JP6986863B2 - Graft polymer - Google Patents

Description

The present invention relates to graft polymers. More specifically, the present invention relates to a graft polymer useful for detergents, cleaning agents, anti-scale agents, dispersants, thickeners, pressure-sensitive adhesives, adhesives, surface coating agents, cross-linking agents, moisturizers and the like.

Conventionally, a polymer obtained by polymerizing an unsaturated carboxylic acid-based monomer such as acrylic acid, a copolymer with another monomer, a polyether compound, and an unsaturated carboxylic acid-based simple substance such as acrylic acid are used. Graft polymers obtained by graft-polymerizing a weight, vinyl acetate or (meth) acrylic acid ester are detergents, cleaning agents, anti-scale agents, dispersants of various inorganic and organic substances, thickeners, pressure-sensitive adhesives, and adhesives. It is widely used in various applications such as agents, surface coating agents, cross-linking agents, and moisturizing agents. In recent years, as an improved version of the graft polymer, attempts have been made to graft-polymerize N-vinylpyrrolidone to a polyether compound.

Regarding such a graft polymer, Patent Document 1 describes a water-soluble polymer obtained by polymerizing a monomer component containing N-vinylpyrrolidone (B) on a polyether compound (A), wherein the N-vinylpyrrolidone (B) is contained. -Vinylpyrrolidone (B) is disclosed as a water-soluble polymer having an amount of 0.01 to 0.3 parts by weight with respect to 1 part by weight of the polyether compound (A). Further, in Patent Document 2, N-vinylpyrrolidone (b1) is indispensable as a monoethylene in 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% ethylene oxide. The graft component (B), which may contain the sex unsaturated monomer (b2), is graft-polymerized so that (B) is 0.1 to 1.2 parts by weight with respect to 1 part by weight of (A). The monoethylene unsaturated monomer (b2) is a carboxyl group-containing monoethylene unsaturated monomer (b2-1) (provided that the monomer (b2-1) is hydrolyzed. It may be a monomer having a structure that becomes a carboxylic acid (salt) depending on the above) and / or it is composed of a cationic monoethylene unsaturated monomer (b2-2) and contains the carboxyl group. When the sex unsaturated monomer (b2-1) contains a monomer having a structure of becoming a carboxylic acid (salt) by the hydrolysis, a carboxyl group generated by hydrolysis of the monomer having the structure (however). , 50 mol% or more of the structural units derived from the monomer (b2-1) have a carboxyl group, including the carboxyl group). The coalescence is disclosed.

Japanese Unexamined Patent Publication No. 2006-336000 Japanese Unexamined Patent Publication No. 2001-106743

As mentioned above, various graft polymers have been developed and their ability to prevent recontamination against hydrophobic stains has been reported. However, conventional graft polymers include hydrophilic substances such as mud and hydrophobic substances such as sebum and soot. There is a problem that the ability to prevent recontamination against complex stains in which substances are combined in a complex manner is 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 having an excellent ability to prevent recontamination against composite stains containing hydrophobic substances and hydrophilic substances as compared with conventional graft polymers. do.

As a result of various studies on graft polymers, the present inventor polymerizes an N-vinyllactam-based monomer at a specific ratio with respect to a polyether compound having a hydrocarbon group having at least one terminal having 1 to 30 carbon atoms. We have found that the graft polymer obtained is superior to the conventional graft polymer in the ability to prevent recontamination against complex stains, and have arrived at the idea that the above-mentioned problems can be solved brilliantly, and the present invention has been reached.

That is, the present invention is a graft polymer obtained by polymerizing a monomer component containing an N-vinyllactam-based monomer (B) to a polyether compound (A), wherein the polyether compound (A) is 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-based monomer (B) is the polyether compound. (A) A graft polymer that is larger than 0.3 parts by mass and 1.5 parts by mass or less with respect to 1 part by mass.

In the graft polymer, the ratio of the structural unit (b) derived from the N-vinyllactam-based monomer (B) is 0.31 to 1.5 parts by mass with respect to 1 part by mass of the polyether compound (A). Is preferable.

In the above-mentioned 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 number of moles of the oxyalkylene group added per molecule of the compound (A) is preferably 4.5 to 100 mol.

The graft polymer of the present invention has the above-mentioned structure and is more suitable for detergents, cleaning agents, etc. because it has an excellent ability to prevent recontamination against composite stains containing hydrophobic substances and hydrophilic substances as compared with conventional graft polymers. Can be used.

Hereinafter, preferred embodiments of the present invention will be specifically described, but the present invention is not limited to the following description, and can be appropriately modified and applied without changing the gist of the present invention. In addition, a form in which two or three or more of the individual preferable forms of the present invention described below are combined also corresponds to the preferred form of the present invention.

<Graft polymer>
Since the graft polymer of the present invention has an N-vinyllactam group derived from the N-vinyllactam-based monomer (B), it is excellent in adsorptivity and dispersibility in hydrophilic substances such as mud. Further, in the graft polymer of the present invention, the polyether compound (A) having a hydrocarbon group having 1 to 30 carbon atoms has an appropriate hydrophobicity. Excellent adsorptivity and dispersibility for hydrophobic substances.
In the graft polymer of the present invention, the ratio of the structural unit (b) derived from the N-vinyllactam-based monomer (B) to 1 part by mass of the above-mentioned polyether compound (A) is 0.3 parts by mass. It is large and is 1.5 parts by mass or less. As a result, the balance between the N-vinyllactam structure and the structure derived from the polyether compound becomes suitable, and the ability to prevent recontamination, disperse ability, and detergency against complex stains in which mud and the like are combined with sebum and soot in a complex manner. Can demonstrate high performance. Furthermore, since the graft polymer of the present invention has such a structure, it is also excellent in the ability to prevent recontamination against hydrophobic stains and the ability to prevent dye transfer in washing of dyed cloth and the like. The ratio 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, and further preferably 0.38 to 1.0 parts by mass. It is 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-vinyllactam-based monomer (B), and is other than the N-vinyllactam-based monomer (B). It may have a structural unit derived from another monomer (E).
In the graft polymer, the ratio 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). It is more preferably 0 to 0.10 parts by mass, further preferably 0 to 0.05 parts by mass, and most preferably 0 parts by mass. Within the above-mentioned preferable range, it becomes possible to maintain a higher level of anti-contamination ability against composite stains.

<Polyester compound (A)>
The above-mentioned 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 the formula (1), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms, and R ² represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, which is the same or different. Represents a divalent linking group. A ¹ O represents the same or different oxyalkylene group having 2 to 20 carbon atoms. P represents the average number of added moles of ^{A 1 O and 1 to 100.} It is a number. Q is a number of 1 to 6), and is preferably a compound represented by.

^{A 1} O in the above formula (1) represents an oxyalkylene group having 2 to 20 carbon atoms. The number of carbon atoms of the alkylene group is preferably 2 to 15, more preferably 2 to 10, further preferably 2 to 5, particularly preferably 2 to 3, and most preferably 2. These oxyalkylene groups are alkylene oxide adducts, and 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 such 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 of the polyether compound (A) in the present invention (the average number of moles of oxyalkylene groups added per molecule of the compound (A)) is preferably 1 to 100. When the average number of moles added is 100 or less, the viscosity of the polyether compound (A) is in a suitable range, and the graft polymer can be easily produced. It is more preferably 3 to 70, still more preferably 5 to 40, particularly preferably 7 to 30, and most preferably 9 to 20.

When the polyether compound (A) is a compound represented by the formula (1), the average number of moles of the oxyalkylene group added per molecule of the compound (A) is that of the oxyalkylene group present in the formula (1). It is represented by the total number, that is, the sum of q existing ps.
q is a number from 1 to 6, when q is 2 or more, polyether compounds represented by the above formula (1) (A), the different carbon atoms of the hydrocarbon group represented by R ¹ above In addition, it has a structure in which the groups represented by ^{-X- (A 1} O) _p- R ² of the above formula (1) ^{are bonded to each other, and -X- (A 1} O) _p- R ² It does not have a repeating structure in which the group represented by is 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. It is more preferably 3 to 70, still more preferably 5 to 40, and particularly preferably 7 to 30.

^{R 1} in the above formula (1) represents a hydrocarbon group having 1 to 30 carbon atoms. Preferably the number of carbon atoms in the hydrocarbon group of R ¹ is 2 to 24. When the number of carbon atoms is 2 or more, the hydrophobicity of the polyether compound (A) is in a more preferable range, and the ability to prevent recontamination against hydrophobic stains is further improved. Further, when the number of carbon atoms is 24 or less, it is possible to more sufficiently suppress the decrease in the adsorptivity to hydrophobic stains due to the decrease in the motility of the polymer. The number of carbon atoms is more preferably 4 to 22, still more preferably 5 to 20, particularly preferably 6 to 18, still more preferably 7 to 16, and most preferably 8 to 14.
^{R 1} in the above formula (1) may have variations in the number of carbon atoms of the hydrocarbon group at the terminal. 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group and a 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 , Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, 1-hexyl-heptyl group and other linear or branched alkyl groups; cyclic such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Alkyl group; linear or branched chain such as vinyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, octadecenyl group, etc. Alkenyl group; phenyl group, benzyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl group, Examples thereof include an aryl group such as a benzhydryl group and a pyrenyl group.

The R ¹ is preferably an alkyl group or an alkenyl group. More preferably, it is an alkyl group, and even more preferably, it 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, it has a more sufficient effect on the environment. It can be suppressed. Further, if R ¹ is a linear alkyl group, the crystallinity of the graft polymer becomes better, and the viscosity of the graft polymer as a solution becomes preferable.
The linear alkyl group includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group and a pentadecyl group. , Hexadecyl group, heptadecyl group, octadecyl group and other alkyl groups having 1 to 30 carbon atoms are preferable.

R ² represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms the same or different. When R ² is a hydrocarbon group having 1 to 30 carbon atoms, the hydrocarbon group is preferably the same as the ^{above-mentioned R 1.}
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- , -NH-. K is 0 or 1. It is preferably a group represented by.).
The divalent linking groups of X present in q in the compound represented by the above formula (1) may all be the same or different.
The above k is preferably 0. The Z is preferably −O−.
That is, the above X is preferably −O−.

The method for obtaining the above-mentioned 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, the alkylene oxide component can be obtained by polymerizing by a usual method in the presence of a reaction compound as a starting point of polymerization. The compound to be reacted is not particularly limited as long as it is a compound that is the starting point of polymerization of the cyclic ether, and examples thereof include alcohols, amines, hydroxylamines, carboxylic acids and the like, and among them, alcohols and amines. Is preferable. 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. Alcohols; secondary alcohols with 3 to 30 carbon atoms such as isopropyl alcohol and alcohols obtained by oxidizing n-paraffin; tertiary alcohols with 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, and examples of amines include ethylenediamine and polyethyleneimine. These may be used alone or in combination of two or more.

The above-mentioned polymerization method is not particularly limited, and for example, (1) an anionic polymerization method using a strong alkali such as an alkali metal hydroxide or alkoxide, or an anion polymerization method using an alkylamine or the like as a base catalyst, or (2) a metal or semi-metal halogen. A cationic polymerization method using a compound, mineral acid, acetic acid, etc. as a catalyst, (3) a coordination polymerization method using a combination of metal alkoxides such as aluminum, iron, zinc, alkaline earth compounds, Lewis acid, etc., as appropriate. You can select it.

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

(In the formula, R ³ , R ⁴ , R ⁵ , and R ⁶ represent the same or different alkyl groups having 1 to 10 carbon atoms which may have a hydrogen atom or a substituent, and m represents 0 to 0. It represents an integer of 4. n represents an integer of 1 to 3).) It is preferable that the structure is represented by.
The carbon number of the alkyl group in the ^R 3 to R ^6, 1 to 6, and more preferably from 1 to 4. The alkyl group is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
The ^{substituents in R 3 to} R ⁶ are not particularly limited, and examples thereof include a carboxyl group, a sulfonic acid group, and an ester or salt thereof; an amino group, a hydroxyl group and the like.
R ^{3 to} R ⁵ are preferably hydrogen atoms. R ⁶ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
The 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, 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. However, one kind or two or more kinds can be used. As the N-vinyllactam, an unsaturated monomer having a pyrrolidone ring is preferable. More preferably, it is N-vinylpyrrolidone.

<Other monomers (E)>
The graft polymer of the present invention is a graft polymer obtained by polymerizing a monomer component containing an N-vinyllactam-based monomer (B), and the above-mentioned monomer component is an N-vinyllactam-based single amount. It may contain other monomers (E) other than the body (B).
The other monomer (E) is not particularly limited as long as it can be copolymerized with the N-vinyllactam-based monomer (B), and is, for example, (meth) acrylic acid, crotonic acid, tigric acid, 3-. Methyl crotonic acid, 2-methyl-2-pentenic acid, itaconic acid, etc .; unsaturated monocarboxylic acid-based monomers such as these monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts; maleic acid, 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. are unsaturated. Dicarboxylic acid-based monomers; 2-acrylamide-2-methylpropanesulfonic acid, (meth) allylsulfonic acid, vinylsulfonic acid, 2-hydroxy-3-allyloxy-1-propanesulfonic acid, 2-hydroxy-3-butene Monomer having a sulfonic acid group such as sulfonic acid; vinyl phosphonic acid, monomer having a phosphonic acid group such as (meth) allylphosphonic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Hydroxyl-containing alkyl (meth) acrylates such as acrylates, 3-hydroxypropyl (meth) acrylates, 2-hydroxybutyl (meth) acrylates, 4-hydroxybutyl (meth) acrylates, α-hydroxymethylethyl (meth) acrylates; Alkyl (meth) obtained by esterification of (meth) acrylic acid such as methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate and an alcohol having 1 to 18 carbon atoms (meth). Meta) acrylates; Amino group-containing acrylates such as dimethylaminoethyl (meth) acrylates or quaternized products thereof; Amid group-containing monomers such as (meth) acrylamide, dimethylacrylamide and isopropylacrylamide; Vinyl esters such as vinyl acetate Classes; alkenes such as ethylene and propylene; aromatic vinyl-based monomers such as styrene, styrene sulfonic acid and 1-vinyl imidazole; maleimide derivatives such as maleimide, phenylmaleimide and cyclohexylmaleimide; nitriles such as (meth) acrylonitrile Group-containing vinyl-based monomers; aldehyde group-containing vinyl-based monomers such as (meth) achlorine; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; vinyl chloride, vinylide chloride. Examples include unsaturated alcohols such as allyl alcohol and isoprenol.

<Manufacturing method of graft polymer>
The production of the graft polymer of the present invention is not particularly limited, but the polyether compound (A) and the monomer component (N-vinyllactam-based monomer (B) and other monomer (E)) are polymerized. Specific examples and preferable examples of the polyether compound and the monomer component are as described above.
The above polymerization is preferably carried out by bulk polymerization (bulk polymerization). Specifically, the amount of the solvent used in the above-mentioned polymerization reaction is preferably 10% by mass or less with respect to the total amount of the reaction system.

The graft polymer of the present invention is preferably produced by a method of polymerizing the polyether compound (A) and the monomer component in the presence of a polymerization initiator.
The polymerization initiator is not particularly limited, but 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, methylacetate acetate peroxide, and acetylacetone peroxide; tert. -Butylhydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, 2- Hydroperoxides such as (4-methylcyclohexyl) -propanehydroperoxide; di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α, α'-bis (tert-butyl peroxide) ) P-Diisopropylbenzene, α, α'-bis (tert-butylperoxy) p-isopropylhexine, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl Dialkyl peroxides such as -2,5-di (tert-butylperoxy) hexin-3;

tert-Butylperoxyacetate, tert-butylperoxylaurate, tert-butylperoxybenzoate, di-tert-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-Butylperoxyisopropyl carbonate, tert-butylperoxyisobutyrate, tert-butylperoxyviverate, tert-butylperoxyneodecanoate, cumylperoxyneodecanoate, tert-butylperoxy-2 -Ethylhexanoate, tert-butylperoxy-3,5,5-trimethylcyclohexanoate, tert-butylperoxybenzoate, tert-butylperoxymaleic acid, tert-butylperoxyoctate, tert-hexylperoxyviva Peroxy esters such as rate, tert-hexyl peroxyneohexanoate, cumylperoxyneohexanoate, tert-butyl-peroxy-iso-propyl monocarbonate; n-butyl-4,4-bis (tert- Butylperoxy) Valeate, 2,2-bis (tert-butylperoxy) butane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert- Peroxyketals such as butylperoxy) cyclohexane, 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-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, bis- (4-). tert-butylcyclohexyl) peroxydicarbonate, dimyristylperoxydicarbonate, di-methoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di-allyl peroxydicarbonate, etc. Peroxydicarbonates of the above; other organic peroxides such as acetylcyclohexylsulfanyl peroxide, tert-butyl peroxyallyl carbonate and the like can be mentioned. 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 substance, whereby, for example, the graft efficiency is sufficiently improved and the above-mentioned water-soluble weight is efficiently used. It is possible to obtain coalescence. In particular, considering the reaction temperature in the polymerization step and the temperature control during storage, di-tert-butyl peroxide, tert-butyl-peroxy-iso-propyl monocarbonate and / or tert-butyl-peroxy-benzoate Is particularly preferred.
In addition, other polymerization initiators (for example, organic peroxides containing aromatics), chain transfer agents, and reducing agents can be used in combination with the above-mentioned organic peroxides containing at least aliphatics, but in this case, The amount of the 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 the aliphatic. More preferably, it is 100 parts by weight or less.

The amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of all the monomer components used for the polymerization. If it is 0.1 part by weight or more, the polymerization rate to the polyether compound (A) can be further improved and the yield can be further improved, and if it is 30 parts by weight or less, for example, an organic peroxide as a polymerization initiator can be used. When an oxide is used, a manufacturing method having excellent economic efficiency can be used. It is more preferably 3 to 20 parts by weight, still more preferably 5 to 10 parts by weight.
The method of adding the polymerization initiator is not particularly limited, and the initial batch charging may be used, or a continuous charging method such as dropping or split charging may be used, but the initiator which is liquid at room temperature can add the solvent. It is preferable because it can be dropped without using it and is not easily restricted by the addition method. Further, the polymerization initiator may be introduced alone into the reaction vessel, or may be mixed in advance 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-vinyllactam-based monomer and generates a lactam compound such as 2-pyrrolidone. In addition, as the solvent, for example, one in which the chain transfer constant of the monomer used as a raw material to the solvent is as small as possible is preferable. Examples of such a solvent include isobutyl alcohol, n-butyl alcohol, tert-butyl alcohol, isopropyl alcohol, ethylene glycol, diethylene glycol, glycerin, triethylene glycol, propylene glycol, ethylene glycol monoalkyl ether, and propylene glycol monoalkyl ether. Alcohols such as; Diethers such as ethylene glycol dialkyl ether and propylene glycol dialkyl ether; Acetic acid such as acetic acid, ethyl acetate, propyl acetate, butyl acetate, acetate of ethylene glycol monoalkyl ether, and acetate of propylene glycol monoalkyl ether. Systems compounds; etc. may be mentioned, and these may be used alone or in combination of two or more. The alkyl group in the alcohols and diethers is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.

The amount of the solvent used is not particularly limited, but for example, assuming that the entire reaction system is 100 parts by weight, it is preferably 20 parts by weight or less. If it exceeds 20 parts by weight, for example, the graft efficiency of the above-mentioned monomer component may not be sufficient. More preferably, it is 0 parts by weight, that is, substantially solvent-free, which makes it possible to significantly increase the graft efficiency, for example, and obtain a polymer having various performances. As described above, the form in which the above-mentioned polymerization step is carried out without a solvent is also one of the preferred forms of the present invention. The above solvent may be initially charged in a batch or may be added sequentially.

The reaction temperature at the time of the polymerization is not particularly limited, but is preferably 110 to 150 ° C, more preferably 120 to 140 ° C.
The reaction pressure at the time of the polymerization is not particularly limited, and may be, for example, any of normal pressure (atmospheric pressure), reduced pressure, and pressurized. In addition, it is preferable to use normal pressure (atmospheric pressure) because the polymerization can be performed easily and at low cost.
Further, the above polymerization is preferably carried out in an atmosphere of an inert gas such as nitrogen gas, argon gas or carbon dioxide gas, but is not limited thereto.

<Use of graft polymer>
Common uses of the graft polymer of the present invention include, for example, detergent additives, anti-scale agents, dispersants of various inorganic and organic substances, thickeners, pressure-sensitive adhesives, adhesives, surface coating agents, cross-linking agents, and the like. Moisturizers and the like can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "part" means "part by weight" and "%" means "mass%".

<Evaluation of recontamination prevention ability of compound stains (clay-carbon black)>
(1) A cotton cloth (CW98 manufactured by Test fabrics) was cut into a size of 5 cm × 5 cm to prepare a white cloth. The whiteness of this white cloth was measured in advance by the reflectance using a color measurement color difference system SE6000 type manufactured by Nippon Denshoku Kogyo Co., Ltd.
(2) Pure water was added to 1.47 g of calcium chloride dihydrate to make 20 kg, and hard water was prepared.
(3) 10 g of a 1% solid content aqueous solution of each evaluation sample was prepared in a 20 mL screw tube.
(4) 100 g of 4% sodium laurylbenzene sulfonate was prepared and used as an aqueous surfactant solution.
(5) Set the turgot meter to 25 ° C, and in each pot, 1 L of hard water of (2), 5.0 g of the sample aqueous solution of (3), 5.0 g of the surfactant aqueous solution of (4), and carbon black (Foundation). 0.25 g of (manufactured by the 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 pieces of cotton cloth were put and stirred at 100 rpm for 10 minutes. (As a reference, a solution to which pure water was added instead of the sample solution of (3) was also evaluated.)
(6) The water of the white cloth was drained by hand, 1 L of the hard water of (2) was put into a pot, the temperature was adjusted to 25 ° C., and the mixture was stirred at 100 rpm for 2 minutes.
(7) After applying a cloth to a white cloth and drying it while smoothing out wrinkles with an iron, the whiteness of the cotton cloth was measured again by the reflectance with the above color difference meter.
(8) From the above measurement results, the recontamination prevention rate (recontamination prevention ability) was determined by the following formula.
Recontamination prevention rate (%) = (whiteness after cleaning) / (whiteness before cleaning) x 100
The larger the value of the recontamination prevention rate, the better the recontamination prevention ability.

<Evaluation of dispersibility of composite stains (carbon black-clay)>
(1) 2.94 g of calcium chloride dihydrate was put in a 500 mL beaker, and pure water was added to make 500 g, and hard water was prepared.
(2) In a 20 mL screw tube, 10 g of a 0.1% solid content aqueous solution of each evaluation sample was prepared.
(3) 7.51 g of glycine, 1.18 g of ethanol, and 7.00 g of 48% NaOH were put in a 1 L beaker, and pure water was added to make 1000 g, and a glycine buffer solution having a pH of 10.5 was prepared.
(4) Next, a 30 mL test tube having an inner diameter of 16 mm was prepared for the number of evaluation samples, and each of them had 0.03 g of carbon black, 0.30 g of JIS 11 type 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 septum. In this way, a suspended aqueous solution containing 1000 ppm of carbon black, 10000 ppm of clay, and 50 ppm of sample solid content was prepared in each test tube.
(5) After slowly reversing each test tube 60 times, 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 of the supernatant at 380 nm was measured using an ultraviolet-visible spectrophotometer UV-1800 manufactured by Shimadzu Corporation. This absorbance was used as the dispersibility. The larger the absorbance value, the higher the dispersibility.

<Example 1>
A compound in which an average of 20 mol of ethylene oxide is added to a linear primary alcohol having 18 carbon atoms in a 500 mL separable flask made of glass equipped with a thermometer, a reflux condenser, and a stirrer. 135.4 g (hereinafter, also referred to as NC1820) was charged, and the temperature was raised to 128 ° C. with stirring. Then, under stirring, 9750 μL of dit-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 in a constant state at 128 ° C. Dropped from the nozzle. The timing of the start of dropping PBD was defined as the start of the reaction. For each dropping time and dropping sequence, PBD was set to a constant rate at 195 minutes from the start of the reaction, and NVP was set to a constant rate from 20 minutes after the start of the reaction to 225 minutes. After the completion of all the droppings, the reaction solution was kept at 128 ° C. for another 70 minutes and aged to complete the polymerization. Then, 58.3 g of pure water was added. In this way, polymer 1 having a solid content of 80% was obtained. The present polymer 1 was excellent in the ability to disperse composite stains (carbon black-clay).

<Example 2>
An average of 20 mol of ethylene oxide was added to a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer with Sophanol 200 manufactured by Nippon Catalyst Co., Ltd. (a linear secondary alcohol having 12 to 14 carbon atoms). It is a compound and is also referred to as SFT200 below.) 168.5 g of the compound was charged, and the temperature was raised to 128 ° C. with stirring. Then, under stirring, 7800 μL of dit-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 in a constant state at 128 ° C. Dropped from the nozzle. The timing of the start of dropping PBD was defined as the start of the reaction. For each dropping time and dropping sequence, PBD was set to a constant rate at 195 minutes from the start of the reaction, and NVP was set to a constant rate from 20 minutes after the start of the reaction to 225 minutes. After the completion of all the droppings, the reaction solution was kept at 128 ° C. for another 70 minutes and aged to complete the polymerization. Then, 61.7 g of pure water was added. In this way, polymer 2 having a solid content of 80% was obtained.

<Example 3>
An average of 9 mol of ethylene oxide was added to a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer with Sophanol 90 manufactured by Nippon Catalyst Co., Ltd. (a linear secondary alcohol having 12 to 14 carbon atoms). It is a compound and is also referred to as SFT90 below.) 135.4 g was charged and the temperature was raised to 128 ° C. with stirring. Then, under stirring, 9750 μL of dit-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 in a constant state at 128 ° C. Dropped from the nozzle. The timing of the start of dropping PBD was defined as the start of the reaction. For each dropping time and dropping sequence, PBD was set to a constant rate at 195 minutes from the start of the reaction, and NVP was set to a constant rate from 20 minutes after the start of the reaction to 225 minutes. After the completion of all the droppings, the reaction solution was kept at 128 ° C. for another 70 minutes and aged to complete the polymerization. Then, 58.3 g of pure water was added. In this way, the polymer 3 having a solid content of 79% was obtained.

<Example 4>
An average of 9 mol of ethylene oxide was added to a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer with Sophanol 90 manufactured by Nippon Catalyst Co., Ltd. (a linear secondary alcohol having 12 to 14 carbon atoms). It is a compound and is also referred to as SFT90 below.) 168.5 g was charged and the temperature was raised to 128 ° C. with stirring. Then, under stirring, 7800 μL of dit-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 in a constant state at 128 ° C. Dropped from the nozzle. The timing of the start of dropping PBD was defined as the start of the reaction. For each dropping time and dropping sequence, PBD was set to a constant rate at 195 minutes from the start of the reaction, and NVP was set to a constant rate from 20 minutes after the start of the reaction to 225 minutes. After the completion of all the droppings, the reaction solution was kept at 128 ° C. for another 70 minutes and aged to complete the polymerization. Then, 61.7 g of pure water was added. In this way, the polymer 4 having a solid content of 80% was obtained.

<Example 5>
A glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer was added with an average of 10 mol of ethylene oxide to a linear primary alcohol having 12 to 13 carbon atoms and Newcol 2310 manufactured by Nippon Embroidery Co., Ltd. 168.5 g of the compound (hereinafter, also referred to as NC2310) was charged, and the temperature was raised to 128 ° C. with stirring. Then, under stirring, 7800 μL of dit-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 in a constant state at 128 ° C. Dropped from the nozzle. The timing of the start of dropping PBD was defined as the start of the reaction. For each dropping time and dropping sequence, PBD was set to a constant rate at 195 minutes from the start of the reaction, and NVP was set to a constant rate from 20 minutes after the start of the reaction to 225 minutes. After the completion of all the droppings, the reaction solution was kept at 128 ° C. for another 70 minutes and aged to complete the polymerization. Then, 61.7 g of pure water was added. In this way, the polymer 5 having a solid content of 78% was obtained.

<Example 6>
Neucol 1020 (2-ethylhexyl alcohol with an average of 20 mol of ethylene oxide added to a 500 mL separable flask made of glass equipped with a thermometer, a reflux condenser, and a stirrer. 168.5 g (referred to as) was charged, and the temperature was raised to 128 ° C. with stirring. Then, under stirring, 7800 μL of dit-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 in a constant state at 128 ° C. Dropped from the nozzle. The timing of the start of dropping PBD was defined as the start of the reaction. For each dropping time and dropping sequence, PBD was set to a constant rate at 195 minutes from the start of the reaction, and NVP was set to a constant rate from 20 minutes after the start of the reaction to 255 minutes. After the completion of all the droppings, the reaction solution was kept at 128 ° C. for another 70 minutes and aged to complete the polymerization. Then, 61.7 g of pure water was added. In this way, the polymer 6 having a solid content of 79% was obtained.

<Comparative Example 1>
An average of 9 mol of ethylene oxide was added to a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer with Sophanol 90 manufactured by Nippon Catalyst Co., Ltd. (a linear secondary alcohol having 12 to 14 carbon atoms). It is a compound and is also referred to as SFT90 below.) 216.6 g was charged and the temperature was raised to 128 ° C. with stirring. Then, under stirring, 5850 μL of dit-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 in a constant state at 128 ° C. Dropped from the nozzle. The timing of the start of dropping PBD was defined as the start of the reaction. For each dropping time and dropping sequence, PBD was set to a constant rate at 195 minutes from the start of the reaction, and NVP was set to a constant rate from 20 minutes after the start of the reaction to 225 minutes. After the completion of all the droppings, the reaction solution was kept at 128 ° C. for another 70 minutes and aged to complete the polymerization. Then, 68.9 g of pure water was added. In this way, the polymer 7 having a solid content of 79% was obtained.

<Comparative Example 2>
84.2 g of polyethylene glycol 600 (polyethylene glycol having a number average molecular weight of 600) manufactured by Wako Pure Chemical Industries, Ltd. was placed in a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and heated to 128 ° C. under stirring. The temperature was raised. Then, under stirring, 3900 μL of dit-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 in a constant state at 128 ° C. Dropped from the nozzle. The timing of the start of dropping PBD was defined as the start of the reaction. For each dropping time and dropping sequence, PBD was set to a constant rate at 195 minutes from the start of the reaction, and NVP was set to a constant rate from 20 minutes after the start of the reaction to 225 minutes. After the completion of all the droppings, the reaction solution was kept at 128 ° C. for another 70 minutes and aged to complete the polymerization. Then, 30.9 g of pure water was added. In this way, the polymer 8 having a solid content of 80% was obtained.

For the graft polymers obtained in Examples 1 to 6 and Comparative Examples 1 and 2, the structure of the polyether compound and the polymerization ratio of N-vinylpyrrolidone to the polyether compound are shown in Table 1. Furthermore, the ability of these polymers to prevent recontamination of composite stains was measured, and the results are shown in Table 2.

Claims (2)

A graft polymer obtained by polymerizing a monomer component containing an N-vinyllactam-based monomer (B) to a polyether compound (A).
The polyether compound (A) has a hydrocarbon group having 4 to 30 carbon atoms at at least one terminal.
In the graft polymer, the ratio of the structural unit (b) derived from the N-vinyllactam-based monomer (B) is larger than 0.3 parts by mass with respect to 1 part by mass of the polyether compound (A). .5 parts by der less is,
The polyether compound (A) is a compound having an oxyalkylene group, the graft weight of the polyether compound (A) average addition mole number of oxyalkylene groups per molecule, wherein 1 to 20 der Rukoto Combined. The polyether compound (A) is a compound having an oxyalkylene group, and the average number of moles of the oxyalkylene group added per molecule of the compound (A) is 4.5 to 20 mol. Item 2. The graft polymer according to Item 1.