JPS638492A - Liquid detergent composition for clothing - 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 Field of Application] The present invention relates to a liquid detergent composition for clothing, and more particularly to a liquid detergent composition for clothing that is excellent in preventing felt shrinkage of clothing.

[Conventional technology and its problems]

BACKGROUND ART Conventionally, when washing clothes, especially wool products, at home, a so-called hand-washing method has been adopted, in which water or lukewarm water is poured into a container such as a basin, a detergent is dissolved, and the clothes are immersed.

However, this method involves massaging or pressing the clothes directly by hand, which takes a long time and requires a lot of effort.
It was necessary. Furthermore, since the hands are immersed in a relatively thick washing liquid for a long time, there is also the drawback that the hands are likely to become rough. Therefore, attempts have been made to wash such clothes using electric washing machines. However, when clothing such as wool products is washed in a washing machine, the strong mechanical force causes the clothing to shrink, causing a problem called felt shrinkage.

[Failure to solve the problem]

Therefore, as a result of intensive research to prevent felt shrinkage, the present inventors discovered that felt shrinkage can be prevented by incorporating a polymer latex with a specific particle size into a liquid detergent composition. This led to the present invention.

That is, in the present invention, the average particle diameter ("M average") is 0.
0.005 to 0.2 μm, and a particle size of 0.005 to 0.005 μm.
A polymer latex made of an organic polymer with a diameter of 2 μm is 95 weight upwind of the total weight, and a polymer latex of 0.0
The present invention provides a liquid detergent composition for clothing containing 1 to 10% of the total amount by weight.

The particle size of the polymer latex used in the present invention is as described above, but if the particle size is too large, the adhesion to the fibers will be reduced and the felt shrinkage prevention property will not be observed. Therefore, latex, which has conventionally been incorporated into detergents and the like as a clouding agent, has an average particle diameter of 0.2 μm or more and a wide particle size distribution, so that the effects of the present invention cannot be achieved.

The polymer latex made of an organic polymer with the above particle size used in the present invention cannot be produced by the conventional emulsion polymerization method, that is, the usual method in which droplets of polymerizable monomers are made to coexist in the polymerization system as an emulsion. .

That is, the polymer latex of the present invention is produced by polymerizing water-insoluble polymerizable monomers in a microemulsion or solubilized state. This microemulsion state can be achieved by selecting an appropriate temperature near the phase inversion temperature using a nonionic surfactant, or by adding an anionic surfactant to an appropriate co-surfactant such as a higher alcohol or a nonionic surfactant. This can be achieved by combining it with Also,
The solubilized state can be achieved by using a large amount of surfactant with respect to the polymerizable monomer. Among these, particularly preferred is the monomerization process using a nonionic surfactant and setting the polymerization temperature near the phase inversion temperature. In this method, the interfacial tension between the polymer and water is set to 7 cm or less, more preferably 0.5 dyne/cm or less, and polymerization is carried out in a microemulsion state.

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.

(1) Addition polymer polymer latex Addition polymer polymer latex has a polymerizable monomer solubilized in micelles formed by a surfactant, and an interfacial tension between the monomer and water of 1 dyne / A latex is obtained by polymerizing the polymerizable monomers while maintaining the microemulsion state using a surfactant water bath solution of less than cm.

As the polymerizable monomer, all known monomers used in emulsion polymerization can be used, such as ethylene, zolopyrene,
Ethylenically unsaturated monomers such as isobutyne and butene-1;
Aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, halodanated styrene, and divinylbenzene; alkyl groups with 1 to 2 carbon atoms such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.
0 acrylic ester; 1 carbon number such as methyl methacrylate, butyl methacrylate, lauryl methacrylate, etc.
~20 methacrylic acid esters; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers with 1 to 20 carbon atoms such as ethyl vinyl ether and phthyl vinyl ether; 1 carbon number such as methyl vinyl ketone and ethyl vinyl ketone ~20 vinyl ketones; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile;
Examples include vinyl halides such as vinyl chloride, vinyl bromide, vinylidene chloride, and vinylidene bromide, and aliphatic conjugated dienes such as hino-loginidene, 1,3-putazoene, and 2-methyl-1,3-putazoene. Can be done. These monomers can be used alone or in combination of two or more, and maleic anhydride can also be added to the above monomers.
Copolymerization can also be carried out by adding a C-soluble monomer, styrene sulfonic acid (salt), vinylnaphthalene sulfone ff1 (salt), acrylic acid [salt], etc.

The most preferred method for devitrification of an addition polymer polymer latex is to prepare an aqueous solution by adding a surfactant to a reaction vessel containing water, and to devitrify the solution once the surfactant micelles undergo phase inversion. Under heating and stirring, the interfacial tension between the monomer and water is 1 dyne 7 cm or less, preferably 0 to 0.5 d.
A polymerizable monomer while maintaining the state of yne/c1n,
If necessary, add an aqueous solution of a radical polymerization initiator to initiate polymerization, and then gradually add a polymerizable monomer so that the interfacial tension between the aqueous surfactant solution and the monomer phase does not fall outside the above range. This is the way to do it.

Here, examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, 2,2'-azobis(2-amizonoglo, Qn) mineral salts, and azobis cyatsubare. Azo compounds such as phosphoric acid and its alkali metal salts and ammonium salts, tartaric acid
Examples include redox initiators such as hydrogen peroxide, Rongalitto peroxide, ascorbic acid peroxide, etc. Among these, when using a cationic surfactant as a polymerization system, 2,2'-azobis (2-amidinozolo, en) Mineral acid salts and persulfates are preferably used in other polymerization systems. The amount of the radical polymerization initiator is 0.1 to 5'M, preferably 0.1 to 3 parts by weight, per 100 parts by weight of the monomers constituting the polymer.

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
A range of ˜50 hours is preferred.

By doing so, the average particle diameter becomes o, o o s ~ 0,
A polymer latex having a particle diameter of 2 μm and having particles within this range weighing more than 95% is obtained.

(2) Polycondensate polymer latex In polycondensate polymer latex, a polycondensable monomer is dissolved in micelles formed by a surfactant, and the interfacial tension between the monomer and water is l dyne. A latex is obtained by polymerizing polycondensable monomers while maintaining a microemulsion state using an aqueous surfactant solution of 7 cm or less.

As the polycondensable monomer, all known monomers used in interfacial polycondensation or low-temperature polycondensation can be used. among them,? Monomers from which lyamide and broken esters can be obtained are preferred. for example? Examples of acid components for producing lyamide include alkylene dicarboxylic acids consisting of hydrocarbons having 1 to 24 carbon atoms, phthalic acids such as dimer acid, terephthalic acid, and isophthalic acid, aromatic polyvalent carpinic acids, and cyclohexyl chloride. Acid chlorides or acid anhydrides corresponding to cycloaliphatic polyhydric carboxylic acids such as carboxylic acids, and thioesters of dicarboxylic acid, and alkylene cyamines consisting of hydrocarbons having 1 to 24 carbon atoms as cyamine components. , aliphatic polyvalent amines such as alkylenetriamine, aromatic polyvalent amines such as phenylenecyamine, and polyvalent amines having a heterocycle such as 4,4'-cyaminophenyl ether.

Also,? Examples of the alcohol component for producing the reester include alkylene diols made of hydrocarbons having 1 to 24 carbon atoms, ethylene glycol condensates such as bis-β-hydroxyethyl terephthalate, hydroquinone,
Examples include aromatic polyhydric alcohols such as bisphenol A, polyhydric alcohols such as glycerin derivatives, and the above-mentioned compounds as acid components.The monomers are not limited to these, and two or more types may also be used. A mixture of these monomers may be used.

To carry out the polycondensation reaction, a surfactant is added to a reactor filled with water, and the acid component is dissolved in aT by stirring, followed by dissolving the cyamine or alcohol in water. Should I add all the ingredients individually to a solution in an organic solvent? After solubilizing each surfactant in an aqueous solution, the two are mixed. When the monomer is solid, it is preferable to dissolve it in an organic solvent and dissolve it together with the solvent in the micelles to perform polycondensation. Benzene, toluene, xylene, etc. are preferably used. The reaction temperature is preferably the temperature in the OT solubilization region near the phase inversion temperature, generally -10 to 50 degrees Celsius, and the reaction time is usually 2 to 6 degrees Celsius, although it varies depending on the type, composition, concentration, temperature, etc. of the monomer.
0 minutes is preferred.

In this way, a polymer latex with an average particle size of 0.005 to 0.2 μm and a number of particles falling within this range of 95]i amount or more can be obtained. (3) Polyaddition polymer polymer latex polyaddition polymerization In the body polymer latex, a polyaddition monomer is dissolved in plate-like micelles formed by a surfactant, and the interfacial tension between the monomer and water is 0.5 dyne.
A latex is obtained by polymerizing a polyaddition monomer in a state where the micro-pollution state is maintained using an aqueous surfactant solution with a particle size of less than / cm.

As the polyaddition monomer, all known monomers used in normal polyaddition reactions can be used, but among them, monomers that can yield polyurethane, broken urea resin, and epoxy resin are used. Body is preferred.

The alcohol component for producing polyurethane includes - a compound having at least two hydroxyl groups in the molecule;
Specifically, ethylene glycol, zoropylene glycol, butylene glycol, hexadiol, neopentyl glycol, polyethylene glycol, ? Literobylene glycol, polyoxytetramethylene glycol,
Glycerin, trimethylolglycerol, en, have two or more hydroxyl groups at the end? Examples of incyanate components include compounds having at least two incyanate groups in the molecule, specifically tolylene isocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4. Illustrative examples include idiphenylmethane diisocyanate, triphenylmethane triincyanate, trimethylolzolonoQ-triisocyanate, te esters, broken ethers, and polyurethanes having two or more incyanate groups at the terminals.

The above-mentioned compounds can be used as the incyanate component for producing diurea, and as the amine component, compounds having at least two amino groups in the molecule, specifically hexamethylenecyamine, dodecylcyamine, etc. Examples include amine, phenylenecyamine, diaminodiphenyl ether, and biperazone.

Epoxy components for producing epoxy resin include:
- Compounds having at least two epoxy groups in the molecule, specifically zoglycidyl ether compounds of bisphenol A, glycysol ester compounds of dimer acid, compounds obtained by oxidizing olefins, etc. are exemplified. Also, as the amine component, the above-mentioned amine compounds can be used. Furthermore, as curing agents, in addition to tertiary amines, boron trifluoride amine complexes, imidazole, amines having functional groups that undergo polyaddition reactions with epoxy groups, etc. Reamin, carboxylic acid anhydride,? All known compounds such as lysulfide, synancyamide, diincyanate, etc. can be used.

The polyaddition reaction is carried out as follows. That is, to obtain polyurethane or polyurea, water is charged in the reactor, a surfactant is added and stirred to dissolve the incyanate component, and then a diol or cyamine water bath solution is added, or
Alternatively, a solution in which both components are individually dissolved in an organic solvent is dissolved in each surfactant aqueous solution, and then both are mixed. Engineering again? Prepolymer or Song Duan to obtain resin? A solution prepared by dissolving an oxygen compound and various curing agents in a solvent is gradually dropped into a heated aqueous surfactant solution.

If the above monomer is a solid or a highly viscous liquid,
It is dissolved in an organic bath agent and dissolved in micelles together with the solvent.
Preference is given to carrying out an addition reaction. This organic solvent is
Any inert solvent that is insoluble in water and does not react with each component
For y<, w, benzene, toluene, xylene, etc. are preferable. The reaction temperature is preferably the temperature in the solubilization region near the phase inversion temperature, generally 20 to 70°C, and the reaction time varies depending on the type, composition, concentration, temperature, etc. of the monomer, but is usually 1.
~50 hours is preferred.

Although the phenol resin is a polycondensate, it can be produced in the same manner as the above-mentioned Nixy resin. To make phenolic resin, phenolic conductors such as phenol and cresol and formaldehyde can be used.
Using resol resin, novolac resin, acid or?
It may also be cured with riamin or the like.

The average particle size of the latex thus obtained was 0.
005 to 0.2 μm, and the number of particles within this range is 9
5 weight or more.

As mentioned above, the average particle diameter of the polymer latex used in the present invention is 0.005 to 0.2 μm in weight average value,
More preferably, it is 0.01 to 0.1 μm. ′! Next,
More than 95% by weight of the polymer latex particles have a particle size of 0.
It falls within the range of 0.005 to 0.2 μm.

Further, among these polymer latexes, it is desirable that the glass transition temperature (Tg) is 300°K or less from the viewpoint of imparting flexibility.

Is Tg less than 300°K? Ethyl acrylate, broken as a rimmer? Polyacrylic esters such as butyl lyacrylate;? 2-ethylhexyl methacrylate, ? Lauryl methacrylate, etc.? Remethacrylic acid esters;? Addition polymer polymer latex such as polyvinyl ethers such as ribtoxyethylene and polymethoxyethylene;
Polyoxytrimethylene oxazoglobyl, polyoxytetramethyleneoxycarbonyl-1,4-cyclohexylenecargenyl, etc.? Reesters;? Lioxy-2-butenyleneoxycarbinyliminohexamethyleneiminocarbonyl, ? Saoxy-2,2-zoethyltrimethyleneoxycarlnylimino-4-methyl-1,3
-Polyurethanes such as phenyleneiminocarbonyl and the like can be mentioned.

Among the above-mentioned polymer latexes, addition polymer latexes are preferred, and among them, glass transition temperature ( Tg) is less than or equal to 300'.

The liquid laundry detergent of the present invention can be produced by directly adding and blending the polymer latex obtained by the nucleation method to a liquid laundry detergent base, or by adding and blending a suspension concentrated to a desired concentration. Manufactured by. Polymer latex is added to liquid laundry detergent as a residue after water is distilled off.
It is preferably blended in an amount of 0% by weight (hereinafter simply referred to as "excellent"), particularly 0.05 to 5%.

In addition to the polymer latex, the liquid laundry detergent composition of the present invention may contain one or more of the following various surfactants.

Among surfactants, anionic surfactants include linear or branched alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl a
(MkX's: '#Shifin sulfonate, alkanesulfonate 1 α-sulfo fatty acid salt or ester, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carbate, amino acid type surfactant, N-acyl Examples include amino acid type surfactants, alkyl or alkenyl phosphates, or salts thereof.

Examples of amphoteric surfactants include carboxy or sulfobetaine type surfactants, and examples of nonionic surfactants include polyoxyalkylene alkyl or alkenyl ethers, oxyethylene alkylphenyl ethers, and higher fatty acid alkanolamides. or alkylene oxide adducts thereof, sucrose/fatty acid esters, fatty acid esters, fatty acid glycerin monoesters, alkylamine oxides, etc. Examples of the cationic surfactants include quaternary ammonium salts.

These surfactants are usually blended in a liquid laundry detergent composition in an amount of 10 to 50%.

Other conventional auxiliary additives may be added to the composition of the invention, such as broken acrylic acid, etc. Polymer electrolytes such as Liaconit M, polyvinyl alcohol, ? Non-dissociable polymers such as ribinyl pyrrolidone, divalent metal ion scavengers such as salts of organic acids such as diglycolic acid and oxycarboxylate, inorganic materials such as sulfates, polyethylene glycol, carboxymethyl cellulose, etc. Anti-recontamination agents, proteases, amylases, reno? Enzymes such as enzymes and cellulase, enzyme stabilizers such as calcium chloride, antioxidants such as tertiary butylated hydroxytoludine and styrenated cresol, solubilizers such as ethanol, lower alcohols, benzenesulfone, etc. acid salts, lower delkylbenzenesulfones such as p-toluenesulfonates, 7'robylene glycols, acetylbenzenesulfonates, acetamides, pyridine dicarboxylic acid amides, benzoates or Fluorescent dyeing agents such as urea,
It may contain a blue tinting agent, flavoring agent, etc., but there are no particular limitations on this, and the mixture may be mixed according to the purpose. [Operation] In general, felt shrinkage is caused by water alone and mechanical force? This occurs even when a surfactant is added, but it is further promoted in a surfactant bath solution, that is, a detergent solution. It is not clear why the polymer latex of the present invention is effective in preventing felt shrinkage, but it is probably because the polymer latex adheres to the fiber surface and acts like a cushion to prevent the fibers from tangling. It is presumed that it has a similar function.

〔Effect of the invention〕

Liquid laundry detergent of the present invention? Even if wool products and the like are laminated using a washing machine, the problem of felt shrinkage does not occur, and an excellent cleaning effect can be obtained.

[Implementation νIj]

Next, reference examples and working examples? The present invention will be further described below.

Reference example 1゜ Add 2 oots of water to a 7/Q rubble flask with a stirrer.

? Lioxyethylene (35) nonylphenyl ether 1
61. 0.6 P of ammonium persulfate was charged, the mixture was sufficiently purged with nitrogen, heated to 62°C with stirring, 90.5 fft of n-butyl acrylate was added dropwise over about 2 hours, and polymerization was carried out for 6 hours to obtain latex A. .

Reference example 2. Referential Example 1 except that ~8° n-butyl acrylate was replaced with the composition of Shinanofu in Table 1. Similarly, latex B~Hk
Get it. In addition, these reference examples and reference 1411. The physical properties of the obtained latex are also shown in Table 1.

Example 1 A liquid laundry detergent composition having the composition shown in Table 2 was prepared using the latex obtained in Reference Examples 1 to 8. Prepared. This liquid detergent composition was examined for felt shrinkage and flexibility. The results are shown in Table-3.

(Composition) Below is the margin (Test method) 1. Measurement of felt shrinkage rate due to washing: (1) Unprocessed wool cloth with stitch thickness g 10 x 10 cm sewn on three sides using a lock sewing machine? After immersing in tap water at room temperature for 30 minutes, it was dehydrated for 30 seconds in a dehydration tank, placed on a net to dry flat, and kept in a 20C, 65% room for more than 4 hours. Four marks were made on this cloth with an oil-based marker, and a number was attached to each mark. After adjusting the humidity again at 20C165%RH, measure the length (vertical a)? r a'2 horizontal b:, b:)
, this length was defined as the original length (RoM).

) Anti-layer method Terg-0-Tomet
er ), put the 3 test cloths obtained in (1) in one pot and rotate at 120 rpm for 10 minutes to wash them. I did it. The concentration of each detergent was 0.25%, and the water temperature was 20C.
And so. As for Susuki, do you rinse it in running water in the pot for the first time? What about the second time? I rinsed my hands with running water in a hand washing tub.

Next, after washing, this sample fabric was applied to the wall of the dehydration tank and dehydrated for 30 seconds, then placed on a net and dried flat at 20°C and 65°C.
Humidity was controlled for more than 4 hours with % volume.

Furthermore, regarding the marks previously added in (1), the length between them - J't jl11 is fixed vertically a, w, aw horizontally bI
W.

b2), from which the felt shrinkage rate and area shrinkage rate were calculated according to the following equations.

(Yield rate) tfn (IWS TM 9 jsu)] Felt shrinkage rate (phrase = R-M-W, M" × 100R, M
・R, M,: Measured value before washing (original length) W, R: Measured value after washing [calculation of area shrinkage rate] W, S,: Shrinkage rate in the horizontal direction, S,: Shrinkage in the vertical direction Rate 2, flexibility test: 30 cm at water temperature 30°C, 0.25% detergent aqueous solution 51
5 x 60 cm acrylic chassis or 1 wool sweater for recontamination prevention test? I washed my hands.

After air-drying, the acrylic chassis or wool sweater was subjected to a tactile test by five judges, and ranked as follows.

○: Finished softer than the standard detergent.

△: The finish was equivalent to that of the standard detergent.

X: Finished harder than the standard detergent.

(Results) Table 3 As shown in Table 3, compared to washing with tap water only,
Washing with an aqueous activator solution accelerates felt shrinkage. However, by adding latex A, B, C, D, E, F, and H, these shrinkages are reduced to the level of tap water.

In addition, it is clear that latex with a high Tg such as styrene is not preferable from the viewpoint of flexibility. The area shrinkage rate of the felt was measured. The results are shown in Table-5.

(Composition) Table-4 *LAS: Straight-chain alkyl CC = 12) Sodium benzenesulfonate (Results) Table-5 As is clear from the results in Table-5, the aqueous solutions containing only the activator contracted more than tap water alone. Although the shrinkage rate increases, by adding polymer latex B to this, the shrinkage rate decreases to almost the same level as when using only tap water.

that's all

Claims (1)

[Claims] 1. Average particle diameter (weight average) is 0.005 to 0.2 μm
A liquid laundry detergent composition containing 0.01 to 10% by weight of a polymer latex made of an organic polymer in which 95% by weight or more of the total particle size is 0.005 to 0.2 μm. thing. 2. The liquid laundry detergent composition according to claim 1, wherein the polymer latex has a glass transition temperature of 300°K or less.