JPH0952915A - Polymer, its production and polymer-containing composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer by polymerizing a specific monomer component using an aqueous medium, having a prescribed constituent unit, excellent in chelating action, dispersing action and biodegradability, useful as a cleaning composition, etc. SOLUTION: This polymer having a constituent unit of formula I [R1 is H, OH, COOR5 (R5 is Na, K or NH4 ) or a group of formula II (R3 is H, OH or CH2 COOR4 ; R4 is H, Na, K or NH4 ); R2 is H, CH3 or CH2 COOR4 ] and 300-8,000,000 weight - average molecular weight is obtained by using an aqueous medium (e.g. water, etc.) and polymerizing a monomer component containing a monomer of formula III, for example, at about 100 deg.C for about 3 hours. The polymer has plural atomic groups containing 2 to 4 carboxyl groups, contains three or more other atoms existing between a carbon constituting the group and a carbon forming the main chain. The atomic groups are bonded to the main chain and the ratio of the atomic groups preferably amounts to >=5wt.% of the whole polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polymer, a method for producing the same, and a novel composition containing the polymer. The above composition is suitably used, for example, as a detergent composition, an inorganic pigment dispersant, a fiber treatment agent, a water treatment agent (scale inhibitor), and a bleaching aid for wood pulp.

[0002]

2. Description of the Related Art Conventionally, for example, detergent compositions, dispersants, coagulants, water treatment agents (scale inhibitors), chelating agents, fiber treatment agents, bleaching aids for wood pulp, pH adjusting agents, etc.
In addition, various organic chelating agents and inorganic chelating agents are used for applications such as cleaning agents.

Of these, a carboxylic acid polymer (a kind of organic chelating agent) obtained by polymerizing a monomer such as maleic acid or acrylic acid exhibits an excellent chelating action and dispersing action on inorganic particles. It is known to be widely used. Further, it is known that organic chelating agents such as ethylenediaminetetraacetate and nitrilotriacetate have a relatively high ability to effectively capture heavy metal ions.

[0004]

However, a carboxylic acid polymer obtained by polymerizing a monomer such as maleic acid or acrylic acid has a carboxyl group directly bonded to the main chain, so that the carboxyl group is free. Rotation is blocked by the main chain. For this reason, the carboxylic acid-based polymers described above have insufficient ability to trap metal ions, and particularly insufficient ability to trap heavy metal ions.

Organic chelating agents such as ethylenediaminetetraacetate and nitrilotriacetate have a relatively small amount of metal ion trapped per unit weight, and further, inorganic particles required for various applications (fields). The dispersive action against is also insufficient.

Therefore, a chelating agent suitable for various uses, that is, a compound having an excellent dispersing action on inorganic particles, a high ability to capture heavy metal ions, and a large amount of metal ions captured per unit weight has been earnestly desired. There is. Further, in general, the chelating agent is required to have excellent biodegradability.

The present invention has been made in view of the above-mentioned conventional problems, and an object thereof is to provide a novel polymer suitable for various uses, a method for producing the same, and a novel polymer containing the above polymer. To provide a different composition.

[0008]

[Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have proposed a novel polymer, a method for producing the same,
In addition, the inventors have earnestly studied a novel composition containing the above polymer. As a result, the polymer having a specific structural unit is water-soluble, has an excellent dispersing effect on inorganic particles, has a high ability to capture heavy metal ions, and has a large amount of metal ions captured per unit weight. Found out.
It was also confirmed that the polymer had excellent biodegradability. Then, the composition containing the above polymer is suitably provided, for example, as a detergent composition, an inorganic pigment dispersant, a fiber treatment agent, a water treatment agent (scale inhibitor), and a bleaching aid for wood pulp. It was found that the present invention was completed.

That is, the invention according to claim 1 has the general formula (1)

[0010]

Embedded image

The present invention relates to a polymer having a structural unit represented by and having a weight average molecular weight of 300 to 8,000,000.

In order to solve the above-mentioned problems, the polymer according to the second aspect of the present invention has two to four carboxyl groups.
And a plurality of other atomic groups having one atom group, and three or more other atoms are present between the carbon atoms forming the carboxyl group and the carbon atoms forming the main chain so that the above atomic group group forms the main chain. And the proportion of the atomic group group in the entire polymer is 5% by weight or more.

In order to solve the above-mentioned problems, the polymer according to the third aspect of the present invention has a plurality of atomic groups having 2 to 4 carboxyl groups, and the carbon atoms constituting the carboxyl group and the main chain. The atomic group group is bonded to the main chain so that an ester bond exists between the carbon atoms constituting the polymer and the ratio of the atomic group group to the entire polymer is 5% by weight or more. It is characterized by being.

According to the above constitution, the polymer has a molecular structure having a large number of carboxyl groups which are not directly bonded to the main chain. The free rotation of the carboxyl group is not hindered by the main chain. Therefore, the polymer is water-soluble, has an excellent dispersing action on inorganic particles, has a high ability to trap heavy metal ions, and has a high metal ion content per unit weight, as compared with conventional chelating agents. A large amount is captured. Further, the polymer has excellent biodegradability. That is, the above-mentioned polymer has an excellent chelating action and a dispersing action and has excellent biodegradability as compared with conventional chelating agents.

In order to solve the above-mentioned problems, the polymer of the invention as claimed in claim 4 has a biodegradation rate of 40% or more, a calcium ion trapping ability of 200 mgCaCO ₃ / g or more, and a calcium ion stability constant. It is characterized by having an iron ion trapping ability of 4.0 or more, an iron ion capturing ability of 9.0 or more, and a clay dispersing ability of 0.5 or more.

In order to solve the above problems, the polymer of the invention according to claim 5 has a biodegradation rate of 10% or more, a calcium ion trapping ability of 350 mgCaCO ₃ / g or more, and a calcium ion stability constant of 4. It is characterized in that the clay dispersibility is 2 or more and the clay dispersibility is 0.5 or more.

According to the above constitution, the polymer is water-soluble, has an excellent dispersing action on inorganic particles, has a high ability to capture heavy metal ions, and has a unit higher than that of conventional chelating agents. The amount of metal ions captured per weight is large. Further, the polymer has excellent biodegradability.
That is, the above polymer, compared to conventional chelating agents,
With outstanding chelating and dispersing effects,
Has excellent biodegradability.

In order to solve the above-mentioned problems, the method for producing a polymer according to the sixth aspect of the present invention uses an aqueous medium,
General formula (2)

[0019]

Embedded image

It is characterized by polymerizing a monomer component containing a monomer represented by:

According to the above method, a polymer having a molecular structure having a large number of carboxyl groups which are not directly bonded to the main chain can be easily obtained. Therefore, according to the above method, it is possible to obtain a polymer having an excellent chelating action and a dispersing action as well as an excellent biodegradability as compared with the conventional chelating agent.

The composition of the invention described in claim 7 is characterized by containing the polymer described in at least any one of claims 1 to 5 in order to solve the above problems. There is.

According to the above constitution, the composition contains a polymer having excellent chelating and dispersing effects and excellent biodegradability as compared with the conventional chelating agent. . Accordingly, the above composition can be suitably used as, for example, a detergent composition, an inorganic pigment dispersant, a fiber treatment agent, a water treatment agent (scale inhibitor), a bleaching auxiliary agent for wood pulp, and the like.

Hereinafter, the present invention will be described in detail. The polymer having the structural unit represented by the general formula (1) according to the present invention is not particularly limited, but in the formula, the substituent represented by R ₁ is a hydrogen atom, an —OH group, -COOR ₅
Base or

[0025]

Embedded image

The substituent represented by R ₂ is a hydrogen atom, a —CH ₃ group or a —CH ₂ COOR ₄ group, and the substituent represented by R ₃ is a hydrogen atom, an —OH group or consists of -CH ₂ COOR ₄ group, substituent represented by R ₄ is a hydrogen atom, sodium atom, it is constituted by a potassium atom or -NH ₄ group, and the substituent represented by the R _5, sodium atom , Potassium atom or -NH
It is a polymer composed of _four groups. The weight average molecular weight (Mw) of the polymer is 300 to 8,000,000.
Is within the range.

The monomer represented by the general formula (2) used as a raw material in the method for producing a polymer according to the present invention is not particularly limited, but in the formula, R
_The substituents represented by _{1 to} R ₄ are monomers composed of the substituents exemplified above. The above-mentioned monomer is obtained by reacting an ethylenically unsaturated carboxylic acid with a hydroxyl group-containing polycarboxylic acid.

Specific examples of the ethylenically unsaturated carboxylic acid include unsaturated monocarboxylic acids such as (meth) acrylic acid, α-hydroxyacrylic acid and crotonic acid, their salts, and their esters. monster;
Maleic acid, maleic anhydride, fumaric acid, itaconic acid,
Unsaturated polycarboxylic acids such as citraconic acid and aconitic acid and salts thereof, and esterified products thereof; and the like. Specific examples of the esterified product include:
Examples thereof include methyl acrylate, methyl methacrylate, methyl maleate and the like. These compounds may be used alone or in combination of two or more.

Specific examples of the above-mentioned hydroxyl group-containing polycarboxylic acid include citric acid, malic acid, tartaric acid, succinic acid, and salts and hydrates of these compounds. These compounds may be used alone or in combination of two or more.

Of the above-exemplified compounds, maleic anhydride is more preferred as the ethylenically unsaturated carboxylic acid,
Citric acid is more preferable as the hydroxyl group-containing polycarboxylic acid. The esterification reaction between maleic anhydride and citric acid is easy, and the polymer obtained by polymerizing the resulting esterified monomer is particularly excellent in physical properties as a chelating agent. Further, the monomer can be obtained in higher purity by subjecting the ethylenically unsaturated carboxylic acid ester (esterified product) and the hydroxyl group-containing polycarboxylic acid to transesterification reaction.

In the above reaction, a solvent may be added to the reaction system, if necessary. Specific examples of the above solvent include organic solvents such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, methylene chloride, hexane, cyclohexane, acetone, methyl ethyl ketone, and dimethylformamide. There is no particular limitation as long as it does not inhibit. The amount of use is not particularly limited. When maleic anhydride is used as the ethylenically unsaturated carboxylic acid, it is preferable to carry out the esterification reaction without a solvent. This can improve the yield of the corresponding monomer.

A catalyst can be used in the above reaction. As the above-mentioned catalyst, specifically, for example, a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid; an organic acid such as paratoluenesulfonic acid; a solid acid such as a heteropolyacid; an acid type ion exchange resin and the like can be used. However, it is not particularly limited.

The reaction temperature of the esterification reaction is
Although not particularly limited, it is preferably set in the range of 10 ° C to 180 ° C, and more preferably set in the range of 50 ° C to 160 ° C in order to improve the yield of the monomer. preferable. Then, the reaction time may be appropriately set depending on the type and combination of the ethylenically unsaturated carboxylic acid, the hydroxyl group-containing polyvalent carboxylic acid, the solvent and the catalyst, the amount used, the reaction temperature, etc., so that the above reaction proceeds sufficiently. Good.
The reaction pressure is not particularly limited, and may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure.

In the above reaction, the obtained monomer has a property of being easily polymerized, so that a polymerization inhibitor such as hydroquinone may be added to prevent the polymerization reaction. Further, in the above reaction, when maleic acid and / or maleic anhydride is used as the ethylenically unsaturated carboxylic acid, a metal such as ferrous ammonium sulfate is used in order to prevent the resulting monomer from being colored. A compound may be added.

The substituent represented by R ₄ in the general formula (2) is a sodium atom, a potassium atom or-.
The monomer composed of the NH ₄ group is obtained by reacting an ethylenically unsaturated carboxylic acid with a hydroxyl group-containing polyvalent carboxylic acid and then producing a compound, for example, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, It can be easily obtained by treating with a basic compound aqueous solution such as aqueous ammonia. The treatment method is not particularly limited.

The polymer according to the present invention is obtained by polymerizing the monomer (monomer component) represented by the above general formula (2) alone or by copolymerizing with the above monomer. It is easily produced by copolymerizing a monomer component containing an unsaturated monomer.

The above ethylenically unsaturated monomer preferably has water solubility, and more preferably has a solubility of 5 g or more in 100 g of water at 100 ° C. The ratio of the monomer represented by the general formula (2) to the ethylenically unsaturated monomer is the molar ratio of the monomer represented by the general formula (2) to the total amount of both. , 1/100 or more and less than 1/1.

The weight average molecular weight of the polymer according to the present invention is preferably in the range of 300 to 8,000,000, more preferably in the range of 500 to 100,000,
The range of 1,000 to 20,000 is more preferable.
In particular, when the polymer, that is, the composition is used as a detergent composition (detergent builder), the weight average molecular weight is 500.
The range of 100 to 100,000 is preferable, and the range of 3,000 to 1
The range of 5,000 is more preferable. If the weight average molecular weight is out of the above range, the physical properties of the composition containing the polymer obtained are deteriorated, which is not preferable.

Specific examples of the ethylenically unsaturated monomer include unsaturated monocarboxylic acids such as (meth) acrylic acid, α-hydroxyacrylic acid, crotonic acid and salts thereof; maleic acid, Unsaturated polycarboxylic acids such as maleic anhydride, fumaric acid, itaconic acid, citraconic acid, aconitic acid and salts thereof; vinyl acetate and the like can be mentioned.

As the ethylenically unsaturated monomer, a compound represented by the general formula (3)

[0041]

[Chemical 6]

(In the formula, R ₆ and R ₇ are H atom or --CH
Represents ₃ group, and, R ₆ and R ₇ are not equal to -CH ₃ group simultaneously, R ₈ is _{-CH 2 -, - (CH 2} ) 2 -
Or -C (CH _{3) 2} - represents, and the number of carbon atoms contained in R _6, R ₇ and R ₈ is the total 3, Y 2 carbon atoms
~ 3 alkylene group, n is an integer of 0-100), a hydroxyl group-containing unsaturated compound represented by, for example, 3-
Methyl-3-buten-1-ol (isoprenol),
3-methyl-2-buten-1-ol (prenol),
2-Methyl-3-buten-2-ol (isoprene alcohol), and 1 mol of ethylene oxide and / or propylene oxide per 1 mol of these compounds.
It is also possible to use a compound added in an amount of 100 to 100 mol.

Further, as the ethylenically unsaturated monomer,
General formula (4)

[0044]

[Chemical 7]

(In the formula, R ₉ represents an H atom or a —CH ₃ group, a, b, c and d are integers of 0 to 100,
And a + b + c + d = 0 to 100, and -O
The order of the C ₂ H ₄ — and —OC ₃ H ₆ — bonds is not limited, and when c + d = 0, Z represents a hydroxyl group, a sulfonic acid group or a (sub) phosphoric acid group, and c + d = 1. ~ 1
In the case of 00, Z represents a hydroxyl group),
For example, 3-allyloxy-2-hydroxypropanesulfonic acid and its salt; glycerol monoallyl ether, and 1 mol to 1 mol of ethylene oxide and / or propylene oxide per 1 mol of this compound.
Unsaturated (meth) allyl ether compounds such as compounds added with 00 mol; vinyl sulfonic acid, allyl sulfonic acid,
Unsaturation of methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, 2-hydroxysulfopropyl (meth) acrylate, sulfoethyl maleimide, etc. Sulfonic acid group-containing compounds and salts thereof; alcohols obtained by adding 0 to 100 mol of ethylene oxide and / or propylene oxide to an alkyl alcohol having 1 to 20 carbon atoms, and monocarboxylic acids such as (meth) acrylic acid and crotonic acid. Or a monoester with a polyvalent carboxylic acid such as maleic acid, fumaric acid, itaconic acid, citraconic acid, or aconitic acid, or a salt of a monoester, and a terminal alkyl group-containing ester unsaturated compound such as a diester ; ( Data) acrylic acid, the unsaturated carboxylic acid 1 mole of crotonic acid, 1 mole to 100 ethylene oxide and / or propylene oxide
Ester compound added by moles, or maleic acid,
1 mol to 10 mol of ethylene oxide and / or propylene oxide to 1 mol of unsaturated carboxylic acid such as fumaric acid, itaconic acid, citraconic acid, and aconitic acid.
It is also possible to use a 0-added monoester compound, a salt of a monoester compound, or an ester unsaturated compound such as a diester compound;

The above ethylenically unsaturated monomers may be used alone or in combination of two or more. Among these exemplified compounds, (meth) acrylic acid (salt) is particularly preferable from the viewpoint of polymerization reactivity and various physical properties of the obtained polymer.

Examples of the polymerization initiator used for producing the polymer according to the present invention include hydrogen peroxide; persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate; 2,2′-azobis. (2-amidinopropane) hydrochloride; 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobisisobutyronitrile, 2,
Azo compounds such as 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, peracetic acid, persuccinic acid, di-t-butylperoxide, t-butylhydro. Examples thereof include organic peroxides such as peroxide and cumene hydroperoxide, but are not particularly limited. One of these polymerization initiators may be used alone, or two or more thereof may be used in combination.

The pH during the polymerization reaction can be set to any value, but since the monomer is acidic, it is preferable to neutralize the reaction solution with a basic compound from the viewpoint of improving the reactivity. . Specific examples of the basic compound suitable for use in neutralization include hydroxides and carbonates of alkali metals such as sodium, potassium and lithium; ammonia; monomethylamine, dimethylamine, trimethylamine and monoethylamine. , Alkylamines such as diethylamine and triethylamine; monoethanolamine,
Alkanolamines such as diethanolamine, triethanolamine, isopropanolamine and isobutanolamine; pyridine; and the like. These basic compounds may be used alone or in combination of two or more.

Further, when the monomers are polymerized in the presence of polyvalent metal ions, the amount of the monomers remaining in the reaction solution after completion of the polymerization can be reduced, and therefore, the molecular weight distribution of the polymer can be reduced. Can be narrowed. Specific examples of the polyvalent metal ions include iron ions, vanadium atom-containing ions, and copper ions. Among these exemplified ions, Fe ³⁺ , Fe ²⁺ , Cu ⁺ , Cu ²⁺ ,
V ²⁺ , V ³⁺ and VO ²⁺ are preferable, Fe ³⁺ , Cu ²⁺ and VO
²⁺ is particularly preferred. These polyvalent metal ions may be used alone or in combination of two or more.

The concentration of polyvalent metal ions is preferably 0.1 ppm to 100 ppm with respect to the total amount of the reaction solution.
When the concentration of the polyvalent metal ion is less than 0.1 ppm, the above-mentioned effects can hardly be expected, which is not preferable. When the concentration of the polyvalent metal ion exceeds 100 ppm, for example, a maleic acid-based copolymer obtained by copolymerizing a maleic acid-based monomer is colored and is difficult to use as a detergent composition or the like. Therefore, it is not preferable. The polymer polymerized in the presence of a polyvalent metal ion is excellent in iron ion capturing ability (so-called iron particle deposition preventing ability) and can be particularly preferably used as a detergent composition and the like.

The method of allowing polyvalent metal ions to be present in the reaction solution is not particularly limited, and for example, a metal compound or a metal which is ionized in the reaction solution may be added to the reaction solution. Specific examples of the above-mentioned metal compounds and metals include vanadium oxytrichloride, vanadium trichloride, vanadium oxalate, vanadium sulfate, vanadian anhydride, ammonium metavanadate, ammonium sulfate hypovanadas [(NH ₄ ) ₂ SO ₄ , VSO ₄ , 6H ₂
O], ammonium sulfate vanadas [(NH ₄ ) V (SO ₄ ).
₂ · 12H ₂ O], copper (II) acetate, copper (II) bromide, copper (II) acetylacetonate, cupric chloride, copper ammonium chloride, copper carbonate, copper (II) chloride, copper citrate ( II),
Copper (II) formate, copper (II) hydroxide, copper nitrate, copper naphthenate, copper (II) oleate, copper maleate, copper phosphate, copper (II) sulfate, cuprous chloride, copper cyanide ( I), copper iodide, copper (I) oxide, copper thiocyanate, iron acetylacetonate, ammonium iron citrate, ferric ammonium oxalate, ferrous ammonium sulfate, ferric ammonium sulfate, iron citrate, Water-soluble metal salts such as iron fumarate, iron maleate, ferrous lactate, ferric nitrate, iron pentacarbonyl, ferric phosphate, ferric pyrophosphate; vanadium pentoxide, copper (II) oxide, Examples thereof include metal oxides such as ferrous oxide and ferric oxide; metal sulfides such as copper (II) sulfide and iron sulfide; copper powder and iron powder; however, they are not particularly limited.

Specific examples of the aqueous medium used in the above polymerization reaction include water; alcohols such as methanol, ethanol and propanol; ethers such as diethyl ether; cellosolves such as ethyl cellosolve and n-butyl cellosolve. Examples thereof include ketones such as methyl ethyl ketone; and the like, but are not particularly limited.

The reaction conditions of the above-mentioned polymerization reaction may be set, for example, to a reaction temperature of about 100 ° C. and a reaction time of about 3 hours, but are not particularly limited, and the monomer, the catalyst and the aqueous medium may be used. It may be appropriately set according to the type and amount of the. The reaction pressure is not particularly limited, and may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure.

As described above, the polymer according to the present invention is
It has a structural unit represented by the general formula (1) and has a weight average molecular weight in the range of 300 to 8,000,000.
Further, as is clear from the structural unit represented by the general formula (1), the polymer has a plurality of atomic groups having 2 to 4 carboxyl groups, and a carbon atom constituting the carboxyl group. A structure in which the atomic group group is bonded to the main chain such that three or more other atoms are present between the main chain and carbon atoms (that is, —C—O—C—). is there. Further, as is clear from the structural unit represented by the general formula (1), the polymer has a plurality of atomic groups having 2 to 4 carboxyl groups, and a carbon atom constituting the carboxyl group. This is a constitution in which the above-mentioned atomic group group is bonded to the main chain such that an ester bond (that is, -COO-) is present between the main chain and carbon atoms. And, as is clear from the composition of the monomer components,
In the polymer according to the present invention, the ratio of the atomic group group in the whole polymer is 5% by weight or more.

Therefore, the polymer has a molecular structure having a large number of carboxyl groups which are not directly bonded to the main chain. The free rotation of the carboxyl group is not hindered by the main chain.

The above-mentioned polymer is water-soluble, has an excellent dispersing action on inorganic particles, has a high ability to capture heavy metal ions, and has a high ability to capture heavy metal ions as compared with conventional chelating agents, and also has a high metal ion content per unit weight. A large amount of is captured. Further, the polymer has excellent biodegradability. That is, the above-mentioned polymer has an excellent chelating action and a dispersing action and has excellent biodegradability as compared with conventional chelating agents.

The polymer according to the present invention has a biodegradation rate of 40% or more and a calcium ion trapping ability of 200 mg.
CaCO ₃ / g or more, calcium ion stability constant of 4.0 or more, iron ion trapping ability of 9.0 or more, and clay dispersing ability of 0.5 or more, or biodegradation rate of 1
0% or more, calcium ion trapping capacity 350mgCaC
O ₃ / g or more, calcium ion stability constant of 4.2 or more, and clay dispersibility of 0.5 or more.

The above calcium ion-capturing ability is a physical property defined as a numerical value (mgCaCO ₃ / g) obtained by converting the amount of calcium ions captured by 1 g of the polymer into calcium carbonate. The calcium ion-capturing ability represents, for example, the degree of detergency (detergency) of a polymer-containing detergent composition (described later), and the higher the value, the better the detergency. Calcium ion capture capacity is 200mg
When it is less than CaCO ₃ / g, for example, when it is used in a detergent composition, an inorganic pigment dispersant, a fiber treating agent, etc., satisfactory performance cannot be obtained, which is not preferable.

The above-mentioned calcium ion stability constant is a numerical value showing the chelating ability to chelate calcium ions in water. The higher the numerical value, the better the chelating ability. That is, the calcium ion stability constant, for example, in a detergent composition, the higher the numerical value, the higher the ability to peel mud stains from fibers by peeling calcium ions present in mud during washing. Indicates. Calcium ion stability constant is 4.
When it is less than 0, for example, when used in a detergent composition or the like, satisfactory performance cannot be obtained, which is not preferable.

The above-mentioned iron ion trapping ability is a numerical value showing the trapping ability for trapping iron ions in water.
It shows that the trapping ability is excellent. That is, for example, in the detergent composition, the higher the value of the iron ion-capturing ability, the higher the ability to prevent the yellowing of clothes during washing. The iron ion capturing ability is more preferably 11.0 or more, further preferably 13.0 or more. An iron ion-capturing ability of less than 9.0 is not preferable because, for example, when used in a detergent composition or the like, satisfactory performance cannot be obtained.

The above-mentioned clay dispersibility is represented by the turbidity of the supernatant of the suspension after the suspension in which the clay is dispersed is allowed to stand for a certain period of time. The higher the value, the higher the dispersibility. It is shown to be excellent. That is, the clay dispersibility is
For example, in the detergent composition, the higher the value, the higher the ability to disperse mud stains and the like from the fibers at the time of washing to disperse the mud. The clay dispersibility is more preferably 1.2 or more, and further preferably 1.4 or more in order to prevent the deposition of mud stains. When the clay dispersibility is less than 0.5, for example, when used in a detergent composition or the like, satisfactory performance cannot be obtained, which is not preferable.

The above-mentioned biodegradation rate, calcium ion trapping ability, calcium ion stability constant, iron ion trapping ability,
The method for measuring the clay dispersibility will be described in detail in Examples.

Further, as described above, the method for producing a polymer according to the present invention uses an aqueous medium to produce the compound represented by the general formula (2).
It is a method of polymerizing a monomer component containing a monomer represented by.

As a result, a polymer having a molecular structure having a large number of carboxyl groups which are not directly bonded to the main chain can be easily obtained. Therefore, according to the above method, it is possible to obtain a polymer having an excellent chelating action and a dispersing action as well as an excellent biodegradability as compared with the conventional chelating agent.

Next, the composition according to the present invention will be described. The composition according to the present invention contains the above-mentioned polymer, for example, a detergent composition, an inorganic pigment dispersant, a fiber treatment agent, a water treatment agent (scale inhibitor), and a bleaching aid for wood pulp. It is preferably used for The compositions used for these applications will be described in detail below.

The above detergent composition contains the polymer, a surfactant and, if necessary, an enzyme.
The proportion of the polymer in the detergent composition is 0.1% by weight to 2%.
0 wt% is preferred, and 0.5 wt% to 15 wt% is more preferred. The surfactant is preferably an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant.

Specific examples of the anionic surfactant include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate and α-sulfo. Fatty acid salt, α-sulfo fatty acid ester salt, alkane sulfonate, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant , An alkyl phosphate ester or a salt thereof, an alkenyl phosphate ester or a salt thereof, and the like.

Specific examples of nonionic surfactants include polyoxyalkylene alkyl ethers,
Polyoxyalkylene alkenyl ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct,
Examples thereof include sucrose fatty acid ester, alkylglycoxide, fatty acid glycerin monoester, and alkylamine oxide.

Specific examples of the amphoteric surfactant include carboxy type or sulfobetaine type amphoteric surfactants. Specific examples of the cationic surfactant include quaternary ammonium salts and the like.

The proportion of the above surfactant in the detergent composition is preferably 5% by weight to 70% by weight, and 20% by weight to
60% by weight is more preferred.

Specific examples of the above-mentioned enzyme include protease, lipase, cellulase and the like. In particular, protease, alkaline lipase, alkaline cellulase and the like, which have high activity in the alkaline washing solution, are preferable. The proportion of the enzyme in the detergent composition is preferably 0.01% by weight to 5% by weight. If the amount of the enzyme compounded is out of this range, the balance with the surfactant may be lost and the detergency may not be improved.

If necessary, the detergent composition may further contain known components such as alkali builder, chelate builder, anti-redeposition agent, fluorescent agent, bleaching agent, and fragrance, which are commonly used in detergent compositions. Good. Examples of alkali builders include silicates, carbonates and sulfates. As the chelate builder, diglycolic acid, oxycarboxylic acid salt, EDTA (ethylenediaminetetraacetic acid), DTPA
(Diethylenetriamine hexaacetic acid), citric acid and the like. Further, zeolite may be further added to improve the detergency.

The above fiber treating agent contains, in addition to the polymer, at least one component selected from the group consisting of dyeing agents, peroxides and surfactants. The fiber treating agent can be used in steps such as scouring, dyeing, bleaching and soaping in fiber treatment. As the dyeing agent, peroxide and surfactant, those used in known fiber treatment agents can be diverted.

When the polymer is a maleic acid-based copolymer, the blending ratio of the dyeing agent, the peroxide, the surfactant and the polymer is, for example, the whiteness of the fiber, color unevenness, and dyeing strength. In order to improve the waxiness, to 1 part by weight of the polymer,
The dye and the like may be added in a proportion of 0.1 to 100 parts by weight. The fibers for which the fiber treatment agent can be used are not particularly limited, and examples thereof include cellulosic fibers such as cotton and hemp; chemical fibers such as polyamide and polyester; animal fibers such as wool and silk; human silk. Semi-synthetic fibers such as; and woven fabrics and blended products using these fibers.

For example, when a fiber treatment agent containing a maleic acid-based copolymer as a polymer is applied to the scouring step, the fiber treatment agent should contain a known alkali agent and surfactant. preferable. Further, for example, when a fiber treatment agent containing a maleic acid-based copolymer as a polymer is applied to the bleaching step, the fiber treatment agent is a peroxide and sodium silicate which is a decomposition inhibitor of an alkaline bleaching agent. And a silicic acid-based agent such as

In addition to the polymer, the above-mentioned inorganic pigment dispersant may contain polymerized phosphoric acid and its salt, phosphonic acid and its salt, polyvinyl alcohol, and anionized modified polyvinyl alcohol, if necessary. There is.

The inorganic pigment dispersant exhibits good performance as a dispersant for heavy or light calcium carbonate used for paper coating or an inorganic pigment used for clay or the like. That is, by adding a small amount of an inorganic pigment dispersant to an inorganic pigment and then dispersing it in water, it has a low viscosity and high fluidity, and does not cause a change with time in these performances, and is a stable high-concentration inorganic pigment. Slurries, for example concentrated calcium carbonate slurries, can be produced. The amount of the inorganic pigment dispersant used is 0.0 with respect to 100 parts by weight of the inorganic pigment.
5 to 2.0 parts by weight is preferable.

In addition to the polymer, the above-mentioned water treatment agent contains, if necessary, a polymeric phosphate, a phosphonate, an anticorrosive agent, a slime control agent, and a chelating agent.
The water treatment agent is useful for scale prevention in a cooling water circulation system, a boiler water circulation system, a seawater desalination apparatus, a pulp digester, a black liquor concentrator, and the like.

The wood pulp bleaching aid contains the polymer. The bleaching aid may be used as a pretreatment agent during bleaching of wood pulp, or may be used in combination with hydrogen peroxide, a chlorine bleaching agent, ozone, etc. during bleaching of wood pulp.

As described above, the composition according to the present invention is
It is a structure containing the above-mentioned polymer. That is, the composition contains a polymer having excellent chelating and dispersing effects and excellent biodegradability as compared with the conventional chelating agent. Therefore, the above composition can be suitably used, for example, as a detergent composition, an inorganic pigment dispersant, a fiber treatment agent, a water treatment agent (scale inhibitor), and a bleaching aid for wood pulp.

[0081]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these. In addition, "part" described in Examples and Comparative Examples means "part by weight".

Example 1 Into a four-necked flask having a capacity of 1 L equipped with a thermometer, a stirrer and a reflux condenser, 490.3 parts of maleic anhydride (as an ethylenically unsaturated carboxylic acid as a raw material of a monomer, 196 parts, 294.3 parts as an ethylenically unsaturated monomer which is a copolymer), citric acid monohydrate (hydroxyl group-containing polycarboxylic acid which is a raw material of a monomer) 4
20 parts, paratoluenesulfonic acid (catalyst) 3 parts, and ferrous ammonium sulfate hexahydrate (metal compound)
0.01 part was charged, the temperature was raised to 120 ° C. with stirring, and the temperature was maintained for 30 minutes.

Next, after the reaction solution was cooled to 80 ° C., 93.75 parts of a 48% by weight aqueous solution of sodium hydroxide as a basic compound and 406.3 parts of pure water as an aqueous medium were further added to the reaction solution. I prepared it. Then, this aqueous solution was heated at normal pressure to a temperature at which it boiled while stirring. Thereby, a maleic acid-citric acid half ester (monoester) as a monomer was prepared.

Next, 257.2 parts of 35 wt% hydrogen peroxide solution as a polymerization initiator was added to this aqueous solution with stirring.
It dripped over 80 minutes. In addition, in parallel with this dropping operation, 2350 parts of a 30% by weight aqueous solution of sodium acrylate as an ethylenically unsaturated monomer was added to the aqueous solution.
The mixture was added dropwise over 0 minutes to carry out a polymerization reaction. The molar ratio of the above monomer, maleic anhydride and sodium acrylate was 24:16:60 in this order. Table 1 shows the amounts (molar ratios) of the above compounds used.

After the completion of the reaction, 209.2 parts of a 48% by weight aqueous solution of sodium hydroxide was added to the above reaction solution to neutralize it.
As a result, an aqueous solution containing 38% by weight of solid content was obtained. As a result of analyzing the aqueous solution by a predetermined method, it was confirmed that the novel polymer according to the present invention was contained.

The weight average molecular weight (Mw) of the polymer obtained as described above (hereinafter referred to as the polymer) and the amount of unreacted monomer (% by weight) were determined by gel permeation chromatography. It was measured. In the above measurement, the column used was Asahi Kasei Asahi Pack GFA-7MF (trade name; manufactured by Asahi Kasei Corporation), and the eluent was
A 0.5 wt% phosphoric acid aqueous solution was used. As a molecular weight standard sample, a sodium polyacrylate standard sample (manufactured by Soka Kagaku Co., Ltd.) was used. As a result, the weight average molecular weight of the polymer was 13,000, and the amount of unreacted monomer was 0.4% by weight.

The biodegradation rate (%) of the above polymer was
It was calculated by performing the following biodegradation test. Furthermore, in order to investigate various properties such as chelating ability of the polymer, calcium ion trapping ability (mgCaCO ₃ / g),
The calcium ion stability constant, iron ion trapping ability, and clay dispersing ability were measured under the measurement conditions shown below.

(A) Biodegradation test The biodegradation test is a modified MITI (Ministry of Act) based on the Chemical Substances Control Law (law concerning examination of chemical substances and regulation of production, etc.)
International Trade and Industry) test.

First, a basal culture medium was prepared by the following method. That is, A liquid, B liquid, C liquid, and D liquid defined in the section of biochemical oxygen consumption amount in JIS K 0102 (Factory wastewater test method) were prepared. Liquid A is
In 1 L of water, 21.75 g of dipotassium phosphate, 8.5 g of monopotassium phosphate, disodium phosphate dodecahydrate 44.
It is an aqueous solution obtained by dissolving 6 g and 1.7 g of ammonium chloride. Solution B is an aqueous solution prepared by dissolving 22.5 g of magnesium sulfate heptahydrate in 1 L of water. Solution C is an aqueous solution prepared by dissolving 27.5 g of anhydrous calcium chloride in 1 L of water. Liquid D is iron chloride (III
) An aqueous solution obtained by dissolving 0.25 g of hexahydrate.
Then, a basic culture medium was prepared by adding 3 ml of each of the above liquids A to D to 1 L of distilled water in this order.

Then, a flask having a capacity of 500 ml was charged with the above-mentioned basic culture medium and a predetermined amount of the polymer as a test substance, and the pH was adjusted to 7 using sodium hydroxide. Then, TOC (Total Organic Carbon) of this mixed solution was measured. Then, the flask was charged with pure water culture sludge (6,000 p) as a biological source.
pm) was charged in a predetermined amount. As a result, 300 ml of a test liquid having a polymer concentration of 100 ppm and a sludge concentration of 30 ppm was obtained.

Further, a predetermined amount of the above-mentioned basic culture medium was charged into a flask having a capacity of 500 ml, and the pH was adjusted to 7 using sodium hydroxide. As a result, the blank test solution 30
0 ml was obtained. Then, the TOC of this blank test solution was measured.

Thereafter, the flask was covered with a cotton plug, and the flask was placed in a constant temperature shaking incubator whose temperature was adjusted to 25 ± 3 ° C. Then, the test solution was cultured for 28 days while being rotated and shaken at 150 times / minute. Similarly, a blank test was conducted using a blank test solution.

Immediately after culturing, the test solution was centrifuged at 3,000 rpm for 10 minutes using a centrifuge to precipitate sludge and obtain a supernatant. Then, the TOC of the supernatant was measured and the TOC of the blank test solution was measured.

The obtained measured values, that is, the measured value S ₀ (mg / L) of the test solution before culturing, the measured value B ₀ (mg / L) of the blank test solution before culturing, and the test value after culturing Measured value S _t (mg
/ L) and the measured value of the blank test solution after culturing B _t (mg
/ L), the following equation, biodegradation rate (%) = [{(S ₀ −B ₀ ) − (S _t −
Accordance _{B t)} / (S 0} -B 0) ] × 100, was calculated biodegradation rate (%). As a result, the biodegradation rate of the polymer was 25%.

(B) Calcium ion scavenging ability The calcium ion scavenging ability was measured by the following measuring method. That is, first, calcium carbonate (CaCO ₃ ) is added to water.
Calcium ion (Ca ²⁺ ) by dissolving
A calcium carbonate aqueous solution having a concentration of 1.0 × 10 ⁻³ mol / L was prepared. Next, after placing 10 mg of the polymer (calculated as solid content) in a beaker having a capacity of 100 ml, 50 ml of the above calcium carbonate aqueous solution was added. And
The obtained measurement liquid is used for 25 with a magnetic stirrer.
The mixture was stirred at 0 ° C for 10 minutes.

After stirring, the calcium ion concentration of the measurement liquid was measured by an ion analyzer (EA920; manufactured by Orion) equipped with a calcium electrode (93-20, manufactured by Orion).
Was measured using. The calcium ion concentration of the measurement liquid before stirring was also measured in the same manner. Then, the difference in calcium ion concentration before and after stirring was calculated.

From the calculated numerical value (mol / L), the amount of calcium ion captured by 1 g of the polymer was determined, and this amount was further calculated as the amount of calcium carbonate (mgCaCO ₃ /
It was converted to g). Then, this converted value was used as the calcium ion capturing ability. As a result, the calcium ion-capturing ability of the polymer was 480 mgCaCO ₃ / g.

(C) Calcium ion stability constant The calcium ion stability constant was measured by the following measuring method. That is, first, calcium chloride (CaCl
₂ ) is dissolved to give a concentration of 0.002 mol /
L, 0.003 mol / L and 0.004 mol / L calcium chloride aqueous solutions were prepared, respectively.

Next, 50 g of the above aqueous solution was placed in three beakers each having a capacity of 100 ml, and then 50 mg of the polymer (as solid content) was added to each of these three types of aqueous solutions. Then, after adjusting the pH of each of the obtained measurement solutions to 10, 0.15 g of sodium chloride (NaCl) as a calcium ion electrode stabilizer was added to these measurement solutions. Then, the free calcium ion concentration in the measurement liquid was measured using a calcium electrode.

Here, the concentration of free calcium ions is [Ca], the concentration of calcium ions immobilized by the polymer is [CaS], the number of all chelate sites in the polymer is [S ₀ ], and The number of free chelate sites [S], the calcium ion stability constant
Assuming log K, [Ca] · [S] / [CaS] = 1 / K [S] = [S ₀ ] − [CaS]. Therefore, from the above equations, [Ca] / [CaS] = (1 / [S ₀ ]) · [Ca] +
It becomes 1 / ([S ₀ ] .K).

Therefore, if [Ca] / [CaS] is plotted on the vertical axis and [Ca] is plotted on the horizontal axis, [S ₀ ] and K can be easily calculated from the slope and intercept of the straight line. . That is, the calcium ion stability constant (log K) can be easily calculated.

The calcium ion stability constant was calculated using the above-mentioned measurement result of the free calcium ion concentration.
As a result, the calcium ion stability constant of the polymer was 6.2.

(D) Iron ion trapping ability The iron ion trapping ability was measured by the following measuring method. That is, first, ferric chloride hexahydrate was dissolved in water to prepare a 0.1 wt% aqueous solution of ferric chloride hexahydrate. Further, a 0.1 wt% sodium hydroxide aqueous solution was prepared by dissolving sodium hydroxide in water.
Further, the polymer was dissolved in water to prepare a 0.1 wt% polymer aqueous solution in terms of solid content.

Next, a test solution was prepared by putting 150 ml of the ferric chloride aqueous solution, 150 ml of the sodium hydroxide aqueous solution, and 150 ml of the polymer aqueous solution into a beaker having a capacity of 500 ml. Then, the obtained test liquid was stirred for 5 minutes using a magnetic stirrer and then left standing for 2 hours.

After standing, the test solution was filtered using 5C filter paper, and the filter paper was dried. Then, the dried filter paper was pressed with a paperback having a black back surface, and further covered with a black box. Use the L value of the above filter paper to calculate the NIHON DE
SZ optical sensor made by NNSYOKU LTD. CO. (Colo
r measuring system).

Further, a blank test solution was prepared by putting 150 ml of the ferric chloride aqueous solution, 150 ml of the sodium hydroxide aqueous solution, and 150 ml of pure water in a beaker having a capacity of 500 ml. Then, the same operation was performed for the obtained blank test liquid, and the blank L value of the filter paper was measured.

From the above L value and blank L value, the iron ion trapping ability was calculated according to the following formula: iron ion trapping ability = L value−blank L value. As a result, the iron ion-capturing ability of the polymer was 14.0.

(E) Clay Dispersibility The clay dispersibility was measured by the following measuring method. That is, first, the polymer was dissolved in water to prepare a 0.5 wt% polymer aqueous solution in terms of solid content. Next, 1 ml of the polymer aqueous solution and 100 g of clean water (clean water of Himeji City) were put into a graduated cylinder having a capacity of 100 ml, and then 1.0 g of Amazon clay (clay) was added. Then, the obtained measurement liquid was stirred for 10 minutes using a magnetic stirrer and then left standing for 18 hours.

After standing still, 10 ml of the supernatant of the measurement solution was sampled, and the absorbance (turbidity) of ultraviolet rays having a wavelength of 380 nm was measured using a 1 cm cell. The clay dispersibility was determined based on the obtained measured value. As a result, the clay dispersibility of the polymer was 1.5.

The above measurement results, that is, the weight average molecular weight of the polymer, the amount of unreacted monomer, the biodegradation rate of the polymer,
Table 2 summarizes the calcium ion-capturing ability, the calcium ion stability constant, the iron-ion capturing ability, and the clay-dispersing ability.

Examples 2 to 8 Table 1 shows the types of the hydroxyl group-containing polycarboxylic acid or the ethylenically unsaturated monomer in Example 1 and / or the amounts used (molar ratio) thereof. The same reaction / operation as in Example 1 was carried out except that the kind and the amount used were changed to obtain a corresponding polymer (hereinafter, referred to as polymer-). And
The same measurements as those in Example 1 were performed for these polymers. The measurement results are summarized in Table 2.

Example 9 A 1 L four-necked flask equipped with a thermometer, a stirrer and a reflux condenser was charged with 500 parts of toluene as a solvent, 172 parts of methyl acrylate as an ethylenically unsaturated carboxylic acid, and a quench. Acid monohydrate 42
0 parts, 3 parts of paratoluene sulfonic acid, and 0.035 parts of hydroquinone which is a polymerization inhibitor were added to 100 parts.
The reaction by-product, methanol, was distilled off while stirring at 3 ° C for 3 hours.

Next, toluene was distilled off by heating the above reaction solution under reduced pressure. Then, in the reaction solution,
0.01 parts of ferrous ammonium sulfate hexahydrate, 93.75 parts of a 48% by weight aqueous solution of sodium hydroxide, and 406.3 parts of pure water were charged. Then, with stirring, the aqueous solution was heated to a boiling temperature under normal pressure. This allows
A monomeric acrylic acid-citric acid ester was prepared.

Next, 257.2 parts of 35 wt% hydrogen peroxide solution as a polymerization initiator and 100 parts of 15 wt% sodium persulfate aqueous solution were added to this aqueous solution with stirring.
It dripped over 80 minutes. Further, in parallel with this dropping operation, 2,506 parts of a 30% by weight aqueous solution of sodium acrylate was dropped into the aqueous solution over 180 minutes. Thereby, a polymerization reaction was performed. The molar ratio of the monomer to sodium acrylate is 20:80 in this order. Also,
Table 1 shows the amount (molar ratio) of each compound used.

After the completion of the reaction, 209.2 parts of a 48% by weight aqueous solution of sodium hydroxide was added to the above reaction solution to neutralize it.
As a result, an aqueous solution containing 36% by weight of solid content was obtained. The aqueous solution contained the novel polymer of the present invention.

The polymer obtained as described above (hereinafter referred to as the polymer) was subjected to the same measurement as in Example 1. The measurement results are summarized in Table 2.

Comparative Example 1 The same measurement as that of Example 1 was carried out for sodium polyacrylate, which is a conventionally known compound. The weight average molecular weight of the sodium polyacrylate was 2,200. The measurement results are summarized in Table 2.

Comparative Example 2 Sodium citrate, which is a conventionally known compound, was subjected to the same measurement as in Example 1. The weight average molecular weight of the sodium citrate was 2,500. The measurement results are summarized in Table 2.

Comparative Example 3 With respect to sodium polymaleate which is a conventionally known compound, the same measurement as in Example 1 was carried out. The weight average molecular weight of the sodium polymaleate was 800. The measurement results are summarized in Table 2.

[0120]

[Table 1]

[0121]

[Table 2]

Example 10 A composition according to the present invention was formed using the above polymers. That is, a detergent composition was formed as a composition containing 20% by weight (as solid content) of the above polymer. Table 3 shows various components and blending amounts (% by weight) blended in the detergent composition.

[0123]

[Table 3]

In addition, artificial dirt was prepared in order to evaluate the performance of each of the above detergent compositions. Table 4 shows various components contained in the artificial dirt and the blending amount (% by weight).

[0125]

[Table 4]

Then, a cleaning test was conducted using the above artificial dirt. First, artificial dirt was dispersed in carbon tetrachloride, and a white cloth made of cotton was passed through the dispersion. Next, the cloth
A soiled cloth of 10 cm × 10 cm was produced by drying and cutting. Next, the contaminated cloth was washed under the washing conditions shown in Table 5.

[0127]

[Table 5]

After washing, the cloth was dried, and the reflectance (%) of the cloth was measured by a predetermined method. Then, based on the following formula, cleaning rate (%) = (reflectance of contaminated cloth after cleaning-reflectance of contaminated cloth before cleaning) / (reflectance of white cloth-reflectance of contaminated cloth before cleaning) x 100 Then, the cleaning rate (%) was calculated from the reflectance. Table 6 shows the results.

Comparative Example 4 Using sodium polyacrylate described in Comparative Example 1 as a detergent composition, Example 10
The same detergency test was performed and the detergency was calculated. Table 6 shows the results.

Comparative Example 5 Using the sodium citrate described in Comparative Example 2 as a detergent composition, the same detergency test as in Example 10 was conducted to calculate the detergency. Table 6 shows the results.

Comparative Example 6 Using sodium polymaleate described in Comparative Example 3 as a detergent composition, Example 10
The same detergency test was performed and the detergency was calculated. Table 6 shows the results.

[0132]

[Table 6]

As is clear from the results of Example 10 and Comparative Examples 4 to 6 described above, the detergent composition using the polymer according to the present invention was compared with the case where a conventionally known compound was used as the detergent composition. It can be seen that the cleaning rate is high.

Example 11 A composition according to the present invention was formed using the above polymers. That is, a fiber treatment agent was formed as a composition containing 2 g / L (as solid content) of the above polymer. The various components and the amounts of the components added to the fiber treatment agent are shown below. The fiber treatment agent is an aqueous solution.

(Component) Any one of polymer 2 g / L hydrogen peroxide 10 g / L sodium hydroxide 2 g / L sodium silicate No. 3 5 g / L Then, a bleaching test is conducted using the above fiber treating agent. It was
As a test cloth, a scoured cotton sheet knit was used. The bleaching conditions are shown below.

(Bleaching Conditions) Hardness of Water Used 35.DH (German Hardness) Bath Ratio 1:25 Temperature 85 ° C. Time 20 minutes Then, the texture of the bleached cloth was judged by a sensory test method.

The whiteness is measured by using a 3M color computer SM-3 manufactured by Suga Test Instruments Co., Ltd.
Lab system whiteness equation, W = 100 - ^{[(100-L) 2 + a} 2 + b 2 ] ^1/2 L: measured lightness a: Chromatic Ness index measured red b: measured blue Chromatic The whiteness (W value) was obtained by the Ness index and evaluated.

Further, the sewability was evaluated by the number of ground thread breakages when four sheets of cloth were piled up and a 30 cm empty stitch was sewn with a lock stitch sewing machine using a needle # 11S. Table 7 shows the results.

[Comparative Examples 7 to 9] The compounds used in Comparative Examples 4 to 6 were used in this order as the fiber treating agent, and Example 1 was used.
Perform the same bleaching test as 1 and judge the texture,
The whiteness and the number of breaks in the ground yarn were measured. Table 7 shows the results.

[0140]

[Table 7]

As is clear from the results of Example 11 and Comparative Examples 7 to 9 described above, the fiber treating agent using the polymer according to the present invention is compared with the case of using a conventionally known compound as the fiber treating agent. And has excellent texture and whiteness,
At the same time, it can be seen that the number of places where the ground yarn breaks is also greatly reduced.

Example 12 A composition according to the present invention was formed using the above polymers. That is, a dispersion liquid was prepared as follows using the above polymer as an inorganic pigment dispersant.

First, in a beaker having a volume of 1 L (material: SUS304, inner diameter 90 mm, height 160 mm), calcite-based cubic light calcium carbonate (primary particle diameter 0.1
Then, 400 parts of a cake (solid content: 65.3% by weight) obtained by dehydrating 5 μm) with a filter press was added. Next, in the beaker, 40% by weight of a polymer as an inorganic pigment dispersant was added.
3.26 parts of an aqueous solution (the ratio of the polymer to the weight of calcium carbonate is 0.5% by weight), and 6.9 parts of water for adjusting the concentration of solid content were added, and a dissolver stirring blade (50 mmφ) was used. Kneading at low speed for 3 minutes. Then, the mixture was dispersed at 3,000 rpm for 10 minutes to obtain a dispersion liquid having a solid content concentration of 64% by weight.

With respect to the obtained dispersion, the viscosity (cP) immediately after dispersion and the viscosity (cP) after left at room temperature for 1 week were measured at 25 ° C. using a B type viscometer. The measurement results are shown in Table 8.

Comparative Examples 10 to 12 Using the compounds used in Comparative Examples 4 to 6 in this order as the inorganic pigment dispersant,
A dispersion was prepared in the same manner as in Example 12, and the viscosity was measured. The measurement results are shown in Table 8.

[0146]

[Table 8]

As is clear from the results of Example 12 and Comparative Examples 10 to 12, the polymers according to the present invention
It can be seen that the dispersion liquid using No. 1 has a higher dispersive power as compared with the dispersion liquid using the conventionally known compound, and still retains good dispersibility even after being left for one week.

Example 13 A composition according to the present invention was formed using the above polymers. That is, using the above polymer as a bleaching aid for wood pulp (pretreatment agent),
The wood pulp was bleached as follows.

First, 30 parts of so-called absolute dry weight of ground pulp was put into a beaker having a capacity of 5 L, 3,000 parts of water at a temperature of 50 ° C. and 0.06 part of a polymer as a bleaching aid (based on the weight of pulp) The proportion of the polymer was 0.2% by weight), and the mixture was stirred at 50 ° C. for 15 minutes. Next, the pulp was so-called No. After filtering with a filter paper No. 2 to separate it from the treatment liquid, 1,500 parts of water was passed through the pulp to wash, and then dehydrated.

Next, the pulp obtained by the above pretreatment was placed in a beaker having a volume of 5 L, water was added so that the final pulp concentration would be 14% by weight, and hydrogen peroxide (of pulp The ratio to the weight was 4% by weight) No. 3 sodium silicate and sodium hydroxide were added to adjust the pH of the treatment liquid to 11.0.

The treatment solution was transferred to a polyethylene bag, the mouth was folded back so that water did not evaporate, and the pulp was bleached by heat treatment for 5 hours in a water bath previously adjusted to 65 ° C. It was Then, the bleached pulp was filtered through a 420-mesh filter cloth and dehydrated. Then, the concentration of hydrogen peroxide remaining in the filtrate was measured. After that, the following formula, hydrogen peroxide consumption rate (%) = [(B−C) / B] × 10
0 B: concentration of hydrogen peroxide in the treatment liquid before bleaching (% by weight) C: consumption rate of hydrogen peroxide (%) based on the concentration of hydrogen peroxide in the treatment liquid after bleaching (% by weight) Was calculated.

Further, a part of the bleached pulp was diluted with water to 3% by weight, and then adjusted to pH 4.5 with an aqueous solution of sulfite to obtain a pulp slurry. Then, using this pulp slurry, the TAPPI standard method (Technical
Two hand-made sheets were created by the Association of the Pulp and Paper Industry). After air-drying the sheet, the Hunter whiteness (%) was measured by a Hunter whiteness meter. Table 9 shows the measurement results.

[Comparative Examples 13 to 15] Using the compounds used in Comparative Examples 4 to 6 in this order as bleaching aids for wood pulp, bleaching of pulp was carried out in the same manner as in Example 13 to remove hydrogen peroxide. The consumption rate and whiteness were measured. Table 9 shows the measurement results.

[0154]

[Table 9]

As is clear from the results of Example 13 and Comparative Examples 13 to 15, the polymers according to the present invention
The bleaching aid using is excellent in whiteness as compared with the bleaching aid using a conventionally known compound, and further, the consumption rate of hydrogen peroxide is low, so that the amount of hydrogen peroxide used can be reduced. Yes, it turns out to be economical.

[0156]

As described above, the present invention has the general formula (1)

[0157]

Embedded image

The present invention relates to a polymer having a structural unit represented by and having a weight average molecular weight of 300 to 8,000,000.

The polymer according to claim 2 of the present invention is
As described above, while having a plurality of atomic groups each having 2 to 4 carboxyl groups, other atoms are not present between the carbon atoms constituting the carboxyl group and the carbon atoms constituting the main chain.
The atomic group group is bonded to the main chain so that one or more of the atomic group group exists, and the ratio of the atomic group group to the entire polymer is 5% by weight or more.

As described above, the polymer according to claim 3 of the present invention has a plurality of atomic groups having 2 to 4 carboxyl groups, and at the same time constitutes a main chain with carbon atoms constituting the carboxyl groups. A constitution in which the atomic group group is bonded to the main chain so that an ester bond exists with a carbon atom, and the proportion of the atomic group group in the whole polymer is 5% by weight or more. Is.

According to the above constitution, the polymer has a molecular structure having a large number of carboxyl groups which are not directly bonded to the main chain. The free rotation of the carboxyl group is not hindered by the main chain. Therefore, the polymer is water-soluble, has an excellent dispersing action on inorganic particles, has a high ability to trap heavy metal ions, and has a high metal ion content per unit weight, as compared with conventional chelating agents. A large amount is captured. Further, the polymer has excellent biodegradability. That is, the above-mentioned polymer has an effect of having excellent chelating action and dispersing action and excellent biodegradability as compared with the conventional chelating agent.

The polymer according to claim 4 of the present invention is
As described above, the biodegradation rate is 40% or more, the calcium ion capturing ability is 200 mgCaCO ₃ / g or more, the calcium ion stability constant is 4.0 or more, and the iron ion capturing ability is 9.
The composition has a clay dispersibility of 0 or more and 0.5 or more.

As described above, the polymer according to claim 5 of the present invention has a biodegradation rate of 10% or more, a calcium ion capturing ability of 350 mgCaCO ₃ / g or more, and a calcium ion stability constant of 4.2 or more. And, the clay dispersibility is 0.5
The above is the configuration.

According to the above constitution, the polymer is water-soluble, has an excellent dispersing action on inorganic particles, has a high ability to capture heavy metal ions, and has a unit higher than that of a conventional chelating agent. The amount of metal ions captured per weight is large. Further, the polymer has excellent biodegradability.
That is, the above polymer, compared to conventional chelating agents,
With outstanding chelating and dispersing effects,
It has the effect of having excellent biodegradability.

In the method for producing a polymer according to claim 6 of the present invention, as described above, the general formula (2) is used using an aqueous medium.

[0166]

Embedded image

This is a method of polymerizing a monomer component containing a monomer represented by:

According to the above method, a polymer having a molecular structure having a large number of carboxyl groups which are not directly bonded to the main chain can be easily obtained. Therefore, according to the above method, it is possible to obtain a polymer having excellent chelating action and dispersing action as well as excellent biodegradability as compared with the conventional chelating agent. .

The composition according to claim 7 of the present invention is
As described above, at least one of claims 1 to 5
It is a constitution comprising the polymer described in the item.

According to the above constitution, the composition contains a polymer having excellent chelating and dispersing effects and excellent biodegradability as compared with the conventional chelating agent. . As a result, the composition can be suitably used, for example, as a detergent composition, an inorganic pigment dispersant, a fiber treatment agent, a water treatment agent (scale inhibitor), and a bleaching aid for wood pulp. Play.

Claims (7)

[Claims] 1. A compound of the general formula (1) The weight average molecular weight of the structural unit represented by
8,000,000 polymer. 2. A plurality of atomic groups having 2 to 4 carboxyl groups and at least 3 other atoms between the carbon atoms constituting the carboxyl group and the carbon atoms constituting the main chain. Thus, the polymer, wherein the atomic group group is bonded to the main chain, and the proportion of the atomic group group in the entire polymer is 5% by weight or more. 3. A plurality of atomic groups having 2 to 4 carboxyl groups are provided, and an ester bond is present between the carbon atoms constituting the carboxyl group and the carbon atoms constituting the main chain, The atomic group group is bonded to the main chain, and the ratio of the atomic group group in the whole polymer is 5
A polymer characterized in that it is at least wt. 4. A biodegradation rate of 40% or more, a calcium ion capturing ability of 200 mgCaCO ₃ / g or more, a calcium ion stability constant of 4.0 or more, and an iron ion capturing ability of 9.0.
Further, the polymer has a clay dispersibility of 0.5 or more. 5. A biodegradation rate of 10% or more, a calcium ion trapping ability of 350 mgCaCO ₃ / g or more, a calcium ion stability constant of 4.2 or more, and a clay dispersing ability of 0.5 or more. And a polymer. 6. A general formula (2): A method for producing a polymer, which comprises polymerizing a monomer component containing a monomer represented by: 7. A composition comprising the polymer according to any one of claims 1 to 5.