JPS63122796A - Liquid detergent 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 [Industrial Application Field] The present invention relates to a liquid detergent composition, and more particularly to a liquid detergent composition that has excellent fragrance retention on clothing.

[Conventional technology and its problems]

Conventionally, clothes have been washed at home by washing with an electric washing machine, dehydrating them, drying them, and then ironing them if necessary. Although the primary purpose of washing is to remove dirt, it would be better if the product could be finished so that a faint fragrance remains even when worn.

To this end, a method has been adopted in which a fragrance having a high boiling point that is difficult to scatter during drying is added to the cleaning agent.

However, when washing, a large amount of washing water (for example, 1 to 9
(30 tons of detergent solution is required for washing clothes), most of the fragrance is discharged by draining the washing water, rinsing, etc., and a small amount of fragrance does not affect the fragrance. It still had the problem that it did not remain.

[Means for solving problems]

In such a situation, as a result of intensive research by the present inventors,
The present invention was completed based on the discovery that a detergent with excellent odor retention can be obtained by containing a polymer latex having a cationic group or a tertiary amine group.

That is, the present invention uses the following three components (,) to (C) (,)
Surfactant 5-50% by weight (b)
Provided is a liquid cleaning composition characterized by containing 0.01 to 10% by weight of a polymer latex having a cationic group or a tertiary amino group (c) 0.001 to 3% by weight of a fragrance. It is something to do.

As the surfactant which is the component (1) 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.

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 ? Lioxyalkylene alkyl or ha alkenyl ether? Lioxyethylene alkylphenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, fatty acid ester, fatty acid glycerin heptanoester, alkylamine oxide, etc., and examples of the cationic surfactant include quaternary ammonium salt, etc. are exemplified respectively.

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

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. Molecular latex (hereinafter abbreviated as "nitrogen-containing polymer latex") is a monomer having a cationic group or tertiary amino group (hereinafter abbreviated as "nitrogen-containing monomer") or other water-insoluble polymers. It is produced by polymerizing polymerizable monomers in a microemulsion or solubilized state. This microemulsion state can be achieved by using a nonionic surfactant at an appropriate temperature near the phase inversion temperature, and 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 with agents. 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 l dyne /3 or less, more preferably 0.
This is a method in which polymerization is carried out in a microemulsion state with a concentration of less than 5 dyn·/crIL.

As the nitrogen-containing monomer, the following general formula (1) or (1) [in the formula, %R1%R2 and R8 may be an alkyl group having 1 to 18 carbon atoms or a substituted alkyl group, or hydrogen, and the three may be the same. They may be different, or three of the three 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 is a halogen group. Alternatively, an ethylenically unsaturated nitrogen-containing monomer unit having a cationic group or a tertiary amino group represented by [indicating an acid residue] can be mentioned.

This ethylenically unsaturated nitrogen-containing monomer unit can be industrially easily converted into a nitrogen-containing polymer latex by copolymerization or chemical reaction of a polymer as described below. That is, examples thereof include monovinyl bilysins such as (-) vinyl bilysine, 2-methyl-5-vinyl bilysine, and 2-ethyl-5-vinyl bilysine; N, N-dimethylaminostyrene, N
, N-dimethylaminomethylstyrene having a sialkylamino group; N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate,
N,N-dimethylaminozorobyl methacrylate, N,
N-dimethylaminozorogyl acrylate, N,N-diethylaminozologyl methacrylate, N,? Esters having a sialkylamino group of acrylic acid or methacrylic acid such as J-zoethylaminoprogyl acrylate; vinyl ethers having a sialkylamino group such as 2-dimethylaminoethyl vinyl ether; N-(N'
, N'-dimethylaminoethyl) methacrylamide s
N-(N', N'-dimethylaminoethyl) acrylamide, N-(NZ, NZ-diethylaminoethyl) methacrylamide, N-(N', N'-diethylaminoethyl) acrylamide, N-(N', N' −
dimethylaminozolopyl) methacrylamide, Nl (
Nl, Nl-dimethylaminozolopyl) acrylamide, N-(N', N'-diethylaminozoropyr)
Acrylamide or methacrylamide having a sialkylamino group such as methacrylamide or N-(N',N'-diethylaminozolobyl)acrylamide and a water-insoluble ethylenically unsaturated monomer are copolymerized by a known method. A polymer obtained by Furthermore, these may be combined with a known quaternizing agent, such as an alkyl halide (having 1 carbon atom in the alkyl group).
to 18, halodane (chlorine, bromine, iodine), halogenated pencils such as benzyl chloride or benzyl bromide, 1 alkyl ester of alkyl or arylsulfonic acid such as methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid (carbon of alkyl group) numbers 1 to 18
), and polymers quaternized with sialkyl sulfate (alkyl group having 1 to 4 carbon atoms), etc., (b) chloromethylstyrene, 3-chloro-1-zolopene, 3-bromo-
1-7'lopene, 2-chloroethyl acrylate, 2-
Chlorethyl methacrylate, 2-bromoethyl acrylate, 2-bromoethyl methacrylate, 3-chlorzolovir acrylate, 3-chlornorovir methacrylate, 3-bromopropyl acrylate, 3-bromonolovir methacrylate, 4-chlorzolovir acrylate, 4-Chlorzolobyl methacrylate, 2-chloroethyl vinyl ether (7) * An ethylenically unsaturated monomer having an oxymethyl group (-CH,X) and a water-insoluble ethylenically unsaturated monomer A copolymer of or? Polymers having halogenated methyl groups, such as chloromethylated polymers of listyrene or copolymers of styrene and other water-insoluble ethylenically unsaturated monomers, and trimethylamine, triethylamine, tripropylamine, tributylamine, trimethylamine Reaction products with aliphatic tertiary amines such as mylamine, n-octyldimethylamine, n-dodecyldimethylamine, and n-tetradecyldimethylamine or aromatic amines such as dimethylaniline, diethylaniline, and tripentylamine, (c ) Engineering? Copolymerization of an ethylenically unsaturated monomer having an xyl group, such as (meth)acrylic acid glycisol, vinyl phenyl glycisol ether, vinyl phenyl ethylene oxide, allyl glycisol ether, etc., and a water-insoluble ethylenically unsaturated monomer. The polymer obtained by the process is treated with a secondary amine. (d) 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate,
A copolymer of an ethylenically unsaturated monomer having N-2- and a hydroxyl group such as droxyethyl acrylamide and a water-insoluble ethylenically unsaturated monomer, or a water-insoluble ethylenically unsaturated monomer and vinyl A polymer having a hydroxyl group such as a saponified copolymer of alcohol with a fatty acid ester and glycysol trimethylammonium hydrochloride or 1d3
- a reaction product with a cationizing agent such as 2-hydroxynolopyltrimethylammonium salt, (,) an ethylenically unsaturated monomer having a tertiary amine group as described in (,) above; Alternatively, the ethylenically unsaturated monomer having a chloromethyl group as described in (b) above is converted into an aliphatic tertiary monomer as described in (b) above. Examples include copolymers of ethylenically unsaturated monomers having a cationic group obtained by reacting with amines and aromatic amines and water-insoluble ethylenically unsaturated monomers.

All of the above (,) to (,) do not necessarily have to be quaternized products or salts, and may be in the form of tertiary salts as shown in general formula (1). This tertiary amine 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, zolopyrene, Ethylenically unsaturated monomers such as isobutyne and butene-1; aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, halodanated styrene, and zopinylbenzene; ethyl acrylate, butyl acrylate, acrylic acid 2 - Acrylic acid esters in which the alkyl group has 1 to 20 carbon atoms such as ethylhexyl; methacrylic esters in which the alkyl group has 1 to 20 carbon atoms such as methyl methacrylate, butyl methacrylate, lauryl methacrylate; vinyl acetate, vinyl propionate Vinyl esters such as ethyl vinyl ether, butyl vinyl ether, etc. having 1 or more carbon atoms
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-putazoene, 2-methyl-1,3-
Examples include aliphatic conjugated cyanogens such as putazoene. These monomers can be used alone or in combination of two or more, and α,β-unsaturated carenoic acid ester monomers such as acrylates and methacrylates are preferred, and the monomers mentioned above are preferred. Maleic anhydride or water-soluble monomer, styrene sulfonic acid (
Salt) % Vinylna-7talenesulfonic acid (salt).

It is also possible to copolymerize by adding acrylic acid (salt) or the like.

In preparing the nitrogen-containing polymer latex of the present invention, the ratio of the nitrogen-containing monomer to the water-insoluble polymerizable monomer is preferably 0.05 to 55%.

The most preferable method for producing nitrogen-containing polymer latex is to prepare an aqueous solution by adding a surfactant to a reaction vessel filled with water, and then heating this at a temperature close to the phase inversion of the surfactant micelles. Under stirring, the interfacial tension between monomer and water is 1
dyne/crs or less, preferably 0-0.5
Polymerization is initiated by adding an aqueous solution of a polymerizable monomer and, if necessary, a radical polymerization initiator while maintaining the state of dyne/preparation, and then the interfacial tension between the aqueous surfactant solution and the monomer phase is within the above range. This is a method in which polymerizable monomers are added gradually so that they do not come out.

Examples of the radical polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate, ammonium persulfate, 2,2'-azobis(2-amizononoronono9ine) mineral salt, and azobissia. Nobuarelic acid and its alkali metal salts and ammonium salts, azo compounds such as 1,1'-azopiscyclohexanecargonitrile,
Examples include redox initiators such as tartaric acid-hydrogen peroxide, Rongalitto peroxide, ascorbic acid-peroxide, etc. Among these, when using a cationic surfactant as a polymerization system, 2,2' -Azobis(2-amizonozolonon9one) mineral acid salts and persulfates are preferably used in other polymerization systems. The amount of the radical polymerization initiator is 0.1 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the monomers constituting the polymer.

In the above method, the reaction temperature is the highest temperature in the solubilization region near the phase inversion temperature, preferably in the range of 50 to 90°C. In addition, the time required for polymerization depends on the type and composition of monomers.
Although it varies depending on the concentration, the concentration of the radical polymerization initiator, the polymerization temperature, etc., it is usually preferably in the range of 5 to 50 hours.

The nitrogen-containing polymer latex preferably has a cationic group or a tertiary amine group in the molecule as explained above, but is not limited to this. A polymer having
It may also act as a protective colloid.

Nitrogen-containing polymer latex on paper usually has a molecular weight of 200 to 300
Since it contains residual monomers of ppm or more, it is preferable to remove this in order to incorporate and use the liquid detergent composition of the present invention.

Examples of the means for removing the residual monomer include methods such as distillation under reduced pressure, steam distillation under reduced pressure, thin film separation under reduced pressure, bubbling by blowing air, and adsorption with an adsorbent.

In addition, the average particle diameter of the nitrogen-containing polymer latex is 0.00
It is preferable that the particles have a particle diameter of 5 to 0.2 tones and that particles falling within this range account for 95% or more of the entire nitrogen-containing polymer latex.

The liquid laundry detergent of the present invention was obtained as on paper (
b) It is manufactured by adding and blending the ingredients 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 fragrance component (C), any substance having a basic structure such as alcohol, ketone, ether, lactone, or ester may be used. For example, 2,6-dinitro-3,5- Zomethyl-4-acetyl-t・rt-butylbenzene, 7-acetyl-1゜1.3,4,4,6-hexamethyltetrahydronaphthalene, synthetic sandal, NoQ Chualco A-% mefcedrylone, 1, 2-benzobilane, 4-(2,6,6
-)dimethyl-2-cyclohexen-1-yl)-3-
Buten-2-one, benzyl salicylate, α-h-hexyl cinnamic aldehyde, 4-(4-hydroxy-
4-Methylpentyl)-3-cyclohexene-1-carboxaldehyde, 3,7-dimethyl-6-octene-
1-ol, β-phenylethyl alcohol, 1-methyl-4-inzolopyl-1-cyclohexen-8-ol, 3,7-dimethyl-1,6-octadien-3-ol, 3,7-dimethyloctano- Ru 3, γ-undecalactone, 3,4-methyl-enezooxypenzaldehyde, petiverol, amyl salicylate, β-naphthol methyl ether, 2-trans-3,7-
Dimethyl-2,6-octazoen-1-ol, 3,7
-dimethyl-1,6-octadien-3-yl acetate)% p-menth-1-en-8-yl acetate, l-methyl-p-isonorobenyl-1-cyclohexene, 2-methyl-6-methylene-two-octane -2-
ol, 3,7-dimethyl-2,6-octazoene-8
-ylnitrile, 5-(2-methylene-6,6-dimethylcyclohexyl)-4-penten-3-one sp
-t・rt-butylcyclohexyl acetate, 2-methoxy-4-allylphenol, 3-hydroxy-2-
Examples include methyl-4-pyrone 5P-tllrt-butyl-α-methylhydrocinnamic aldehyde.

These (c) components are 0.0% in the liquid detergent composition components.
It is blended in an amount of 1 to 10%, preferably 0.05 to 5%.

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

Other optional ingredients include, for example, ethanol o-51, low R alcohols, lower alkylbenzenesulfonates such as benzenesulfonates and p-toluenesulfonates, glycols such as zorogylene gelicol, and acetylbenzenesulfone. Solubilizing agents such as acid salts, acetamides, pyridine dicarboxylic acid amides, benzoates or urea; acrylic acid, ? Polyelectrolytes such as liaconitic acid; vinyl alcohol, ? Non-dissociable polymers such as ribinylpyrrolidone; divalent metal ion scavengers such as salts of organic acids such as diglycolic acid and oxycarboxylic acid salts; inorganic electrolytes such as sulfates; Anti-recontamination agents such as oxymethyl cellulose; Enzymes such as f-lothiase, amylase, 9-ase, and cellulase; Enzyme stabilizers such as calcium chloride; Antioxidants such as tert-butylated hydroxytoluene and zostyrenated resol; Examples include fluorescent dyes and blue tinting agents, but these are not particularly limited and may be blended depending on the purpose.

〔Effect of the invention〕

The liquid detergent composition of the present invention is excellent in that a good fragrance remains on clothes even after washing and rinsing using a large amount of washing water, despite the addition of a trace amount of fragrance.

〔Example〕

Next, the present invention will be explained in more detail with reference to Reference Examples and Examples.

Reference example 1 (1) 343f% water in a mono 9 rubble flask with a stirrer
? Lioxyethylene (35) nonylphenyl ether 2
A solution obtained by dissolving 0.8 f of 1f and 2,2'-azobis(2-amizonozolo/Qn) hydrochloride in 8 f 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 to form n-butyl acrylate 97 and N,N'-dimethylaminoethyl acrylate).
32 was added dropwise over a period of about 2 hours, and polymerization was further carried out for 7 hours. After the reaction was completed, the mixture was cooled and filtered through a 200-mesh wire mesh to obtain latex A (n-butyl acrylate/dimethylaminoethyl acrylate=97/3, residual monomer amount 300 ppm).

(i) The latex obtained in (1) was steam-distilled at 90°C for 4 hours to obtain a purified latex with a residual content of 40 ppm (weight average particle size 0.07μ, particle size o, o
os~0.2μ (100% of the total) was obtained.

Example 1 A liquid detergent composition having the composition shown below was prepared using purified latex A obtained in Reference Example 1, and its odor was evaluated.

The results are shown in Table 1.

(Composition)? α1 oxyethylene alkyl (CIt~I3) ether 15 (%) coconut fatty acid monoethanolamide
3 Purified latex A O
or 1 fragrance” Table 1 Ethanol 5 Water
The balance fragrance used had the following composition.

r-undecalactone l
NoQ Chuli Alcohol
31.2-benzobilane 7
3.4-Methyl-enezooxypenzaldehyde
5 peteverol 1
Amyl salicylate 8 synthetic sandals 5β
-Phenylethyl alcohol 20β
-Naphthol methyl ether 23
．． 7-dimethyl-1,6-octazoen-3-ol
14p-menth-1-en-8-yl acetate
10 total
100% (Test method) (1) Washing method Put a cotton broadcloth with a size of 30 x 30 cm* into a small washing machine (NA-35 model; manufactured by Matsushita Electric Industrial) and wash it at a density of 0.
Washing is carried out for 10 minutes with 3 tons of 25% detergent solution. For rinsing, after draining all the cleaning liquid, use tap water for 31 minutes. The process of injecting and rinsing for 2 minutes in the same washing machine was repeated twice. Next, the cloth was dehydrated for 30 seconds in a washing machine centrifugal dehydration tank and left at 20° C. and 65% RH for 24 hours.

(2) Odor evaluation We asked three Noqners (18-year-old female (A), 425-year-old female (B), and 31-year-old male (C)) to rate the odor and choose the most aromatic. The average score was calculated from 1 to 5, with 1 being the strongest.

Table 1 Reference example 2 Reference example 1 (1) In the same manner as (i+), latex B
(n-butyl acrylate/dimethylaminoethyl acrylate) = 70/30, residual monomer amount is 35 Ppm
) s and purified latex B (weight average particle diameter 0.
10 μ, particle size o, oos ~ 0.2% of the total 9
6%).

Example 2 A liquid detergent composition having the composition shown below was prepared using the purified latex B obtained in Reference Example 2, and the odor was further evaluated in the same manner.

The results are shown in Table 2.

(Composition)? α0 Oxyethylene alkyl (C+t-+s) ether 15(%) Coconut fatty acid monoethanolamide 3 Purified latex B
Q or 1.5 fragrance Table 2 Ethanol 5 Water
The balance fragrance used had the following composition.

1-Methyl-p-isozorobenyl-1-cyclohexene 15 (%) 2-Methyl-6-methylene-two-octan-2-ol 33.7-Dimethyl-1,6-octazoen-3-ol 122-trans-3,7- Dimethyl-2,6-octazoe 125-1-ol 1-methyl-4-isozorobyl-1-cyclohexene
5-8-ol β-phenylethyl alcohol
20pt@rt-butylcyclohexyl acetate 102-methoxy-4-allylphenol 53-hydroxy-2-methyl-4-
Pyron 0.5 table 2 or more

Claims (1)

[Claims] 1. The following three components (a) to (c) (a) 5 to 50% by weight of a surfactant (b) A polymer latex having a cationic group or a tertiary amino group as a polymer A liquid cleaning composition characterized in that it contains 0.01 to 10% by weight (c) 0.001 to 3% by weight of fragrance.