(2) A 2-liter flask was equipped with a stirrer, a dropping funnel, a condenser and a thermometer, and the above-mentioned compound of the first step, AlCl ₃ and chlorobenzene was added, and the temperature was raised to 70 ° C., and resorcinol And the mixture was reacted at 80 DEG C for 6 hours.

Next, the chlorobenzene was recovered by distillation, the temperature was lowered to 25 캜, and the resultant was filtered and dried to prepare a two-step composite.

(3) A 2 liter flask was equipped with a stirrer, a dropping funnel, a condenser and a thermometer, and the above two-stage compound and dimethylformamide (DMF) were injected. Then, the mixture was heated to 80 ° C with stirring, K ₂ CO ₃ was introduced, 1-bromomethane was dropped for 30 minutes, stirred at the same temperature for 2 hours, cooled to 25 ° C Washed with water and then with methanol, followed by drying to obtain a final compound represented by the following formula (1-2).

[Formula 1-2]

In Formula 1-2, R ¹ is an alkoxy group of Cl, and R ² and R ³ are each a hydrogen atom.

Examples 1 to 11 and Experimental Example 1: Experiment for selecting appropriate emulsifier

Experiments were conducted to select suitable emulsifiers for liquefying the final compound represented by Formula 1-2 prepared in Preparation Example 1, and the results are shown in Tables 1 and 2 below.

In Examples 1 to 11, the emulsifier and amount (parts by weight) shown in Table 1 below were used for 100 parts by weight of the final composition, and the degree of emulsion dispersibility was shown in Table 2. The emulsion dispersibility was determined based on the change with time after leaving at 25 ° C.

division
(Parts by weight) Anionic emulsifier Nonionic emulsifier Cationic system
Emulsifier Mixed emulsifier
(Mixing ratio 1: 1 weight ratio) One 2 3 4 5 6 7 1 + 4 2 + 5 2 + 6 1 + 7 Example 1 10 Example 2 10 Example 3 10 Example 4 10 Example 5 10 Example 6 10 Example 7 10 Example 8 10 Example 9 10 Example 10 10 Example 11 10 1: sodium lignin sulfonate
2: Formaldehyde-2-naphthalenesulfonic acid copolymer sodium salt
3: Sodium alkylsulfonate
4: polyoxyethylene ether
5: Polyoxyethylene glycol mono (tristyrylphenyl) ether
6: Polyoxyethylene sorbitan monoalkylate
7: Polyoxyethylene alkylamine

division Degree of emulsifying acidity Example 1 ○ Example 2 ○ Example 3 X Example 4 ○ Example 5 ○ Example 6 X Example 7 X Example 8 ◎ Example 9 ◎ Example 10 △ Example 11 X X: poor emulsion dispersibility,?: Normal,?: Good,?: Very good

Production Example 1: Production of daylight fastness improving agent

(1) 10 parts by weight of an emulsifier containing sodium lignin sulfonate and polyoxyethylene ether in a weight ratio of 1: 1 to 100 parts by weight of the final composition prepared in Example 8, and pre-emulsion ).

Next, the pre-emulsion was pulverized and dried by using a milling machine so that an average particle size of 1 mu m or less was 70% or more, thereby preparing a liquid light fastness enhancer.

Next, the liquid light fastness enhancer was adjusted to pH 6.5.

Preparation Example 2: Preparation of a saline solution for daylight fastness treating fabrics

(1) At 40 占 폚, 0.5 g / l of a dispersing leveling agent, 0.2 g / l of a pH adjusting agent and 3-5% owf of the light fastness enhancer of Preparation Example 1 were added and stirred for 10 minutes. Next, the dyes and amounts shown in Table 3 below were added as dyes, respectively, to prepare beige and gray dyes.

Comparative Production Examples 1 to 6

(ICEI All Product), EPC (ICEI All Product), KGC (ICEI All Product), A Product (product H), B (All Products) Comparative Production Example 1 to Comparative Production Example 6 were respectively carried out by preparing a salt solution using the products (product H) and product C (product K).

division Production Example 1 Production Example 2 Basic color (Beige color) Gray color Yellow 0.240% o.w.f. 0.195% o.w.f. Red 0.085% o.w.f. 0.130% o.w.f. Blue 0.066% o.w.f. 0.420% o.w.f. Brown 0.128% o.w.f. 0.051% o.w.f. Yellow: Dorospers Yellow KHM
Red: Dorospers Red KAS
Blue: Dorospers Blue KGLFN
Brown: Foron Brown AS-3LR

Experimental Example  2 : Lab  Dyeing and Light fastness  Test

(1) A PET fabric for automobile seat was put into a beige and gray colored salt solution prepared in Production Example 2, and then dyed while raising the temperature to 135 캜 at a heating rate of 1 캜 / min.

Next, after reaching 135 캜, the temperature was maintained for 40 minutes to be dyed, and then cooled to 25 캜 to 30 캜 at a cooling rate of 2 캜 / minute, and PET staining for car seat dyed in beige and gray Fabrics were prepared.

The dyeing fabric was cured at 200 ° C for 10 minutes to confirm the survival at high temperature.

(2) A PET fabric for beige and gray car seats was produced in the same manner, except that the dyeing preparations of Comparative Production Examples 1 to 6 were used instead of the dyeing preparations prepared in Production Example 1, and dyeing in beige and gray colors PET fabric for automobile seat was prepared.

(3) Daylight fastness test

1) UV-2000 tester test

M ² at 80 ° C for 20 hours and 40 hours, respectively, using a UV-2000 tester manufactured by ATLAS Co., Ltd., and graded on a Gray scale by visual observation. The results are shown in Figs. 1 and 2 And Table 4.

2) Fade-O-Meter test

A specimen of a predetermined size was irradiated with 84 MJ / m ² (300 to 400 nm) by using a Ci-4000 tester manufactured by ALTAS, and then irradiated with 84 MJ / m ² (300 to 400 nm), and compared with a blank of the same sample, The car was graded on a gray scale and the results are shown in Figures 3 and 5 below.

division Light fastness (grade) UV-2000 Tester (Beige) UV-2000 Tester (Gray) Blank 1 to 1.5 1 to 1.5 Production Example 2 3.5 3.5 Comparative Preparation Example 1 3.0 3.0 Comparative Production Example 2 2.0 to 2.5 2.0 to 2.5 Comparative Production Example 3 2 2 Comparative Production Example 4 2 2 Comparative Preparation Example 5 2.0 to 2.5 3.0 Comparative Preparation Example 6 2.0 to 2.5 2.0 to 2.5 Grade Criteria: Gray Scale (grades 1-5) with higher light fastness.

division Light fastness (grade) Fade-O-Meter Test (Beige) Blank 1 to 1.5 Production Example 2 3.5 Comparative Preparation Example 1 3.0 Comparative Production Example 2 2.5 Comparative Production Example 3 2.5 Comparative Production Example 4 2.0 to 2.5 Grade Criteria: Gray Scale (grades 1-5) with higher light fastness.

The results of the UV-2000 tester experiment shown in Table 4 and FIG. 1 to FIG. 2 show that the color fading was lowest in Production Example 2 after irradiation with ultraviolet light, and that it maintained a higher light fastness than Comparative Production Examples 1 to 6 I could.

In addition, the results of the Fade-O-Meter of Table 5 and FIG. 3 show that the color fading was the lowest in Production Example 2, and thus showed a higher light fastness than Comparative Production Examples 1 to 4.

(4) Anti-seizure test

A TGA measurement was performed to test stability at a high temperature, and about 1 g was measured as a sample while raising the temperature from 50 DEG C to 400 DEG C at a rate of 10 DEG C / min.

The results are shown in Table 6. The weights representing the weight percent of light fastness remaining on the basis of 1 g of each sample at each temperature are shown in weight% and measured for Production Example 2 and Comparative Production Examples 1 and 2.

Temperature (℃) Production Example 2 Comparative Preparation Example 1 Comparative Production Example 2 50 100 100 100 100 100 100 100 150 93 94 98 200 90 71 94 250 87 62 62 300 75 58 8 350 55 41 3 400 45 23 One Unit: Weight%

When the results of Table 6 are examined, the weight% of Comparative Production Example 1 and Comparative Production Example 2 at 150 ° C is higher than that of Production Example 1 because the solid content is about twice as high as that of Comparative Production Example 1 and Comparative Production Example 2, Numbers seem to be visible. However, in Comparative Production Example 1 and Comparative Production Example 2, a weight loss of about 40% was observed at a practical processing temperature of 200 to 250 ° C, while a small weight loss of about 10 to 13% It looked. This means that the thermal decomposition in the high temperature processing step after the dyeing process is minimized, and the reduction of the light fastness to the final product is obtained.

Through the above Examples and Experimental Examples, it can be confirmed that the light fastness improving agent of the present invention can reduce the decrease in the fastness of light fastness before and after exposure to sunlight, because it is not sublimated in the processing step after dyeing, and sublimation is minimized . By using such a present invention, it is expected that a product such as a fiber, a fabric and a sheet (or a sheet cover) using the same having an excellent light fastness of light can be provided.

Claims (15)

A compound represented by Formula 1 below;
An emulsifier containing at least one selected from anionic emulsifiers and nonionic emulsifiers,
A pH of 6.2 to 6.8 when diluted to a concentration of 10 vol.% In distilled water, and a solids content of 22 to 27 wt.% When dried at 105 DEG C for 40 minutes;
[Chemical Formula 1]

Wherein R ¹ is a hydrogen atom, -OH, a C 1 to C 5 alkyl group or a C 1 to C 5 alkoxy group, R ² and R ³ are each independently a hydrogen atom, a C 1 to C 5 alkyl group or a C 2 to C 5 Lt; / RTI > The light fastness improving agent according to claim 1, wherein the compound represented by Formula 1 is a compound represented by Formula 1-1.
[Formula 1-1]

Wherein R ¹ is a hydrogen atom, -OH, a C 1 to C 5 alkyl group or a C 1 to C 5 alkoxy group, R ² and R ³ are each independently a hydrogen atom, a C 1 to C 5 alkyl group or a C ² to C 5 alkoxy group, To C5 alkylene group. The light fastness improving agent according to claim 2, wherein R ¹ is a C ¹ to C 3 alkoxy group, and R ² and R ³ are each independently a hydrogen atom or a C 1 to C 3 alkyl group. [3] The method of claim 1, wherein the anionic emulsifier is at least one selected from the group consisting of sodium lignin sulfonate and formaldehyde-2-naphthalenesulfonic acid copolymer sodium salt. Wherein the light fastness enhancer is selected from the group consisting of: The nonionic emulsifier according to claim 1, wherein the nonionic emulsifier comprises at least one selected from the group consisting of polyoxyethylene alkyl ether and polyoxyethylene glycol mono (tristyrylphenyl) ether Wherein the light fastness enhancer is a light fastness enhancer. The light fastness improving agent according to claim 1, wherein the emulsifier is contained in an amount of 10 to 50 parts by weight based on 100 parts by weight of a compound represented by the following formula (1). The light fastness improving agent according to claim 1, wherein the emulsifier comprises an anionic emulsifier and a nonionic emulsifier at a weight ratio of 1: 0.1-30. The light fastness improving agent according to claim 1, further comprising at least one selected from the group consisting of antifoaming agents and thickeners. The light fastness improving agent according to claim 1, wherein the ratio of particles having an average particle size of 1 占 퐉 or less is 70% or more. delete The light fastness improving agent according to any one of claims 1 to 9, which is in a yellowish liquid state.
A dyeing preparation according to any one of claims 1 to 9, which comprises a light fastness improving agent. 12. A fiber comprising the dyeing aid of claim 12. A sheet comprising the fibers of claim 13. 15. The sheet according to claim 14, wherein the sheet is an automotive sheet.

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