JP6990062B2 - 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) a graft base of a polymer having no monoethylenically unsaturated unit, and (B) polymerization of a cyclic N-vinylamide having a specific structure. Disclosed is a graft polymer containing a side chain of the polymer formed by, wherein the proportion of the side chain (B) in the total polymer is ≧ 60% by mass. Further, Patent Document 2 describes (A) a graft base of a polymer having no monoethylenically unsaturated unit and (B) two different monoethylenically unsaturated monomers having at least one nitrogen-containing heterocycle (B1). ) And (B2), a graft polymer containing a side chain of a polymer formed from the copolymer, wherein the proportion of the side chain (B) in the total polymer is greater than 55% by mass is disclosed.

Japanese Patent Publication No. 2005-509064 Special Table 2005-509065

As described above, various graft polymers have been developed, and Patent Documents 1 and 2 report on the prevention of color transfer 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 rinsing can be performed with a small amount of water. The conventional graft polymer is not sufficient in achieving both the ability to prevent recontamination of composite stains containing hydrophilic substances and hydrophobic substances and the suppression of foaming.

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 capable of achieving both the ability to prevent recontamination of composite stains and the suppression of foaming.

As a result of various studies on graft polymers, the present inventor has found that at least one terminal has a hydrocarbon group having 1 to 30 carbon atoms, and ethylene oxide (EO) and an alkylene oxide (AO) having 3 to 20 carbon atoms. A graft polymer obtained by polymerizing an N-vinyllactam-based monomer at a specific ratio to a polyether compound having a specific ratio of the derived structural unit is excellent in the ability to prevent recontamination of composite stains and to suppress foaming. We have found this and arrived at the present invention with the idea 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-vinyllactam-based monomer (B) to a polyether compound (A), wherein the polyether compound (A) is It has a hydrocarbon group having 1 to 30 carbon atoms at at least one terminal, and has a structural unit derived from ethylene oxide (EO) and an alkylene oxide (AO) having 3 to 20 carbon atoms, and has an average addition molar of AO. The number is 0.01 to 1 mol with respect to 1 mol of the average addition mole of EO, and the above-mentioned graft polymer has a ratio of the structural unit (b) derived from the N-vinyllactam-based monomer (B). , 0.01 to 1.5 parts by mass with respect to 1 part by mass of the polyether compound (A).

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

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

The graft polymer of the present invention has the above-mentioned structure and is excellent in the ability to prevent recontamination of composite stains and suppress foaming, so that it can be suitably used for detergents, cleaning agents and the like.

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 0.01 to 1. 5 parts by mass. 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.
The ratio 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, and further preferably 0.3 to 0.8 parts by mass. It is particularly preferably 0.4 to 0.7 parts by mass, and 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-vinyllactam-based monomer (B), and is other than the N-vinyllactam-based monomer (B). It may have a structural unit (e) derived from another monomer (E).
In the graft polymer, the ratio 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). .. 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.

<Polyether compound (A)>
The above-mentioned polyether compound (A) has a hydrocarbon group having 1 to 30 carbon atoms at at least one terminal, and has a structural unit derived from ethylene oxide (EO) and an alkylene oxide (AO) having 3 to 20 carbon atoms. The average number of moles of AO added is 0.1 to 1 mol with respect to the average number of moles of EO added. Since the polyether compound (A) has such a structure, the solubility of the graft polymer in water is in a suitable range, the defoaming property (defoaming property) is improved, and foaming can be suppressed. .. Further, in the graft polymer, if the average number of moles of AO added is too large, the ability to prevent recontamination of the composite stain and the graft efficiency may decrease. However, if the average number of moles of AO added is in the above range, foam rupture occurs. It has excellent properties (defoaming properties), and can sufficiently suppress the ability to prevent recontamination of composite stains and the deterioration of graft efficiency.
The average number of moles of AO added is preferably 0.01 to 1, more preferably 0.05 to 0.8, and further preferably 0.1 to 0.6 with respect to the average number of moles of EO added. Particularly preferably, it is 0.2 to 0.4, and most preferably 0.25 to 0.36.

The length of the polyethylene glycol chain of the polyether compound (A) (the average number of moles of oxyethylene groups added per molecule of the compound (A)) is preferably 4.1 to 300. When the average number of added moles is 300 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 4.2 to 100, still more preferably 4.3 to 60, still more preferably 4.5 to 50 parts by mass, particularly preferably 4.8 to 30, and most preferably 5. It is 0.0 to 20.

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

In the formula (1), the average number of moles of oxyethylene groups (s ¹ ) per molecule of the compound (A) is represented by the sum of r existing ps 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 is within the above preferable range, but is preferably the same or different, and is preferably 0.1 to 300. It is more preferably 0.3 to 100, still more preferably 0.5 to 50, still more preferably 0.8 to 30, particularly preferably 1.0 to 20, and most preferably 5.0. ~ 15.

In the formula (1), the average number of moles of substance (s ² ) of the oxyalkylene group having 3 to 20 carbon atoms per molecule of the compound (A) is represented by the sum of q existing in r pieces, and is 0.01 s ¹ . ~ ^S1 .
As s2, it is preferable that the range is obtained by multiplying the preferable range of the average number of moles of AO to the above ^- mentioned average number of moles of EO of ¹ by s1.
q is not particularly limited as long as s ² is within the above preferable range, but is preferably the same or different, and is preferably 0.001 to 300. It is more preferably 0.003 to 100, still more preferably 0.005 to 50, still more preferably 0.008 to 30, particularly preferably 0.01 to 20, and most preferably 0.05. ~ 15.

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

The AO in the above formula (1) represents the same or different oxyalkylene group having 3 to 20 carbon atoms. The number of carbon atoms of the alkylene group is preferably 3 to 15. As a result, the foam breaking property of the graft polymer is further improved, and foaming can be suppressed more sufficiently. It is more preferably 3 to 10, still more preferably 3 to 8, particularly preferably 3 to 5, and most preferably 3. These oxyalkylene groups are alkylene oxide adducts, and such alkylene oxides include, for example, propylene oxide (PO), isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, and the like. Examples thereof include tetramethylethylene oxide, butadiene monooxide, octylene oxide, styrene oxide, and 1,1-diphenylethylene oxide. 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 embodiment 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 ^R1 is preferably 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. It is more preferably an alkyl group, and even more preferably 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, it has a more sufficient effect on the environment. It can be suppressed. Further, if R ¹ is a branched alkyl group, the crystallinity of the graft polymer becomes better, and the viscosity of the graft polymer as a solution becomes preferable.
The branched alkyl group includes an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 2-ethylhexyl group, an isooctyl group, a 2,3,5-trimethylhexyl group and a 4-ethyl-. Alkyl groups having 1 to 30 carbon atoms such as a 5-methyloctyl group and a 1-hexyl-heptyl group are preferable.

^R2 represents a hydrocarbon group having the same or different hydrogen atom or carbon atom number of 1 to 30. 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);
_-Yk -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 r 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 to. It represents an integer of 4. n represents an integer of 1 to 3).) It is preferable that the structure is represented by.
The number of carbon atoms of the alkyl group in R ³ to R ⁶ is preferably 1 to 6, and more preferably 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, an ester or a 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 sulphonic acid, 2-methyl-2-pentenoic 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 with sulfonic acid group such as sulfonic acid; Monomer having phosphonic acid group such as vinylphosphonic acid, (meth) allylphosphonic acid; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Phosphonate-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) acrylates such as methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate with alcohols having 1 to 18 carbon atoms (meth). Meta) acrylates; Amino group-containing acrylates such as dimethylaminoethyl (meth) acrylates or quaternized products thereof; Amido group-containing monomers such as (meth) acrylamide, dimethylacrylamide and isopropylacrylamide; Vinyl esters such as vinyl acetate Classes; alkens 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 it can be produced by polymerizing the polyether compound (A) and the monomer component containing the N-vinyllactam-based monomer (B). .. Specific examples and preferable examples of the polyether compound and the monomer component are as described above. The ratio of the N-vinyllactam-based monomer (B) and the other monomer (E) in the monomer component is the structural unit (1 part by mass of the polyether compound (A) in the above-mentioned 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 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, cumenehydroperoxide, diisopropylbenzenehydroperoxide, 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 -2,5-Dialkyl peroxides such as 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-butylperoxyvivarate, 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 to be used is preferably 300 parts by mass or less with respect to 100 parts by mass of the organic peroxide containing at least the aliphatic. More preferably, it is 100 parts by mass or less.

The amount of the above-mentioned polymerization initiator used is not particularly limited, but for example, the polyether compound (A) and the monomer component (N-vinyllactam-based monomer (B) and other monomers (E) used for the polymerization are used. )) Is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass. If it is 0.1 part by mass 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 mass or less, for example, it is an organic peroxide as a polymerization initiator. When an oxide is used, a manufacturing method having excellent economic efficiency can be used. It is more preferably 3 to 20 parts by mass, and even more preferably 5 to 10 parts by mass.
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 N-vinyllactam-based monomers and generates lactam compounds 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 is preferably 20 parts by mass or less with respect to 100 parts by mass of all the monomer components. Thereby, the graft efficiency of the above-mentioned monomer component can be made more sufficient.
In the polymerization step, a form in which the amount of the solvent used is in the above preferable range is also one of the suitable forms of the present invention. That is, it is a method for producing the above-mentioned graft polymer, and the above-mentioned production method is a step of graft-polymerizing the polyether compound (A) and the monomer component containing the N-vinyllactam-based monomer (B). The above-mentioned polymerization step also includes a 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 of the total of the polyether compound (A) and the monomer component. It is one of the inventions.
The amount of the solvent used is more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and most preferably 0 parts by mass, that is, substantially no solvent. As a result, for example, the graft efficiency can be significantly improved, and a polymer having various performances can be obtained.
When a solvent is used, the 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 mass" and "%" means "% by mass".

<Evaluation of the ability to prevent recontamination of composite stains (clay-carbon black)>
(1) A polyester cloth (PW19 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.

<Evaluation of foam suppression>
(1) 1.69 g of calcium chloride dihydrate was put in a 500 mL beaker, and pure water was added to make 1000 g, and hard water having a hardness of 100 ppm (calcium carbonate equivalent) 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) 100 g of 10% polyoxyethylene lauryl ether sodium sulfate (10% Kao Emar 20C) was prepared and used as a 10% aqueous surfactant solution.
(4) Weigh 19.4 g of hard water of (1), 0.50 g of sample aqueous solution of (2), and 0.10 g of surfactant aqueous solution of (3) into a 100 mL screw tube so as not to foam with a magnetic stirrer chip. Was stirred. In this way, an aqueous solution containing 97 ppm of hardness, 25 ppm of sample, and 500 ppm of surfactant was prepared in each screw tube. (As a reference, a solution to which pure water was added instead of the sample aqueous solution of (2) was also evaluated.)
(5) The height of the liquid level of the aqueous solution in each screw tube adjusted in (4) was recorded.
(6) After reversing each screw tube 60 times at a pace of about once per second, it was placed in a horizontal and stable place, and the height of the bubble surface in each screw tube was recorded.
(7) From the above measurement results, the bubble height was determined by the following formula.
Bubble height (cm) = height of bubble surface after stirring-height of liquid level before stirring Bubble suppression rate (%) = (bubble height of pure water-bubble height of sample) / (bubble height of pure water) x 100
The larger the value of the foam suppression rate, the better the foam suppression ability.

<Example 1>
An average of 12 mol of ethylene oxide was added to a linear secondary alcohol having 12 to 14 carbon atoms in a 500 mL separable flask made of glass equipped with a thermometer, a reflux condenser, and a stirrer, and then an average of 3 propylene oxide was added. 84.2 g of the molarly added compound was charged, and the temperature was raised to 128 ° C. with stirring. 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. 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 500 mL separable flask made of glass equipped with a thermometer, a reflux condenser, and a stirrer, and then an average of 2 propylene oxide was added. 54.1 g of the compound to which 5.5 mol was added was charged, and the temperature was raised to 128 ° C. with stirring. 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. In this way, polymer 2 having a solid content of 98.2% was obtained.

<Comparative Example 1>
216.6 g of a compound in which an average of 6 mol of ethylene oxide was added to 2-ethylhexyl alcohol was charged in a 500 mL separable flask made of glass equipped with a thermometer, a reflux condenser and a stirrer, and the temperature was raised to 128 ° C. under 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 3 having a solid content of 80.1% 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 4 having a solid content of 80.0% was obtained.

<Comparative Example 3>
In a glass 500 mL separable flask equipped with a thermometer, a reflux condenser, and a stirrer, 135.4 g of a compound obtained by adding an average of 7 mol of ethylene oxide to a linear secondary alcohol having 12 to 14 carbon atoms is charged and stirred. Below, the temperature was raised to 128 ° C. 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 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 in which an average of 9 mol of ethylene oxide was added to a linear secondary alcohol having 12 to 14 carbon atoms. 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 6 having a solid content of 79.2% was obtained.

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

Claims (3)

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 1 to 30 carbon atoms at at least one terminal, and has a structural unit derived from ethylene oxide (EO) and an alkylene oxide (AO) having 3 to 20 carbon atoms. The average number of moles of AO added is 0.01 to 1 mol with respect to the average number of moles of EO added.
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). A graft polymer characterized by having a mass of 1.5 parts by mass or less . The polyether compound (A) has the following formula (1);
R ^1- [X- (EO) _p- (AO) _q -R ² ] _r (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. EO represents an oxyethylene group. AO represents the same or different oxyalkylene group having 3 to 20 carbon atoms. Oxyethylene group per molecule of compound (A). The average number of added moles (s ¹ ) is represented by the sum of r existing ps and is 4.1 to 300. The average number of oxyalkylene groups having 3 to 20 carbon atoms per molecule of compound (A). The number of added moles (s ² ) is represented by the sum of r existing q, 0.01 s ¹ to s ^1. r is a number of 1 to 6). The graft polymer according to claim 1. The method for producing the graft polymer according to claim 1 or 2.
The production method comprises a step of graft-polymerizing the polyether compound (A) and the monomer component containing the N-vinyllactam-based monomer (B).
The polymerization step is a method for producing a graft polymer, wherein 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.