NZ506208A

NZ506208A - Wool treatment agent comprising organopolysiloxane and nonionic emulsifying agents with a specific HLB

Info

Publication number: NZ506208A
Application number: NZ506208A
Authority: NZ
Inventors: Hiroki Ishikawa; Tsutomu Naganawa; Isao Ona
Original assignee: Dow Corning Toray Silicone
Priority date: 1999-08-09
Filing date: 2000-08-08
Publication date: 2002-02-01
Also published as: EP1076129A3; KR20010050015A; AU5188300A; EP1076129A2

Abstract

The agent is an aqueous emulsion composition consisting of; a) an amino group containing organopolysiloxane, b) a nonionic emulsifying agent with an HLB of less than 15, c) a nonionic emulsifying agent with an HLB of 15 or greater, and d) water. This aqueous emulsion composition is stable against ionic substances and is useful as an anti-shrinking agent. Examples of the organopolysiloxane are given in the formula above, wherein; R indicates a substituted or unsubstituted monovalent C1-20 hydrocarbon group, and R1 is H or a monovalent hydrocarbon group.

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number 506208 PATENTS FORM NO. 5 Patents Act 1953 No 11-224835 Date: 9th August, 1999 COMPLETE SPECIFICATION WOOL TREATMENT AGENT We, DOW CORNING TORAY SILICONE CO. LTD., a Japanese company of 2-2, Chigusa Kaigan, Ichihara-shi, Chiba Prefecture, Japan, hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: I " 8 AU6 2(&Q RcPrr ■ TSL1542 WOOL TREATMENT AGENT DETAILED DESCRIPTION OF THE INVENTION The present invention concerns a wool treatment agent, and more specifically concerns a wool treatment agent that shows superior stability against ionic substances. It is known that wool fabrics suffer from the drawback of extensive shrinkage and conversion to felt when laundered in the household. Conventional methods for preventing such shrinkage (anti-shrinkage treatment methods) have included methods in which wool fibers are chemically treated or treated with organic resins. Furthermore, methods involving treatment with organosilanes or amino-group containing organopolysiloxanes are known as methods for endowing such fabrics with a good hand (JP-A 4-119173). Among these methods, the most widely utilized is the Chlorine Hercosett Process, generally represented by US Patent 5928380. See also Senshoku Kogyo, Vol. 36, pp. 260-269). In this treatment method, wool is subjected to a chlorination treatment, and is then treated with a finishing agent. Ordinarily, the chlorine is neutralized using sodium sulfite, etc., following the chlorination treatment. Next, the treatment with a finishing agent is performed after the unnecessary ionic substances generated and the excess sodium sulfite have been removed in a rinsing tank. However, trace amounts of ionic substances still remain even after being passed through a rinsing tank. As result, if an emulsion of an organopolysiloxane which has ionizable functional groups, such as amino groups is used, the result is often separation and destruction of the emulsion. As a result of diligent research conducted to solve the abovementioned, we have found that an aqueous emulsion composition that is stable against ionic substances is obtained by using a nonionic emulsifying agent that has an Hydrophobic Lipophilic Balance of less than 15 and a nonionic emulsifying agent that has an HLB of 15 or greater. This discovery led to the perfection of the present invention. Specifically, the object of the present invention is to provide a wool treatment agent which shows a superior stability against ionic substances, and which is useful as an anti-shrinkage finishing agent. TSL1542 The present invention is a wool treatment agent which is characterized by the fact that said agent is an aqueous emulsion composition consisting of (A) an amino-group containing organopolysiloxane, (B) a nonionic emulsifying agent with an HLB of less than 15, (C) a nonionic emulsifying agent with an HLB of 15 or greater, and (D) water. The amino-group containing organopolysiloxane of component (A) may be any organopolysiloxane that has at least one amino group per molecule. There are no particular restrictions on the type, of organopolysiloxane used; however, organopolysiloxanes in which amino groups are bonded to silicon atoms via carbon atoms are highly desirable. Such amino-group containing organopolysiloxanes may be linear, branched or cyclic. Examples of such organopolysiloxanes include organopolysiloxanes having the following average molecular formulae: Chemical Formula 1 R R R X — (SiO)m(SiO)nSi — X R R Q — (NHCH2CH2)aNHR1 or R R X — (SiO)m(SiO)n — Y R Q —(NHCH2CH2)a NHR1 In said formulae, R indicates a substituted or unsubstituted monovalent hydrocarbon group which has 1 to 20 carbon atoms. Concrete examples include aliphatic saturated hydrocarbon groups, such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, decyl groups and dodecyl groups, aliphatic unsaturated hydrocarbon groups such as vinyl groups, allyl groups and hexenyl groups, alicyclic unsaturated hydrocarbon TSL1542 groups such as cyclopentyl groups or cyclohexyl groups, aromatic hydrocarbon groups such as phenyl groups, tolyl groups and naphthyl groups, and substituted hydrocarbon groups in which the hydrogen atoms bonded to carbon atoms of the abovementioned groups are partially replaced by halogen atoms. These groups need not be the same in each molecule; combinations of two or more different types of groups may be used. Among these groups, methyl groups, or combinations of methyl groups with other organic groups, are especially desirable. R1 indicates a hydrogen atom or a monovalent hydrocarbon group examples of such hydrocarbon groups include methyl groups, ethyl groups, propyl groups, phenyl groups and cyclohexyl groups. X indicates a group selected from a set consisting of the aforementioned groups expressed by R, hydroxy groups and alkoxy groups with 1 to 5 carbon atoms. Examples of such alkoxy groups include methoxy groups, ethoxy groups and propoxy groups. Among these groups, hydroxy groups or alkoxy groups are especially desirable. Y indicates a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. Q indicates a divalent hydrocarbon group. Concrete examples of such hydrocarbon groups include alkylene groups, such as methylene groups, ethylene groups, propylene groups and butylene groups; arylene groups expressed by the formula -C6H4-; and alkylene-arylene groups expressed by the formula -{CH^Q^-. Among these groups, propylene groups are especially desirable, m and n are integers of 1 or greater. It is desirable that the dynamic viscosity of the organopolysiloxane used be 10 mm2/s or greater at 25°C. A viscosity in the range of 50 to 10,000 mm2/s is even more desirable, a indicates an integer from 0 to 5, and is preferably 0 or 1. The amino-group containing organopolysiloxane of this invention can be manufactured by subjecting a hydro lytic condensation product obtained by hydrolyzing, an organoalkoxysilane expressed by the formula H2N(CH2)3Si(CH3)(OCH3)2, and [b] a dimethylpolysiloxane, to an equilibrium reaction while heating to a temperature of 80 to 110°C using a basic catalyst, such as sodium hydroxide. Then, the basic catalyst is neutralized by means of an acid when the reaction product has reached the desired viscosity (see JP-A 53-98499). Diorganopolysiloxanes expressed by the following average molecular formulae are examples of amino-group containing organopolysiloxanes that are used as Component A. TSL1542 Chemical Formula 2 ch3 ch3 ch3 ch3 II II CH3-SiO(SiO)40o(SiO)fl—Si-CHa II II CH3 CH3 I CH3 / V c3h6nh ch3 ch3 ch3 ch3 H3CO-SiO(SiO)380(SiO)8-Si-OCH3 II II ch3 ch3 i ch3 c3h6nh2 ch3 ch3 ch3 ch3 II II HO-SiO(SiO)200(SiO)10-Si-OH ch3 ch3 ch3 c3h6nhc2h4nh2 ch3 ch3 I I hsc20—( sio)^gg( slo) 3c2h5 I I ch3 c3h6nh2 Components (B) and (C) of the present invention are nonionic emulsifying agents. These emulsifying agents are characterized by the fact that the nonionic emulsifying agent of component (B) has an HLB of less than 15, and the nonionic emulsifying agent of component (C) has an HLB of 15 or greater. In particular, it is desirable that component (B) have an HLB in the range of 9 to 13, and an HLB in the range of 10 to 12 is even more desirable. Examples of useful nonionic emulsifying agents that can be used include polyoxyethylene alkyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene alkyl esters, sorbitan alkyl esters and polyoxyalkylene sorbitan alkyl esters. One or more compounds with an HLB of less than 15 are selected from these compounds for use as component (B), and one or more compounds with an HLB of 15 or greater are also selected from these compounds for use as component (C). In regard to the amount used, it is desirable that the total amount of components (B) and (C) be in the range of 2 to 100 parts by weight per 100 parts by weight of component (A); and an amount TSLI542 in the range of 2 to 60 parts by weight per 100 parts by weight of component (A) is even more desirable. In regard to the ratio of component (B) to component (C), these components are ordinarily used in the range of (1 : 99) to (99 : 1) (weight ratio), and a weight ratio in the range of (50 : 50) to (99 : 1) is even more desirable. Furthermore, the abovementioned "HLB" is an indicator of the balance of hydrophilic groups and lipophilic groups in the emulsifying agent molecule. The following calculation formulae have been proposed for nonionic emulsifying agents: for example, in cases where the emulsifying agent used is a fatty acid ester of a polyhydric alcohol, HLB is conveniently calculated using the formula HLB = 20 x (1 - S/A) (in this formula, S is the degree of saponification of the ester, and A is the acid value of the fatty acid). Furthermore, in cases where only polyoxyethylene groups are included as hydrophilic groups, HLB is calculated using the formula HLB = E/5 (in this formula, E is the weight percentage of oxyethylene groups). The nonionic emulsifying agents of components (B) and (C) can be used simultaneously in the emulsification of the amino-group containing organopolysiloxane of component (A). Alternatively, this emulsification can be performed using one of the emulsifying agents; and the other emulsifying agent can then be added to the aqueous emulsion thus obtained. The emulsifying agents used for the aqueous emulsion composition of the present invention may consist only of the above mentioned components (B) and (C). If necessary, however, cationic emulsifying agents or amphoteric emulsifying agents such as aliphatic amine salts, quaternary ammonium salts or alkylpyridinium salts, may also be used in combination with these claimed components. The water of component (D) is used to form the above mentioned components (A) through (C) into an emulsion. There are no particular restrictions on the amount of water used; ordinarily, however, the amount used is in the range of 100 to 1,000,000 parts by weight per 100 parts by weight of component (A). The aqueous emulsion composition of the present invention consists of the abovementioned components (A) through (D). If necessary, however, organopolysiloxanes other than component (A); alkoxysilanes such as methyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, y -aminopropyltrimethoxysilane, y-aminopropyltriethoxysilane, N-(P-aminoethyl)-y- TSL1542 aminopropyltrimethoxysilane or y-glycidoxypropyltrimethoxysilane, and the hydrolyzates of the preceding, colloidal silica; metal salts of organic acids, such as dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dilaurate, dioctyltin diacetate, tin octylate, zinc stearate, zinc octylate or iron octylate, condensation reaction catalysts, e. g., amine compounds such as n-hexylamine or guanidine, and other additives such as anti-wrinkling agents, thickeners, coloring agents, preservatives, anti-mold agents and anti-rust agents, may also be used in addition to the abovementioned components. Furthermore, the mean particle size of the aqueous emulsion of the present invention is ordinarily 0.1 (j.m or greater. This wool treatment agent of the present invention is stable against ionic substances; in particular, it is characterized by the fact that there is no separation or destruction of the emulsion caused by sodium sulfite or ionic substances generated by the neutralization process that is performed following the chlorination treatment. This wool treatment agent of the present invention imparts superior anti-shrinkage properties and a good hand to all types of wool, such as tops, bulk wool, knitwear and cloth. EXAMPLES Next, the present invention will be described in detail in terms of working examples. In these examples, all parts and percentages are parts by weight or weight percentages. Furthermore, all viscosity values are values measured at 25°C. Example 1 30 parts of an amino-group containing diorganopolysiloxane expressed by the average molecular formula TSL1542 Chemical Formula 3 ch3 ch3 ch3 ch3 III I HO — SiO (SiO)390 (SiO)3 — Si—OH III I ch3 ch3 i ch3 c3h6nhc2h4nh2 2 parts of a polyoxyethylene (ethylene oxide - 6 moles) lauryl ether (HLB = 11.8) and 1 part of a polyoxyethylene (ethylene oxide - 20 moles) lauryl ether (HLB = 16.6) were uniformly mixed. Afterward, 3 parts of water were added and the resulting mixture was agitated to a uniform consistency. Next, this mixture was emulsified using a colloid mill and an additional 64 parts of water were added. A uniform aqueous emulsion composition was thus produced. The mean particle size of this aqueous emulsion composition was 0.31 (J.m. Three pieces (45 x 45 cm) of an undyed 100% wool clothing-material serge were immersed for 30 seconds in a treatment bath using the above aqueous emulsion composition as a treatment liquid. Afterward, these samples were wrung out by means of mangle rollers with the wringing rate adjusted to 100%. The samples were then spread on a metal mesh and dried for one day and night at room temperature. Next, the samples were heat-treated for 5 minutes at 130°C in a hot air drier. After the samples were allowed to stand until they cooled to room temperature, 30 cm marks were applied at three places each in the warp and woof directions; and the samples were laundered under the laundering conditions described below. Following this laundering, the wool material samples were spread horizontally and dried. The laundering shrinkage rate (%) was measured for the warp and woof directions. TSL1542 Laundering Conditions After being laundered once under the following conditions, the material samples (from which the detergent had been removed) were rinsed twice with water under the same conditions. Bath ratio 1 : 50 Temperature 40°C Detergent ZABU™ (a weakly alkaline detergent manufactured by Kao K.K.) Time 15 minutes To investigate the stability of the above mentioned aqueous emulsion composition against ionic substances, 3 parts of the above mentioned emulsion was uniformly dispersed in 97 parts of water, after which 10 parts of a 10% aqueous solution of sodium sulfite were added and uniformly mixed. Afterward, the resulting mixture was allowed to stand at room temperature until the following day, and the external appearance of the emulsion was investigated by visual inspection. The results obtained are shown in Table 1. Example 2 30 parts of an amino-group containing diorganopolysiloxane expressed by the average molecular formula Chemical Formula 4 ch3 ch3 ch3 ch3 III I HO — SiO (SiO)390 (SiO)3 — Si — OH III I ch3 ch3 i ch3 c3h6nhc2h4nh2 and 3 parts of a polyoxyethylene (ethylene oxide - 6 moles) lauryl ether (HLB = 11.8) were uniformly mixed. Afterward, 3 parts of water were added, and this mixture was agitated to a uniform consistency. Next, this mixture was emulsified using a colloid mill, and 63 parts of water were added and uniformly mixed. Then, 1 part of a polyoxyethylene (ethylene oxide - 20 TSL1542 moles) lauryl ether (HLB = 16.6) was added, thus producing an aqueous emulsion composition. The mean particle size of this aqueous emulsion composition was 0.30 fim. Using the aqueous emulsion composition thus obtained, the laundering shrinkage rate and stability against ionic substances were measured in the same manner as Example 1. The results obtained are shown in Table 1. Comparative Example 1 30 parts of an amino-group containing diorganopolysiloxane expressed by the average molecular formula [Chemical Formula 5] ch3 ch3 ch3 ch3 III I HO — SiO (SiO)39o (SiO)3 — Si — OH III I ch3 ch3 i ch3 C3H6NHC2H4NH2 and 3 parts of a polyoxyethylene (ethylene oxide - 6 moles) lauryl ether (HLB = 11.8) were uniformly mixed. Afterward, 3 parts of water were added, and this mixture was agitated to a uniform consistency. Next, this mixture was emulsified using a colloid mill, and 64 parts of water were added and uniformly mixed, thus producing an aqueous emulsion composition. The mean particle size of this aqueous emulsion composition was 0.30 nm. Using the aqueous emulsion composition thus obtained, the laundering shrinkage rate and stability against ionic substances were measured in the same manner as Example 1. The results obtained are shown in Table 1. TSL1542 Comparative Example 2 30 parts of an amino-group containing diorganopolysiloxane expressed by the average molecular formula ch3 ch3 ch3 ch3 111 I HO — SiO (SiO)390 (SiO)3 — Si — OH III I ch3 ch3 i ch3 C3II()MIC2H4Mb and 3 parts of a polyoxyethylene (ethylene oxide - 20 moles) lauiyl ether (HLB = 16.6) were uniformly mixed. Afterward, 3 parts of water were added, and this mixture was agitated to a uniform consistency. Next, this mixture was emulsified using a colloid mill and 64 parts of water were added and uniformly mixed, thus producing an aqueous emulsion composition. However, this aqueous emulsion composition separated after only a few hours. Comparative Example 3 30 parts of an amino-group containing diorganopolysiloxane expressed by the average molecular formula Chemical Formula 7 ~ ch3 ch3 ch3 ch3 III I HO — SiO (SiO)39o (SiO)3 — Si — OH III I ch3 ch3 i ch3 c3h6nhc2h4nh2 TSLI542 2 parts of a polyoxyethylene (ethylene oxide - 6 moles) lauryl ether (HLB = 11.8) and 1 part of a polyoxyethylene (ethylene oxide - 10 moles) lauryl ether (HLB = 14.1) were uniformly mixed. Afterward, 3 parts of water were added, and this mixture was agitated to a uniform consistency. Next, this mixture was emulsified using a colloid mill, and 64 parts of water were added and uniformly mixed, thus producing an aqueous emulsion composition. The mean particle size of this aqueous emulsion composition was 0.32 jim. Using the aqueous emulsion composition thus obtained, the laundering shrinkage rate and stability against ionic substances were measured in the same manner as Example 1. The results obtained are shown in Table 1. Comparative Example 4 The laundering shrinkage rate of a 45 x 45 cm sample of an undyed 100% wool clothing-material serge that had not been treated by means of the above-mentioned aqueous emulsion composition was measured in the same manner as Example 1. The results obtained are shown in Table 1. Table 1 HLB of Emulsifying Agent Laundering Shrinkage Rate (%) Stability Against Ionic Substances Comprehensive Evaluation Warp Direction Woof Direction Total Example 1 11 8 16 6 48 27 7.5 Stable Extremely Good Example 2 11 8 166 46 2 5 7 1 Stable Extremely Good Comparative Example 1 11 8 — 49 24 73 Emulsion Separated Stability Insufficient Comparative Example 2 166 -- — — — Storage Stability Unsatisfactory Comparative Example 3 11 8 14 1 47 26 73 Emulsion Separated Stability Insufficient Comparative Example 4 — — 103 7.4 177 — — TSL1542 Example 3 30 parts of an amino-group-containing diorganopolysiloxane expressed by the average molecular formula Chemical Formula 8 ch3 ch3 ch3 ch3 III I HO — SiO (SiO)390 (SiO)3 — Si — OH III I ch3 ch3 i ch3 C3H6nhc2h4nh2 3 parts of a polyoxyethylene (ethylene oxide - 6 moles) lauryl ether (HLB = 11.8) and 1 part of a cationic emulsifying agent expressed by the formula (CH3)3(C12H25)N+Cr were uniformly mixed. Afterward, 4 parts of water were added, and this mixture was agitated to a uniform consistency. Next, this mixture was emulsified using a colloid mill. Then, 51 parts of water and 1 part of a polyoxyethylene (ethylene oxide - 20 moles) lauryl ether (HLB = 16.6) were added and uniformly dissolved and dispersed. Afterward, 0.5 part of methyltrimethoxysilane and 9.5 parts of water were added, thus producing a uniform aqueous emulsion composition. The mean particle size of this aqueous emulsion composition was 0.29 jxm. Using the aqueous emulsion composition obtained as described above, the stability against ionic substances was measured in the same manner as Example 1. The results obtained are shown in Table 2. TSL1542 Comparative Example 5 30 parts of an amino-group-containing diorganopolysiloxane expressed by the average molecular formula Chemical Formula 9 ch3 ch3 ch3 ch3 III I HO — SiO (SiO)390 (SiO)3 — Si — OH III I ch3 ch3 i ch3 C3HjNHC2H4NH2 3 parts of a polyoxyethylene (ethylene oxide - 6 moles) lauryl ether (HLB = 11.8) and 1 part of a cationic emulsifying agent expressed by the formula (CH3)3(C12H25)N+Cr were uniformly mixed. Afterward, 4 parts of water were added, and this mixture was agitated to a uniform consistency. Next, this mixture was emulsified using a colloid mill. Then, 52 parts of water were added and uniformly dissolved and dispersed. Then, 0.5 part of methyltrimethoxysilane and 9.5 parts of water were added, thus producing a uniform aqueous emulsion composition. The mean particle size of this aqueous emulsion composition was 0.30 jam. Using the aqueous emulsion composition obtained above, the stability against ionic substances was measured in the same manner as Example 1. The results obtained are shown in Table 2. Table 2 HLB of Emulsifying Agents Stability Against Ionic Substances Example 3 11.8 16.6 Stable Comparative Example 5 11.8 - Emulsion separated TSL1542 Example 4 29.5 parts of an amino-group containing diorganopolysiloxane expressed by the average molecular formula Chemical Formula 10 ch3 ch3 I I h5c2° —(SiO)4oo (Si°)8c2H5 I I CH3 C3H5NH2 0.5 part of a partial hydrolysis product of methyltriethoxysilane (dynamic viscosity: 75 mm2/s) and 3.5 parts of a polyoxyethylene (6 mole) lauryl ether (HLB = 11.8) were uniformly mixed. Afterward, 3 parts of water were added and the resulting mixture was agitated. Next, this mixture was emulsified using a colloid mill, after which 65.5 parts of water and 1.0 parts of a polyoxyethylene (45 moles) nonyl ether (HLB = 18.1) were added. Thus a uniform aqueous emulsion composition was produced with a mean particle size of 0.33 p.m. Using the aqueous emulsion composition obtained as described above, the stability against ionic substances was measured in the same manner as Example 1. As a result, it was found that the stability was good, with no destruction of the emulsion being seen. Furthermore, when the laundering shrinkage rate was measured in the same manner as Example 1, the total of the laundering shrinkage rates in the warp and woof directions was only 7.5%. In contrast, the laundering shrinkage rate of an untreated sample of the same material was 18.9%. Thus, it was confirmed that laundering shrinkage rate can expeditiously be lowered by more than half by treating the material with the aqueous emulsion composition of the present invention. It is apparent from this that the aqueous emulsion composition of the present invention has an extremely favorable effect as an anti-shrinkage finishing agent. The wool treatment agent of the present invention is an aqueous emulsion composition comprising the above-mentioned components (A) through (D). Therein, the above-mentioned nonionic emulsifying agent of component (B) has an HLB of less than 15, and the above- </div>

Claims

<div class="application article clearfix printTableText" id="claims"> TSL1542 mentioned nonionic emulsifying agent of component (C) has an HLB of 15 or greater. As a result, the wool treatment agent of the present invention shows superior stability against ionic substances, and is useful as an anti-shrinkage finishing agent. TSL1542 What we claim is:-

1. A wool treatment agent characterized by the fact that said agent is an aqueous emulsion composition consisting of (A) an amino-group containing organopolysiloxane, (B) a nonionic emulsifying agent with an HLB of less than 15, (C) a nonionic emulsifying agent with an HLB of 15 or greater, and (D) water.

2. The wool treatment agent of Claim 1, in which component (A) is an amino-group containing diorganopolysiloxane in which both ends of the molecular chain are selected from hydroxy groups, alkoxy groups, monovalent hydrocarbon groups of 1 to 20 carbon atoms, and combinations thereof. DOW CORNING TORAY SILICONE CO. LTD. by its Patent Attorneys, WATERMARK PATENT & TRADEMARK ATTORNEYS MEUfCTUAL PHOPBTiY OFFICE I- OF NZ TSL1542 ABSTRACT A wool treatment agent is disclosed herein which is characterized by the fact that said agent is an aqueous emulsion composition consisting of (A) an amino-group containing organopolysiloxane, (B) a nonionic emulsifying agent with an HLB of less than 15, (C) a nonionic emulsifying agent with an HLB of 15 or greater, and (D) water. The present invention introduces a wool treatment agent that shows superior stability against ionic substances, and is useful as an anti-shrinkage finishing agent. </div>