JP2012057085A - Acrylate based polymer and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylate based polymer having an ether bond, which can exhibit excellent ability to prevent resoiling during washing while having excellent compatibility with a surfactant, and also to provide its manufacturing method.SOLUTION: The acrylate based polymer contains, in a specific range, followings having specific structures: (i) a structural unit (a) originated from an acrylate-based monomer (A); (ii) a structural unit (b) originated from a monomer (B) selected from a monomer (B-1) containing an amino group, a cyclic N-vinyllactam monomer (B-2), a hydroxyalkyl(meth)acrylate monomer (B-3), a (meth)acrylate ester (B-4) having a 1-20C alkyl group, and a carboxylic acid vinyl (B-5) containing a carboxyl group; and (iii) a structure (c) originated from a compound (C) selected from a bisulfite (salt) (C-1), a hydrogen peroxide (C-2), and a hypophosphorous acid (salt) (C-3).

Description

The present invention relates to an acrylate polymer and a method for producing the same. More specifically, the present invention relates to an acrylate polymer that is useful as a raw material for detergent additives and the like, and a method for producing the same.

Conventionally, polymers have been used in various industrial fields such as inorganic pigment dispersants, dispersants for coal, detergent compositions, water treatment agents, etc., for example, detergent effects for clothing, cleaning effects In order to improve the above, it has been practiced to blend detergent aids such as carboxymethyl cellulose, polyethylene glycol, polyvinyl pyrrolidone, sodium polyallylate and the like.
For example, Patent Document 1 discloses a polymer having a structural unit (A) represented by general formula (I) and a structural unit (B) represented by general formula (II). It is disclosed that the polymer can be used as a recontamination preventive agent for preventing “recontamination” in which dirt once removed during washing of clothes or the like adheres to the clothes again and becomes contaminated.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a linear or branched alkylene group having 1 to 3 carbon atoms, and n R ^{2 s} may be the same or different. ³ represents a hydrogen atom, or a linear or branched alkyl group having 1 to 22 carbon atoms, an alkenyl group, an alkylaryl group, or a phenyl group, and X represents —O—, —CH ₂ —O—, —CO—. O—, —CO—NH— or —CO—NR ⁵ — (R ⁵ represents a linear or branched alkyl group having 1 to 4 carbon atoms), and n represents the average number of moles of R ² O added. It is a number from 1 to 200 shown.)

(Wherein R ¹ represents the above-mentioned meaning, and R ⁴ represents a linear, branched or cyclic alkyl group or alkenyl group having 1 to 22 carbon atoms, arylalkyl group, alkylaryl group, alkenylaryl group or phenyl group. These groups may have one hydroxyl group as a substituent, and Y represents —O—, —CH ₂ —O—, —CO—O—, —CO—NH—, —CO—NR. ^5- (R ⁵ represents the above meaning) or -O-CO-)
On the other hand, Patent Document 2 discloses the following formula:

(Wherein R ₁ represents a hydrogen atom or an organic residue, R ₂ represents a hydrogen atom, a counter ion, or an organic residue, and G represents a sugar residue). An acrylic ester polymer having a molecular weight of 1,000 to 2,000,000 is disclosed, and is disclosed to be useful as a surfactant.

JP 2009-249743 A JP-A-8-325303

As described above, as described in Patent Document 1, for example, polymers having various structures have been studied as a polymer used for a recontamination preventing agent. On the other hand, as patent document 2, what has various structures is examined as an acrylic ester-type polymer used for uses other than a recontamination prevention agent.
By the way, in recent years, consumers' awareness of the environment has increased, and for the purpose of saving water, washing such as using the remaining hot water of a bath for washing has become established. As a result, it becomes a problem that the dirt component contained in the remaining hot water of the bath adheres to the fibers during washing, or the hard water component is concentrated due to the chasing of the bath, so even under higher hardness, The ability to suppress the reattachment of dirt components to the fiber during washing (referred to as “recontamination prevention ability”) has been demanded more severely than before. In addition, liquid detergents whose demand is currently increasing are concentrated liquid detergents having a surfactant content of 50% or more, so that detergent additives are suitable for blending into such concentrated liquid detergents. Therefore, there is a need for a detergent additive that is more compatible with a surfactant than before.
However, it cannot be said that the conventional polymer can sufficiently satisfy the recent severe requirements regarding the performance of the above-mentioned applications, and exhibits higher performance corresponding to such new needs. There was room for further improvement of the polymer that can be suitably used as a detergent additive.
This invention is made | formed in view of the said present condition, and it aims at providing the acrylate-type polymer which can exhibit the recontamination prevention ability outstanding at the time of washing | cleaning, and its manufacturing method.

The present inventor has studied a polymer that can be suitably used for detergent additives and the like, and has a structural unit derived from an acrylate ester monomer having a specific structure and a structure derived from a specific monomer. It has been found that an acrylate polymer having a unit can exhibit a very good ability to prevent recontamination even under high hardness and has high compatibility with a surfactant. Furthermore, by adjusting the content of each structural unit in the polymer to a specific range, the above-described performance is further improved, and such a polymer is suitable as a detergent additive that meets new needs. As a result, the inventors have found that the above problem can be solved brilliantly, and have reached the present invention.
That is, the present invention comprises (i) a structural unit (a) derived from an acrylate ester monomer (A) represented by the following general formula, (ii) an amino group-containing monomer (B-1), Cyclic N-vinyl lactam monomer (B-2), hydroxyalkyl (meth) acrylate monomer (B-3), (meth) acrylic acid ester having an alkyl group having 1 to 20 carbon atoms (B- 4) a structural unit (b) derived from a monomer (B) selected from vinyl carboxylate (B-5), (iii) bisulfite (salt) (C-1), hydrogen peroxide (C- 2) an acrylic ester polymer comprising a structural unit (c) derived from a compound (C) selected from hypophosphorous acid (salt) (C-3), the acrylic ester The total amount of structural units derived from all monomers forming the polymer is 10 Relative to the weight% comprises 1-99 wt% of structural units (a), an acrylic acid ester polymer which comprises 1 to 99 wt% of structural units (b).

(Wherein R ₁ represents a hydrogen atom or an organic residue, R ₂ represents a hydrogen atom, a counter ion, or an organic residue, and G represents a sugar residue).
The present invention also includes (i) an acrylate ester monomer (A) represented by the following general formula, (ii) an amino group-containing monomer (B-1), a cyclic N-vinyllactam monomer Body (B-2), hydroxyalkyl (meth) acrylate monomer (B-3), (meth) acrylic acid ester (B-4) having an alkyl group having 1 to 20 carbon atoms, vinyl carboxylate (B -5) a monomer (B) selected from (iii) bisulfite (salt) (C-1), hydrogen peroxide (C-2), hypophosphorous acid (salt) (C-3) ) In the presence of the compound (C) selected from the above, the method for producing an acrylate polymer comprising the step of polymerizing, wherein the production method is based on 100% by mass of the total amount of all monomers used. 1 to 99% by mass of an acrylic acid ester monomer (A) represented by the following general formula (1), Serial is also a method for producing acrylic acid ester polymer, characterized by using 1 to 99 wt% of the monomer (B).

(Wherein R ₁ represents a hydrogen atom or an organic residue, R ₂ represents a hydrogen atom, a counter ion, or an organic residue, and G represents a sugar residue).

The acrylic ester polymer of the present invention can exhibit excellent anti-recontamination ability at the time of washing, for example, and is excellent in compatibility with surfactants, so it can be blended into highly concentrated liquid detergents. It can be used suitably as a raw material for detergent additives and the like.

The present invention is described in detail below.

[Acrylic ester polymer of the present invention]
<Acrylic acid ester monomer (A)>
The acrylic ester polymer of the present invention (also referred to as the polymer of the present invention) is a structural unit (a) derived from an acrylic ester monomer (A) represented by the following general formula (1). It is an essential polymer.

(Wherein R ₁ represents a hydrogen atom or an organic residue, R ₂ represents a hydrogen atom, a counter ion, or an organic residue, and G represents a sugar residue). By having such a structure, the acrylic ester monomer (A) contributes to stabilization of dispersion of inorganic particles and dirt components. Therefore, when used for detergent applications, a good ability to prevent recontamination is exhibited.
In addition, when the acrylate ester polymer of the present invention is blended in a liquid detergent or the like, the compatibility with the surfactant is increased due to the sugar residue structure and the like. Property (separation stability) can be made excellent.
In the general formula (1), among the substituents represented by R ₁ and R ₂ , the organic residue is specifically a linear, branched or cyclic group having 1 to 18 carbon atoms. Alkyl group; hydroxyalkyl group having 1 to 8 carbon atoms; alkoxyalkyl group having 2 to 20 carbon atoms; halogenated alkyl group having 1 to 8 carbon atoms; aryl group; — (CHR ₄ CH ₂ O) nR ₅ group (here R ₄ is a hydrogen atom or a methyl group, R ₅ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and n represents a number from 1 to 200); Indicates.

  Specific examples of the organic residue include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, isobutyl group, octyl group, lauryl group, stearyl group, cyclohexyl group, and 2-ethylhexyl group. Alkyl group such as hydroxyethyl group, hydroxybutyl group, hydroxyoctyl group, etc .; aryl such as phenyl group, benzyl group, phenethyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group Group; and the like are exemplified.

R ₁ and R ₂ are an alkyl group having 1 to 12 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, and a carbon number because the ability to prevent re-contamination of the acrylic ester polymer of the present invention is improved. More preferably, they are a 1-12 alkoxyalkyl group and a C6-C12 aryl group.

In the general formula (1), among the substituents represented by R ₂ , specifically, the counter ion is, for example, an alkali metal such as lithium, sodium, potassium, cesium, etc .; magnesium, calcium, strontium, barium, etc. Alkaline earth metals; transition metals such as zinc, nickel, tin, lead and silver; ammonium compounds such as ammonia, monomethylamine, dimethylamine, trimethylamine and triethylamine; is not.
R ₂ is particularly preferably a hydrogen atom or a counter ion from the viewpoint of improving the ability to prevent recontamination of the resulting polymer.

  Specifically, the substituent represented by G in the general formula (1) includes a hemiacetal hydroxyl group at the terminal having all saccharides, that is, saccharides such as monosaccharides, oligosaccharides and polysaccharides as a basic skeleton. A group in which the hydrogen atom of the hydroxyl group at the 1-position has been eliminated from all the saccharides, or a group in which the alkyl group of the acetal group at the 1-position has been eliminated from all of the saccharides that are glycosidically bonded to the alkyl group. In addition, some or all of the hydroxyl groups other than the 1-position hydroxyl group (or acetal group) of the saccharide are protected by an ester bond such as an acetyl group, an acetal bond such as an isopropylidene group, or a halogen atom such as a bromo group. May be.

  Among the saccharides, specific examples of monosaccharides include hexoses such as glucose, galactose, mannose, glucosamine, galactosamine, mannosamine, N-acetylglucosamine, N-acetylgalactosamine, N-acetylmannosamine, and the like. Pentoses such as xylose, ribose and arabinose; Specific examples of the oligosaccharide include, for example, disaccharides such as maltose, lactose, cellobiose, trehalose, isomaltose, gentiobiose, melibiose, laminaribiose, chitobiose, xylobiose, mannobiose, and solohose; Examples thereof include maltotriose, mannotriose, manninotriose, maltotetraose, and maltopentaose. Specific examples of the polysaccharide include cellulose, amylose (starch), chitin, and chitosan.

  The acrylic ester polymer of the present invention has a structural unit (a) derived from the above acrylic ester monomer (A). The structural unit (a) is a structure in which the carbon-carbon double bond of the acrylate ester monomer (A) is a single bond, and is represented by the following general formula (5).

(Wherein R ₁ represents a hydrogen atom or an organic residue, R ₂ represents a hydrogen atom, a counter ion, or an organic residue, and G represents a sugar residue).

The acrylate ester polymer of the present invention has “structural unit (a) derived from acrylate monomer (A)” means that the finally obtained polymer has the above general formula ( It means having a structural unit represented by 2). That is, in the “structural unit (a) derived from the acrylate ester monomer (A)” in the present invention, the above acrylate ester monomer (A) is synthesized, and then the other unit amount. In addition to what is introduced into the polymer by copolymerizing with the body component, for example, the main chain portion of the acrylate ester polymer is first formed by copolymerization, and then side chains having a specific structure are introduced. In other words, the formation process includes those before and after the polymerization reaction.
Moreover, the structural unit (a) possessed by the acrylic ester polymer of the present invention may be only one type or two or more types.

The acrylic ester polymer of the present invention is a total amount of structural units derived from all monomers forming the acrylic ester polymer (structural units (a), structural units (b) and (e) described later). 1 to 99% by mass of the structural unit (a) is included with respect to 100% by mass. If the content of the structural unit (a) is within the above range, when the polymer of the present invention is used as a detergent builder, the dirt component particles can be dispersed and the ability to prevent recontamination can be exhibited. It becomes. The content of the structural unit (a) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 15 to 70% by mass.
When the structural unit (a) contains a carboxylate, that is, when R ₂ is a counter ion in the general formula (5), the mass ratio (% by mass) to the total amount of structural units derived from all monomers is , And corresponding acid conversion (for example, when including -COONa, calculate as -COOH). Moreover, when calculating the mass ratio (mass%) with respect to the total amount of all the monomers of an acid group containing monomer, it shall calculate by corresponding acid conversion. The same applies to the calculation of the mass ratio (% by mass) of the structural units derived from the initiator and the chain transfer agent with respect to the total amount of structural units derived from all monomers.

  <Method for Producing Acrylic Ester Monomer (A)>

It does not restrict | limit especially as a preparation method of the acrylate-type monomer (A) represented by the said General formula (1), It can prepare by arbitrary appropriate methods. As such a preparation method, since the acrylate ester monomer (A) can be produced in a high yield, for example, acrylates represented by the following general formula (2), and An acetalization reaction with a saccharide containing a hemiacetal hydroxyl group at the terminal represented by the general formula (3), and / or the acrylate ester, and an alkyl glycoside represented by the following general formula (4), That is, the acetal exchange reaction between an alkyl group and a glycoside-bonded saccharide can be easily produced by performing it in the presence of a catalyst (for example, produced under the reaction conditions described in JP-A-8-325303). be able to).

（式中、Ｒ_１は水素原子または有機残基を表し、Ｒ_２は水素原子、対イオン、または有機残基を表す）。

(In the formula, R ₁ represents a hydrogen atom or an organic residue, and R ₂ represents a hydrogen atom, a counter ion, or an organic residue).

（式中、Ｇは糖残基を表す）。

(In the formula, G represents a sugar residue).

(In the formula, G represents a sugar residue, and R ₃ represents an organic residue).

The acrylic acid ester represented by the general formula (2) is not particularly limited, but is an α-hydroxyalkyl acrylic acid ester. Specifically, for example, methyl-α-hydroxymethyl acrylate, ethyl -Α-hydroxymethyl acrylate, n-butyl-α-hydroxymethyl acrylate, 2-ethylhexyl-α-hydroxymethyl acrylate, methyl-α- (1-hydroxyethyl) acrylate, ethyl-α- (1-hydroxyethyl) acrylate Alkyl-α-hydroxyalkyl acrylates such as n-butyl-α- (1-hydroxyethyl) acrylate, 2-ethylhexyl-α- (1-hydroxyethyl) acrylate; α-hydroxymethyl acrylate, α-hydroxymethyl acrylic Acid sodium; etc. . These acrylic esters may be used alone or in a suitable mixture of two or more.
In addition, the manufacturing method of acrylic acid ester represented by General formula (2) is not specifically limited. The acrylic acid ester represented by the general formula (2) is a conventionally known method, for example, reacting a corresponding acrylate compound and an aldehyde compound in the presence of a catalyst such as a basic ion exchange resin (for example, No. 6-135896, etc.) can be easily obtained.

  The saccharide containing the hemiacetal hydroxyl group represented by the general formula (3) is not particularly limited, but specifically, for example, the above saccharides, that is, monosaccharides, oligosaccharides, polysaccharides, etc. Examples include all saccharides containing a hemiacetal hydroxyl group at a terminal having a saccharide as a basic skeleton. Only one kind of the saccharide may be used, or two or more kinds may be appropriately mixed and used.

  The alkyl glycosides represented by the general formula (4) are not particularly limited. Specifically, for example, methyl glucoside, methyl galactoside, methyl maltoside, methyl mannoside, methyl xyloside, methyl lactoside , Ethyl glucoside, ethyl galactoside, ethyl mannoside, ethyl xyloside, propyl glucoside, isopropyl glucoside, butyl glucoside, butyl galactoside, butyl xyloside, butyl mannoside and the like. The alkyl glycosides may be used alone or in a suitable mixture of two or more.

  In the production of the monomer (A), the saccharide represented by the general formula (3) and / or the alkyl represented by the general formula (4) with respect to the acrylate ester represented by the general formula (2). The amount of glycosides to be added is not particularly limited. For example, the amount of glycosides is more preferably within a range of 0.01 mol to 10 mol with respect to 1 mol of the acrylate ester represented by the general formula (2). The range of 0.02 mol to 5 mol is more preferable, the range of 0.03 mol to 2 mol is particularly preferable, and the range of 0.05 mol to 1 mol is most preferable.

  Reaction of the acrylate ester represented by the general formula (2) with the compound represented by the general formula (3) and / or the compound represented by the general formula (4) (hereinafter also referred to as reaction A) As the above-mentioned catalyst, an acidic catalyst is more preferable. Specifically, for example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, and partially neutralized salts thereof; tungstophosphoric acid, molybdophosphoric acid, tungstosilicic acid , Heteropolyacids such as molybdosilicic acid, and partially neutralized salts thereof; organic sulfonic acids such as methanesulfonic acid and paratoluenesulfonic acid: protonic acids such as organic carboxylic acids such as formic acid, acetic acid, lauric acid, and oleic acid; Lewis acids such as boron, boron chloride, aluminum chloride, tin dichloride and tin tetrachloride; the base resin is phenolic resin or styrene resin, gel type, An acidic ion exchange resin that exhibits at least one of a porous type and a macroporous type and contains at least one ion exchange group selected from the group consisting of a sulfonic acid group and an alkylsulfonic acid group; . These catalysts may be used alone or in combination of two or more. Among the above-exemplified catalysts, an acidic catalyst such as a protonic acid is an acrylic acid ester and a saccharide represented by the general formula (3) and / or an alkyl glycoside represented by the general formula (4). This is preferable because the reactivity can be further increased.

  The amount of the catalyst added to the acrylic acid ester represented by the general formula (2) in the reaction A depends on the acrylic acid ester and the type of the catalyst used. For example, the ratio to the acrylic acid ester is In the range of 0.001% to 20% by weight, preferably in the range of 0.005% to 15% by weight, more preferably in the range of 0.01% to 10% by weight, and still more preferably in the range of 0.001% by weight. What is necessary is just to make it become the range of 1 to 5 weight%. When the addition amount of the catalyst is less than 0.001% by weight, the catalyst activity is not sufficiently exhibited, the reaction time becomes too long, and the acrylate derivative cannot be efficiently produced, which is not preferable. . On the other hand, even if the added amount of the catalyst is more than 20% by weight, further improvement of the catalytic effect such as shortening of the reaction time in proportion to the increase of the catalyst amount cannot be expected, and a part of the added catalyst is wasted. This is not preferable because it is economically disadvantageous.

The reaction conditions and the like for carrying out the reaction A are not particularly limited, but the acrylic acid esters represented by the general formula (2) as a raw material and the monomer (A ) Is preferably added to the reaction system with a polymerization inhibitor (or polymerization inhibitor) or molecular oxygen (for example, air).
Specific examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, pt-butylcatechol, and phenothiazine, but are not particularly limited. These polymerization inhibitors may be used alone or in combination of two or more. The addition amount of the polymerization inhibitor is not particularly limited. For example, the ratio to the monomer (A) is in the range of 0.001 wt% to 5 wt%, more preferably 0.005 wt. % To 1% by weight, more preferably 0.01% to 0.1% by weight. When the addition amount of the polymerization inhibitor is less than 0.001% by weight, it is difficult to sufficiently suppress the polymerization, which is not preferable. On the other hand, even if the addition amount of the polymerization inhibitor is more than 5% by weight, further improvement of the polymerization prevention effect in proportion to the increase in the polymerization inhibitor amount cannot be expected, and a part of the added polymerization inhibitor is wasted. This is not preferable because it is economically disadvantageous.

  The reaction for producing the monomer (A) can be carried out in a solvent, but can also be carried out without a solvent when a part of the raw material is liquid. The reaction temperature in the reaction for producing the monomer (A) is not particularly limited, but is preferably in the range of 0 ° C to 200 ° C and in the range of 30 ° C to 120 ° C in order to suppress polymerization. Is particularly preferred. The reaction pressure is not particularly limited, and may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure.

After completion of the reaction for producing the monomer (A), the reaction solution may be neutralized using a neutralizing agent as necessary. Specific examples of the neutralizing agent include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like, but are not particularly limited. These neutralizing agents may be used as, for example, powdered or granular solids or aqueous solutions.
In the monomer (A), when R ₂ is a hydrogen atom or a counter ion, the acrylate monomer (A) does not contain an acrylate group, but acrylic acid is used in the present invention. Included in the ester monomer (A).

Further, the reaction solution for the reaction for producing the monomer (A) may contain, for example, catalyst residues, by-products, impurities contained in the raw materials, polymerization inhibitors, and the like. . Therefore, the monomer (A) may be purified by a purification means such as distillation or filtration and then used for polymerization. The purification means is not particularly limited. <Monomer (B)>
The acrylic ester polymer of the present invention comprises an amino group-containing monomer (B-1), a cyclic N-vinyl lactam monomer (B-2), a hydroxyalkyl (meth) acrylate monomer (B -3), a structural unit derived from a monomer (B) selected from (meth) acrylic acid ester (B-4) having a C 1-20 alkyl group and vinyl carboxylate (B-5) (b) ) Is an essential polymer.
The main role of the monomer (B) in the acrylic ester polymer of the present invention is (i) improving the adsorptivity to hydrophobic substances to the acrylic ester polymer, Improving dispersion stability, (ii) Arranging the structure derived from the monomer (A) at a preferred position of the polymer, or controlling the acrylate polymer of the present invention to an appropriate molecular weight or molecular weight distribution It plays a role of a bond between the monomers (A) for the purpose.

The amino group-containing monomer (B-1) is a monomer having a primary to quaternary amino group, for example, a vinyl having a cyclic amine structure such as vinylpyridine, vinylimidazole, vinylmorpholine, vinylpyrrole, etc. Cyclic amine monomers; aminoalkyl (meth) acrylates such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, and aminoethyl methacrylate; allylamines such as diallylamine and diallyldimethylamine, (meth) allylglycidyl Monomers obtained by reacting an epoxy ring of ether, isoprenyl glycidyl ether, or vinyl glycidyl ether with primary to tertiary amines (salts); and a quaternized structure of these amino groups The body is mentioned.
Examples of the amines include alkylamines such as methylamine, ethylamine, dimethylamine, diethylamine, diisopropylamine, and di-n-butylamine; alkanolamines such as diethanolamine and diisopropanolamine; and cyclic amines such as morpholine and pyrrole. Can be mentioned. In the case where the cationic group-containing monomer has a quaternized amino group, a cationic group-containing monomer having a primary to tertiary amino group is quaternized with a known quaternizing agent. Examples of the quaternizing agent include alkyl halides and dialkyl sulfuric acid.
Specific examples of the tertiary amine salt include trimethylamine hydrochloride and triethylamine hydrochloride. Examples of the salt include hydrochloride and organic acid salt.

The cyclic N-vinyllactam monomer (B-2) is a monomer having a cyclic lactam ring, and includes N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyl-4-butylpyrrolidone, N- Vinyl-4-propylpyrrolidone, N-vinyl-4-ethylpyrrolidone, N-vinyl-4-methylpyrrolidone, N-vinyl-4-methyl-5-ethylpyrrolidone, N-vinyl-4-methyl-5-propylpyrrolidone N-vinyl-5-methyl-5-ethylpyrrolidone, N-vinyl-5-propylpyrrolidone, N-vinyl-5-butylpyrrolidone, N-vinyl-4-methylcaprolactam, N-vinyl-6-methyl Examples include caprolactam, N-vinyl-6-propylcaprolactam, and N-vinyl-7-butylcaprolactam.
Among the structures derived from the cyclic N-vinyl lactam monomer (B-2), the effect of improving the ability to prevent re-contamination of an acrylate polymer is high, and therefore it is derived from N-vinyl pyrrolidone and N-vinyl caprolactam. It preferably has a structure.

The hydroxyalkyl (meth) acrylate monomer (B-3) is preferably a monomer having a hydroxyalkyl group having 1 to 4 carbon atoms, such as 2-hydroxyethyl (meth) acrylate and (meth) acrylic. Examples include 2-hydroxypropyl acid, 2-hydroxybutyl (meth) acrylate, and (meth) acrylic acid-hydroxymethyl.
Among the structures derived from hydroxyalkyl (meth) acrylate monomers (B-3), 2-hydroxyethyl (meth) acrylate is highly effective in improving the ability to prevent recontamination of acrylic ester polymers. It preferably has a structure derived from 2-hydroxypropyl (meth) acrylate.

As the (meth) acrylic acid ester (B-4) having an alkyl group having 1 to 20 carbon atoms,
A methacrylic acid ester having an alkyl group having 1 to 20 carbon atoms and an acrylate ester having an alkyl group having 1 to 20 carbon atoms, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl ( Examples include (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate and the like. Among the structures derived from the monomer (B-4), an acrylate ester having an alkyl group having 1 to 4 carbon atoms is preferable because the effect of improving the ability to prevent recontamination of the acrylate ester polymer is high. Particularly preferred are acrylates and ethyl acrylates.

Examples of vinyl carboxylate (B-5) include vinyl acetate, vinyl propionate and vinyl butyrate.
The acrylic ester polymer of the present invention is a total amount of structural units derived from all monomers forming the acrylic ester polymer (structural units (a) and (b) and structural units (e) described later). The structural unit (b) is contained in an amount of 1 to 99% by mass with respect to 100% by mass. When the content of the structural unit (b) is within the above range, the dispersibility of the dirt component particles and the pigment and the ability to prevent recontamination can be preferably exhibited. Moreover, the remarkable improvement effect of compatibility with surfactant can be acquired. The content of the structural unit (b) is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 30 to 85% by mass.
In the case where the structural unit (b) is a structural unit derived from an amino group-containing monomer, the mass ratio relative to the total amount of structural units derived from all monomers, When calculating the mass ratio with respect to the total amount of monomers, it shall be calculated as the mass ratio of the corresponding unneutralized amine. For example, when the amino group-containing monomer (B-1) is vinylamine hydrochloride, the mass ratio (% by mass) of vinylamine that is the corresponding unneutralized amine is calculated.
In addition, when calculating the mass ratio (mass%) of a monomer containing a quaternized amino group or a structural unit derived therefrom, the mass of the counter anion is not taken into account (not including) Shall.
The same applies to the calculation of the mass ratio (% by mass) of the structural units derived from the initiator and the chain transfer agent with respect to the total amount of structural units derived from all monomers.

The acrylic ester polymer of the present invention has the structural unit (b) in the above range, and only one or more of the structural unit (b-1) is 1 of the structural unit (b-2). Only 1 type or 2 types or more, 1 type or 2 types or more of structural unit (b-3), 1 type or 2 types or more of structural unit (b-4), 1 type of structural unit (b-5) or Although it may be only two or more types, the structural unit (b-1), the structural unit (b-2), the structural unit (b-3), the structural unit (b-4), the structural unit (b-5) ), A plurality of different structural unit groups may be included.
Among the structural unit (b-1), the structural unit (b-2), the structural unit (b-3), the structural unit (b-4), and the structural unit (b-5), the acrylic acid ester polymer It is preferable to have at least one selected from dimethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and N-vinylpyrrolidone, since the effect of improving the antifouling ability is particularly high.

<Other monomers>
The acrylic ester polymer of the present invention has a structural unit (e) derived from another monomer (E) (a monomer other than the monomer (A) and the monomer (B)). You may do it. The acrylic ester polymer may have only one type of structural unit (e), or may have two or more types of structural units (e).

  The structural unit (e) derived from the other monomer (E) is a structural unit in which the unsaturated double bond of the other monomer (E) is replaced with a single bond. The acrylic ester polymer of the present invention has “structural unit (e) derived from other monomer (E)” means that the finally obtained polymer is of monomer (E). It means having a structural unit in which an unsaturated double bond is replaced with a single bond.

Examples of the other monomer (E) include unsaturated monocarboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid and salts thereof. ; Unsaturated dicarboxylic acids such as itaconic acid, fumaric acid, maleic acid, 2-methyleneglutaric acid and salts thereof; unsaturated dicarboxylic acid monomers such as salts thereof; an unsaturated dicarboxylic acid and an alcohol having 1 to 22 carbon atoms; Half ester, half amide of unsaturated dicarboxylic acid and amine having 1 to 22 carbon atoms, half ester of unsaturated dicarboxylic acid and glycol having 2 to 4 carbon atoms; vinyl sulfonic acid, (meth) allyl sulfonic acid, isoprene sulfone Acid, 3-allyloxy-2-hydroxypropanesulfonic acid, acrylamido-2-methylpropanesulfonic acid and these Sulfonic acid group-containing monomers such as salts thereof; vinyl aryl monomers such as styrene and indene; alkenes such as isobutylene; N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylformamide, N- N-vinyl cyclic amide monomers such as vinyl-N-methylacetamide and N-vinyloxazolidone; acrylamides such as (meth) acrylamide and (meth) isopropylacrylamide; and hydroxyl-containing single monomers such as (meth) allyl alcohol and isoprenol Examples include monomers obtained by adding 1 to 200 moles of alkylene oxide to the body, and polyalkylene glycol chain-containing monomers such as (meth) acrylic acid esters of alkoxy polyalkylene glycols.
Examples of the salt include metal salts, ammonium salts, organic amine salts (organic ammonium salts) and the like.
When the acrylic ester polymer of the present invention has a structural unit (e) derived from the other monomer (E) as an optional component, all monomers that form the acrylic ester polymer The structural unit (e) is preferably contained in an amount of 0 to 60% by mass with respect to 100% by mass of the total amount of structural units derived from (ie, the total amount of the structural units (a), (b) and (e)). More preferably, it is 0-50 mass%.
When the structural unit (e) is a structural unit derived from an acid group-containing monomer, the mass ratio (% by mass) to the total amount of structural units derived from all monomers is calculated in terms of the corresponding acid. And Moreover, when calculating the mass ratio (mass%) with respect to the total amount of all the monomers of an acid group containing monomer, it shall calculate by corresponding acid conversion. The same applies to the calculation of the mass ratio (% by mass) of the structural units derived from the initiator and the chain transfer agent with respect to the total amount of structural units derived from all monomers.

<Other structural units>
The polymer of the present invention has a structure derived from a compound (C) selected from bisulfite (salt) (C-1), hydrogen peroxide (C-2), and hypophosphorous acid (salt) (C-3). It is essential to include the unit (c). That is, a sulfonic acid (salt) group derived from bisulfite (salt) (C-1), a hydroxyl group derived from hydrogen peroxide, a phosphinate group derived from hypophosphorous acid (salt), and the like are essential. When the polymer of the present invention contains the structural unit (c), the ability to prevent recontamination of the polymer of the present invention is significantly improved. In particular, it is preferable that the polymer of the present invention has a sulfonic acid (salt) group because the salt resistance of the polymer is improved.
Since the compound (C) usually acts as an initiator or a chain transfer agent, the structural unit (c) is usually introduced at the molecular end (however, hypophosphorous acid (salt) has two reaction sites). , Introduced at the end of the molecule or into the molecule).
The structural unit derived from the initiator and the chain transfer agent (in terms of acid type in the case of an acid group salt) is 0.05 to 10% by mass with respect to 100% by mass of the structure derived from all monomers. More preferably, it is more preferably 0.1 to 5% by mass.
<Other physical properties of acrylate polymer>
The acrylic acid ester-based polymer of the present invention is only required that the structural units (a), (b) and, if necessary, the structural units (e) are introduced at a specific ratio as described above. Each structural unit may exist in a block shape or a random shape.
Moreover, the weight average molecular weight of the said acrylate ester-type polymer can be set suitably, and is not specifically limited. Specifically, the weight average molecular weight of the acrylate polymer is preferably 2,000 to 200,000, more preferably 3,000 to 100,000, and most preferably 4,000 to 60,000. 000. If the weight average molecular weight is within the above range, the ability to prevent recontamination tends to be improved.
The number average molecular weight of the acrylate polymer is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, and most preferably 2,000 to 25,000. is there. If the number average molecular weight is within the above range, the recontamination preventing ability tends to be improved.
In the present specification, the weight average molecular weight and the number average molecular weight are measured values by GPC (gel permeation chromatography), and can be measured by an apparatus and measurement conditions described in Examples described later. .
The acrylic ester-based polymer of the present invention has a high recontamination prevention ability, but the recontamination prevention ratio is preferably 75% or more. More preferably, it is 76% or more.
The recontamination prevention rate can be measured in the same manner as in the examples described later.
[Acrylate ester polymer composition]
The acrylic ester polymer of the present invention may constitute an acrylic ester polymer composition together with other components. As said other component, a polymerization initiator residue, a residual monomer, the by-product at the time of superposition | polymerization, a water | moisture content, etc. are mentioned, These 1 type (s) or 2 or more types can be contained. The acrylate polymer composition preferably contains 1 to 100% by mass of the acrylate polymer of the present invention with respect to 100% by mass of the total amount of the acrylate polymer composition. One of the preferred forms of the acrylate polymer composition is a form containing 40 to 60% by mass of the acrylate polymer of the present invention and 40 to 60% by mass of water.
[Method for Producing Acrylic Ester Polymer of the Present Invention]
The acrylic ester polymer of the present invention comprises (i) an acrylic ester monomer (A) (monomer (A)) represented by the general formula (1) and (ii) an amino group-containing polymer. Monomer (B-1), cyclic N-vinyl lactam monomer (B-2), hydroxyalkyl (meth) acrylate monomer (B-3), having an alkyl group having 1 to 20 carbon atoms The monomer (B) selected from (meth) acrylic acid ester (B-4) and vinyl carboxylate (B-5) is essential, and other monomers (E) (monomer ( E)) in a predetermined proportion, (iii) bisulfite (salt) (C-1), hydrogen peroxide (C-2), hypophosphorous acid (salt) (C-3) It can manufacture by copolymerizing in presence of the compound (C) chosen from these.
In the method for producing an acrylic ester polymer of the present invention, the composition ratio of each monomer used for polymerization is 100 in total of all monomers (monomer (A), (B), (E)). A monomer (A) is 1-99 mass% and a monomer (B) is 1-99 mass% with respect to mass%. If the content of the monomer (A) is less than 1% by mass, the detergency of the stain component and the ability to prevent recontamination may be reduced, which may reduce the cleaning power. Moreover, there exists a possibility that the molecular weight and molecular weight distribution of a polymer cannot be controlled as content of a monomer (B) is less than 1 mass%. The composition ratio of each monomer used for polymerization is preferably 5 to 90% by mass of monomer (A) and 10 to 95% by mass of monomer (B), more preferably monomer. (A) is 10 to 80% by mass, monomer (B) is 20 to 90% by mass, and particularly preferably, monomer (A) is 15 to 70% by mass and monomer (B) is 30%. It is -85 mass%.
Moreover, even if it contains the monomer (E) in the ratio of 0-60 mass% with respect to the total amount 100 mass% of all the monomers (monomer (A), (B), (E)). Good. More preferably, it is 0-50 mass%, More preferably, it is 0-10 mass%, Most preferably, it is 0 mass%.
The polymerization method for obtaining the acrylate ester-based polymer of the present invention is not particularly limited, and a commonly used polymerization method or a modified method thereof can be employed. Examples of the polymerization method include a radical polymerization method, specifically, an oil-in-water emulsion polymerization method, a water-in-oil emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, and a solution polymerization method. An aqueous solution polymerization method, a bulk polymerization method, or the like can be employed. Among the polymerization methods exemplified above, it is preferable to employ a solution polymerization method because it is highly safe and can reduce production costs (polymerization costs).
In the solution polymerization method, the monomer component is polymerized in a solvent, but the solvent is not particularly limited, and a solvent usually used in the solution polymerization method can be used. As said solvent, water-based solvents, such as water, alcohol, glycol, glycerol, polyethyleneglycol, are suitable, for example. Among these, water is more preferable.
The said solvent may use only 1 type and may use 2 or more types together. Moreover, in order to improve the solubility of the monomer component in the solvent, an organic solvent may be appropriately added within a range that does not adversely affect the polymerization reaction.
The organic solvent is not particularly limited, and any appropriate organic solvent can be used. Examples of such an organic solvent include lower alcohols such as methanol and ethanol; amides such as dimethylformaldehyde; ethers such as diethyl ether and dioxane;
As for the said organic solvent, only 1 type may be used and 2 or more types may be used together.
The amount of the solvent used is preferably 40 to 300 parts by mass, more preferably 45 to 200, with respect to 100 parts by mass of the total amount of all monomers (monomers (A), (B), (E)). It is the range of 50 mass parts, More preferably, it is 50-150 mass parts. When the amount of the solvent used is less than 40 parts by mass relative to 100 parts by mass of the total amount of all monomers, the molecular weight of the resulting polymer may be too high. On the other hand, when the amount of the solvent used exceeds 300 parts by mass with respect to 100 parts by mass of the total amount of all monomers, the concentration of the resulting polymer is lowered, and in some cases, the solvent may need to be removed. .
The solvent may be partly or wholly charged in the reaction vessel in the initial stage of polymerization, but a part of the solvent may be added (dropped) into the reaction system during the polymerization reaction, or the monomer. Components, initiators, and the like may be added (dropped) into the reaction system during the polymerization reaction together with these components in a form in which the components and initiator are dissolved in advance.
The reaction form of the solution polymerization method is not particularly limited, and the reaction can be carried out according to a commonly used form. Typically, for example, in the solvent charged in advance in the reaction system, the single monomer is used. The form which reacts by dripping the solution containing a body component, the solution containing the said compound (C), and the solution containing a polymerization initiator (henceforth "initiator") is mentioned. In such a reaction form, the concentration of each solution to be dropped is not particularly limited, and any appropriate concentration can be adopted.
As a form which reacts by dripping the solution containing the said monomer component and the solution containing an initiator in the solvent previously prepared in the said reaction system, a monomer (A), a single quantity, for example During the polymerization, the body (B), the monomer (E), if necessary, the initiator component, and other additives as necessary, are dissolved in the solvent, or without being dissolved in the solvent. The form which superposes | polymerizes by adding (dropping) suitably in a reaction system is mentioned. In the reaction form, a part or all of the total amount of the monomer (A) used can be added to the reaction system in advance (initial charge) before the start of polymerization.
In the polymerization reaction by the solution polymerization method, it is preferable that the addition of the monomer (A) to the reaction system is completed earlier than the addition of the monomer (B). And it is more preferable that 5-100 mass% is unadded among the total usage-amount of a monomer (B) at the time of completion | finish of addition of a monomer (A). More preferably, 10 to 50% by mass of the total amount of the monomer (B) used is not added at the end of the addition of the monomer (A), and 15% of the total amount of the monomer (B) used. It is particularly preferable that ˜35% by mass is not added. By performing polymerization by adding by such an addition method, the polymerizability of the acrylate ester monomer (A) can be improved, and thus the dispersibility of the obtained polymer, the ability to prevent recontamination, etc. Can be improved.
<Polymerization initiator>
As the polymerization initiator used in the above production method, those usually used can be used. Specifically, hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; 2,2′-azobis (2-amidinopropane) hydrochloride, 4,4′-azobis-4-cyanoparellin Azo compounds such as acid, azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl Organic peroxides such as peroxide and cumene hydroperoxide are preferred. Of these polymerization initiators, hydrogen peroxide, persulfate, and 2,2′-azobis (2-amidinopropane) hydrochloride are preferred, and persulfate and 2,2′-azobis (2-amidinopropane) hydrochloric acid. Most preferred are salts. These polymerization initiators may be used alone or in combination of two or more.
<Chain transfer agent>
In the above production method, if necessary, a chain transfer agent may be used as a molecular weight regulator of the polymer within a range that does not adversely affect the polymerization.
Specific examples of the chain transfer agent include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropion, 3-mercaptopropion, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2- Thiol chain transfer agents such as mercaptoethanesulfonic acid, n-dodecyl mercaptan, octyl mercaptan, butylthioglycolate; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane; Secondary alcohol; phosphorous acid; hypophosphorous acid (salt) (C-3), that is, hypophosphorous acid and its salt (for example, sodium hypophosphite, potassium hypophosphite, etc.); bisulfite (salt) (C-1), that is, sulfite, hydrogen sulfite, nitrous acid Phosphate, metabisulfite and salts thereof (sodium bisulfite, potassium bisulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.), etc., can be mentioned. The said chain transfer agent may be used independently, and 2 or more types may be mixed and used for it.
When a chain transfer agent is used, there is an advantage that a polymer to be produced can be prevented from having a higher molecular weight than necessary, and a low molecular weight acrylate polymer can be produced efficiently.
In the said manufacturing method, it is a preferable form to use a bisulfite (salt) (C-1) as a chain transfer agent. In that case, a polymerization initiator is used in addition to bisulfite (salt) (C-1). Furthermore, you may use a heavy metal ion together as a reaction accelerator mentioned later.
The bisulfite (salt) (C-1) means a compound that reacts with hydrogen sulfite or water to generate hydrogen sulfite or a salt thereof. Especially, the form whose hydrogen sulfite is a salt is suitable. When sulfite and / or hydrogen sulfite is a salt, a salt of a metal atom, ammonium or organic ammonium is preferred in addition to the above examples.
Examples of the metal atom include monovalent metal atoms of alkali metals such as lithium, sodium and potassium; divalent metal atoms of alkaline earth metals such as calcium and magnesium; trivalent metal atoms such as aluminum and iron Etc. are preferred.
As the organic ammonium (organic amine), alkanolamines such as ethanolamine, diethanolamine, and triethanolamine, and triethylamine are preferable. Further, the bisulfite (salt) (C-1) may be an ammonium salt.
Therefore, examples of the sulfite preferably used in the present invention include sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium sulfite, potassium sulfite, ammonium sulfite and the like, and sodium bisulfite is particularly suitable. The bisulfite (salt) (C-1) may be used alone or in combination of two or more.
<Reaction accelerator>
In the above production method, a reaction accelerator may be added for the purpose of reducing the amount of initiator used. Examples of the reaction accelerator include heavy metal ions. In the present invention, the heavy metal ion means a metal having a specific gravity of 4 g / cm ³ or more. As said metal ion, iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium etc. are preferable, for example. These heavy metals can be used alone or in combination of two or more. Among these, iron is more preferable. The valence of the heavy metal ion is not particularly limited. For example, when iron is used as the heavy metal, the iron ion in the initiator may be Fe ²⁺ or Fe ³⁺ , and both of them may be used. It may be included.
Although the said heavy metal ion will not be specifically limited if it is contained as a form of ion, Since it is excellent in handleability, it is suitable to use the solution formed by melt | dissolving a heavy metal compound. The heavy metal compound used in that case should just contain the heavy metal ion desired to contain in an initiator, and can be determined according to the initiator to be used. When iron is used as the heavy metal ion, the mole salt (Fe (NH ₄ ) ₂ (SO ₄ ) ₂ · 6H ₂ O), ferrous sulfate · 7 hydrate, ferrous chloride, ferric chloride, etc. It is preferable to use a heavy metal compound or the like. Moreover, when using manganese as a heavy metal ion, manganese chloride etc. can be used suitably. Since these are all water-soluble compounds, they can be used in the form of an aqueous solution and have excellent handleability. The solvent of the solution obtained by dissolving the heavy metal compound is not limited to water, and does not interfere with the polymerization reaction in the production of the acrylate polymer of the present invention, and is a heavy metal compound. As long as it dissolves.
The method for adding the heavy metal ions is not particularly limited, but it is preferably added before the monomer addition is completed, and it is particularly preferable to initially charge the entire amount. Further, the amount used is preferably 100 ppm or less, more preferably 70 ppm or less, still more preferably 50 ppm or less, and particularly preferably 30 ppm or less, based on the total amount of the reaction solution. If it exceeds 100 ppm, the effect of addition is not observed, and the resulting polymer is highly colored, which may be unusable when used as a detergent composition.
The content of the heavy metal ions is preferably 0.1 to 10 ppm with respect to the total mass of the polymerization reaction solution at the completion of the polymerization reaction. If the content of heavy metal ions is less than 0.1 ppm, the effect of heavy metal ions may not be sufficiently exhibited. On the other hand, if the content of heavy metal ions exceeds 10 ppm, the color tone of the resulting polymer may be deteriorated. Moreover, when there is much content of heavy metal ion, when using the polymer which is a product as a detergent builder, there exists a possibility of becoming a cause of coloring stain | pollution | contamination.
The time when the polymerization reaction is completed means the time when the polymerization reaction is substantially completed in the polymerization reaction solution and a desired polymer is obtained. For example, when the polymer polymerized in the polymerization reaction solution is neutralized with an acid component, the content of heavy metal ions is calculated based on the total mass of the polymerization reaction solution after neutralization. When two or more kinds of heavy metal ions are included, the total amount of heavy metal ions may be in the above range.
In the above production method, in the polymerization, a decomposition catalyst for the polymerization initiator or a reducing compound may be added to the reaction system in addition to the above-described compounds.
Examples of the decomposition catalyst for the polymerization initiator include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid, nitric acid and the like. Metal salts of inorganic acids; Carboxylic acids such as formic acid, acetic acid, propionic acid, lactic acid, isolacic acid, benzoic acid, their esters and their metal salts; heterocyclic amines such as pyridine, indole, imidazole, carbazole and their derivatives Can be mentioned. These decomposition catalysts may be used alone or in combination of two or more.
Examples of the reducing compound include organic metal compounds such as ferrocene; iron naphthenate, copper naphthenate, nickel naphthenate, cobalt naphthenate, manganese naphthenate, and the like, such as iron, copper, nickel, cobalt, and manganese. Inorganic compounds capable of generating metal ions; boron trifluoride ether adducts, potassium permanganate, perchloric acid and other inorganic compounds; sulfur dioxide, sulfite, sulfate, bisulfite, thiosulfate, sulfoxide, Sulfur-containing compounds such as benzenesulfinic acid and its substitutes, and homologues of cyclic sulfinic acid such as para-toluenesulfinic acid; octyl mercaptan, dodecyl mercaptan, mercaptoethanol, α-mercaptopropionic acid, thioglycolic acid, thiopropionic acid, α -Sodium thiopropionate sulfopropyl ester Mercapto compounds such as stealth and α-thiopropionic acid sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, β-hydroxyethylhydrazine and hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, isovaleraldehyde Aldehydes such as ascorbic acid and the like. These reducing compounds may also be used alone or in combination of two or more. Further, a reducing compound such as a mercapto compound may be added as a chain transfer agent.
The combination of the chain transfer agent, the initiator, and the reaction accelerator is not particularly limited as long as at least one compound (C) is contained, and can be appropriately selected from the above examples. For example, combinations of chain transfer agent, initiator and reaction accelerator include sodium bisulfite / sodium persulfate, sodium bisulfite / Fe (ion), sodium bisulfite / hydrogen peroxide / Fe (ion), sodium bisulfite Forms such as / sodium persulfate / Fe (ion), sodium bisulfite / sodium persulfate / hydrogen peroxide, sodium bisulfite / oxygen / Fe (ion) are preferable. More preferred are sodium persulfate / hydrogen peroxide, sodium persulfate / hydrogen peroxide / Fe (ion), sodium bisulfite / sodium persulfate, sodium bisulfite / sodium persulfate / Fe (ion), and most preferred. Are sodium bisulfite / sodium persulfate / Fe (ion) and sodium persulfate / hydrogen peroxide / Fe (ion).
<Amount of polymerization initiator used>
The amount of the polymerization initiator used is not particularly limited as long as it is an amount capable of initiating copolymerization of monomers, but the total amount of all monomer components (monomer (A), (B) and (E)) is 1 It is preferable that it is 15 g or less with respect to mol. More preferably, it is 1-12g.
When hydrogen peroxide is used as an initiator, the amount of hydrogen peroxide added is preferably 1.0 to 10.0 g with respect to 1 mol of the total amount of all monomer components, and 2.0 to 8 More preferably, it is 0.0 g. If the amount of hydrogen peroxide added is less than 1.0 g, the polymerization average molecular weight of the resulting polymer tends to increase. On the other hand, when the addition amount exceeds 10.0 g, an effect sufficient to meet the increase in the addition amount cannot be obtained, and further, the remaining hydrogen peroxide amount is adversely affected.
When using a persulfate as an initiator, the amount of the persulfate added is preferably 1.0 to 5.0 g with respect to 1 mol of the total amount of all monomer components, and 2.0 to 4 More preferably, it is 0.0 g. If the amount of persulfate added is less than the above range, the molecular weight of the resulting polymer tends to increase. On the other hand, if the addition amount is more than the above range, an effect corresponding to the increase in the addition amount cannot be obtained, and further, the purity of the obtained polymer is adversely affected.
When hydrogen peroxide and persulfate are used together as an initiator, the addition ratio of hydrogen peroxide and persulfate is such that the weight ratio of persulfate to hydrogen peroxide is 0.1 to 5.0. Preferably, it is 0.2-2.0. If the weight ratio of persulfate is less than 0.1, the weight average molecular weight of the resulting copolymer tends to be high. On the other hand, if the weight ratio of persulfate exceeds 5.0, the effect of lowering the molecular weight due to the addition of persulfate cannot be obtained enough to meet the increase in the amount added, and the persulfate is wasted in the polymerization reaction system. Will be consumed.
As a method for adding hydrogen peroxide, the amount to be added by dripping substantially continuously is preferably 85% by weight or more of the necessary predetermined amount, more preferably 90% by weight or more, and 100 Most preferably, the weight percent, ie the whole amount, is added dropwise. When hydrogen peroxide is continuously dropped, the dropping speed may be changed.
When hydrogen peroxide is dropped under the appropriate reaction conditions (temperature, pressure, pH, etc.) described later, it is delayed after the start of dropping of the monomer (excluding the initially charged monomer). It is preferable to start. Specifically, preferably after 1 minute or more has elapsed since the start of dropping of the monomer (A), more preferably after 3 minutes or more, still more preferably after 5 minutes or more, and most preferably after 10 minutes or more have elapsed. It is to start dropping of hydrogen oxide. By delaying the start of the dropwise addition of hydrogen peroxide, it is possible to smooth the initial polymerization start and narrow the molecular weight distribution.
The time for delaying the start of dropwise addition of hydrogen peroxide is preferably within 60 minutes, more preferably within 30 minutes after the start of dropping of the monomer.
It is possible to start the dropping of hydrogen peroxide simultaneously with the dropping of the monomer, or to charge hydrogen peroxide in advance before dropping of the monomer. Is preferably 10% or less. More preferably, it is 7% or less, More preferably, it is 5% or less, Most preferably, it is 3% or less.
If more than 10% of the required amount of hydrogen peroxide is added before the start of the dropwise addition of the monomer, for example, when a persulfate is used in combination, the ratio of the concentration of hydrogen peroxide to the persulfate increases, and polymerization is May stop. On the other hand, if it starts later than 60 minutes from the start of the dropping of the monomer, the chain transfer reaction due to hydrogen peroxide does not occur, so the molecular weight at the initial stage of polymerization increases.
Further, the dropping of hydrogen peroxide is preferably terminated simultaneously with the end of dropping of the monomer when the reaction is performed under suitable reaction conditions (temperature, pressure, pH, etc.) described later. Moreover, it is more preferable to complete | finish 10 minutes or more earlier than monomer dropping completion time, and it is especially preferable to complete | finish 30 minutes or more early. In addition, even if it complete | finishes later than the dripping completion time of a monomer, it does not have a bad influence in a polymerization system especially. However, since the added hydrogen peroxide is not completely decomposed by the end of the polymerization, unreacted hydrogen peroxide cannot be obtained and is wasted. Further, it is not preferable that a large amount of hydrogen peroxide remains because it may adversely affect the thermal stability of the obtained polymer.
The method for adding the persulfate is not particularly limited, but considering the decomposability and the like, it is preferable that the amount added by dripping continuously is 50% by weight or more of the required predetermined amount. . More preferably, it is 80 weight% or more, and it is most preferable that 100 weight%, ie, the whole quantity is dripped. When the persulfate is continuously dropped, the dropping speed may be changed.
Although the dropping time is not particularly limited, in the case of performing the reaction under the preferable reaction conditions (temperature, pressure, pH, etc.) described later, since persulfate is a relatively quick initiator, It is preferable to continue dropping until the dropping end time. Moreover, it is more preferable to complete | finish dripping within 30 minutes after completion | finish of monomer dripping, and it is especially preferable to complete dripping within 5 to 20 minutes after monomer dripping. Thereby, the residual amount of the monomer in the produced polymer can be remarkably reduced.
It should be noted that, even if the dropping of these initiators is completed before the dropping of the monomer is completed, it does not particularly adversely affect the polymerization, and the initiator depends on the residual amount of the monomer in the obtained polymer. What is necessary is just to set the dripping end time.
For initiators that are relatively quick to decompose, such as the persulfate, the preferred range for the dropping end time has been described, but the dropping start time is not limited in any way and may be set as appropriate. For example, the start of dropping of the initiator may be started before the start of dropping of the monomer. When two or more kinds of initiators are used in combination, the start of dropping of one initiator is started and a certain time has elapsed. You may start dripping another initiator after or after dripping is complete | finished. In either case, the initiator dropping start time may be appropriately set according to the decomposition rate of the initiator and the reactivity of the monomer.
The concentration of the initiator solution when the polymerization initiator is added dropwise is not particularly limited, but is preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight. If the concentration of the initiator is less than 5% by weight, the monomer concentration during the polymerization will be very low as a result. The residual amount of becomes very large. Further, the efficiency and productivity of transportation and the like are lowered, which is not preferable from the economical aspect. On the other hand, if it exceeds 60% by weight, there is a problem in terms of safety and ease of dripping.
The addition amount of the chain transfer agent is not limited as long as the monomers (A), (B) and (E) are polymerized satisfactorily, but preferably the monomers (A), (B) and (E ) To 1 to 20 g, more preferably 2 to 15 g, based on 1 mol of all monomer components. If it is less than 1 g, the molecular weight may not be controlled. On the other hand, if it exceeds 20 g, a large amount of impurities may be produced, and the pure polymer content may be reduced. In particular, when bisulfite (salt) (C-1) is used, surplus bisulfite (salt) (C-1) may be decomposed in the reaction system to generate sulfurous acid gas. Furthermore, there is a risk that it may be economically disadvantageous.
As a combination of the initiator and the chain transfer agent, it is most preferable to use one or more of persulfate and bisulfite (salt) (C-1). In this case, the mixing ratio of persulfate and bisulfite (salt) (C-1) is not particularly limited, but bisulfite (salt) (C-1) 0. It is preferable to use 5 to 5 parts by mass. The lower limit of the amount of bisulfurous acid (salt) (C-1) is more preferably 1 part by mass, and most preferably 2 parts by mass with respect to 1 part by mass of persulfate. Further, the upper limit of the amount of bisulfite (salt) (C-1) is more preferably 4 parts by mass, and most preferably 3 parts by mass with respect to 1 part by mass of persulfate. If the bisulfite (salt) (C-1) is less than 0.5 parts by mass with respect to 1 part by mass of the persulfate, the total amount of initiator required may increase when the molecular weight is reduced. If it exceeds 5 parts by mass, side reactions may increase and impurities may increase.
The total amount of the chain transfer agent, the initiator, and the reaction accelerator used is 2 to 20 g with respect to 1 mol of the total amount of all monomer components composed of the monomers (A), (B), and (E). It is preferable that By setting it as such a range, the polymer of this invention can be produced efficiently and the molecular weight distribution of an acrylate ester-type polymer can be made into a desired thing. More preferably, it is 4-18g, More preferably, it is 6-15g.
In the above production method, as a method for adding the monomer component, the polymerization initiator and the chain transfer agent to the reaction vessel, a continuous charging method such as dropping or divided charging can be applied. In addition, each may be introduced alone into the reaction vessel, or may be mixed in advance with other components, a solvent, or the like.
As a specific addition method, a method in which all of the monomer components are charged into a reaction vessel and copolymerization is performed by adding a polymerization initiator into the reaction vessel; a portion of the monomer components are charged into the reaction vessel. A method of carrying out copolymerization by adding a polymerization initiator and the remaining monomer component continuously or stepwise (preferably continuously) into a reaction vessel; charging a polymerization solvent into the reaction vessel; A method of adding the total amount of the monomer component and the polymerization initiator; and the like. Among these methods, since the molecular weight distribution of the polymer obtained can be narrowed (sharpened) and the dispersibility of dirt and the ability to prevent recontamination can be improved, a polymerization initiator and a monomer component It is preferable to carry out the copolymerization by successively dropping them into a reaction vessel. Such polymerization can be carried out either batchwise or continuously.
<Polymerization conditions>
In the said manufacturing method, superposition | polymerization conditions, such as superposition | polymerization temperature, are suitably determined by the superposition | polymerization method used, a solvent, a polymerization initiator, etc., However, It is preferable that it is 25-200 degreeC as superposition | polymerization temperature. More preferably, it is 50-150 degreeC, More preferably, it is 60-120 degreeC, Most preferably, it is 80-110 degreeC. If the polymerization temperature is too low, the weight average molecular weight of the resulting polymer may be too high, or the amount of impurities generated may increase.
The polymerization temperature does not necessarily need to be kept almost constant in the polymerization reaction. For example, the polymerization is started from room temperature, the temperature is raised to a set temperature with an appropriate temperature increase time or rate, and then the set temperature is increased. You may make it hold | maintain and you may carry out temperature fluctuation (temperature rise or temperature fall) with time during a polymerization reaction according to dripping methods, such as a monomer component and an initiator. The polymerization temperature refers to the temperature of the reaction solution for the polymerization reaction. Moreover, about the measuring method and control means of superposition | polymerization temperature, arbitrary appropriate methods and means can be employ | adopted. For example, the measurement may be performed using a generally used apparatus.
The pressure during the polymerization in the above production method is not particularly limited, and any appropriate pressure can be adopted. For example, it may be under normal pressure (atmospheric pressure), reduced pressure, or increased pressure. Further, the atmosphere in the reaction system may be an air atmosphere or may be an inert gas atmosphere. When the atmosphere in the reaction system is an inert gas atmosphere, for example, the reaction system can be replaced with an inert gas such as nitrogen before the start of polymerization. As a result, atmospheric gas (for example, oxygen gas) in the reaction system is dissolved in the liquid phase and acts as a polymerization inhibitor.
In the said manufacturing method, it is preferable that solid content concentration in the reaction solution (polymer solution) at the time of completion | finish of addition of the said addition component complete | finished and the polymerization reaction in a reaction system is 35 mass% or more. If it is less than 35% by mass, the productivity of the resulting polymer may not be significantly improved. More preferably, it is 40-70 mass%, More preferably, it is 45-65 mass%. Thus, if the solid content concentration at the end of the polymerization reaction is 35% by mass or more, the polymerization can be carried out at a high concentration and in one stage. Therefore, a polymer can be obtained efficiently. For example, the concentration step can be omitted, the productivity of the polymer is greatly improved, and an increase in manufacturing cost can be suppressed. The time point at which the polymerization reaction is completed represents the time point at which the addition of all the added components is completed. However, even when a predetermined aging time thereafter (when the polymerization is completed), The solid content concentration is preferably in the above-described range.
The solid content concentration can be calculated by obtaining the non-volatile content after processing for 1 hour with a 130 ° C. hot air dryer.
The aging time is preferably 1 to 120 minutes, more preferably 5 to 60 minutes, and still more preferably 10 to 30 minutes. When the aging time is less than 1 minute, the monomer component may remain because of insufficient aging, and there is a possibility that performance may be deteriorated due to impurities derived from the remaining monomer. If the aging time exceeds 120 minutes, the polymer solution may be colored.
In the above production method, the polymerization time is not particularly limited, but is preferably 30 to 420 minutes, more preferably 45 to 390 minutes, still more preferably 60 to 360 minutes, and most preferably 90 to 300 minutes. It is. In the present invention, “polymerization time” represents the time during which a monomer is added, that is, the time from the start of addition of the monomer to the end unless otherwise specified.
The acrylic ester polymer of the present invention that can be produced by the above production method can exhibit high performance in aqueous applications, hard water resistance, detergency, recontamination prevention ability, clay dispersibility, surface activity. Since the interaction with the agent is high, particularly excellent performance can be exhibited when used in a dispersant, a detergent builder, a detergent composition, a cleaning agent, and a water treatment agent.
[Use of acrylic ester polymer and acrylic ester polymer composition of the present invention]
The acrylic ester polymer (or acrylic ester polymer composition) of the present invention comprises a coagulant, a flocculant, a printing ink, an adhesive, a soil conditioner (modifier), a flame retardant, a skin care agent, and a hair care agent. , Shampoos, hair sprays, soaps, cosmetic additives, anion exchange resins, dye mordants and auxiliaries for fibers and photographic films, pigment spreaders in papermaking, paper strength enhancers, emulsifiers, preservatives, textiles and paper As softener, lubricant additive, water treatment agent, fiber treatment agent, dispersant, detergent additive, scale inhibitor (scale inhibitor), metal ion sealant, thickener, various binders, emulsifier, etc. Can be used. As a detergent builder, it can be used by adding to detergents for various uses such as clothing, tableware, dwelling, hair, body, toothpaste, and automobile.
<Water treatment agent>
The acrylic ester polymer (or acrylic ester polymer composition) of the present invention can be used as a water treatment agent. For the water treatment agent, polymerized phosphates, phosphonates, anticorrosives, slime control agents, and chelating agents may be used as other compounding agents as necessary.
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 concentration tank, and the like. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effects.
<Fiber treatment agent>
The acrylic ester polymer (or acrylic ester polymer composition) of the present invention can also be used as a fiber treatment agent. The fiber treatment agent includes at least one selected from the group consisting of a dye, a peroxide, and a surfactant, and the acrylic ester polymer (or acrylic ester polymer composition) of the present invention.
The content of the acrylic ester polymer of the present invention in the fiber treatment agent is preferably 1 to 100% by weight, more preferably 5 to 100% by weight, based on the entire fiber treatment agent. Further, any appropriate water-soluble polymer may be included as long as the performance and effects are not affected.
Below, the compounding example of a fiber processing agent is shown. This fiber treatment agent can be used in the steps of refining, dyeing, bleaching and soaping in fiber treatment. Examples of dyeing agents, peroxides, and surfactants include those usually used for fiber treatment agents.
The blending ratio of the acrylic acid ester-based polymer of the present invention to at least one selected from the group consisting of a dye, a peroxide and a surfactant is, for example, the whiteness of the fiber, the color unevenness, and the dyeing tempering degree. For the improvement, at least one selected from the group consisting of a dye, a peroxide and a surfactant is 0.1 to 0.1 part by weight of the polymer of the present invention in terms of a pure amount of the fiber treatment agent. It is preferable to use a composition blended at a ratio of 100 parts by weight as a fiber treatment agent.
Arbitrary appropriate fibers can be adopted as a fiber which can use the above-mentioned textile treating agent. Examples thereof include cellulosic fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, semi-synthetic fibers such as human silk, and woven fabrics and blended products thereof.
When the fiber treatment agent is applied to the refining process, it is preferable to blend the polymer of the present invention with an alkali agent and a surfactant. When applied to the bleaching step, it is preferable to blend the polymer of the present invention, a peroxide, and a silicic acid-based agent such as sodium silicate as a decomposition inhibitor for the alkaline bleaching agent.
<Inorganic pigment dispersant>
The acrylic ester polymer (or acrylic ester polymer composition) of the present invention can also be used as an inorganic pigment dispersant. In the inorganic pigment dispersant, condensed phosphoric acid and a salt thereof, phosphonic acid and a salt thereof, and polyvinyl alcohol may be used as other compounding agents as necessary.
The content of the acrylic ester polymer of the present invention in the inorganic pigment dispersant is preferably 5 to 100% by weight with respect to the whole inorganic pigment dispersant. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effect.
The inorganic pigment dispersant can exhibit good performance as a dispersant for heavy or light calcium carbonate or clay inorganic pigment used in paper coating. For example, by adding a small amount of an inorganic pigment dispersant to an inorganic pigment and dispersing it in water, high concentration calcium carbonate having low viscosity and high fluidity and good aging stability of their performance. High concentration inorganic pigment slurries such as slurries can be produced.
When the inorganic pigment dispersant is used as a dispersant for an inorganic pigment, the amount of the inorganic pigment dispersant used is preferably 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the inorganic pigment. When the amount of the inorganic pigment dispersant used is within the above range, a sufficient dispersion effect can be obtained, and an effect commensurate with the addition amount can be obtained, which can be economically advantageous.
<Detergent Builder>
The acrylic ester polymer (or acrylic ester polymer composition) of the present invention can also be used as a detergent builder. As a detergent builder, it can be used by adding to detergents for various uses such as clothing, tableware, residential, hair, body, toothpaste, and automobile.
<Detergent composition>
The acrylic ester polymer (or acrylic ester polymer composition) of the present invention can also be added to a detergent composition.
The content of the acrylic ester polymer in the detergent composition is not particularly limited. However, from the viewpoint of exhibiting excellent builder performance, the content of the acrylic ester polymer is preferably 0.1 to 15% by mass with respect to 100% by mass of the total amount of the detergent composition, More preferably, it is 0.3-10 mass%, More preferably, it is 0.5-5 mass%.
Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. Specific forms of these surfactants and additives are not particularly limited, and knowledge generally known in the detergent field can be appropriately referred to. The detergent composition may be a powder detergent composition or a liquid detergent composition.
The surfactant is one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant. When two or more kinds are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 100% by mass based on the total amount of the surfactant. It is 60 mass% or more, More preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more.
Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or its ester salt, alkane sulfonate Salt, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate ester Or its salt etc. are suitable. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these anionic surfactants.
Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters. Esters, alkylamine oxides and the like are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these nonionic surfactants.
As the cationic surfactant, a quaternary ammonium salt or the like is suitable. As the amphoteric surfactant, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant, and the like are suitable. The alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may be branched from an alkyl group such as a methyl group.
The blending ratio of the surfactant is usually 10 to 60% by mass, preferably 15 to 50% by mass, and more preferably 20 to 45% by mass with respect to 100% by mass of the total amount of the detergent composition. Especially preferably, it is 25-40 mass%. If the blending ratio of the surfactant is too small, sufficient detergency may not be exhibited, and if the blending ratio of the surfactant is too large, the economy may be lowered.
Additives include anti-redeposition agent to prevent redeposition of contaminants such as alkali builder, chelate builder, sodium carboxymethyl cellulose, stain inhibitor such as benzotriazole and ethylene-thiourea, soil release agent, color transfer Inhibitors, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, dyes A solvent or the like is preferable. In the case of a powder detergent composition, it is preferable to blend zeolite.
The detergent composition may contain other detergent builders in addition to the acrylate polymer (or acrylate polymer composition) of the present invention. Other detergent builders are not particularly limited, but include, for example, alkali builders such as carbonates, bicarbonates, silicates, tripolyphosphates, pyrophosphates, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, citric acid. Examples thereof include acid salts, (meth) acrylic acid copolymer salts, acrylic acid-maleic acid copolymers, chelate builders such as fumarate and zeolite, and carboxyl derivatives of polysaccharides such as carboxymethylcellulose. Examples of the counter salt used in the builder include alkali metals such as sodium and potassium, ammonium and amine.
The total blending ratio of the additive and other detergent builder is preferably 0.1 to 50% by mass with respect to 100% by mass of the cleaning composition. More preferably, it is 0.2-40 mass%, More preferably, it is 0.3-35 mass%, Most preferably, it is 0.4-30 mass%, Most preferably, it is 0.5-20 mass% or less. It is. If the total blending ratio of additives and other detergent builders is less than 0.1% by mass, sufficient detergent performance may not be exhibited, and if it exceeds 50% by mass, the economy may be reduced.
In addition, the concept of the above-mentioned detergent composition includes specific detergents such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance one of the components. Detergents that are only used are also included.
When the said detergent composition is a liquid detergent composition, it is preferable that the moisture content contained in a liquid detergent composition is 0.1-75 mass% with respect to the whole quantity of a liquid detergent composition, More preferably, it is 0. .2 to 70% by mass, more preferably 0.5 to 65% by mass, even more preferably 0.7 to 60% by mass, particularly preferably 1 to 55% by mass, and most preferably It is 1.5-50 mass%.
When the detergent composition is a liquid detergent composition, the detergent composition preferably has a kaolin turbidity of 200 mg / L or less, more preferably 150 mg / L or less, and even more preferably 120 mg / L or less. Especially preferably, it is 100 mg / L or less, Most preferably, it is 50 mg / L or less.
<Measurement method of kaolin turbidity>
A sample (liquid detergent) uniformly stirred in a 50 mm square cell having a thickness of 10 mm was removed and air bubbles were removed. Then, a NDU2000 manufactured by Nippon Denshoku Co., Ltd. Kaolin turbidity: mg / L) is measured.
Proteases, lipases, cellulases, and the like are suitable as enzymes that can be incorporated into the cleaning composition. Of these, proteases, alkaline lipases, and alkaline cellulases that are highly active in an alkaline cleaning solution are preferred.
The amount of the enzyme added is preferably 5% by mass or less with respect to 100% by mass of the cleaning composition. If it exceeds 5% by mass, improvement in detergency cannot be seen, and the economy may be reduced.
As the alkali builder, silicate, carbonate, sulfate and the like are preferable. As the chelate builder, diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), STPP (sodium tripolyphosphate), citric acid and the like are preferable. Other water-soluble polycarboxylic acid-based polymers other than the polymer of the present invention may be used.
The above detergent composition should be a detergent with excellent dispersibility, extremely high quality agent performance and excellent stability that is less likely to cause performance degradation when stored for a long time and precipitation of impurities when held at low temperatures. Can do.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.
The quantification of monomers and reaction intermediates and the measurement of various physical properties were performed by the following methods.
<Measurement conditions of weight average molecular weight and number average molecular weight (GPC)>
Apparatus: L-7000 series manufactured by Hitachi, Ltd. Detector: HITACHI RI Detector L-7490
Column: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B manufactured by Showa Denko Co., Ltd.
Column temperature: 40 ° C
Flow rate: 0.5 ml / min
Calibration curve: POLYETHYLENE GLYCOL STANDARD made by GL Sciences Inc.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio).

<Monomer determination method>
Monomer quantification was performed using high performance chromatography under the following conditions.
Measuring device: 8020 series manufactured by Tosoh Corporation Column: CAPCELL PAK C1 UG120 manufactured by Shiseido Co., Ltd.
Temperature: 40.0 ° C
Eluent: 10 mmol / L Disodium hydrogen phosphate.12 hydrate aqueous solution (adjusted to pH 7 with phosphoric acid) / acetonitrile = 45/55 (volume ratio)
Flow rate: 1.0 ml / min
Detector: RI, UV (detection wavelength: 215 nm).
<Measurement of solid content>
In an oven heated to 130 ° C. in a nitrogen atmosphere, 1.0 g of an acrylate polymer composition containing the acrylate polymer of the present invention plus 1.0 g of water is left for 1 hour to dry. Processed. From the mass change before and after drying, the solid content (%) and the volatile component (%) were calculated.
<Synthesis of acrylic ester monomer (A)>
[Synthesis Example 1]
A 300 mL reaction vessel equipped with a thermometer and a stirrer was charged with 65.0 g of ethyl-α-hydroxymethyl acrylate as an acrylate ester and 1.30 g of pt-butylcatechol as a polymerization inhibitor. Stir. Next, after adding 18.0 g of glucose as a saccharide containing a hemiacetal hydroxyl group and 0.7 g of paratoluenesulfonic acid monohydrate as a catalyst to the above reaction vessel, gradually heat while stirring. did. The reaction solution was then stirred at 100 ° C. and normal pressure for 2 hours to complete the reaction. After completion of the reaction, the reaction solution was neutralized with a 2N sodium hydroxide aqueous solution as a neutralizing agent, and then concentrated under reduced pressure using a predetermined method. The obtained concentrated liquid was separated and purified using column chromatography. In column chromatography, a solution of chloroform: methanol = 9: 1 was used as a developing solvent. Silica gel was used as the adsorbent. In this way, RHMA-Gl monomer (1) was obtained. The structure was confirmed by ¹ HNMR.

<Production of acrylic ester polymer>
[Example 1]
A 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 150.0 g of pure water and 0.0045 g of Mole salt and heated to 90 ° C. while stirring to polymerize. The reaction system was used. Next, 200.0 g of hydroxyethyl acrylate (hereinafter referred to as HEA), 50.0 g of monomer (1), 15% sodium persulfate aqueous solution in a polymerization reaction system maintained at 90 ° C. with stirring. (Hereinafter referred to as 15% NaPS) 50.7 g, 35% sodium bisulfite (hereinafter referred to as 35% SBS) 43.5 g and pure water 140.5 g were dropped from separate nozzles.
The start of dropping of each solution is simultaneous, and the dropping time of each solution is 120 minutes for HEA, 60 minutes for monomer (1), 130 minutes for 15% NaPS, 120 minutes for 35% SBS, and The pure water was 120 minutes. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of 15% NaPS, the reaction solution was maintained at 90 ° C. for 30 minutes (ripening) to complete the polymerization. In this way, an aqueous solution (polymer composition (1)) containing the copolymer (1) having a solid content concentration of 45% was obtained.

[Example 2]
A 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 150.0 g of pure water and 0.0050 g of Mole salt, and heated to 90 ° C. while stirring to polymerize. The reaction system was used. Next, 200.0 g of dimethylaminoethyl acrylate (hereinafter referred to as DAA), 50.0 g of monomer (1), and 42.0 g of 15% NaPS in a polymerization reaction system maintained at 90 ° C. with stirring. , And 227.1 g of pure water were dropped from separate nozzles.
The dropping start of each solution is simultaneous, and the dropping time of each solution is 120 minutes for DAA, 60 minutes for monomer (1), 130 minutes for 15% NaPS, and 120 minutes for pure water. did. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of 15% NaPS, the reaction solution was maintained at 90 ° C. for 30 minutes (ripening) to complete the polymerization. Thus, the aqueous solution (polymer composition (2)) containing the copolymer (2) with a solid content concentration of 40% was obtained.

[Comparative Example 1]
Methoxypolyethylene glycol (9 mol) methacrylate (NK ester M-90G; manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as MMP9) 47.7 g, methyl methacrylate (hereinafter referred to as MMA) 32.3 g, ethanol 46 .3 g were uniformly mixed, put into a glass separable flask having an internal volume of 300 mL, and stirred for a certain time under a nitrogen atmosphere. The reaction solution was heated to about 80 ° C., and 0.84 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (V-65; manufactured by Wako Pure Chemical Industries, Ltd.) was added to ethanol 7. A solution dissolved in 6 g was added. Polymerization and aging were carried out by holding at around 80 ° C. for 6 hours. By cooling this reaction solution, a comparative polymer (1) was obtained as a 60 wt% ethanol solution of the polymer.

  As a result of the liquid chromatography measurements of the polymer compositions (1) and (2), the residual monomer was 1000 ppm or less, and it was confirmed that a polymer (see Table 1) having a composition as prepared was obtained. .

[Example 3]
For the copolymers (1), (2) and the comparative copolymer (1) obtained in Examples 1 and 2 and Comparative Example 1, the compatibility with the surfactant was evaluated as follows. The results are shown in Table 1. <Compatibility with surfactant>
A detergent composition containing a test sample (acrylic acid ester polymer or acrylic acid ester polymer composition) was prepared with the following composition.
SFT-70H (Nippon Shokubai Co., Ltd., polyoxyethylene alkyl ether); 40 g
Neoperex F-65 (manufactured by Kao Corporation, sodium dodecylbenzenesulfonate); 7.7 g (active ingredient 5 g)
Coatamine 86W (manufactured by Kao Corporation, stearyltrimethylammonium chloride); 17.9 g (active ingredient 5 g)
Diethanolamine; 5g
Ethanol; 5 g
Propylene glycol; 5g
Test sample (solid content conversion): 1.5 g
Ion-exchanged water; balance (the amount of ion-exchanged water is appropriately adjusted so that the total amount is 100 g, with the amount of test sample used as the actual amount used).
Thoroughly stir the components so that they are uniform, and the turbidity value at 25 ° C. is measured using a turbidimeter (“NDH2000” manufactured by Nippon Denshoku Co., Ltd.) and Turbidity (kaolin turbidity: mg / l) Measured with
Evaluation was made according to the following criteria.
○: Kaolin turbidity (0 or more, less than 50 (mg / l)), visually separated, not precipitated or clouded.
(Triangle | delta): Kaolin turbidity (50 or more, less than 200 (mg / l)), and it is slightly cloudy visually.
X: Kaolin turbidity (200 or more (mg / l)), visually turbid.

[Example 6]
Further, the copolymer (1) obtained in Example 1, the copolymer (2) obtained in Example 2, and the comparative copolymer (1) obtained in Comparative Example 1 were recontaminated as follows. The ability to prevent was evaluated.
The recontamination prevention rate of the copolymer (1) was 80%, and the recontamination prevention rate of the copolymer (2) was 76%. On the other hand, the recontamination prevention rate of the comparative copolymer (1) was 73%.
<Recontamination prevention test>
The recontamination prevention test was performed according to the following procedure.
(1) A polyester cloth obtained from Test fabric was cut into 5 cm × 5 cm to prepare a white cloth. The whiteness of the white cloth was measured by reflectance using a colorimetric color difference meter SE2000 type manufactured by Nippon Denshoku Industries Co., Ltd. in advance.
(2) Pure water was added to 1.1 g of calcium chloride dihydrate to 15 kg to prepare hard water.
(3) Pure water was added to 4.0 g of polyoxyethylene (20) lauryl ether to make 100.0 g to prepare a surfactant aqueous solution. The pH was adjusted to 8.5 with sodium hydroxide.
(4) A targot meter was set at 25 ° C., 1 L of hard water, 5 g of an aqueous surfactant solution, 1 g of a 5% polymer aqueous solution in terms of solid content, and 1.0 g of carbon black were placed in a pot and stirred at 150 rpm for 1 minute. . Then, 5 white cloths were put and stirred at 100 rpm for 10 minutes.
(5) Water of the white cloth was drained by hand, 1 L of tap water adjusted to 25 ° C. was put in the pot, and stirred at 100 rpm for 2 minutes.
(6) A white cloth was applied and dried while stretching the wrinkles with an iron, and then the whiteness of the white cloth was measured again with the above colorimetric colorimeter with reflectance.
(7) The recontamination prevention rate was calculated from the above measurement results using the following equation.
Recontamination prevention rate (%) = (whiteness after washing) / (whiteness of raw white cloth) × 100.

  From the results of Examples and Comparative Examples, it was found that the polymer of the present invention was excellent in compatibility with a surfactant and had excellent anti-recontamination ability under high hardness.

Claims (3)

(I) Structural unit (a) derived from an acrylate ester monomer (A) represented by the following general formula, (ii) amino group-containing monomer (B-1), cyclic N-vinyl lactam Monomer (B-2), hydroxyalkyl (meth) acrylate monomer (B-3), (meth) acrylic acid ester (B-4) having an alkyl group having 1 to 20 carbon atoms, carboxylic acid Structural unit (b) derived from monomer (B) selected from vinyl (B-5), (iii) bisulfite (salt) (C-1), hydrogen peroxide (C-2), hypochlorous acid A structure (c) derived from a compound (C) selected from phosphoric acid (salt) (C-3), and an acrylate ester polymer, wherein the acrylate ester polymer is For a total amount of 100 mass% of structural units derived from all monomers forming the polymer, the structure Position: (a) comprises 1-99 wt%, acrylic acid ester polymer which comprises 1 to 99 wt% of structural units (b).

(Wherein R ₁ represents a hydrogen atom or an organic residue, R ₂ represents a hydrogen atom, a counter ion, or an organic residue, and G represents a sugar residue). (I) Acrylic ester monomer (A) represented by the following general formula, (ii) amino group-containing monomer (B-1), cyclic N-vinyl lactam monomer (B-2) ), A hydroxyalkyl (meth) acrylate monomer (B-3), a (meth) acrylic acid ester (B-4) having a C1-C20 alkyl group, and vinyl carboxylate (B-5). A monomer selected from (iii) bisulfite (salt) (C-1), hydrogen peroxide (C-2), and hypophosphorous acid (salt) (C-3) In the presence of (C), a method for producing an acrylic ester polymer comprising a step of polymerizing, wherein the production method comprises the following general formula ( 1 to 99% by mass of the acrylate monomer (A) represented by 1), the monomer (B Method for producing acrylic acid ester polymer, characterized by using 1 to 99% by weight.

(Wherein R ₁ represents a hydrogen atom or an organic residue, R ₂ represents a hydrogen atom, a counter ion, or an organic residue, and G represents a sugar residue). A detergent composition comprising the acrylic ester polymer according to claim 1.