JP2018203925A - Graft polymer - Google Patents

Abstract

To provide a graft polymer excellent in re-pollution prevention performance to a composite stains containing more hydrophobic materials and hydrophilic materials than conventional ones.SOLUTION: There is provided a graft polymer by polymerizing a monomer component containing an N-vinyllactam monomer (B) with a polyether compound (A), in which the polyether compound (A) has a hydrocarbon group having 1 to 30 carbon atoms at at least one terminal, the graft polymer has a ratio of a structural unit (b) derived from the N-vinyllactam monomer (B) of more than 0.3 pts.mass and 1.5 pts.mass or less based on 1 pts.mass of the polyether compound (A).SELECTED DRAWING: None

Description

The present invention relates to a graft polymer. More specifically, the present invention relates to a graft polymer useful for detergents, cleaning agents, scale inhibitors, dispersants, thickeners, pressure-sensitive adhesives, adhesives, surface coating agents, crosslinking agents, humectants, and the like.

Conventionally, a polymer obtained by polymerizing an unsaturated carboxylic acid monomer such as acrylic acid, a copolymer with another monomer, a polyether compound, an unsaturated carboxylic acid monomer such as acrylic acid, etc. Graft polymer obtained by graft polymerization of polymer, vinyl acetate or (meth) acrylic acid ester, detergent, cleaning agent, scale inhibitor, various inorganic and organic dispersants, thickener, adhesive, adhesive Widely used in various applications such as agents, surface coating agents, crosslinking agents, humectants. In recent years, an attempt has been made to graft-polymerize N-vinylpyrrolidone to a polyether compound as an improved graft polymer.

Regarding such a graft polymer, Patent Document 1 discloses a water-soluble polymer obtained by polymerizing a monomer component containing N-vinylpyrrolidone (B) to a polyether compound (A). -The water-soluble polymer whose vinylpyrrolidone (B) is 0.01-0.3 weight part with respect to 1 weight part of this polyether compound (A) is disclosed. Patent Document 2 discloses that a polyether compound (A) having a number average molecular weight of 200 or more obtained by polymerizing an alkylene oxide component containing at least 50 mol% of ethylene oxide, N-vinylpyrrolidone (b1) is essential and monoethylene. Graft polymerization is carried out so that the graft component (B), which may contain the polymerizable unsaturated monomer (b2), is 0.1 to 1.2 parts by weight of (B) with respect to 1 part by weight of (A). The monoethylenically unsaturated monomer (b2) is a carboxyl group-containing monoethylenically unsaturated monomer (b2-1) (provided that the monomer (b2-1) is hydrolyzed. And / or a cationic monoethylenically unsaturated monomer (b2-2), and the carboxyl group-containing monoethylene. When the unsaturated unsaturated monomer (b2-1) includes a monomer having a structure that becomes a carboxylic acid (salt) by the hydrolysis, a carboxyl group (provided by hydrolysis of the monomer having the structure, provided that In the case of a carboxylate salt, it is also regarded as a carboxyl group), and the graft weight is such that 50 mol% or more of the structural units derived from the monomer (b2-1) have a carboxyl group. Coalescence is disclosed.

JP 2006-336000 A JP 2001-106743 A

As described above, various graft polymers have been developed and reported on the ability to prevent re-contamination against hydrophobic soils. However, conventional graft polymers have hydrophilic substances such as mud and hydrophobic substances such as sebum and wrinkles. There was a problem that the ability to prevent re-contamination of composite soils combined with substances in combination was not sufficient.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a graft polymer that is more excellent in the ability to prevent recontamination of a composite soil containing a hydrophobic substance and a hydrophilic substance than a conventional graft polymer. To do.

The inventor conducted various studies on the graft polymer, and polymerized N-vinyl lactam monomer at a specific ratio with respect to the polyether compound having a hydrocarbon group having 1 to 30 carbon atoms at at least one terminal. The present inventors have found that the grafted polymer is superior in the ability to prevent recontamination against composite soils than conventional grafted polymers, and arrived at the present invention by conceiving that the above problems can be solved brilliantly.

That is, the present invention is a graft polymer obtained by polymerizing a monomer component containing an N-vinyl lactam monomer (B) to a polyether compound (A), wherein the polyether compound (A) The graft polymer has a hydrocarbon group having 1 to 30 carbon atoms at at least one terminal, and the proportion of the structural unit (b) derived from the N-vinyllactam monomer (B) is a polyether compound. (A) The graft polymer is greater than 0.3 parts by weight and less than 1.5 parts by weight with respect to 1 part by weight.

In the graft polymer, the proportion of the structural unit (b) derived from the N-vinyl lactam monomer (B) is 0.31 to 1.5 parts by mass with respect to 1 part by mass of the polyether compound (A). It is preferable that

In the polyether compound (A), it is preferable that at least one terminal hydrocarbon group is an alkyl group.
The polyether compound (A) is a compound having an oxyalkylene group, and the average added mole number of the oxyalkylene group per molecule of the compound (A) is preferably 4.5 to 100 mol.

The graft polymer of the present invention has the above-described structure, and is superior in the ability to prevent recontamination of composite soil containing a hydrophobic substance and a hydrophilic substance as compared with conventional graft polymers. Can be used.

Although the preferable form of this invention is demonstrated concretely below, this invention is not limited only to the following description, In the range which does not change the summary of this invention, it can change suitably and can apply. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more also corresponds to the preferable form of this invention.

<Graft polymer>
Since the graft polymer of the present invention has an N-vinyl lactam group derived from the N-vinyl lactam monomer (B), it has excellent adsorptivity and dispersibility to hydrophilic substances such as mud. In the graft polymer of the present invention, the polyether compound (A) having a hydrocarbon group having 1 to 30 carbon atoms has appropriate hydrophobicity. Excellent adsorptivity and dispersibility for hydrophobic substances.
In the graft polymer of the present invention, the proportion of the structural unit (b) derived from the N-vinyl lactam monomer (B) is 0.3 parts by mass with respect to 1 part by mass of the polyether compound (A). It is large and is 1.5 parts by mass or less. As a result, the balance between the N-vinyl lactam structure and the structure derived from the polyether compound is suitable, and the anti-contamination ability, dispersibility, and detergency for composite dirt in which mud and the like are combined with sebum, wrinkles, etc. High performance can be demonstrated. Furthermore, since the graft polymer of the present invention has such a structure, it is excellent in the ability to prevent re-contamination against hydrophobic soils and the ability to prevent dye transfer during washing of dyed fabrics. The proportion of the structural unit (b) is preferably 0.31 to 1.5 parts by mass, more preferably 0.35 to 1.2 parts by mass, still more preferably 0.38 to 1.0 parts by mass. Yes, particularly preferably 0.41 to 0.70 parts by mass, and most preferably 0.43 to 0.67.

The graft polymer of the present invention is a graft polymer obtained by polymerizing a monomer component containing an N-vinyl lactam monomer (B), and other than the N-vinyl lactam monomer (B). You may have a structural unit derived from another monomer (E).
In the graft polymer, the proportion of the structural unit derived from the other monomer (E) is preferably 0 to 0.20 parts by mass with respect to 1 part by mass of the polyether compound (A). More preferably, it is 0-0.10 mass part, More preferably, it is 0-0.05 mass part, Most preferably, it is 0 mass part. If it is the said preferable range, it will become possible to maintain the recontamination prevention capability with respect to composite dirt at a higher level.

<Polyether compound (A)>
The polyether compound (A) is not particularly limited as long as it has a hydrocarbon group having 1 to 30 carbon atoms at at least one terminal, but the following formula (1);
_{^{R 1 - [X- (A 1}} O) p -R 2] q (1)
(In Formula (1), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms. R ² is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. X Represents a divalent linking group, A ¹ O is the same or different and represents an oxyalkylene group having 2 to 20 carbon atoms, p represents the average number of moles of A ¹ O added, and 1 to 100 It is preferable that q is a number represented by 1) to 6).

A ¹ O in the above formula (1) represents an oxyalkylene group having 2 to 20 carbon atoms. Preferably it is 2-15 as carbon number of the said alkylene group, More preferably, it is 2-10, More preferably, it is 2-5, Especially preferably, it is 2-3, Most preferably. These oxyalkylene groups are alkylene oxide adducts. Examples of such alkylene oxides include ethylene oxide (EO), propylene oxide (PO), isobutylene oxide, 1-butene oxide, 2-butene oxide, and trimethylethylene oxide. , Tetramethylene oxide, tetramethylethylene oxide, butadiene monooxide, octylene oxide, styrene oxide, 1,1-diphenylethylene oxide, and the like. Among these alkylene oxides, ethylene oxide, propylene oxide, and butylene oxide are preferable, and ethylene oxide and propylene oxide are more preferable.

The length of the (poly) alkylene glycol chain (average number of added oxyalkylene groups per molecule of the compound (A)) of the polyether compound (A) in the present invention is preferably 1 to 100. If the said average addition mole number is 100 or less, the viscosity of a polyether compound (A) will become a suitable range, and manufacture of a graft polymer will become easy. More preferably, it is 3-70, More preferably, it is 5-40, Most preferably, it is 7-30, Most preferably, it is 9-20.

When the polyether compound (A) is a compound represented by the formula (1), the average number of added oxyalkylene groups per molecule of the compound (A) is the number of oxyalkylene groups present in the formula (1). It is represented by the total number, that is, the sum total of q existing p.
q is a number from 1 to 6, and when q is 2 or more, the polyether compound (A) represented by the above formula (1) is a carbon atom having a different hydrocarbon group represented by the above R ^1. in, there than having a structure group represented by the above formula _{^{(1) -X- (a 1 O}} ) p -R 2 is bonded, _{^{respectively, -X- (a 1 O) p}} -R 2 It does not have a repeating structure having a repeating unit as a repeating unit. When q is 2 or more, the groups represented by X— (A ¹ O) _p —R ² may be the same or different. The q is preferably 1 to 4, more preferably 1 to 2, and most preferably 1.
p is preferably 1 to 100. More preferably, it is 3-70, More preferably, it is 5-40, Most preferably, it is 7-30.

R ¹ in the above formula (1) represents a hydrocarbon group having 1 to 30 carbon atoms. The number of carbon atoms of the hydrocarbon group in R ¹ is preferably 2-24. When the number of carbon atoms is 2 or more, the hydrophobicity of the polyether compound (A) becomes a more suitable range, and the ability to prevent recontamination against hydrophobic soil is further improved. Moreover, if the number of carbon atoms is 24 or less, it is possible to more sufficiently suppress a decrease in the adsorptivity to hydrophobic soil due to a decrease in the mobility of the polymer. More preferably, it is 4-22 as a carbon atom number, More preferably, it is 5-20, Especially preferably, it is 6-18, More preferably, it is 7-16, Most preferably, it is 8-14.
R ¹ in the above formula (1) may vary in the number of carbon atoms of the terminal hydrocarbon group. In this case, the carbon number of the hydrocarbon group of R ¹ means the average number of carbon atoms, and the preferable range of the average number of carbon atoms is also as described above.

Examples of the hydrocarbon group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, and heptyl. Group, octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, 2,3,5-trimethylhexyl group, decyl group, undecyl group, 4-ethyl-5-methyloctyl group, dodecyl group, tridecyl group, tetradecyl group Linear or branched alkyl groups such as pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, 1-hexyl-heptyl group; cyclic groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl Alkyl group; vinyl group, allyl group, 1-buteni Group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, octadecenyl group and the like linear or branched alkenyl group; phenyl group, benzyl group, phenethyl group, Examples include aryl groups such as o-, m- or p-tolyl groups, 2,3- or 2,4-xylyl groups, mesityl groups, naphthyl groups, anthryl groups, phenanthryl groups, biphenylyl groups, benzhydryl groups, and pyrenyl groups. It is done.

R ¹ is preferably an alkyl group or an alkenyl group. More preferred is an alkyl group, and even more preferred is a linear alkyl group. If R ¹ does not have an aromatic ring, it is less harmful to the environment even when it is decomposed, and even when the graft polymer of the present invention is discharged into the environment, the effect on the environment is more fully affected. Can be suppressed. If R ¹ is a linear alkyl group, the crystallinity of the graft polymer will be better, and the viscosity of the graft polymer solution will be favorable.
As the linear alkyl group, methyl group, ethyl group, propyl group, n-butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group And an alkyl group having 1 to 30 carbon atoms such as a hexadecyl group, a heptadecyl group, and an octadecyl group.

R ² is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. When R ² is a hydrocarbon group having 1 to 30 carbon atoms, the hydrocarbon group is preferably the same hydrocarbon group as R ¹ described above.
R ² is preferably a hydrogen atom.

As the divalent linking group in X of the above formula (1), the following formula (2);
-Y _k -Z- (2)
(In the formula, Y represents a p-phenylene group or a carbonyl group. Z represents any of —O—, —S—, —SO ₂ —, and —NH—. K is 0 or 1. It is preferable that it is group represented by.
In the compound represented by the above formula (1), q divalent linking groups of X may be all the same or different.
The k is preferably 0. Z is preferably -O-.
That is, X is preferably —O—.

The method for obtaining the polyether compound (A) is not particularly limited as long as the obtained polyether compound (A) has a hydrocarbon group having 1 to 30 carbon atoms at at least one terminal. For example, it can be obtained by polymerizing the alkylene oxide component by a conventional method in the presence of a reaction target compound serving as a polymerization starting point. The compound to be reacted is not particularly limited as long as it is a compound that becomes a polymerization starting point of cyclic ether, and examples thereof include alcohols, amines, hydroxylamines, carboxylic acids, and the like. Among them, alcohols, amines Is preferred. Examples of alcohols include primary aliphatic alcohols having 1 to 30 carbon atoms such as methanol, ethanol, n-propanol, and n-butanol; aromatics such as phenol, isopropylphenol, octylphenol, tert-butylphenol, nonylphenol, and naphthol. Alcohol: secondary alcohol having 3 to 30 carbon atoms such as alcohol obtained by oxidizing isopropyl alcohol or n-paraffin; tertiary alcohol having 4 to 30 carbon atoms such as tert-butanol; ethylene glycol, diethylene glycol, propanediol, Diols such as butanediol and propylene glycol; triols such as glycerin and trimethylolpropane; polyols such as sorbitol and the like. Examples of amines include ethylenediamine , Polyethyleneimine, and the like. In addition, these may be used independently and may use 2 or more types together.

The polymerization method is not particularly limited. For example, (1) an anionic polymerization method using a strong alkali such as an alkali metal hydroxide or alcoholate, an alkylamine or the like as a base catalyst, and (2) a metal or metalloid halogen. As appropriate, a cationic polymerization method using a fluoride, mineral acid, acetic acid or the like as a catalyst, and (3) a coordination polymerization method using a combination of an alkoxide of a metal such as aluminum, iron or zinc, an alkaline earth compound, a Lewis acid, etc. Just choose.

<N-vinyl lactam monomer (B)>
The N-vinyl lactam monomer (B) is not particularly limited as long as it is a monomer having a cyclic N-vinyl lactam structure, but the following formula (3);

(In formula, R < ³ >, R < ⁴ >, R < ⁵ >, R < ⁶ > is the same or different, and represents the C1-C10 alkyl group which may have a hydrogen atom or a substituent. It represents an integer of 4. n is preferably a structure represented by 1 to 3).
As carbon number of the alkyl group in said R < ³ > -R < ⁶ >, 1-6 are preferable, More preferably, it is 1-4. The alkyl group is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
Although it does not restrict | limit especially as a substituent in said R < ³ > -R < ⁶ >, A carboxyl group, a sulfonic acid group, these esters and salts; An amino group, a hydroxyl group, etc. are mentioned.
R ^{3 to} R ⁵ are preferably hydrogen atoms. R ⁶ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
m is preferably an integer of 0 to 2, more preferably an integer of 0 to 1, and most preferably 0.
n is preferably 1 or 2, and more preferably 1.

Examples of the compound represented by the above formula (3) include N-vinylpyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, 1- (2-propenyl) -2-pyrrolidone and the like. 1 type, or 2 or more types can be used. As N-vinyl lactam, an unsaturated monomer having a pyrrolidone ring is preferable. More preferred is N-vinylpyrrolidone.

<Other monomer (E)>
The graft polymer of the present invention is a graft polymer obtained by polymerizing a monomer component containing an N-vinyl lactam monomer (B), and the monomer component is an N-vinyl lactam monomer. Other monomers (E) other than the body (B) may be included.
The other monomer (E) is not particularly limited as long as it can be copolymerized with the N-vinyl lactam monomer (B). For example, (meth) acrylic acid, crotonic acid, tiglic acid, 3- Methylcrotonic acid, 2-methyl-2-pentenoic acid, itaconic acid and the like; unsaturated monocarboxylic acid monomers such as monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts; maleic acid, Unsaturation of itaconic acid, mesaconic acid, citraconic acid, fumaric acid, etc., their monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, etc., their anhydrides, half esters, half amines, etc. Dicarboxylic acid monomer; 2-acrylamido-2-methylpropanesulfonic acid, (meth) allylsulfonic acid, vinylsulfonic acid, 2-hydroxy-3-allyloxy-1-propane Monomers having sulfonic acid groups such as sulfonic acid and 2-hydroxy-3-butenesulfonic acid; monomers having phosphonic acid groups such as vinylphosphonic acid and (meth) allylphosphonic acid; 2-hydroxyethyl (meta ) Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α-hydroxymethylethyl (meth) acrylate, etc. Hydroxyl group-containing alkyl (meth) acrylates; (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and C 1-18 Alkyl (meth) obtained by esterification with alcohol Acrylates; amino group-containing acrylates such as dimethylaminoethyl (meth) acrylate or quaternized products thereof; amide group-containing monomers such as (meth) acrylamide, dimethylacrylamide and isopropylacrylamide; vinyl esters such as vinyl acetate; Alkenes such as ethylene and propylene; aromatic vinyl monomers such as styrene, styrenesulfonic acid and 1-vinylimidazole; maleimide derivatives such as maleimide, phenylmaleimide and cyclohexylmaleimide; nitrile groups such as (meth) acrylonitrile Vinyl monomers; aldehyde group-containing vinyl monomers such as (meth) acrolein; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether; vinyl chloride, vinyl chloride ; Allyl alcohol, unsaturated alcohols such as isoprenol can be mentioned.

<Method for producing graft polymer>
Although the production of the graft polymer of the present invention is not particularly limited, the polyether compound (A) and the monomer component (N-vinyl lactam monomer (B) and other monomer (E)) are polymerized. Specific examples and preferred examples of the polyether compound and the monomer component are as described above.
The polymerization is preferably performed by bulk polymerization (bulk polymerization). Specifically, the amount of the solvent used in the polymerization reaction is preferably 10% by mass or less based on the total amount of the reaction system.

The graft polymer of the present invention is preferably produced by a method in which the polyether compound (A) and the monomer component are polymerized in the presence of a polymerization initiator.
Although it does not specifically limit as a polymerization initiator, An organic peroxide is suitable. Examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide; -Butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 2- Hydroperoxides such as (4-methylcyclohexyl) -propane hydroperoxide; di-tert-butyl peroxide, tert-butyl group Ruperoxide, dicumyl peroxide, α, α′-bis (tert-butylperoxy) p-diisopropylbenzene, α, α′-bis (tert-butylperoxy) p-isopropylhexyne, 2,5-dimethyl Dialkyl peroxides such as -2,5-di (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3;

tert-butyl peroxyacetate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, di-tert-butyl peroxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxyisopropyl carbonate, tert-butylperoxyisobutyrate, tert-butylperoxybivalate, tert-butylperoxyneodecanoate, cumylperoxyneodecanoate, tert-butylperoxy-2 -Ethylhexanoate, tert-butylperoxy-3,5,5-trimethylcyclohexanoate, tert-butylperoxybenzoate, tert-butylperoxymaleic acid, cumylperoxyoctoate Peroxyesters such as tert-hexyl peroxybivalate, tert-hexyl peroxyneohexanoate, cumyl peroxyneohexanoate, tert-butyl-peroxy-iso-propyl monocarbonate; n-butyl-4, 4-bis (tert-butylperoxy) valerate, 2,2-bis (tert-butylperoxy) butane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, Peroxyketals such as 1-bis (tert-butylperoxy) cyclohexane and 2,2-bis (tert-butylperoxy) octane;

Acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,3,5-trimethylcyclohexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4- Diacyl peroxides such as dichlorobenzoyl peroxide and m-toluyl peroxide; di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis- (4- tert-butylcyclohexyl) peroxydicarbonate, dimyristylperoxydicarbonate, di-methoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxy) Chill) peroxydicarbonate, di - peroxydicarbonate such as allyl peroxy dicarbonate; acetyl cyclohexyl sulfanyl peroxide, etc. and organic peroxides such as tert- butylperoxy allyl carbonate. These may be used alone or in combination of two or more.

Among these polymerization initiators, in the present invention, it is preferable to use an organic peroxide containing at least an aliphatic, whereby, for example, the graft efficiency is sufficiently improved, and the above water-soluble heavy weight is efficiently obtained. Coalescence can be obtained. Among these, in consideration of the reaction temperature in the polymerization process, temperature control during storage, etc., di-tert-butyl peroxide, tert-butyl-peroxy-iso-propyl monocarbonate and / or tert-butyl-peroxy-benzoate It is particularly preferred to use
In addition, to the organic peroxide containing at least aliphatic, other polymerization initiator (for example, organic peroxide containing aromatic), a chain transfer agent, and a reducing agent can be used in combination. The amount of other polymerization initiator, chain transfer agent, and reducing agent used is preferably 300 parts by weight or less with respect to 100 parts by weight of the organic peroxide containing at least aliphatic. More preferably, it is 100 parts by weight or less.

Although the usage-amount of the said polymerization initiator is not specifically limited, For example, it is preferable to set it as 0.1-30 weight part with respect to 100 weight part of all the monomer components used for superposition | polymerization. If it is 0.1 parts by weight or more, the polymerization rate to the polyether compound (A) can be further improved, and the yield can be further improved. If it is 30 parts by weight or less, for example, an organic solvent as a polymerization initiator can be used. When using an oxide, it can be set as the manufacturing method excellent in economical efficiency. More preferably, it is 3-20 weight part, More preferably, it is 5-10 weight part.
The method for adding the polymerization initiator is not particularly limited, and it may be initially batch-charged, or may be based on a continuous charging method such as dropwise addition or split charging. It is preferable because it can be dropped without being used and is not easily restricted by the addition method. In addition, the polymerization initiator may be introduced alone into the reaction vessel, or may be previously mixed with the polyether compound (A), the monomer component, the solvent and the like.

In the above polymerization, a solvent may be used, but water is not preferable because it decomposes the N-vinyl lactam monomer and generates a lactam compound such as 2-pyrrolidone. In addition, as the solvent, for example, a solvent having a chain transfer constant to the solvent of the monomer used as a raw material is as small as possible. Examples of such solvents include isobutyl alcohol, n-butyl alcohol, tert-butyl alcohol, isopropyl alcohol, ethylene glycol, diethylene glycol, glycerin, triethylene glycol, propylene glycol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether. Alcohols such as ethylene glycol dialkyl ethers, diethers such as propylene glycol dialkyl ethers; acetic acid such as acetic acid, ethyl acetate, propyl acetate, butyl acetate, acetates of ethylene glycol monoalkyl ether, acetates of propylene glycol monoalkyl ether, etc. These may be used alone or in combination of two or more. . In addition, it does not specifically limit as an alkyl group in the said alcohols and diethers, For example, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned.

Although the usage-amount of the said solvent is not specifically limited, For example, when the whole reaction system is 100 weight part, it is preferable to set it as 20 weight part or less. If it exceeds 20 parts by weight, for example, the graft efficiency of the monomer component may not be sufficient. More preferably, it is 0 part by weight, that is, substantially no solvent, which makes it possible to remarkably increase, for example, the grafting efficiency, and to obtain a polymer superior in various performances. Thus, the form in which the polymerization step is performed in the absence of a solvent is also a preferred form of the present invention. In addition, the said solvent may be initially prepared and may be added sequentially.

Although it does not specifically limit as reaction temperature at the time of the said superposition | polymerization, it is suitable to set it as 110-150 degreeC, More preferably, it is 120-140 degreeC.
The reaction pressure during the polymerization is not particularly limited, and may be, for example, normal pressure (atmospheric pressure), reduced pressure, or increased pressure. In addition, it is suitable to set it as a normal pressure (atmospheric pressure) at the point which can superpose | polymerize simply and at low cost.
In addition, the polymerization is preferably performed in an atmosphere of an inert gas such as nitrogen gas, argon gas, carbon dioxide gas, but is not limited thereto.

<Use of graft polymer>
General uses of the graft polymer of the present invention include, for example, detergent additives, scale inhibitors, various inorganic and organic dispersants, thickeners, adhesives, adhesives, surface coating agents, crosslinking agents, A moisturizer etc. are mentioned.

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%”.

<Evaluation of ability to prevent re-contamination of composite dirt (clay-carbon black)>
(1) A cotton cloth (CW98 manufactured by Test fabrics) 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 system SE6000 manufactured by Nippon Denshoku Kogyo Co., Ltd. in advance.
(2) Hard water was prepared by adding pure water to 1.47 g of calcium chloride dihydrate to 20 kg.
(3) 10 g of a solid content 1% aqueous solution of each evaluation sample was prepared in a 20 mL screw tube.
(4) 100 g of 4% sodium laurylbenzenesulfonate was prepared and used as a surfactant aqueous solution.
(5) A targot meter is set at 25 ° C., 1 L of hard water (2), 5.0 g of a sample aqueous solution (3), 5.0 g of a surfactant aqueous solution (4), carbon black (foundation) 0.25 g of Washing Science Association) and 0.50 g of clay (1-11 kinds of powder for JIS test (Kanto loam baked product)) were placed in a pot and stirred at 100 rpm for 1 minute. Then, 5 cotton cloths were put and stirred at 100 rpm for 10 minutes. (As a reference, evaluation was made by adding pure water instead of the sample solution of (3).)
(6) Water of the white cloth was drained by hand, 1 L of hard water of (2) was put in a pot, the temperature was adjusted to 25 ° C., and the mixture was stirred at 100 rpm for 2 minutes.
(7) A white cloth was applied and dried while stretching the wrinkles with an iron. Then, the whiteness of the cotton cloth was measured again with the above colorimetric color difference meter.
(8) From the above measurement results, the recontamination prevention rate (precontamination prevention ability) was determined by the following formula.
Recontamination prevention rate (%) = (whiteness after washing) / (whiteness before washing) × 100
The larger the value of the recontamination prevention rate, the better the recontamination prevention ability.

<Dispersion evaluation of composite dirt (carbon black-clay)>
(1) 2.94 g of calcium chloride dihydrate was put into a 500 mL beaker and 500 g was added with pure water to prepare hard water.
(2) 10 g of a solid content 0.1% aqueous solution of each evaluation sample was prepared in a 20 mL screw tube.
(3) In a 1 L beaker, 7.51 g of glycine, 1.18 g of ethanol and 7.00 g of 48% NaOH were added, and purified water was added to 1000 g to prepare a glycine buffer solution having a pH of 10.5.
(4) Next, 30 mL test tubes with an inner diameter of 16 mm were prepared for the number of evaluation samples, and 0.03 g of carbon black, 0.30 g of JIS11 class clay, 1.50 g of hard water of (1), and an aqueous sample solution of (2) 1. 50 g and 27.0 g of the glycine buffer solution of (3) were added and capped with a septum. In this way, a suspension aqueous solution containing 1000 ppm of carbon black, 10000 ppm of clay, and 50 ppm of sample solid content in each test tube was prepared.
(5) Each test tube was slowly reversed 60 times, and then the cap was removed and the test tube was allowed to stand in a horizontal and stable place for 1 hour. After 1 hour, 5 mL of the supernatant was collected using a whole pipette.
(6) The absorbance at 380 nm of this supernatant was measured using an ultraviolet-visible spectrophotometer UV-1800 manufactured by Shimadzu Corporation. This absorbance was defined as dispersibility. A larger absorbance value means higher dispersibility.

<Example 1>
To a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer, Nippon Emulsifier Co., Ltd. New Coal 1820 (compound in which 20 moles of ethylene oxide was added on average to a linear primary alcohol having 18 carbon atoms) (Hereinafter, also referred to as NC1820) was charged, and the temperature was raised to 128 ° C. with stirring. Next, 9750 μL of di-t-butyl peroxide (hereinafter also referred to as PBD) and 90.2 g of N-vinylpyrrolidone (hereinafter also referred to as NVP) were separately added dropwise to the polymerization reaction system at a constant temperature of 128 ° C. with stirring. It dripped from the nozzle. The timing of the start of dropping PBD was set as the reaction start. For each dropping time and dropping sequence, PBD was set at a constant rate in 195 minutes from the start of the reaction, and NVP was set at a fixed rate in 225 minutes after 20 minutes from the start of the reaction. After completion of all the dropwise additions, the reaction solution was kept at 128 ° C. for 70 minutes for further ripening to complete the polymerization. Thereafter, 58.3 g of pure water was added. Thus, polymer 1 having a solid content of 80% was obtained. The present polymer 1 was excellent in the dispersibility of the composite soil (carbon black-clay).

<Example 2>
To a glass 500 mL separable flask equipped with a thermometer, reflux condenser, and stirrer, Nippon Shokubai Co., Ltd. Softanol 200 (an average of 20 mol of ethylene oxide was added to a linear secondary alcohol having 12 to 14 carbon atoms) It is a compound and is hereinafter also referred to as SFT200.) 168.5 g was charged and heated to 128 ° C. with stirring. Next, 7800 μL of di-t-butyl peroxide (hereinafter also referred to as PBD) and 72.2 g of N-vinylpyrrolidone (hereinafter also referred to as NVP) were separately added dropwise to the polymerization reaction system at a constant temperature of 128 ° C. with stirring. It dripped from the nozzle. The timing of the start of dropping PBD was set as the reaction start. For each dropping time and dropping sequence, PBD was set at a constant rate in 195 minutes from the start of the reaction, and NVP was set at a fixed rate in 225 minutes after 20 minutes from the start of the reaction. After completion of all the dropwise additions, the reaction solution was kept at 128 ° C. for 70 minutes for further ripening to complete the polymerization. Thereafter, 61.7 g of pure water was added. Thus, a polymer 2 having a solid content of 80% was obtained.

<Example 3>
To a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer, Nippon Shokubai Co., Ltd. Softanol 90 (an average of 9 mol of ethylene oxide was added to a linear secondary alcohol having 12 to 14 carbon atoms) The compound, hereinafter also referred to as SFT90.) 135.4 g was charged and heated to 128 ° C. with stirring. Next, 9750 μL of di-t-butyl peroxide (hereinafter also referred to as PBD) and 90.2 g of N-vinylpyrrolidone (hereinafter also referred to as NVP) were separately added dropwise to the polymerization reaction system at a constant temperature of 128 ° C. with stirring. It dripped from the nozzle. The timing of the start of dropping PBD was set as the reaction start. For each dropping time and dropping sequence, PBD was set at a constant rate in 195 minutes from the start of the reaction, and NVP was set at a fixed rate in 225 minutes after 20 minutes from the start of the reaction. After completion of all the dropwise additions, the reaction solution was kept at 128 ° C. for 70 minutes for further ripening to complete the polymerization. Thereafter, 58.3 g of pure water was added. Thus, polymer 3 having a solid content of 79% was obtained.

<Example 4>
To a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer, Nippon Shokubai Co., Ltd. Softanol 90 (an average of 9 mol of ethylene oxide was added to a linear secondary alcohol having 12 to 14 carbon atoms) It is a compound and is hereinafter also referred to as SFT90.) 168.5 g was charged and heated to 128 ° C. with stirring. Next, 7800 μL of di-t-butyl peroxide (hereinafter also referred to as PBD) and 72.2 g of N-vinylpyrrolidone (hereinafter also referred to as NVP) were separately added dropwise to the polymerization reaction system at a constant temperature of 128 ° C. with stirring. It dripped from the nozzle. The timing of the start of dropping PBD was set as the reaction start. For each dropping time and dropping sequence, PBD was set at a constant rate in 195 minutes from the start of the reaction, and NVP was set at a fixed rate in 225 minutes after 20 minutes from the start of the reaction. After completion of all the dropwise additions, the reaction solution was kept at 128 ° C. for 70 minutes for further ripening to complete the polymerization. Thereafter, 61.7 g of pure water was added. In this way, a polymer 4 having a solid content of 80% was obtained.

<Example 5>
To a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer, Nippon Emulsifier Co., Ltd. New Coal 2310 (an average of 10 moles of ethylene oxide was added to a linear primary alcohol having 12 to 13 carbon atoms) 168.5 g), and the temperature was raised to 128 ° C. with stirring. Next, 7800 μL of di-t-butyl peroxide (hereinafter also referred to as PBD) and 72.2 g of N-vinylpyrrolidone (hereinafter also referred to as NVP) were separately added dropwise to the polymerization reaction system at a constant temperature of 128 ° C. with stirring. It dripped from the nozzle. The timing of the start of dropping PBD was set as the reaction start. For each dropping time and dropping sequence, PBD was set at a constant rate in 195 minutes from the start of the reaction, and NVP was set at a fixed rate in 225 minutes after 20 minutes from the start of the reaction. After completion of all the dropwise additions, the reaction solution was kept at 128 ° C. for 70 minutes for further ripening to complete the polymerization. Thereafter, 61.7 g of pure water was added. Thus, polymer 5 having a solid content of 78% was obtained.

<Example 6>
To a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer, Nippon Emulsion Co., Ltd. New Coal 1020 (a compound obtained by adding an average of 20 moles of ethylene oxide to 2-ethylhexyl alcohol, hereinafter referred to as NC1020) 168.5 g was charged, and the temperature was raised to 128 ° C. with stirring. Next, 7800 μL of di-t-butyl peroxide (hereinafter also referred to as PBD) and 72.2 g of N-vinylpyrrolidone (hereinafter also referred to as NVP) were separately added dropwise to the polymerization reaction system at a constant temperature of 128 ° C. with stirring. It dripped from the nozzle. The timing of the start of dropping PBD was set as the reaction start. For each dropping time and dropping sequence, PBD was set at a constant rate in 195 minutes from the start of the reaction, and NVP was set at a fixed rate in 255 minutes after 20 minutes from the start of the reaction. After completion of all the dropwise additions, the reaction solution was kept at 128 ° C. for 70 minutes for further ripening to complete the polymerization. Thereafter, 61.7 g of pure water was added. In this way, a polymer 6 having a solid content of 79% was obtained.

<Comparative Example 1>
To a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer, Nippon Shokubai Co., Ltd. Softanol 90 (an average of 9 mol of ethylene oxide was added to a linear secondary alcohol having 12 to 14 carbon atoms) This compound is hereinafter also referred to as SFT90.) 216.6 g was charged, and the temperature was raised to 128 ° C. with stirring. Next, 5850 μL of di-t-butyl peroxide (hereinafter also referred to as PBD) and 54.2 g of N-vinylpyrrolidone (hereinafter also referred to as NVP) were separately added dropwise to the polymerization reaction system at a constant temperature of 128 ° C. with stirring. It dripped from the nozzle. The timing of the start of dropping PBD was set as the reaction start. For each dropping time and dropping sequence, PBD was set at a constant rate in 195 minutes from the start of the reaction, and NVP was set at a fixed rate in 225 minutes after 20 minutes from the start of the reaction. After completion of all the dropwise additions, the reaction solution was kept at 128 ° C. for 70 minutes for further ripening to complete the polymerization. Thereafter, 68.9 g of pure water was added. In this way, a polymer 7 having a solid content of 79% was obtained.

<Comparative Example 2>
A glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 84.2 g of polyethylene glycol 600 (polyethylene glycol having a number average molecular weight of 600) manufactured by Wako Pure Chemical Industries, Ltd., and the mixture was stirred at 128 ° C. The temperature rose. Next, 3900 μL of di-t-butyl peroxide (hereinafter also referred to as PBD) and 36.1 g of N-vinylpyrrolidone (hereinafter also referred to as NVP) were separately added dropwise to the polymerization reaction system at a constant temperature of 128 ° C. with stirring. It dripped from the nozzle. The timing of the start of dropping PBD was set as the reaction start. For each dropping time and dropping sequence, PBD was set at a constant rate in 195 minutes from the start of the reaction, and NVP was set at a fixed rate in 225 minutes after 20 minutes from the start of the reaction. After completion of all the dropwise additions, the reaction solution was kept at 128 ° C. for 70 minutes for further ripening to complete the polymerization. Thereafter, 30.9 g of pure water was added. Thus, a polymer 8 having a solid content of 80% was obtained.

Table 1 shows the structure of the polyether compound and the polymerization ratio of N-vinylpyrrolidone relative to the polyether compound for the graft polymers obtained in Examples 1 to 6 and Comparative Examples 1 and 2. Further, these polymers were measured for their ability to prevent recontamination of composite soil, and the results are shown in Table 2.

Claims (2)

A graft polymer obtained by polymerizing a polyether component (A) with a monomer component containing an N-vinyl lactam monomer (B),
The polyether compound (A) has a hydrocarbon group having 1 to 30 carbon atoms at at least one terminal,
In the graft polymer, the proportion of the structural unit (b) derived from the N-vinyl lactam monomer (B) is larger than 0.3 parts by mass with respect to 1 part by mass of the polyether compound (A). A graft polymer characterized by being 5 parts by mass or less. The polyether compound (A) is a compound having an oxyalkylene group, and the average added mole number of the oxyalkylene group per molecule of the compound (A) is 4.5 to 100 mol. Item 4. The graft polymer according to Item 1.