JPS62146998A - Granular detergent additive and its production - 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 The present invention relates to additives for granular detergents, and particularly to additives used in granular detergents containing anionic surfactants.

Conventional Drum WheelsUsually, when washing clothes at home to make them soft,
After washing with detergent, rinse off the detergent ingredients with plenty of water,
Thereafter, a method is adopted in which a softening agent whose main component is a cationic surfactant such as a quaternary ammonium salt is added for treatment.

This is because, although cationic surfactants have excellent softening effects and antistatic effects, they cannot provide sufficient softening effects when used together with detergents. The reason for this is that household detergents generally have anionic surfactants as their main ingredient, so when cationic surfactants are added during washing, the anionic surfactants in the detergent are This is because they lose their ionicity and become dispersed and stabilized, making it difficult for them to be absorbed by clothing.

However, performing washing and softening separately requires extra time and effort, and consumers are demanding detergents that combine cleaning and softening.

Conventionally, it has been proposed to granulate a cationic surfactant with an inorganic or organic salt or an organic dispersion inhibitor as a method of adding a cationic surfactant at the same time as washing to give a sufficient softening effect to clothing ( Japanese Patent Publication No. 36-8927, U.S. Patent No. 4,073,735, Japanese Patent Publication No. 55-86
895, JP-A-53-41312, =4- JP-A-49-98403).

However, although these proposals were found to be effective in improving the flexibility of synthetic fibers, their softening effects on cotton were insufficient.

The present inventors previously proposed blending an acrylamide polymer as a technique for improving the softening effect on cotton fabric (Japanese Patent Application No. 125364/1983,
No. 25365). However, although these technologies increase the adsorption amount of cationic surfactants, which are softness-imparting ingredients, on clothes after washing, they also cause dirt that has fallen off during washing to re-adhere and re-contaminate the clothes after washing. This caused the problem of darkening of clothing.

The present inventors have also previously proposed a method for producing a softening agent in which fine acrylamide powder is added and uniformly dispersed in a quaternary ammonium salt melt (Japanese Patent Application No. 59-238
No. 531). According to this method, the desired effect can be achieved by achieving uniform dispersion through a simplified process by omitting the water evaporation step, but the acrylamide-based polymer has a strong tendency to deteriorate due to shearing during mixing. Low shear rate (5
~801/5ec), and as a result,
It was found that some coarse particles were formed, causing problems in terms of workability, such as strainer clogging.

The present invention can perform cleaning and soft finishing at the same time.
The present invention provides a granular detergent additive that has an excellent softening effect even on cotton cloth and prevents clothes from becoming dark after washing.

The present invention also provides a simplified process.

Moreover, the present invention provides a method for producing a granular detergent additive that prevents the generation of coarse particles and has an excellent softening effect even on cotton.

l Sarabe Toyoyo The granular detergent additive of the present invention is characterized by containing the following components (a) and (b).

(a) Di-long chain alkyl quaternary ammonium salt = 99.8~
50% by weight and (b) a copolymer of an acrylamide monomer represented by the following general formula (1), a carboxy group-containing monomer, and a sulfone group-containing monomer = 0.2 to 50% by weight [In the formula, R1 , R2, R', R', R', A, B.

Y1. Y2. n, m, and n each represent the following.

RL, R4, Rs: hydrogen or methyl group R2, R
3: Hydrogen, substituted alkyl group such as an alkyl group or hydroxyalkyl group A: Alkylene group having 0 to 5 carbon atoms B: Alkylene group having 0 to 5 carbon atoms, benzene ring unsubstituted or substituted with an alkyl group, 10CH2+ x C-00 CH2+ y [xv y is an integer of O to 5] or R'' Yl, Y2: ratio of hydrogen, alkali metal or alkaline earth metal fl, m, n; Q: m: n = (9
8, 9-50): (1-50): (0', 1-20
)] In the method for producing the granular detergent additive of the present invention, a molten di-long-chain alkyl quaternary ammonium salt is added with an average particle size of 150
A copolymer of an acrylamide monomer represented by the above general formula (I), a carboxyl group-containing monomer, and a sulfone group-containing monomer having a size of 10 μm or less is added, and a shear rate of 50 to
The method is characterized in that the copolymer is uniformly dispersed in the melt under conditions of 1501/see, and then powdered.

The present invention will be explained in more detail below.

Examples of the di-long chain alkyl quaternary ammonium salt of component (a) include those represented by the following general formula (]I).

(However, R@, R7 represents a C2-C0 alkyl group, R', R' is a C1-C4 alkyl group, a benzyl group,
02 to C4 hydroxyalkyl group or polyoxyalkylene group, or halogen, CH, So4. C:
, H, So, or CH, -〇-so. ) Specific examples of the cationic surfactant as component (a) include: distearyldimethylammonium salt, dihydrogenated beef tallow alkyldimethylammonium salt, dihydrogenated beef tallow alkylbenzylmethylammonium salt, distearylmethylbenzylammonium salt, Examples include distearylmethylhydroxyethylammonium salt, distearylmethylhydroxypropylammonium salt, distearyldihydroxyethylammonium salt, and the like. Further, specific examples of halogen as a counter ion include chloride, bromide, and methosulfate.

Examples of the acrylamide monomer (I-1) which is a constitutional unit of the copolymer of component (b) include acrylamide monomer (R1:H),
There is methacrylamide monomer (R1: CH3),
Specific examples of R2 and R3 are hydrogen, -CH3, -C2H
-CH(CH3)2, -〇 (CR3)3, -C8H
□7, Alkyl-10- group such as C(CH3)2CH2C(CHa)3; -CH20H1-CH2CR20H5-CH2CH
2CH, OH.

Examples include hydroxyalkyl groups such as L-CH(CH3)CH, OR; substituted alkyl groups such as rCH20C4Hg, -CH2QC2H, (CH3)2, -0(CH3)2CH2COCH3, and the like.

Further, as a specific example of the carboxyl group-containing monomer (I-2), acrylic acid (R':H, A:0, Yl:H
), methacrylic acid (R': C:R3, A: 0, Y
l:H) or salts thereof.

As a specific example, ethylene sulfonic acid (R5: H, B
:O, Y”:H), propenesulfonic acid (R”: CH
3, B: O, Y2: H), methylpro'/X
) L'ho'-' acid (Rs: CR3+ B:
CR2t Y ” :H), styrene sulfonic acid (R'
: H, B Knee () Y” : H), 2-acrylamido-2-methylproB Knee C-0CH2CH2-
, Y2: H), or salts thereof.

The copolymerization ratio of the copolymer of component (b) is l:m:n
= (98,9-50) : (1-50) : (
0,1-20), preferably (90-60):
(10-30): (0,5-10).

In the copolymer of component (b), an anionic monomer,
That is, when the sum of the carboxyl group-containing monomer and the sulfonic group-containing monomer exceeds the acrylamide monomer, the reaction between the cationic surfactant and the ionic monomer becomes significant, and the softening effect deteriorates. However, unless the proportion of anionic monomer exceeds that of acrylamide monomer, the effect of this reaction is slight. If the proportion of the carboxyl group-containing monomer or sulfone group-containing monomer is too small, the re-staining prevention effect will not be sufficiently exhibited. The degree of polymerization of the copolymer (b) is suitably 1,000 or more, preferably 10,000 or more.

The copolymer (b) of the present invention is usually obtained by copolymerizing an acrylamide monomer and an anionic monomer. It can also be obtained by hydrolysis.

The granular detergent additive of the present invention contains 99.8 to 50% by weight, preferably 95% by weight of the quaternary ammonium salt of component (a).
The proportion of the copolymer of component (b) is 0.2 to 50% by weight, preferably 5 to 30% by weight. (b) If the amount of the component is less than the above, the softening effect on cotton and the recontamination prevention effect will not be sufficient6.Optional ingredients include nonionic cellulose derivatives such as methylcellulose and hydroxyethylcellulose, mirabilite,
It is also possible to coexist various inorganic compounds such as M g S 04g Ca C12 and various organic compounds such as higher alcohols, fatty acids, and nonionic activators.

The granular detergent additive of the present invention can be prepared by various methods (a)
Although it can be obtained by blending the component and the component (b), it is preferable that both components are mixed uniformly. As such a manufacturing method, a method of adding the copolymer of component (b) as a solution and a method of adding it as a powder can be considered. However, the former method usually requires a large amount of solvent (generally water) to make the copolymer into a solution, requires expensive equipment for drying, and is less effective in preventing recontamination.

In the method of adding powder, it is desirable to add the copolymer of component (b) in fine powder, with an average particle size of 150
It is appropriate to add and mix with a thickness of 100 μm or less, preferably 100 μm or less. If the particle size of the copolymer powder is too large, the softening effect will be reduced.

A polymeric substance such as a copolymer of component (b) usually has a 0.
It is often made into granules of about 5 to 2 mm (500 to 2000 μII+), and most of the copolymers of this type currently on the market are also in the form of granules. Therefore, it is appropriate to use it after pulverizing it. Any suitable method can be used for pulverization, such as using a knife cutter or a hammer mill, grinding with a screw or the like, or jet grinding with a high-speed air stream. Furthermore, if necessary, the particle size is adjusted using a sieve or air classification. The effect of improving the flexibility of cotton is better as the particle size of the copolymer is finer.

However, depending on the pulverization method, if the pulverization is carried out under conditions that make the particle size too small, the molecular chains of the polymer will be cut and the degree of polymerization will decrease, which may reduce the flexibility improvement effect.

Further, as a method for obtaining a fine copolymer without pulverization, there is a method of producing a copolymer by reverse-phase suspension polymerization or reverse-phase emulsion polymerization. According to this method, a polymer having a small particle size can be obtained without causing a decrease in the degree of polymerization of the copolymer.

The copolymer with a small particle size obtained in this way easily absorbs moisture, and it absorbs moisture during pulverization or storage over time, and usually
Contains 5-30% water by weight. If a copolymer with a high moisture content is used, the copolymer will easily turn into coarse particles when mixed with the quaternary ammonium salt of component (a), and these coarse particles will form on clothes when washed at low temperatures. It will stick.

In order to prevent the occurrence of mamako, the water content should be reduced to 10% by weight.
It is preferably at most 7% by weight, particularly preferably at most 7% by weight. As a method for removing water in the copolymer,
Appropriate equipment such as a hot air dryer, a vacuum dryer, a fluidized bed dryer, a freeze dryer, etc. can be used.

In order to uniformly mix the quaternary ammonium salt of the component (a) and the copolymer of the component (b), a fine powder of the component (b) is added to the heated and melted component (a) and mixed. The quaternary ammonium salt of component (a) is preferably heated and melted at 100 to 130°C. If this temperature is less than 100°C, the viscosity will increase rapidly and the copolymer cannot be uniformly dispersed. On the other hand, when the temperature is higher than 130°C, the quaternary ammonium salt decomposes and the softening effect deteriorates. This uniform dispersion is achieved at a shear rate of 50 to 1501/ssc, preferably 80 to
It is preferable to mix under stirring conditions of 1301/see. If the shear rate is less than 501/see, coarse particles will be generated during dispersion, resulting in clogging of the strainer, resulting in poor workability. Moreover, if the shear rate is 501/sec or more, even if the water content in the copolymer of component (b) is large, generation of coarse particles can be suppressed and uniform dispersion can be achieved. On the other hand, if the shear rate exceeds 1501/see, the copolymer will change in quality and the softening effect will deteriorate.

For dispersing the copolymer of component (b), for example, a paddle type,
A propeller type mixer is used.

The obtained homogeneous dispersion is granulated by jet cooling or pulverization and granulation after cooling and assimilation.

The granular detergent additive of the present invention is preferably formed into particles with an average particle size of 700 μm or less by an appropriate granulation method. If the particle size is large, not only will it be difficult to uniformly impart a softening effect to the items to be washed, but also the additive particles may adhere to the items to be washed as they are at the end of washing, which is undesirable.

Note that if the particle size is too small, such as 100 μm or less, caking of the detergent may occur. In this case, it is appropriate to add the fine powder by agglomerating it using an appropriate inorganic coating agent such as calcium carbonate, white carbon, or zeolite, or an organic binder such as a nonionic activator or polyethylene glycol. It is.

The amount of the additive of the present invention added to the detergent is preferably in the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight as a quaternary ammonium salt, based on the detergent.

Effects of the Invention According to the granular detergent additive of the present invention, di-long chain alkyl 4
By blending a copolymer of a specific acrylamide monomer, a carboxyl group-containing monomer, and a sulfone group-containing monomer with a class ammonium salt, it has an excellent flexibility imparting effect not only to synthetic fibers but also to cotton. It is possible to suppress the occurrence of recontamination, and it is possible to prevent darkening of clothes after washing.

In addition, according to the production method of the present invention, the above-mentioned pulverized copolymer is added to the molten quaternary ammonium salt and uniformly dispersed with high shear force, thereby preventing the formation of coarse particles and increasing the productivity. It is possible to produce granular detergent additives that are flexible and have excellent softening effects.

Example 1 Dihydrogenated beef tallow alkyldimethylammonium chloride powder (purity 94%) with an average particle size of 70 μm was heated to 120 μm in an oil bath.
℃ and stirred. The copolymer powder [component (b)] shown in Table 1 was added thereto, stirred for 30 minutes, and then cooled to room temperature. Here, the copolymer used was one prepared by aqueous solution polymerization, dried, and pulverized with a jet mill to have an average particle size of 4 μm and a moisture content of 7%.

The obtained block is crushed to have an average particle size of 50 to 100 μm.
A granular material of
A 75% aqueous solution of Ma=40o) was sprayed to form an agglomerate to obtain a granular detergent additive having an average particle size of 400 to 600 μm.

These additives were added to a granular detergent having the following composition in an amount of 4% by weight as a quaternary ammonium salt. Further, as a control, only dihydrogenated beef tallow alkyldimethylammonium chloride was similarly blended (Nα1 in Table 1). These compositions were washed and their softening effects and restaining properties on cotton fabrics were measured and are shown in Table 1.

Jukuten I “1 Commandment Linear Alkylbenzene Sulfonic Acid Sodium (C□2 Alkyl) 20wt%
Sodium silicate 10wt%
Soda carbonate 10wt% zeolite (A-type zeolite, average particle size 0.7μm) 1
5wt% carboxymethyl cellulose 0.
6wt% soap (beef tallow fatty acid)
0, 7wt% polyethylene glycol (molecular weight 600
0) 0.5 sit% sodium citrate
0.8wt% fluorescent agent 0.5
wt% fragrance 0.2
wt% Sodium sulfate, water Balance Softness imparting effect testing method Nylon tricot cloth (30 denier) 30g
x4 pieces acrylic jersey cloth 90g
x2 cotton towels 80g
2 pieces of bleached cotton cloth 50gX4
A test cloth consisting of 85g x 4 sheets of cotton knitted cloth was washed for 15 minutes using the above granular detergent and tap water at 60'C, and then rinsed three times for 3 minutes each using tap water at 60'C. Preprocess. Next, this test cloth was placed in a jet-type household electric washing machine, and was washed with a composition containing the above-mentioned granular detergent and various additives and tap water at 25°C at a detergent concentration of 0.13% and a bath ratio of 30 times. After washing for 10 minutes under these conditions and dehydrating for 1 minute, rinsing with tap water at 25° C. for 3 minutes and dehydrating for 1 minute was repeated twice. After drying, the test fabric was air-dried for 24 hours, then at 25°C and 65% RH.
The air-dried test fabric was conditioned under the following conditions.

A cotton towel was taken out from the test cloth obtained in this way, and its feel was judged by five judges, and the flexibility imparting effect of the additive composition was evaluated based on the average of the five judges. The feel was evaluated based on the following criteria and compared with the feel of a cotton towel obtained by the same procedure as above except that a detergent containing no additives was used.

Extremely soft 5 points Quite soft 4 points Soft 3 points Slightly soft 2 points Slightly soft 1 point' Test method Seven skin shirts worn for two days and a 25 x 8 cm piece of cloth sewn onto the collar of the shirt to remove stains from the collar. 30 pieces of cotton, tet cotton, nylon, acrylic, and polyester cloth for restaining test were placed in a household electric washing machine, and a composition containing the detergent and each additive was added to the detergent and washed with tap water at 25°C. Washing was carried out for 10 minutes using a detergent concentration of 0.133% and a bath ratio of 30 times. Next, after dehydrating for 1 minute,
The procedure of rinsing with 5° C. tap water for 3 minutes and dehydrating for 1 minute was repeated twice.

The reflectance of the cloth for the restainability test was measured using a reflectance meter (Nippon Heavy Industries, Colorimeter Model 100IDP),
The recontamination property was evaluated by determining the difference ΔR from the reflectance before cleaning. Visual identification is possible when ΔR is 1 or more. Table 1 shows the values of the polyester with the highest restaining property.

Example 2 Using di-long-chain alkyldimethylammonium methosulfate (purity 92%) as a quaternary ammonium salt, the same treatment as in Example 1 was carried out, and the compounds shown in Table 2 were added in the same manner as in Example 1. Add the copolymer powder to create a melt. This melt was placed in a countercurrent air flow at 15°C at a discharge pressure of 40K.
Spray cooling was performed at g/al to obtain particles with an average particle size of 150 to 300 μm.

Powdered zeolite (A-type zeolite, average particle size 2μ) is added to this.
m) was blended with 374 of the anti-spray coolant to obtain a granular detergent additive. The obtained additive was evaluated in the same manner as in Example 1, and the results are shown in Table 2.

(Left below) Example 3 Using a propeller-type stirrer, a copolymer was dispersed in a quaternary ammonium salt melt under the conditions shown in Table 3.
The mixture was pulverized to obtain a granular detergent additive. In addition, the abbreviations in the table indicate the following copolymers and quaternary salts, respectively. Here, the numbers in parentheses are copolymerization ratios.

A Niacrylamide (go) Sodium Niacrylate (10
): 2-acrylamide-2-methylpropanesulfonic acid Na (10) B Niacrylamide (60) Niacrylic acid Na (10
): Sodium 2-acrylamido-2-methylpropanesulfonate (30) C Ni-hydrogenated beef tallow alkyl dimethyl ammonium chloride D Ni-distearyl dimethyl ammonium chloride Regarding the obtained additive, the dispersibility of the copolymer and the amount of coarse particles formed were evaluated. It was evaluated as follows, and the results are shown in Table 3.

``Gei J vote 1 good example'''' Illusion 1 All of the obtained additive particles were observed using a polarized light microscope photograph,
The dispersibility of the copolymer was evaluated.

O: Good dispersion X: poor dispersion ○: 0.01% or less x: More than 0.01% (Margin below)

Claims (1)

[Claims] 1. (a) Di-long chain alkyl quaternary ammonium salt: 99.
8 to 50% by weight and (b) a copolymer of an acrylamide monomer represented by the following general formula (I), a carboxy group-containing monomer, and a sulfone group-containing monomer: 0.2 to 50% by weight ▲Math. There are chemical formulas, tables, etc. ▼ (I) [In the formula, R^1, R^2, R^3, R^4, R^5, A
, B, Y^1, Y^2, l, m, and n represent the following, respectively. R^1, R^4, R^5: hydrogen or methyl group R^2,
R^3: hydrogen, substituted alkyl group such as an alkyl group or hydroxyalkyl group A: alkylene group having 0 to 5 carbon atoms B: alkylene group having 0 to 5 carbon atoms, benzene ring unsubstituted or substituted with an alkyl group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [x, y are integers from 0 to 5] or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Y^1, Y^2: Hydrogen, alkali metal or alkaline earth metal l , m, n ratio; l:m:n=(98.9~50):(
1-50):(0.1-20)] A granular detergent additive characterized by containing the following. 2. Add a copolymer of an acrylamide monomer represented by the following general formula (I) having an average particle size of 150 μm or less, a carboxyl group-containing monomer, and a sulfone group-containing monomer to the melt of the di-long-chain alkyl quaternary ammonium salt. Add,
A method for producing a granular detergent additive, which comprises uniformly dispersing the copolymer in the melt at a shear rate of 50 to 150 l/sec, and then powdering it.