JPS63254199A - Softener composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a softener composition that can impart a wide range of flexibility to various types of clothing, hair, etc., particularly powder, granule or tablet forms with improved solubility and antistatic properties. type of softener composition.

[Conventional technology]

Traditionally, liquid type fabric softeners containing about 4% cationic fabric softener have been the mainstream, but recently there has been an active effort to develop high-concentration fabric softeners that contain a higher amount of fabric softener. . Specifically, the content of the cationic softener is 7 to 1.
Concentrated liquid softeners with concentrations increased to 5% by weight have been provided, but several methods have also been reported in which the softener is used in powder form as a means of concentration. As these powder type softeners, for example, Japanese Patent Application Laid-Open No. 59-8800 describes
A method is disclosed in which a cationic softener powder having an average primary particle size of 150 μm or less and fine silica powder are mixed and granulated using a nonionic surfactant as a binder.

It is true that cationic softener powder needs to be finely dispersed because the finer the particle size, the more efficient it is at adsorbing it to clothing, etc., which is generally processed. It has the disadvantage that it cannot be finely dispersed into primary particles in water. Furthermore, since the cationic softener is made to have a thickness of 150 μm or less in advance, the production cost becomes high and it is not economical.

Further, JP-A-59-106575 discloses a method of incorporating a softening agent into synthetic silicic acid, but in the softened particles produced by this method, the synthetic silicic acid is water-insoluble. Therefore, when used during rinsing, the washing solution becomes cloudy, which is undesirable.Furthermore, when the cation is a dialkyl quaternary ammonium salt that is substantially insoluble in water, the cation trapped in the voids of the silicic acid particles is Since it is not released, its performance as a softener cannot be achieved sufficiently.

On the other hand, various proposals have been made to improve the performance, particularly the antistatic effect, of softeners containing cationic softeners. For example, JP-A-61-102480 discloses that by combining a cationic activator with a specific phenol compound, not only the antistatic effect but also the water absorption can be improved. However, the phenolic compound used here has a biodegradability problem.

[Problem that the invention seeks to solve]

Therefore, the present invention provides a powder, granule, or tablet type fabric softener composition that easily dissolves when added to water and can impart excellent antistatic properties to clothing. The purpose is to

[Means for solving problems]

In the present invention, when a cationic softener is used in the form of adsorbed to a water-soluble powder with a large oil absorption capacity, when the powder softener is added to water, regardless of the powder composition and particle size of the agent before addition, Based on the knowledge that a considerable amount of the cations added are dispersed into particles of 105 μm or less and do not cause turbidity in the liquid, and that when used in combination with a polycarboxylic acid or its salt, the antistatic effect is significantly improved. It was done.

That is, the present invention provides a cationic softener (A), a polyhydric carboxylic acid or its salt (B), and an oil absorption amount of 35 mg/1.
00g or more of a water-soluble powder (C).

As the component (A) of the present invention, all those that can impart flexibility to fibers, hair, etc., such as various amine salts and quaternary ammonium salts, can be used. Usually, a poorly water-soluble or water-insoluble quaternary ammonium salt type cationic surfactant, such as a quaternary ammonium salt having at least two alkyl or alkenyl groups having 8 to 26 carbon atoms in the molecule, is used. . Among these, quaternary ammonium salts having two alkyl groups or alkenyl groups having 10 to 24 carbon atoms in the molecule are preferred, such as ammonium salts and amido ammonium salts represented by the following general formula (1), and general formula (
Examples include imidazolinium salts represented by n) and (III).

(In the formulas ■, ■, and ■, R1 and R2 each have 10 to 10 carbon atoms.
24 alkyl group, hydroxyalkyl group or alkenyl group, R3 and R4 are each an alkyl group having 1 to 3 carbon atoms, hydroxyalkyl or benzyl group, -(C2
H, O) Hi3= 1-5), Y+
, Y2 is an ethylene group or a propylene group, L
, L represents a number of 0 or 1, and X represents a halogen or a monoalkyl sulfate group having 1 to 3 carbon atoms. ) Specifically, dilauryldimethylammonium chloride, civalmitylmethylhydroxyethylammonium methylsulfate, dihydrogenated beef tallow alkyldimethylammonium chloride, distearylmethylpolyoxyethylene (average degree of polymerization 5 mol) ammonium chloride, dihydrogenated beef tallow Alkylethylbenzylammonium chloride, ditetradecyldimethylammonium chloride, di[(2-dodecanoylamide)ethyldimethylammonium chloride, di[(2-octadecanoylamide)ethylfudimethylammonium methosulfate, ethyl-1,41 Tadekalylamidoethyl-2-heptadecylimidazolinium ethosulfate, Methyl-1-tallowamidoethyl-2-tallowalkylimidazolinium methosulfate, Methyl-1-oleylamidoethyl-2-oleylimidazolinium methosulfate, It is one type or a mixture of two or more types, such as methyl-1-(2-isostearoylaminoethyl)-2-isopeptadecylimidazolinium methosulfate.

The blending amount in the softener composition is 1 to 50% by weight (hereinafter referred to as % by weight).
is called %. ), preferably 5 to 30%.

As the polyvalent carboxylic acid or its salt as component (B) used in the present invention, any polyvalent carboxylic acid having 5 or less carbon atoms per carboxyl group can be used. Examples of such polycarboxylic acids include oxalic acid,
Acids such as malonic acid, succinic acid, methylmalonic acid, malic acid, citric acid, tricarballylic acid, maleic acid, fumaric acid, tartaric acid, itaconic acid, curtaric acid, adipic acid, and ethylenediaminetetraacetic acid, or salts thereof. In the present invention,
There is no problem even if the polyhydric carboxylic acid forms a salt in any form. However, in general, alkali metal salts, alkaline earth metal salts, and ammonium salts are preferred in terms of availability, but the present invention is not limited by the counter ion of the polyhydric carboxylic acid. In addition, polyhydric carboxylic acids may form partially neutralized salts depending on their valence (e.g., sodium dihydrogen citrate, disodium hydrogen citrate, etc.); Type salt can also be used. Furthermore, polyhydric carboxylic acids may form hydrates such as citric acid hydrate, and such hydrates can also be used in the present invention. In addition, the content of component (B) in the softener composition is 0.1 to 20
% is preferably 0.5 to 10%, but as described later, when component (C) is used in the form of an acid and also serves as a neutralizing agent, the component (C) may be added up to about an equivalent amount of component (C). (B) can be contained.

The water-soluble powder of component (C) used in the present invention has an oil absorption of 35 iff/100 g, preferably 40 iff/100.
Any substance may be used as long as it has a weight of at least 100 g and is soluble in water. Note that the oil absorption amount is based on Japanese Industrial Standard (JIS) K6221-6, 1.2 B, method (19
82) using n-butyl phthalate. One specific example of the powder component (C) is sodium carbonate, which has a large oil absorption capacity. Normally, sodium carbonate is produced by the 5olvay method, which is bicarbonate.) Fine powder light ash made by reacting IJum in a power calcining furnace (oil absorption 72w)
d! Two types are commercially available: powdered ash (oil absorption: 25me/100g) and powdered ash (oil absorption: 25me/100g), which is made by adding water to light ash and re-drying it, but powdered ash has a low oil absorption and is not preferred.

Urea is also usually sold in beaded and granular forms, but the oil absorption of granular urea is only 25 me/100
In contrast, for example, when beaded urea is ground in a mortar or the like, the oil absorption increases to 45ml/100g. In addition, Nippon Kagaku powder 1 spray-dried with sodium silicate
The oil absorption amount of No. silica soda is also large at 42-/100g. In addition, a concentrated aqueous solution (in some cases slurry form) of water-soluble powder
Spray drying is an effective method for increasing the oil absorption of powder, and depending on the drying conditions, powders with various oil absorption can be obtained. Other powders with high oil absorption include sodium bicarbonate (oil absorption 39mg/100g), calcium chloride (oil absorption 47+ng/100g), etc.These powders may be used alone or , two or more types may be combined as necessary.Also, these powders may be granulated by a known method before adsorbing component (A).In addition, as component (C) is about 50 to about 2.0
It is preferable to use particles having an average particle size of about 00 μm.

The content of component (C) in the softener composition is preferably 20 to 98%, preferably 30 to 90%.

The present invention uses the above components (A), (B), and (C) as essential components, and the component (Δ) is adsorbed onto the component (C) or the component (A
) is preferably used in the form of adsorption on components (B) and (C). Adsorption here means coating component (C) or components (B) and (C) with component (A), or coating component (Δ) with component (C) or components (B) and (C). Component (C) or component (B) and (C
) is used as a carrier, and component (A) is retained on this carrier. That is, component (A) may be adsorbed to a mixture of component (B) and component (C), or components (B) and (C) may each have adsorbed component (A). After adsorbing component (Δ) to component (C), component (
B) may be blended. In this way, the component (B
), component (B) may be added at the time of re-granulation as described below. The ratio of components (A), (B) and (C) is arbitrary, but (A>/ (B + C) = 1/99
~50150 (weight ratio), preferably 5/95~30
/70. Also, (A)/(B)-100/1~1150
, preferably 20/1 to 1/10. In addition, as an adsorption method, component (A) is dissolved in a solvent compatible with component (A) such as 2-propanol, and this is mixed with component (A).
C) Or a method of removing the solvent after mixing component (C) and component (B), or a method of removing the solvent after mixing component (C) and component (B), or melting component (A) and component (C), or melting component (A) and component (C) and (B). ) and the like.

In the present invention, various components can be added in addition to the above components. That is, 1 part of the alkylene oxide addition type nonionic surfactant (D) that is compatible with component (A) is
A species or two or more species can be added. Examples of the nonionic surfactant (D) include alkylene oxide adducts such as higher alcohols, fatty acids, fatty acid amides, fatty acid amines, alkylphenols, and synthetic alcohols obtained by oxidizing n-paraffins, α-olefins, and n-olefins. It is. Further, as the alkylene oxide, ethylene oxide, propylene oxide, a mixture thereof, and butylene oxide are usually used, but ethylene oxide is preferred. Number of moles of alkylene oxide added is 20
In the above case, microdispersion is insufficient, which is not preferable. Specifically, component (D) has an alkyl group having 8 to 20 carbon atoms, and has an average number of added moles of ethylene oxide of 1 to 20.
20, and POE alkyl ether having an alkyl group having 6 to 12 carbon atoms and having an average number of added moles of ethylene oxide of 1 to 20. Specifically, 1 is POE (P=10') palmityl ether,
POE (P= 10) syTS/l/ x -7-
le, POE (P=2)%/, lt, -), POE (
P=5) Coconut fatty acid monoethanolamide, oxyethylene (P=1) nonylphenyl ether, POE (
P-3)012-14 Secondary alkyl ethers, etc. are mentioned. In addition, in the above compound, the ruled line indicates the average number of added moles of ethylene oxide, and POE indicates polyoxyethylene (the same applies hereinafter). The weight ratio of (A)/(D) is 10
/1 to 1/3, preferably 10/1 to 1/1, and the blending amount of component (D) is 1 to 30% by weight.

In the present invention, when a salt such as sodium carbonate is used in the powder of component (C), it is more preferable for the treated fibers and hair to have a pH of the treatment liquid from neutral to weak. in this case,
Component (B) of the present invention may be used in the form of an acid in an amount that neutralizes component (C), or the pH may be adjusted using a non-carboxylic acid such as sodium bisulfite or sulfamic acid. It's okay. In addition to the chemical formula expressed as NaH3O3, the term sodium hydrogen sulfite refers to sodium bisulfite (Na2S20).
s) etc. as impurities. The method of adding these regulators can be based on the method of adding component (B).

The cationic surfactant component (Δ) used in the present invention is usually synthesized in a state containing a lower alcohol (for example, 2-propatol) or water as a solvent. Therefore, since the water in the cationic surfactant dissolves some of the inorganic salts, and lower alcohols are undesirable in terms of odor, it is desirable to remove them as much as possible (for example, by topping treatment, etc.), but in practice there are It does not matter if some amount is mixed in. In addition, component (A) is a quaternary ammonium salt, and component (A) is a quaternary ammonium salt.
If D) does not react with the quaternization reagent (alkyl halide, dialkyl sulfate, etc.), add component (D) to the tertiary amine that is the raw material for component (A), and then add component (D) in an amount equimolar to component (Δ). A known quaternization reaction may be performed by reacting with a quaternization reagent. In this case, at the end of the reaction, a mixture of components (A) and (D) is obtained, so component (C) or component (
C) and (B) can be added and powdered, and it is reasonable to save the time and effort of removing the solvent.

The product of the present invention may be used in a form in which component (A) or components (A) and (D) are adsorbed to component (C) or components (C) and (B), but ease of use may be improved. For this purpose, it may be re-granulated or used as a tablet.

The granulation method is not particularly specified, but Knee Important Cultural Property, Higashihata Heiichi, PA Kagaku Kogyo I [”p, 75. Tokyo Kagaku Doujin (1977
), and the like. Specifically, (1) A binder consisting of polyethylene glycol, liquid paraffin, a nonionic surfactant, a cellulose derivative, an aqueous starch solution, etc. is added to the product of the present invention, and the product is granulated using a transfer drum type granulator. Method.

(11) A method in which the product of the present invention and a binder are kneaded and then crushed and granulated.

(iii) A method of forming and then crushing tablets as described below.

etc.

When used as tablets, foaming agents consisting of acidic and basic substances, polysaccharides such as multi-dose used as a binder for tablets, pennite minerals, caseins, and starch to make the tablets crumble are added. By adding one or more kinds of disintegrants such as cellulose derivatives, etc.
It is possible to form an agent. The tabletting method, additives, etc. are specifically described in Kyosuke Tsuda, Uenomae, ``Drug Manufacturing Methods (Part 1) Basic Course on Pharmaceutical Development XI'', Chidaishokan.

The products of the present invention further include fragrances, dyes, pigments, silicones,
Bactericidal agents, antioxidants, ultraviolet absorbers, optical brighteners, etc. can be added.

〔Effect of the invention〕

The softener composition of the present invention has excellent solubility, and when added to water, the cationic softener becomes finely dispersed in a short time.

In particular, when stirring using a washing machine, most of the cationic softeners adsorbed on the inorganic powder are 105 μm or less, and when an alkylene oxide-added nonionic surfactant is used together, they become even finer and become 10 μm or less. In some cases, it is microdispersed in water to a size of 5 μm or less.

Therefore, the cationic particles are evenly adsorbed on the cloth without causing uneven adsorption, so that no stains occur, an excellent softening effect can be imparted to the treated cloth, and the treatment liquid does not become cloudy.

Furthermore, the addition of component (B) significantly improves the antistatic effect.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.

〔Example〕

The method for preparing the softener composition and the determination of microdispersibility in the examples were as follows.

・Preparation method of softener composition A slurry-like material containing 75% of the component (Δ) (25% of which is water and a solvent consisting of 2-propanol) is heated to form a mixture of water and 2-propertool.
-Removed property tools.

This product contained 95% of component (A). Component (D), a nonionic surfactant, was added as needed and mixed while heating. Component (C) and component (B) were added to the mixture, thoroughly stirred and mixed, and cooled to room temperature. Incidentally, pulverization was performed as necessary.

- Determination of microdispersibility The softener was weighed out so that the component (A) in the softener composition was 1 g. A household washing machine (Mitsubishi Electric Model CW-660) containing 30 liters of water at 25° C. was inverted and stirred, and the softener was added thereto and stirred for 3 minutes. Immediately after stirring, pass this dispersion through a JIS150 mesh sieve (pore size: 105μ).
m) and a membrane filter with a pore size of 10 μm, and the amount of component (A) in the filtrate was determined. The amount of component (A) that passed through this JIS150 mesh sieve and 10 μm membrane filter was 105 μm and 10 μm.
It is assumed that the components are dispersed down to micrometers or less (
It is expressed as a weight ratio (%) to the amount of A>.

・Performance evaluation Using cotton towel and acrylic cloth (acrylic jersey),
These were washed with a commercially available detergent, rinsed thoroughly, and thoroughly dried indoors, and then used as test cloths.

Put 30 liters of 25°C water and 1 kg of test cloth into a washing machine, weigh out the softener so that the amount of component (A) in the softener composition is 1 g, stir for 3 minutes after adding, Rinsed and treated.

After the fabric treated in this way was air-dried indoors, it was left for 24 hours at 25°C and 65% RH to evaluate the softening effect.
In addition, the products for which antistatic effect was measured were left for 72 hours under the conditions of 20° C. and 45% RH, and then subjected to each test.

(1) Flexibility The feel of the test fabric before and after the treatment was compared and evaluated according to the following criteria.

◎: Very soft ○: Soft △: Slightly soft ×: Same as before treatment (2) Antistatic Static Honest Meter (TYPE) manufactured by Shishido Shokai
15109), the cloth was charged with an applied voltage of 7 kV and a target distance of 20+ nm, and the half-life (seconds) of the charged voltage was measured after the applied voltage was removed. In addition, untreated acrylic)
The half-life of was more than 300 seconds.

Example 1 (A) Dicured beef tallow alkyldimethylane 20%
Monium chloride (95% pure) (B) Component 0 or 5
%(C) Ingredient 70~
Granules (softener compositions) consisting of 80% (D) phosphoryoxyethylene (p = 2) monooleate 0 or 5% were prepared. The chemical formula of the light ash and powdered ash used as component (B) is Na2cO3, but the oil absorption is 72d/100% of the light ash.
g, powdered ash 25mf/100g. The performance of these granules is summarized in Table-1.

Table 1 shows that when a water-soluble powder having a specific oil absorption amount or more is used as component (C), most of component (A) is dispersed in water.
It can also be seen that the particles are 105 μm or less. Furthermore, the component (D
), if it contains a nonionic surfactant, an additional 10 μm
It can also be seen that when the component (B) is microdispersed to a level below, and component (B) is further added, the antistatic effect is significantly improved.

Example 2 Compositions were prepared with various blending amounts, etc., and their performance was evaluated. The results are shown in Table-2. All of these compositions exhibited high microdispersibility and excellent antistatic and softening effects. Further, all of the processing solutions treated with these processing solutions were neutral.

Toto Example 3 (A) 15 parts of di-hardened beef tallow alkyldimethylammonium chloride (purity 95%) (D) POE (P=2) A molten mixture consisting of 4 parts of monooleate was mixed with (B) baking soda (oil absorption: 39/- 100g) was impregnated into 44.4 parts. After cooling this, 22.2 parts of fumaric acid (B), 14 parts of β-cornstarch (disintegrant), 0.2 parts of red powder pigment,
0.2 part of floral powder fragrance was added and mixed thoroughly. 3 g of this mixture was compressed using a tablet press at a pressure of 1 t/c.
nt (tablet diameter 20+++n).

When two of these tablets were placed in a 30A washing machine and evaluated for microdispersibility and antistatic property in the same manner as in Example 1, the amount of particles of 10 μm or less was 75%, and the antistatic property was 1.
It was seconds. Moreover, this tablet was crushed using a crushing granulator, and particles between 16 and 32 meshes were sieved using a sieve. Using this granulated powder softener, microdispersibility and antistatic properties were evaluated in the same manner as in Example 1.
The amount of particles smaller than μm was 80%, and the antistatic property was 1 second.

Claims (5)

[Claims] (1) A softener characterized by containing a cationic softener (A), a polyhydric carboxylic acid or its salt (B), and a water-soluble powder (C) having an oil absorption of 35 ml/100 g or more. agent composition. (2) Component (A) to component (C) or component (B) and component (
The softener composition according to claim (1), which is in the form of adsorption in a mixture with C). (3) The softener composition according to claim (1), wherein component (B) is a compound having 5 or less carbon atoms per carboxyl group. (4) The softener composition according to claim (1), which is in a granulated form. (5) The softener composition according to claim (1), which is in the form of a tablet.