JP2019031591A - Graft polymer - Google Patents

Abstract

To provide a graft polymer that achieves both re-contamination prevention ability of composite stains and inhibition of foaming.SOLUTION: The graft polymer is produced by polymerizing a monomer component including (B) an N-vinyllactam monomer on (A) a polyether compound. The polyether compound (A) has a 1-30C hydrocarbon group in at least one terminal and has a structural unit derived from ethylene oxide (EO) and a 3-20C alkylene oxide (AO) in which an average addition mole number of AO is 0.01 to 1 mole per 1 mole of an average addition mole number of EO. The graft polymer has a ratio of (b) a structural unit derived from the N-vinyllactam monomer (B) based on 1 pt.mass of the polyether compound (A) is 0.01 to 1.5 pts.mass.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.

With regard to such a graft polymer, Patent Document 1 discloses (A) polymerization of a cyclic N-vinylamide having a specific structure and (B) having a graft base of a polymer having no monoethylenically unsaturated units. A graft polymer is disclosed that contains the side chains of the polymer formed by the process, wherein the proportion of side chains (B) in the total polymer is ≧ 60% by mass. Patent Document 2 also discloses (A) a graft base of a polymer having no monoethylenically unsaturated units and (B) two different monoethylenically unsaturated monomers (B1) each having at least one nitrogen-containing heterocycle. ) And (B2), which contain polymer side chains, wherein the proportion of side chains (B) in the total polymer is greater than 55% by weight.

JP 2005-509064 gazette Special table 2005-509065 gazette

As described above, various graft polymers have been developed, and Patent Documents 1 and 2 report prevention of color migration in detergents. In recent years, from the viewpoint of increasing environmental awareness and saving water, it is required not only to have excellent detergency but also to suppress excessive foaming so that it can be rinsed with a small amount of water. Conventional graft polymers have not been sufficient in achieving both the ability to prevent re-contamination of composite soil containing a hydrophilic substance and a hydrophobic substance and suppressing foaming.

This invention is made | formed in view of the said present condition, and it aims at providing the graft polymer which can make the recontamination prevention capability of composite stain | pollution | contamination and foaming suppression compatible.

As a result of various studies on the graft polymer, the present inventor has a hydrocarbon group having 1 to 30 carbon atoms at least at one terminal, and ethylene oxide (EO) and alkylene oxide (AO) having 3 to 20 carbon atoms. A graft polymer obtained by polymerizing an N-vinyl lactam monomer at a specific ratio with respect to a polyether compound having a specific proportion of structural units derived from is excellent in the ability to prevent re-contamination of composite soil and to suppress foaming. As a result, the inventors have 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) Having a structural unit derived from ethylene oxide (EO) and alkylene oxide (AO) having 3 to 20 carbon atoms, and having an average addition mole of AO The number is 0.01 to 1 mol with respect to 1 mol of the average added mole number of EO, and the graft polymer has a proportion of the structural unit (b) derived from the N-vinyl lactam monomer (B). The graft polymer is 0.01 to 1.5 parts by mass with respect to 1 part by mass of the polyether compound (A).

The polyether compound (A) is represented by the following formula (1);
R ^1- [X- (EO) _p- (AO) _q -R ² ] _r (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, EO represents an oxyethylene group, AO is the same or different and represents an oxyalkylene group having 3 to 20 carbon atoms, Compound (A) oxyethylene groups per molecule The average number of moles added (s ¹ ) is expressed by the sum of r existing p and is 4.1 to 300. The average number of oxyalkylene groups having 3 to 20 carbon atoms per molecule of the compound (A) The number of added moles (s ² ) is a compound represented by the total of r existing qs, and is 0.01 s ^{1 to} s ^1. r is a number of 1 to 6. Is preferred.

The present invention is also a method for producing the graft polymer, wherein the production method grafts a polyether compound (A) and a monomer component containing an N-vinyl lactam monomer (B). Including the step of polymerizing, and the polymerization step is a method for producing a graft polymer in which the amount of the solvent used is 10 parts by mass or less with respect to 100 parts by mass in total of the polyether compound (A) and the monomer component. But there is.

Since the graft polymer of the present invention has the above-described configuration and is excellent in the ability to prevent re-contamination of composite dirt and the suppression of foaming, it can be suitably used for detergents and cleaning agents.

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 from 0.01 to 1 with respect to 1 part by mass of the polyether compound (A). 5 parts by mass. 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.
The proportion of the structural unit (b) is preferably 0.1 to 1.2 parts by mass, more preferably 0.2 to 1.0 parts by mass, still more preferably 0.3 to 0.8 parts by mass. Yes, particularly preferably 0.4 to 0.7 parts by mass, most preferably 0.43 to 0.67 parts by mass.

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 the structural unit (e) derived from another monomer (E).
In the graft polymer, the proportion of the structural unit (e) 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) has a structural unit derived from ethylene oxide (EO) and alkylene oxide (AO) having 3 to 20 carbon atoms and having a hydrocarbon group having 1 to 30 carbon atoms at at least one terminal. The average added mole number of AO is 0.1 to 1 mole relative to 1 mole of the average added mole number of EO. When the polyether compound (A) has such a structure, the solubility of the graft polymer in water is in a suitable range, the foam breaking property (antifoaming property) is improved, and foaming can be suppressed. . Moreover, in the graft polymer, if the average added mole number of AO is too large, there is a risk that the anti-contamination ability and graft efficiency of the composite soil may be lowered. It is excellent in the property (antifoaming property), and the ability to prevent re-contamination of the composite soil and the graft efficiency can be sufficiently suppressed.
The average added mole number of AO with respect to the average added mole number of EO is preferably 0.01 to 1, more preferably 0.05 to 0.8, still more preferably 0.1 to 0.6. Particularly preferred is 0.2 to 0.4, and most preferred is 0.25 to 0.36.

The length of the polyethylene glycol chain of the polyether compound (A) (average added mole number of oxyethylene groups per molecule of the compound (A)) is preferably 4.1 to 300. If the said average addition mole number is 300 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 4.2-100, More preferably, it is 4.3-60, More preferably, it is 4.5-50 mass parts, Especially preferably, it is 4.8-30, Most preferably 0.0-20.

The polyether compound (A) is represented by the following formula (1);
R ^1- [X- (EO) _p- (AO) _q -R ² ] _r (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, EO represents an oxyethylene group, AO is the same or different and represents an oxyalkylene group having 3 to 20 carbon atoms, Compound (A) oxyethylene groups per molecule The average number of moles added (s ¹ ) is expressed by the sum of r existing p and is 4.1 to 300. The average number of oxyalkylene groups having 3 to 20 carbon atoms per molecule of the compound (A) The number of added moles (s ² ) is a compound represented by the total of r existing qs, and is 0.01 s ^{1 to} s ^1. r is a number of 1 to 6. Is preferred.

In the formula (1), the average added mole number (s ¹ ) of the oxyethylene group per molecule of the compound (A) is represented by the sum of r existing, and is 4.1 to 300.
r is a number of 1 to 6, preferably 1 to 4, more preferably 1 to 2, and most preferably 1.
p is not particularly limited as long as s ¹ falls within the above preferred range, but is the same or different and is preferably 0.1 to 300. More preferably, it is 0.3-100, More preferably, it is 0.5-50, More preferably, it is 0.8-30, Especially preferably, it is 1.0-20, Most preferably, it is 5.0. ~ 15.

In the formula (1), the average added mole number (s ² ) of the oxyalkylene group having 3 to 20 carbon atoms per molecule of the compound (A) is represented by the sum of r existing q, and 0.01 s ¹ it is a ~s ^1.
s ² is preferably a range obtained by multiplying a preferable range of the average added mole number of AO with respect to 1 mole of the above average added mole number of EO by s ¹ .
q is not particularly limited as long as s ² falls within the above preferred range, but is the same or different and is preferably 0.001 to 300. More preferably, it is 0.003-100, More preferably, it is 0.005-50, More preferably, it is 0.008-30, Especially preferably, it is 0.01-20, Most preferably, it is 0.05. ~ 15.

In the formula (1), the addition form of the EO chain and AO chain represented by-(EO) _p- (AO) _q- is not particularly limited, and may be a block shape or a random shape.

AO in the above formula (1) is the same or different and represents an oxyalkylene group having 3 to 20 carbon atoms. Preferably it is 3-15 as carbon number of the said alkylene group. Thereby, the foam breaking property of the graft polymer is further improved, and foaming can be more sufficiently suppressed. More preferably, it is 3-10, More preferably, it is 3-8, Most preferably, it is 3-5, Most preferably, it is 3. These oxyalkylene groups are alkylene oxide adducts. Examples of such alkylene oxides include propylene oxide (PO), isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, Tetramethylethylene oxide, butadiene monooxide, octylene oxide, styrene oxide, 1,1-diphenylethylene oxide and the like can be mentioned. Among such alkylene oxides, propylene oxide and butylene oxide are preferable, and propylene oxide is most preferable.
Since propylene oxide (propylene oxide) is industrially easily available and inexpensive, the form in which the oxyalkylene group having 3 to 20 carbon atoms is an oxypropylene group is one of the preferred embodiments of the present invention. .

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 branched 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. Further, as long as it is an alkyl group of R ¹ is branched, the crystallinity of the graft polymer is made more excellent, the viscosity becomes suitable when a solution of the graft polymer.
As the branched alkyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, isooctyl group, 2,3,5-trimethylhexyl group, 4-ethyl- Alkyl groups having 1 to 30 carbon atoms such as 5-methyloctyl group and 1-hexyl-heptyl group are preferred.

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), all r divalent linking groups of X may be 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; and 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, it can be produced by polymerizing the polyether compound (A) and the monomer component containing the N-vinyl lactam monomer (B). . Specific examples and preferred examples of the polyether compound and the monomer component are as described above. In addition, the ratio of the N-vinyl lactam monomer (B) and the other monomer (E) in the monomer component is a structural unit (based on 1 part by mass of the polyether compound (A) in the kraft polymer). It is the same as the ratio of b) and the ratio of the structural unit (e).

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 mass or less with respect to 100 parts by mass of the organic peroxide containing at least aliphatic. More preferably, it is 100 parts by mass or less.

Although the usage-amount of the said polymerization initiator is not specifically limited, For example, the polyether compound (A) used for superposition | polymerization and a monomer component (N-vinyl lactam type monomer (B) and other monomers (E )) Is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass in total. If it is 0.1 parts by mass 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 mass or less, for example, an organic solvent as a polymerization initiator. When using an oxide, it can be set as the manufacturing method excellent in economical efficiency. More preferably, it is 3-20 mass parts, More preferably, it is 5-10 mass parts.
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. Further, 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, it is preferable to set it as 20 mass parts or less with respect to 100 mass parts of all the monomer components. Thereby, the grafting efficiency of the monomer component can be further improved.
In the polymerization step, a form in which the amount of the solvent used is in the above preferred range is also a preferred form of the present invention. That is, a method for producing the graft polymer, the method comprising graft polymerization of a polyether compound (A) and a monomer component containing an N-vinyl lactam monomer (B). In the polymerization step, the method for producing a graft polymer in which the amount of the solvent used is 20 parts by mass or less with respect to 100 parts by mass in total of the polyether compound (A) and the monomer component is also present. It is one of the inventions.
The amount of the solvent used is more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, and most preferably 0 part by mass, that is, substantially no solvent. Thereby, for example, graft efficiency can be remarkably increased, and a polymer superior in various performances can be obtained.
In addition, when using a solvent, 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 mass” and “%” means “% by mass”.

<Evaluation of ability to prevent re-contamination of composite dirt (clay-carbon black)>
(1) A polyester cloth (PW19 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) 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.

<Bubbling suppression evaluation>
(1) Into a 500 mL beaker, 1.69 g of calcium chloride dihydrate was added, and pure water was added to 1000 g to prepare hard water having a hardness of 100 ppm (calcium carbonate equivalent).
(2) 10 g of a solid content 0.1% aqueous solution of each evaluation sample was prepared in a 20 mL screw tube.
(3) 100 g of 10% sodium polyoxyethylene lauryl ether sulfate (10% Kao-made Emar 20C) was prepared to give a 10% surfactant aqueous solution.
(4) Weigh 19.4 g of hard water from (1), 0.50 g of sample aqueous solution from (2), and 0.10 g of aqueous surfactant solution from (3) into a 100 mL screw tube, and avoid bubbles with a magnetic stirrer chip. Was stirred. In this way, an aqueous solution containing a hardness of 97 ppm, a sample of 25 ppm, and a surfactant of 500 ppm was prepared in each screw tube. (As a reference, evaluation was made by adding pure water instead of the sample aqueous solution of (2).)
(5) The height of the liquid level of the aqueous solution in each screw tube adjusted in (4) was recorded.
(6) Each screw tube was inverted 60 times at a rate of about once per second, then placed in a horizontal and stable place, and the height of the bubble surface in each screw tube was recorded.
(7) The bubble height was calculated from the above measurement results using the following equation.
Foam height (cm) = height of the foam surface after stirring−the height of the liquid surface before the stirring bubble suppression rate (%) = (foam height of pure water−bubble height of sample) / (foam height of pure water) × 100
The larger the value of the bubble suppression rate, the better the bubble suppression ability.

<Example 1>
To a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer, 12 moles of ethylene oxide was added to 12 to 14 linear secondary alcohols on average. 84.2 g of the compound added in moles was charged, and the temperature was raised to 128 ° C. with stirring. 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. In this way, Polymer 1 having a solid content of 99.1% was obtained.

<Example 2>
An average of 7 mol of ethylene oxide was added to a linear secondary alcohol having 12 to 14 carbon atoms in a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer. The compound (54.1 g) added with 0.5 mol was charged, and the temperature was raised to 128 ° C. with stirring. 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. In this way, Polymer 2 having a solid content of 98.2% was obtained.

<Comparative Example 1>
A glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 216.6 g of a compound obtained by adding 6 mol of ethylene oxide to 2-ethylhexyl alcohol and heated 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, Polymer 3 having a solid content of 80.1% 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 4 having a solid content of 80.0% was obtained.

<Comparative Example 3>
A glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 135.4 g of a compound having an average of 7 mol of ethylene oxide added to a linear secondary alcohol having 12 to 14 carbon atoms and stirred. The temperature was raised to 128 ° C. 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. In this way, Polymer 5 having a solid content of 77.8% was obtained.

<Comparative example 4>
A glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 135.4 g of a compound having an average of 9 moles of ethylene oxide added to a linear secondary alcohol having 12 to 14 carbon atoms, 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. In this way, a polymer 6 having a solid content of 79.2% was obtained.

<Comparative Example 5>
A glass 500 mL separable flask equipped with a thermometer, reflux condenser, and stirrer was charged with 84.2 g of a compound having an average of 15 moles of ethylene oxide added to a linear secondary alcohol having 12 to 14 carbon atoms and stirred. The temperature was raised to 128 ° C. 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. In this way, a polymer 7 having a solid content of 99.4% was obtained.

Claims (3)

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 structural unit derived from ethylene oxide (EO) and alkylene oxide (AO) having 3 to 20 carbon atoms and having a hydrocarbon group having 1 to 30 carbon atoms at at least one terminal. And the average added mole number of AO is 0.01 to 1 mole with respect to 1 mole average added mole number of EO,
In the graft polymer, the proportion of the structural unit (b) derived from the N-vinyl lactam monomer (B) is 0.01 to 1.5 parts by mass with respect to 1 part by mass of the polyether compound (A). A graft polymer characterized in that The polyether compound (A) has the following formula (1);
R ^1- [X- (EO) _p- (AO) _q -R ² ] _r (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, EO represents an oxyethylene group, AO is the same or different and represents an oxyalkylene group having 3 to 20 carbon atoms, Compound (A) oxyethylene groups per molecule The average number of moles added (s ¹ ) is expressed by the sum of r existing p and is 4.1 to 300. The average number of oxyalkylene groups having 3 to 20 carbon atoms per molecule of the compound (A) The number of added moles (s ² ) is a compound represented by the total of r existing qs, and is 0.01 s ^{1 to} s ^1. r is a number of 1 to 6. The graft polymer according to claim 1, wherein A method for producing the graft polymer according to claim 1, comprising:
The production method includes a step of graft polymerization of a polyether compound (A) and a monomer component containing an N-vinyl lactam monomer (B),
In the polymerization step, the amount of the solvent used is 10 parts by mass or less with respect to 100 parts by mass in total of the polyether compound (A) and the monomer component.