JPS6336640B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water and oil repellent composition, particularly to a water and oil repellent composition for imparting water and oil repellency and stain resistance to raw cotton for knitting fabrics. Antifouling treatment of knitted fabrics, especially carpets, has traditionally been
This is done by spraying a water and oil repellent on the carpet obtained by spinning or by dipping it in a water and oil repellent, but this method does not allow the treatment agent to penetrate into the interior of the carpet fibers. Since it does not penetrate, it has the disadvantage that sufficient water and oil repellency and dry cleaning resistance cannot be imparted. Therefore, regarding this carpet treatment, a method of treating the raw cotton before weaving with a perfluoroalkyl acrylic copolymer or a perfluoroalkyl urethane compound as a water and oil repellent is also being considered; This has the disadvantage that the treated raw cotton lacks lubricity and flexibility, resulting in poor spinnability, and the carpet woven from it lacks dry cleaning resistance. Although the flexibility is improved, the disadvantage is that the system becomes sticky and the spinnability becomes poor. The present invention relates to a water- and oil-repellent composition for treating raw cotton that solves these disadvantages, and which contains 70 to 99.9 parts by weight of a perfluoroalkyl urethane compound, an epoxy group, a hydroxyl group, an amino group,
It is characterized by comprising 0.1 to 30 parts by weight of an organopolysiloxane containing a functional group selected from the group consisting of a carboxyl group, an amide group, and a polyether group. To explain this, the present inventors conducted various studies on improving water and oil repellents used in carpet raw cotton treatment, and found that an organopolysiloxane having the above-mentioned functional group was added to a conventionally known perfluoroalkyl urethane compound. As a result, they discovered that it was possible to obtain raw cotton with excellent water and oil repellency as well as excellent spinnability for processing into carpets, and they also conducted research on the type of organopolysiloxane and the amount added. The present invention has been completed. The perfluoroalkyl urethane compound as the main material constituting the water and oil repellent composition of the present invention may be one conventionally known as a raw carpet treatment agent, and this compound has the following formula: 1) R _f -A-OH R _f is a linear or branched perfluoroalkyl group having 4 to 16 carbon atoms, and A is

【formula】

[Formula] (R is a hydrogen atom or a divalent organic group selected from an alkyl group having 12 or less carbon atoms, a substituted alkyl group), a phenylene group, and a diorganosiloxy group]; a perfluoroalkyl group-containing alcohol;
or expression

[Formula] (where B is an unsubstituted or substituted divalent hydrocarbon group or a diorganosiloxy group, R ¹ is an unsubstituted or substituted divalent hydrocarbon group or a thioalkylene group, and R _f is the same as above. same) or expression (Here, B, R ¹ R _f are the same as above, m, n are 1
500) and 2) an organic isocyanate or an isocyanate polymer. Alcohols represented by this formula R _f -A-OH include C ₄ F ₉ CH ₂ OH, C ₈ F ₁₇ CH ₂ CH ₂ OH, and C ₈ F ₁₇ SO ₂ N.
_{( CH3} ) _{CH2CH2OH , C8F17SO2N ( C3H7 )}
CH ₂ OCH ₂ CH ₂ CH ₂ OH, C ₆ F ₁₃ CON (C ₃ H ₇ )
CH ₂ CH ₂ OH, C ₁₀ F ₂₁ CH ₂ CH ₂ OH,

【formula】

[Formula] etc. are expressions.

Regarding the glycol represented by [Formula], etc. are exemplified, and the formula For glycols represented by Examples include. In addition, as the above-mentioned isocyanate, 2,4-
Examples include tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, trimethylolpropane, tolylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. The perfluoroalkyl urethane compound used in the present invention can be obtained by reacting the above perfluoroalkyl group-containing alcohol or glycol with an organic isocyanate in a solvent such as acetone or methyl ethyl ketone. It may be used as an aqueous solution or an emulsion, and when used as an emulsion, it may be used as an amine acetate as a self-emulsifying type. On the other hand, the organopolysiloxane constituting the water and oil repellent composition of the present invention is required to have a functional group in its molecule, which has the general formula

[Formula] [where A is the formula -R ³ X (R ³ is a divalent unsubstituted or substituted hydrocarbon having 1 to 10 carbon atoms, and a functional group selected from the group consisting of a polyether group), ^R2 is a monovalent unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, 0.01≦a<3.0≦b<2, 1≦ a
+b≦3], which is exemplified by the following formula. The water and oil repellent composition of the present invention is made by blending the above-described perfluoroalkyl urethane compound and a functional group-containing organopolysiloxane.
If it is less than 0.1% by weight, the raw cotton will not have lubricity,
Furthermore, if this amount exceeds 30% by weight, the water and oil repellency of the raw cotton decreases, so it may be composed of 70 to 99.9 parts by weight of a perfluoroalkyl urethane compound and 0.1 to 30 parts by weight of a functional group-containing organopolysiloxane. In particular, it is preferable to use 2 to 5 parts by weight of the functional group-containing organopolysiloxane.
Antistatic agents, softeners, smoothing agents, dyes, etc. may be added to this composition as required. To treat raw cotton with the water and oil repellent composition of the present invention, raw cotton made of natural fibers, polyester, acrylic, or synthetic fibers such as nylon is immersed in an aqueous or solvent solution of this composition, or raw cotton is treated with this solution. All you have to do is spray it and then dry it. This gives the raw cotton excellent water and oil repellency as well as lubricity and spinnability. Therefore, carpets etc. made from this raw cotton have water repellency and It has the advantage of being excellent in oil repellency, washing resistance, dry cleaning resistance, and stain resistance, as well as having a soft texture. Next, reference examples and examples of the present invention will be given. In the examples, parts indicate parts by weight and % indicates weight %, and the physical properties of raw cotton and carpet are the results of measurement by the following method. It is. 1. Spinnability of raw cotton After opening the cotton, it is treated with an oil agent consisting of a perfluoroalkyl urethane compound and a functional group-containing siloxane, and then the dried material is passed through a sowing machine or gill to remove impurities and become a sliver. The quality of spinnability was determined by observing chargeability and lubricity. 2 Water and oil repellency of carpet Water repellency ... AATCC 22-1671 spray method Oil repellency ... Method according to AATCC 118-1766 3 Stain resistance of carpet 〇 Test method ... Place the sample ( 20cm×20
cm), put 5 drops of white mineral oil and stain oil on it, cover it with 7.5cm x 7.5cm polyethylene paper, and then place a 2kg weight on it.
After 60 seconds, remove the weight and polyethylene paper,
Wipe off excess oil with absorbent paper. 〇 Judgment: Spread the test cloth on a black-painted test stand, place the judgment photographic plate in front of the test stand, 1 m from the floor, and irradiate it with a standard light source. 〇 Judgment grade... 1.0 Significant stains 2.0 Considerably 〃 〃 3.0 Slightly 〃 〃 4.0 Not noticeable stains 5.0 No stains Reference example 1 Contains a perfluoroalkyl group represented by the formula C ₄ F ₉ CH ₂ CH ₂ OH 100 parts of a perfluoroalkyl urethane compound made from 2 moles of alcohol and 1 mole of hexamethylene diisocyanate is dissolved in methyl isobutyl ketone, and then octadecyldimethylamine hydrochloride is added thereto to emulsify it to form a repellent with a solid content of 30%. A water and oil repellent (sample A) was produced. Next, this was diluted 10 times with water, acrylic raw cotton was immersed in it, heat treated at 150℃ for 5 minutes, the spinnability of the raw cotton thus obtained was examined, and then this raw cotton was woven. When a carpet was made and the water and oil repellency and stain resistance of this carpet were examined, the results shown in Table 1 below were obtained. Reference example 2 formula 2 moles of perfluoroalkyl group-containing glycol shown by, 1 mole of dimer acid diisocyanate,
A water-soluble urethane compound prepared by quaternizing a perfluoroalkyl urethane compound made from 3 moles of methylene bis diisocyanate and 2 moles of diethanolamine with hydrochloric acid was produced as a water and oil repellent (sample B) with a solid content of 30%. Next, using this sample B, acrylic raw cotton was treated in the same manner as in Reference Example 1, and the spinnability of the raw cotton treated in this way and the physical properties of a carpet made from this raw cotton were examined, and the results are shown in Table 1. Similar results were obtained. Reference example 3 formula A water-soluble urethane compound prepared by adding lactic acid to a perfluoroalkyl urethane compound made from 2 moles of perfluoroalkyl group-containing glycol, 3 moles of tolylene diisocyanate, and 1 mole of diethanolamine shown in 30
Add water to make a water and oil repellent (Sample C)
was prepared. Next, using this sample C, acrylic raw cotton was treated in the same manner as in Reference Example 1, and the spinnability of the raw cotton treated in this way and the physical properties of a carpet made from this raw cotton were examined, and the results are shown in Table 1. The results shown were obtained. Reference example 4 20 parts of a perfluoroalkyl compound represented by the formula C ₈ F ₁₇ CH ₂ CH ₂ COOCH=CH ₂ , 6 styrene
emulsifier Brj35 (trade name manufactured by Kao Atlas Co., Ltd.) to a monomer composition consisting of
5 parts by adding 1 part of (NH ₄ ) ₂ S ₂ O ₈ and 65 parts of water.
The reaction was carried out at 100° C. for 1 hour, and the emulsion was filtered to prepare a water and oil repellent (sample D) with a solid content of 30%. Next, using this sample D, acrylic raw cotton was treated in the same manner as in Reference Example 1, and the spinnability of the raw cotton treated in this way and the physical properties of a carpet made from this raw cotton were examined, and the results are shown in Table 1. The results shown were obtained. Example 1 Formula Functional group-containing organopolysiloxane 30
emulsion obtained by adding 2 parts of polyoxyethylene nonyl phenyl ether and 68 parts of water to
100 parts of Sample A obtained in Reference Example 1 was added to 10 parts to prepare a water and oil repellent composition (Sample E). Next, this was diluted 10 times with water, acrylic raw cotton was immersed in it, heat treated at 150℃ for 5 minutes, the spinnability of the raw cotton thus obtained was examined, and then this raw cotton was woven. When a carpet was made and the water and oil repellency and stain resistance of this carpet were examined, the results shown in Table 1 below were obtained. Example 2 Formula Add 5 parts of polyoxyethylene tridecyl alcohol ether and 65 parts of water to 30 parts of the epoxy group-containing organopolysiloxane shown by to make an emulsion, and add 100 parts of sample B obtained in Reference Example 2 and water to 10 parts of this emulsion. An emulsion type water and oil repellent composition (Sample F) having a solid content of 30% was prepared. Next, this composition was diluted 10 times with water, sprayed on acrylic raw cotton, and heat-treated at 150°C for 5 minutes.The spinnability of the raw cotton thus treated was examined, and carpets made from this raw cotton were investigated. When the physical properties of the material were investigated, the results shown in Table 1 below were obtained. Example 3 γ-Aminopropylmethyldimethoxysilane 3
parts, 27 parts of octamethylcyclotetrasiloxane,
Emulsifier Cortamine 24P (product name manufactured by Kao Atlas Co., Ltd.)
Add 2 parts and 3 parts of KOH to 65 parts of water, emulsify, and heat at 70℃.
After reacting for 10 hours, a 1% aqueous HCl solution was added to neutralize. Next, 100 parts of Sample C obtained in Reference Example 3 was added to 10 parts of this emulsion, and water was further added to form a water and oil repellent composition with a solid content of 30% (Sample G).
It was created. Next, using this sample G, acrylic raw cotton was treated in the same manner as in Example 1, and the spinnability of the raw cotton treated in this way and the physical properties of a carpet made from this raw cotton were examined, and the results are shown in Table 1. The results shown were obtained. Example 4 Formula Add 100 parts of Sample A obtained in Reference Example 1 to 10 parts of an emulsion obtained by adding 2 parts of polyoxyethylene nonyl phenyl ether and 68 parts of water to 30 parts of the carboxyl group-containing organopolysiloxane represented by and emulsifying the mixture. A water and oil repellent composition (Sample H) was obtained. Next, using this sample H, acrylic raw cotton was treated in the same manner as in Example 1, and the spinnability of the treated raw cotton and the physical properties of a carpet made from this raw cotton were investigated, and the results are shown in Table 1. Similar results were obtained. Example 5 Formula To 10 parts of an emulsion obtained by adding 2 parts of polyoxyethylene nonyl phenyl ether and 68 parts of water to 30 parts of an organopolysiloxane having two functional groups, an amide group and a polyoxyethylene group, and emulsifying the mixture, , 100 parts of Sample A obtained in Reference Example 1 was added to prepare a water and oil repellent composition (Sample I). Next, using this sample I, acrylic raw cotton was treated in the same manner as in Example 1, and the spinnability of the treated raw cotton and the physical properties of a carpet made from this raw cotton were examined, and the results were as shown in Table 1. The results were obtained.

【table】

Claims (1)

[Claims] 1. Perfluoroalkyl urethane compound 70-
99.9 parts by weight and 0.1 to 30 parts by weight of an organopolysiloxane containing a functional group selected from the group consisting of an epoxy group, a hydroxyl group, an amino group, a carboxyl group, an amide group, and a polyether group. Water and oil repellent composition. 2 Organopolysiloxane containing functional groups has the general formula [Here, A is the formula - R ³ X (R ³ is 2 with a carbon number of 1 to 10
^R2 is an unsubstituted group having 1 to 10 carbon atoms; or substituted monovalent hydrocarbon group, 0.01≦a<3, 0≦b<
2, 1≦a+b≦3].