JP4634022B2 - Liquid detergent builder and liquid detergent - Google Patents

Description

  The present invention relates to a novel liquid detergent builder and a liquid detergent.

Water-soluble polymers are preferably used for detergent builder applications, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, α-hydroxyacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and citraconic acid. System (co) polymers are well known.
Furthermore, in order to improve the performance for builder use for detergents, research on improving the (co) polymer has been actively conducted in recent years.
In particular, the unsaturated carboxylic acid-based (co) polymer and its improved product-based detergent builder as shown in Patent Document 1 have been able to exhibit a relatively high level of performance when used as a powder detergent.
However, the above-mentioned conventional detergent builder comprising an unsaturated carboxylic acid (co) polymer has extremely poor compatibility with a surfactant, and therefore has a drawback that it is not suitable for liquid detergent applications.
Further, citric acid has been used as a chelating agent in liquid detergents, but citric acid has no dispersibility of clay (mud), and a dispersing agent has been desired to improve detergency.
In powder detergents, polyacrylic acid (salt) is used as a dispersant, but these were not compatible with high detergent concentration liquid detergents.

JP 2002-12627 A

  Therefore, the problem to be solved by the present invention is a novel builder for liquid detergents, which has excellent compatibility with surfactants, high transparency when used as a liquid detergent, and extremely excellent detergent performance. And a novel liquid detergent comprising the liquid detergent builder, and a liquid detergent comprising an acrylic polymer (salt) excellent in clay dispersibility and compatibility with a surfactant.

The present inventor has intensively studied to solve the above problems. As a result, attention was paid to acrylic acid / maleic acid (system) copolymer (salt) or acrylic acid / HAPS (system) copolymer (salt) having a specific composition and molecular weight. The above-mentioned problem that cannot be solved by a builder composed of a conventional unsaturated carboxylic acid (co) polymer is the specific acrylic acid / maleic acid (system) copolymer (salt) or acrylic acid / HAPS (system). ) It has been found that the use of a copolymer (salt) in a builder for a liquid detergent can solve the problem. Moreover, the said subject can be solved with the liquid detergent containing the acrylic polymer (salt) of specific concentration and specific molecular weight, and high concentration surfactant.
The present invention was thus completed.

In order to solve the above problems, the present invention provides the following configurations.
(1) An acrylic acid / maleic acid (system) copolymer (salt) containing 5 to 90 mol% of maleic acid (salt) with respect to 100 mol% of acrylic acid (salt) and maleic acid (salt). An acrylic having a product (MA × Mw) of 450,000 or less of the weight average molecular weight Mw of the polymer (salt) and the ratio [MA (mol%)] of the maleic acid (salt) in the copolymer (salt) A builder for liquid detergents comprising an acid / maleic acid (system) copolymer (salt).
(2) The builder for liquid detergents according to the above (1), wherein the acrylic acid / maleic acid (system) copolymer (salt) has a calcium ion scavenging ability of 280 mgCaCO ₃ / g or more.
(3) The acrylic detergent / maleic acid (system) copolymer (salt) is a builder for liquid detergents according to the above (1) or (2), wherein the clay dispersibility in high-hardness water is 0.30 or more.
(4) A liquid detergent comprising the liquid detergent builder according to any one of (1) to (4) above.
(5) Contains 1 to 50 mol% of HAPS (salt) with respect to 100 mol% of acrylic acid (salt) and 3-allyloxy-2-hydroxy-1-propanesulfonic acid (HAPS) (salt), and has a weight average molecular weight Mw A builder for liquid detergents comprising an acrylic acid / HAPS (system) copolymer (salt) having a ≦ 100,000 or less.
(6) The builder for liquid detergents according to the above (5), wherein the acrylic acid / HAPS (system) copolymer (salt) has a calcium ion scavenging ability of 120 mgCaCO ₃ / g or more.
(7) The acrylic detergent / HAPS (system) copolymer (salt) is a builder for liquid detergent according to the above (5) or (6), wherein the clay dispersibility in high-hardness water is 0.30 or more.
(8) A liquid detergent comprising the builder for liquid detergent according to any one of the above (5) to (7).
(9) A liquid detergent comprising 0.5% by mass or more of a builder for liquid detergent comprising an acrylic acid polymer (salt) having a weight average molecular weight Mw of 4500 or less.
(10) The acrylic polymer (salt) according to (9) above, wherein the copolymer component is at least one selected from maleic acid (salt), fumaric acid (salt), and methacrylic acid (salt). Liquid detergent.
(11) The liquid detergent according to (9) or (10), wherein the acrylic acid polymer (salt) has a clay dispersibility in high-hardness water of 0.5 or more.
(12) The acrylic polymer (salt) is a liquid detergent according to any one of the above (9) to (11), which has a calcium ion scavenging ability of 150 mgCaCO ₃ / g or more.

  According to the present invention, a liquid detergent builder comprising an acrylic acid / maleic acid (system) copolymer (salt) or an acrylic acid / HAPS (system) copolymer (salt) having a specific composition and molecular weight, and an acrylic acid system. The polymer (salt) is excellent in both calcium ion scavenging ability and clay dispersibility in high hardness water, and is excellent in compatibility with a surfactant when used as a liquid detergent. Demonstrates excellent cleaning power even under high hardness water.

The builder for liquid detergents of the present invention is acrylic acid / maleic acid (based) copolymer (salt) (hereinafter also referred to as copolymer 1 for the present invention) or acrylic acid / HAPS (based) copolymer (salt). (Hereinafter also referred to as the copolymer 2 for the present invention), and may be composed of only the copolymer 1 or 2 for the present invention, or other polymers may be used in combination. May be.
The liquid detergent of the present invention essentially comprises an acrylic acid polymer (salt) (hereinafter also referred to as the polymer for the present invention).

[Copolymer 1 for the present invention]
The copolymer 1 for the present invention is an acrylic acid / maleic acid (system) copolymer (salt) containing 5 to 90 mol% of maleic acid (salt) with respect to 100 mol% of acrylic acid (salt) and maleic acid (salt). The product (MA × Mw) of the weight average molecular weight Mw of the copolymer (salt) and the ratio [MA (mol%)] of the maleic acid (salt) in the copolymer (salt) is 450. , 000 or less.
The (system) of acrylic acid / maleic acid (system) copolymer (salt) in the copolymer 1 for the present invention refers to maleic acid (salt) and acrylic acid (salt) for the copolymer 1 for the present invention. ) In which the total amount of structural units derived from the respective monomers is 90 mol% or more and the structural units derived from other copolymerizable monomers are contained in an amount of 10 mol% or less. Preferably, the total amount of structural units derived from each monomer of maleic acid (salt) and acrylic acid (salt) is 100 mol% with respect to copolymer 1 for the present invention. In the present application, the other polymer, for example, the copolymer 2 of the present invention is also synonymous with the above when simply referred to as (system) hereinafter.
In addition, in the copolymer 1 for the present invention, 5 to 90 mol% of maleic acid (salt) with respect to 100 mol% of acrylic acid (salt) and maleic acid (salt) means that acrylic acid (salt) units / maleic It contains at least acrylic acid (salt) and maleic acid (salt) so that the acid (salt) unit is in a molar ratio of 95 to 10/5 to 90.
Here, (salt) means in this application that it may be an acid type, a partial salt type, a complete salt type, or a mixture thereof, and hereinafter, these are simply expressed as (salt). Examples of the salt include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, and organic amine salts such as ammonium salt, monoethanolamine and triethanolamine. These salts may be used alone or as a mixture of two or more. A preferable form in the case of a salt is an alkali metal salt such as sodium or potassium, particularly preferably a sodium salt.

  The copolymerizable monomer other than acrylic acid (salt) and maleic acid (salt) used for copolymer 1 for use in the present invention is not particularly limited. For example, methacrylic acid (salt), α-hydroxyacrylic acid ( Salt), itaconic acid (salt), fumaric acid (salt), crotonic acid (salt), citraconic acid (salt), styrene; styrene sulfonic acid; vinyl acetate; (meth) acrylonitrile; (meth) acrylamide; methyl (meth) Acrylate; ethyl (meth) acrylate; butyl (meth) acrylate; 2-ethylhexyl (meth) acrylate; dimethylaminoethyl (meth) acrylate; diethylaminoethyl (meth) acrylate; allyl alcohol; 3-methyl-3-butene-1- All; 3-methyl-2-buten-1-ol; 2-methyl-3-butene 2-ol; 3- (meth) acryloxy-1,2-dihydroxypropane; 3- (meth) acryloxy-1,2-di (poly) oxyethylene ether propane; 3- (meth) acryloxy-1,2-di (Poly) oxypropylene ether propane; 3- (meth) acryloxy-1,2-dihydroxypropane phosphate and its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt, or alkyl having 1 to 4 carbon atoms Mono- or diesters of groups; 3- (meth) acryloxy-1,2-dihydroxypropane sulfate and its monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, or alkyl groups having 1 to 4 carbon atoms Ester; 3- (meth) acryloxy-2-hydroxypropanesulfonic acid and its monovalent metal salt, 2 Valent metal salt, ammonium salt, organic amine salt, or ester of alkyl group having 1 to 4 carbon atoms; 3- (meth) acryloxy-2- (poly) oxyethylene ether propanesulfonic acid and its monovalent metal salt, 2 Valent metal salt, ammonium salt, organic amine salt, or ester of alkyl group having 1 to 4 carbon atoms; 3- (meth) acryloxy-2- (poly) oxypropylene ether propanesulfonic acid and its monovalent metal salt, 2 Metal salt, ammonium salt, organic amine salt, or ester of an alkyl group having 1 to 4 carbon atoms; 3-allyloxypropane-1,2-diol; 3-allyloxypropane-1,2-diol phosphate; 3 -Allyloxypropane-1,2-diol sulfonate; 3-allyloxypropane-1,2-diol sulfate 3-allyloxy 1,2-di (poly) oxyethylene ether propane; 3-allyloxy 1,2-di (poly) oxyethylene ether propane phosphate; 3-allyloxy 1,2-di (poly) oxyethylene ether propane sulfonate 3-allyloxy 1,2-di (poly) oxypropylene ether propane; 3-allyloxy 1,2-di (poly) oxypropylene ether propane phosphate; 3-allyloxy 1,2-di (poly) oxypropylene ether propane sulfonate 6-allyloxyhexane-1,2,3,4,5-pentaol; 6-allyloxyhexane-1,2,3,4,5-pentaol phosphate; 6-allyloxyhexane-1,2, 3,4,5-pentaolsulfonate; 6-ant Oxyhexane-1,2,3,4,5-penta (poly) oxyethylene ether hexane; 6-allyloxyhexane-1,2,3,4,5-penta (poly) oxypropylene ether hexane; 3-allyloxy 2-hydroxypropanesulfonic acid and its monovalent metal salt, divalent metal salt, ammonium salt, or organic amine salt, or phosphate ester or sulfate ester of these compounds and their monovalent metal salt, divalent metal Salt, ammonium salt, or organic amine salt; 3-allyloxy 2- (poly) oxyethylenepropanesulfonic acid and its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt, or compounds thereof Phosphoric acid esters or sulfuric acid esters and their monovalent metal salts, divalent metal salts, Monium salt or organic amine salt; 3-allyloxy 2- (poly) oxypropylenepropane sulfonic acid and its monovalent metal salt, divalent metal salt, ammonium salt, or organic amine salt, or phosphorus of these compounds And acid esters or sulfates and their monovalent metal salts, divalent metal salts, ammonium salts, or organic amine salts. Polyalkylene glycol-containing monomers can also be used. For example, polyalkylene glycol (meth) acrylic acid ester, allyl alcohol polyalkylene oxide adduct, 3-methyl-3-buten-1-ol alkylene oxide adduct and the like can be mentioned. Glycol and polyethylene oxide are preferred.

  It does not specifically limit as a copolymerization method for manufacturing the copolymer 1 for this invention, For example, it can be based on a conventionally well-known method. Specific examples include polymerization in a solvent such as water, an organic solvent, or a mixed solvent of a water-soluble organic solvent and water. The catalyst system that can be used for these polymerizations is not particularly limited, and examples thereof include persulfates and hydrogen peroxide, and accelerators (such as bisulfite and ascorbic acid) can be used in combination. In addition, azo initiators, organic peroxides, and the like can be used, and accelerators such as amine compounds can be used in combination. From the viewpoint of proceeding the reaction advantageously, a persulfate or a catalyst system using hydrogen peroxide and ascorbic acid in combination is preferable. Further, chain transfer agents such as mercaptoethanol, mercaptopropionic acid and sodium hypophosphite may be used in combination as a molecular weight adjuster.

The weight average molecular weight of the copolymer 1 according to the present invention is such that the product (MA × Mw) is 450,000 or less, preferably 420,000 or less, more preferably 400,000 or less, particularly preferably 370,000 or less, most preferably. Is preferably 350,000 or less, preferably 1000 to 90,000, more preferably 1500 to 70,000, still more preferably 2000 to 50,000, particularly preferably 2500 to 30,000, most preferably Is 3000 to 20,000. Further, the acrylic acid (salt) unit / maleic acid (salt) unit in the copolymer 1 for use in the present invention has a molar ratio of 95 to 10/5 to 90, preferably 90 to 15/10 to 85, and more preferably 85. It is -20 / 15-80, Most preferably, it is 80-30 / 20-70, Most preferably, it is 75-40 / 25-60.
In the present invention, the reason for limiting the MA and product (MA × Mw) is to ensure compatibility with the surfactant, and as the proportion of maleic acid (salt) units increases, the molecular weight increases. This is because the calcium ion scavengeability increases, but the clay dispersibility tends to decrease, so that the calcium ion scavenge ability and the clay dispersibility are secured.
The present invention copolymer for 1 is preferably calcium ion trapping ability is 280mgCaCO ₃ / g or more, more preferably at least 290mgCaCO ₃ / g, more preferably 300mgCaCO ₃ / g or more, 310mgCaCO ₃ / g or more and particularly 320 mgCaCO ₃ / g or more is most preferable.
The copolymer 1 for use in the present invention preferably has a clay dispersibility in high-hardness water of 0.30 or more, more preferably 0.33 or more, still more preferably 0.35 or more, and 0.38 or more. Is particularly preferable, and 0.40 or more is most preferable.
In addition, the definition of the said calcium ion capture | acquisition ability and clay dispersibility is as describing in an Example.
Furthermore, it is preferable that the clay dispersibility in low hardness water is high, the clay dispersibility in low hardness water is preferably 0.40 or more, more preferably 0.45 or more, and 0.50 or more. More preferably, 0.55 or more is particularly preferable, and 0.60 or more is most preferable. The low hardness water in the present invention is a concentration of 50 ppm in terms of CaCO ₃ .

[Builder 1 for liquid detergents]
The builder 1 for liquid detergents according to the present invention is characterized by using the above-described copolymer 1 for the present invention as an essential component.
Specifically, the builder 1 for liquid detergents according to the present invention may consist of the above-described copolymer 1 for the present invention alone, or may be used by mixing with other known detergent builders.
The other detergent builder is not particularly limited. For example, sodium citrate, sodium tripolyphosphate, sodium pyrophosphate, sodium silicate, bow glass, sodium carbonate, sodium nitrilotriacetate, sodium ethylenediaminetetraacetate or potassium, zeolite , Polysaccharide carboxyl derivatives, water-soluble polymers, and the like.

Examples of the water-soluble polymer used in combination include the following water-soluble polycarboxylic acid polymers.
Examples of the water-soluble polycarboxylic acid polymer include acrylic acid (based) polymer (salt), methacrylic acid (based) polymer (salt), α-hydroxyacrylic acid (based) polymer (salt), and acrylic. Acid / sulfonic acid group-containing monomer (system) copolymer (salt), methacrylic acid / sulfonic acid group-containing monomer (system) copolymer (salt), acrylic acid / hydroxyl group-containing monomer (system) Copolymer (salt), methacrylic acid / hydroxyl group-containing monomer (system) copolymer (salt), and the like may be used, and these may be used alone or as a mixture of two or more. . Here, the polymer (salt) means in this application that it may be an acid type, a partial salt type, a complete salt type, or a mixture thereof, and hereinafter, these are simply expressed as a polymer (salt). .
Among these polymers, an acrylic acid (based) polymer (salt) and an acrylic acid / sulfonic acid group-containing monomer (based) copolymer (salt) are particularly preferable.
The acrylic acid (based) polymer (salt) contains 90 mol% or more of structural units derived from acrylic acid and 10 mol% or less of structural units derived from other copolymerizable monomers. Examples of the copolymerizable monomer include those exemplified as those that can be used in combination with the copolymer 1 for the present invention.

Although the weight average molecular weight of acrylic acid (system) polymer (salt) is not specifically limited, it is 1000-100,000, Preferably it is 1500-75,000, More preferably, it is 2000-50,000, Most preferably, it is 3 30,000 to 30,000, most preferably 4,000 to 20,000.
The clay dispersibility of the acrylic acid (based) polymer (salt) in high hardness water is preferably 0.15 or more, more preferably 0.25 or more, particularly preferably 0.35 or more, and most preferably 0.40 or more. .
Calcium ion capturing ability of acrylic acid (based) polymer (salt) is preferably 100mgCaCO ₃ / g or more, 150mgCaCO ₃ / g or more, and particularly preferably 200mgCaCO ₃ / g or more, and most preferably more than 220mgCaCO ₃ / g .
The acrylic acid (based) polymer (salt) is a mass ratio of the copolymer 1 / acrylic acid (based) polymer (salt) for the present invention to the builder 1 for liquid detergents of the present invention, preferably 10-100 / It can mix | blend so that it may become 90-0, More preferably, 20-100 / 80-0, Especially preferably, 30-100 / 70-0, Most preferably, 50-100 / 50-0.
The acrylic acid (based) polymer (salt) may include an acrylic acid polymer (salt) that is a polymer for the present invention.

  Acrylic acid / sulfonic acid group-containing monomer (system) copolymer (salt), methacrylic acid / sulfonic acid group-containing monomer (system) copolymer (salt) that can be used in the builder 1 for liquid detergents of the present invention The content of the structural unit derived from the sulfonic acid group-containing monomer in is preferably 5 to 50 mol%, more preferably 6 to 40 mol%, particularly preferably 7 to 30 mol%, most preferably 8 to 20 mol. %.

Examples of the sulfonic acid group-containing monomer include vinyl sulfonic acid (salt), allyl sulfonic acid (salt), methallyl sulfonic acid (salt), sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, Examples include 3-allyloxy-2-hydroxypropanesulfonic acid (salt), styrenesulfonic acid (salt), 2-acrylamido-2-methylpropanesulfonic acid (salt), 2-hydroxy-3-butenesulfonic acid (salt), and the like. It is done. These may be used alone or in a mixture of two or more. Preferred are 3-allyloxy-2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (salt), sulfoethyl acrylate, sulfoethyl methacrylate, and 2-hydroxy-3-butenesulfonic acid (salt). .
The weight average molecular weight of the acrylic acid / sulfonic acid group-containing monomer (system) copolymer (salt) is not particularly limited, but is 1,000 to 100,000, preferably 1500 to 75000, more preferably 2000 to 50000, and particularly preferably. Is 3000 to 30000, most preferably 4000 to 20000. If the weight average molecular weight deviates from these ranges, the clay dispersibility in high hardness water may be remarkably lowered, which is not preferable.
The clay dispersibility of the acrylic acid / sulfonic acid group-containing monomer (system) copolymer (salt) in high hardness water is 0.30 or more, preferably 0.35 or more, more preferably 0.40 or more. Particularly preferably 0.45 or more, and most preferably 0.50 or more.
The calcium ion scavenging ability of the acrylic acid / sulfonic acid group-containing monomer (system) copolymer (salt) is 120 mgCaCO ₃ / g or more, preferably 130 mgCaCO ₃ / g or more, more preferably 140 mgCaCO ₃ / g or more.
The acrylic acid / sulfonic acid group-containing monomer (system) copolymer (salt) is added to the liquid detergent builder 1 of the present invention by the copolymer 1 / (acrylic acid / sulfonic acid group-containing monomer ( System) copolymer (salt)) by weight, preferably 10/90 to 100/0, more preferably 20/80 to 100/0, particularly preferably 30/70 to 100/0, most preferably 50. It can mix | blend so that it may become / 50-100 / 0.

Below, when using the copolymer 1 for this invention (it describes as the polymer A) and another polymer (it describes as the polymer B) for the builder 1 for liquid detergents of this invention, the mixing method is demonstrated, for example. . Although the mixing method of the polymer A and the polymer B is not specifically limited, For example, the following method is mentioned. The same applies when mixing three or more kinds of polymers.
(1) After both the polymer A and the polymer B are produced in advance, they are mixed so that a desired ratio is obtained.
(2) One polymer is produced in advance. Next, while producing the other polymer, this pre-manufactured polymer is added to the desired ratio, resulting in a mixture.
(3) One polymer is manufactured, and the other polymer is continuously manufactured so that a desired ratio is obtained, and as a result, a mixture is manufactured.
Among these, the method (1) is preferable from the viewpoint of the simplicity of the design of the polymer mixture and the stability of the quality.

Next, the above (1) to (3) will be described in more detail.
Regarding the method of (1), specifically, a solution-solution mixture in which both are mixed in a solution state, a powder-powder mixture in which both are mixed in a powder state, or a solution in which one is a solution and the other is mixed in a powder state -Powder mixing etc. are mentioned. In solution-solution mixing and solution-powder mixing in which the state after mixing is a solution state, a mixture solution that is uniform as a whole is obtained by stirring. In the powder-powder mixing in which the state after mixing is a powder state, in order to make it uniform as a whole, it is preferable that both polymers are preferably finely pulverized powder and sufficiently mixed and stirred. When it is not uniform as a whole, that is, when there is a bias in the mixture components, there is a fear that a specific part with the bias does not satisfy a specific function.

In this method, the polymer A and the polymer B may be produced in advance, but these production methods are not particularly limited as described above, but preferably in an aqueous solvent. This is homogeneous stirring polymerization. There is no particular limitation on the pulverization method when both or any one of them is used in a powder state, and the powder may be pulverized by a conventionally known method. In the present application, the powder state is used in a broad sense and includes all of so-called powder, granule, pellet, and in some cases, paste, gel, and the like.
By the method as described above, a uniform mixture as a whole can be obtained in the form of a solution or powder. Of course, the properties of the mixture may be in a state according to the purpose, and the mixture obtained in the form of a solution may be made into a powder in some cases, and the mixture obtained in the form of a powder may be used as a solution in some cases. It doesn't matter.

  Next, the method (2) will be described. In this method, during the production of one polymer, a mixture is obtained by adding the other previously produced polymer in a desired ratio. The method for producing the polymer is as described above. The addition method of the polymer produced in advance is not particularly limited, and may be any time in the initial stage of polymerization, in the middle of polymerization, or just before the end of polymerization. Also, it may be uniform or non-uniform. It may be added as a solution or as a powder. What is necessary is just to set suitably according to the objective as needed. However, after the polymerization is substantially completed, the pre-manufactured polymer is added to the method (1).

  Further, the method (3) will be described. In this method, one polymer is produced, and the other polymer is further produced so as to obtain a desired ratio. This method is a modification of the method of (2) above, in which a polymer that has been produced in advance during the production of one polymer is initially added. The difference from the method (2) is that the production of the other polymer is started before the production of one polymer is completed, and has a kind of continuous polymerization element. This kind of continuous polymerization method may be carried out in the same reaction vessel or may be produced continuously in two or more reaction vessels.

The builder 1 for liquid detergent of the present invention preferably contains 10 to 100% by mass of the copolymer 1 for the present invention, more preferably 20 to 90% by mass, and 30 to 80% by mass. Is particularly preferable, and most preferably 40 to 70% by mass is contained. However, this blending ratio is calculated by excluding water that can be contained in the builder 1 for liquid detergent.
The liquid detergent builder 1 of the present invention may be in the form of a powder such as a lump, powder, sol, or gel, or may be a solution (for example, an aqueous solution).

  The builder 1 for a liquid detergent according to the present invention is excellent for a liquid detergent in that it is excellent in compatibility with a surfactant and becomes a highly concentrated liquid detergent when used in a liquid detergent described later. is there. By being excellent in compatibility with the surfactant, the transparency of the liquid detergent is improved, and the problem of separation of the liquid detergent caused by turbidity can be prevented. And it can be set as a highly concentrated liquid detergent by being excellent in compatibility, and it leads also to the improvement of the detergent capability of a liquid detergent.

[Copolymer 2 for the present invention]
The copolymer 2 for the present invention contains 1 to 50 mol% of HAPS (salt) with respect to 100 mol% of acrylic acid (salt) and 3-allyloxy-2-hydroxy-1-propanesulfonic acid (HAPS) (salt). And the weight average molecular weight Mw is 100,000 or less.
The (system) of the acrylic acid / HAPS (system) copolymer (salt) in the copolymer 2 for the present invention is different from the acrylic acid (salt) and the HAPS (salt) for the copolymer 2 for the present invention. The total amount of structural units derived from the monomers is 90% by mole or more, and the copolymer contains structural units derived from other copolymerizable monomers at 10% by mole or less. The total amount of structural units derived from the respective monomers of acrylic acid (salt) and HAPS (salt) is 100 mol% with respect to copolymer 2 for invention.
In addition, in the copolymer 2 for this invention, it means that acrylic acid (salt) unit / HAPS contains (1-50) mol% of HAPS (salt) with respect to 100 mol% of acrylic acid (salt) and HAPS (salt). The (salt) unit contains at least acrylic acid (salt) and HAPS (salt) so that the molar ratio is 99 to 50/1 to 50.

  The copolymerizable monomer other than acrylic acid (salt) and HAPS (salt) used in the copolymer 2 for the present invention is not particularly limited. For example, the same as those mentioned for the copolymer 1 for the present invention. Are exemplified.

  It does not specifically limit as a copolymerization method for manufacturing the copolymer 2 for this invention, It can manufacture similarly to the copolymer 1 for this invention.

The weight average molecular weight Mw of the copolymer 2 for use in the present invention is 100,000 or less, preferably 1500 to 75,000, more preferably 2000 to 50,000, particularly preferably 3000 to 30,000, most preferably 4000 to 20,000. Further, the acrylic acid (salt) unit / HAPS (salt) unit in the copolymer 2 for use in the present invention is 99 to 50/1 to 50, preferably 95 to 60/5 to 40, and more preferably 94 to 70 in molar ratio. / 6-30, most preferably 93-75 / 7-25.
In the present invention, the reason for limiting the composition and Mw of acrylic acid / HAPS (system) copolymer (salt) is to ensure compatibility with surfactants while satisfying calcium ion scavenging ability and clay dispersibility. Because.
The present invention copolymer for 2 preferably has a calcium ion trapping ability is 120mgCaCO ₃ / g or more, more preferably 130mgCaCO ₃ / g or more, 140mgCaCO ₃ / g or more is particularly preferable.
The copolymer 2 for use in the present invention preferably has a clay dispersibility in high-hardness water of 0.30 or more, more preferably 0.35 or more, and particularly preferably 0.4 or more.
In addition, the definition of the said calcium ion capture | acquisition ability and clay dispersibility is as describing in an Example.

[Builder 2 for liquid detergents]
The builder 2 for a liquid detergent according to the present invention is characterized by using the above-described copolymer 2 for the present invention as an essential component.
Specifically, the builder 2 for liquid detergent according to the present invention may be composed of only the above-described copolymer 2 for the present invention, or may be used by mixing with other known detergent builder.
Although it does not specifically limit as said other builder for detergents, For example, what was illustrated by the builder 1 for liquid detergents is mentioned.

Examples of the water-soluble polymer used in combination include the following water-soluble polycarboxylic acid polymers.
Examples of the water-soluble polycarboxylic acid polymer include acrylic acid (based) polymer (salt), acrylic acid / maleic acid (based) copolymer (salt), methacrylic acid (based) polymer (salt), α-hydroxyacrylic acid (system) polymer (salt), acrylic acid / hydroxyl group-containing monomer (system) copolymer (salt), methacrylic acid / hydroxyl group-containing monomer (system) copolymer (salt), etc. These may be used alone or as a mixture of two or more.
Among these polymers, acrylic acid (based) polymers (salts) and acrylic acid / maleic acid (based) copolymers (salts) are particularly preferable.
The acrylic acid (based) polymer (salt) contains 90 mol% or more of structural units derived from acrylic acid and 10 mol% or less of structural units derived from other copolymerizable monomers. Examples of the monomer that can be merged include those exemplified as those that can be used in combination with the copolymer 1 for the present invention.

The weight average molecular weight of the acrylic acid (based) polymer (salt) is not particularly limited, but is preferably 1,000 to 100,000, more preferably 1,500 to 75,000, still more preferably 2000 to 50,000, Preferably it is 3000-30000, Most preferably, it is 4000-20000.
The calcium ion scavenging ability of the acrylic acid (based) polymer (salt) is preferably 200 mgCaCO ₃ / g or more, more preferably 230 mgCaCO ₃ / g or more, particularly preferably 250 mgCaCO ₃ / g or more.
The clay dispersibility of the acrylic acid (based) polymer (salt) in high hardness water is preferably 0.20 or more, more preferably 0.25 or more, particularly preferably 0.30 or more, and most preferably 0. .35 or more.
The acrylic acid (based) polymer (salt) is preferably 1 to 100/99 by mass ratio of the copolymer 2 for the present invention / acrylic acid (based) polymer (salt) for the liquid detergent builder 2 of the present invention. To 0, more preferably 5 to 100/95 to 0, particularly preferably 10 to 100/90 to 0, and most preferably 20 to 100/80 to 0.
The acrylic acid (based) polymer (salt) may include an acrylic acid polymer (salt) that is a polymer for the present invention.

As acrylic acid / maleic acid (system) copolymer (salt) that can be used in combination with acrylic acid / HAPS (system) copolymer (salt), acrylic acid (salt) and maleic acid (salt) are 100 mol%. Acrylic acid / maleic acid (system) copolymer (salt) containing 5 to 90 mol% of maleic acid (salt) in the weight average molecular weight Mw of the copolymer (salt) and the copolymer (salt) It is preferable that the product (MA × Mw) with the ratio [MA (mol%)] of the maleic acid (salt) is 450,000 or less acrylic acid / maleic acid (system) copolymer (salt), The MA content is more preferably 10 to 85 mol%, still more preferably 15 to 80 mol%, particularly preferably 20 to 70 mol%, most preferably 25 to 60 mol%, and the weight average molecular weight Mw is preferably 1000 to 90,000, more preferred The 1500～70,000, more preferably 2000～50,000, particularly preferably 2500～30,000, most preferably 3000～20,000.
The acrylic acid / maleic acid (system) copolymer (salt) is obtained by adding the copolymer 2 for the present invention / (acrylic acid / maleic acid (system) copolymer (salt)) to the liquid detergent builder 2 of the present invention. It is blended so that the mass ratio is preferably 10 to 100/90 to 0, more preferably 20 to 100/80 to 0, particularly preferably 30 to 100/70 to 0, and most preferably 50 to 100/50 to 0. It is preferred that

  For example, when the copolymer 2 for the present invention (denoted as polymer A) and another polymer (denoted as the polymer B) are used for the liquid detergent builder 2 of the present invention, the mixing method thereof is described as follows. 1 can be used.

The builder 2 for liquid detergent of the present invention preferably contains 10 to 100% by mass of the copolymer 2 for the present invention, more preferably 20 to 90% by mass, and 30 to 80% by mass. Is particularly preferable, and most preferably 40 to 70% by mass is contained. However, this blending ratio is calculated by excluding water that can be contained in the builder 2 for liquid detergent.
The liquid detergent builder 2 of the present invention may be in the form of a powder such as a lump, powder, sol, or gel, or may be a solution (for example, an aqueous solution).

  The builder 2 for a liquid detergent according to the present invention is excellent for a liquid detergent in that it is excellent in compatibility with a surfactant and becomes a highly concentrated liquid detergent when used in a liquid detergent described later. is there. By being excellent in compatibility with the surfactant, the transparency of the liquid detergent is improved, and the problem of separation of the liquid detergent caused by turbidity can be prevented. And it can be set as a highly concentrated liquid detergent by being excellent in compatibility, and it leads also to the improvement of the detergent capability of a liquid detergent.

[Polymer for the present invention]
The polymer for the present invention is an acrylic acid polymer (salt) and has a weight average molecular weight Mw of 500 to 4500, preferably 700 to 4000, more preferably 800 to 3500, and particularly preferably 900 to 3000, most preferably 1000-2500.
In the polymer for the present invention, the content of the structural unit derived from acrylic acid (salt) is 50 mol% or more and 100 mol% or less, the structural unit derived from another copolymerizable monomer is 50 mol% or less, It is preferably 40 mol% or less, more preferably 30 mol% or less, more preferably 20 mol% or less, and particularly preferably 10 mol% or less. And those exemplified as those that can be used together in the copolymer 1 for the present invention.

  The copolymerizable monomer other than acrylic acid (salt) used in the polymer for use in the present invention is not particularly limited, and examples thereof include those similar to those exemplified in the copolymer 1 for use in the present invention. Examples of the copolymerizable monomer include maleic acid (salt), fumaric acid (salt), and methacrylic acid (salt). The acrylic acid (salt) unit / other monomer units are in a molar ratio, preferably 50-100 / 50-0, more preferably 70-100 / 30-0, more preferably 80-100 / 20-0, particularly preferably. Is from 90 to 100/10 to 0, most preferably from 95 to 100/5 to 0.

  The polymerization or copolymerization method for producing the polymer for use in the present invention is not particularly limited, but it is preferable to use a chain transfer agent, and it is more preferable that a sulfonic acid group is present at the end of the polymer.

  In the present invention, the reason for limiting the composition and Mw of the acrylic acid polymer (salt) is to ensure compatibility with the surfactant while satisfying calcium ion scavenging ability and clay dispersibility.

The clay dispersibility of the polymer for use in the present invention under high hardness water is preferably 0.5 or more, more preferably 0.6 or more, particularly preferably 0.7 or more, and most preferably 0.8 or more.
Calcium ion trapping ability of the present invention for the polymer is preferably at least _{150mgCaCO 3 / g, 160mgCaCO 3 /} g or more, and particularly preferably 170mgCaCO ₃ / g or more, 180mgCaCO ₃ / g or more is most preferred.
In addition, the definition of the said calcium ion capture | acquisition ability and clay dispersibility is as describing in an Example.

[Builder 3 for liquid detergents]
The builder 3 for liquid detergent according to the present invention contains the above-described polymer for the present invention as an essential component.
Specifically, the builder 3 for liquid detergent according to the present invention may be composed of only the above-described polymer for the present invention, or may be used by mixing with other known detergent builder.
Although it does not specifically limit as said other builder for detergents, For example, what was illustrated by the builder 1 for liquid detergents is mentioned.

Examples of the water-soluble polymer used in combination include the following water-soluble polycarboxylic acid polymers.
Examples of the water-soluble polycarboxylic acid polymer include acrylic acid (based) polymer (salt), acrylic acid / maleic acid (based) copolymer (salt), methacrylic acid (based) polymer (salt), α-hydroxyacrylic acid (system) polymer (salt), acrylic acid / hydroxyl group-containing monomer (system) copolymer (salt), methacrylic acid / hydroxyl group-containing monomer (system) copolymer (salt), etc. These may be used alone or as a mixture of two or more.
Among these polymers, acrylic acid (based) polymers (salts) and acrylic acid / maleic acid (based) copolymers (salts) are particularly preferable.
The acrylic acid (based) polymer (salt) contains 90 mol% or more of structural units derived from acrylic acid and 10 mol% or less of structural units derived from other copolymerizable monomers. Examples of the monomer that can be merged include those exemplified as those that can be used in combination with the copolymer 1 for the present invention.

The weight average molecular weight of the acrylic acid (based) polymer (salt) is not particularly limited, but is preferably 500 to 4500, more preferably 700 to 4000, still more preferably 800 to 3500, particularly preferably 900 to 3000, and most preferably. Is 1000-2500.
The calcium ion scavenging ability of the acrylic acid (based) polymer (salt) is preferably 200 mgCaCO ₃ / g or more, more preferably 230 mgCaCO ₃ / g or more, particularly preferably 250 mgCaCO ₃ / g or more.
The clay dispersibility of the acrylic acid (based) polymer (salt) in high hardness water is preferably 0.20 or more, more preferably 0.25 or more, particularly preferably 0.30 or more, and most preferably 0. .35 or more.
The acrylic acid (based) polymer (salt) is preferably 1-100 / 99-0, more preferably by weight ratio of the polymer for the present invention / acrylic acid (based) polymer (salt) to the builder 3 for liquid detergent. Can be blended so as to be 5 to 100/95 to 0, particularly preferably 10 to 100/90 to 0, and most preferably 20 to 100/80 to 0.

The acrylic acid / maleic acid (salt) copolymer (salt) that can be used in combination with the acrylic acid polymer (salt) is maleic acid (salt) based on 100 mol% of acrylic acid (salt) and maleic acid (salt). Acrylic acid / maleic acid (system) copolymer (salt) containing 5 to 90 mol%, wherein the weight average molecular weight Mw of the copolymer (salt) and the maleic acid (salt) in the copolymer (salt) ) Ratio [MA (mol%)] and the product (MA × Mw) is preferably an acrylic acid / maleic acid (system) copolymer (salt) of 450,000 or less, more preferably the MA. Is 10 to 85 mol%, more preferably 15 to 80 mol%, particularly preferably 20 to 70 mol%, most preferably 25 to 60 mol%, and the weight average molecular weight Mw is preferably 1000 to 90,000, Preferably 1500-7 , 000, more preferably 2000～50,000, particularly preferably 2500～30,000, most preferably 3000～20,000.
The acrylic acid / HAPS (system) copolymer (salt) is preferably 10 by mass ratio of the polymer for the present invention / (acrylic acid / maleic acid (system) copolymer (salt)) to the liquid detergent builder 3. -100 / 90-0, more preferably 20-100 / 80-0, particularly preferably 30-100 / 70-0, most preferably 50-100 / 50-0.

  For example, when the polymer for the present invention (denoted as polymer A) and another polymer (denoted as polymer B) are used as the liquid detergent builder 3, the mixing method is the same as that for the builder 1 for detergent. Can be used.

The builder 3 for liquid detergent preferably contains 10 to 100% by mass of the polymer for the present invention, more preferably 20 to 90% by mass, particularly preferably 30 to 80% by mass, 40 Most preferably, it is contained at 70% by mass. However, this blending ratio is calculated by excluding water that can be contained in the builder 3 for liquid detergent.
In addition, the builder 3 for liquid detergents used for the liquid detergent of this invention may be a powder form, such as a lump shape, a powder form, a sol form, and a gel form, and may be a solution (for example, aqueous solution).

  The builder 3 for liquid detergent is excellent as a liquid detergent in that it is excellent in compatibility with a surfactant and used as a highly concentrated liquid detergent when 0.5% by mass or more is used in the liquid detergent described later. Is. By being excellent in compatibility with the surfactant, the transparency of the liquid detergent is improved, and the problem of separation of the liquid detergent caused by turbidity can be prevented. And it can be set as a highly concentrated liquid detergent by being excellent in compatibility, and it leads also to the improvement of the detergent capability of a liquid detergent.

[Liquid detergent]
A liquid detergent comprising the liquid detergent builder 1 or 2 according to the present invention is referred to as a liquid detergent a.
In the liquid detergent a according to the present invention, the liquid detergent builder 1 or 2 of the present invention that is contained is excellent in compatibility with the surfactant, so that transparency when used as a liquid detergent is improved, and turbidity occurs. The problem of separation of liquid detergent can be prevented. And it can be set as a highly concentrated liquid detergent by being excellent in compatibility, and it leads also to the improvement of the detergent capability of a liquid detergent.

Since the liquid detergent a according to the present invention includes the liquid detergent builder 1 or 2 according to the present invention that can impart excellent detergent ability, it can also exhibit superior washing ability as compared with conventional liquid detergents. it can.
In addition to the liquid detergent builder 1 or 2 according to the present invention, the liquid detergent a according to the present invention usually contains a detergent surfactant.

The surfactant is at least one selected from an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant, and these surfactants are used alone or in combination of two or more. Can be used. When two or more kinds are used, the combined use amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably 70% by mass or more based on the entire active agent. Is particularly preferable, and 80% by mass or more is most preferable.
Specific examples of anionic surfactants include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate, saturated Examples thereof include unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof.
The alkyl chain and alkenyl chain of these anionic surfactants may be branched by an additional alkyl group such as a methyl group.

Specific examples of nonionic surfactants include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, alkyl glycoxide, fatty acid glycerin monoester And alkylamine oxide. An alkyl group such as a methyl group may be branched between the alkyl group and alkenyl group of these nonionic surfactants.
Specific examples of the cationic surfactant include quaternary ammonium salts.
Specific examples of the amphoteric surfactant include a carboxyl type or sulfobetaine type amphoteric surfactant.
An alkyl group such as a methyl group may be branched between the alkyl group and alkenyl group of these cationic surfactants and amphoteric surfactants.

The compounding ratio of the surfactant contained in the liquid detergent a according to the present invention is usually 10 to 60% by mass, preferably 15 to 50% by mass, more preferably 20 to 45% by mass, particularly in the liquid detergent. Preferably it is 25-40 mass%. When the blending ratio of the surfactant is less than 10% by mass, sufficient detergent performance cannot be exhibited. On the other hand, when it exceeds 60 mass%, economical efficiency will fall.
The blending ratio of the liquid detergent builder 1 or 2 of the present invention contained in the liquid detergent a is usually 0.1 to 40% by mass, preferably 0.2 to 30% by mass, more preferably 0 in the detergent. .3 to 20% by mass, particularly preferably 0.4 to 15% by mass, and most preferably 0.5 to 10% by mass. When the blending ratio of the liquid detergent builder 1 or 2 is less than 0.1% by mass, sufficient detergent performance cannot be exhibited. On the other hand, when it exceeds 40 mass%, economical efficiency will fall.

Next, a liquid detergent (hereinafter referred to as “liquid detergent b”) that essentially includes the liquid detergent builder 3 will be described.
The liquid detergent b is 0.5% by mass or more, preferably 0.6 to 30% by mass, more preferably 0.7 to 20% by mass, and particularly preferably 0.8 to 10% by mass of the builder 3 for liquid detergent. Most preferably, it comprises 0.9 to 5% by mass.
In the liquid detergent b according to the present invention, the liquid detergent builder 3 is excellent in compatibility with the surfactant, so that the transparency when the liquid detergent is obtained is good, and the problem of separation of the liquid detergent caused by turbidity is caused. Can be prevented. And it can be set as a highly concentrated liquid detergent by being excellent in compatibility, and it leads also to the improvement of the detergent capability of a liquid detergent.
When the blending ratio of the builder 3 for liquid detergent is less than 0.5% by mass, sufficient detergent performance cannot be exhibited. On the other hand, when it exceeds 30 mass%, economical efficiency will fall.

  Since the liquid detergent b which concerns on this invention contains the builder 3 for liquid detergents which can provide the outstanding detergent capability, it can also exhibit the outstanding cleaning capability compared with the conventional liquid detergent.

The surfactant contained in the liquid detergent b is at least one selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and these surfactants Can use 1 type (s) or 2 or more types. When two or more kinds are used, the combined use amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably 70% by mass or more based on the entire active agent. Is particularly preferable and 80% by mass or more is most preferable.
As the surfactant, the same surfactants as exemplified for the liquid detergent a can be used.
The amount of the surfactant contained in the liquid detergent b of the present invention is 25% by mass or more, preferably 27.5-60% by mass, more preferably 30-50% by mass, particularly preferably 32.5-45% by mass. .

  The amount of water contained in the liquid detergent of the present invention is usually 0.1 to 75% by mass, preferably 0.2 to 70% by mass, more preferably 0.5 to 65% by mass, and still more preferably 0.7 to 0.7%. 60% by mass, particularly preferably 1 to 55% by mass, most preferably 1.5 to 50% by mass.

  In addition, the liquid detergent of this invention may use the builder 1 and 2 for liquid detergents, and the builder 3 for liquid detergents individually or in combination, respectively, and the mixture ratio in the detergent in the case of using the builder 1 and 2 for liquid detergents together is The above-described liquid detergent builder 1 or 2 alone may be replaced by the sum of both, and the copolymer for the present invention 1 / the polymer for the present invention is preferably in a mass ratio of 99 to 1/1 to 99, Preferably, it is 98-10 / 2-90, Especially preferably, it is 97-30 / 3-70, Most preferably, it is 96-50 / 4-50, Copolymer 1 or 2 / this invention for this invention The polymer for use is preferably 1 to 99/99 to 1, more preferably 98 to 2/2 to 98, particularly preferably 97 to 3/3 to 97, and most preferably 96 to 4 in mass ratio. / 4 to 96.

The kaolin turbidity of the liquid detergent of the present invention is preferably 200 mg / l or less, more preferably 150 mg / l or less, further preferably 120 mg / l or less, particularly preferably 100 mg / l or less, and most preferably 50 mg / l or less.
Separately, the acrylic acid / maleic acid (based) copolymer (salt) and / or acrylic acid / HAPS (based) copolymer (salt) and / or acrylic acid polymer (salt) of the present invention is used as a liquid detergent. The change (difference) in kaolin turbidity with and without the addition is preferably 500 mg / l or less, more preferably 400 mg / l or less, still more preferably 300 mg / l or less, particularly preferably 200 mg / l or less, 100 mg / l or less is most preferable.

  Various additives conventionally used in detergents can be added to the builder 1, 2 or 3 for a liquid detergent according to the present invention. For example, sodium carboxymethylcellulose to prevent re-deposition of contaminants, contamination inhibitors such as benzotriazole and ethylene-thiourea, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, Foaming agents, foam stabilizers, polishes, bactericides, bleaches, enzymes, dyes, solvents and the like.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples. “%” Indicates “% by mass”.
(Physical property measurement method)
First, a method for measuring calcium ion scavenging ability and clay dispersibility in high hardness water, which are important parameters forming the basis of the present invention, will be described. For reference, since the weight average molecular weight of the polymer used was also measured, a method for measuring the weight average molecular weight is also described.

<Calcium ion scavenging ability>
50 g of 0.01 mol / l, 0.001 mol / l, 0.0001 mol / l aqueous solution was prepared using calcium chloride dihydrate as a calcium ion standard solution for a calibration curve, and 4.8% Adjust to pH 9-11 with NaOH aqueous solution, add 1 ml of 4 mol / l potassium chloride aqueous solution (hereinafter abbreviated as 4M-KCl aqueous solution), and further stir well using magnetic stirrer for calibration curve A sample solution was prepared. In addition, as a test calcium ion standard solution, a necessary amount (50 g per sample) of a 0.001 mol / l aqueous solution was similarly prepared using calcium chloride dihydrate.
Next, 10 mg of the test sample (polymer) in a 100 cc beaker was weighed in terms of solid content, 50 g of the above-mentioned calcium ion standard solution for test was added, and the mixture was sufficiently stirred using a magnetic stirrer. Further, as with the calibration curve sample, a pH of 9 to 11 was adjusted with a 4.8% NaOH aqueous solution, and 1 ml of 4M-KCl aqueous solution was added to prepare a test sample solution.
The calibration curve sample solution and the test sample solution thus prepared were measured with a calcium ion electrode 93-20 and a reference electrode 90-01 manufactured by Orion Co., Ltd. using a titration device COMITE-550 manufactured by Hiranuma Sangyo Co., Ltd. I did it.
From the calibration curve and the measured value of the sample solution for the test, the amount of calcium ions captured by the sample (polymer) is obtained by calculation, and the value is expressed in mg of calcium carbonate equivalent of the amount captured per 1 g of polymer solids. This value was defined as the calcium ion scavenging ability value.

<Clay dispersibility under high hardness water> (200 ppm in terms of CaCO ₃ : under high hardness water)
Pure water was added to 67.56 g of glycine, 52.6 g of sodium chloride, and 2.4 g of NaOH to make 600 g (this is referred to as buffer (1)). To 60 g of buffer (1), 0.3268 g of calcium chloride dihydrate was added, and pure water was further added to make 1000 g (this is referred to as buffer (2)). 36 g of buffer (2) was added to 4 g of a 0.1% by weight aqueous solution (in terms of solid content) of the copolymer to be measured, and stirred to obtain a dispersion. After putting 0.3 g of clay (made by Japan Powder Industrial Technology Association, 11 types of test dust) into a test tube (IWAKI GLASS: diameter 18 mm, height 180 mm), add 30 g of the above dispersion and seal To do.
The test tube was shaken to uniformly disperse the clay. Thereafter, the test tube was left in the dark for 20 hours. After 20 hours, 5 cc of the supernatant of the dispersion was taken and the absorbance was measured with a UV spectrometer (Shimadzu Corporation, UV-1200; 1 cm cell, wavelength 380 nm).
Under low hardness water, it is performed at 50 ppm in terms of CaCO ₃ .

<Measurement method of weight average molecular weight (Mw)>
(1) Measured by GPC (gel permeation chromatography). The column used for the measurement was G-3000PWXL (manufactured by Tosoh Corporation), and the mobile phase was 34.5 g of disodium hydrogen phosphate dodecahydrate and 46.2 g of sodium dihydrogen phosphate dihydrate (both were reagent-grade, In the following, pure water was added to all the reagents used in the measurement, which were special grades, to a total amount of 5000 g, and then an aqueous solution filtered through a 0.45 micron membrane filter was used.
(2) The pump used was L-7110 (manufactured by Hitachi), the mobile phase flow rate was set to 0.5 ml / min, and the detector was RI (SHODEX SE-61 manufactured by Showa Denko KK). . At that time, the column temperature was kept constant at 35 ° C.
(3) Further, as a calibration curve, a sodium polyacrylate standard sample (manufactured by Sowa Kagaku) was used, and the weight average molecular weight of the polymer was measured by these samples.
<Measurement of solid content>
Solid content was made into the non volatile matter after drying 1 g (co) polymer aqueous solution for 1 hour with a 170 degreeC hot-air dryer.

(Synthesis Example 1)
Synthesis of Copolymer 1 Copolymer 1 as an acrylic acid / maleic acid copolymer having a molar ratio of 52/48 was produced. That is, 34.5 g of ion-exchanged water (hereinafter referred to as pure water), 40% disodium maleate aqueous solution (into a 2.5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser) Hereinafter, 1155.7 g of 40% MANa ₂ was initially charged, and the aqueous solution was heated to the boiling point reflux state with stirring. Next, while maintaining the reflux state with stirring, 287.1 g of 80% acrylic acid aqueous solution (hereinafter referred to as 80% AA) and 73 g of 35% hydrogen peroxide aqueous solution (hereinafter referred to as 35% H ₂ O ₂ ) Over 264 minutes from the start of polymerization, 85.5 g of 15% sodium persulfate aqueous solution (hereinafter referred to as 15% NaPS) was added over 275 minutes from the start of polymerization, and 137.9 g of pure water was added from 95 to 180 minutes after the start of polymerization. It was dripped continuously at a uniform speed from each separate dripping nozzle. Furthermore, after maintaining the boiling point reflux state for 30 minutes after completion of all the dropwise addition, after completing the polymerization, 87.9 g of 48% aqueous sodium hydroxide (hereinafter referred to as 48% NaOH) was added and stirred for 30 minutes. did. Thereafter, 21.1 g of a 35% aqueous sodium hydrogen sulfite solution (hereinafter referred to as 35% sodium hydrogen sulfite Na), 14 g of 48% NaOH and 106.9 g of pure water were added to obtain a copolymer 1. The weight average molecular weight measured as described above was 5000. The solid content was 37%.

(Synthesis Example 2)
Synthesis of Copolymer 2 Copolymer 2 which was an acrylic acid / maleic acid copolymer having a molar ratio of 60/40 was produced. That is, 295 g of pure water was initially charged into a 2.5 liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser, and the aqueous solution was heated to a boiling point reflux state with stirring. Next, while maintaining the reflux state with stirring, 156.8 g of maleic anhydride (hereinafter referred to as anhydrous MA) was added over a period of 100 minutes from the start of polymerization, and 216 g of 80% AA and 256.7 g of 48% NaOH were added from the start of polymerization. Over a period of 68.6 g of 35% H ₂ O ₂ over 120 minutes from the start of polymerization and 106.7 g of 15% NaPS over 190 minutes from the start of polymerization, each continuously from a separate dropping nozzle. It was dripped at a speed. Furthermore, after maintaining the boiling point reflux state for 60 minutes after the completion of all the dropwise additions, after completing the polymerization, 140 g of 48% NaOH was added and stirred for 30 minutes to obtain a copolymer 2. The weight average molecular weight measured as described above was 4800. The solid content was 39%.

(Synthesis Example 3)
Synthesis Example of Copolymer 3 Copolymer 3 which was an acrylic acid / maleic acid copolymer having a molar ratio of 71/29 was produced. Specifically, 35.7 g of pure water and 722 g of 40% MANa ₂ were initially charged in a 2.5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser, and the aqueous solution was stirred under stirring. The temperature was raised to the boiling point reflux state. Next, while maintaining the reflux state with stirring, 401.7 g of 80% AA and 89.3 g of 35% H ₂ O _{2 were} fed for 240 minutes from the start of polymerization, and 124.7 g of 15% NaPS was fed for 245 minutes from the start of polymerization. Then, 177.5 g of pure water was continuously dropped at a uniform rate from separate dropping nozzles over 90 to 156 minutes from the start of polymerization. Furthermore, after the completion of the dropwise addition, the boiling point reflux state was maintained for 30 minutes. After the polymerization was completed, 263 g of 48% NaOH was added and stirred for 30 minutes. Thereafter, 27.9 g of 35% sodium bisulfite Na, 50.9 g of 48% NaOH and 128.6 g of pure water were added to obtain a copolymer 3. When the weight average molecular weight was measured as described above, it was 11,000. The solid content was 36%.

(Synthesis Example 4)
Synthesis Example of Copolymer 4 Copolymer 4 which was acrylic acid / 3-allyloxy-2-hydroxy-1-sodium propanesulfonate (HAPS) copolymer having a molar ratio of 91/9 was produced. That is, 774 g of pure water was initially charged into a 5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser, and the aqueous solution was heated to the boiling point reflux state with stirring. Next, while maintaining the reflux state under stirring, 47.8 g of 80% AA, 957.7 g of 37% sodium acrylate (hereinafter referred to as 37% SA), and 9.6 g of 35% H ₂ O ₂ were added from the start of polymerization. Over 25 minutes, 370.9 g of 25% HAPS aqueous solution (hereinafter referred to as 25% HAPS) was added dropwise over 90 minutes from the start of polymerization, and 97.2 g of 15% NaPS was added dropwise over 140 minutes from the start of polymerization. It was dripped continuously from the nozzle at a uniform speed. Copolymer 4 was obtained. When the weight average molecular weight was measured as described above, it was 3000. The solid content was 45%.

(Synthesis Example 5)
Synthesis Example of Copolymer 5 Copolymer 5 that was an acrylic acid / maleic acid copolymer having a molar ratio of 50/50 was produced. That is, 132.5 g of pure water, 400 g of 48% NaOH, and 235.2 g of anhydrous MA were initially charged in a 2.5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser. The aqueous solution was heated to the boiling point reflux state. Next, while maintaining the reflux state with stirring, 216 g of 80% AA was added for 180 minutes from the start of polymerization, and 57.6 g of 35% aqueous hydrogen peroxide solution was added for 96 g of 15% NaPS and 90% for 90 minutes after the start of polymerization. 160 g of water was continuously dropped at a uniform rate from separate dropping nozzles over 100 minutes from 90 minutes to 190 minutes after the start of polymerization. Furthermore, the boiling point reflux state was maintained for 30 minutes after the completion of the dropwise addition, and the polymerization was completed to obtain a copolymer 5. The weight average molecular weight measured as described above was 10,000. The solid content was 45%.

(Synthesis Example 6)
Synthesis Example of Copolymer 6 Copolymer 6 that was an acrylic acid / maleic acid copolymer having a molar ratio of 70/30 was produced. That is, 83.0 g of pure water, 250 g of 48% NaOH, and 147.0 g of anhydrous MA were initially charged in a 2.5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser, and stirred. The aqueous solution was heated to the boiling point reflux state. Next, while maintaining the reflux state under stirring, 315.0 g of 80% AA was added for 120 minutes from the start of polymerization, and 66.7 g of 15% NaPS and 393.3 g of pure water were supplied for 130 minutes from the start of polymerization. It dripped continuously at a uniform speed from a separate dripping nozzle. Furthermore, the boiling point reflux state was maintained for 30 minutes after the completion of the dropwise addition, and the polymerization was completed to obtain a copolymer 6. When the weight average molecular weight was measured as described above, it was 50,000. The solid content was 40%.

(Synthesis Example 7)
Synthesis Example of Polymer 1 Polymer 1 which is a low molecular weight acrylic acid homopolymer was produced. That is, 560 g of pure water was initially charged into a 2.5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to a boiling point reflux state with stirring. Next, while maintaining the reflux state under stirring, 360 g of 80% AA and 283 g of 48% NaOH were added for 240 minutes from the start of polymerization, and 56 g of 15% NaPS and 600 g of pure water were added for 250 minutes from the start of polymerization. Then, it was dropped at a uniform speed continuously from each separate dropping nozzle. Furthermore, the boiling point reflux state was maintained for 30 minutes after completion of all the dropwise additions, and the polymerization was completed to obtain a polymer 1. Similarly, when the weight average molecular weight was measured, it was 6000. The concentration was adjusted to a solid content of 45%.

(Synthesis Example 8)
Synthesis Example of Polymer 2 Polymer 2 which is an acrylic acid homopolymer was produced. That is, 150 g of pure water was initially charged in a 5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 90 ° C. with stirring. Next, while maintaining 90 ° C. with stirring, 285.7 g of 35% sodium hydrogen sulfite Na was polymerized over 90 minutes from the start of polymerization for 10 minutes, 900 g of 80% AA, and 41.67 g of 48% NaOH. Over the course of 180 minutes from the start, 142.9 g of 35% NaPS was continuously dropped at a uniform rate from separate drop nozzles over the course of 190 minutes from the start of the polymerization. Further, after completion of the dropwise addition, 30 ° C. was maintained for 30 minutes to complete the polymerization, and then 750 g of 48% NaOH was added to adjust the concentration to obtain a polymer 2 having a solid content of 45%. Similarly, when the weight average molecular weight was measured, it was 2000.

(Synthesis Example 9)
Synthesis Example of Polymer 3 Polymer 3 which is an acrylic acid homopolymer was produced. That is, 145 g of pure water was initially charged into a 2.5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 90 ° C. with stirring. Then, while maintaining 90 ° C. with stirring, 405 g of 80% AA and 127.0 g of 37% sodium acrylate were added over the course of 240 minutes from the start of polymerization, 80.0 g of 25% NaPS, 85.7 g of sodium acrylate. 35% Na-bisulfite Na was dripped continuously at a uniform rate from separate dripping nozzles over 250 minutes from the start of polymerization. Further, after completion of the dropwise addition, 30 ° C. was maintained for 30 minutes to complete the polymerization, and then 333 g of 48% NaOH was added to adjust the concentration to obtain a polymer 3 having a solid content of 45%. Similarly, when the weight average molecular weight was measured, it was 4100.

(Synthesis Example 10)
Synthesis Example of Polymer 4 Polymer 4 which is an acrylic acid homopolymer was produced. That is, 175 g of pure water was initially charged into a 2.5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to 90 ° C. with stirring. Then, while maintaining 90 ° C. with stirring, 450 g of 80% AA and 20.83 g of 48% NaOH were added over 300 minutes from the start of polymerization, and 66.7 g of 15% NaPS was added over 310 minutes from the start of polymerization. Over the course of 290 minutes from the start of polymerization, 71.4 g of 35% Na hydrogen sulfite Na was continuously dropped at a uniform rate from separate dropping nozzles. Further, after completion of the dropwise addition, 30 ° C. was maintained for 30 minutes to complete the polymerization, and then 375 g of 48% NaOH was added to adjust the concentration to obtain a polymer 4 having a solid content of 45%. Similarly, when the weight average molecular weight was measured, it was 6000.

(Synthesis Example 11)
Synthetic Example of Copolymer 7 A maleic acid / acrylic acid copolymer 7 having a molar ratio of 5/95 was produced. Specifically, a 2.5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser was initially charged with 190 g of pure water, 29.4 g of maleic anhydride, and 2.5 g of 48% NaOH. The temperature was raised to 90 ° C. with stirring. Next, while maintaining 90 ° C. with stirring, 513 g of 80% AA and 23.8 g of 48% NaOH were added over 180 minutes from the start of polymerization, and 200.0 g of 15% NaPS was added over 185 minutes from the start of polymerization. Over the course of 175 minutes from the start of polymerization, 171.4 g of 35% sodium hydrogen sulfite Na was added dropwise at a uniform rate continuously from separate dropping nozzles. Further, after completion of the dropwise addition, 30 ° C. was maintained for 30 minutes to complete the polymerization, and then 420 g of 48% NaOH was added to adjust the concentration to obtain a copolymer 7 having a solid content of 45%. Similarly, when the weight average molecular weight was measured, it was 3600.

(Synthesis Example 12)
Synthetic Example of Copolymer 8 A maleic acid / acrylic acid copolymer 8 having a molar ratio of 5/95 was produced. Specifically, a 2.5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser was initially charged with 190 g of pure water, 29.4 g of maleic anhydride, and 2.5 g of 48% NaOH. The temperature was raised to 90 ° C. with stirring. Next, while maintaining 90 ° C. with stirring, 513 g of 80% AA and 23.8 g of 48% NaOH were added over 180 minutes from the start of polymerization, and 160.0 g of 15% NaPS were added over 185 minutes from the start of polymerization. Then, 137.1 g of 35% sodium hydrogen sulfite Na was continuously dropped at a uniform rate from separate dropping nozzles over 175 minutes from the start of polymerization. Further, after completion of the dropwise addition, 30 ° C. was maintained for 30 minutes to complete the polymerization, and then 420 g of 48% NaOH was added to adjust the concentration to obtain a copolymer 8 having a solid content of 45%. Similarly, when the weight average molecular weight was measured, it was 7200.

(Example 1-1)
The thing consisting only of the copolymer 1 was made into the builder for liquid detergents.
(Example 1-2)
The thing which consists only of the copolymer 2 was made into the builder for liquid detergents.
(Example 1-3)
The thing consisting only of the copolymer 3 was made into the builder for liquid detergents.

(Example 1-4)
24.3 g of copolymer 1 aqueous solution and 2.2 g of polymer 1 aqueous solution were mixed until they were completely uniform. Thus, the builder for liquid detergents whose mass ratio of copolymer 1 / polymer 1 is 90/10 was manufactured.
(Example 1-5)
In Example 1-4, a builder for liquid detergent was produced by performing the same operation except that the mass ratio of copolymer 1 / polymer 1 was changed to 80/20.
(Example 1-6)
In Example 1-4, the same operation was performed except that the copolymer 3 was used instead of the copolymer 1, and a builder for liquid detergent having a mass ratio of copolymer 3 / polymer 1 of 90/10 was obtained. Manufactured.

(Example 1-7)
In Example 1-5, the same operation is performed except that the copolymer 4 is used instead of the polymer 1, and a builder for liquid detergent in which the mass ratio of the copolymer 1 / copolymer 4 is 80/20 is obtained. Manufactured.
(Example 1-8)
In Example 1-6, the same operation was performed except that the copolymer 4 was used instead of the polymer 1, and a builder for liquid detergent having a mass ratio of copolymer 3 / copolymer 4 of 90/10 was obtained. Manufactured.

(Comparative Example 1-1)
The thing which consists only of the copolymer 5 was made into the builder for liquid detergents.
(Comparative Example 1-2)
The thing consisting only of the copolymer 6 was made into the builder for liquid detergents.
(Comparative Example 1-3)
The thing which consists only of the polymers 1 was made into the builder for liquid detergents.

Formed by dissolving 1% by mass of each builder for liquid detergent in the liquid detergent builder (1) and (2) shown in Table 1 below and the calcium ion scavenging ability of the above builder for liquid detergent, clay dispersibility in high hardness water The kaolin turbidity of the liquid detergent was measured and made compatible. The results are shown in Table 2. In addition, regarding the compatibility, the case where the kaolin turbidity was 200 mg / l or less was evaluated as ◯, and the case where it exceeded 200 mg / l was evaluated as x. The compatibility is good if the compatibility is good with respect to any of the liquid detergents (1) and (2).
The kaolin turbidity was measured by measuring the turbidity value at 25 ° C. after sufficiently stirring to remove the bubbles. Turbidity value measured Turbidity (kaolin turbidity: mg / l) using NDH2000 (turbidimeter) manufactured by Nippon Denshoku Co., Ltd.
In addition, the numerical value of the addition amount in a table | surface represents solid content or active ingredient conversion, and a numerical value represents the mass%. In addition, Neoperex F-65 in the table is sodium dodecylbenzenesulfonate made by Kao Corporation and pure content of about 65%, SFT-70H is Softanol 70H, manufactured by Nippon Shokubai Co., Ltd., polyoxyethylene alkyl It is an ether, and Cotamine 86W represents stearyltrimethylammonium chloride having a pure content of about 28% manufactured by Kao Corporation.

以上の結果より、本発明用共重合体１を含む液体洗剤用ビルダーおよび液体洗剤は、カルシウムイオン捕捉能、高硬度水下におけるクレー分散能および相溶性に優れていることが確認された。

From the above results, it was confirmed that the builder for liquid detergents and the liquid detergent containing the copolymer 1 for the present invention are excellent in calcium ion scavenging ability, clay dispersibility in high hardness water, and compatibility.

  In addition, as described in the examples, the high-hardness water in the present invention is water adjusted under predetermined conditions, and JIS test powder I, 11 types (Kanto loam, fine particles: Japanese powder) This is water with a calcium concentration of 200 ppm in terms of calcium carbonate, obtained by using 0.3 g of clay from the Japan Industrial Technology Association and adjusting it under predetermined conditions using a test tube or the like.

(Example 2-1)
The thing consisting only of the copolymer 4 was made into the builder for liquid detergents.
(Example 2-2)
The same thing as Example 1-7 was made into the builder for liquid detergents.

(Example 2-3)
The same thing as Example 1-8 was made into the builder for liquid detergents.
(Comparative Example 2-1)
The same liquid detergent builder as Comparative Example 1-3 was produced.
The liquid detergent builders of Examples 2-1 to 3 and Comparative Example 2-1 have calcium ion scavenging ability, clay dispersibility in high-hardness water, and liquid detergent composition (3) shown in Table 3 below. The compatibility of the liquid detergent formed by dissolving 1% by mass of the builder for use was measured in the same manner as described above. The results are shown in Table 4.

  From the above results, it was confirmed that the builder for liquid detergent and the liquid detergent containing the copolymer 2 for the present invention are excellent in calcium ion scavenging ability, clay dispersibility in high hardness water, and compatibility.

(Example 3-1)
In each of the liquid detergent compositions (4) and (5) shown in Table 5 below, 1% by mass of the polymer 2 was dissolved to prepare a liquid detergent.
(Example 3-2)
1% by mass of the polymer 3 was dissolved in each of the liquid detergent compositions (4) and (5) shown in Table 5 below to prepare a liquid detergent.

(Comparative Example 3-1)
In each of the liquid detergent compositions (4) and (5) shown in Table 5 below, 1% by mass of the polymer 4 was dissolved to prepare a liquid detergent.
The calcium ion scavenging ability, the clay dispersibility in high hardness water, and the compatibility of the liquid detergent of the polymers of Examples 3-1 to 2 and Comparative Example 3-1 were measured in the same manner as described above. The results are shown in Table 6. In Table 5, Emar 270J is sodium polyoxyethylene lauryl ether sulfate having a pure content of about 70% manufactured by Kao Corporation.

  From the above results, it was confirmed that the polymer for use in the present invention and the liquid detergent containing the polymer were excellent in calcium ion scavenging ability, clay dispersibility in high hardness water, and compatibility.

(Example 4-1)
1% by mass of copolymer 7 was dissolved in a liquid detergent composition (6) shown in Table 7 to obtain a liquid detergent.

(Comparative Example 4-1)
1% by mass of a liquid detergent composition (6) copolymer 8 shown in Table 7 below was dissolved to prepare a liquid detergent.
The copolymers of Example 4-1 and Comparative Example 4-1 were measured for calcium ion scavenging ability, clay dispersibility in high hardness water, and compatibility of liquid detergent in the same manner as described above. The results are shown in Table 8.

  From the above results, it was confirmed that the polymer for use in the present invention and the liquid detergent containing the polymer were excellent in calcium ion scavenging ability, clay dispersibility in high hardness water, and compatibility.

Claims (4)

  It contains 1 to 50 mol% of HAPS (salt) with respect to 100 mol% of acrylic acid (salt) and 3-allyloxy-2-hydroxy-1-propanesulfonic acid (HAPS) (salt), and the weight average molecular weight Mw is 2000 to 2000 A liquid detergent builder comprising an acrylic acid / HAPS (based) copolymer (salt) that is 50,000. A liquid detergent comprising the liquid detergent builder according to claim 1. The liquid detergent of Claim 2 containing 10-60 mass% of surfactant. The liquid detergent according to claim 2, wherein the water content is 1.5 to 50% by mass.