JPH11315123A - Tartramide-based copolymer, its production and detergent containing the same copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tartramide-based copolymer having excellent builder ability and useful as a builder for detergents by including a specific monocarboxylic acid structural unit and a specific tartramide structural unit at a specific ratio. SOLUTION: This copolymer comprises 50-95 mol.% structural unit of formula I (M is H, an alkali metal or ammonium; R1 to R3 are each H or an alkyl) and 5-50 mol.% structural unit of formula II (R4 to R9 are each H, an alkyl or an aryl; X and Y are each a single bond or a group of formula III; R10 and R11 are each H, an alkyl or an aryl). The copolymer is obtained by subjecting preferably an unsaturated monocarboxylic acid-based monomer of formula IV (e.g. acrylic acid) to radical polymerization with a tartramide-based monomer of formula V (e.g. N,N-diallyltartramide) in water solvent usually by using a radical polymerization initiator such as potassium persulfate. The copolymer has preferably about 10,000-50,000 number-average molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tartaramide copolymer useful as a builder contained in a detergent, a method for producing the same, and a detergent containing the copolymer.

[0002]

2. Description of the Related Art Builders contained in detergents improve the cleaning effect of surfactants and soaps contained in detergents by blocking polyvalent metal ions (Ca ²⁺ , Mg ^2+, etc.) in water. Has the function of causing. Hitherto, sodium tripolyphosphate (hereinafter, referred to as STPP) has been widely used as a builder, but is hardly used at present due to the problem of eutrophication of lakes, marshes, rivers, and sea areas by phosphates.

As a substitute for STPP, zeolite occupies the mainstream, and this zeolite has a sequestering ability as a builder function, but does not have a dispersing action on stains or an alkali buffering action. In addition, since zeolite is insoluble in water, it has a drawback that it easily causes problems such as adhesion to laundry and clogging of piping. In view of the above problems, in recent years, polymer electrolytes such as polyacrylates and acrylic acid-maleic acid copolymers have been developed as builders to replace STPP and zeolite.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel copolymer having excellent builder activity, which has not been described in any literature, a method for producing the same, and a detergent containing the copolymer. .

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, the following general formula (1)
A structural unit represented by, succeeded in synthesizing a novel tartrate amide copolymer comprising a structural unit represented by the following general formula (2), moreover the copolymer Ca ^2+, M
The inventors have found a new fact that they have excellent sequestering ability of polyvalent metal ions such as g ^2+, and have completed the present invention.

That is, the tartaramide copolymer of the present invention has the structural unit 5 represented by the following general formula (1):
0 to 95 mol% and 5 to 50 mol% of the structural unit represented by the following general formula (2).

Embedded image (In the formula, M represents a hydrogen atom, an alkali metal or ammonium group, and R ₁ , R ₂ and R ₃ are the same or different and represent a hydrogen atom or an alkyl group.)

Embedded image [Wherein R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are the same or different and represent a hydrogen atom, an alkyl group or an aryl group, and X and Y are the same or different and represent a single bond or a group:

Embedded image (Wherein, R ₁₀ and R ₁₁ are the same or different and each represent a hydrogen atom, an alkyl group, or an aryl group). ]

The copolymer of the present invention has the following general formula (3):

Embedded image (In the formula, M, R ₁ , R ₂ , and R ₃ are the same as described above.)
(Including a free acid or a salt thereof, the same applies hereinafter) represented by the following general formula (4):

Embedded image (Wherein, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , X and Y are the same as described above), and are obtained by copolymerizing with a tartaramide monomer.

[0008] The copolymer of the present invention has a number average molecular weight of 50.
It is good to be in the range of 0-100,000. Acrylic acid and / or methacrylic acid are suitable as the unsaturated monocarboxylic acid monomer. As the tartaric acid amide monomer, N, N'-diallyl tartaric acid diamide is preferable. The copolymer of the present invention is obtained by radical polymerization of an unsaturated monocarboxylic acid-based monomer represented by the general formula (3) and a tartaramide amide-based monomer represented by the general formula (4) in an aqueous solvent. It can be manufactured by doing. In particular, the method of the present invention is suitable for producing a copolymer by radical polymerization of acrylic acid and N, N'-diallyltartaryl diamide in an aqueous solvent. The copolymer obtained by radical polymerization is neutralized, if necessary, in whole or in part.
It can be a water-soluble polymer.

The copolymer of the present invention has a high builder ability because of its excellent ability to block polyvalent metal ions such as Ca ²⁺ and Mg ²⁺ . Accordingly, the present invention also provides a detergent containing the above-mentioned copolymer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the alkyl group include an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group and an isopropyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. Further, the general formulas (2) and (4)
In the above, the case where X and Y are a single bond means that the nitrogen atom in the tartaramide residue (tartaroylimino group) and the carbon atom in the polymer main chain or one of the carbon atoms in the double bond are directly bonded to each other. It refers to the case where they are combined.

The copolymer of the present invention has a structural unit represented by the general formula (1) of 50 to 95 mol%, preferably 60 to 95 mol%.
90 mol%, more preferably 70 to 90 mol%, and 5 to 50 mol%, preferably 10 to 40 mol%, and more preferably 10 to 30 mol% of the structural unit represented by the general formula (2). It is a water-soluble polymer composed. Further, the copolymer of the present invention has a number average molecular weight of about 500 to 10,000.
0, preferably about 10,000 to 50,000.

The copolymer of the present invention comprises, for example, an unsaturated monocarboxylic acid monomer capable of forming a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2). It can be obtained by polymerizing a tartaramide monomer having two double bonds which can be obtained. The unsaturated monocarboxylic acid-based monomer is a compound represented by the general formula (3), for example, acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid,
-Alkali metal salts such as pentenoic acid, their sodium salts and potassium salts, or ammonium salts. These may be used alone or in combination of two or more.

The alkali metal salt or ammonium salt is obtained by neutralizing or partially neutralizing the corresponding free acid. The degree of neutralization is 0 to 100 mol%, preferably 10 to 85 mol%. For neutralization, an alkali metal base or an ammonium base is used. Examples of the alkali metal base include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like.
In particular, it is preferable to use sodium hydroxide or potassium hydroxide. As the ammonium base, for example, ammonia, methylamine, propylamine, dimethylamine, di-n-butylamine, dihexylamine, trimethylamine, triethylamine, amines such as triethanolamine, further, tetramethylammonium hydroxide, trimethyllauryl ammonium hydroxide,
Trimethylbenzylammonium hydroxide and the like can be mentioned, and it is particularly preferable to use ammonia.

The neutralization is preferably performed on a copolymer obtained by copolymerizing an unsaturated monocarboxylic acid monomer in the form of a free acid. The tartaramide monomer is represented by the general formula (4),
For example, N, N'-diallyl tartaric acid diamide, N-allyl-N'-vinyl tartaric acid diamide, N, N'-divinyl tartaric acid diamide, N, N'-di (1-pentenyl) tartaric acid diamide, N, N'-distyryl Tartaric diamide, N,
N'-di (2-butenyl) tartaric diamide, N, N'-
Di (styrylmethyl) tartaric diamide, N-allyl-
N'-2-hexenyltartaric acid diamide, N- (3-methyl-2-butenyl) -N'-vinyltartaric acid diamide,
N, N '-(1-methyl-2-butenyl) tartaric diamide, N- (1,1-dimethyl-2-propenyl) -N'
-Allyl tartaric diamide and the like, and these may be used alone or in combination of two or more.

In the present invention, in addition to the above-mentioned monomer, a third
The copolymer may be obtained by adding various other monomers as the monomer (1). Examples of the third monomer include unsaturated polycarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, and alkali metal salts and ammonium salts thereof; and C ₂ -C ₆ of carboxylic acids such as vinyl acetate.
Alkenyl esters; further include allyl acetic acid or its alkali metal salts and ammonium salts. The amount of the third monomer can be arbitrarily determined without departing from the spirit of the present invention.
Preferably it is ４０40 mol%.

The copolymer of the present invention comprises 50 to 95 mol%, preferably 60 mol% of the unsaturated monocarboxylic acid monomer.
~ 90 mol%, more preferably 70-90 mol%,
5 to 50 mol%, preferably 10 to 40 mol%, more preferably 10 to 40 mol% of the tartaramide monomer
And is produced by copolymerizing As a polymerization method, an ordinary method of polymerizing a water-soluble monomer can be adopted, and any method can be adopted. Specifically, bulk polymerization, an aqueous solution polymerization method for polymerizing a monomer aqueous solution itself, solution polymerization for polymerizing a monomer solution of an organic solvent, reverse phase suspension polymerization or reverse phase emulsion polymerization for dispersing an aqueous monomer solution in a hydrocarbon solvent And the like, and it is preferable to use a water-soluble polymerization method. In addition, any of batch, semi-batch or continuous polymerization can be employed.

Examples of the organic solvent include lower alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclohexane; acetone, ethyl acetate; Ketone compounds such as methyl ethyl ketone; dityl formamide, 1,4-dioxane and the like. Further, as the hydrocarbon solvent,
For example, the above-mentioned aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and the like can be mentioned.

When producing a water-soluble polymer according to the present invention, a radical polymerization initiator is usually used. The radical polymerization initiator is appropriately selected and used from a water-soluble polymerization initiator and a water-insoluble polymerization initiator depending on the polymerization method used. As the water-soluble polymerization initiator, for example, hydrogen peroxide,
Disulfate peroxide, a mixture of hydrogen peroxide and disulfate, and the like are used. Examples of the disulfate peroxide include disulfate peroxides such as lithium, sodium, potassium, and ammonium, and specifically, potassium persulfate, ammonium persulfate, and the like. The above-mentioned hydrogen peroxide or disulfuric acid salt is optionally used as a reducing agent such as iron sulfate (I
I), sodium sulfite, sodium bisulfite, sodium dithionite, triethanolamine, ascorbic acid, and the like, can be used in the form of a so-called redox initiator.

Further, water-soluble organic peroxides such as acetylacetone peroxide, methyl ethyl ketone peroxide, tertiary butyl peroxide, cumene hydroperoxide and the like can be used as the water-soluble polymerization initiator. These water-soluble organic peroxides can be used together with the above-mentioned reducing agent. Further, for example, 2,2'-azobis-
(2-amidinopropane) dihydrochloride, 2,2′-azobis- (N, N′-dimethylene) -isobutylamidine dihydrochloride, 2-carbamoylazo-isobutyronitrile,
4,4′-azobis- (4-cyanovaleric acid),
Azo initiators such as 2,2-azobis (2-methylpropionamidine) dihydrochloride can also be used.

Examples of the water-insoluble polymerization initiator include, for example, dibenzoyl peroxide, dicyclohexyl peroxydicarbonate, dilauryl peroxide, azobisisobutyronitrile and the like. These polymerization initiators are used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 15 parts by weight, based on the total amount of the monomers used for the polymerization. The polymerization initiator, simultaneously with the monomer,
Alternatively, separately from the monomer, it is added continuously or intermittently in the form of a solution.

The above polymerization in the present invention may be carried out in the presence of a usual polymerization regulator. Such polymerization regulators include, for example, formaldehyde, acetaldehyde,
Aldehyde compounds having 1 to 4 carbon atoms, such as propionaldehyde and isobutyraldehyde; formic acid; ammonium formate; hydroxylammonium sulfate; , Glycerin, isobutanol and the like. The modifier is preferably used in a proportion of 25% by weight or less based on the total amount of the monomers. When the copolymerization is carried out in the presence of the regulator, the minimum amount of the regulator is 0.2% by weight based on the total amount of the monomers.

As described above, various methods of polymerization can be employed. For example, when a monomer is discontinuously polymerized in the form of an aqueous solution by a batch method, each monomer, polymerization initiator and If necessary, a regulator is simultaneously introduced into the polymerization reactor, and the polymerization is carried out by heating to a predetermined polymerization temperature in an inert gas atmosphere. The polymerization temperature is generally between 20 and 2
The temperature is preferably 00 ° C, preferably 40 to 150 ° C. The copolymer of the present invention obtained as described above is substantially water-soluble, but when it is not easily dissolved in water, it is entirely or completely prepared using sodium hydroxide, potassium hydroxide, ammonia, amine, or the like. It can be made water-soluble by neutralizing a part.

The copolymer of the present invention is blended in a detergent composition as a detergent builder. In that case, the copolymer is added in powder, solid or liquid form. Detergents are usually based on surfactants and builders. The mixing ratio of the builder blended in the detergent is not particularly limited,
Usually about 0.1 to 50% by weight, preferably about 5 to 40% by weight, based on the total amount of the detergent. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. Particularly, an anionic surfactant or a nonionic surfactant is used. Is preferred. The content of the surfactant is about 1 to 5 with respect to the total amount of the detergent.
0% by weight, usually about 5-40% by weight.

In addition to these, known detergent components such as an alkaline buffer, a re-staining inhibitor, a bulking agent, an enzyme, a solubilizing agent,
Needless to say, a fluorescent enhancer, a fragrance and a flavor may be added. Further, in the above detergent composition, in addition to the copolymer of the present invention, conventionally known detergent builders, for example, STPP, zeolite, sodium silicate, sodium carbonate, sodium citrate, polyacrylate and acrylic acid- A polymer electrolyte such as a maleic acid copolymer may be used in combination. The use amount of these conventionally known builders is not particularly limited, but the ratio of the builders in the detergent composition including the copolymer of the present invention is usually about 0.1 to 6.
Suitably, it is 0% by weight, preferably about 5 to 50% by weight.

[0025]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to only these examples. In the following examples, the number average molecular weight and Ca ion sequestering ability were measured by the following methods.

(Measurement method of Ca ion sequestering ability)
Place the sample (ie, obtained in each example) in a 100 ml beaker
10-20 mg was weighed, and 1.3 M
CaCl_Two-0.1 MNH_Three-NH _Four100 Cl solution
Then, the mixture was kept at 25 ° C. Then, calcium ion
Electrode (manufactured by Horiba, pH / ion meter F-2)
Measure the calcium ion concentration of the solution using 3).
Specified. From this measurement, it is blocked by 1 g of sample
Calculate the number of mg of calcium carbonate
On-blocking ability.

(Method of measuring number average molecular weight) The number average molecular weight of the copolymer of the present invention was measured by gel permeation chromatography (GPC). The columns were OH-Pack SB-G and SB-804 manufactured by Showa Denko KK
What connected two HQ was used. Polyethylene glycol and pullulan were used as standard substances.

Example 1 After charging 200 g of ion-exchanged water into a glass reactor equipped with a reflux cooling pipe, a gas injection pipe, a thermometer, and a stirrer, nitrogen was introduced through the gas injection pipe, and the temperature was raised to 90 ° C. Was done. Then, 16.21 g of acrylic acid (225 m
mol) was completely neutralized with 45 g of 20% aqueous NaOH, 5.706 g of N, N'-diallyltartaric diamide
(25 mmol), 2.703 g of potassium persulfate (10
30 g of an aqueous solution of (mmol) was simultaneously introduced from separate introduction tubes continuously over 1 hour. Thereafter, the temperature was kept at 90 ° C. for 2 hours to complete the polymerization. After cooling, concentration was performed to obtain an aqueous solution of a copolymer (crosslinked polymer). The solids content of this solution was 9.84%.

FIG. 1 shows the infrared absorption (IR) spectrum of the obtained copolymer, FIG. 2 shows the nuclear magnetic resonance ( ¹ H-NMR) spectrum, and FIG. 2 shows the measurement results of the number average molecular weight and Ca ion blocking ability. The results are shown in Table 1.

Example 2 N, N'-diallyltartaric acid diamide was charged first, then ammonium persulfate was added, acrylic acid was added dropwise to carry out polymerization, and after completion of the polymerization reaction, 71.34 g of 10% NaOH aqueous solution was added. An aqueous solution of a copolymer was obtained in the same manner as in Example 1 except that the solution was neutralized with the above. The solids content of this solution is 22.
4%. The IR spectrum of the obtained copolymer is shown in FIG. 3, the ¹ H-NMR spectrum is shown in FIG. 4, and the number average molecular weight and the measurement result of Ca ion sequestering ability are shown in Table 1.

[0031]

[Table 1]

[0032]

As described in detail above, the copolymer of the present invention has an effect of being excellent in the ability to block Ca as a builder ability.

[0033]

[Brief description of the drawings]

FIG. 1 is an IR spectrum of a copolymer obtained in Example 1.

FIG. 2 is a ¹ H-NMR spectrum of the copolymer obtained in Example 1.

FIG. 3 is an IR spectrum of the copolymer obtained in Example 2.

FIG. 4 is a ¹ H-NMR spectrum of the copolymer obtained in Example 2.

Claims (4)

[Claims] 1. A structural unit represented by the following general formula (1):
And 50 to 95 mol% of the following general formula (2).
Tartrate comprising 5 to 50 mol% of the structural unit
Copolymers. Embedded image(Where M is a hydrogen atom, an alkali metal or ammonium
A group represented by₁, R _TwoAnd R_ThreeIs a hydrogen atom or a
Represents a alkyl group. )[Wherein, R_Four, R_Five, R₆, R₇, R₈And R₉Is the same
One or different hydrogen atom, alkyl group or aryl
X and Y are the same or different and represent a single bond or
Is the group:(Where R_TenAnd R₁₁Are the same or different
, An alkyl group or an aryl group. ). ] 2. The following general formula (3): (Wherein, M represents a hydrogen atom, an alkali metal or ammonium group, and R ₁ , R ₂ , and R ₃ represent a hydrogen atom and an alkyl group).
The following general formula (4): [Wherein R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are the same or different and represent a hydrogen atom, an alkyl group or an aryl group, and X and Y are the same or different and represent a single bond or a group: Embedded image (Wherein, R ₁₀ and R ₁₁ are the same or different and each represent a hydrogen atom, an alkyl group, or an aryl group). ]
The copolymer according to claim 1, which is obtained by copolymerizing a tartaramide monomer represented by the formula (1). (3) An unsaturated monocarboxylic acid monomer represented by the general formula (3) according to the above (2) and a tartaramide monomer represented by the general formula (4) according to the above (2) in an aqueous solvent. A method for producing a tartaric acid amide-based copolymer, characterized by performing radical polymerization in a solution. 4. A detergent containing the copolymer according to claim 1 or 2.