JPS6389596A - Liquid detergent composition - 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 liquid detergent composition, and more particularly to a liquid detergent composition that is excellent in preventing felt shrinkage of clothing and has excellent storage stability. Conventionally, when washing clothes at home, especially wool products, the so-called hand-washing method has been adopted, which involves pouring water or lukewarm water into a container such as a basin, dissolving detergent, and soaking the clothes. .

However, this method requires a lot of time and effort since the clothes are massaged or washed directly by hand. Furthermore, since the hands are immersed in a relatively thick washing liquid for a long time, there is a drawback that the hands are likely to become rough. Therefore, attempts have been made to wash such clothes using an electric flow core machine. 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.

[Means to solve the problem]

Therefore, as a result of intensive research in order to prevent this felt shrinkage, the present inventors found that a polymer latex having a cationic group or #'i tertiary amino group with a low residual monomer content and solubilized in a liquid detergent composition. The present invention was completed based on the discovery that the occurrence of felt shrinkage can be effectively prevented by incorporating a specific amount of the agent, and that the obtained liquid detergent composition has excellent storage stability.

Therefore, the present invention provides the following three components (Todoroki) to (c) (-)
Surfactant 5-50% by weight, (b)
Polymer latex having a cationic group or tertiary amino group with a residual monomer content of 100 ppm or less
0.01-10% by weight and (c) solubilizer
The present invention provides a liquid detergent composition characterized in that it contains 1 to 10% by weight.

As the surfactant which is the component (,) of the present invention, any of those conventionally blended in liquid detergent compositions can be used, and one or more of them may be blended.

(Todoroki) Among the components, anionic surfactants include linear or branched alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkanesulfonates, α- Examples include sulfo fatty acid 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 salts thereof.

In addition, examples of amphoteric surfactants include carboxy or sulfobetaine type surfactants, and examples of nonionic surfactants include ? Cationic surfactants such as lyoxyalkylene alkyl or alkenyl ether, seroxyethylene alkylphenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, fatty acid ester, fatty acid glycerin monoester, alkylamino oxide, etc. Examples include quaternary ammonium salts and the like.

These (-) components are usually contained in a liquid detergent composition of 5 to 5
0% by weight (hereinafter simply expressed as %), preferably 10 to 40
% is added.

If it is less than 5%, sufficient cleaning power cannot be obtained, and if it exceeds 50%, it is unfavorable in terms of liquid stability. The polymer latex having a cationic group or a tertiary amino group is obtained by extracting residual monomers from a polymer latex having a cationic group or a tertiary amino group (hereinafter abbreviated as "nitrogen-containing polymer latex") obtained by a conventionally known method. Nitrogen-containing subpolymer latex is obtained by removing the nitrogen-containing polymer latex until its concentration becomes 100 pprn or less. and other water-insoluble polymerizable monomers in a microemulsion or solubilized state. This microemulsion state is
By using a nonionic surfactant and selecting an appropriate temperature near the phase inversion temperature, or by combining an anionic surfactant with an appropriate co-surfactant such as a higher alcohol or a nonionic surfactant. It can be realized. 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 adjust the interfacial tension between the monomer and water to l dyn·/c! L or less, more preferably F
This is a method in which polymerization is carried out in a microemulsion state with i O,5 dyns/crn or less.

As a nitrogen-containing monomer, the following general formula (1) or (1) [wherein "I", R2 and R1 are an alkyl group or a substituted alkyl group having 1 to 18 carbon atoms, or hydrogen, and the three are the same or different. Alternatively, the king among the kings may be linked together to form a heterocycle such as a bilisol group or an imidazoyl group, a cycloalkyl group, or a heterocycloalkyl group, and Y may be a halodane or an acid residue. This ethylenically unsaturated nitrogen-containing monomer unit has a cationic group or a tertiary amino group represented by Alternatively, a nitrogen-containing polymer latex can be obtained by chemical reaction of polymers. Examples thereof include monovinyl bilysine, 2-methyl-5-vinyl bilysine, 2-ethyl-5-vinyl bilysine, etc. Bilicins; N, N-zomethylaminostyrene, N
, N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoether methacrylate, N,N-diethylamino ethyl acrylate),
N,N-dimethylaminozolopyl methacrylate, N,
Esters having a sialkylamino group of acrylic acid or methacrylic acid such as N-dimethylaminozologyl acrylate, N,N-noethylamino(propyl methacrylate), N,N-diethylaminozologyl acrylate; Vinyl ethers having a sialkylamino group such as metheraminoethyl 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'-dimethylaminozolopyl)methacrylamide, N-(Nl,
Nl-dimethylaminozorobyl) acrylamide, N
-(N', N'-zoethylamino derovil) methacrylamide, N-(N', N'-zoethylamino derovil) acrylamide or methacrylamide having a sialkylamino group such as acrylabad, and water. A polymer obtained by copolymerizing an insoluble ethylenically unsaturated monomer by a known method. Moreover, these are converted into alkyl halides (
Alkyl radicals having 1 to 18 carbon atoms, halogens being chlorine, bromine, iodine), benzyl halides, such as benzyl chloride or benzyl bromide, alkyl or arylsulfonic acids, such as methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid. Polymers quaternized with known quaternizing agents such as esters (alkyl groups having 1 to 18 carbon atoms) and sialkyl sulfates (alkyl groups having 1 to 4 carbon atoms), (b) chloromethylstyrene, 3- Chlor-1-propene, 3-bromo-1-zolopene, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-bromoethyl acrylate, 2-bromoether methacrylate, 3-chloropropyl acrylate, 3-chlorozologyl methacrylate , 3-bromozorobyl acrylate, 3-bromozorobyl methacrylate, 4-chlor 7°
Ethylenically unsaturated monomers having a xhalodanated methyl group (-CH, Copolymer or? Polymers having halodanated methyl groups such as listerene or chloromethylated copolymers of styrene and other water-insoluble ethylenically unsaturated monomers, trimethylamino, triethylamino, trizolobylamino, tributylamino, etc.之, triamylamino, n-octyldimethylamino, n-dodecyldimethylamino, n-
aliphatic tertiary aminos such as tetradecyldimethylamino or reactants with aromatic aminos such as dimethylaniline, diethylaniline, tribenzylamino; (c) ethylenically unsaturated monomers having hydroxy groups, e.g. A secondary amino acid is reacted on a polymer obtained by copolymerizing (meth)acrylic acid glycisol, vinyl phenyl glycisol ether, vinyl phenyl ethylene oxide, allyl glycisol ether, etc. with a water-insoluble ethylenically unsaturated monomer. (d) 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate; Copolymer or water-insoluble ethylenically unsaturated monomer having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, N-2-hydroxyethylacrylamide and a water-insoluble ethylenically unsaturated monomer A polymer having a hydroxyl group, such as a copolymer of an ethylenically unsaturated monomer and a fatty acid ester of vinyl alcohol, and glycizol trimethylammonium hydrochloride or 3
- a reaction product with a cationizing agent such as chloro-2-hydroxyzolopyltrimethylammonium salt, (・) an ethylenically unsaturated monomer having a tertiary amino group as described in (,) above; Either quaternizing the ethylenically unsaturated monomer having a chloromethyl group as described in (b) above using a quaternizing agent as described in K. Copolymers of an ethylenically unsaturated monomer having a cationic group obtained by reacting with amino or aromatic amino and a water-insoluble ethylenically unsaturated monomer can be mentioned.

The above (IL) to (,) do not necessarily all need to be quaternized products or salts, and may be in the form of tertiary salts as shown in general formula (1). This tertiary amino group has weak cationic properties in an aqueous solution (neutral to acidic solution).

The water-insoluble polymerizable monomers used in the preparation of the polymers (,) to (・) above include all known monomers used in emulsion polymerization, such as ethylene and zoropylene. Ethylenically unsaturated monomers such as , isobutyne, butene-1; aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, halogenated styrene, zopinylbenzene; ethyl acrylate, butyl acrylate, acrylic@ Acrylic esters whose alkyl group has 1 to 20 carbon atoms such as 2-ethylhexyl; methacrylic esters whose alkyl group has 1 to 20 carbon atoms such as methyl methacrylate, butyl methacrylate, diuryl methacrylate; vinyl acetate, zolopion Vinyl esters such as acid vinyl; carbon atoms such as ethyl vinyl ether, butyl vinyl ether, etc. from 1 to
20 vinyl ethers; vinyl ketones with 1 to 20 carbon atoms such as methyl vinyl ketone and ethyl vinyl ketone;
Vinyl cyanide monomers such as acrylonitrile and methacrylaterile; vinyl chloride, vinyl bromide, vinylidene chloride,
Vinyl halides such as vinylidene bromide and vinylidene halides, 1,3-butacyane, 2-methyl-1,3-
Examples include aliphatic conjugated cyanogens such as butadiene. These monomers can be used alone or in combination of two or more. Among them, it is preferable to use α, β-unsaturated carboxylic acid ester monomers such as acrylate and methacrylate. Maleic anhydride or water-soluble monomers, styrene sulfonic acid (
It is also possible to copolymerize by adding vinylnaphthalene sulfonic acid (salt), acrylic acid (salt), etc.

In the preparation of the nitrogen-containing polymer latex of the present invention, the ratio of the nitrogen-containing monomer to the water-insoluble polymerizable monomer is preferably 0.0 to 55% of the nitrogen-containing monomer. The most preferred method for producing molecular 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 monomer and water is l
dyne/cm or less, preferably 0-0.5 d
Polymerization is initiated by adding an aqueous solution of a polymerizable monomer and, if necessary, a radical polymerization initiator while maintaining a state of This is a method in which polymerization is carried out by gradually adding a polymerizable monomer so as not to exceed the range. Here, examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate; 2,2'-Azobis(2-amizonozolonoQ') mineral acid salt, azobiscyanobuarelic acid and its alkali metal salts and ammonium salts, 1,1'-Azo compounds such as azobiscyclohexanecarbonitrile, tartaric acid- Examples include redox initiators such as hydrogen peroxide, Rongalitto peroxide, and ascorbic acid peroxide.
Among these, when using a cationic surfactant as a polymerization system, 2,2'-azobis (2-amizonopro,
Qn) Persulfates are preferably used in mineral acid salts and other polymerization systems. The amount of the radical polymerization initiator is 0.1 to 5 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the monomers constituting the polymer. The highest temperature within the solubilization region is around the temperature, preferably in the range of 50 to 90°C. The time required for polymerization varies depending on the monomers 'B', composition, concentration, concentration of radical polymerization initiator, polymerization temperature, etc., but is usually preferably in the range of 5 to 50 hours.

The nitrogen-containing polymer latex preferably has a cationic group or a tertiary amino group in the molecule as explained above, but it is not limited to this. The polymer may act as a protective colloid agent.

The nitrogen-containing polymer latex mentioned above usually has a molecular weight of 200 to 300
Since it contains more than ppm of residual monomer, it is necessary to remove this in order to incorporate and use it in the liquid detergent composition of the present invention. Examples of means for removing residual monomers include ordinary vacuum distillation, steam distillation under reduced pressure, thin film separation under reduced pressure, non-pulling by blowing air,
Examples include methods such as adsorption using an adsorbent. The amount of residual monomer needs to be 100 pprn or less,
40 ppm or less, especially 10 PPm or less is preferable. If the amount of residual monomer exceeds 100 pprn, the composition cannot have good storage stability.
The liquid laundry detergent of the present invention was obtained as described above (
b) It is manufactured by adding and blending the components directly to a liquid detergent base, or by adding and blending a suspension concentrated to a desired concentration.

Component (b) is preferably blended in the liquid detergent composition in an amount of 0.01 to 10%, particularly 0.05 to 5%, as a residue after water is distilled off.

Furthermore, as the solubilizing agent for component (c), for example, lower alcohols such as ethanol, benzene sulfonate, p
Examples include lower alkylbenzenesulfonates such as toluenesulfonates, glycols such as progylene gellicol, acetylbenzenesulfonates, acetamides, viridi/dicarboxylic acid amides, benzoates, and urea.

This (C) component is blended in the liquid detergent composition in an amount of 1 to 10%, preferably 3 to 7%. If the amount of component (C) is less than 1%, the storage stability, especially the anti-caking effect at low temperatures, will be insufficient, and if the amount exceeds 10%, precipitation will occur at high temperatures, which is undesirable. .

The liquid detergent composition of the present invention is prepared by blending the three components (,) to (,) described above according to a conventional method, but other optional components may be further blended as necessary.

What other optional ingredients are there, for example? Lyacrylic acid? Polyelectrolytes such as liaconitic acid? lipinyl alcohol,
? Non-dissociated polymers such as lipinylpyrrolidone, divalent metal ion scavengers such as salts of organic acids such as diglycolic acid and oxyca-s-gnate, inorganic electrolytes such as sulfates, etc. Recontamination inhibitors such as lyethylene glycol and carboxymethylcellulose, zolotease, amylase, sono-9-ase,
Examples include enzymes such as cellulase, enzyme stabilizers such as calcium chloride, antioxidants such as tertiary-butylated hydroxytoluene and styrenated cresol, fluorescent dyes, blue tinting agents, and fragrances, but these are not particularly limited. However, the combination may be made depending on the purpose.

[Effect]

Generally, felt shrinkage occurs even when mechanical force is applied to water alone, but it is further accelerated in a surfactant aqueous solution, that is, a detergent solution. It is not clear why the purified nitrogen-containing 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 protects the cuticle on the wool surface. It is presumed that it functions to prevent the fibers from tangling.

〔Effect of the invention〕

Even when wool products and the like are washed in a washing machine using the liquid laundry detergent of the present invention, the problem of felt shrinkage does not occur, and excellent cleaning effects can be obtained. Furthermore, the liquid detergent composition of the present invention is stable even when stored for a long period of time (1), and has high commercial value.

〔Example〕

Next, the present invention will be explained in more detail by referring to Reference Examples and Examples.0Reference Example 1 (1) 343f of water in a seven-year-old rubble flask with a stirrer,
? Lioxyethylene (35) nonylphenyl ether 2
A solution prepared by dissolving 0.8 t of 2'-asohis(2-amizonozolonon9one) hydrochloride in 8 t of water was charged, and the mixture was sufficiently purged with nitrogen. Next, nitrogen gas was blown in and the mixture was heated to 62°C with stirring, and 97f of h-butyl acrylate and 3t of N,N'-dimethylaminoethyl acrylate were added dropwise over about 2 hours, and polymerization was continued for an additional 7 hours. After the O reaction was completed, it was cooled and passed through a 200-mesh wire mesh to give a latex material (n-butyl acrylate/
Dimethylaminoethyl acrylate = 97/3) was obtained. The amount of residual monomer in this latex A is 300 p
It was pm.

(i) Latex A obtained in (1) was heated to 90°C for 2.4
and steam distillation for 6 hours, each with a residual monomer amount of 15
Purified latex products of 0 ppm, 40 ppm, and 4 ppm were obtained.

Example 1 A liquid detergent composition shown in Table 1 was prepared using the latex obtained in Reference Example 1 and purified latex A, and its felt shrinkability and storage stability were examined. The results are also shown in Table 1. In addition, felt shrinkage (felt shrinkage rate) and storage stability were measured by the following methods.

(Test method) L Measurement of felt shrinkage rate due to washing: (1) Preparation of test cloth A raw wool cloth with a size of 10 x 103 sewn on three sides using a lock sewing machine was soaked in tap water at room temperature for 30 minutes, and then placed in a dehydration tank. Dehydrated for 30 seconds, placed on a net and dried at 20°C.
The humidity was controlled in a room with 65% R)i for 4 hours or more. Four marks were made on this cloth with an oil-based marker and a number was attached to each. After conditioning the humidity at 20° C. and 65% RH again, the length was measured (vertical '1 + horizontal b1 + b), and this length was defined as the original length (R, M,).

(2) Washing method T@rg-0-Tomete
r ), combine the three test fabrics obtained in (1) into one ? The detergent concentration was 0.25%, the water temperature was 20°C, and the first rinse was performed by spinning at 120 rpm for 10 minutes. What about the second time rinsing with running water in the bathtub? I rinsed my hands with running water in a hand washing tub. Next, this 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.
The humidity was controlled at 20° C. and 65% RH for 4 hours or more.

Furthermore, measure the length between the marks made in (1) above again.
From this, the felt shrinkage rate and area shrinkage rate were calculated according to the following equations.

[Calculation of shrinkage rate (IWSTM9)] R, M.

R, M, : Measured value before washing (original length) W, M, : Measured value after washing [calculation of area shrinkage rate] W, S, : Shrinkage rate in the horizontal direction I,, S, : Vertical direction Shrinkage rate (3) Storage stability The sample was placed in a screw tube (4 cm in diameter, 10 scratches in height) and stored at 40°C and room temperature -5°C, and solidified after 1 month of storage.
Separation and precipitation were determined visually.

○: It was a transparent liquid.

×: Caking, separation, or precipitation occurred.

Reference Examples 2 to 5 Below are margins.Reference Examples 2 to 5 Purified latex B-F was obtained by processing in the same manner as in Reference Example 1 according to the monomer composition and purification conditions shown in Table 2 below.

The amount of residual monomer in these purified latexes is also shown in Table 2.

Example 2 Below, a liquid detergent composition having the composition shown in Table 3 was prepared, and its felt shrinkability and storage stability were examined in the same manner as in Example 1.

The results are also shown in Table 3.

Margin below

Claims (1)

[Scope of Claims] 1. The following three components (a) to (c) (a) 5 to 50% by weight of a surfactant; (b) a cationic group or tertiary amino acid with a residual monomer content of 100 ppm or less; Polymer latex with groups 0
．． (c) a solubilizing agent; and (c) a solubilizing agent.