JP2012057094A - Polymer containing amino group and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer containing amino group, which can exhibit excellent ability to prevent resoiling during washing while excelling in compatibility with a surfactant, and to provide its manufacturing method.SOLUTION: The polymer contains, as necessary components, followings having specific structures: (i) a structural unit, originated from a monomer containing an amino group; and (ii) a structural unit originated from a nonionic monomer and/or a monomer containing an amino group.

Description

The present invention relates to an amino group-containing polymer and a method for producing the same. More specifically, the present invention relates to an amino group-containing polymer useful as a raw material for detergent additives and the like and a method for producing the same.

Conventionally, amino group-containing polymers are coagulants, flocculants, printing inks, adhesives, detergent additives, soil conditioners (modifiers), flame retardants, shampoos, hair sprays, soaps, cosmetic additives, In a wide range of fields, including anion exchange resins, dye mordants and auxiliaries for fibers and photographic films, pigment spreaders in papermaking, paper strength enhancers, emulsifiers, preservatives, fabric and paper softeners, and lubricant additives It is used.
For example, Patent Document 1 discloses that a polymer having the following general formula exhibits excellent performance in applications such as cleaning agents.

For example, Patent Document 2 discloses that a detergent composition containing a polymer compound containing a structural unit derived from a monomer having a vinylpyridine moiety exhibits high detergency.

JP 2005-170977 A JP 2008-1770 A

As described above, amino group-containing polymers having various structures have been studied.
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 can not be said that the conventional amino group-containing polymer can sufficiently satisfy recent strict requirements regarding the performance of such aqueous applications, and responds to such new needs. There was room for further improvement of the polymer that can be suitably used for detergent additives that exhibit higher performance.
The present invention has been made in view of the above situation, and can exhibit an excellent ability to prevent recontamination at the time of washing, and an amino group-containing polymer excellent in compatibility with a surfactant and a method for producing the same The purpose is to provide.

The present inventor has examined a polymer that can be suitably used for detergent additives and the like, a structural unit derived from an amino group-containing monomer having a specific structure, a nonionic monomer and / or other than the above The amino group-containing polymer having a structural unit derived from the amino group-containing monomer can exhibit a very good ability to prevent recontamination even under high hardness, and has compatibility with a surfactant. I found it expensive. 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 relates to (i) a structural unit (a) derived from an amino group-containing monomer (A) and (ii) a nonionic monomer (B-1) and / or a monomer (A) other than An amino group-containing polymer essentially comprising the structural unit (b) derived from the amino group-containing monomer (B-2), wherein the amino group-containing monomer (A) has the following general formula: (1) or (1 ′);

(Wherein R ₀ represents a hydrogen atom or a CH ₃ group. R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a direct bond. R ₂ , R ₃ and R ₄ may be the same or different. Represents an organic group having 1 to 20 carbon atoms, R ₅ and R ₆ are the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and Y ₁ is the same or different and has 2 carbon atoms. Represents an alkylene group of ˜20, n is the average number of added moles of the oxyalkylene group (—Y ₁ —O—), and represents a number of ₁ to 300. X ₁ ^— represents a counter anion.) The amino group-containing polymer has a structure represented by the formula (1) with respect to 100 mass% of the total amount of structural units derived from all monomers forming the polymer: 99% by mass and 1 to 99% by mass of structural unit (b) Roh is a group-containing polymer.
The present invention also provides (i) an amino group-containing monomer (A) and (ii) a nonionic monomer (B-1) and / or an amino group-containing monomer other than the monomer (A) ( B-2) is a method for producing an amino group-containing polymer, wherein the production method comprises the following general formula (1) with respect to 100% by mass of the total amount of all monomers used:

(Wherein R ₀ represents a hydrogen atom or a CH ₃ group. R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a direct bond. R ₂ , R ₃ and R ₄ may be the same or different. Represents an organic group having 1 to 20 carbon atoms, R ₅ and R ₆ are the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and Y ₁ is the same or different and has 2 carbon atoms. Represents an alkylene group of ˜20, n is the average number of added moles of the oxyalkylene group (—Y ₁ —O—), and represents a number of ₁ to 300. X ₁ ^— represents a counter anion.) 1 to 99% by mass of a polyalkylene glycol monomer (A) represented by a nonionic monomer (B-1) and / or an amino group-containing monomer other than the monomer (A) ( B-2) is used in an amount of 1 to 99% by mass. It is also a manufacturing method.

The amino group-containing polymer of the present invention exhibits, for example, excellent dispersibility and anti-recontamination ability of dirt components during washing, and exhibits excellent compatibility with surfactants. Can also be blended and can be suitably used as a raw material for detergent additives and the like.

The present invention is described in detail below.
[Amino group-containing polymer of the present invention]
<Amino group-containing monomer (A)>
The amphoteric polymer of the present invention is a polymer essentially comprising the structural unit (a) derived from the amino group-containing monomer (A) represented by the following general formula (1) or (1 ′).

In the formula, R ₀ represents a hydrogen atom or a CH ₃ group. R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a direct bond. R ₂ , R ₃ and R ₄ are the same or different and each represents an organic group having 1 to 20 carbon atoms. R ₅ and R ₆ are the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. Y ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. n is an average addition mole number of an oxyalkylene group (—Y ₁ —O—), and represents a number of 1 to 300. X ₁ ⁻ represents a counter anion.
In addition, the amphoteric polymer in the present invention is derived from the monomer (A) represented by the general formula (1) as the structural unit (a) and the single unit represented by the general formula (1 ′). Any material having at least one structural unit among those derived from the body (A) may be used. That is, either one of them or both may be included.
In the general formula (1) or (1 ′), the case where R ₁ is a direct bond means that H ₂ C═C (R ₀ ) —R ₁ —O in the general formula (1) or (1 ′). It means that − is represented by H ₂ C═C (R ₀ ) —O—. That _{H 2 C = C (R 0} ) -R 1 - is, _{R 0} is CH _3, methallyl group when _{R 1} is a CH ₂ group, _{R 0} is CH _{3, R 1} is _CH 2 CH ₂ group Is an isoprenyl group, R ₀ is a CH ₃ group, R ₁ is a direct bond, an isopropenyl group, R ₀ is a hydrogen atom, R ₁ is a CH ₂ group, an allyl group, R ₀ is a hydrogen atom, R _{When 1} is a CH ₂ CH ₂ group, it is a butenyl group, R ₀ is a hydrogen atom, and when R ₁ is a direct bond, it is a vinyl group.
As the group having a polymerizable carbon-carbon double bond in the amino group-containing monomer (A), that is, as H ₂ C═C (R ₀ ) —R ₁ —, an isoprenyl group, a methallyl group, an allyl group, A vinyl group is preferred. From the viewpoint of enhancing the polymerizability, an isoprenyl group, a methallyl group, and an allyl group are more preferable, and an isoprenyl group and a methallyl group are particularly preferable.
R ₂ , R ₃ and R ₄ in the general formula (1) are the same or different and represent an organic group having 1 to 20 carbon atoms. R ₅ and R ₆ in the general formula (1 ′) are the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. The organic group having 1 to 20 carbon atoms is not limited as long as it has 1 to 20 carbon atoms as a whole, but is preferably an alkyl group, an aryl group, or an alkenyl group. The alkyl group, aryl group, and alkenyl group may be an unsubstituted group or a group in which one or more hydrogen atoms are substituted with another organic group. In this case, as other organic groups, when the organic group represented by R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is an alkyl group, the organic group after substitution is totally It corresponds to an unsubstituted alkyl group.), Aryl group, alkenyl group, alkoxy group, hydroxyl group, acyl group, ether group, amide group, ester group, ketone group, carboxyl group, carboxyl group salt, sulfonic acid group, sulfone Examples include acid group salts.
_{R 2, R 3, R 4} , R 5 and the carbon number of _{R 6} is from 1 to 8, more preferably 1 to 5, 1 to 2 is more preferred. If the number of carbon atoms is in the above range, the amino group-containing monomer (A) can be produced with a high yield, so that the polymerizability of the monomer and the purity of the resulting polymer are improved. In addition, the ability to prevent recontamination of the resulting polymer is improved.
Specifically, alkyl groups such as methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, isobutyl group, octyl group, lauryl group, stearyl group, cyclohexyl group, 2-ethylhexyl group; butylene group , An alkenyl group such as an octylene group and a nonylene group; an aryl group such as a phenyl group, a benzyl group, a phenethyl group, a 2,3- or 2,4-xylyl group, a mesityl group, a naphthyl group, or one of these hydrogen atoms A group in which a part is substituted with an alkoxy group, a carboxy ester group, an amino group, an amide group, a hydroxyl group, a carboxyl group, a salt of a carboxyl group, a sulfonic acid group, a salt of a sulfonic acid group, such as a hydroxyethyl group, a hydroxypropyl group, etc. Is mentioned. Among these, a methyl group and an ethyl group are preferable from the viewpoint of improving the ability to prevent recontamination of the obtained polymer.
R ₂ and R ₃ in the general formula (1) or R ₅ and R ₆ in the general formula (1 ′) may be bonded to each other to form a cyclic structure. In this case, the cyclic structure formed by the nitrogen atom, R ₂ and R ₃ (or R ₅ and R ₆ ) is a _{3- to} 7-membered ring, that is, R ₂ and R _{3 in} that the cyclic structure is stabilized. And the total number of carbon atoms (or the sum of R ₅ and R ₆ ) is preferably 2-6.
In the above general formula (1) or (1 ′), Y ₁ is the same or different and is an alkylene group having 2 to 20 carbon atoms, which improves the polymerizability of the amino group-containing monomer (A). From the viewpoint, Y ₁ is preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an alkylene group having 2 to 3 carbon atoms. Specifically, an alkylene group having 2 to 4 carbon atoms such as an ethylene group, a propylene group, or a butylene group is preferable, and an alkylene group having 2 to 3 carbon atoms such as an ethylene group or a propylene group is more preferable. As said alkylene group, 1 type (s) or 2 or more types can be used, but when using 2 or more types, the oxyalkylene group represented by -Y < ₁ > -O- is a random addition, a block addition, and alternate addition. Any additional form such as these may be used.
In the general formula (1), n is an average addition mole number of the oxyalkylene group _(-Y 1 -O-), represents the number of 1 to 300. N tends to be 5 or more, more preferably 10 or more, and still more preferably 20 or more, because the re-contamination preventing ability of the resulting polymer tends to be improved. Further, from the viewpoint of improving the polymerizability of the amino group-containing monomer (A), n is preferably 200 or less, more preferably 150 or less, and even more preferably 100 or less.
If the amino group-containing monomer (A) has a quaternized nitrogen atom, the nitrogen atom vicinity quaternized, counter anion X ₁ ^- so that there is. The type of the counter anion X ₁ ⁻ is not particularly limited, but an ion of a halogen atom and an alkyl sulfate ion are preferable. Specific examples of the halogen atom ion include ions such as a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom. Of these, ions of chlorine atom, bromine atom and iodine atom are preferable, and ion of chlorine atom is more preferable. Specific examples of the alkyl sulfate ion include methyl sulfate ion and ethyl sulfate ion. Of these, methyl sulfate ion is preferable.
The amino group-containing polymer of the present invention has a structural unit (a) derived from the amino group-containing monomer (A). The structural unit (a) is a structure in which the carbon-carbon double bond of the amino group-containing monomer (A) is a single bond, and can be represented by the following general formula (2) or (2 ′).

In the formula, R ₀ represents a hydrogen atom or a CH ₃ group. R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a direct bond. R ₂ , R ₃ and R ₄ are the same or different and each represents an organic group having 1 to 20 carbon atoms. R ₅ and R ₆ are the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. Y ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. n is an average addition mole number of an oxyalkylene group (—Y ₁ —O—), and represents a number of 1 to 300. X ₁ ⁻ represents a counter anion.

Note that the amino group-containing polymer of the present invention contains the “structural unit (a) derived from the amino group-containing monomer (A)” means that the finally obtained polymer has the general formula (2). And / or including a structural unit represented by (2 ′). That is, in the “structural unit (a) derived from the amino group-containing monomer (A)” in the present invention, the amino group-containing monomer (A) is synthesized and then the other monomer components are synthesized. For example, the main chain portion of an amino group-containing polymer is first formed by copolymerization, and then a side chain having a specific structure is introduced. In some cases, the forming process extends before and after the polymerization reaction.
The content of the structural unit (a) in the amino group-containing polymer of the present invention is the total amount of structural units derived from all monomers forming the amphoteric polymer (structural unit (a), structural unit (b) described later. ) And (e) is 100% by mass or more and 1% by mass or more and 99% by mass or less. When the content of the structural unit (a) is within the above range, a remarkable improvement effect of the ability to prevent re-contamination of the polymer and the compatibility with the surfactant can be obtained. The content of the structural unit (a) is preferably 5% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 80% by mass or less, and further preferably 15% by mass or more and 70% by mass. It is as follows.
In addition, the mass ratio (mass%) with respect to the total amount of the structural unit derived from all the monomers of the said structural unit (a), and the mass ratio with respect to the total amount of all the monomers of the said monomer (A) are calculated. In the case of having a quaternary amine salt, the mass of the counter anion is not taken into consideration (not including), and in the case of having an amino group salt, the amino group salt is the corresponding amino acid. Calculate as the basis.
Further, the structural unit (a) of the amino group-containing polymer of the present invention may be only one type or two or more types.
The amphoteric polymer is derived from the monomer (A) represented by the general formula (1) as the structural unit (a) and the monomer (A) represented by the general formula (1 ′). In the case where both are derived, the content of the structural unit (a) is calculated as the total amount of both.
Since the structural unit (a) in the amino group-containing polymer of the present invention has a particularly high effect of improving the ability to prevent recontamination, the structural unit represented by the general formula (2) is preferably essential. The content of the structural unit represented by the general formula (2) is 1% by mass or more and 99% by mass with respect to 100% by mass of the total amount of structural units derived from all monomers forming the amino group-containing polymer. % Or less is preferable.
<Method for producing amino group-containing monomer (A)>
The amino group-containing monomer (A) can be produced by an applicable known production method, but the amino group-containing monomer (A) has a structure represented by the general formula (1). When it has, it is preferable to manufacture by the method of following (1)-(4). According to this method, the amino group-containing monomer (A) can be produced with high yield. Moreover, when the said amino group containing monomer (A) has a structure represented by the said general formula (1 '), it is preferable to manufacture by the following process (A) and (C).
In the production method (1), (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the following general formula (3), an epihalohydrin, and an alkali compound (step A), and (ii) step A This is a method including a step of reacting the obtained reaction product with a tertiary amine salt (step B).
In the production method (2), (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the following general formula (3), an epihalohydrin, and an alkali compound (step A), and (ii) step A A method comprising a step of reacting the obtained reactant with a secondary amine (Step C), and (iii) a step of reacting the reactant obtained in Step C with a quaternizing agent (Step D). is there.
In the production method (3), (i) a step of reacting a polyalkylene glycol chain-containing monomer represented by the following general formula (3) with an epihalohydrin in the presence of a catalyst (step E), and (ii) step E And a step (step F) of reacting the reaction product obtained in step 3 with a tertiary amine.
The production method (4) is a method including (i) a step (step G) of reacting a polyalkylene glycol chain-containing monomer represented by the following general formula (3) with a glycidyl trialkylammonium salt.

In the formula, R ₀ represents a hydrogen atom or a CH ₃ group. R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a direct bond. Y ₁ is the same or different and represents an alkylene group having 2 to 20 carbon atoms. n is an average addition mole number of an oxyalkylene group (—Y ₁ —O—), and represents a number of 1 to 300.
_A preferable embodiment of R 0, _{R 1} and _{Y 1} are the same as the preferred form of _R 0, _{R 1} and _{Y 1} in the general formula (1).
As the polyalkylene glycol chain-containing monomer represented by the general formula (3), an alkylene oxide is known as an alkylene glycol monovinyl ether, (meth) allyl alcohol, isoprenol or an alcohol having an alkylene oxide addition structure thereof. What was added and manufactured by the method can be used. Thereby, the purity of the amino group containing containing monomer (A) obtained can be made high.
As an epihalohydrin used in the said manufacturing method (1)-(3), what is represented by following General formula (4) is preferable.

式中、Ｘ’はハロゲン原子を表す。エピハロヒドリンとして、具体的には、エピクロルヒドリン、エピブロモヒドリン、エピヨードヒドリン等が挙げられる。中でも、工業的に安価なことから、エピクロルヒドリンが好ましい。
上記製造方法（１）において用いられる三級アミン塩としては、下記一般式（５）で表されるものが好ましい。

In the formula, X ′ represents a halogen atom. Specific examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, and the like. Among these, epichlorohydrin is preferable because it is industrially inexpensive.
As a tertiary amine salt used in the said manufacturing method (1), what is represented by following General formula (5) is preferable.

In formula, R < ₂ >, R < ₃ > and R < ₄ > are the same or different and represent a C1-C20 organic group. R ₂ and R ₃ may combine to form a cyclic structure. X ⁻ represents a counter anion.
Said _R 2 in the general formula _{(5), R 3, R} 4 and X ^- preferred form _{of, R 2, R 3, R} 4 and X in the general formula (1) ^- are the same as the preferred form.
Specific examples of the tertiary amine salt include trimethylamine, dimethylethylamine, dimethylisopropylamine, dimethyl-n-propylamine, dimethylcyclohexylamine, triethylamine, triisopropylamine, tri-n-propylamine, tributylamine, and trilauryl. Hydrochloride, hydrobromide, hydroiodide, nitrate of tertiary amines such as amine, tristearylamine, tricyclohexylamine, tri-2-ethylhexylamine, triethanolamine, tris (2-hydroxypropyl) amine , Acetate, perchlorate, paratoluenesulfonate, and the like. Among these, trimethylamine hydrochloride, triethylamine hydrochloride, and dimethylethylamine hydrochloride are preferable because the amino group-containing monomer (A) of the present invention can be produced with high yield.
As a secondary amine used in the said manufacturing method (2), what is represented by following General formula (6) is preferable.

式中、Ｒ_２及びＲ_３は、同一若しくは異なって、水素原子又は炭素数１〜２０の有機基を表す。Ｒ_２とＲ_３とは結合して環状構造を形成してもよい。
上記一般式（６）におけるＲ_２及びＲ_３の好ましい形態は、上記一般式（１）におけるＲ_２及びＲ_３の好ましい形態と同じである。
上記二級アミンとして、具体的には、ジメチルアミン、メチルエチルアミン、ジエチルアミン、ジイソプロピルアミン、ジ−ｎ−プロピルアミン、ジ−ｎ−ブチルアミン、ジオクチルアミン、ジラウリルアミン、ジステアリルアミン、ジシクロヘキシルアミン、ジ−２−エチルヘキシルアミン等のジアルキルアミン類；ジエタノールアミン、ビス（２−ヒドロキシプロピル）アミン等のジアルカノールアミン類；モルホリン、ピロール等の環状アミン類が挙げられる。中でも、高い収率でカチオン性基含有単量体（Ａ）を製造することができることから、ジメチルアミン、メチルエチルアミン、ジエチルアミン、ジエタノールアミンが好ましい。
上記製造方法（２）において用いられる四級化剤としては、塩化メチル、塩化エチル、臭化メチル、臭化エチル、ヨウ化メチル、ヨウ化エチル等のハロゲン化アルキル；塩化ベンジル、臭化ベンジル、ヨウ化ベンジル等のハロゲン化ベンジル；ジメチル硫酸、ジエチル硫酸等のジアルキル硫酸；パラトルエンスルホン酸メチル、パラトルエンスルホン酸エチル等のスルホン酸アルキルが挙げられる。中でも、工業的に入手が容易なことから、塩化メチル、塩化ベンジル、ジメチル硫酸が好ましい。
上記一般式（１’）で表される構造を有するアミノ基含有単量体（Ａ）を上記工程（Ａ）及び（Ｃ）により製造する場合、工程（Ｃ）においては、上述した二級アミンに代えてアンモニア又は一級アミンを用いてもよい。
上記一級アミンとして、具体的には、メチルアミン、エチルアミン、イソプロピルアミン、ｎ−プロピルアミン、ｎ−ブチルアミン、オクチルアミン、ラウリルアミン、ステアリルアミン、シクロヘキシルアミン、２−エチルヘキシルアミン等のアルキルアミン類；エタノールアミン、２−ヒドロキシプロピルアミン等のアルカノールアミン類が挙げられる。中でも、高い収率でアミノ基含有単量体（Ａ）を製造することができることから、メチルアミン、エチルアミン、エタノールアミンが好ましい。
上記製造方法（３）において用いられる三級アミンとしては、下記一般式（７）で表されるものが好ましい。

In the formula, R ₂ and R ₃ are the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. R ₂ and R ₃ may combine to form a cyclic structure.
Preferred forms of _{R 2} and _{R 3} in the general formula (6) is the same as the preferred form of _{R 2} and _{R 3} in the general formula (1).
Specific examples of the secondary amine include dimethylamine, methylethylamine, diethylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, dioctylamine, dilaurylamine, distearylamine, dicyclohexylamine, and diamine. And dialkylamines such as -2-ethylhexylamine; dialkanolamines such as diethanolamine and bis (2-hydroxypropyl) amine; and cyclic amines such as morpholine and pyrrole. Among these, dimethylamine, methylethylamine, diethylamine, and diethanolamine are preferable because the cationic group-containing monomer (A) can be produced with high yield.
Examples of the quaternizing agent used in the production method (2) include alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide, ethyl iodide; benzyl chloride, benzyl bromide, Examples thereof include benzyl halides such as benzyl iodide; dialkyl sulfates such as dimethyl sulfate and diethyl sulfate; alkyl sulfonates such as methyl paratoluenesulfonate and ethyl paratoluenesulfonate. Of these, methyl chloride, benzyl chloride, and dimethyl sulfate are preferred because they are easily available industrially.
When the amino group-containing monomer (A) having the structure represented by the general formula (1 ′) is produced by the steps (A) and (C), in the step (C), the secondary amine described above is used. Instead of ammonia or primary amines may be used.
Specific examples of the primary amine include alkylamines such as methylamine, ethylamine, isopropylamine, n-propylamine, n-butylamine, octylamine, laurylamine, stearylamine, cyclohexylamine, and 2-ethylhexylamine; ethanol Examples thereof include alkanolamines such as amine and 2-hydroxypropylamine. Of these, methylamine, ethylamine, and ethanolamine are preferred because the amino group-containing monomer (A) can be produced with high yield.
As a tertiary amine used in the said manufacturing method (3), what is represented by following General formula (7) is preferable.

In formula, R < ₂ >, R < ₃ > and R < ₄ > are the same or different and represent a C1-C20 organic group. R ₂ and R ₃ may combine to form a cyclic structure.
A preferred form of the above in the general formula _(7), R 2, _{R 3} and _{R 4} are the same as the preferred form of _R 2, _{R 3} and _{R 4} in the general formula (1).
Specific examples of the tertiary amine include trimethylamine, dimethylethylamine, dimethylisopropylamine, dimethyl-n-propylamine, dimethylcyclohexylamine, triethylamine, triisopropylamine, tri-n-propylamine, tributylamine, and trilaurylamine. , Trialkylamines such as tristearylamine, tricyclohexylamine and tri-2-ethylhexylamine; trialkanolamines such as triethanolamine and tris (2-hydroxypropyl) amine. Among them, trimethylamine, dimethylethylamine, triethylamine, and triethanolamine are preferable because the amino group-containing monomer (A) can be produced with high yield.
As a glycidyl trialkyl ammonium salt used in the said manufacturing method (4), what is represented by following General formula (8) is preferable.

In formula, R < ₂ >, R < ₃ > and R < ₄ > are the same or different and represent a hydrogen atom or a C1-C20 organic group. R ₂ and R ₃ may combine to form a cyclic structure. X ″ ⁻ represents a halogen atom ion or a monoalkyl sulfate ion.
In the general formula _(8), the preferred form of R 2, _{R 3} and _{R 4} are the same as the preferred form of _R 2, _{R 3} and _{R 4} in the general formula (1).
Specific examples of the glycidyltrialkylammonium salt include glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, glycidyltrimethylammonium bromide, glycidyltriethylammonium bromide, and the like. Among these, glycidyltrimethylammonium chloride is preferable because it is easily available industrially.
Each step in the production methods (1) to (4) is represented by the following reaction formula.

The reaction of the above step A is performed in the presence of an alkali compound and, if necessary, a phase transfer catalyst and / or a solvent.
Although it does not specifically limit as said alkali compound, Alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, are preferable.
The amount of the alkali compound used is the molar ratio of the hydroxyl group (in terms of hydroxyl value) of the polyalkylene glycol chain-containing monomer represented by the general formula (3) to the alkali compound, (hydroxyl group) / (alkali compound) = It is preferable to set it as 15/1-1/15. More preferably, it is 5/1-1/5, More preferably, it is 3/1-1/3.
The alkali compound may be added to the reaction system as it is or may be used in the form of an aqueous solution. When used as an aqueous solution, the reaction may be carried out while removing water (including water produced as a by-product as the reaction proceeds).
The type of the phase transfer catalyst is not particularly limited, but quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium chloride, tetraoctylammonium chloride, benzyltrimethylammonium chloride, triethylammonium chloride, triethylammonium bromide; tetrabutylphosphonium chloride And phosphonium salts such as tetrabutylphosphonium bromide; crown ethers such as 15-crown-5 and 18-crown-6.
The usage-amount of the epihalohydrin used for reaction of the said process A or the process E is the molar ratio of the hydroxyl group (hydroxyl value conversion) and epihalohydrin of the polyalkylene glycol chain containing monomer represented by the said General formula (3), ( Hydroxyl group) / (epihalohydrin) = 1/1 to 1/30 is preferable. More preferably, it is 1/1 to 1/10, and more preferably 1/1 to 1/5. Outside the above range, a cross-linking component may occur, and there is a risk of gelation during polymerization.
Step A is a so-called slurry reaction and can be carried out in a reaction apparatus having a general stirring apparatus. For example, using a stirred tank reactor, any of batch, semi-batch, and continuous tank reactors can be used. After the reaction in Step A, it is preferable to carry out Step B and Step C after performing steps such as desalting and removal of excess epihalohydrin. The desalting step can be carried out by sedimentation separation, centrifugation, filtration or the like, and is not particularly limited. The conditions for carrying out the desalting step may be suitably carried out so that the salt is sufficiently removed, and it is preferably carried out at a temperature of 15 ° C. to 100 ° C. from the viewpoint of obtaining a sufficient separation rate. Excess epihalohydrin can be easily removed by distillation, evaporation or the like.
The amount of the tertiary amine salt used in the above step B is (glycidyl group) / (tertiary amine salt) = 2/1 in terms of a molar ratio with respect to the number of moles of glycidyl groups in the reaction product obtained in step A. It is preferable that it is -1/2. More preferably, it is 1.5 / 1-1 / 1.5, More preferably, it is 1.3 / 1-1 / 1.3.
The tertiary amine salt may be used in the form of an aqueous solution. In this case, an aqueous solution containing 5% by mass or more of a tertiary amine salt is preferable. An aqueous solution containing 10% by mass or more of a tertiary amine salt is more preferable, and an aqueous solution containing 15% by mass or more of a tertiary amine salt is more preferable. When the content of the tertiary amine salt is less than 5% by mass, the selectivity of the amino group-containing monomer (A) obtained by the reaction may decrease.
The amount of the secondary amine used in the above step C is (glycidyl group) / (secondary amine) = 2/1 to 1 in terms of molar ratio with respect to the number of moles of the glycidyl group of the reaction product obtained in step A. / 2 is preferable. More preferably, it is 1.5 / 1-1 / 1.5, More preferably, it is 1.3 / 1-1 / 1.3.
The amount of the quaternizing agent used in the reaction of the above step D is (amino group) / (quaternizing agent) = 2 with respect to the number of moles of amino groups in the reaction product obtained in step C. / 1 to 1/2 is preferable. More preferably, it is 1.5 / 1-1 / 1.5, More preferably, it is 1.3 / 1-1 / 1.3.
In the reaction in Step E, an acid or a base can be used as a catalyst, but an acid is preferably used. The acid may be a Lewis acid or a Bronsted acid, but a Lewis acid is preferred. As a Lewis acid, what is generally called Lewis acid can be used, for example, boron trifluoride, tin tetrachloride, tin dichloride, zinc chloride, ferric chloride, aluminum chloride, titanium tetrachloride, Examples thereof include magnesium chloride and antimony pentachloride.
The amount of the tertiary amine used in the step F is (halogen group) / (tertiary amine) = 2/1 to 1 in terms of a molar ratio with respect to the number of moles of halogen groups in the reaction product obtained in the step E. / 2 is preferable. More preferably, it is 1.5 / 1-1 / 1.5, More preferably, it is 1.3 / 1-1 / 1.3.
Process F may be performed after performing a process such as washing after completion of the reaction in process E.
Reaction of the said process G is performed in presence of a catalyst as needed. Examples of the catalyst used in the reaction include alkali metal salts such as sodium hydroxide, potassium hydroxide, potassium carbonate and sodium carbonate; quaternary ammonium salts (similar to those exemplified as the phase transfer catalyst used in the above step A), etc. Is mentioned.
The amount of glycidyl trialkylammonium salt used in the reaction of Step G is a molar ratio with respect to the hydroxyl group (in terms of hydroxyl value) of the polyalkylene glycol chain-containing monomer represented by the general formula (3). Hydroxyl group) / (glycidyl trialkylammonium salt) = 5/1 to 1/5 is preferable. More preferably, it is 3/1-1/3, More preferably, it is 1.5 / 1-1 / 1.5.
The reaction in the above steps A to G is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is preferable from the viewpoint of improving volumetric efficiency, but may be carried out in the presence of a solvent. The solvent that can be used is not particularly limited as long as it does not adversely affect the reaction. For example, in the above steps A, E, and G, hydrocarbons such as hexane, octane, decane, cyclohexane, benzene, and toluene; diethyl ether, Examples include ethers such as tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; and chlorine-based hydrocarbons such as dichloromethane and dichloroethane.
Examples of the steps B, C, D, and F include water; alcohols such as methanol, ethanol, and isopropanol; ethers such as diethyl ether, tetrahydrofuran, and dioxane; and ketones such as acetone and methyl ethyl ketone.
The solvent mentioned above may be used individually by 1 type, and may use 2 or more types together.
Although there is no restriction | limiting in particular in the usage-amount of the solvent in each process, By mass ratio with respect to the polyalkylene glycol chain containing monomer represented by the said General formula (3), or the reaction material obtained at the previous process. It is preferable that it is 0.005 to 5 times. More preferably, it is 0.01 to 3 times.
When the phase transfer catalyst in Step A, the catalyst in Step E, or the catalyst in Step G is used, the amount of the catalyst used is that of the polyalkylene glycol chain-containing monomer represented by the general formula (3). It is preferable that (hydroxyl group) / (catalyst) = 1 / 0.0001 to 1 / 0.3 in terms of molar ratio with respect to the hydroxyl group (in terms of hydroxyl value). More preferably, it is 1 / 0.001 to 1 / 0.2, and further preferably 1 / 0.005 to 1 / 0.1. When the amount of the catalyst used is less than the above range, a sufficient catalytic effect cannot be obtained. Moreover, even if it uses more than the range mentioned above, there is no further effect and it is economically disadvantageous.
It is preferable to implement reaction in the said process AG at the temperature which does not produce a problem in stirring. Specifically, the reaction temperature in Steps A to G is preferably 0 to 200 ° C. More preferably, it is 15-150 degreeC, More preferably, it is 30-100 degreeC.
The reaction time in Steps A to G is preferably 0.1 to 50 hours. More preferably, it is 0.5-30 hours, More preferably, it is 1-15 hours.
The reaction in steps A to G may be performed in an air atmosphere or an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure.
In Steps B, C, D and F, when a catalyst is used in the previous step, the reaction may be performed as it is under the remaining catalyst.
The reaction of Steps B, C, D, E, F and G may be performed in a batch system or a continuous system. For example, the reaction can be performed in either a tank-type reactor or a tubular reactor.
Although the said amino group containing monomer (A) can be manufactured by said method, you may provide a refinement | purification process as needed. By performing a purification step by extraction or washing, the amount of the crosslinking component that causes gelation during polymerization can be reduced.
As the method for producing the amino group-containing monomer (A), among the production methods (1) to (4), since the raw materials are inexpensive and the production is simple, the production method (1). -(3) is preferred.
Furthermore, according to the manufacturing method (1), the production | generation of the crosslinking component which causes gelling at the time of superposition | polymerization can be suppressed. In the production method (2), selection of the counter anion in the amino group-containing monomer (A) is easy. Furthermore, according to the production method (3), waste generated in the reaction process can be reduced. Among these, the production method (1) is more preferable.
The counter anion in the amino group-containing monomer (A) can be converted into a desired anion species by an ion exchange method after being obtained by the above production method, but desired by appropriately selecting the raw material used in each production method. It is preferable to introduce the anionic species because of its simplicity. That is, in the production method (1), the anion of the tertiary amine salt used in the step (B) can be introduced as the counter anion. In the production method (2), the counter anion can be introduced by the quaternizing agent in the step (D). In addition, in the production method (3), the halogen atom of the epihalohydrin in the step (E) is used, and in the production method (4), the counter anion of the glycidyl trialkylammonium salt in the step (G) is used as the amino group-containing monomer (A). It can be introduced as a counter anion. <Monomer (B)>
The amino group-containing polymer of the present invention comprises an amino group-containing monomer (B-2) other than the nonionic monomer (B-1) and / or the monomer (A) (hereinafter referred to as a monomer). (B) may be referred to as a structural unit (b).
The main role of the monomer (B) in the amino group-containing polymer of the present invention is to arrange the structure derived from the amino group-containing monomer (A) at a preferred position of the polymer, Since (A) is poor in homopolymerizability, it is a connecting role between the monomers (A) for controlling to an appropriate molecular weight and molecular weight distribution. Therefore, the copolymerizability with the monomer (A) is good, the monomer (B) itself is homopolymerizable, and the structure derived from the monomer (B) ) Is not required to inhibit the effects of the derived structure.

The nonionic monomer (B-1) is a nonionic monomer. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2- (Meth) acrylic acid alkyl ester monomers such as ethylhexyl (meth) acrylate and dodecyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2- Such as hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α-hydroxymethylethyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyneopentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, etc. Meta) Acry Acid hydroxyalkyl monomers; vinyl aryl monomers such as styrene, indene and vinylaniline; alkenes such as isobutylene; vinyl carboxylates such as vinyl acetate; N-vinylpyrrolidone, N-vinylformamide, N-vinyl N-vinyl cyclic amide monomers such as acetamide, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide, N-vinyloxazolidone; acrylamides such as (meth) acrylamide and (meth) isopropylacrylamide, Examples thereof include (meth) acrylic acid esters of alkoxypolyalkylene glycol.
Among these, since the copolymerizability with the monomer (A) is good and the anti-recontamination ability of the obtained copolymer is good, (meth) acrylic acid alkyl ester monomers, ( Preference is given to hydroxyalkyl methacrylate monomers, vinylaryl monomers, vinyl carboxylates, N-vinyl cyclic amide monomers and acrylamides.
Here, the monomer having the structure of the general formula (3) (including a monomer having a structure in which the terminal hydroxyl group of the monomer is modified with another organic group) is the same as the monomer (A). Since the binary copolymerization is insufficient and it is difficult to produce the polymer of the present invention, it is excluded from the monomer (B).

As the amino group-containing monomer (B-2) other than the monomer (A), a monomer having a polymerizable carbon-carbon unsaturated double bond and a primary to quaternary amino group and / or a salt thereof. (Excluding monomers corresponding to monomer (A)), for example, vinyl cyclic amine monomers having a cyclic amine structure such as vinylpyridine, vinylimidazole, morpholine, vinylpyrrole; dimethylaminoethyl Aminoalkyl (meth) acrylates such as acrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate, aminoethyl methacrylate; allylamines such as diallylamine and diallyldimethylamine, (meth) allyl glycidyl ether, isoprenyl glycidyl ether, vinyl glycidyl ether In the epoxy ring of Monomer obtained by reacting the amine (salts) like; and monomers quaternized structure of these amino group.
Among these, since the copolymerizability with the monomer (A) is good and the anti-recontamination ability of the obtained copolymer is good, the vinyl cyclic amine monomer, aminoalkyl (meth) Acrylates, allylamines, vinyl carboxylates, N-vinyl cyclic amide monomers and acrylamides are preferred.
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. When the amino group-containing monomer other than the monomer (A) has a quaternized amino group, the amino group-containing monomer other than the monomer (A) having a primary to tertiary amino group Examples include monomers obtained by quaternizing the product with known quaternizing agents, and examples of known quaternizing agents include alkyl halides and dialkyl sulfuric acid.
Specific examples of the tertiary amine salt include trimethylamine hydrochloride and triethylamine hydrochloride. As the salt, the amino group-containing polymer of the present invention including hydrochloride, organic acid salt and the like is the total amount of structural units derived from all monomers forming the amino group-containing polymer (structural unit (a), 1 to 99% by mass of the structural unit (b) with respect to 100% by mass of (b) and the total amount of the structural unit (e) described later). If the content of the structural unit (b) is within the above range, the molecular weight of the polymer to be produced and the polymerizability of the monomer (A) can be suitably controlled. It is possible to preferably exhibit the dispersibility of the soil component particles and the pigment and the ability to prevent recontamination. 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 addition, when the structural unit (b) is a structural unit derived from an amino group-containing monomer other than the monomer (A), the mass ratio relative to the total amount of structural units derived from all monomers, When calculating the mass proportion of the amino group-containing monomer other than the monomer (A) with respect to the total amount of all monomers, it is calculated as the mass proportion of the corresponding unneutralized amine. For example, when the amino group-containing monomer (B-2) other than the monomer (A) is vinylamine hydrochloride, the mass ratio (% by mass) of vinylamine that is the corresponding non-neutralized 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.

<Other monomers>
The amino group 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)). May be. The amino group-containing 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 amino group polymer of the present invention has “structural unit (e) derived from other monomer (E)” means that the finally obtained polymer is unsaturated of monomer (E). It means having a structural unit in which a double bond is replaced with a single bond.

Examples of the other monomer (E) include a monomer having a structure of the general formula (3) (a monomer having a structure in which the terminal hydroxyl group of the monomer is modified with another organic group) ) And the like. Monomers having the structure of the general formula (3) (including monomers having a structure in which the terminal hydroxyl group of the monomer is modified with another organic group) are binary with the monomer (A). Although the copolymerizability is not sufficient, since it has a copolymerizability similar to that of the monomer (A), the copolymerizability with the monomer (B) is good. The polymerization property of ternary or quaternary or higher which essentially requires the monomer (B) and the monomer having the structure of the general formula (3) is generally good.
When the amino group-containing polymer of the present invention has a structural unit (e) derived from the other monomer (E) as an optional component, it is derived from all monomers that form the amino group-containing polymer. It is preferable that the structural unit (e) is included in an amount of 0 to 60% by mass with respect to 100% by mass of the total amount of structural units (that is, the total amount of the structural units (a), (b) and (e)). More preferably, it is 0-50 mass%.
<Other physical properties of amino group-containing polymer>
In the amino group-containing polymer of the present invention, the structural units (a) and (b) and, if necessary, the structural unit (e) may be introduced at a specific ratio as described above.
Moreover, the weight average molecular weight of the said amino group containing polymer can be set suitably, and is not specifically limited. Specifically, the weight average molecular weight of the amino group-containing polymer is preferably 2,000 to 200,000, more preferably 3,000 to 100,000, and most preferably 4,000 to 60,000. It is. 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 amino group-containing polymer is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, and most preferably 2,000 to 25,000. . 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 amino group-containing polymer of the present invention has a high recontamination preventing ability, but the recontamination prevention rate is preferably 70% or more. More preferably, it is 75% or more.
The recontamination prevention rate can be measured in the same manner as in the examples described later.
[Amino group-containing polymer composition]
The amino group-containing polymer of the present invention may constitute an amino group-containing 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 amino group-containing polymer composition preferably contains the amino group-containing polymer of the present invention in an amount of 1 to 100% by mass based on 100% by mass of the total amount of the amino group-containing polymer composition. One of the preferable forms of the said amino group containing polymer composition is a form which contains 40-60 mass% of amino group containing polymers of this invention, and contains 40-60 mass% of water.
[Method for producing amino group-containing polymer of the present invention]
The amino group-containing polymer of the present invention includes (i) an amino group-containing monomer (A) (monomer (A)) represented by the general formula (1) and (ii) a nonionic monomer. An amino group-containing monomer (B-2) other than (B-1) and / or monomer (A) is essential, and other monomers (E) (monomer (E) as required ) Can be produced by copolymerization at a predetermined ratio.
In the method for producing an amino group-containing polymer of the present invention, the composition ratio of each monomer used for the polymerization is 100 masses in total of all monomers (monomer (A), (B), (E)). % Of the monomer (A) is 1 to 99% by mass, and the monomer (B) is 1 to 99% by 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. Further, if the content of the monomer (B) is less than 1% by mass, the molecular weight of the polymer and the polymerizability of the monomer (A) may not be controlled. 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 amino group-containing 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. A mode in which a reaction is performed by dropping a solution containing a body component and a solution containing a polymerization initiator (hereinafter also referred to as “initiator”). 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 amino group-containing monomer (A) can be improved, so that the dispersibility of the polymer obtained, the ability to prevent recontamination, etc. are improved. 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 and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionic acid, metabisulfite and salts thereof (hydrogen sulfite) Sodium, potassium bisulfite, Sodium dithionite, potassium dithionite, sodium metabisulfite, metabisulfite potassium, etc.) and the like, lower oxides and salts thereof. The said chain transfer agent may be used independently, and 2 or more types may be mixed and used for it.
The use of a chain transfer agent has the advantage that the polymer to be produced can be prevented from having a higher molecular weight than necessary, and a low molecular weight amino group-containing polymer can be produced efficiently.
In the above production method, it is a preferred form to use sulfurous acid and / or sulfite (hereinafter also referred to as “sulfurous acid (salt)”) as a chain transfer agent. In that case, a polymerization initiator is used in addition to sulfurous acid (salt). Furthermore, you may use a heavy metal ion together as a reaction accelerator mentioned later.
The above sulfurous acid (salt) means sulfurous acid, hydrogen sulfite, or a salt thereof. Among these, a form in which sulfite and / or hydrogen sulfite is a salt is preferable. 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 sulfite 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 said sulfurous acid (salt) may be used independently, and 2 or more types may be mixed and used for it.
<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. Note that 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 amino group-containing polymer of the present invention. Any material that dissolves may be used.
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, and can be appropriately selected from the above examples. For example, combinations of chain transfer agent, initiator and reaction accelerator include sodium bisulfite / hydrogen peroxide, sodium bisulfite / sodium persulfate, sodium bisulfite / Fe (ion), sodium bisulfite / hydrogen peroxide / Forms such as Fe (ion), sodium bisulfite / 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 sulfite is used, surplus sulfite is decomposed in the reaction system, and sulfurous acid gas may be generated. 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 persulfates and sulfites. In this case, the mixing ratio of persulfate and sulfite is not particularly limited, but it is preferable to use 0.5 to 5 parts by mass of sulfite with respect to 1 part by mass of persulfate. The lower limit of the amount of sulfite is more preferably 1 part by mass with respect to 1 part by mass of persulfate, and most preferably 2 parts by mass. Moreover, as for the upper limit of the amount of sulfites, it is more preferable that it is 4 mass parts with respect to 1 mass part of persulfate, Most preferably, it is 3 mass parts. If the sulfite 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 be increased when the molecular weight is lowered. There is a risk that the reaction will increase and impurities will 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 amino group containing 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 amino group-containing polymer of the present invention that can be produced by the production method described above can exhibit high performance in aqueous applications, hard water resistance, detergency, recontamination prevention ability, clay dispersibility, surfactant Therefore, when used as a dispersant, a detergent builder, a detergent composition, a cleaning agent, or a water treatment agent, particularly excellent performance can be exhibited.
[Use of amino group-containing polymer and amino group-containing polymer composition of the present invention]
The amino group-containing polymer (or amino group-containing 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, a hair care agent, and a shampoo.・ Hair spray, soap, cosmetic additives, anion exchange resins, dye mordants and auxiliaries for fibers and photographic films, pigment spreaders in papermaking, paper strength enhancers, emulsifiers, preservatives, textile and paper softeners , Lubricating oil additives, water treatment agents, fiber treatment agents, dispersants, detergent additives, scale inhibitors (scale inhibitors), metal ion sealants, thickeners, various binders, emulsifiers, etc. Can do. 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 amino group-containing polymer (or amino group-containing 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 amino group-containing polymer (or amino group-containing 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 amino group-containing polymer (or amino group-containing polymer composition) of the present invention.
The content of the amino group-containing 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 amino group-containing 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, an improvement in the whiteness, color unevenness, and dyeing tempering of the fiber. For this purpose, at least one selected from the group consisting of a dye, a peroxide and a surfactant is added in an amount of 0.1 to 100 per 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 the composition mix | blended in the ratio of the weight part as a fiber processing 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 amino group-containing polymer (or amino group-containing 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 amino group-containing 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 amino group-containing polymer (or amino group-containing 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 amino group-containing polymer (or amino group-containing polymer composition) of the present invention can also be added to a detergent composition.
The content of the amino group-containing polymer in the detergent composition is not particularly limited. However, from the viewpoint that excellent builder performance can be exhibited, the content of the amino group-containing polymer is preferably 0.1 to 15% by mass with respect to 100% by mass of the total amount of the detergent composition, and 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.
In addition to the amino group-containing polymer (or amino group-containing polymer composition) of the present invention, the detergent composition may contain other detergent builders. 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.

<Quantification of amino group-containing monomer and reaction intermediate>
The intermediate product of the amino group-containing monomer was quantified by liquid chromatography under the following conditions. Further, the yield of the amino group-containing monomer was calculated from the conversion rate by quantifying the intermediate of the amino group-containing single-quantity product by liquid chromatography.
Measuring apparatus: Hitachi High-Technologies Corporation column: Shiseido Co., Ltd. CAPCELL PAK C18 MGII 4.6 mmΦ × 250 mm 5 μm
Temperature: 40.0 ° C
Eluent: 0.1 wt% formic acid / acetonitrile = 6/4 (volume ratio)
Flow rate: 1.0 ml / min
Detector: RI, UV (detection wavelength 210 nm).

<Monomer determination method>
Except where otherwise noted, monomer quantification was performed by high-speed 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 conditions of weight average molecular weight and number average molecular weight (GPC)>
Apparatus: Hitachi, Ltd. L-7000 Series Detector: HITACHI RI Detector L-7490
Column: Tosoh TSK-guard column + TSK-GEL α-3000 + TSK-GEL α-2500
Column temperature: 40 ° C
Flow rate: 0.4 mL / min
Calibration curve: POLYETHYLENE GLYCOL made by GL Sciences Inc.
Eluent: boric acid 100 mM (pH 9.2) / acetonitrile = 4/1 (wt / wt).
<Measurement of solid content>
In an oven heated to 130 ° C. in a nitrogen atmosphere, 1.0 g of water added to 1.0 g of the polyalkylene glycol polymer composition containing the amino group-containing polymer of the present invention is allowed to stand for 1 hour and dried. did. From the mass change before and after drying, the solid content (%) and the volatile component (%) were calculated.
<Amino group-containing monomer (A)>
In the following monomer synthesis examples, the following compounds were used as the polyalkylene glycol chain-containing monomer represented by the general formula (3).
Isoprenol ethylene oxide average 10 mol adduct (hereinafter also referred to as “IPN10”): hydroxyl value 106.5 (mgKOH / g).
Isoprenol ethylene oxide average 25 mol adduct (hereinafter also referred to as “IPN25”): hydroxyl value 47.3 (mgKOH / g).

[Synthesis Example 1]
Using a 1 liter four-necked flask, 400 g of IPN10, 351.4 g of epichlorohydrin, and 94.9 g of 48% by mass aqueous sodium hydroxide (hereinafter also referred to as “48% NaOH”) were charged, and the temperature was kept at 50 ° C. Stir for hours to react. After the reaction, the generated salt was removed, and then the epichlorohydrin and water were removed from the remaining organic layer to obtain 451.2 g of a reaction solution containing 324.9 g of intermediate (IPEG10) and 64.1 g of IPN10. . Next, using a 1 liter four-necked flask, 451.2 g of a reaction solution containing 324.9 g of IPEG10 and 268.7 g of a 30% by mass trimethylamine hydrochloride aqueous solution were charged and reacted for 8 hours while maintaining the temperature at 50 ° C. 719.9 g of a reaction solution (hereinafter referred to as monomer (1)) containing 336.4 g of cationized product (hereinafter also referred to as IPEC10) and 63.8 g of IPN10 was obtained. The reaction solution was concentrated with an evaporator to obtain a reaction solution containing 61.7% by mass of IPEC10.

[Synthesis Example 2]
100.0 g of a reaction solution containing IPEG10 synthesized in the same manner as in Synthesis Example 1 and 17.4 g of diethanolamine were charged and stirred for 8 hours while maintaining at 80 ° C., thereby obtaining 117.4 g of monomer (2). As a result of analysis by liquid chromatography, an amination product of IPN10 (that is, a compound in which R ₅ and R ₆ are —CH ₂ CH ₂ OH groups in the general formula (1 ′), hereinafter also referred to as IPEA10-DEA) is 84. 6 g and 17.0 g of IPN10 were contained.

[Synthesis Example 3]
100.0 g of a reaction solution containing IPEG10 synthesized in the same manner as in Synthesis Example 1 and 23.2 g of dibutylamine were charged and stirred for 8 hours while maintaining the temperature at 100 ° C. to obtain 123.2 g of monomer (3). As a result of analysis by liquid chromatography, 83.6 g of an amination product of IPN10 (that is, those in which R ₅ and R ₆ are —C ₄ H ₉ groups in the general formula (1 ′), hereinafter also referred to as IPEA10-DBuA). , IPN10 was contained 10.2g.

[Synthesis Example 4]
Using a 1 liter four-necked flask, 500 g of IPN25, 233.7 g of epichlorohydrin, and 25.3 g of NaOH in pellet form were charged, and the mixture was stirred and reacted for 16 hours while maintaining at 50 ° C. After the reaction, the generated salt was removed, and then epichlorohydrin and water were removed from the remaining organic layer to obtain 499.4 g of a reaction solution containing 389.1 g of intermediate (IPEG25) and 43.5 g of IPN25. Next, 499.4 g of a reaction solution containing 389.1 g of IPEG25 and 143.6 g of a 30% by weight trimethylamine hydrochloride aqueous solution were charged using a 1 liter four-necked flask and reacted for 12 hours while maintaining the temperature at 50 ° C. 643.0 g of a reaction solution (hereinafter referred to as monomer (4)) containing 376.7 g of cationized product (hereinafter also referred to as IPEC25) and 41.3 g of IPN25 was obtained.

[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 0.0054 g of Mole salt, and the temperature was raised to 70 ° C. while stirring to polymerize. The reaction system was used. Next, in a polymerization reaction system maintained at 70 ° C. with stirring, 165.9 g of hydroxyethyl acrylate (hereinafter referred to as HEA), 179.2 g of monomer (1), 15% aqueous sodium persulfate solution (Hereinafter referred to as 15% NaPS) 76.8 g, 35% sodium hydrogen sulfite (hereinafter referred to as 35% SBS) 32.9 g, and 158.7 g of pure water were added dropwise from separate nozzles.
The start of dropping of each solution is simultaneous, and the dropping time of each solution is 180 minutes for HEA, 150 minutes for monomer (1), 190 minutes for 15% NaPS, 180 minutes for 35% SBS, and The pure water was 180 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 kept at 70 ° C. (ripening) for 30 minutes to complete the polymerization. In this way, an aqueous solution (copolymer composition (1)) containing the copolymer (1) having a solid 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 70 ° C. while stirring to polymerize. The reaction system was used. Next, in a polymerization reaction system maintained at 70 ° C. with stirring, 165.9 g of HEA, 134.4 g of monomer (1), 13.2 g of 80% IPN10, 15% sodium persulfate aqueous solution (hereinafter, 15% 75.2 g, 35% sodium bisulfite (hereinafter referred to as 35% SBS) 32.2 g, and 135.1 g of pure water were added dropwise from separate nozzles.
The dripping start of each solution is simultaneous, and the dripping time of each solution is 180 minutes for HEA, 150 minutes for monomer (1), 150 minutes for 80% IPN10, 190 minutes for 15% NaPS, 35 The% SBS was 180 minutes and the pure water was 180 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 kept at 70 ° C. (ripening) for 30 minutes to complete the polymerization. In this way, an aqueous solution (copolymer composition (2)) containing the copolymer (2) having a solid concentration of 45% was obtained.

[Example 3]
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 0.0063 g of Mole salt, and the temperature was raised to 70 ° C. while stirring to polymerize. The reaction system was used. Next, 204.5 g of dimethylaminoethyl acrylate (hereinafter referred to as DAA), 221.0 g of monomer (1), and 79% 15% NaPS in a polymerization reaction system maintained at 70 ° C. with stirring. 0.1 g and 242.1 g of pure water were dropped from separate nozzles.
The dripping start of each solution is simultaneous, and the dripping time of each solution is 180 minutes for HEA, 150 minutes for monomer (1), 190 minutes for 15% NaPS, and 180 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 kept at 70 ° C. (ripening) for 30 minutes to complete the polymerization. In this way, an aqueous solution (copolymer composition (3)) containing the copolymer (3) having a solid content concentration of 45% was obtained.

[Example 4]
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 0.0060 g of molle salt and heated to 70 ° C. while stirring to polymerize. The reaction system was used. Next, in a polymerization reaction system maintained at 70 ° C. with stirring, DAA 204.5 g, monomer (1) 165.7 g, 80% IPN10 16.3 g, 15% NaPS 77.2 g, and Pure water 212.8g was dripped from each separate nozzle.
The dripping start of each solution is simultaneous, and the dropping time of each solution is 180 minutes for DAA, 150 minutes for monomer (1), 150 minutes for 80% IPN10, 190 minutes for 15% NaPS, and The pure water was 180 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 kept at 70 ° C. (ripening) for 30 minutes to complete the polymerization. In this way, an aqueous solution (copolymer composition (4)) containing the copolymer (4) having a solid content concentration of 45% was obtained.

[Example 5]
A 2000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 150.0 g of pure water and 0.0060 g of Mole salt, and heated to 70 ° C. while stirring to polymerize. The reaction system was used. Next, in a polymerization reaction system maintained at 70 ° C. with stirring, 144.8 g of HEA, 144.8 g of monomer (2), 17.3 g of 80% IPN10, 94.2 g of 15% NaPS, 17.3 g of 35% SBS and 227.4 g of pure water were added dropwise from separate nozzles.
The dripping start of each solution is simultaneous, and the dripping time of each solution is 180 minutes for HEA, 120 minutes for monomer (1), 120 minutes for 80% IPN10, 190 minutes for 15% NaPS, 35 The% SBS was 180 minutes and the pure water was 180 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 kept at 70 ° C. (ripening) for 30 minutes to complete the polymerization. Thus, the aqueous solution (copolymer composition (5)) containing the copolymer (5) with a solid content concentration of 45% was obtained.

[Example 6]
A 2000-mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 150.0 g of pure water and 0.0074 g of molle salt, and the temperature was raised to 70 ° C. while stirring to polymerize. The reaction system was used. Next, in a polymerization reaction system maintained at 70 ° C. with stirring, 257.4 g of DAA, 178.5 g of monomer (2), 21.3 g of 80% IPN10, 96.5 g of 15% NaPS, And 328.6 g of pure water was dropped from separate nozzles.
The drop start of each solution is simultaneous, and the drop time of each solution is 180 minutes for DAA, 120 minutes for monomer (2), 120 minutes for 80% IPN10, 190 minutes for 15% NaPS, and The pure water was 180 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 kept at 70 ° C. (ripening) for 30 minutes to complete the polymerization. Thus, the aqueous solution (copolymer composition (6)) containing the copolymer (6) with a solid content concentration of 45% was obtained.

[Comparative Example 1]
40 g of polyethyleneimine (Mw 9,500, Mn 6,500) was charged into a glass 100 ml separable flask equipped with a reflux condenser, a thermometer, and a stirrer, and Denacol EX-121 (manufactured by Nagase ChemteX Corporation, 2 -10 g of ethylhexyl glycidyl ether (hereinafter referred to as 2EHGE) was added. This polymer mixture was heated to 60 ° C. with stirring and reacted for 4 hours to obtain a comparative polymer (1). The comparative polymer (1) is completely dissolved at an arbitrary ratio with respect to water, and is derived from a methine proton generated by opening an epoxy ring at around 3.5 ppm in NMR spectrum measurement in D ₂ O. The generation was confirmed by the detection of the signal.

When the aqueous solution of the copolymers (1) to (6) was dried and ¹ H-NMR was measured, a peak due to the residual monomer was not detected, and a polymer having a composition according to the charged amount (see Table 1) was obtained. I was able to confirm.

[Example 7]
The copolymers (1) to (6) and the comparative copolymer (1) obtained in Examples 1 to 6 and Comparative Example 1 were evaluated for compatibility with the surfactant as follows. The results are shown in Table 1.
<Compatibility with surfactant>
A detergent composition containing a test sample (amino group-containing polymer or amino group-containing 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 8]
Further, the copolymer (1) obtained in Example 1, the copolymer (2) obtained in Example 2, the copolymer (3) obtained in Example 3, and the copolymer obtained in Example 5 (5) About the comparative copolymer (1) obtained by the comparative example 1, the recontamination prevention ability was evaluated as follows.
The recontamination prevention rate of the copolymer (1) is 78%, the recontamination prevention rate of the copolymer (2) is 78%, the recontamination prevention rate of the copolymer (3) is 76%, and the copolymer (5 ) Was 80%. On the other hand, the recontamination prevention rate of the comparative copolymer (1) was 65%.
<Recontamination prevention test>
The recontamination prevention test using carbon black 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 amino group-containing 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 amino group-containing monomer (A), (ii) Nonionic monomer (B-1) and / or amino group-containing unit other than monomer (A) An amino group-containing polymer essentially comprising the structural unit (b) derived from the monomer (B-2), wherein the amino group-containing monomer (A) is represented by the following general formula (1) or ( 1 ');

(Wherein R ₀ represents a hydrogen atom or a CH ₃ group. R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a direct bond. R ₂ , R ₃ and R ₄ may be the same or different. Represents an organic group having 1 to 20 carbon atoms, R ₅ and R ₆ are the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and Y ₁ is the same or different and has 2 carbon atoms. Represents an alkylene group of ˜20, n is the average number of added moles of the oxyalkylene group (—Y ₁ —O—), and represents a number of ₁ to 300. X ₁ ^— represents a counter anion.) The amino group-containing polymer has a structure represented by the formula (1) with respect to 100 mass% of the total amount of structural units derived from all monomers forming the polymer: 99% by mass and 1 to 99% by mass of structural unit (b) Roh group-containing polymer. (I) an amino group-containing monomer (A), (ii) a nonionic monomer (B-1) and / or an amino group-containing monomer (B-2) other than the monomer (A) A method for producing an amino group-containing polymer comprising a step of polymerizing a polymer, wherein the production method comprises the following general formula (1) with respect to 100% by mass of the total amount of all monomers used:

(Wherein R ₀ represents a hydrogen atom or a CH ₃ group. R ₁ represents a CH ₂ group, a CH ₂ CH ₂ group or a direct bond. R ₂ , R ₃ and R ₄ may be the same or different. Represents an organic group having 1 to 20 carbon atoms, R ₅ and R ₆ are the same or different and each represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and Y ₁ is the same or different and has 2 carbon atoms. Represents an alkylene group of ˜20, n is the average number of added moles of the oxyalkylene group (—Y ₁ —O—), and represents a number of ₁ to 300. X ₁ ^— represents a counter anion.) 1 to 99% by mass of a polyalkylene glycol monomer (A) represented by a nonionic monomer (B-1) and / or an amino group-containing monomer other than the monomer (A) ( B-2) is used in an amount of 1 to 99% by mass. Manufacturing method. A detergent composition comprising the amino group-containing polymer according to claim 1.