KR0169190B1 - Soil retardant composite - Google Patents

Abstract

The present invention relates to an antifouling agent composition, and more particularly, by mixing a water / oil repellent composition and an urethane compound for antifouling process to prepare an aqueous dispersion emulsion to treat it on the fabric surface of a carpet or interior, as well as the antifouling property of the fabric surface. The present invention relates to an antifouling agent composition capable of enhancing water repellency and oil repellency.

Description

Antifouling agent composition

The present invention relates to an antifouling agent composition, and more particularly, by mixing a water and oil repellent composition and an urethane compound for antifouling process to prepare an aqueous dispersion emulsion to treat it on the fabric surface of a carpet or interior, as well as the antifouling property of the fabric surface. The present invention relates to an antifouling agent composition capable of enhancing water repellency and oil repellency.

Perfluoro compound is characterized by water repellency and oil repellency by treatment with textile processing agent on fabric surface, especially in case of perfluoro-containing compound containing urethane compound as antifouling agent It is used for carpets and interiors because it has excellent adhesion and hardened coating film.

The manufacturing method of the antifouling agent is already well known [US Patent No. 3,484,281, Japanese Patent Laid-Open No. 53-112,855, Small 54-133,485, Small 56-129,281, Small 59-157,166], Antifouling processing The agent has good antifouling performance but low water and oil repellency. The reason why the antifouling performance of these antifouling agents is high is that the urethane compound is contained in the antifouling agent, and thus, the perfluoro-containing urethane compound is excellent in adhesiveness on the surface of the fiber when processing to textile fabrics, thereby increasing durability. It is difficult to disperse in water because of poor solubility in water or general organic solvents. Therefore, in order to enhance the solubility of the urethane compound in the solvent, a hydrophilic group is introduced into the antifouling agent, in which case the water repellency and the oil repellency naturally decrease. However, when used in combination with an antifouling agent containing a water and oil repellent composition and a urethane compound, it is possible to improve not only antifouling property but also water repellency and oil repellency. However, the conventional water and oil repellent agent does not contain a urethane compound and is much higher in water repellency and oil repellency than an antifouling agent containing only a urethane component.

Accordingly, an object of the present invention is to provide an aqueous dispersion type antifouling agent composition obtained by mixing a water / oil repellent composition and an antifouling urethane compound as an antifouling agent having excellent water repellency and oil repellency as well as antifouling property.

Hereinafter, the present invention will be described in detail.

The present invention relates to an antifouling agent comprising 10 to 90% by weight of a water- and oil-repellent composition copolymerized with a perfluoro alkyl group-containing compound, a compound having a radically reactive unsaturated double bond, and a halogenated hydrocarbon compound, and 90 to 10% by weight of an antifouling urethane compound. It relates to a composition.

The present invention will be described in more detail as follows.

The present invention relates to an aqueous dispersion antifouling agent composition formed by mixing a water / oil repellent composition and an antifouling urethane compound, wherein the water / oil repellent composition is represented by the following structural formulas (I), (II), (III) and (IV) It selects from the compound containing perfluoro alkyl group, and is used individually or in mixture of 2 or more types.

In the above formulas,

R ¹ is a hydrogen atom or a methyl group,

R ² is a C ₁ to C ₃ alkyl group,

k is an integer of 3 to 21.

In addition, examples of the compound having a radically reactive unsaturated double bond that may be used in preparing the water / oil repellent composition include benzyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth). Vinyl compounds such as acrylate, acrylonitrile, acrylamide, vinyl acetate, styrene, or vinylidene compounds, N-methylol (meth) acrylamide, N-methylol acrylamide butyl ether, and N-butoxy (meth) ) Acrylamide, 2-hydroxy (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like or a mixture of two or more selected from crosslinking group-containing monomers.

In addition, the water- and oil-repellent composition is prepared in a water dispersion type by adding a halogenated hydrocarbon compound to the monomers, it is not particularly limited to the solid content concentration in the prepared composition is generally 15 to 30% by weight.

The halogenated hydrocarbon compounds used in the water and oil repellent composition include trichlorofluoromethane, dichlorodifluoromethane, trichlorotrifluoroethane, chloropentafluoroethane, dichlorohexafluoropropane, bromotrifluoromethane and dibro. Halogenated alkane compounds such as motetrafluoroethane, carbon tetrachloride, 1,1,1, -trichloroethane, dichlorofluoromethane, chlorodifluoromethane, dichlorodifluoroethane, chlorodifluoroethane and dichlorodifluoro Single or a mixture of two or more selected from halogenated alkenes such as ethylene, chlorotrifluoroethylene, dichlorotetrafluoropropylene, dibromodifluoroethylene, and 1,1,1-trichloroethylene.

When preparing a water / oil repellent composition using the above monomer, 20 to 80% by weight of a perfluoro alkyl group-containing compound, 25 to 75% by weight of a compound having a radically reactive unsaturated double bond, and 5 to 40% by weight of a halogenated hydrocarbon compound To prepare a copolymer using a known polymerization method.

Meanwhile, the antifouling urethane compound emulsion contains a perfluoro alcohol compound represented by the following structural formula (V), an alcohol compound having three hydroxyl groups represented by the following structural formula (VI), and an ethylene oxide group represented by the following structural formula (VII). An urethane compound obtained by synthesizing an alcohol compound and a compound containing two isocyanate groups represented by the following structural formula (VIII) is emulsified in water using a surfactant.

In the above formula,

R _f is a _{C k · F 2k '+ 1} ,

R is a methyl group or a butyl group,

X is CH ₃ C-, C ₂ H ₅ C-, N-, H ₂ NC- E or HC-,

Y is -CH _2- , -CH ₂ (OCH ₂ CH ₂ ) _n- , -Ch ₂ [OCH ₂ CH (CH ₃ )] _n- , -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n -or -C ₆ H _4- ,

Z is an aromatic or aliphatic hydrocarbon group,

k 'is an integer from 4 to 15,

m is an integer from 2 to 17,

n is an integer of 1-6.

Here, specifically illustrating the perfluoro alcohol compound represented by the structural formula (V),

And, specifically exemplifying an alcohol having three hydroxyl groups represented by the structural formula (VI),

Examples of the ethylene oxide group-containing alcohol compound represented by the structural formula (VII) include polyethylene glycol methyl ether (molecular weight added ethylene oxide group 2 to 17), polyethylene glycol butyl ether (molecular weight added ethylene oxide group 2 to 14) and the like.

Finally, examples of the compound containing two isocyanate groups represented by the above formula (VIII) include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and the like.

When preparing a urethane compound with such a compound, 20 to 80% by weight of a perfluoro alcohol compound, 1 to 20% by weight of an alkoxy compound having three hydroxy groups, 5 to 60% by weight of an ethylene oxide group-containing alcohol compound and two isocyanate groups 5 to 70% by weight of the compound to be mixed is prepared by a conventional method. In the case of the perfluoro alcohol compound represented by the structural formula (V), if the content is less than 20% by weight, there is a problem that the water repellency and oil repellency is lowered, and if it is contained in excess of 80% by weight, of course, it lacks economic efficiency There is a problem that is difficult to disperse in water. If the content of the hydrophilic monomer, that is, the alcohol compound having three hydroxyl groups represented by the above formula (VI) and the ethylene oxide group containing alcohol compound represented by the above formula (VII) is less than the above range, the perfluoro-containing urethane compound prepared Since the solubility in water solvents or general organic solvents is poor, there is a problem that it is difficult to disperse in the solvent as a result, and when the content of these hydrophilic monomers is excessive, there is a problem in that water repellency and oil repellency are lowered. In addition, when the content of the compound containing two isocyanate groups represented by the above formula (VIII) is less than 5% by weight, there is a problem that the antifouling property is lowered, and when contained in excess of more than 70% by weight, water and oil repellency may be reduced. Can be.

The urethane compound thus prepared is dispersed in an aqueous solution using a conventional nonionic or cationic surfactant to prepare an emulsion.

The water- and oil-repellent composition prepared as described above and the urethane compound emulsion are mixed, wherein the mixing ratio is 10 to 90% by weight of the water and oil repellent composition and 90 to 10% by weight of the antifouling urethane compound.

At this time, when the amount of the water / oil repellent composition used is less than 10% by weight, there is a problem in that water repellency and oil repellency are lowered, and when it is added in excess of 90% by weight, there is a problem in that the antifouling property is lowered.

Here, the mixing method uses a general stirring method.

The prepared antifouling agent composition is used as an aqueous dispersion in textile fabrics by conventional methods such as spraying, dipping or padding, and excess liquid is removed using a compression roller and the fabric is dried. The dried fabric is usually cured by heating to 140-180 ° C. for 60-180 seconds, which will enhance resilience and durability.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

Fabrics treated with the aqueous dispersion antifouling agent of the present invention was evaluated for water repellency, oil repellency and antifouling property by the following test method.

1. Textile treatment of antifouling agent

In order to evaluate the performance of the aqueous dispersion antifouling agent, the prepared antifouling agent should be treated on the surface of nylon fabric. The nylon cloth (20 cm wide x 20 cm wide) is immersed in an aqueous dispersion of 0.5 wt% solids for 1 minute and moistened, and the excess nylon cloth is removed using a compression roller. The pick-up of the aqueous dispersion is then about 75%. The treated fabric is dried at 105 ° C. for 3 minutes and then cured at 160 ° C. for 3 minutes.

2. Water repellency

The treated textile product was measured for water repellency using a test model of Japanese Industrial Standard JIS L 1092 (1977). In this method, an 18cm diameter fabric cloth treated with an antifouling agent was placed on a slope of 45 °, and about 250ml of water was sprayed through a nozzle at a constant height, and the surface of the fabric was observed to determine the water repellency grade. The judgment criteria are as Table 1 below.

3. Oil repellent

Oil repellency was measured using the American Textile Chemists and Dyeers Association Standard AATCC TM-118 (1983) method. In this method, the fabrics treated with antifouling agents are placed horizontally, and the AATCC (American Association of Textile, Chemist and Colorist) standard test solution is dropped from the lower grade into the dropper. After 30 seconds, observe the state of the droplets. If the droplets do not penetrate or bleed, drop the next test solution. If there is no wetting or bleeding in the same way, drop the next test solution. If wetting or bleeding is determined for all grades. The oil repellent test solution and oil repellency grade are shown in Table 2 below.

In general, treated fabrics having a degree of oil repellency of 5 or higher can be said to have good or excellent resilience to oil.

4. Antifouling measurement

3 pieces of nylon cloth (5 cm x 5 cm) treated with antifouling agent were put in a cylindrical plastic pail together with dry contaminants (Table 3) and ceramic balls (5 mm in diameter, approx. 420) at a ball mill roller for 3 minutes at 150 rpm. Rotate After this, a vacuum cleaner is used to remove excess material on the sample cloth. Antifouling property is determined by comparing the standard scale of Table 4 with the contaminated sample and the standard sample. The larger the numerical value of the scale, the more easily the sample can be contaminated and the lower the antifouling performance.

Example 1

The water and oil repellent composition was prepared by the following procedure.

60 g of perfluoroalkylethyl acrylate represented by CFCHCHOCOCH = CH, 32 g of stearyl (meth) acrylate, 15 g of vinylidene chloride, and N-methylol in a 1 l pressure reactor equipped with a temperature controller and a stirrer 2 g of acrylamide, 5 g of polyoxyethylene lauryl ether (the average number of moles of ethylene oxide group added), 1 g of stearyltrimethylammonium chloride, 60 g of acetone, 368 g of distilled water, 1,0 g of azobisisobutyl amidine dihydrochloride and 1 2 g of 1,1-trichloroethylene was added thereto, followed by nitrogen replacement for about 30 minutes with stirring. The temperature of the reaction solution was raised to 60 ° C., the polymerization reaction was carried out for 15 hours, and then cooled to obtain a water-dispersible water / oil repellent composition having a solid content of 20%.

The antifouling urethane emulsion was prepared as follows.

74 g of perfluoroalcohol (CFCHOH), 104.5 g of toluene diisocyanate, 80 g of trimethylpropane ethoxylate, polyethylene glycol methyl ether (average number of moles of ethylene oxide added) 189 g in a glass pressure reactor 1I equipped with a temperature controller and a stirrer , 192 g of dioxane and 0.6 g of dibutyl tin dilaurate were added thereto. The urethane compound (UC01) was synthesized by reacting for 10 hours while maintaining at 70 ℃ in a closed reactor. Then, 32.4 g of urethane compound (UC01), 10.0 g of methoxyethyl ether, 3.6 g of polyoxyethylene nonylphenyl ether (mole number of ethylene oxide base moles), 2.5 g of lauryltrimethylammonium chloride, and 178.0 g of water were stirred together. A perfluoro containing urethane emulsion was obtained.

Next, the antifouling agent composition was prepared by mixing and stirring the water / oil repellent composition and the urethane-containing emulsion in a weight ratio of 60/40. The water repellency of the prepared antifouling agent is 100, oil repellency is 8, the antifouling property is 1.

[Examples 2 to 8 and Comparative Examples 1 to 3]

An antifouling agent was prepared in the same manner as in Example 1, except that the mixing ratio of the water / oil repellent composition and the urethane-containing emulsion for antifouling process was different as shown in Table 5 below.

From the above results, the antifouling agent composition prepared by mixing 10 to 90% by weight of the water and oil repellent composition and 90 to 10% by weight of the antifouling urethane compound as in the present invention has water and oil repellency compared to using each composition alone. It is understood that this is excellent while the antifouling property is excellent.

Claims (5)

10 to 90% by weight of a water and oil repellent composition prepared by copolymerizing a perfluoro alkyl group-containing compound, a compound having a radically reactive unsaturated double bond, and a halogenated hydrocarbon compound, and 90 to 10% by weight of an antifouling urethane compound. Antifouling agent composition. The antifouling agent according to claim 1, wherein the perfluoroalkyl group-containing compound is a single or a mixture of two or more selected from compounds represented by the following structural formulas (I), (II), (III) and (IV): Composition. In the above formulas, R ¹ is a hydrogen atom or a methyl group, R ² is an alkyl group of C ₁ to C ₃ , k is an integer of 3 to 21. The antifouling agent composition according to claim 1, wherein the compound having a radically reactive unsaturated double bond is stearyl (meth) acrylate, N-methylol (meth) acrylamide or a mixture thereof. The method of claim 1, wherein the halogenated hydrocarbon compound is selected from dichlorodifluoroethylene, chlorotrifluoroethylene, dichlorotetrafluoropropylene, dibromodifluoroethylene and 1,1,1-trichloroethylene alone or 2 An antifouling agent composition, characterized in that at least one halogenated alkene compound. According to claim 1, wherein the urethane compound is 20 to 80% by weight of a perfluoro alcohol compound represented by the following structural formula (V), 1 to 20% by weight of an alcohol compound having three hydroxyl groups represented by the following structural formula (VI), 5 to 60% by weight of an ethylene oxide group-containing alcohol compound represented by the following formula (VII) and 5 to 70% by weight of a compound comprising two isocyanate groups represented by the following formula (VIII) . Wherein R _f is C _{k .F 2k '+ 1} , R is a methyl group or a butyl group, X is CH ₃ C-, C ₂ H ₅ C-, N-, H ₂ NC- or HC-, Y is -CH _2- , -CH ₂ (OCH ₂ CH ₂ ) _n- , -Ch ₂ [OCH ₂ CH (CH ₃ )] _n- , -CH ₂ CH ₂ (OCH ₂ CH ₂ ) _n -or -C ₆ H _4- , Z is an aromatic or aliphatic hydrocarbon group, k 'is an integer from 4 to 15, m is an integer from 2 to 17, n is an integer from 1 to 6.