JPH0114344B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a softener composition that can impart flexibility and antistatic properties to a wide variety of clothing, hair, etc., and particularly to a softener composition that has improved water absorption. [Prior Art] Various fabric softeners are used to impart flexibility and antistatic properties to clothing after washing. These softeners generally contain dilong-chain alkyl di-short-chain alkyl quaternary ammonium salts or imidazolinium salts as main components. Among these, di-long-chain alkyl di-short-chain alkyl ammonium salts are particularly often used because they have excellent softening ability.
Since this material has high lipophilicity, it has the disadvantage that it adsorbs onto the surface of fibers, imparting flexibility and water repellency at the same time. Therefore, when textiles or clothing are treated with a fabric softener containing this surfactant, the water absorption rate of the fibers decreases, resulting in a decrease in the amount of water absorbed per unit time, which is undesirable as it causes problems such as a decrease in apparent water absorption. . In order to overcome these drawbacks of textile softeners, we developed a new cationic activator with a high affinity for water that does not reduce the apparent water absorption of textiles when used in textile softening treatment (especially 1977-
No. 66546, JP-A-56-92251, JP-A-59-30965
No.) is being carried out. Also, attempts have been made to use di-long-chain alkyl di-short-chain alkyl quaternary ammonium salts in combination with other surfactants having high water affinity. For example, the combined use of fatty acid ethanolamide polyglycol ether (JP-A-56-20677) and glycerin ether (JP-A-56-20678). However, new cationic activators still require careful consideration, including whether they can impart flexibility and antistatic properties to chemical fibers, how much apparent water absorption can be maintained, and their effects on the human body. Few have been put into practical use. These include, for example, the US
Distributed by Sherex Chemicals
There are Varisoft3690 and Rewoquat W3690 sold by Rewochemische Werke, West Germany.
All of these are methyl-1-oleylamidoethyl-2-oleylimidazolinium methyl sulfate (iodine value 80-90), but this product alone has the disadvantage of insufficient antistatic properties for chemical fibers. Therefore, it is necessary to provide it in combination with other cationic or nonionic softeners. On the other hand, attempts to use di-long-chain alkyl di-short-chain alkyl quaternary ammonium salts in combination with other surfactants with high water affinity have shown that while providing the same flexibility as the quaternary ammonium salt alone, Moreover, it is difficult to sufficiently prevent a decrease in apparent water absorbency, which is not satisfactory. In view of these points, the inventors of the present application have conducted extensive research with the aim of providing a practical fabric softener composition that can impart excellent flexibility and antistatic properties, as well as exhibit less deterioration in water absorption. We have proposed a softener composition using a combination of a di-long-chain di-short-chain type quaternary ammonium salt having an unsaturated bond and a polyoxyethylene-added nonionic surfactant.
No. 59-278685). However, as a result of subsequent studies, although this softener composition had excellent effects in terms of imparting flexibility, imparting antistatic properties, and suppressing a decrease in water absorption, it was found that it was difficult to store it as an aqueous dispersion at high temperatures for a long period of time. They discovered that the viscosity increases significantly when the liquid is used, and liquid separation occurs at low temperatures, resulting in insufficient dispersion stability. [Problems to be solved by the invention] Therefore, the present invention can impart excellent flexibility and antistatic properties to clothing, hair, etc. without impairing the water absorbency of fibers, and has even better dispersion stability. An object of the present invention is to provide an aqueous liquid fabric softener composition. [Means for solving the problem] The present invention provides an aqueous liquid softener containing a quaternary ammonium salt having a specific amount of unsaturated bonds in the molecule, a polyoxyethylene-added nonionic surfactant, and an aqueous vehicle. This was done based on the knowledge that the above problems can be solved by incorporating an inorganic electrolyte and a compound having specific organic and inorganic values in the organic conceptual diagram into the agent composition. That is, the present invention provides (A) a quaternary ammonium salt having an iodine value in the range of 35 to 100, (B) a polyoxyethylene-added nonionic surfactant, and (C) an organic value in the organic conceptual diagram. is in the range of 140 to 280,
and a compound with an inorganic value in the range of 60 to 120, (D)
Provided is a softener composition comprising an inorganic electrolyte and (E) an aqueous vehicle. Examples of the quaternary ammonium salt of component (A) used in the present invention include mono-long chain, di-long chain, and tri-long chain alkyl, alkenyl, quaternary ammonium salts, imidazolinium salts, and amide quaternary salts. Ru. Among these, it is particularly preferable to use one or a mixture of two or more quaternary ammonium salts represented by the following general formula []. (In the formula, R ₁ and R ₂ are alkyl groups or alkenyl groups having 14 to 24 carbon atoms, R ₃ and R ₄ are methyl groups, ethyl groups, polyoxyethylene groups, or polyoxypropylene groups, and X ^- is an anion. ) The quaternary ammonium salt represented by the general formula () usually contains unsaturated higher fatty acids such as oleic acid, linoleic acid, and linolenic acid, or palm oil fatty acids,
It is produced using natural fatty acids such as soybean oil fatty acids, safflower oil fatty acids, tall oil fatty acids, mixtures thereof, or mixtures of these and beef tallow fatty acids as starting materials. Among these, especially oleic acid,
Mixtures of oleic acid and tallow fatty acids, palm oil fatty acids are preferred. R ₁ and R ₂ in the general formula () have 14 to 24 carbon atoms, preferably 16 to 22 carbon atoms, and may have a distribution within that range. Furthermore, R ₁ and R ₂ may be the same or different. When the number of carbon atoms is less than 14, for example, a quaternary ammonium salt synthesized from coconut oil fatty acid has poor flexibility and is not preferred. On the other hand, R ₃ and R ₄ are selected from the group consisting of a methyl group, an ethyl group, a polyoxyethylene group or a polyoxypropylene group having an average degree of polymerization of 1 to 5, and among them, a methyl group is preferred. Furthermore, R ₃ and R ₄ may be the same or different. X is usually a halogen atom or a group represented by R ₅ SO ₄ . Examples of the halogen atom include chlorine, bromine and iodine, with chlorine being preferred. Also, R ₅ has 1 or more carbon atoms.
3, which is a methyl group, ethyl group, or propyl group. In the present invention, it is particularly necessary that the quaternary ammonium salt has an iodine value in the range of 35 to 100, preferably 40 to 90, such as ordinary beef tallow fatty acid, semi-hardened or hardened beef tallow fatty acid, hardened palm oil fatty acid. If the iodine value is less than 35, as in the case of raw materials such as stearic acid, palmitic acid, and pehenic acid, the water absorbency of softened textile products, especially cotton fibers, will deteriorate significantly, while if it exceeds 100, the This is because flexibility and antistatic properties for synthetic fibers deteriorate. However, in the present invention, each quaternary ammonium salt itself has a
It is not necessary that the quaternary ammonium salt has an iodine value of 35 to 100 as a whole by mixing quaternary ammonium salts with a low iodine value and those with a high iodine value. It is sufficient that it is within the range of . In addition, here the iodine value is
It is easily measured by the method described in JIS K-0070. Component (A) is a component that has the effect of imparting flexibility and antistatic properties to clothing, and the amount incorporated in the softener composition is 1 to 30% by weight (hereinafter abbreviated as %), preferably 3 to 20% by weight. %. If the amount is less than 1%, a large amount of softener must be used to impart flexibility, and if it is more than 30%, the fluidity of the softener composition decreases and it becomes difficult to pour out from the container. etc., which is inconvenient in practice. Component (B) used in the present invention includes polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl (or alkenyl) ether, polyoxyethylene fatty acid amide, polyoxyethylene alkyl or alkenyl amine, and polyoxyethylene sorbitan fatty acid ester. Examples include POE (=10-70) alkyl (C8-12) phenyl ether and/or POE (
=10-70) alkyl (C10-22) ether is preferred. In the above compounds, POE indicates polyoxyethylene, C indicates the average number of added moles of ethylene oxide, and C indicates the number of carbon atoms (the same applies below). The amount of component (B) in the softener composition is 0.02 to 20
%, preferably 0.1-10%. The blending ratio of component (A) and component (B) can be arbitrary, but (A)/(B) is 100/1 to 2/1 (weight ratio), preferably 20/1 to 4/1. It is desirable to do so. Component (C) used in the present invention is a substance having an organic value in the range of 140 to 280 and an inorganic value in the range of 60 to 120 in the organic conceptual diagram. For organic conceptual diagrams, see Chemistry Area vol.11, No.10
(October 1957 issue), p. 719 et seq., and Systematic Organic Qualitative Analysis (Purity Edition), Kazama Shobo (1970), etc., describe in detail that organic compounds are composed of a chain of covalent bonds between carbon chains. Hydrocarbon “organic”
Focusing on the fact that it is made up of two factors, ``inorganic'' and ``inorganic'' due to the influence of electrostatic properties present in substituents (functional groups), we identify individual organic compounds by these ``organic'' and ``inorganic''. It is something to do. The organic value is calculated as 20 per carbon in the structural formula of the compound, and the inorganic value is calculated using the values established for each functional group described in the above publication. The organic value used in the present invention is 140 to 280
Specifically, a compound with an inorganic value in the range of 60 to 120 is 3,7-dimethyl-1,6-octadien-3-ol (organic value 200, inorganic value 104). ), 3,7-dimethyl-2,
6-octadiene-1-ol (organic value 200,
(inorganic value 104), phenyl methyl alcohol (organic value 140, inorganic value 115), phenylethyl alcohol (organic value 160, inorganic value 115), 2-amyl-3-phenylpropyl alcohol (organic value 160, inorganic value 115) sexual value
280, inorganic value 117), 3,7-dimethyl-2,6
-Octadien-1-ylbutyrate (organic value
280, inorganic value 64), 5-(2,6,6-trimethyl-2-cyclohexen-1-yl)-4-penten-3-one (organic value 280, inorganic value 77), phenylmethyl Examples include acetate (organic value 180, inorganic value 75), 5-methyl-2-isopropyl-cyclohexanol (organic value 200, inorganic value 110). These may be used alone or in combination. The amount of component (C) in the softener composition is
It is 0.001-3%, preferably 0.005-1%. As component (D) used in the present invention, an inorganic electrolyte that can be dissociated in an aqueous vehicle is used. For example, sodium chloride, potassium chloride, magnesium chloride, aluminum chloride, sodium sulfate,
Examples of electrolytes include ammonium sulfate, sodium nitrate, magnesium nitrate, etc., but sodium chloride is particularly preferred. The amount of component (D) in the softener composition is 0.001 to 3%, preferably 0.01 to 1%. The blending ratio of component (C) and component (D) can be arbitrary. It is desirable that (C)/(D) be 100/1 to 1/100 (weight ratio), preferably 10/1 to 1/10. Component (E) used in the present invention is usually water, but preferably contains 1 to 20% of a hydrotrope such as ethylene glycol, propylene glycol, glycerin, hexylene glycol, ethanol, isopropyl alcohol, or urea. The blending amount of component (E) in the softener composition is the amount that is the balance to make 100% in addition to the blending amounts of the essential components and optional components of the present invention. In the present invention, by using an inorganic electrolyte together with a compound having a specific range of organic and inorganic properties, a quaternary ammonium salt having an unsaturated bond - polyoxyethylene-added nonionic surfactant - The stability of the aqueous vehicle-based aqueous dispersion is increased, and viscosity changes over time during high-temperature storage and liquid separation during low-temperature storage can be suppressed. Although the mechanism of this action is unknown, the addition of components (C) and (D) affects the interfacial potential of the dispersed particles and the viscosity of the dispersion medium, and acts to suppress particle coalescence. It is considered that The present invention requires the above five components, but in addition to these, optional components such as a PH adjuster, a bactericide, a pigment, a dye, a fragrance, an antioxidant, an ultraviolet absorber, a fluorescent brightener, etc. are also included as appropriate. can do. [Effects of the Invention] The softener composition of the present invention does not significantly reduce the water absorption of objects, so it can impart excellent feel to various textile products, and the water absorption of cotton fibers such as diapers can be substantially reduced. It is a highly value-added material that can be retained and impart excellent antistatic properties to chemical fibers. In addition, it does not thicken even when stored at high temperatures (45°C) for long periods of time, and does not cause liquid separation even when stored at low temperatures (5°C) for long periods, making it excellent for practical use. . Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto. [Example] The preparation method, viscosity change, and presence/absence of separation of the softener compositions in Examples were determined by the following methods. Γ Method for preparing aqueous dispersion Dissolve components other than component (A) in water and stir at 45°C.
A molten mixture of component (A) containing a small amount of lower alcohol and water was added dropwise thereto while stirring to uniformly disperse the mixture, and then cooled to 25°C. Γ Viscosity measurement method The viscosity was measured using a B-type viscometer (manufactured by Tokyo Keiki) after storage at 45° C. for one month. Method for determining Γ separation A sample was placed in a transparent cylinder bolt with an inner diameter of 45 mm to a depth of 7 cm from the bottom, and after being stored at 5°C for one month, the separation length was measured. Judgment ○: No separation △: Separation length less than 3 mm ×: Separation length 3 mm or more Γ Finishing method Commercially available cotton towels, bleached cloth, and acrylic cloth were washed at 50℃ using a commercially available laundry detergent in an electric washing machine. After repeated washing, the cloth was thoroughly rinsed with tap water at room temperature to prepare a test cloth. Next, the softener composition was added to 30 g of tap water at 25° C. so that the amount of component (A) added was 1 g to form a homogeneous solution. Dip each test cloth in this at 30 times the bath ratio.
After processing for a minute, it was dehydrated for 2 minutes. After air-drying the fabrics treated in this way, cotton towels and bleached fabrics for evaluating the softening effect and water absorption were tested at 25℃ and 65%RH.
Leave it for 24 hours, and leave the acrylic cloth for antistatic effect evaluation for 72 hours at 20℃ and 55%RH.
It was used for each evaluation test. Γ Evaluation method (a) Flexibility: The feel of the cotton towel before and after treatment was compared and evaluated according to the following criteria. +5...Very soft +4...Quite soft +3...Soft +2...Slightly soft +1...Slightly soft 0...Same as before treatment (B) Water absorption: According to JISL1003, a 2cm x 15cm bleached cloth was colored with ink. It was immersed in pure water (25°C) for 5 mm, and the height of the water rising in 5 minutes was measured.
According to this measurement, the commercial value of fabric softener is 70
(mm) or more is desirable. (c) Antistatic property: Using a static honest meter (manufactured by Shishido Shokai), apply a voltage to the acrylic cloth.
A 7KV target was charged at a distance of 20 mm, and the half-life (seconds) of the charged voltage was measured after the voltage was removed. Example 1 (A) Dioleyldimethylammonium chloride [iodine value 60] 5.0% (B) POE=40) Nonyl phenyl ether 0.5% (C) Components 0.005-0.1% (D) Sodium chloride 0.04% (E) Ethylene An aqueous softener composition consisting of 4% glycol and the balance water was prepared and evaluated for performance and storage stability. Table 1 shows the name of the compound used as component (C), its blending amount, and the stability evaluation results. In addition, flexibility is +3 to +4, water absorption is 85 to 90 mm,
The antistatic property showed a value of 45 to 55 seconds. From the results in Table 1, it can be seen that the product of the present invention shows little change in viscosity even when stored at high temperatures (45°C) for long periods of time, and has extremely excellent dispersion stability without liquid separation. . On the other hand, the compounds shown in the comparative examples showed large viscosity changes and a tendency for liquid separation, indicating that they lacked dispersion stability.

【table】

[Table] Example 2 Various softener compositions were prepared and their performance and storage stability were evaluated. The composition and stability evaluation results are summarized in Table 2. In all compositions, the flexibility was +3 or more, the water absorption was 80 mm or more, and the antistatic property was 100 seconds or less. From the results in Table 2, it can be seen that the product of the present invention has excellent dispersion stability.

【table】

【table】

Claims (1)

[Scope of Claims] 1 (A) A quaternary ammonium salt having an iodine value in the range of 35 to 100, (B) A polyoxyethylene-added nonionic surfactant, (C) In the organic conceptual diagram, an organic A softener composition comprising: a compound having an inorganic value in the range of 140 to 280 and an inorganic value in the range of 60 to 120; (D) an inorganic electrolyte; and (E) an aqueous vehicle. 2. The softener composition according to claim 1, wherein component (A) is dioleyldimethylammonium chloride. 3 Component (B) is polyoxyethylene (=10-70)
Claim 1, which is an alkyl ( _C8 - _C12 ) phenyl ether and/or a polyoxyethylene (=10-70) alkyl ( _C10 - _C22 ) ether
The softener composition described in . 4 Component (C) is 3,7-dimethyl-1,6-octadien-3-ol, 3,7-dimethyl-2,
6-octadien-1-ol, phenylmethyl alcohol, phenylethyl alcohol, 2-amyl-3-phenylpropyl alcohol, 3,7
-dimethyl-2,6-octadien-1-ylbutyrate, 5-(2,6,6-trimethyl-2-
cyclohexen-1-yl)-4-pentene-3
2. The softener composition according to claim 1, wherein the softener composition is at least one selected from the group consisting of -one, phenylmethyl acetate, and 5-methyl-2-isopropyl-cyclohexanol.