JPS63113100A - Neutral detergent composition for clothes - Google Patents

Abstract

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

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a neutral liquid detergent composition for clothing. There was the problem of so-called felt shrinkage, where clothing shrinks due to strong mechanical forces. For this reason, the so-called hand-washing method has been adopted for washing woolen products, in which water or lukewarm water is poured into a container such as a basin, the detergent is dissolved, and the clothes are immersed.

However, even with this method, the problem of felt shrinkage still occurs, and there is also the problem that hands are immersed in relatively thick washing liquid for a long time, which tends to cause roughness.

In order to minimize these problems, wool detergents do not contain the alkaline agents that are included in 5-heavy detergents, and are neutral in liquid (according to the Household Product Quality Labeling Act, neutral means pH
is maintained within the range of 6 to 8). In addition, nonionic surfactants have been widely used as cleaning bases for detergents, but liquid detergents using these surfactants have a problem in that their pH decreases when stored at high temperatures for long periods of time.

[Means for solving problems]

Therefore, the present inventors investigated the occurrence of felt shrinkage and p■
As a result of intensive research to prevent this decline, it was discovered that the above problems could be solved by blending an organic polymer latex with a hydroxycardate, and the present invention was completed.

That is, the present invention provides the following components (, ), (b) and (C
), (&) general formula % formula % (wherein, R is an alkyl group having 10 to 20 carbon atoms, an alkenyl group, or an alkylphenyl group having 6 to 12 carbon atoms in the alkyl group, and n is a number of 1 to 20 5 to 50% by weight of a nonionic surfactant represented by
．． 01 to 10% by weight, (c) 0 hydroxycardate having 2 to 6 carbon atoms,
0.005 to 0.25% by weight of a neutral liquid detergent composition for clothing.

The nonionic surfactant component (Jl) used in the present invention is represented by the above general formula.

If the number of moles of ethylene oxide added, represented by n, exceeds 20, the foaming power and detergency of the detergent will be reduced. Among these, those with an added mole number of 6 to 16 are desirable.

The (-) component is blended in the composition in an amount of 5 to 50% by weight (hereinafter abbreviated as %), usually 10 to 40%.

The organic polymer latex of component (b) is produced by polymerizing a water-insoluble polymerizable monomer in a microemulsion or solubilized state. In this microemulsion-LtQtd, a nonionic surfactant is used to select an appropriate temperature near the phase inversion temperature. This can be achieved by combining it with Further, the solubilized state can be achieved by using a large amount of surfactant relative to the polymerizable monomer.

Among these, it is particularly preferable to use a nonionic surfactant, set the polymerization temperature near the phase inversion temperature, and set the interfacial tension between the monomer and water to be ldyn/α or less, more preferably 0.
This is a method in which polymerization is carried out in a microemulsion state by setting the polymerization concentration to 5 dyn·/1 or less.

Below, the method for producing the polymer latex used in the present invention will be further explained together with the polymerizable monomers used in the production.

Polymer latex is produced by using an aqueous surfactant solution in which the polymerizable monomer is solubilized in micelles formed by the surfactant, and the interfacial tension between the monomer and water is l dyn・/α or less. As the zero-polymerizable monomer obtained by polymerizing the polymerizable monomer while maintaining the microemulsion state, all known monomers used in emulsion polymerization can be used, such as ethylene, zoropyrene, etc. Ethylenically unsaturated monomers such as , isobutyne, and butene-1; Aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, 710-gated styrene, and zopinylbenzene; Ethyl acrylate, phthyl acrylate, and acrylic acid 2
- Acrylic acid esters in which the alkyl group has 1 to 20 carbon atoms such as ethylhexyl; 1 to 2 carbon atoms in the alkyl group such as methyl methacrylate, butyl methacrylate, lauryl methacrylate, etc.
0 methacrylic acid esters; vinyl esters such as vinyl acetate and vinyl zolopionate; ethyl vinyl ether,
Vinyl ethers with 1 to 20 carbon atoms such as butyl vinyl ether; Vinyl ketones with 1 to 20 carbon atoms such as methyl vinyl ketone and ethyl vinyl ketone; Vinyl cyanide monomers such as acrylonitrile and methacrylate trile; vinyl chloride and bromide vinyl, vinylidene halodane and vinylidene hyhalogenide such as vinylidene chloride and vinylidene bromide; 1.
Examples include aliphatic conjugated cyanogens such as 3-butacyan and 2-methyl-1,3-butacyan. These monomers can be used alone or in combination of two or more, and among them, α, acrylate, methacrylate, etc.
Preferably, β-unsaturated carbo/acid ester monomers are used. Furthermore, maleic anhydride or a water-soluble monomer, styrene sulfonic acid ([), vinylnaphthalene sulfonic acid (salt), acrylic acid (salt), heptamer having a cationic group or tertiary amino group, etc. are added to the above monomer. Preferably, those obtained by addition and copolymerization are used.

The monomer having a cationic group or a tertiary amine group (hereinafter abbreviated as "nitrogen-containing monomer") has the following general formula (a) or (a) (R2 and (a) (in the formula % 81% R2 and R8 is an alkyl group or a substituted alkyl group having 1 to 8 carbon atoms, or hydrogen, and the three groups may be the same or different, or the king of the two groups may be connected together with the adjacent nitrogen atom to form a girisol group or an imidazoyl group. An ethylenically unsaturated nitrogen-containing monomer having a cationic group or a tertiary amino group may form a heterocyclic ring, cycloalkyl group, or heterocycloalkyl group such as (where Y represents a halogen or an acid residue) Examples include monovinylpyricines such as vinylpyricine, 2-methyl-5-vinylbilicine, and 2-ethyl-5-vinylbilicine; N,N-dimethylaminostyrene, N,N
- Styrenes having a sialkylamino group such as dimethylamine methylstyrene: N,N-dimethylaminoethyl methacrylate, N,N-dimethylamine ethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate, N,
N-dimethylaminozolopyl methacrylate, N,N-
Sialkylamino group-containing esters of acrylic acid or methacrylic acid such as dimethylaminozolobyl acrylate, N,N-diethylaminozorobyl methacrylate, and N,N-zoethylaminoglobyl acrylate; 2-
Vinyl ethers having a sialkylamino group such as dimethylaminoethyl vinyl ether; N-(N'.

N'-dimethylaminoethyl) methacrylamide, N-
(N',N'-dimethylaminoethyl-acrylamide, N-(N',N'-diethylaminoethyl)methacrylamide, N-(N').

N'-diethylaminoethyl)acrylamide, N-(
N',N'-dimethylaminozorogyl)methacrylamide, N-(N',N'-dimethylaminozorogyl)acrylamide, N-(N'.

N'-diethylaminozorobyl) methacrylamide, N
Examples include acrylamide or methacrylamide having a sialkylamino group such as -(N',N'-diethylaminonolopyl)acrylamide. Furthermore, they can be added to alkyl halides (alkyl group having 1 to 18 carbon atoms, chlorine, bromine, iodine as halogen), benzyl halides such as benzyl chloride or benzyl bromide, alkyl or aryl sulfonic acids such as methanesulfo/acid, benzene. Sulfonic acid or alkyl ester of toluenesulfonic acid (alkyl group having 1 to 1 carbon atoms)
8), and those quaternized with known quaternizing agents such as sialkyl sulfate (alkyl group having 1 to 4 carbon atoms), and these do not necessarily all need to be quaternized products or salts. It may be in the form of a tertiary salt as shown in general formula (a). This tertiary amino group has weak cationic properties in an aqueous solution (neutral to acidic solution).

The most preferable method for producing polymer latex is to prepare an aqueous solution by adding a surfactant to a reaction vessel filled with water, and heating and stirring this at a temperature near the phase inversion of the surfactant micelles. , the interfacial tension between the monomer and water is l dy
n・7cm or less, preferably 0 to 0.5 dyne/
Initiate polymerization by adding an aqueous solution of a polymerizable monomer and, if necessary, a radical polymerization initiator while maintaining the state of crn, and then remove the interfacial tension between the surfactant aqueous solution and the monomer phase to outside the above range. In this method, polymerizable monomers are gradually added to prevent the polymerization from occurring.

Here, as the radical polymerization initiator, for example, persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, 2,2'-azobis(2-amizononoronoq), 1,1'-azobis(cyclohexanecarboxylate), etc. Mineral acid salts such as nitrile), azo compounds such as azobisciatubarelic acid and its alkali metal salts and ammonium salts, redox systems such as tartaric acid-hydrogen peroxide, a-garitol peroxide, ascorbic acid-peroxide, etc. Among these, when using a cationic surfactant as a polymerization system, 2,2'-azobis(2-amizonozolo, Qn) mineral acid salt is used, and for other polymerization systems, persulfuric acid is used. The amount of the 0-razole polymerization initiator in which the salt is preferably used is 0.1 to 5 parts by weight per 100 parts by weight of the monomers constituting the polymer;
Preferably it is 0.1 to 3 parts by weight.

The reaction temperature is the highest temperature in the solubilization region near the phase inversion temperature, and is preferably in the range of 50 to 90°C. The time required for polymerization varies depending on the type, composition, concentration of monomer, concentration of radical polymerization initiator, polymerization temperature, etc., but usually
~50 hours #! Preferably.

Among the polymer latex obtained in this way, in the present invention, the average particle diameter is o, o o s ~ 0.2.
It is desirable to use a polymer latex in which the particle diameter is .mu.m and 95% by weight or more of particles fall within this range. In addition, 0.0 % of heptad units having a cationic group or a tertiary amino group are added to the polymer.
Particularly preferred are polymeric latexes having a content of 0.05% to 55%.

Furthermore, among these polymer latexes, those having a glass transition temperature (Tg) of 300 K or less are desirable from the viewpoint of imparting flexibility.

Component (b), the polymer latex, is the residue left after water is distilled off, that is, as an organic polymer, o,
oi to 10i amount% (hereinafter simply expressed as %), especially 0.0
It is preferable that numbers 5 to 59 are also blended.

Examples of the hydroxycal and zenate salts having 2 to 6 carbon atoms used in the present invention include sodium, potassium, and alkanolamine salts such as glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid. . Among them, lactate is the most preferable because it has the best effect of preventing a decrease in pH and does not impede the stability of the system.

The blending amount of component (c) is 0.005 to 0.25%.
If it is less than 0.005%, the pH drop prevention effect is insufficient (,
If it exceeds 0.25%, the soft finishing effect will be inhibited.

Organic acid salts other than hydroxycarboxylic acid salts, such as acetic acid,
Lower aliphatic monocarboxylic acid salts such as butyric acid, cicarpic acid salts such as oxalic acid and succinic acid, or inorganic salts such as phosphates cannot prevent the pH from decreasing.

In addition to the nonionic active agent, the liquid detergent composition for clothing of the present invention may contain one or more of the following various surfactants as long as they do not impede the effects of the present invention.

Among surfactants, anionic surfactants include linear or branched alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkanesulfonates, and α-sulfo fatty acids. Examples include salts or esters, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acylamino acid type surfactants, alkyl or alkenyl phosphate esters or their salts.

In addition, examples of amphoteric surfactants include carboxy or sulfobetaine type surfactants, and examples of nonionic surfactants include -lyoxyalkylene alkyl or ha alkenyl ether, d-s, 4-xyethylene alkylphenyl ether, and higher Examples of the cationic surfactant include fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, fatty acid ester, fatty acid glycerin monoester, and alkylamine oxide. Examples of the cationic surfactant include quaternary ammonium salts.

゛Other customary auxiliary additives may be added to the composition of the present invention, such as: Lyacrylic acid, I? Polyelectrolytes such as liaconitic acid:? Non-dissociated polymers such as lipinyl alcohol, -lipinylpyrrolidone; Divalent metal ion scavengers such as salts of organic acids such as diglycolate; Inorganic electrolytes such as sulfates: ?
Anti-recontamination agents such as lyethylene glycol and carboxymethyl cellulose; protease, amylase, and dino-9
Enzymes such as enzymes and cellulases; Enzyme stabilizers such as calcium chloride; Antioxidants such as tertiary-butylated hydroxytoluene and styrenated cresol; Lower alcohols such as ethanol, benzenesulfonate, and p-toluenesulfonate Solubilizers such as lower alkylbenzenesulfonates, recalls such as propylene glycol, acetylbenzenesulfonates, acetamides, pyridine dicarboxylic acid amides, benzoates or urea; fluorescent dyes, blue tinting agents, Flavors etc. can be added.

[Effect]

Generally, felt shrinkage occurs even when mechanical force is applied to water alone, but it is further accelerated in an aqueous surfactant solution, that is, a detergent solution. It is not necessarily clear why the detergent composition of the present invention has such an effect of preventing felt shrinkage, but it is probably because the polymer latex adheres to the fiber surface and prevents the fibers from getting entangled with each other.

〔Effect of the invention〕

The cleaning composition of the present invention does not cause felt shrinkage, and also maintains stamina during long-term storage, especially storage at high temperatures.
It is characterized by no decrease in pH.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

Reference example 1 2002% water in a SE/Q rubble flask with a stirrer? Lioxyethylene (35) nonylphenyl ether 1a t
s i[0.6 t of ammonium acid was charged, the mixture was sufficiently purged with nitrogen, heated to 62°C with stirring, n-butyl acrylate 90,5 F was added dropwise over about 2 hours, and polymerization was further carried out for 6 hours to form a latex. I got an A.

Reference Examples 2 to 8 Latexes B to G were obtained in the same manner as in Reference Example 1, except that n-butyl acrylate was replaced with the seven-mer composition shown in Table 1. The physical properties of the latexes obtained in Reference Examples and Reference Example 1 are also shown in Table-1.

Margin Example 1 The liquid detergent shown in Table 2 was prepared below, and the felt shrinkage and finish flexibility when washed using this, as well as the change in pH when the liquid detergent was stored, were investigated. Table the results.
Shown in 2.

(Test method) 1. Measurement of felt shrinkage rate due to washing: (a) After soaking a raw wool cloth with a prepared size 10XIG scratch on the three sides of the test cloth using a lock sewing machine in tap water at room temperature for 30 minutes, Dehydrate for 30 seconds in a dehydration tank, then dry flat on a net at 20°C.
The humidity was controlled for 4 hours or more in a room with 65% RH. Four marks were made on this cloth with an oil-based marker and a number was attached to each. After adjusting the humidity again at 20℃ and 65%RH, measure the length. r ” (horizontal), and this length was taken as the original length (n, yt).

(2) Washing method Terg-0-Tom@t@
r), and combine the three test fabrics obtained in (l) into one ? The clothes were washed by placing them in a washing machine and spinning at 120 rpm for 10 minutes. The concentration of each detergent was 0.25%, and the water temperature was 20°C. As for the first rinse? The second time, I rinsed my hands with running water in a hand-washing tub. Next, the sample fabric was attached to the wall of the dehydration tank of the washing machine and dehydrated for 30 seconds, then placed on a net and dried flat.
The humidity was controlled at 0° C. and 65% RH for 4 hours or more.

Furthermore, measure the length between the marks made in (a) above again, vertically.7. ．． 7 horizontal bv.

b'S) % From this, the felt shrinkage rate and area shrinkage rate were calculated according to the following equations.

[Calculation of shrinkage rate (from IWSTM9)] R, M, : Measured values before washing (original length) W, M, : Measured values after washing [Calculation of area shrinkage rate] W, S, XL, S.

Area shrinkage rate (to)==W, S, +L, S, -□W, S
, : Shrinkage rate in the horizontal direction, S, : Shrinkage rate in the vertical direction Z pH measurement According to JIS Z8802, the pH immediately after blending at 25℃ and the pH after storage for 1 month at 5.30.40℃. It was measured using a glass electrode pH meter.

λ Softness test Water temperature: 30℃, 30cj with 5t of 0.25% detergent aqueous solution
Five Ex60cIL acrylic chassis or one wool sweater for recontamination prevention testing were hand washed. After air-drying the acrylic chassis or wool sweater,
A tactile test was conducted by a number of judges, and the results were ranked as follows.

○: Finished softer than the standard detergent.

Δ: 0 with the same finish as the standard detergent ×: Finished harder than the standard detergent.

As shown in Margin Table 2 below, compared to cleaning with tap water only,
Washing with an aqueous activator solution accelerates felt shrinkage. However, by adding latex A, B, C, D, E, F, and G, these shrinkages are reduced to the level of tap water.Also, from the viewpoint of flexibility, high Tg latex such as styrene is It is clear that h is preferred. moreover,
During long-term storage, the presence of hydroxycarboxylic acid salts can prevent a decrease in s PH.

that's all

Claims (1)

[Claims] 1. The following components (a), (b) and (c), (a) General formula R-O-(CH_2CH_2O)-_nH (wherein R is alkyl having 10 to 20 carbon atoms) 5 to 50% by weight of a nonionic surfactant represented by a group, an alkenyl group, or an alkylphenyl group having 6 to 12 carbon atoms, where n is a number of 1 to 20; Molecular latex as organic polymer 0.0
1 to 10% by weight, (c) Hydroxycarboxylic acid salt having 2 to 6 carbon atoms 0.00
5 to 0.25% by weight of a neutral liquid detergent composition for clothing. 2. The organic polymer latex has an average particle diameter (weight average)
is 0.005 to 0.2 μm, and the particle size is 0.005 to 0.005 μm.
2. The neutral liquid detergent composition for clothing according to claim 1, wherein 95% or more of the composition has a particle size of 0.2 μm. 3. The neutral liquid detergent composition for clothing according to claim 1 or 2, wherein the organic polymer latex has a cationic group or a tertiary amino group.