JPS6131499A - Laundry aid 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 The present invention relates to laundry aid compositions containing cationic surfactants, particularly for use with detergents containing anionic surfactants. The present invention relates to laundry aid compositions.

In general, the washing process using a washing machine involves pouring water, washing, dehydration,
It consists of rinsing and dehydration, and laundry aids such as fabric softeners are added after washing to maximize their effectiveness.

In the past, it was common for housewives to operate each process of a washing machine in sequence, and in such cases, first add detergent to complete the washing process, then add fabric softener,
Adding laundry aids such as bleach and starch agents was not very burdensome and there was no great resistance. However, recently, semi-automatic and fully automatic washing machines have become popular.
As time went on, housewives were freed from intermediate operations, but they were not completely freed due to the addition of auxiliary agents.

In order to use a laundry aid by incorporating it into a detergent composition in advance, the active ingredients are protected during washing, are adsorbed to the clothes and brought into the rinsing process, and are added to the rinsing solution at the same time as rinsing begins. It is necessary to elute the

41 stores in one room that the moonlight is about to decide.

Coating the laundry aid with a polymer that is virtually insoluble in alkaline cleaning solutions but soluble in neutral rinsing fluids protects the laundry aid components from the alkaline cleaning fluid during washing, and protects them during the rinsing process. The auxiliary component can be eluted into the rinsing solution, which allows the auxiliary agent to exert its effectiveness effectively, and the laundry auxiliary agent, which conventionally had to be added during the rinsing process, can be effectively incorporated from the beginning. This eliminates the need for adding auxiliary agents.

Several polymers whose solubility changes with pH have been known for a long time. For example, polyvinyl acetal diethylaminoacetate is insoluble in water in a neutral range, but soluble in water in an acidic range from pH 5.8. In addition, the copolymer of vinyl pyridine and acrylic acid is soluble in water with a pH of 7.4 or lower and a pH of 7.4 or higher, and is insoluble in water in the p+ range between 4 and 7. However, it is insoluble in alkaline water. Until now, no polymers were known that are soluble in neutral to acidic water and whose solubility changes over a narrow pH range. The auxiliary agent was first proposed in Japanese Patent Application No. 58-247997.

However, when a fabric softener is used as a laundry aid, there is a problem in that its effectiveness is reduced.

Since cationic surfactants such as quaternary ammonium salts are used as fabric softeners, the cationic surfactants are consumed by the anionic surfactants remaining in the rinsing solution. As a result, the effect of adding the auxiliary agent is reduced, and an excess of two softening agents must be added.

Means for Solving the Problems The present invention aims to provide a laundry aid composition that is stably protected in an alkaline washing solution during washing, is eluted in a rinsing solution, and exhibits a sufficient additive effect. purpose.

That is, the laundry aid of the present invention includes the following (A), (B) and ( C) It is characterized by being coated with a copolymer containing three monomers.

(A) At least one basic monomer represented by the general formula ■
Species R1 and R2 are each an alkyl group having 1 to 3 carbon atoms, and X is an integer of 1 to 4.) (B) at least one water-insoluble or poorly water-soluble monomer and (C) at least one water-soluble monomer. The above copolymers are virtually insoluble in alkaline aqueous solutions and soluble in neutral to acidic aqueous solutions, but are used as laundry aids in alkaline water with a pH of about 9.5 or higher. is insoluble and soluble in slightly alkaline or acidic water with a pH of about 8.5 or less, and preferably has a large solubility ratio in the presence of a surfactant. From this point of view (
a) The copolymerization ratio of the copolymer is expressed by the general formula (II) / (
k + Q 10m) = 0.05-0.8, Q/(k
+Q0m)=0.05 to 0.8, preferably k/(k+Q+m)=0.
05~0.6, Q/(k+Q+m)=f1.
It is 1 to 0.7.

(In the formula, B umbrella and CI+ represent structural units derived from monomers (B) and (C), respectively.) In addition, the degree of polymerization +R+m is suitably 100 to 50,000, preferably 300 to 20,000. It is.

Moreover, as a composition example of a more suitable copolymer, one shown in the following general formula (III) can be mentioned.

R: H or -CH3 R1: 01-C3 alkyl group R'': C1-C3 alkyl group x: Integer from 1-4 R': H or C1-C4 alkyl group R': H or C□-C4 an alkyl group or -GOOR11(R
" is an alkyl group of C~C1゜) R' C00R12, -0COR12 (R" is an alkyl group of C~C□) -CGHSR': H or 01
~C4 alkyl group R7, R': may be the same or different 01~C4 alkyl group J: Integer from 1 to 4 R': H or C□~C4 alkyl group R'' 0
H1-CN, -(CH2)yOH (y=1 to 4)
, 10 ON (R13 and R'' are the same and R'' may also be different H or a C1 to C11 alkyl group),
-Coo(CH2CH20)PH1-COO(CH2C
H2) PCH, (however, p = 1 to 30) k / (k + Q + m + n) = 0.05-0.8
Q/Ck+n +m+n) =0.05-0.8m
/ (k+Q +m+n) =0.05-0.8n
/ (k+Q++n+n) = O~0.5 Among these, more preferred copolymers are shown below, divided into cases in which the fourth component is included (n≠0) and cases in which the fourth component is not substantially included. .

(I) When containing a fourth component R: H, -CH.

R1: -CH3 or -C2HS R2: -CH, or -○, H.

R": H R': Hl-CH3, -COOR"(R" is 01-C
I+ alkyl group) R': -COOR"(R" is a C1-C1l alkyl group) or -0 COCR.

R': Hl-CH3 R7, RII: -CH3, -C,H.

J: 1-4 Rg:Hl-CH3 R” Knee Coo (CH, CH, 0) PH (however, p=
1 to 5), T-COO(CH2CH20)PCH3 (however, p=1
~5), -CON(CH3)2, -cON(C2H5
)zk/(k+Q+m+n)=0.05~0.5
,Q/(k+Q+mten)=0.1~0.6
5, m/(k+Q+m+n)=0.1-0.
6, n / (k + m + n) = 0.01 ~ 0.
5(2) When the fourth component is not substantially included (n=o)R:
H, -CH3 R1 knee CH3, -C2H9 R2 knee CH,, -C2H5 R3:H R':Hl-CH3, -GOOR"(R'JtC□~
C8 alkyl group) R5: -COOR"(R" is a C1-C alkyl group) or -0C0CR.

R': Hl-CH.

R', R': -CH,, -C2H,.

J: 1~4k/(k+11+m)=0.05-0.6, Q
/ (k + m) = 0.1~0.7, m/ (
k10+m)=0.1-0.7 Further, specific examples of each monomer component (A), (B), and (C) are as follows.

(A) The basic monomer represented by the general formula (I) (
The second component of general formula
, N-dimethylaminomethyl, N-acrylate, N-dimethylaminobutyl, N-acrylate, N-dimethylaminopropyl, N-methacrylate, N-dimethylaminoethyl, N-methacrylate, N-dimethylaminomethyl, N-methacrylate , N-dimethylaminobutyl, N methacrylate
, N-dimethylaminopropyl, N-acrylate, N-diethylaminoethyl, N-acrylate, N-diethylaminomethyl, N-acrylate, N-diethylaminobutyl,
N-acrylate, N-diethylaminopropyl, N-methacrylate, N-diethylaminoethyl, N-methacrylate,
Examples include N-diethylaminomethyl, N-methacrylate, N-diethylaminobutyl, N-methacrylate, and N-diethylaminopropyl, which may be used alone or in combination.
Used in combination with more than one species.

The water-insoluble or poorly water-soluble monomer (B) (the first component of general formula , methacrylate, crotonate, itaconate, vinyl acetate, and styrene. When using each alkyl ester of acrylic acid, methacrylic acid, crotonic acid, and itaconic acid as the monomer (B), those having an ester-bonded alkyl group with a carbon chain length of 1 to 18 can be used, but if the alkyl chain is long In this case, the dissolution of the resulting copolymer in a slightly alkaline aqueous solution becomes slow, so it is more preferable that these alkyl groups have 1 to 8 carbon atoms. Particularly preferred representative examples include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and ethyl methacrylate.

The water-soluble monomer (C) (the third and fourth components of the general formula (2)) is a component that contributes to expanding the soluble PH region of the pH-sensitive copolymer, and specific examples thereof include N, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N.

N-dimethylaminomethylacrylic acid (or methacrylic acid) amide, N,N-dimethylaminoethyl acrylic acid (or methacrylic acid) amide, N,N-dimethylaminobutylacrylic acid (or methacrylic acid) amide,
N,N-dimethylaminoacrylic acid (or methacrylic acid) amide, 2-hydroxyethyl acrylic acid (or methacrylic acid), 2-hydroxypropylacrylic acid (
Alternatively, one or more types selected from esters of methacrylic acid), polyethylene glycol, or methoxypolyethylene glycol (in each case, the average number of added moles of ethylene glycol p = 1 to 30) and acrylic acid or methacrylic acid can be mentioned.

The copolymer used in the present invention can be obtained by conventional radical polymerization under normal pressure or increased pressure. Acetone and the like can be used as the polymerization solvent, and azobisisobutyronitrile and the like can be used as the polymerization initiator.

The polymerization temperature and time vary depending on the polymerization solvent and monomer combination used, but generally 5 to 20 hours at 40 to 90°C is appropriate.

In the present invention, a mixture of (a) a cationic surfactant and (b) a cationic polymer and/or a nonionic polymer is coated with this copolymer.

Representative examples of cationic surfactants include di-long-chain alkyldimethylammonium salts, 1-methyl-1-long-chain alkanoylaminoethyl-2-long-chain alkylimidazolinium salts, and these salts include: chloride,
Methyl sulfate, ethyl sulfate and the like are preferred. These cationic surfactants are used as softening agents, and can also be used in combination with fatty acid salts. The cationic surfactant is preferably used in the form of powder with a particle size of 200 μm or less.

Examples of cationic polymers used include polydimethylaminoethyl methacrylate, copolymers of dimethylaminoethyl methacrylate and acrylamide, and cationically modified polymers of polyacrylamide.As nonionic polymers, polyacrylamide and partially hydrated polyacrylamide are used. Examples include decomposition products. The molecular weight of cationic polymer and nonionic polymer is 500,000 to 1
,0 million range is appropriate, preferably 1 million to
1,000,000. Moreover, it is preferable to use the cationic polymer and the nonionic polymer in the form of powder particles with a particle size of 200 μm or less.

The amount of the cationic polymer and nonionic polymer is 1 to 50 parts by weight per 100 parts by weight of the cationic surfactant.
Parts by weight are appropriate, preferably 2 to 10 parts by weight.

Although any suitable method may be used to prepare a mixture of a cationic surfactant and a cationic polymer or a nonionic polymer, a mixture of the two may be granulated using the coating copolymer of the present invention as a binder. You can also do that.

To produce the laundry aid composition of the present invention, for example, 1 to
The coating copolymer is dissolved to a concentration of 20% by weight, and then coated onto particles of a mixture of a cationic polymer or a nonionic polymer and a cationic surfactant prepared in advance in a pan or fluidized bed. do it.

Alternatively, a 30 to 60% by weight solution of the coating copolymer in an organic solvent, a cationic polymer or nonionic polymer, and a cationic surfactant are mixed, and then a portion of the organic solvent is removed under reduced pressure. A laundry aid composition coated with the copolymer may be prepared by pulverizing the particles to a predetermined particle size and completely removing the organic solvent under reduced pressure. The coated detergent aid obtained in this way has a particle size of 50 to 500 μm.
It is appropriate to prepare it so that it becomes.

In addition, the coating amount is 5 to 50 wt% of the laundry aid particles.
It is appropriate to do so.

Effect According to the present invention, the cationic surfactant is coated with a pH-sensitive copolymer, so that the cationic surfactant is protected in the alkaline washing liquid, and is eluted in the rinsing liquid and does not stick to clothes. It imparts flexibility and antistatic ability to the material. At this time, the cationic surfactant is attacked and consumed by the anionic surfactant remaining in the rinsing solution, but the presence of the cationic polymer and/or nonionic polymer prevents the consumption of the cationic surfactant. It is effectively prevented and the desired flexibility imparting effect is achieved.

As described above, the detergent additive composition of the present invention is especially effective when added to a granular detergent containing an anionic surfactant, and it is convenient to use it by blending it into a detergent in advance. Of course, store it separately from the detergent composition.
They may be individually added to the washing liquid during washing. Moreover, it can also be used alone without being used in combination with a detergent.

Effects According to the present invention, the cationic surfactant is protected in the cleaning solution and is eluted during the rinsing step to exert its effects. Furthermore, since the anionic surfactant remaining in the rinsing solution is prevented from being consumed, a large addition effect can be obtained with a small amount.

-18 = 11 animals Example 1 40% by weight acetone solution of copolymer having the structure shown below 4
5 parts by weight, 45 parts by weight of distearyldimethylammonium chloride powder (particle size 20-100 μm), 5 parts by weight silica powder, partial hydrolyzate of polyacrylamide (hydrolysis rate 5%, molecular weight 5 million, particle size 20-100 μm)
) were mixed and the pressure was reduced to remove acetone. Then, the mixture was crushed and sieved to a particle size of 35 to 150 mesh. Subsequently, these were placed in a pan and a 5% by weight acetone solution of the copolymer was sprayed to coat the pans so that the solid content was 5% by weight, thereby preparing a laundry aid composition.

(k/(k10 m+n)=0.35. D/(k
+Q 10m+n)=0.25゜m/(k10 10m+
n)=0.3. k+ Q +m+n=2,000~3
,000) Laundry aid composition 2 thus obtained
g and 40 g of commercially available detergent (heavy detergent whose main ingredient is sodium alkylbenzene sulfonate) in a washing machine (water volume: 30 g).
Q), the clothes (1 kg of cotton underwear, 0.3 kg of acrylic shirt) were washed for 10 minutes, and then transferred to a dehydration tank for dehydration. The dehydrated clothes were placed in a bathtub, and as a rinsing step, the operation of adding water from Step 31 and stirring for 3 minutes to dehydrate the clothes was repeated twice, and then dried indoors.

Example 2 In Example 1, a copolymer of dimethylaminoethyl methyl acrylate and acrylamide (degree of cationization 30 mol%,
The same operation as in Example 1 was repeated except that a particle having a molecular weight of 5 million to 6 million and a particle size of 20 to 100 μm was used.

Comparative Example 1 The same operations as in Example 1 were repeated except that the entire amount of polyacrylamide partial hydrolyzate in Example 1 was replaced with silica powder.

Comparative Example 2 Clothes were washed in the same manner as in Example 1 using only a commercially available detergent without using the laundry aid composition.

The softness of the cotton towels obtained as described above was evaluated by Scheffe's paired comparison method.
A relative comparison was made based on the judgment. The results are shown in Figure 1.

[Brief explanation of drawings]

FIG. 1 is a graph showing the effect of imparting flexibility in Examples.

Claims (1)

[Claims] 1. A mixture of (a) a cationic surfactant and (b) a cationic polymer and/or a nonionic polymer, (A) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc. ▼(I) (wherein R is hydrogen or a methyl group, R^1 and R^2 are each an alkyl group having 1 to 3 carbon atoms, and x is an integer of 1 to 4) A laundry product coated with a copolymer containing at least one basic monomer, (B) at least one water-insoluble or poorly water-soluble monomer, and (C) at least one water-soluble monomer. Auxiliary composition.