KR20160084913A - Manufacturing method of uv-light blocking fabric treatment agent and fabric treatment agent made by the same - Google Patents

Abstract

The present invention relates to a fabric treatment agent manufacturing method by which elasticity and a UV-blocking function of a fabric can be improved, a fabric treatment agent manufactured by using the same, and a fibrous base material treated with this fabric treatment agent and, more particularly, to a UV-blocking fabric treatment agent manufacturing method in which a UV absorber containing a benzophenone-type vinyl monomer and butyl acrylate is added to a polyurethane-based emulsion composition manufactured by a manufacturing method including a first step in which a polyol mixture containing 20 to 40 mol% of polytetramethylene glycol (PTMG), 5 to 20 mol% of polydimethylsiloxane (PDMS), and 40 to 60 mol% of N-nitrosodiethanolamine (NDEA) is heated to 70 to 120 degrees Celsius, a second step in which the polyol mixture of the first step and isophorone diisocyanate (IPDI) are mixed at a molar ratio of 1 : 1 to 1.2, a catalyst is added, and curing is performed with the temperature lowered to 40 degrees Celsius, a third step in which neutralizing agent addition and neutralization are performed at 40 degrees Celsius, and a fourth step in which aqueous dispersion is performed, a fabric treatment agent manufactured by using the same, and a fibrous base material treated with this fabric treatment agent.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for producing a fiber processing agent having ultraviolet shielding ability,

The present invention relates to a method for producing a fiber processing agent capable of improving the elasticity and ultraviolet blocking ability of a fiber, a fiber processing agent produced thereby, and a fibrous substrate treated with the fiber processing agent.

In order to increase the elasticity of the knitted fabric, elastic silicone oil emulsified products and water-soluble urethane products are generally used as elastic working agents. However, the elastic silicone oil emulsified product has a disadvantage in that it has an excellent soft touch but insufficient elasticity and antifouling property, and the water-soluble urethane product has the characteristics of elasticity, sweat and quick drying, In order to compensate for the disadvantages of the elastic silicone oil emulsified product and the water-soluble urethane product, there are products processed to include water-soluble urethane in the elastic silicone oil emulsified product or processed to include the elastic silicone oil emulsified product in the water- Most of these products also have insufficient storage stability and lack touch. Further, in the case of the above-mentioned fiber processing agents, since the particle size is not less than 500 nm, gumming occurs due to lack of stability, which causes a problem that a high defect rate is exhibited in the processing step. Therefore, it is necessary to develop a fiber finishing agent that reduces the problems listed above.

Recently, ultraviolet rays of sunlight are not properly absorbed into the ozone layer due to the destruction of the ozone layer due to environmental pollution, and a large amount of ultraviolet rays are transmitted to the ground, causing diseases such as skin damage and the like. Ultraviolet rays are light of a wavelength range of 290 to 400 nm. If the human body is exposed to ultraviolet rays for a long time, it may cause various damage such as skin pigmentation, stain, burns, and skin cancer. In order to prevent such damage to the human body, various products and processing methods for protecting the human body from the damage of ultraviolet rays have been developed.

Ultraviolet absorbers are organic compounds that absorb ultraviolet light and are mostly aromatic compounds with benzene nuclei. These materials convert the ultraviolet energy absorbed by the organic compound into a resonance structure, convert it into heat or low energy long wavelength light, and return to the original structure. As ultraviolet absorbers currently used, salicylic acid-based compounds, benzophenone-based compounds and the like are used.

Korean Patent Publication No. 10-1989-0005317 (May 15, 1989) Korean Patent Publication No. 10-1997-0043389 (July 26, 1997)

An object of the present invention is to provide a process for producing a fiber processing agent which is treated on fibers to reduce the shrinkage ratio of the fibers, improve the elasticity of the fibers, and impart ultraviolet barrier property to the fibers.

It is another object of the present invention to provide a fiber processing agent produced by the above-mentioned production method.

It is another object of the present invention to provide a fibrous base material processed with the above-mentioned fiber processing agent.

According to an aspect of the present invention, there is provided a process for producing a polyimide precursor, which comprises 20 to 40 mol% of polytetramethylene glycol (PTMG), 5 to 20 mol% of polydimethylsiloxane (PDMS) and N-nitrosodiethanolamine To 60 mol% of the polyol mixture is heated to 70 to 120 캜; Mixing the polyol mixture of step 1 with isophorone diisocyanate (IPDI) at a molar ratio of 1: 1 to 1.2, adding a catalyst, and curing the mixture by lowering the temperature to 40 占 폚; Neutralizing by adding a neutralizing agent at 40 캜; And a water-dispersible polyurethane emulsion composition, wherein an ultraviolet absorber comprising a benzophenone-type vinyl monomer and butyl acrylate is added to the polyurethane emulsion composition prepared by the process comprising the steps of: A process for producing a fiber finishing agent having barrier properties is provided.

The catalyst may be added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the polyol mixture.

In addition, acetone may be added after the temperature is lowered to 40 ° C in the second step.

The neutralizing agent may be added so that the molar ratio of the neutralizing agent to the polyol mixture is 1: 0.3-1.

In addition, the ultraviolet absorber may be added in an amount of 0.1 to 10% by volume based on 100% by volume of the total amount of the fiber processing agent to be produced.

According to another aspect of the present invention, there is provided a fiber processing agent having a UV blocking ability, which is produced by a manufacturing method according to one aspect of the present invention.

In addition, the polyurethane emulsion particle size included in the fiber processing agent may be 120 to 150 nm.

According to another aspect of the present invention, there is provided a fibrous substrate having a UV blocking ability, which is processed with a fiber processing agent according to another aspect of the present invention.

The fiber processing agent produced by the manufacturing method according to one aspect of the present invention can improve the absorbency, shrinkage, elasticity, tactile feeling, and ultraviolet ray shielding ability of the fiber when treated with the fiber.

Further, since the fiber processing agent produced by the manufacturing method according to one aspect of the present invention has excellent stability by reducing the cracking phenomenon of the silicone oil, it is possible to reduce the defective rate in the processing step when applied to the processing step of the fiber .

The present invention relates to a process for producing a polyurethane-based fiber processing agent having an ultraviolet shielding ability, a fiber processing agent produced thereby, and a fibrous substrate produced by processing the same.

Hereinafter, a method for producing a fiber finishing agent according to an embodiment of the present invention will be described in detail

The process for preparing a fiber finishing agent according to one embodiment of the present invention includes the steps of mixing a polyol containing polytetramethylene glycol (PTMG), polydimethylsiloxane (PDMS) and N-nitrosodiethanolamine (NDEA) And heating the mixture to 70 to 120 캜. 20 to 40 mol% of polytetramethylene glycol, 5 to 20 mol% of polydimethylsiloxane and 40 to 60 mol% of nitrosodiethanolamine, and the temperature inside the reactor was increased to 70 to 120 DEG C and mixed while stirring to obtain a polyol mixture . In the case where polytetramethylene glycol, polydimethylsiloxane and nitrosodiethanolamine are mixed at the mixing ratio described above, the fiber processing agent produced according to the production method of the present invention can be treated with fibers to improve the elasticity and tactility of the fibers . The internal temperature of the reactor is preferably 70 to 80 ° C.

In the method for producing a fiber finishing agent according to an embodiment of the present invention, the polyol mixture prepared in the above step 1 is mixed with isophorone diisocyanate (IPDI) in a molar ratio of 1: 1 to 1.2, To < RTI ID = 0.0 > 40 C < / RTI > The mixing ratio of the polyol mixture and the isophorone diisocyanate may be mixed in the same molar ratio, and it is preferable that the isophorone diisocyanate is mixed with the polyol mixture excessively in view of the fact that a large amount of isocyanate groups (-NCO) participating in the reaction is preferable . The catalyst may be selected from the group consisting of dibutyl tin dilaurate (DBTDL), tetraethylenediamine (TEDA), tetramethylenediamine (TMDA) and tin (Tin) But it is not limited thereto. Preferably, dibutyl tin dilaurate is selected as the catalyst. The catalyst may be added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the polyol mixture. When the polyol mixture is reacted with isophorone diisocyanate in the presence of a catalyst to initiate curing, the reaction of the glycol component rapidly increases the viscosity of the solution. When the viscosity of the solution in which polyol and isocyanate-based material react with each other during polyurethane synthesis is high There may arise a problem that the degree of crosslinking of the polyurethane is lowered. Therefore, in order to reduce the viscosity of the solution, the temperature for the reaction is lowered to 40 占 폚 and, if necessary, further solvent may be added to further reduce the viscosity of the solution. The solvent includes, for example, acetone, but is not limited thereto. And reacted at 40 ° C for 2 to 5 hours to synthesize a polyurethane.

The method for fabricating a fiber finishing agent according to an embodiment of the present invention includes three steps of neutralizing the polyurethane reaction solution by adding a neutralizing agent while maintaining the temperature at 40 ° C. The neutralizing agent may include at least one selected from the group consisting of water-soluble organic acids, inorganic acids, and mixtures thereof. For example, nitric acid or hydrochloric acid may be added to the solution to neutralize it, but not limited thereto. The content of the neutralizing agent to be added is not particularly limited, and may be, for example, in a molar ratio of 1: 0.3 to 1 based on the polyol mixture.

The method for producing a fiber processing agent according to an embodiment of the present invention includes four steps of preparing an emulsion by dispersing the synthesized polyurethane resin in water. Water may be added to the resin, or water may be added to the resin by adding water to the resin. In order to avoid the loss of the resin and reduce the manufacturing cost, it is preferable to add water to the resin and disperse the resin in water. The particle size of the emulsion produced may be between 120 and 150 nm. When the particle size of the prepared emulsion falls within the above range, the fixability to the fibrous substrate can be further improved, and the percentage of defects occurring during the processing of the fibrous substrate can be reduced.

The method for producing a fiber finishing agent according to an embodiment of the present invention comprises the steps of: mixing a polyurethane emulsion composition prepared through steps 1 to 4 with an acrylic resin containing a benzophenone type vinyl monomer and butyl acrylate And adding an ultraviolet absorber. The benzophenone type vinyl monomers are, for example, 4-phenylbenzophenone, 2-hydroxy-4-n-octyloxy-benzophenone, 2-hydroxy- Dihydroxy-4,4'-dimethoxybenzophenone, but it is not limited thereto. The content of the benzophenone type vinyl monomer and butyl acrylate is not particularly limited. For example, the content of the benzophenone type vinyl monomer is 0.1 to 50 wt%, the content of the butyl acrylate And a rate of 0.1 to 50 wt%, but is not limited thereto. The ultraviolet absorber may further contain water or an alcohol as a solvent in addition to the benzophenone type vinyl monomer and the butyl acrylate. The content of the solvent is not particularly limited and may be, for example, 10 to 50 wt% based on 100 wt% of the ultraviolet absorber. If desired, the ultraviolet absorber may be selected from surfactants, fragrances, screening agents, preservatives, proteins, polymers other than those of the present invention, vegetable oils, mineral oils or synthetic oils and other additives commonly used in textile finishing compositions Or more of the above additives.

The fiber finishing agent produced according to an embodiment of the present invention includes a polyurethane material, thereby improving the absorbency, shrinkage, elasticity, and tactile feeling of the fiber when the fiber is treated on the fiber. In addition, the fiber processing agent prepared according to one embodiment of the present invention includes an acrylic ultraviolet absorbent, so that ultraviolet blocking ability can be imparted to the fiber when the fiber processing agent is treated with the fiber.

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples in order to facilitate understanding of the present invention. It will be apparent to those skilled in the art that these embodiments are illustrative of the present invention and are not intended to limit the scope of the appended claims and that various changes and modifications may be made to the embodiments within the scope and spirit of the invention , And it is natural that such variations and modifications fall within the scope of the appended claims.

Example

≪ Preparation of fiber processing agent >

[Production Example] Preparation of polyurethane emulsion composition

The reactor was charged with 24 g (0.024 mol) of polytetramethylene glycol, 16 g (0.008 mol) of polydimethylsiloxane and 4.77 g (0.04 mol) of nitrosodiethanolamine, and the inside temperature of the reactor was raised to 75 ° C. and stirred at 200 rpm for 30 minutes . Next, 19.2 g (0.0864 mol) of isophorone diisocyanate was added, and 0.02 g of dibutyltin dilaurate was added as a catalyst. When the viscosity was checked with a viscometer, when the viscosity increased, the temperature inside the reactor was lowered to 40 ° C, acetone was added to lower the viscosity, and the mixture was reacted for 3 hours while stirring. Next, an aqueous solution of 35% (v / v) hydrochloric acid was added in an amount of 11.9 ml to a molar ratio of 1: 0.55 to the total molar amount of polytetramethylene glycol, polydimethylsiloxane and nitrosodiethanolamine, and neutralization reaction was carried out at 40 ° C for 3 hours . Next, the polyurethane-based resin composition thus prepared was slowly added with distilled water for 3 hours while stirring at 400 rpm, followed by water dispersion to prepare a polyurethane emulsion composition.

[Example 1]

The emulsion composition and the ultraviolet absorber of the above production example were mixed with water to prepare a fiber finishing agent. The ultraviolet absorber was synthesized from benzophenone and butyl acrylate. 2 wt% of butyl acrylate, 1 wt% of benzophenone-4, 20 wt% of ethanol and 77 wt% of water. 16 wt% of the polyurethane emulsion composition of the above Production Example, and 1 wt% of the ultraviolet absorber were added to 100 wt% of the total 100 wt% of the fibers, and water was added as a solvent.

[Examples 2 to 10]

The fiber was prepared in the same manner as in Example 1, except that the ultraviolet absorber was added in an amount of 100 parts by weight based on 100 parts by weight of the total amount of the additives.

[Comparative Example 1]

A polyurethane-based emulsion composition of the above production example and a solvent to which no ultraviolet absorber was added were prepared.

[Comparative Example 2]

The procedure of Example 1 was repeated except that no ultraviolet absorber was added.

[Comparative Example 3]

The procedure of Example 1 was repeated except that the polyurethane-based emulsion composition of the above Production Example was not added.

[Comparative Example 4]

Except that a salicylic acid-based ultraviolet absorber was added as an ultraviolet absorber.

Polyurethane emulsion composition (wt%) Ultraviolet absorber (wt%) Example 1 16 One Example 2 16 2 Example 3 16 3 Example 4 16 4 Example 5 16 5 Example 6 16 6 Example 7 16 7 Example 8 16 8 Example 9 16 9 Example 10 16 10 Comparative Example 1 - - Comparative Example 2 16 - Comparative Example 3 - One Comparative Example 4 16 One

≪ Fiber treatment of textile processing agent >

10 × 10 cm 40 cotton knit was prepared, and the cotton knit was immersed in the fiber working agent produced in the above Examples and Comparative Examples. Padded under 1 bar, dried at 120 ° C for 2 minutes, and heat-treated at 170 ° C for 2 minutes to prepare processed fibers. The properties of the processed fibers were measured by the methods of the following test examples, and the results are shown in Tables 2 to 3 below.

[Test Example]

1. Measurement of elastic recovery rate

The elastic recovery rate of the processed fiber was measured by applying an external force to the fiber, measuring the length, removing the external force, measuring the length again, and using the following formula 1.

[Equation 1]

(%) = (Reduced length when removing external force) / (length stretched when external force is applied)

2. Shrinkage measurement

The shrinkage rate of the processed fiber was measured by calculating the length of the warp and weft by measuring the length of warp and weft of the fiber in dry condition, washing and drying the fiber, and then measuring the length of warp and weft.

3. Color change measurement

The degree of color change of the processed fiber was measured by using L ^* a ^* b ^* display value, whiteness and yellowing value using CCM. The whiteness and eclipticity were measured according to ASTM E 313 method.

4. Measurement of UV blocking rate

The ultraviolet light blocking ratio of the processed fiber was measured using a UV-visible light spectrum meter with a wavelength range of 200 to 400 탆 and a wavelength interval of 10 탆.

Recovery length
(cm) Elasticity Recovery Rate (%) After drying (cm) Shrinkage (%) slope Weft slope Weft Example 1 10.7 90.00 10.3 9.3 3.0 -7.0 Example 2 10.8 88.57 10 9.4 0 -6.0 Example 3 10.7 90.00 10.1 9.5 1.0 -5.0 Example 4 10.6 91.43 10 9.5 0 -5.0 Example 5 10.89 88.57 10 9.5 0 -5.0 Example 6 11 85.71 10.2 9.4 2.0 -6.0 Example 7 10.8 88.57 10.3 9.4 3.0 -6.0 Example 8 11 85.71 10.2 9.5 2.0 -5.0 Example 9 11 85.71 9.9 9.4 -1.0 -6.0 Example 10 10.9 87.14 10.1 9.3 1.0 -7.0 Comparative Example 1 13 57.14 9.9 8.5 -1.0 -15.0 Comparative Example 2 10.4 94.29 10 9.5 0 -5.0 Comparative Example 3 11.8 74.29 10 9.3 0 -7.0

D65-10 Whiteness ecliptic UV-rays
Blocking rate L ^* a ^* b ^* ΔE Example 1 90.25 -0.77 4.82 3.71 52.65 7.93 91.1 Example 2 90.21 -0.77 5.34 4.22 50.05 8.76 94.2 Example 3 89.98 -0.81 5.61 4.58 48.36 9.21 96.0 Example 4 90.06 -0.99 6.12 5.04 46.76 9.77 97.4 Example 5 90.00 -0.93 6.20 5.12 46.08 9.97 97.9 Example 6 90.42 -0.82 5.69 4.51 48.88 9.24 98.2 Example 7 90.13 -0.86 5.75 4.62 48.32 9.29 98.9 Example 8 90.05 -0.91 6.19 5.09 46.30 9.92 99.2 Example 9 89.75 -1.54 7.54 6.55 41.22 11.49 99.1 Example 10 90.15 -1.06 6.24 5.14 46.62 9.86 99.2 Comparative Example 1 91.33 -0.37 1.29 - 71.80 2.36 31.2 Comparative Example 2 89.70 -0.62 5.11 4.16 50.17 8.49 33.0 Comparative Example 3 91.25 -0.57 2.05 0.79 67.94 3.53 89.7

In the case of Comparative Example 4, when the polyurethane-based emulsion composition and the acrylic ultraviolet absorbent were mixed, aggregation occurred and the fibers could not be processed, and the properties of the fibers processed in Comparative Example 4 could not be measured.

The results are shown in Table 2. Referring to Table 2, it can be seen that Examples 1 to 10 using the fiber processing agent according to the present invention have improved elastic recovery and ultraviolet shielding ability while maintaining an excellent shrinkage ratio.

Claims (8)

A polyol containing 20 to 40 mol% of polytetramethylene glycol (PTMG), 5 to 20 mol% of polydimethylsiloxane (PDMS) and 40 to 60 mol% of N-nitrosodiethanolamine (NDEA) A step of heating the mixture to 70 to 120 캜;
Mixing the polyol mixture of step 1 with isophorone diisocyanate (IPDI) at a molar ratio of 1: 1 to 1.2, adding a catalyst, and curing the mixture by lowering the temperature to 40 占 폚;
Neutralizing by adding a neutralizing agent at 40 캜; And
Water-dispersed polyurethane-based emulsion composition according to the present invention,
A process for producing a fiber finishing agent having a UV blocking ability, which comprises adding an ultraviolet absorber comprising a benzophenone type vinyl monomer and butyl acrylate.
The method of claim 1, wherein the catalyst is added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the polyol mixture.
The method according to claim 1, wherein acetone is added after lowering the temperature to 40 占 폚 in the second step.
4. The method according to claim 3, wherein the neutralizing agent is added so that the molar ratio of the neutralizing agent to the polyol mixture is 1: 0.3-1.
The method according to claim 1, wherein the ultraviolet absorber is added in an amount of 0.1 to 10% by volume based on 100% by volume of the total amount of the fiber processing agent to be produced.
A fiber finishing agent having an ultraviolet blocking property, which is produced by the production method according to any one of claims 1 to 5.
The fiber finishing agent according to claim 6, wherein the size of the polyurethane emulsion particle contained in the fiber finishing agent is 120 to 150 nm.
A fibrous substrate having ultraviolet shielding ability, which is processed with the fiber processing agent according to claim 6.