JPH02182972A - Solid soft-finishing agent - Google Patents

Abstract

PURPOSE:To provide a solid soft-finishing agent containing a cationic softener having a specific hydrocarbon group, a quaternary ammonium salt and a com pound such as urea as a dispersion assistant at specific weight ratios and exhibiting excellent dispersibility and solubility even after the storage over a long period. CONSTITUTION:A powdery soft-finishing agent having excellent dispersibility and solubility can be produced by melting and mixing (A) 30-60wt.% of a cationic softener such as a quaternary ammonium salt, imidazolinium salt, etc., having two 10-36C hydrocarbon groups (which may contain O or N atom), (B) 5-30wt.% of a quaternary ammonium salt having one 8-36C hydrocarbon group (which may contain O or N atom) and (C) 15-60wt.% of urea, a urea derivative or an alkylene oxide adduct of a polyamine containing >=3 nitrogen atoms. The dispersibility of the agent in water can be further improved by compounding the granular agent with a foamable component, a water-soluble inorganic salt and a binder.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a powder, granule, or tablet type solid fabric softener having excellent dispersibility and solubility.

[Conventional technology and its problems]

Most fabric softeners are liquid types that contain 3 to 15% by weight of di-long-chain alkyl cationic softeners, but in order to achieve higher concentrations, solid powder or tablet types are available. Things are also being studied. The biggest problem when solidifying a softener and using it as a fabric softener is that it must be easily dispersed and dissolved when added to water.

JP-A-57-193574 discloses that urea may be added to improve the dispersion efficiency of non-cationic softener particles. JP-A No. 59-8800 discloses that di-long chain alkyl type quaternary ammonium salt powder with an average particle size of 150 or less is mixed with fine silica powder, and after granulation with the addition of a nonionic surfactant. It is disclosed that a granular softener with good water dispersibility can be obtained by further adding zeolite and granulating it. Also, JP-A No. 62-253698
The issue describes a granular softener with improved dispersion solubility obtained by granulating a foamed composition consisting of acidic powder and alkaline carbonate powder and di-long-chain alkyl type quaternary ammonium salt powder. Disclosed.

JP-A No. 63-138000 discloses a powder or tablet-type softener with improved solubility by adsorbing a cationic softener base to a water-soluble powder with a high oil absorption such as urea or light ash. It is disclosed that it can be obtained.

However, the dispersion and solubility of these solid softeners in the form of powder, granules, or tablets, especially after long-term storage, is still insufficient, and there are problems in their practical use.

[Means to solve the problem]

In view of these circumstances, the present inventors have conducted intensive research and found that if a mono-long chain alkyl type quaternary ammonium salt is used in combination with urea or its salt, conductor, or polyamine alkylene oxide adduct, di-length can be increased. The inventors have discovered that the dispersion solubility of chain alkyl type cationic flexible base particles is significantly increased, and have completed the present invention.

That is, the present invention comprises: (A) 30 to 60% by weight of a cationic flexible base having two hydrocarbon groups having 10 to 36 carbon atoms (which may contain an oxygen atom or a nitrogen atom); (B) 1 hydrocarbon group having 8 to 36 carbon atoms (may contain an oxygen atom or a nitrogen atom)
5 to 30% by weight of a quaternary ammonium salt, and (C) 15 to 60% of an alkylene oxide adduct of urea, a urea derivative, or a polyamine having 3 or more nitrogen atoms.
% by weight of a solid fabric softener.

Examples of the cationic flexible base of component (A) include those having the following structure.

1) A quaternary ammonium salt represented by the following general formula (I).

(In the formula, R,, R1 has 10 to 36 carbon atoms, preferably 1
Represents 4 to 24 straight or branched, saturated or unsaturated hydrocarbon groups. The hydrocarbon group may have a substituent such as a hydroxyl group, and the hydrocarbon group may have a -〇- nitrogen atom.

R3 and R represent an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, a benzyl group, or a polyoxyethylene group having 10 or less added moles.

X is an inorganic or organic anion, for example CHsSOt
, CJsSO*, IC1lHz-++COO, n is 0~
17゜C1111t,,,OPO, n is 8~1B, l
0C) IICOO.

2) An imidazolinium salt represented by the following general formula (II).

(In the formula, R1 represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, a benzyl group, or a polyoxyethylene group having 10 or less added moles, and Rs and Rh represent an alkyl group having 1 to 3 carbon atoms.
26, preferably 14 to 24, straight chain or branched, saturated or unsaturated hydrocarbon group. The hydrocarbon group may have a substituent such as a hydroxyl group.

X is an inorganic or organic anion, for example CHsSOt
, CJsSO*, C-1h, 14+COO, where n is 0 to 1
At 7°C, Hz--+0POt, n is 8~IELHOC1
lzCOO + Specific examples of these cationic surfactants include dicetyldimethylammonium chloride, distearyldimethylammonium chloride, tocosyldodecyldimethylammonium chloride, octadecyldodecyldimethylammonium chloride, his(2-dodecylhexadecyl)dimethylammonium chloride. , diisostearyl dimethyl ammonium chloride, di-hardened tallow alkyl dimethyl ammonium chloride, di-hardened tallow alkyl dimethyl ammonium chloride, di-tallow alkyl dimethyl ammonium methyl sulfate, (distilled hardened rapeseed oil alkyl)-(distilled hardened coconut oil alkyl) dimethyl ammonium chloride, (distillation-hardened tallow alkyl)-(distillation-hardened coconut oil alkyl) dimethylammonium chloride, dihardened tallow alkylhydroxyethylmethylammonium chloride, dihardened tallow alkylhydroxyethylmethylammonium chloride, (octadecyloxycarbonylmethyl)-dodecyl-dimethylammonium chloride ,chloride(
tocosyloxycarbonylmethyl)-dodecyl-dimethylammonium, methylsulfate bis(octadecanoyloxyethyl)-(hydroxyethyl)-methylammonium, methylsulfate-1-stearylamidoethyl-2-stearyl-3-methylimidazolinium, Methyl sulfate
1-Oleylamidoethyl-2-oleyl-3-methylimidazolinium, methyl sulfate-1-hardened beef tallow amidoethyl-2-hardened beef tallow-3-methylimidazolinium, methyl sulfate-1-beef tallow amidoethyl-2-beef tallow. Examples include 3-methylimidazolinium.

It is particularly preferable to use these quaternary ammonium salts and imidazolinium salts as the main ingredients of the flexible base, but tertiary amines before quaternizing the above quaternary ammonium salts,
Imidacilline compound before quaternizing imidazolinium salt, tri-long-chain alkyl type quaternary ammonium salt, sorbitol, mannitol, higher fatty acid ester of pentaerythritol or its polyoxyalkylene adduct, ethylene oxide/propylene oxide block It is also possible to use nonionic activators such as polymers, anionic activators such as fatty acid salts, amphoteric activators such as alkylaminoacetic acid betaine, alkylamine oxide, alkylcarboxymethylhydroxyimidazolium betaine, higher fatty acids, etc. It also functions as a binder, which will be described later.

The softening base (A) is blended in the solid softening agent in an amount of 30 to 60% by weight, preferably 40 to 55% by weight.

If it is less than 30% by weight, a considerable amount of powder is required to obtain sufficient flexibility, and if it is more than 60% by weight, the dispersibility in water will be poor.

Examples of the quaternary ammonium salt of component (B) include compounds represented by the following general formula (III).

(In the formula, R7 has 10 to 36 carbon atoms, preferably 15 to 30 carbon atoms.
represents a linear or branched, saturated or unsaturated hydrocarbon group, which may have a substituent such as a hydroxyl group, and may further have -0- nitrogen atom in the chain.

R1, R9, and R1° represent an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a polyoxyethylene group having a number of moles of benzyl L added to IQ or less.

X is an inorganic or organic anion, for example CHsSO*
.

CzllsSOt, Cl1Hz-4+COO and n is O~
17. C, 1lh-+OPO:+ and n is 8-18. H.O.
CH, COO.

Component (B) is used to assist the dispersion of the soft base component (8) in water, and includes, for example, trimethyloctadecyl ammonium chloride, trimethyl hardened beef tallow alkyl ammonium chloride, 2-dodecylhexadecyl-trimethylammonium chloride, octadecyl ammonium chloride, Examples include noyloxyethyl-bis(hydroxyethyl)-methylammothiram chloride.

Component (B), which is a dispersion aid, is present in the solid softener in an amount of 5 to 50%.
It is blended in an amount of 30% by weight, preferably 15 to 30% by weight.

The dispersion aid of component (C) is urea, N-methylurea, N-
These are urea derivatives such as ethyl urea, and polyoxyalkylene adducts of polyamines having three or more nitrogen atoms.

Examples of the polyamine compound include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine.

Further, among derivatives of these polyamines, such as partially amidated products and N-alkyl substituted polyamines, those having three or more active hydrogens can be used.

A polyether compound which is a polyoxyalkylene adduct can be easily obtained by adding an alkylene oxide that essentially contains ethylene oxide to a polyamine compound having three or more active hydrogens using a conventional method. Among these, ethylene oxide alone or a block or partially block adduct of ethylene oxide and propylene oxide is particularly preferred, and the order of addition may be in any order, but it is preferable to add propylene oxide first and then ethylene oxide. A good dispersion aid is obtained.

The molecular weight of the polyether compound is 5.000 to 200.0
00, preferably 10.000 to 100.000
It is good that it is within the range of Further, the total weight of the ethylene oxide chain portions is 50% by weight or more, preferably 80% by weight or more of the total molecular weight.

The dispersion aid component (C) is 15 to 60% in the solid softener.
It is blended in an amount of 20 to 40% by weight, preferably 20 to 40% by weight.

The method for producing the powdered softener containing components (A), (B), and (C) is not particularly limited, but may include a method in which the three components are melted, mixed, cooled and solidified, and then crushed into powder. , a powdered softener having particularly good dispersion and solubility can be obtained.

Although the particle size of the powder also affects the dispersion solubility, it is preferable that the powder has the following particle size distribution.

The amount of particles having a particle size of 106 μm or less should be 5% by weight or less, preferably 1% by weight or less, and if the amount is more than 5% by weight, agglomeration of the softener powder will be promoted.

The lognormal probability paper in Figure 1 shows the logarithm of the particle diameter on the horizontal axis.
On the vertical axis, the cumulative under-sieve % (weight), that is, the amount passed through (weight %) is calibrated with a special scale, and it is widely distributed by the Japanese Standards Association and other organizations.

The cumulative % under sieve (weight) obtained using the sieves at various stages is plotted on this log-normal probability paper to obtain a log-normal distribution diagram (Figure 1). In the lognormal distribution diagram obtained, ta represents the slope of the straight line obtained by connecting the two points 250 m (60 meshes) and 1000100 meshes).
It is preferable that nα is 2.0 or more, preferably 3.0 or more. If tanα is less than 2.0, the variation in particle size will be too large and particle aggregation will be promoted.

Note that even if the obtained lognormal distribution diagram is a curve, a mixture of a straight line and a curve, or has an inflection point, the 250
tanα of the straight line obtained by connecting the two points of the passing amount (weight%) of 4 (60 meshes) and 1000100 meshes)
It is sufficient if it is 2.0 or more.

The solid fabric softener of the present invention may be used in the form of a powder, or the powder may be formed into granules or tablets. At this time, component (A), component (B)
, and a foamable composition (D) to the melted and mixed powdered product of (C).
, a water-soluble inorganic salt (E) and a binder (F) can be blended to prevent agglomeration of the molten mixed powder and further improve the dispersibility in water.

When the foaming composition (D) is used, the acidic substance and the alkaline carbonate are dissolved in water to generate carbon dioxide, and this foaming power transforms the solids into components (A) and (B).

The molten mixed powder consisting of (C) is disintegrated finely into primary particles.

Examples of the acidic substance in the foamable composition (D) include strongly acidic inorganic salts such as aluminum salts, organic acids such as citric acid and succinic acid, or their anhydrides. Examples of alkaline carbonates include sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, and the like.

The foamable composition (D) has a weight ratio of (D)/(^)=1/3 to 1/1, preferably 1 to the flexible base (A).
It is preferable that the content be 2/2 to 2/3. Moreover, it is preferable that the weight ratio of the acidic substance and the alkaline carbonate is acidic substance/alkaline carbonate=2/1 to 1/3.

Examples of the water-soluble inorganic salt (E) include halides, sulfates, and nitrates of alkali metals and alkaline earth metals, and specific examples include sodium chloride, sodium sulfate, magnesium sulfate, and potassium nitrate.

The water-soluble inorganic salt (E) is contained in a weight ratio of (E)/(A) = 1/3 to 3/1, preferably 1/2 to 1/1 with respect to the flexible base (A). It's good.

Binders (F) include anionic surfactants such as poly(alkyl oxide) adducts of long-chain alcohols, liquid paraffin, polyethylene glycol, cellulose,
Examples include cellulose TII, S powder, starch derivatives, casein, and gelatin. Natural waxes such as carnauba wax, synthetic waxes, and higher alcohols also act as binders.

The weight ratio of the binder (F) to the flexible base (A) is (F
) / (A) = 11500 to 1/100, and (
It is preferable that (E) + (F) )/(A) = 1/3 to 3/1.

The solid fabric softeners of the present invention may contain other additives, such as perfumes and defoamers.

In this case, it is effective whether it is mixed into the flexible base or mixed during molding.

〔Effect of the invention〕

The solid fabric softener of the present invention exhibits excellent dispersion and solubility during fabric softening treatment even after long-term storage.

By melting and mixing the soft base (A), the dispersion aid (B), and the dispersant (C) into a powder, the dispersion solubility in water is further increased.

Furthermore, by providing a specific particle size distribution, particles can be prevented from agglomerating during storage.

Since the fabric softener of the present invention is in solid form, the amount used can be easily controlled depending on the amount of clothing. Furthermore, since the volume is smaller than that of liquid products, it is easier to carry and has the advantage of not taking up much space.

〔Example〕

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

After melting and mixing the composition components shown below, the composition components shown below were pulverized and sieved to prepare various solid fabric softeners having particle size distributions as shown in Table 1. A lognormal distribution diagram obtained from each particle size distribution is shown in FIG.

The storage stability of various solid fabric softeners was evaluated.

Softener composition> Distearyldimethylammonium chloride...
50% ・Stearyltrimethylammonium chloride...
15% by weight ・Urea...35% by weight Storage stability test method> 1 g of the solid softener composition was left in a constant temperature and humidity room at 20'C and 26o% RH for one month, and then stored at 25°C and 3.5% by weight.゜D1
1 Add to hard water 11 and stir for 5 minutes (50r, p, m)
After washing, pass through a 200-mesh wire mesh to check for any residue.

These results are shown in Table-1.

SJ111 After melting and mixing the fabric softener composition components shown in Table 2, they were pulverized, and the particle size distribution was adjusted by sieving to obtain various solid fabric softeners. The storage stability (presence or absence of residue) and flexibility of the obtained solid fabric softener were evaluated.

Softness test method> (11) A commercially available cotton towel was washed 5 times with a commercially available detergent Zabu (manufactured by Kao Corporation, registered trademark) to remove the detergent from the cloth, and then a cotton towel treated as described above was washed. 1
Using 2g of fabric softener powder per kg,
．． Stirring treatment was carried out for 5 minutes in 5° DH hard water at 25° C. and a bath ratio of 1/30. After air drying the above treated cloth at room temperature, 25℃, 65℃
It was left in a constant temperature and humidity room at %RH for 24 hours.

(2) Regarding the above treated fabric, each soft base (
A pairwise comparison of softness was performed using a cotton towel treated with the 5% aqueous dispersion of A) so that the softening base had the same treatment concentration, and the softness was evaluated using the following evaluation criteria.

+2 Softer than the control +1 Slightly softer than the control 0 Same as control -1 control is slightly softer -2 Control is softer These results are shown in Table-2.

J1 female 1 After melting and mixing the fabric softener composition components shown in Table 3, they were pulverized to obtain various solid fabric softeners. Foaming composition powder, water-soluble inorganic salt,
After mixing the binder and adjusting the particle size distribution by sieving, 3 g of the mixture was compressed under appropriate pressure (30 kg/cm2) to obtain tablets with a diameter of 20 mm and a height of 12 mm.

Using this tablet, storage stability (presence or absence of residue) and flexibility were evaluated. Flexibility test method: 1 tablet per 1k cotton towel
Same as Example 2 except that g was softened.

These results are shown in Table 3.

4,

[Brief explanation of the drawing]

FIG. 1 is a log-normal distribution diagram on a log-normal establishment paper showing the particle size distribution of products of the present invention Magnets 1 to Kan 3. No. Miko lognormal distribution diagram normal II 111 paper aq (ti diameter (μm))

Claims (1)

[Claims] 1. (A) 30 to 60% by weight of a cationic flexible base having two hydrocarbon groups having 10 to 36 carbon atoms (which may contain an oxygen atom or a nitrogen atom); B) Carbon number 8-36
5 to 30% by weight of a quaternary ammonium salt having one hydrocarbon group (which may contain an oxygen atom or a nitrogen atom), and (C) having three or more urea, urea derivatives, or nitrogen atoms. A solid fabric softener characterized by containing 15 to 60% by weight of an alkylene oxide adduct of polyamine.