JP3208209B2 - Laundry aid composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laundry auxiliary composition, and more particularly to a laundry auxiliary composition which can be used together with an alkaline detergent when washing clothes or the like.

[0002]

2. Description of the Related Art Generally, a washing process using a washing machine is performed by pouring water → washing → draining → dehydrating → pouring → rinsing → draining →
In general, laundering aids such as softeners and pastes are added during the rinsing step, especially during the final rinsing step, in order to fully exert their effects. However, in some cases, the finishing agent may be forgotten to be added during the rinsing process, or it may not be necessary to add the finishing agent because it takes time and effort. Further, in recent years, with the spread of fully automatic washing machines, no workers are present at all until the entire washing process is completed, and adding a washing aid during the rinsing process is painful for the worker, and thus these Use of laundry aids has been reduced. Therefore, there is a demand for a laundry auxiliary agent that has a sufficient effect even when used together with a detergent during the washing process of washing, not during the rinsing process.

[0003] In response to these demands, for example, in the case of a softener, a granulated material is added to a detergent to suppress dissolution and dispersion, or a soft base is coated with a high-melting-point film so that it can be used at the end of washing. Means for slowly releasing the soft component during hot air drying have been considered. However, in the former, there is a problem that the soft base is combined with the detergent component, thereby deteriorating both the washing effect and the softening effect. The latter has a problem that it is effective for a high-temperature washing-type washing machine and a dryer, but cannot exert a sufficient effect with other washing methods.

Also, attention has been paid to the fact that when an alkaline detergent is used, the washing liquid becomes alkaline at the time of washing and becomes neutral at the time of rinsing, and a method of coating a washing auxiliary with a polymer whose solubility changes depending on pH is known. ing. For example,
JP 50-77406 discloses a laundry aid coated with a water-soluble film comprising polyvinyl acetal diethylaminoacetate and an organic acid. However, this water-soluble film dissolves without problems in an acidic region lower than pH 6 or lower, but is not practically satisfactory because it dissolves slowly in a neutral region such as during rinsing.
JP-A-59-115398 discloses a laundry aid coated with a specific tertiary amine group-containing water-soluble polymer, and JP-A-61-28596 discloses a specific basic monomer. A laundry aid coated with a mixture of a copolymer contained as an essential component and a water-insoluble inorganic compound or a nonionic polymer compound is disclosed. However, with these polymers, the pH of the wash water (9-11) and the pH of the rinsing water (7-
The change in solubility with 8) is not yet sufficient, and the effect of the auxiliary agent is not sufficiently exhibited.

[0005]

Under these circumstances, the present inventors have conducted intensive studies to solve the above problems, and as a result, by using a polymer which is insoluble in an alkaline washing liquid, an auxiliary component was obtained. Can be avoided and the polymer becomes soluble in a neutral rinsing solution,
The auxiliary component was also dissolved and dispersed, and it was found that the effect of the auxiliary agent could be efficiently exhibited, and the present invention was completed.

That is, according to the present invention, the laundry auxiliary component is represented by the following general formula (A):

[0007]

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Wherein R represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² may be the same or different;
Each represents hydrogen or an alkyl group having 1 to 4 carbon atoms, a hydroxyethyl group, or a hydroxypropyl group;
Indicates an integer of 5. (B) at least one kind of a substantially water-insoluble monomer; (C) at least one kind of a water-soluble monomer containing no dialkylaminoalkyl group in the molecule; -100 mol%, (B) 0-95 mol%, (C) 0-95
mol% (where at least one of (B) and (C) is 0 % )
(not mol%) , and is coated with a copolymer obtained by polymerization . Further, the present invention relates to the above (A) wherein
Polymerizing at least one of the basic monomers shown
Laundry characterized by being coated with the resulting polymer
An auxiliary composition is provided.

The polymer or copolymer according to the present invention has a pH of 9
It is preferably substantially insoluble in the above alkaline water, soluble in weakly alkaline to neutral to acidic water having a pH of 8 or less, and having a large solubility ratio depending on pH conditions. In addition, such a copolymer contains monomer (A) as an essential component, and
(B) and (C) may be combined in the above ratio. Less than
Below, "copolymer" includes a polymer of monomer (A)
And

Specific examples of the monomer represented by the general formula (I) of (A) include N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N, N-dimethylaminomethylacrylic acid (or Methacrylic acid) amide,
N, N-dimethylaminoethylacrylic acid (or methacrylic acid) amide, N, N-dimethylaminobutylacrylic acid (or methacrylic acid) amide and the like can be mentioned.

Specific examples of the substantially water-insoluble monomer (B) include one or more selected from acrylates, methacrylates, crotonates, itaconic esters, vinyl acetate and styrene. Can be When each of the alkyl esters of acrylic acid, methacrylic acid, crotonic acid, and itaconic acid is used as the monomer (B), those having a carbon chain length of 1 to 18 of the alkyl group bonded to the ester can be used, If so, the dissolution of the resulting copolymer in a slightly alkaline aqueous solution will be delayed, so that these alkyl groups have 1 to 12 carbon atoms.
Is more preferable. Esters of acrylic acid or methacrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and ethyl methacrylate are more preferred.

Specific examples of the water-soluble monomer (C) that does not contain a dialkylaminoalkyl group include 2-hydroxyethylacrylic acid (or methacrylic acid),
An ester of hydroxypropylacrylic acid (or methacrylic acid), polyethylene glycol or methoxypolyethylene glycol (ethylene oxide (EO) average addition mole number = 1-30) and acrylic acid or methacrylic acid,
Examples thereof include vinylpyrrolidone, and N, N-dialkylacryl (or methacryl) amide such as N, N-dimethylacrylamide and N, N-dimethylmethacrylamide. Furthermore, even a water-soluble monomer containing a dialkylaminoalkyl group in the molecule can be used as a quaternized one by a known method. Specifically, acrylate-N, N-dimethylaminoethyl, acrylate-N, N-
Dimethylaminomethyl, -N, N-dimethylaminobutyl acrylate, -N, N-dimethylaminopropyl acrylate, -N, N-dimethylaminoethyl methacrylate, -N, N-dimethylaminomethyl methacrylate, methacrylic acid -N, N-dimethylaminobutyl, methacrylic acid-N, N-
Dimethylaminopropyl, -N, N-diethylaminoethyl acrylate, -N, N-diethylaminomethyl acrylate, -N, N-diethylaminobutyl acrylate, -N, N-diethylaminopropyl acrylate, methacrylic acid-
N, N-diethylaminoethyl, methacrylic acid-N, N-diethylaminomethyl, methacrylic acid-N, N-diethylaminobutyl, methacrylic acid-N, N-diethylaminopropyl, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) ) Amide, N, N-dimethylaminomethylacrylic acid (or methacrylic acid) amide, N, N-dimethylaminoethylacrylic acid (or methacrylic acid) amide, N, N-dimethylaminobutylacrylic acid (or methacrylic acid) amide And the like are quaternized by a known method.

The weight ratio (mol%) of these three components is (A) /
(B) / (C) = 5-100 / 0-95 / 0-95 (However,
At least one of (B) and (C) is not 0 mol%) , preferably (A) / (B) / (C) = 10-90 / 10-90 / 10-90 (only
And at least one of (B) and (C) is not 0 mol%) .

The copolymer used in the present invention can be obtained by ordinary radical polymerization under normal pressure or under pressure. Acetone and the like can be used as a polymerization solvent, and azobisisobutyronitrile and the like can be used as a polymerization initiator. The polymerization temperature and time vary depending on the polymerization solvent used and the combination of monomers, but are generally at 40 to 90 ° C.
~ 20 hours is appropriate.

In the present invention, the laundry auxiliary refers to an agent added for a purpose other than washing in the washing step, and specifically includes a softening agent, an antifoaming agent, a bleaching agent, a paste, a fluorescent enhancer, and the like. Whitening agents and the like. Examples of the auxiliary component include a soft base, a paste base, and an antifoam base. In the present invention, these auxiliary components are coated with the copolymer according to the present invention, but when optional components are blended, they may be coated including them.

In particular, as the flexible base, the following general formula (1)
One or two or more selected from the group consisting of a substantially water-insoluble quaternary ammonium salt, a substantially water-insoluble amine, and a substantially water-insoluble amine neutralized salt represented by the following formulas (5) to (5).

[0017]

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[0018]

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R ⁹ : an alkyl or alkenyl group having 11 to 21 carbon atoms R ¹⁰ : an alkyl or alkenyl group having 12 to 22 carbon atoms p: 2-3 m: 1 to 5 n: 1 to 3 Q: -O - or -NH- Y, Z: X indicates either always H H or CH _{3: halogen, CH 3 SO 4, C 2} H 5 SO 4, 1 / 2SO 4, HCO 2, CH 3 CO
₂ or HOCH ₂ CO ₂ In the formula, R ³ , R ⁴ , and R ¹⁰ are preferably an alkyl group or an alkenyl group having 16 to 22 carbon atoms, particularly preferably 16 to 18 carbon atoms;
R ⁷ , R ⁸ and R ⁹ are preferably an alkyl or alkenyl group having 15 to 21 carbon atoms, particularly preferably having 15 to 17 carbon atoms. Specifically, as R ³ and R ⁴ in the compound represented by the above general formula,
It may be an oleyl group or a hardened tallow alkyl group,
R ^7, R ⁷ comprises a ^{R 8, R 9 CO, R} 8 CO, groups R ⁹ CO may be a fatty acid residue or hardened tallow fatty acid residue, such as oleic acid. When the composition of the present invention is used as a softening agent,
The above-mentioned flexible base is generally incorporated in the composition in an amount of 5 to 90% by weight, preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight. The copolymer according to the present invention has a weight ratio of the flexible base to the copolymer of 99.99 / 0.01 to 99.99 / 0.01.
It is common to mix in a range of 50/50.

The paste composition may be prepared by coating a paste base such as cationized starch with the copolymer according to the present invention. When using the composition of the present invention as a paste composition,
The size base is 5 to 90% by weight in the composition, preferably 10 to 60%.
In general, it is blended by weight. Further, the copolymer according to the present invention, the weight ratio of the paste base and the copolymer is 99.99
It is common to mix in the range of /0.01 to 50/50.

In the case of other laundry aids, they may be prepared using known laundry aid components. Examples of the defoaming base for preparing the laundry auxiliary of the present invention as a defoaming agent composition include silicone oil and the like. Further, in order to prepare a bleach composition, hypochlorite, percarbonate, perborate, organic peracid, organic peracid precursor, bluing agent, fluorescent brightener, enzyme, A component generally used for a bleach such as a fragrance is blended with the copolymer according to the present invention. When the composition of the present invention is used as these laundry aids, the weight ratio of the above-mentioned laundry aid component to the copolymer of the present invention is in the range of 99.99 / 0.01 to 50/50. Is common.

The laundry aid composition of the present invention may contain, as an optional component, a dispersion accelerator for promoting the dispersion and dissolution of the laundry aid in water. As the dispersion accelerator, a nonionic or cationic water-soluble dispersion accelerator is used. In particular, the dispersion accelerator is obtained by adding an alkylene oxide containing EO as an essential component to a compound having three or more active hydrogens, and Polyoxyethylene (hereinafter ethylene oxide
Polyether compounds or derivatives thereof having a total weight of the chain portions (abbreviated as EO) of at least 50% of the total weight and a molecular weight of 5,000 to 2,000,000 are preferred. Examples of the compound having three or more active hydrogens as a starting material of the polyoxyalkylene adduct include glycerin, pentaerythritol, sorbitol, sucrose, and polyhydric alcohol.
Polyglycerin, polyvinyl alcohol, partially saponified polyvinyl acetate, etc., polyhydric phenols include phenolic resins and formalin condensates of alkylphenols, and polyamine compounds include diethylene triamine, triethylene tetramine, tetraethylene pentamine, Examples include pentaethylenehexamine and polyethyleneimine, and alkanolamines such as diethanolamine can also be used. Further, a partially amidated compound or an N-alkyl-substituted polyamine which is a derivative of these polyamines can be used as long as three or more active hydrogens remain. The polyether compound which is a polyoxyalkylene adduct can be easily produced by adding an alkylene oxide containing EO as an essential component to a compound having three or more active hydrogens by a usual method. Among them, EO alone or a block or partially block adduct of EO and propylene oxide (hereinafter abbreviated as PO) is preferred, and the order of addition may be any order, but after adding PO first, The case where EO is added is good.

The molecular weight of the polyether compound or its derivative is from 5,000 to 2,000,000, preferably from 5,000 to 1,000.
000,000, particularly preferably in the range 5,000 to 200,000. The total weight of the EO chain is 50% by weight of the total molecular weight.
Or more, preferably 80% by weight or more, more preferably
85% by weight or more. As the polyether compound, R ¹¹ NH (C _s H _2s NH) _r H [R ¹¹ is a hydrocarbon group having 12 to 22 carbon atoms, an alkanoyl group or an alkenoyl group, s is 2 or 3, r is 1 to 3 is there. And the alkylene oxide adduct of the compound represented by the formula:

Examples of derivatives of the polyether compound include sulfates, phosphorus oxides, carboxyalkylated products, fatty acid esterified products of terminal hydroxyl groups of the polyether compound, and those obtained by cationizing a part of nitrogen atoms. Among them, cationized products are particularly preferable. Examples of the cationized compound include a compound obtained by cationizing a polyether compound with a dialkyl sulfate, an alkyl halide, or the like, and a cationized product obtained by neutralizing the polyether compound with acetic acid, alkylbenzenesulfonic acid, or the like.

In addition to the above, as a dispersion accelerator, urea, paratoluenesulfonate, inorganic salt, monoalkyl cation, water-soluble polymer (hydroxyalkylcellulose, carboxymethylcellulose, agar, hydroxyalkylated starch, cation Starch, polyvinyl alcohol, polystyrene sulfonate, etc.), polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, pluronic nonionic surfactant, fatty acid ester higher fatty acid ester, polyoxyethylene adduct and mono / diglyceride And the like. In the present invention, the weight ratio between the laundry auxiliary component and the dispersion accelerator is preferably in the range of 95/5 to 50/50.
When the weight ratio is more than 95/5, the dispersibility of the laundry auxiliary component in water is reduced, and the laundry auxiliary component is not sufficiently transferred to laundry.
The effect may be reduced. On the other hand, if the ratio is less than 50/50, the effect may be reduced because the amount of the laundry auxiliary component is small.

In addition, according to the purpose as an auxiliary, a bactericide, an antibacterial agent, an antioxidant, a fragrance, a fluorescent whitening agent, a silicone for improving iron slip, a salt, an ammonium chloride,
Water-soluble salts such as calcium chloride can also be blended.

The form of the laundry auxiliary composition of the present invention is not particularly limited, but may be solid, for example, powder, granules, granules, or may be formed into tablets. In that case, it is manufactured by a known method such as a solidification pulverization method, an extrusion granulation method, and a spray cooling method. Further, it may be mixed with a film-forming water-soluble polymer to form a film, or may be adsorbed and absorbed on the film.

The laundry auxiliary composition of the present invention may be absorbed and adsorbed on a water-insoluble substrate. The shape and material of the water-insoluble substrate are not particularly limited, but the shape is preferably sheet-like, block-like or spherical, and the material is cloth, non-woven fabric,
A porous body such as paper, sponge, and styrene foam is used. As the non-woven fabric, polyester, polyethylene-polypropylene conjugate fiber, polypropylene fiber, pulp, rayon, nylon and the like are used.

As a method for supporting the laundry auxiliary composition of the present invention on a water-insoluble substrate, a method of dipping / printing in a bath, a spraying method, or depending on the material of the substrate, the method of the present invention may be used at the time of molding the substrate. The composition may be mixed with a laundry aid composition. Regardless of the presence or absence of the substrate, the laundry aid and the copolymer according to the present invention may be mixed and molded or coated. Alternatively, after forming and coating only with the aid, the outer layer may be coated with the copolymer. Coalescence may be coated.

The laundry auxiliary composition of the present invention may be stored separately from the detergent composition, and may be individually added to the detergent solution for washing. Further, they can be used alone without being used in combination with a detergent. Furthermore, it is convenient to mix it in a detergent and use it as a detergent composition. In addition, the copolymer according to the present invention has good hydrolysis resistance, and a composition having excellent long-term storage stability can be obtained.

[0031]

The laundry aid composition of the present invention can sufficiently obtain the effect of the aid even when used together with a detergent. In particular, in the case of using a fully automatic washing machine that has been rapidly spreading in recent years, there is a merit for the user such as a mistake due to forgetting to put the washing machine and a trouble.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

The processing method and the performance evaluation method in the embodiment will be described below. (Washing / assistant treatment) Using a fully automatic washing machine (Hitachi Co., Ltd. “Shigo-Mae” 4.5 kg), commercially available cotton knitted underwear, polyester / cotton blended (65/35) Y-shirt, 1 kg in total, and mud contamination Cloth (10cm × 10cm), carbon / oil-contaminated cloth (10cm × 10cm)
Five sheets of each composition, each composition shown in the table, and 30 g of a commercially available detergent "Attack" (manufactured by Kao Corporation) were added, and washed and rinsed in 3.5 ° DH hard water (36 liters) using a standard course.
Incidentally, the pH of the washing water was 10.2.

(Evaluation of Performance) The clothes treated by the above method were hung and dried in a room, air-dried, and then left in a constant temperature and humidity room of 20 ° C. and 65% RH for 24 hours. With respect to these clothes, the performance evaluation of the assistant was performed by sensory evaluation. The evaluation of the performance of the auxiliary agent was performed by comparing only the auxiliary agent which was not coated and mixed with the copolymer, and the treated clothing was used as a control. At this time, the treatment concentration of each of the product of the present invention, the comparative product and the control was made constant depending on the type of the auxiliary. The evaluation criteria are expressed as follows. +2; more effective than control. +1; slightly more effective than the control. 0; same as control. -1; the control was slightly more effective. -2: The control was more effective.

Example 1 A copolymer of (A), (B), (C) and other monomers shown in Table 1 and a powder of a laundry auxiliary component (D) (particle diameter: 300 to 500 μm)
m) were mixed and (D) was coated with a copolymer by a conventional method to prepare various laundry auxiliary compositions. The copolymer was used so that the blending amount in the composition was 10% by weight. Using these laundry aid compositions, performance was evaluated as described above. Table 1 shows the results.

[0036]

[Table 1]

Example 2 Tablets of a washing aid component (D) (diameter 2 cm × height 0,0), which is a copolymer comprising (A), (B), (C) and other monomers shown in Table 2
5 cm 2) to prepare various laundry aid compositions.
The copolymer was used such that the blending amount in the composition was 1% by weight. Using these laundry aid compositions, performance was evaluated as described above. Table 2 shows the results.

[0038]

[Table 2]

Example 3 A non-woven fabric (20 cm × 20 cm, polypropylene / polyester = 50/50, basis weight 25 g / m ² ) obtained by dispersing or dissolving the laundry aid (D) component shown in Table 3 in an appropriate solvent was used. After impregnating and removing the solvent, the nonwoven fabric containing the component (D) is coated with a copolymer composed of (A), (B), (C) and other monomers shown in Table 3. The copolymer was used so that the blending amount in the composition excluding the nonwoven fabric portion was 3% by weight. Using these laundry aid compositions, performance was evaluated as described above. Table 3 shows the results.

[0040]

[Table 3]

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) D06M 13/46 D06M 15/21-15/353

Claims (6)

(57) [Claims] 1. A laundry auxiliary component comprising: (A) a compound represented by the general formula (I): (Wherein, R represents hydrogen or an alkyl group having 1 to 4 carbon atoms, R ¹ and R ² may be the same or different, and each represents hydrogen or an alkyl group having 1 to 4 carbon atoms, a hydroxyethyl group, Represents a propyl group, and x represents an integer of 1 to 5.) (B) at least one kind of substantially water-insoluble monomer (C) having a dialkylaminoalkyl group in the molecule. at least one water-soluble monomer not containing, (a) 5~100mol%, ( B) 0~95 mol%, (C) 0~95
mol% (where at least one of (B) and (C) is 0 % )
(not mol%) , which is coated with a copolymer obtained by polymerization . 2. The washing auxiliary component is represented by the following general formula (I) : (Wherein, R represents hydrogen or an alkyl group having 1 to 4 carbon atoms)
And R ¹ and R ² may be the same or different,
Elemental or C1-C4 alkyl group or hydroxyethyl
A hydroxypropyl group, x is an integer of 1 to 5
Show. ) At least one of the basic monomers represented by
Characterized by being coated with a polymer obtained by polymerization
Laundry auxiliary composition. 3. The method according to claim 1, wherein the substantially water-insoluble monomer (B) is
Lylic acid ester, methacrylic acid ester, crotonic acid
Stele, itaconic ester, vinyl acetate and styrene
And at least one member selected from the group consisting of
3. The laundry auxiliary composition according to 1 or 2. 4. A washing auxiliary component comprising a substantially water-insoluble 4
Graded ammonium salts, substantially water-insoluble amines and substantially
1 selected from the group consisting of neutralized salts of water-insoluble amines
A seed or two or more kinds of flexible bases.
The laundry auxiliary composition according to claim 1. 5. A flexible base represented by the following general formulas (1) to (5):
Ammonium salts, amines and neutralized salts of amines
The washing according to claim 4, wherein the washing is at least one kind selected from the group consisting of:
A rinse aid composition. Embedded image Embedded image R ⁹ : an alkyl or alkenyl group having 11 to 21 carbon atoms R ¹⁰ : an alkyl or alkenyl group having 12 to 22 carbon atoms p: 2-3 m: 1 to 5 n: 1 to 3 Q: -O- or- NH- Y, Z: H or CH ₃ , one of which always represents H X: Halogen, CH ₃ SO ₄ , C ₂ H ₅ SO ₄ , 1 / 2SO ₄ , HCO ₂ , CH ₃ CO ₂
Or HOCH ₂ CO ₂ . ] 6. The laundry auxiliary component is a paste base.
Item 4. The laundry aid composition according to any one of Items 1 to 3.