JP2020117562A - Polyalkyleneimine derivative - Google Patents

Abstract

To provide a novel polymer which can exhibit excellent color migration prevention ability.SOLUTION: A polyalkyleneimine derivative in which at least a part of primary amine groups of polyalkyleneimine is a tertiary amino group with a cyclic structure, and the tertiary amino group with a cyclic structure is a tertiary amino group with a structure represented by general formula (1), is disclosed.(In general formula (1), a dotted line represents a single bond or a double bond, R, R, and X are any one of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom, n represents the number of atoms, n is a number equal to 0 or more, and at least two atoms selected from R, R, and X are a part of atoms constituting the cyclic structure in an aliphatic cyclic structure which may have a substituent or an aromatic cyclic structure which may have a substituent.)SELECTED DRAWING: None

Description

The present invention relates to polyalkyleneimine derivatives.

As a technique for preventing color transfer from laundry such as clothes, various additives such as polymers have been developed. Such additives are generally called dye transfer inhibitors (color transfer inhibitors).

As a dye transfer inhibitor, for example, a polymer having polyvinylpyrrolidone as a basic skeleton is known (Patent Document 1). However, conventional polymers used as dye transfer inhibitors have not been able to exhibit sufficient dye transfer prevention ability, and there is room for improvement.

Tokuyohei 8-505166

An object of the present invention is to provide a novel polymer capable of expressing an excellent dye transfer inhibiting ability.

（一般式（１）において、点線は単結合または二重結合を表し、Ｒ^１、Ｒ^２、およびＸは、炭素原子、酸素原子、窒素原子、硫黄原子、リン原子のいずれかであり、ｎは原子の数を表し、ｎは０以上の数であり、Ｒ^１、Ｒ^２およびＸから選択される少なくとも２つの原子は、置換基を有していてもよい脂肪族環状構造または置換基を有していてもよい芳香族環状構造における環状構造の構成原子の一部である。） The polyalkyleneimine derivative of the present invention is
At least a part of the primary amino group of the polyalkyleneimine is a tertiary amino group having a cyclic structure,
The tertiary amino group having the cyclic structure is a tertiary amino group having a structure represented by the general formula (1).

(In the general formula (1), a dotted line represents a single bond or a double bond, R ¹ , R ² , and X are any of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom, and n Represents the number of atoms, n is a number of 0 or more, and at least two atoms selected from R ¹ , R ² and X represent an aliphatic cyclic structure which may have a substituent or a substituent. It is a part of the constituent atoms of the cyclic structure in the aromatic cyclic structure that may have.)

In one embodiment, 1 mol% to 95 mol% of the primary amino group of the polyalkyleneimine is a tertiary amino group having the cyclic structure.

（一般式（２）において、Ｒ^１とＲ^２を結ぶ点線は単結合もしくは二重結合を表し、Ｒ^１，Ｒ^２を含む円弧およびＲ^１とＲ^２を結ぶ点線から構成される構造は、置換基を有していてもよい脂肪族環状構造または置換基を有していてもよい芳香族環状構造を表す。） In one embodiment, the tertiary amino group having a cyclic structure is a tertiary amino group having a structure represented by the general formula (2).

(In the general formula (2), the dotted line connecting ^{R 1} and ^{R 2} represents a single bond or a double ^bond, structure composed of a dotted line connecting the circular arc and ^{R 1} and ^{R 2} containing R 1, ^{R 2} are, It represents an aliphatic cyclic structure which may have a substituent or an aromatic cyclic structure which may have a substituent.)

The dye transfer inhibitor of the present invention contains the polyalkyleneimine derivative of the present invention.

The detergent composition of the present invention contains the polyalkyleneimine derivative of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, the novel polymer which can express the outstanding dye transfer prevention ability can be provided.

When the expression "mass" is used in the present specification, it may be read as "weight" which is conventionally commonly used as a unit of weight, and conversely, the expression "weight" is used in the present specification. When there is, it may be read as “mass” which is commonly used as an SI system unit showing weight.

≪Polyalkyleneimine derivative≫
Polyalkyleneimine is a water-soluble polymer obtained by polymerizing alkyleneimine, has a primary amino group, a secondary amino group, and a tertiary amino group, and has a branched structure.

Examples of the polyalkyleneimine include polyethyleneimine, polypropyleneimine, polybutyleneimine, and the like. Polyethyleneimine is preferable as the polyalkyleneimine from the viewpoint that the effect of the present invention can be further exhibited.

The weight average molecular weight Mw of the polyalkyleneimine is preferably 100 to 150,000, more preferably 150 to 120,000, further preferably 200 to 100,000, and particularly preferably 250 to 80,000. When the weight average molecular weight Mw of the polyalkyleneimine is within the above range, the polyalkyleneimine derivative of the present invention can exhibit more excellent dye transfer inhibiting ability.

In the polyalkyleneimine derivative of the present invention, at least a part of the primary amino group of the polyalkyleneimine is a tertiary amino group having a cyclic structure, and the tertiary amino group having the cyclic structure is It is a tertiary amino group having a structure represented by the general formula (1). The polyalkyleneimine derivative of the present invention having such a specific structure can exhibit an excellent ability to prevent migration.

In the general formula (1), the dotted line represents a single bond or a double bond, R ¹ , R ² , and X are any of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom, and n is Represents the number of atoms, n is a number of 0 or more, and at least two atoms selected from R ¹ , R ² and X have an aliphatic cyclic structure which may have a substituent or a substituent. It is a part of the constituent atoms of the cyclic structure in the aromatic cyclic structure which may be formed.

The above “at least two atoms selected from R ¹ and R ² and X have the same structure as the aliphatic cyclic structure which may have a substituent or the cyclic structure of the aromatic cyclic structure which may have a substituent. The term “a part of the constituent atoms” means a substituent in which the tertiary amino group of the structure represented by the general formula (1) contains at least two atoms selected from R ¹ and R ² and X. It means that it has an aliphatic cyclic structure which may have or an aromatic cyclic structure which may have a substituent. Any appropriate substituent can be adopted as the substituent. Examples of such substituents include alkyl groups, cycloalkyl groups, aryl groups, hydroxyl groups, carboxyl groups, carboxyl groups and their esters and salts, sulfonic acid groups and their esters and salts, amino groups, and combinations thereof. And the like. The "salt" is preferably an alkali metal salt such as sodium salt or potassium salt; an alkaline earth metal salt such as calcium salt or magnesium salt; ammonium salt; an organic amine salt such as monoethanolamine salt or triethanolamine salt ; And the like.

The number of substituents in the cyclic structure (aliphatic cyclic structure which may have a substituent or aromatic cyclic structure which may have a substituent) is within a range not impairing the effect of the present invention. , Any suitable number may be employed. The number of such substituents is preferably 0 to 10. The substituent may further have a substituent, and as the substituent of the substituent, the above-mentioned examples of the substituent can be directly used as the examples of the substituent.

In the polyalkyleneimine derivative of the present invention, at least a part of the primary amino group of the polyalkyleneimine is a tertiary amino group having a cyclic structure, and the effect of the present invention can be further exhibited. Preferably, 1 mol% to 95 mol% of the primary amino group of the polyalkyleneimine is a tertiary amino group having a cyclic structure.

The lower limit of the conversion ratio of the primary amino group of the polyalkyleneimine to the tertiary amino group having a cyclic structure is more preferably 3 mol%, further preferably 5 mol%, and further preferably 7 mol%, more preferably 10 mol%, further preferably 13 mol%, further preferably 15 mol%, further preferably 17 mol%, particularly preferably 20 mol%. .. The upper limit of the conversion ratio of the primary amino group of the polyalkyleneimine to the tertiary amino group having a cyclic structure is more preferably 90 mol%, further preferably 85 mol%, and further preferably Is 80 mol %, more preferably 70 mol %, further preferably 60 mol %, further preferably 55 mol %, further preferably 50 mol %, particularly preferably 45 mol %. is there. Since the conversion ratio of the primary amino group of the polyalkyleneimine to the tertiary amino group having a cyclic structure is within the above range, the polyalkyleneimine derivative of the present invention has a more excellent dye transfer inhibiting ability. Can be expressed.

As the aliphatic cyclic structure which may have a substituent, any suitable aliphatic cyclic structure which may have any appropriate substituent can be adopted. Examples of such an aliphatic cyclic structure which may have a substituent include a cyclohexane structure which may have a substituent and an adamantane structure which may have a substituent.

As the aromatic cyclic structure which may have a substituent, any suitable aromatic cyclic structure which may have any suitable substituent can be adopted. Examples of such an aromatic cyclic structure which may have a substituent include a benzene structure which may have a substituent, a naphthalene structure which may have a substituent, and a substituent which has a substituent. Examples thereof include an anthracene structure, a pyridine structure, a thiophene structure, a quinoline structure, and a furan structure.

The number of carbon atoms of the cyclic structure (aliphatic cyclic structure which may have a substituent or aromatic cyclic structure which may have a substituent) may be any number as long as the effect of the present invention is not impaired. An appropriate carbon number can be adopted. Such carbon number is preferably 30 or less, more preferably 24 or less. When the cyclic structure has a substituent, the number of carbon atoms including the substituent is preferably within the above range.

The tertiary amino group having a cyclic structure is preferably a tertiary amino group having a structure represented by the general formula (2).

In the general formula (2), the dotted line connecting ^{R 1} and ^{R 2} represents a single bond or a double ^bond, structure composed of a dotted line connecting the circular arc and ^{R 1} and ^{R 2} containing R 1, ^{R 2} is substituted It represents an aliphatic cyclic structure which may have a group or an aromatic cyclic structure which may have a substituent.

The "structure composed of a dotted line connecting the circular arc and R ¹ and R ² containing R ¹ and R ² may aromatic optionally having an aliphatic cyclic structure which may have a substituent or substituents The term "representing a group cyclic structure" means that the tertiary amino group of the structure represented by the general formula (2) may have a substituent, including an aliphatic cyclic structure or a substituent containing R ¹ and R ^2. It means that it has an aromatic ring structure which may have a group. Regarding the substituents, the number of substituents, and the number of carbon atoms in the cyclic structure, the description in the above general formula (1) can be directly applied.

Since the polyalkyleneimine derivative of the present invention has a tertiary amino group having a structure represented by the general formula (2), it can exhibit more excellent dye transfer inhibiting ability.

The polyalkyleneimine derivative of the present invention is one in which at least a part of the primary amino group of the polyalkyleneimine is a tertiary amino group having a structure represented by the general formula (1). The weight average molecular weight Mw of the imine derivative is preferably 100 to 200,000, more preferably 150 to 150,000, further preferably 200 to 120,000, and particularly preferably 250 to 100,000. When the weight average molecular weight Mw of the polyalkyleneimine derivative of the present invention is within the above range, the polyalkyleneimine derivative of the present invention can exhibit more excellent dye transfer inhibiting ability.

<<Method for producing polyalkyleneimine derivative>>
The polyalkyleneimine derivative of the present invention can be produced by any appropriate method as long as the effects of the present invention are not impaired.

The polyalkyleneimine derivative of the present invention can be produced, for example, by reacting the polyalkyleneimine with the acid anhydride represented by the general formula (3). The reaction between the polyalkyleneimine and the acid anhydride may be performed under any appropriate condition.

In the general formula (3), the dotted line represents a single bond or a double bond, R ¹ , R ² , and X are any of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom, and n is Represents the number of atoms, n is a number of 0 or more, and at least two atoms selected from R ¹ , R ² and X have an aliphatic cyclic structure which may have a substituent or a substituent. It is a part of the constituent atoms of the cyclic structure in the aromatic cyclic structure which may be formed. For the details of these explanations, the explanation in the general formula (1) can be directly applied.

<<Applications of polyalkyleneimine derivatives>>
The polyalkyleneimine derivative of the present invention can be used for any appropriate application. Examples of such applications include a flocculant, a thickener, a pressure-sensitive adhesive, an adhesive, a surface coating agent, a cross-linking agent for inorganic fibers, a cross-linking agent for organic fibers, a cross-linkable composition, and the like. Include detergent builders, detergent compositions, dye transfer inhibitors, pigment dispersants, heavy metal scavengers, scale inhibitors, water treatment agents, metal surface treatment agents, dyeing assistants, dye fixing agents, foam stabilizers, emulsion stabilizers. Agents, ink dye dispersants, water-based ink stabilizers, paint pigment dispersants, paint thickeners, pressure-sensitive adhesives, paper adhesives, stick glues, medical adhesives, adhesives for patches, adhesives for cosmetic packs Agent, filler dispersant for resin, hydrophilic agent for resin, coating agent for recording paper, surface treatment agent for inkjet paper, dispersant for photosensitive resin, antistatic agent, humectant, binder for fertilizer, binder for pharmaceutical tablets, Examples thereof include a resin compatibilizer, a photographic additive, a cosmetic preparation additive, a hair styling aid, a hair spray additive, and a sunscreen composition additive.

The polyalkyleneimine derivative of the present invention can be preferably used in a dye transfer inhibitor, a detergent composition, a water treatment agent, a fiber treatment agent, and an inorganic pigment dispersant. More preferably, the polyalkyleneimine derivative of the present invention can be used in a dye transfer inhibitor or a detergent composition. The dye transfer inhibitor of the present invention contains the polyalkyleneimine derivative of the present invention. The detergent composition of the present invention contains the polyalkyleneimine derivative of the present invention.

<Transfer prevention agent>
The dye transfer inhibitor of the present invention contains the polyalkyleneimine derivative of the present invention. As a kind of dye that the dye transfer inhibitor of the present invention can exhibit the dye transfer inhibiting ability, any appropriate dye can be adopted as long as the effect of the present invention is not impaired. Such dyes may be, for example, dyes usually used for dyeing clothes, and include, for example, direct dyes, acid dyes, basic dyes, mordant dyes, acid mordant dyes, vat dyes, disperse dyes, and reaction dyes. Examples include dyes and fluorescent whitening dyes. The dye is preferably a water-soluble dye such as a direct dye or an acid dye. Since the water-soluble dye easily loses its color during washing, the technical significance of the present invention can be exhibited more effectively.

<Detergent composition>
The detergent composition of the present invention contains the polyalkyleneimine derivative of the present invention. Any appropriate content ratio can be adopted as the content ratio of the polyalkyleneimine derivative with respect to the detergent composition. From the viewpoint of exhibiting excellent builder performance, the content ratio of the polyalkyleneimine derivative is preferably 0.1% by mass to 20% by mass, more preferably 0.1% by mass, based on the total amount of the detergent composition. It is 1% by mass to 15% by mass, and more preferably 0.1% by mass to 10% by mass.

Detergent compositions used in detergent applications usually include surfactants and additives used in detergents.

Any appropriate surfactant or additive can be adopted as the surfactant or additive.

The detergent composition may be a powder detergent composition or a liquid detergent composition.

The surfactant is preferably at least one selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. When two or more of these surfactants are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more based on the total amount of the surfactant. %, more preferably 60% by mass or more, further preferably 70% by mass or more, and particularly preferably 80% by 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 ester salt, alkane sulfone. Acid 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 Examples thereof include esters or salts thereof. The alkyl group or alkenyl group in these anionic surfactants may be a branched alkyl group such as a methyl group.

Examples of nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkylglycoxides, and fatty acids. Examples thereof include glycerin monoester and alkylamine oxide. The alkyl group or alkenyl group in these nonionic surfactants may be a branched alkyl group such as a methyl group.

The cationic surfactant preferably includes a quaternary ammonium salt and the like.

Examples of the amphoteric surfactant include a carboxyl-type amphoteric surfactant and a sulfobetaine-type amphoteric surfactant. The alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may be branched alkyl groups such as methyl groups.

The blending ratio of the surfactant is preferably 10% by mass to 60% by mass, more preferably 15% by mass to 50% by mass, and further preferably 20% by mass to 45% with respect to the total amount of the detergent composition. Mass%, and particularly preferably 25 mass% to 40 mass%. If the blending ratio of the surfactant is too small, it may not be possible to exhibit sufficient detergency, and if the blending ratio of the surfactant is too large, economical efficiency may be reduced.

Examples of the additive include alkali builders, chelate builders, anti-redeposition agents for preventing redeposition of contaminants such as sodium carboxymethyl cellulose, stain inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, Anti-color transfer agent, softening agent, alkaline substance for pH adjustment, perfume, solubilizing agent, fluorescent agent, coloring agent, foaming agent, foam stabilizer, polish agent, bactericide, bleaching agent, bleaching auxiliary agent, enzyme , Dyes, solvents and the like. Further, in the case of a powder detergent composition, it is preferable to add zeolite.

The detergent composition may include other detergent builders.

As the other detergent builder, any appropriate other detergent builder can be adopted. Examples of such other detergent builders include alkali builders such as carbonates, hydrogen carbonates, and silicates, tripolyphosphates, pyrophosphates, glauber's salt, nitrilotriacetic acid salts, ethylenediaminetetraacetic acid salts, and citrate salts. , A (meth)acrylic acid copolymer salt, an acrylic acid-maleic acid copolymer, a fumarate, a chelate builder such as zeolite, and a carboxyl derivative of a polysaccharide such as carboxymethyl cellulose. Examples of the counter salt used for the other detergent builders include salts of alkali metals such as sodium and potassium, ammonium salts, and amine salts.

In the detergent composition, the total compounding ratio of the additive and the other detergent builder is preferably 0.1% by mass to 50% by mass, more preferably 0.2% by mass to 40% by mass, It is more preferably 0.3% by mass to 35% by mass, particularly preferably 0.4% by mass to 30% by mass, and most preferably 0.5% by mass to 20% by mass or less. If the total mixing ratio of the additive in the detergent composition and the other detergent builders is less than 0.1% by mass, sufficient detergent performance may not be exhibited, and if it exceeds 50% by mass. Economic efficiency may be reduced.

The concept of detergent composition is used only for specific applications such as synthetic detergents for household detergents, textile detergents and other industrial detergents, hard surface cleaners, as well as bleaching detergents that have enhanced one of its components. Detergent is also included.

When the detergent composition is a liquid detergent composition, the amount of water contained in the liquid detergent composition is preferably 0.1% by mass to 75% by mass, more preferably the total amount of the liquid detergent composition. 0.2% by mass to 70% by mass, more preferably 0.5% by mass to 65% by mass, further preferably 0.7% by mass to 60% by mass, particularly preferably 1% by mass to 55%. % By mass, and most preferably 1.5% by mass to 50% by mass.

When the detergent composition is a liquid detergent composition, the detergent composition has a kaolin turbidity of preferably 200 mg/L or less, more preferably 150 mg/L or less, and further preferably 120 mg/L or less. Yes, particularly preferably 100 mg/L or less, and most preferably 50 mg/L or less. As a method for measuring kaolin turbidity, for example, a 50 mm square cell having a thickness of 10 mm is charged with a uniformly stirred sample (liquid detergent), air bubbles are removed, and then NDH2000 (trade name, manufactured by Nippon Denshoku Co., Ltd., A method of measuring Tubidity (kaolin turbidity: mg/L) at 25° C. using a turbidimeter).

Examples of enzymes that can be incorporated into the detergent composition include protease, lipase, cellulase and the like. Among these enzymes, protease, alkaline lipase, and alkaline cellulase, which have high activity in the alkaline washing solution, are preferable.

The amount of enzyme added is preferably 5% by mass or less based on the total amount of the detergent composition. If it exceeds 5% by mass, no improvement in detergency can be seen, and there is a risk that the economy will decrease.

Examples of the alkali builder include silicates, carbonates and sulfates. Examples of chelate builders include diglycolic acid, oxycarboxylic acid salts, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), STPP (sodium tripolyphosphate), and citric acid. In addition, you may use other water-soluble polycarboxylic acid type polymers other than the polymer essentially used in this invention.

The detergent composition can be a detergent having excellent dispersibility and having extremely high quality agent performance and excellent stability in which deterioration of performance when stored for a long period of time and precipitation of impurities when kept at low temperature are unlikely to occur.

<Water treatment agent>
The polyalkyleneimine derivative of the present invention can be used as a water treatment agent. As the water treatment agent, if necessary, a polymeric phosphate, a phosphonate, an anticorrosive, a slime control agent, a chelating agent and the like may be used as other compounding agents.

The water treatment agent is useful for scale prevention in a cooling water circulation system, a boiler water circulation system, a seawater desalination apparatus, a pulp digester, a black liquor concentrator, and the like. Further, any appropriate water-soluble polymer may be contained within a range that does not affect the performance and effect.

<Fiber treatment agent>
The polyalkyleneimine derivative of the present invention can be used as a fiber treating agent. The fiber treatment agent preferably contains at least one selected from the group consisting of a dyeing agent, a peroxide, and a surfactant, and the polyalkyleneimine derivative of the present invention.

The content of the polyalkyleneimine derivative of the present invention in the fiber treatment agent is preferably 0.1% by mass to 100% by mass, more preferably 0.1% by mass to 50% by mass, based on the entire fiber treatment agent. %. Further, any appropriate water-soluble polymer may be contained within a range that does not affect the performance and effect.

The fiber treatment agent can be used in the steps of refining, dyeing, bleaching and soaping in fiber treatment. The fiber treatment agent preferably contains at least one selected from the group consisting of a dyeing agent, a peroxide, and a surfactant. Dyeing agents, peroxides, and surfactants include those commonly used in fiber treating agents.

The compounding ratio of the polyalkyleneimine derivative of the present invention and at least one selected from the group consisting of a dyeing agent, a peroxide, and a surfactant is, for example, whiteness of the fiber, uneven color, or improvement in dyeing resistance. In order to achieve the above, at least one selected from the group consisting of a dyeing agent, a peroxide, and a surfactant is added to 1 part by mass of the polyalkyleneimine derivative of the present invention in terms of pure amount of the fiber treating agent. It is preferable to mix in a ratio of 0.1 to 100 parts by mass.

Any appropriate fiber can be adopted as the fiber for which the fiber treatment agent can be used. 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; woven fabrics and blended products thereof.

When the fiber treatment agent is applied to the refining step, it is preferable to mix the polyalkyleneimine derivative of the present invention with an alkali agent and a surfactant. When applied to the bleaching step, it is preferable to blend the polyalkyleneimine derivative of the present invention, a peroxide, and a silicic acid agent such as sodium silicate as a decomposition inhibitor of an alkaline bleaching agent.

<Inorganic pigment dispersant>
The polyalkyleneimine derivative of the present invention can be used as an inorganic pigment dispersant. The inorganic pigment dispersant may contain condensed phosphoric acid and its salt, phosphonic acid and its salt, and polyvinyl alcohol as other compounding agents, if necessary.

The content of the polyalkyleneimine derivative of the present invention in the inorganic pigment dispersant is preferably 1% by mass to 100% by mass based on the whole inorganic pigment dispersant. Further, any appropriate water-soluble polymer may be contained within a range that does not affect the performance and effect.

The inorganic pigment dispersant can exhibit good performance as a dispersant for inorganic pigments such as heavy or light calcium carbonate and clay used for paper coating. For example, by adding a small amount of an inorganic pigment dispersant to an inorganic pigment and dispersing it in water, a high-concentration calcium carbonate having low viscosity, high fluidity, and good stability over time in its performance is obtained. High concentration inorganic pigment slurries such as slurries can be produced.

When the inorganic pigment dispersant is used as a dispersant for the inorganic pigment, the amount of the inorganic pigment dispersant used is preferably 0.05 parts by mass to 10 parts by mass with respect to 100 parts by mass 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, an effect corresponding to the added amount can be obtained, and it can be economically advantageous.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, "part" means "part by mass" and "%" means "% by mass" unless otherwise specified.

<Adsorption evaluation on cotton cloth>
The adsorption of the polymer onto cotton cloth was evaluated by the following method. First, the polymer was diluted with an appropriate amount of water to prepare a polymer aqueous solution having a solid content concentration of 1.0%. 2.5 g of the 1% aqueous polymer solution was placed in a 300 ml beaker, and 50 ppm (Ca/Mg=3/1) hardness water was added to make it 250.0 g. To this diluted polymer aqueous solution, 10 g of 5 cm×5 cm cotton cloth (manufactured by Testfabrics, Style460-6) was added and stirred for 10 minutes. The total organic carbon content (TOC) of the aqueous polymer solution (after the addition of the cotton cloth) obtained in the above step and the total organic carbon content before the addition of the cotton cloth in the above step were measured, and based on the following formula, The adsorption rate was calculated. The total organic carbon content was measured using a TOC meter (TOC-L manufactured by Shimadzu Corporation). When the adsorption rate was over 20%, it was evaluated as ◯ and when it was 20% or less, it was evaluated as x.

<Evaluation of transfer prevention ability>
The dye transfer prevention ability was measured by the following method. In the evaluation of the dye transfer prevention ability, first, a liquid detergent formulation and a 1.0% polymer aqueous solution were prepared. The liquid detergent composition was 25% polyoxyethylene lauryl ether sodium sulfate aqueous solution (product name: Emar 20C, manufactured by Kao) 11.0 g, and polyoxyethylene lauryl ether (product name: Emulgen 108, manufactured by Kao) 2.8 g. , 16% sodium dodecylbenzenesulfonate aqueous solution (product name: Neoperex G-15, manufactured by Kao) 17.2 g, propylene glycol 3 g, sodium oleate 1.2 g, and ethanol 1 g, and deionized water was added to 50 It was prepared by stirring after adjusting to 0.0 g. The 1.0% polymer aqueous solution used was prepared by diluting each polymer synthesized in the examples described below with an appropriate amount of water to adjust the solid content concentration to 1.0% by mass.
A rounder meter (L-20Z) manufactured by Daiei Kagaku Seiki Seisakusho was used for the evaluation of the transfer prevention ability. An aqueous solution for evaluation by adding 250 g of 50 ppm hardness water (Ca/Mg=3/1) to a 500 ml pot of a rounder meter and adding 0.5 g of the prepared liquid detergent composition and 0.5 g of a 1.0% polymer aqueous solution. Was prepared and the temperature was adjusted to 25°C. A 5 cm×5 cm cotton cloth (manufactured by Testfabrics, product name: Style460-6) 1.0 g and 5 cm×5 cm EMPA277 (manufactured by SWISSATEST) 6.4 g and 5 cm×5 cm EMPA496 (manufactured by SWISSATEST) in the aqueous solution for evaluation 3 0.6 g was added, and the mixture was stirred with a round meter for 30 minutes. Then, the obtained cotton cloth was rinsed with 250 g of 50 ppm hardness water for 5 minutes with a rounder meter, and then air-dried overnight to obtain a post-evaluation cloth. The ΔE ^* _ab represented by the following formula with respect to the white cotton cloth before evaluation of the cloth after evaluation obtained in the above steps was measured by a color difference meter to evaluate the dye transfer inhibiting ability of the polymer. ΔE ^* _ab shows that the smaller the value is, the smaller the color difference from the white cloth before evaluation is, the less the color dyeing is suppressed, that is, the higher the dye transfer preventing ability is. When the value of ΔE ^* _ab was smaller than 4, it was evaluated as ◯, and when it was 4 or more, it was evaluated as x.

<LC measurement conditions>
The measurement conditions of liquid chromatography (LC) are as follows.
Column used: Waters, Atlantis dC18 5μ, 1 4.6×250 mm Eluent: Water/acetonitrile=10/90 (mass ratio)
Sample: A sample prepared by the above-mentioned eluent to be 0.5%.
Sample injection amount: 100 μL
Flow rate: 1.0 mL/min Column temperature: 40°C
System: manufactured by Waters, alliance 2695
Detector: Waters, 2414 RI detector analysis software: Waters, Empower2 Software

[Example 1]
5.0 g of polyethyleneimine (manufactured by Nippon Shokubai Co., average molecular weight 600) was charged into a glass reaction container equipped with a nitrogen introduction tube, a reflux condenser and a stirrer, and the inside of the reaction container was replaced with nitrogen at 60° C. under stirring. Then, while stirring, 0.86 g of phthalic anhydride dissolved in 3 ml of ethanol was slowly dropped into the reaction vessel over 10 minutes. After the dropping was completed, the temperature was raised to 80° C. and the reaction was continued for 8 hours. After completion of the reaction, it was confirmed by liquid chromatography that phthalic anhydride was completely consumed. Then, the reaction mixture was heated under reduced pressure at 60° C., and ethanol was distilled off to obtain a phthalimidated product (1) of polyethyleneimine. The results are shown in Table 1.

[Example 2]
5.0 g of polyethyleneimine (manufactured by Nippon Shokubai Co., average molecular weight 600) was charged into a glass reaction container equipped with a nitrogen introduction tube, a reflux condenser and a stirrer, and the inside of the reaction container was replaced with nitrogen at 60° C. under stirring. Then, with stirring, 1.72 g of phthalic anhydride dissolved in 3 ml of ethanol was slowly dropped into the reaction vessel over 10 minutes. After the dropping was completed, the temperature was raised to 80° C. and the reaction was continued for 10 hours. After completion of the reaction, it was confirmed by liquid chromatography that phthalic anhydride was completely consumed. Then, the reaction mixture was heated under reduced pressure at 60° C., and ethanol was distilled off to obtain a phthalimidized product (2) of polyethyleneimine. The results are shown in Table 1.

[Example 3]
5.0 g of polyethyleneimine (manufactured by Nippon Shokubai Co., average molecular weight 600) was charged into a glass reaction container equipped with a nitrogen introduction tube, a reflux condenser and a stirrer, and the inside of the reaction container was replaced with nitrogen at 60° C. under stirring. Then, with stirring, 3.44 g of phthalic anhydride dissolved in 6 ml of ethanol was slowly dropped into the reaction vessel over 10 minutes. After the dropping was completed, the temperature was raised to 80° C. and the reaction was continued for 12 hours. After completion of the reaction, it was confirmed by liquid chromatography that phthalic anhydride was completely consumed. Then, the reaction mixture was heated under reduced pressure at 60° C., and ethanol was distilled off to obtain a phthalimidized product (3) of polyethyleneimine. The results are shown in Table 1.

The polyalkyleneimine derivative of the present invention can be used as a dye transfer inhibitor, a detergent composition, a water treatment agent, a fiber treatment agent, an inorganic pigment dispersant, and the like.

Claims (5)

At least a part of the primary amino group of the polyalkyleneimine is a tertiary amino group having a cyclic structure,
The tertiary amino group having the cyclic structure is a tertiary amino group having a structure represented by the general formula (1),
Polyalkyleneimine derivative.

(In the general formula (1), a dotted line represents a single bond or a double bond, R ¹ , R ² , and X are any of a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom, and n Represents the number of atoms, n is a number of 0 or more, and at least two atoms selected from R ¹ , R ² and X represent an aliphatic cyclic structure which may have a substituent or a substituent. It is a part of the constituent atoms of the cyclic structure in the aromatic cyclic structure that may have.) The polyalkyleneimine derivative according to claim 1, wherein 1 mol% to 95 mol% of the primary amino group of the polyalkyleneimine is a tertiary amino group having a cyclic structure. The polyalkyleneimine derivative according to claim 1, wherein the tertiary amino group having a cyclic structure is a tertiary amino group having a structure represented by the general formula (2).

(In the general formula (2), the dotted line connecting ^{R 1} and ^{R 2} represents a single bond or a double ^bond, structure composed of a dotted line connecting the circular arc and ^{R 1} and ^{R 2} containing R 1, ^{R 2} are, It represents an aliphatic cyclic structure which may have a substituent or an aromatic cyclic structure which may have a substituent.) A dye transfer inhibitor comprising the polyalkyleneimine derivative according to any one of claims 1 to 3. A detergent composition comprising the polyalkyleneimine derivative according to any one of claims 1 to 3.