JP4291723B2 - Vinyl polymer modifier - Google Patents

Description

  The present invention relates to a vinyl polymer modifier. More specifically, the present invention relates to a modifier that can be modified by copolymerization during production of a vinyl polymer.

Conventionally, vinyl polymers such as (meth) acrylonitrile, unsaturated carboxylic acids or salts thereof, alkyl esters of unsaturated carboxylic acids, amides of unsaturated carboxylic acids, halogen-containing monomers, aromatic vinyl monomers and aliphatic In order to modify polymers of vinyl monomers such as hydrocarbon monomers, there is a technology that attempts to incorporate a modifier into the polymer using an anionic modifier having a vinyl group. is there. For example, Patent Document 1 proposes a modifier having a (meth) acryloyl group for the purpose of improving the dyeability of the polymer, antistatic properties, characteristics of a film obtained from the emulsion, and the like. Patent Document 2 proposes a modifier having an allyl group structure for the purpose of obtaining an emulsion having good polymerization stability and good mechanical and chemical stability during emulsion polymerization.
However, recent demands for antistatic properties for resins have become even higher, and conventional modifiers have not been able to provide sufficient antistatic properties. In addition, the aqueous polymer dispersion obtained by emulsion polymerization using a conventional modifier is insufficient in the emulsifying dispersibility of the modifier. The water resistance of the coating film was sometimes insufficient. Further, the stability over time after long-term storage of the aqueous dispersion was insufficient.
JP-A-60-170611 JP 57-28111 A

  An object of the present invention is to provide a vinyl polymer modifier that can exhibit the antistatic property of a vinyl polymer, and that the emulsion of the polymer exhibits good polymerization stability, water resistance of a dry coating film, and stability over time. There is to do.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to achieve the above object.
That is, the present invention provides a vinyl polymer modifier (first) comprising a vinyl monomer (A) represented by the general formula (1) and a vinyl monomer (B) represented by the general formula (2). Invention); one or more selected from the group consisting of (A) and / or (B) and vinyl monomers (C) to (G) represented by general formulas (3) to (7) A vinyl polymer modifier comprising a vinyl monomer (second invention);
A modified vinyl polymer (P1) obtained by copolymerizing the modifier with another vinyl monomer (H); in the presence of the modifier, other vinyl Modified vinyl polymer emulsion (P11) obtained by emulsion polymerization of monomer (H); and presence of vinyl polymer (P ₀ ) containing vinyl monomer (H) as a constituent monomer Below is a modified vinyl polymer (P2) obtained by polymerizing the modifier.

In formula (1), R ¹ is a hydrogen atom or a methyl group, A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 2 to 50, M ¹ is a hydrogen atom or a monovalent or divalent cation, m is 1 or 2 and represents the valence of M ¹ .

In formula (2), R ² and R ³ are residues of an alcoholic hydroxyl group-containing compound, and at least one of R ² and R ³ is a residue of (meth) allyl alcohol or an oxyalkylene ether thereof. M ² is a hydrogen atom or a monovalent or divalent cation, p is 1 or 2, and represents the valence of M ² .

In formulas (3) to (7), R ^{4 to} R ⁹ are residues of the alcoholic hydroxyl group-containing compound, A is an alkylene group having 2 to 4 carbon atoms, Ph is a benzene ring, Q ¹ is a hydrogen atom or —SO _3. M ³ and Q ² are hydrogen atoms or —SO ₃ M ⁴ , M ^{3 to} M ⁷ are monovalent cations, k is 0 or 1, q and r are 10 to 50, s, t and u are 1 to 50 Represents an integer.

The modifier of the present invention provides a vinyl polymer with excellent antistatic properties.
The polymer emulsion obtained by emulsion polymerization using the modifier of the present invention has few aggregates of polymer particles, and the resulting dried coating film has excellent water resistance.
The polymer emulsion using the modifier of the present invention is excellent in long-term stability over time at 40 ° C.

The vinyl monomer (A) and vinyl monomer (B) used in the first invention of the present invention will be described below.
The vinyl monomer (A) in the present invention is represented by the general formula (1), and A in the general formula (1) is an alkylene group having 2 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, and a butylene group. It is done. Preferably, it is an ethylene group and / or a propylene group, and if A is an ethylene group and / or a propylene group, the stability in the case of producing an aqueous dispersion of a vinyl polymer described later is more easily exhibited.
The type A may be used alone or in combination of two or more. Moreover, when using 2 or more types, a block structure or a random structure may be sufficient.

n is an integer of 2 to 50, preferably 2 to 30, and more preferably 3 to 15. If n is 2-30, since compatibility with other vinyl monomers is good and copolymerization is easy, the resulting coating film has good water resistance.
It is more preferable that two or more of n A are propylene groups, and it is particularly preferable that only propylene groups are 3 to 20 from the viewpoint of water resistance of the coating film.

M ¹ is a hydrogen atom or a monovalent or divalent cation, such as an alkali metal (such as lithium, sodium, potassium and rubidium), an alkaline earth metal (such as beryllium, magnesium, calcium and strontium), ammonium, Examples thereof include organic amine cations (such as alkanolamines having 1 to 6 carbon atoms and alkylamines having 1 to 6 carbon atoms). Of these, preferred are alkali metals and ammonium, and particularly preferred are sodium, potassium and ammonium.
m is 1 or 2, preferably 1.

(A) can be obtained by a known method. Specifically, (i) a method in which alkylene oxide is added to (meth) acrylic acid, sulfated with a sulfating agent, and converted into a salt if necessary.
In (i), as a method of adding alkylene oxide to (meth) acrylic acid, in the presence of a catalyst in a pressure-resistant reaction vessel, preferably at a temperature of 30 to 120 ° C., preferably at a pressure of 0 to 0.6 MPa, the alkylene oxide is randomly selected. Or the method of adding a block is mentioned.
A known catalyst can be used as the catalyst. For example _{BF 3, BCl 3, AlCl 3} , FeCl 3 and SnCl ₃ or the like Lewis acids, and their complex [e.g. BF ₃ ether complex, BF ₃ tetrahydrofuran complex _{(BF 3 · THF)];} H 2 SO 4, HClO 4 Protic acids such as KClO ₄ , NaClO _{4 and} other alkali metal perchlorates; Ca (ClO ₄ ) ₂ and alkaline earth metal perchlorates such as Mg (ClO ₄ ) ₂ ; Al (ClO ₄ ) perchlorate or the like of a metal other than the above such as _3, hydroxides of alkali metals or alkaline earth metals [KOH, NaOH, CsOH, Ca (OH) 2 , etc.]; alkali metal or alkaline earth metal oxides (K ₂ O, CaO, BaO, etc.); an alkali metal (Na, K, etc.), and their hydrides (NaH, KH and the like); triethylamine, amines such as trimethylamine and the like It is below. Of these, BF ₃ ether complex and BF ₃ tetrahydrofuran complex (BF ₃ · THF), KOH, NaOH or CsOH are preferred.
Examples of the sulfating agent include fuming sulfuric acid, sulfuric acid, chlorosulfuric acid, sulfamic acid, and the like. In the reaction, if necessary, a reaction such as dichloroethylene, dichloropropane, methyl ethyl ketone, and / or hydrocarbon (such as cyclohexane) is performed at a reaction temperature of −10 ° C. to 100 ° C. for 1 to 50 hours. Thereafter, neutralization is performed with an alkali metal or alkaline earth metal hydroxide, aqueous ammonia, an organic amine, or the like. When sulfamic acid is used as the sulfating agent, this operation is not necessary because a salt is formed.

Vinyl monomer (B) in the present invention is represented by the general formula (2), R ² and R ³ in the general formula (2) is a group given by removing hydroxyl groups from alcoholic hydroxyl group-containing compound, R ² and At least one of R ³ is a residue obtained by removing a hydroxyl group from (meth) allyl alcohol or an oxyalkylene ether thereof. Specific examples of the alcoholic hydroxyl group-containing compound include the following.
(A-1) Alcohols 1) Aliphatic saturated alcohols C1-C24, preferably 8-20 linear or branched saturated alcohols (methanol, ethanol, n- and iso-propanol, butanol, pentanol, hexanol) , Heptanol, octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, eicosyl alcohol, henecosyl alcohol, Docosyl alcohol, tricosyl alcohol and tetracosyl alcohol, etc.)
2) aliphatic unsaturated alcohol cis- or trans- unsaturated aliphatic alcohol having 2 to 24 carbon atoms (ethenyl alcohol, 1-propenyl alcohol, allyl alcohol, methallyl alcohol, butenyl alcohol, pentynyl alcohol, hexenyl) Alcohol, peptenyl alcohol, nonenyl alcohol, decenyl alcohol, undecenyl alcohol, dodecenyl alcohol, tridecenyl alcohol, tetradecenyl alcohol, pentadecenyl alcohol, hexadecenyl alcohol, hepta Decenyl alcohol, octadecenyl alcohol, nonadecenyl alcohol, eicosenyl alcohol, henecocenyl alcohol, dococenyl alcohol, tricocenyl alcohol and tetracocenyl alcohol, oxo method Alcohol (Shell Oil Ltd., "Dobanol", such as manufactured by Mitsubishi Chemical "Diamond Doll"), secondary alcohol (made by UCC "Tergitol"), etc.)
3) Alicyclic alcohols and aromatic alcohols cyclopentanol, cyclohexanol, benzyl alcohol, etc.)

(A-2) Active hydrogen-containing compound Specific examples of the polyoxyalkylene ether active hydrogen group-containing compound include the following.
1) Examples of alcohols (a-1) 2) Phenols Phenols having a hydrocarbon group having 0 to 24 carbon atoms (octylphenol, nonylphenol, dodecylphenol, polystyrylphenol, polystyrylcumylphenol, polystyrylcresol) etc)
3) Carboxylic acid fatty acid having 8 to 24 carbon atoms (lauric acid, oleic acid, stearic acid, etc.)
4) Amines C8-24 alkylamines (laurylamine, stearylamine, etc.)
Examples of the alkylene oxide constituting the polyoxyalkylene ether chain include alkylene oxides having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, butylene oxide, two or more of these) and substituted alkylene oxides (such as styrene oxide). It is done. Among the alkylene oxides, preferred are ethylene oxide, propylene oxide, and combinations thereof (random, block).
The added mole number of alkylene oxide is usually 1 to 10, preferably 1 to 5.

Among R ² and R ³ , one is preferably a residue of (meth) allyl alcohol, particularly allyl alcohol, and the other is linear or branched aliphatic saturation having 8 to 20 carbon atoms, particularly 10 to 15 carbon atoms. It is a residue of alcohol.

M ² may be the same as M ¹ described above, and preferred ones are also the same. P is 1 or 2, and preferably 1.

(B) can be synthesized by the method described in Japanese Patent No. 2747780. For example, first, 1 to 1.2 mol of the first alcohol to be introduced is charged into a reaction vessel with respect to maleic anhydride or fumaric acid, and reacted at 40 to 120 ° C. for 1 to 30 hours to obtain a monoester. If necessary, an organic solvent (toluene, xylene, hexane, cyclohexane, dichloroethane, dichloropropane, etc.) can be used for the reaction.
Then, a diester body is obtained by adding 1-1.3 mol of 2nd alcohol, halogenated hydrocarbons, etc. (for example, allyl chloride etc.), and esterifying with respect to the obtained monoester body. The catalyst in the diesterification reaction is an acidic catalyst (such as p-toluenesulfonic acid) when using an alcohol, and a tertiary amine (such as triethylamine or tri-n-propylamine) when using a halogenated hydrocarbon. It is 1 to 30 hours at 40 to 130 ° C.
Thereafter, 0.9 to 2 equivalents of an alkali metal sulfite (sodium salt, potassium salt, etc.) or 0.45 to 1 equivalents of an alkali metal disulfite (sodium salt, potassium salt, etc.), diester of the obtained diester form A solvent such as water, methanol, propanol and / or acetone in an amount of 0.2 to 5 times the total weight of the body and alkali metal sulfite is added and reacted at 50 to 130 ° C. for 1 to 20 hours to give a monomer (B ) Can be obtained.

  In the second invention of the present invention, the vinyl monomers (C) to (G) used in combination with (A) and / or (B) will be described below.

The vinyl monomer (C) is represented by the general formula (3), and R ⁴ in the general formula (3) is a residue obtained by removing the hydroxyl group from the alcoholic hydroxyl group-containing compound. For example, R ² and R described above The same group as ³ is mentioned. A is an alkylene group having 2 to 4 carbon atoms, and examples thereof include the same groups as A described above.
q represents an integer of 10 to 50. Q ¹ is a hydrogen atom or —SO ₃ M ³ , and M ³ is a monovalent cation, such as an alkali metal (lithium, sodium, potassium, rubidium, etc.), ammonium, an organic amine cation (having 1 to 6 carbon atoms). Alkanolamines and alkylamines having 1 to 6 carbon atoms). Preferred among M ³ are alkali metals and ammonium, and particularly preferred are sodium, potassium and ammonium. k is 0 or 1, and 0 is particularly preferable.
Monomer (C) can be synthesized by the method described in JP-A-62-221431. As an example of a commercial item, Aqualon RN series (Daiichi Kogyo Seiyaku Co., Ltd.) is mentioned.

The monomer (D) is represented by the general formula (4), and R ⁵ in the general formula (4) is a residue obtained by removing the hydroxyl group from the alcoholic hydroxyl group-containing compound. For example, R ² and R ³ described above The same group is mentioned. A is an alkylene group having 2 to 4 carbon atoms, and examples thereof include the same groups as those described above for A. .
r represents an integer of 10 to 50. Q ² is a hydrogen atom or —SO ₃ M ⁴ , and M ⁴ is a monovalent cation. Examples thereof include the same as those described above for M ^3, and preferred examples are also the same.
The monomer (D) can be synthesized by the method described in JP-A-62-2104802. As an example of a commercial item, Adekaria soap ER or NE series (Asahi Denka Kogyo Co., Ltd. product) is mentioned.

Monomer (E) is represented by the general formula (5), R ⁶ and R ⁷ in the general formula (5) is a group given by removing hydroxyl groups from alcoholic hydroxyl group-containing compounds, for example, the aforementioned R ² and R The same group as ³ is mentioned. A is an alkylene group having 2 to 4 carbon atoms, and examples thereof include the same groups as those described above for A.
s and t represent the integer of 1-50. M ⁵ is a monovalent cation, and examples thereof include those similar to M ³ described above, and preferred ones are also the same.
The monomer (E) can be synthesized by the method described in JP-A No. 62-11534. An example of a commercially available product is Antox MS-60 (manufactured by Nippon Emulsifier Co., Ltd.).

The monomer (F) is represented by the general formula (6), and R ⁸ in the general formula (6) is a residue obtained by removing the hydroxyl group from the alcoholic hydroxyl group-containing compound. For example, the same as R ² and R ³ described above The group of is mentioned. M ⁶ is a monovalent cation, and examples thereof include those similar to M ³ described above, and preferred ones are also the same.
The monomer (F) can be synthesized by the method described in JP-A-58-203960. As an example of a commercially available product, LATEMUL S series (manufactured by Kao Corporation) can be mentioned.

The monomer (G) is represented by the general formula (7), and R ⁹ in the general formula (7) is a residue obtained by removing the hydroxyl group from the alcoholic hydroxyl group-containing compound. For example, the same as R ² and R ³ described above The group of is mentioned. A is an alkylene group having 2 to 4 carbon atoms, and examples thereof include the same groups as those described above for A. u represents an integer of 1 to 50. M ⁷ is a monovalent cation, and examples thereof include those similar to M ³ described above, and preferred ones are also the same.
A monomer (G) is compoundable by the method described in Unexamined-Japanese-Patent No. 2001-163938. As an example of a commercial item, Aqualon KH series (Daiichi Kogyo Seiyaku Co., Ltd.) is mentioned.
Among the monomers (C) to (G), (D) and (G) are preferable, and a monomer (D) in which k in the general formula (4) is 0 is more preferable.

  The modifier of the first invention is a modifier consisting only of (A) and (B), and the modifier of the second invention has (A) and (B) as essential components (C) to (G) 1) or more modifiers selected from (C) to (G) as essential components, and (B) as essential components (C). ) To (G) are included. Among the second inventions, preferred are (A) and (B) as essential components and a modifier comprising at least one selected from (C) to (G), and (A) as an essential component (C) to A modifier comprising at least one selected from (G), and particularly preferred is a modifier comprising at least one selected from (C) to (G) with (A) and (B) as essential components. It is.

  The weight ratio of (A) and (B) in the modifier of the present invention is preferably 99/1 to 30/70, more preferably 95/5 to 50/50, and particularly preferably 90/10 to 75/25. It is. When the weight ratio is 99/1 to 30/70, when an aqueous dispersion of a polymer is produced, aggregates are not generated and the polymerization stability tends to be good.

  The weight ratio of (A) and / or (B) in the modifier of the second invention of the present invention is 60% or more (in the following, unless otherwise specified,% represents% by weight). Preferably, it is 80% or more. If it is 60% or more, when an aqueous dispersion of a polymer is produced, aggregates are not generated and the polymerization stability tends to be good.

The modified vinyl polymer (P1) of the present invention is a polymer obtained by copolymerizing the aforementioned modifier and another vinyl monomer (H). One or more kinds of vinyl monomers can be mentioned.
(H1) Nitrile group-containing monomer (meth) acrylonitrile etc. (h2) Unsaturated carboxylic acid or salt thereof (meth) acrylic acid, maleic acid, fumaric acid and itaconic acid, etc., or their alkali metals (sodium and potassium etc.) ), Ammonia, alkaline earth metals (calcium, magnesium, etc.), alkanolamines having 1 to 6 carbon atoms, or alkylamines having 1 to 6 carbon atoms (h3) esters of unsaturated carboxylic acids (Meth) acrylates with alcohols having 20 alkyl groups (methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and 2-ethylhexyl); glycols (ethylene glycol, propylene glycol, 1,4-butanediol, Polyethylene glycol and Mono- or di (meth) acrylates such as (propylene glycol); diesters or half esters of maleic acid, fumaric acid or itaconic acid with the above alcohols, etc. (h4) amides of unsaturated carboxylic acids, etc. (h5) Halogen atom-containing monomers Vinyl chloride, vinylidene chloride, chloroprene, etc. (h6) Aromatic vinyl monomers Styrene, α-methylstyrene, chlorostyrene, vinyltoluene, divinylbenzene, etc. (h7) Aliphatic hydrocarbon monomers Ethylene , Propylene, butadiene, isobutylene, etc. (h8) Carboxylic acid vinyl ester or (meth) allyl ester Vinyl acetate, vinyl propionate, divinyl phthalate, allyl acetate, diallyl phthalate, etc. Preferred among these (H1), (h2), (h3), (h6), (h7), (h8) and combinations thereof are particularly preferred, and (meth) acrylonitrile, (meth) acrylic acid, ( (Meth) acrylic acid ester, styrene, butadiene, vinyl acetate and combinations of two or more thereof.

  In the modified vinyl polymer (P1) in the present invention, the weight ratio of the modifier is preferably 0.1 to 70%, more preferably 0.5 to 20% based on the weight of (H), Especially preferably, it is 1 to 15%. If the total weight of the modifier is 0.1% or more, when the aqueous dispersion of (P1) is produced, aggregates are hardly generated and the polymerization stability is good, and if it is 70% or less, The dry film produced from the aqueous dispersion of P1) has good water resistance.

(P1) can be obtained by a known method, and examples thereof include the following methods.
(P-1) Mediumless method A modifier, (H), a polymerization initiator and, if necessary, a chain transfer agent are charged into the reactor, and after the inside of the container is replaced with nitrogen, the temperature is from room temperature to 150 ° C. with stirring. For 1 to 30 hours. The reactor may be charged all at once or by a dropping method.
(P-2) Medium method The method is the same as (p-1) except that a medium is used. The medium is water; aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol and isopropanol; acetone; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; lower carboxylic acid alkyl esters such as ethyl acetate and butyl acetate; ethers such as tetrahydrofuran and diethyl ether; hydrocarbons such as cyclohexane, toluene and n-hexane; halogens such as dichloroethane, dichloromethane and trichloroethane Hydrocarbons; and amide compounds such as dimethylformamide can be used.
Examples of the polymerization form in (p-1) include solution polymerization, emulsion polymerization, and suspension polymerization.

  Examples of the polymerization initiator that can be used in the production of (P1) include inorganic peroxides (persulfates such as ammonium persulfate and potassium persulfate), organic peroxides (diacyl peroxide such as benzoyl peroxide and the like), and dialkyl peroxides. For example, di-t-butyl peroxide, hydroperoxide such as cumene hydroperoxide), azo compounds (azoisobutyronitrile, azobisdimethylvaleronitrile, etc.) and inorganic or organic peroxides and reducing agents (Sulphites such as sodium sulfite; acidic sulfites such as sodium hydrogen sulfite; ferrous salts such as ferrous ammonium sulfate and the like). Of these, inorganic peroxides are preferred. The amount of the polymerization initiator used is usually 0.01 to 2%, preferably 0.05 to 1% with respect to the vinyl monomer.

  As chain transfer agents, mercaptans (such as dodecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, polyoxyethylene glycol di-2-mercaptoethyl ether), thiuram disulfide, xanthogen disulfide, phenol, sulfur, selenium, phosphines , Carbon tetrachloride, amines, nitroso compounds and the like. The amount of the chain transfer agent used is usually 0.01 to 10%, preferably 0.1 to 5% with respect to the vinyl monomer.

The modified vinyl polymer emulsion (P11) of the present invention is obtained by emulsion polymerization of (H) in the above method (p-2) using water as a medium and in the presence of the aforementioned modifier. Vinyl polymer emulsion. In the production of (P11), it is preferable that the modifying agent has an emulsifying action, and among (A), n in the general formula (1) is preferably 3 to 15, particularly preferably 5 to 13, Among B), one of R ² and R ³ in the general formula (2) is preferably an alkyl group having 10 to 15 carbon atoms.
An emulsifier (I) other than the modifier of the present invention may be used for the purpose of improving the emulsion dispersion stability during the emulsion polymerization step. The amount of (I) used is 0.1 to 50%, preferably 1 to 20%, based on the weight of the modifier of the present invention. Examples of (I) include the following, and two or more of these may be used in combination.

(I1) an anionic surfactant;
A carboxylic acid or ether carboxylic acid salt having a hydrocarbon group having 8 to 24 carbon atoms [(poly) oxyethylene (degree of polymerization = 1 to 100) sodium lauryl ether acetate, etc.], a hydrocarbon group having 8 to 24 carbon atoms Sulfate ester salt or ether sulfate ester salt [(poly) oxyethylene (degree of polymerization = 1 to 100) sodium lauryl sulfate, etc.], sulfosuccinate having a hydrocarbon group having 8 to 24 carbon atoms [mono- or dialkyl sulfosuccinate ester di Or monosodium, (poly) oxyethylene (degree of polymerization = 1-100) mono or dialkyl sulfosuccinate di- or monosodium, etc.], (poly) oxyethylene (degree of polymerization = 1-100) coconut oil fatty acid monoethanolamide sodium sulfate , Hydrocarbon groups having 8 to 24 carbon atoms Sulfonates [sodium dodecylbenzenesulfonate, etc.], phosphate esters having a C 8-24 hydrocarbon group [sodium lauryl phosphate, (poly) oxyethylene (degree of polymerization = 1-100) lauryl ether phosphorus Acid sodium etc.], fatty acid salts [sodium laurate, triethanolamine laurate, etc.], acylated amino acid salts [sodium coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N-coconut] Oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid sodium, lauroylmethyl-β-alanine sodium, etc.].

(I2) a nonionic surfactant;
Aliphatic alcohol (carbon number 8-24) alkylene oxide (carbon number 2-8) adduct (polymerization degree = 1-100), (poly) oxyalkylene (carbon number 2-8, polymerization degree = 1-100) Higher fatty acid (carbon number 8-24) ester [polyethylene glycol monostearate (polymerization degree = 20), polyethylene glycol distearate (polymerization degree = 30), etc.], polyvalent (divalent to 10-valent or higher) alcohol fatty acid (Carbon number 8-24) ester [glyceryl monostearate, ethylene glycol monostearate, sorbitan monolaurate, etc.], (poly) oxyalkylene (carbon number 2-8, degree of polymerization = 1-100) multivalent (divalent) -10 valence or higher) alcohol higher fatty acid (carbon number 8-24) ester [polyoxyethylene monolaurate (polymerization) = 10) Sorbitan, polyoxyethylene (degree of polymerization = 50) dioleic acid methyl glucoside, etc.], fatty acid alkanolamide [1: 1 type coconut oil fatty acid diethanolamide, 1: 1 type lauric acid diethanolamide, etc.], (poly) oxy Alkylene (carbon number 2-8, polymerization degree = 1-100) alkyl (carbon number 1-22) phenyl ether, (poly) oxyalkylene (carbon number 2-8, polymerization degree = 1-100) alkyl (carbon number 8) -24) Amino ether and alkyl (carbon number 8-24) dialkyl (carbon number 1-6) amine oxide [lauryl dimethylamine oxide etc.] etc. are mentioned.

(I3) a cationic surfactant;
Quaternary ammonium salt type [stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, ethyl sulfate lanolin fatty acid aminopropylethyl dimethyl ammonium, etc.], amine salt type [diethylaminoethylamide stearate lactate, dilaurylamine] Hydrochloride, oleylamine lactate, etc.].

(I4) an amphoteric surfactant;
Betaine-type amphoteric surfactants [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, laurylhydroxysulfobetaine, lauroylamidoethylhydroxy Ethyl carboxymethyl betaine hydroxypropyl phosphate sodium and the like] and amino acid type amphoteric surfactants [sodium β-laurylaminopropionate and the like].

The weight of the modifier remaining in (P11) is preferably 35% or less, more preferably 20% by weight or less based on the weight of the modifier used.
If it is 35% or less, the water resistance of the dry film prepared from the emulsion is good.

The vinyl polymer (P2) of the present invention was modified by polymerizing the aforementioned modifier in the presence of the vinyl polymer (P ₀ ) having the aforementioned (H) as a constituent monomer. Vinyl polymer.
(P ₀ ) can be obtained by the same method as (p-1) or (p-2) described above except that only (H) is used as a monomer.
In the case of producing (P ₀ ) by the method (p-2), and in the case of emulsion polymerization, it is preferable to use the above-mentioned emulsifier (I) other than the modifier of the present invention as an emulsifier, The amount of (I) used is preferably 1 to 10%, more preferably 2 to 8%, based on the total weight of the monomers.
Moreover, when manufacturing (P2), the weight ratio of the modifier based on the weight of (P ₀ ) is preferably 1 to 20%, more preferably 2 to 10%.
(P2) is a method similar to (p-1) or (p-2) described above, wherein a modifier is added in the presence of (P ₀ ), and a temperature of room temperature to 150 ° C. for 1 to 30 hours. It can be obtained by reacting. The emulsion (P2) obtained by the emulsion polymerization method is particularly excellent in stability over time. Moreover, the coating film obtained from this emulsion has water resistance and hydrophilicity, and has the effect that the contact angle of water is low.

<Example>
In the following, the present invention will be specifically described with reference to synthesis examples and examples, but the present invention is not limited to these examples.

Synthesis Example 1 [Synthesis of Compound (A-1) Represented by General Formula (1)]
Add 100 parts of propylene oxide methacrylate adduct (“Blenmer PP-500” manufactured by NOF Corporation) and 100 parts of methyl ethyl ketone in a glass reaction vessel, and cool to 5 ° C. To this, 20 parts of chlorosulfonic acid was dropped over 3 hours and aged at 10 ° C. for 5 hours. After adding 200 parts of water and 3.6 parts of sodium hydroxide to this, methyl ethyl ketone was distilled off under reduced pressure to obtain 121 parts of a 36% aqueous solution of sodium sulfate (A-1) of propylene oxide methacrylate adduct. It was.

  As the compound (B-1) represented by the general formula (2), “Eleminol JS-2” [manufactured by Sanyo Chemical Industries, Ltd .: alkyl (carbon number 12 to 13) sodium allylsulfosuccinate (solid content 38%)] It was used.

  As a compound (C-1) shown by General formula (3), "Aqualon HS-20" [Daiichi Kogyo Seiyaku Co., Ltd. product: solid content 97% or more] was used.

  As the compound (D-1) represented by the general formula (4), “ADEKA rear soap SE-10N” [manufactured by Asahi Denka Kogyo Co., Ltd .: solid content 99% or more] was used.

  As the compound (E-1) represented by the general formula (5), “Antox MS-60” [manufactured by Nippon Emulsifier Co., Ltd .: solid content 90%] was used.

  As the compound (F-1) represented by the general formula (6), “Latemul S-180” [manufactured by Kao Corporation: solid content 50%] was used.

  As a compound (G-1) shown by General formula (7), "Aqualon KH-10" [Daiichi Kogyo Seiyaku Co., Ltd. product: solid content 97% or more] was used.

Example 1
A mixture of 8 parts of (A-1) and 2 parts of (B-1) was put into a 5 mmHg vacuum dryer at 40 ° C. and dried for 5 hours to remove moisture, and the modifier (AB-1) was added to 3. 6 parts were obtained.
In a nitrogen atmosphere, 50 parts of methyl methacrylate, 2 parts of (AB-1) and 0.1 part of lauroyl peroxide are charged into a glass mold, polymerized by heating at 60 ° C. for 4 hours, and a polymer having a thickness of 2 mm I got a plate. After cooling, the polymer taken out from the mold was a glassy resin with good transparency. When the surface resistivity of this resin plate was measured by the method of JIS K6911-1979, it was 7 × 10 ¹⁰ Ω and the antistatic property was good.

Comparative Example 1
(A-1) 10 parts were put into a 5 mmHg vacuum drier at 40 ° C. and dried for 5 hours to remove moisture, thereby obtaining 3.6 parts of a modifier (A′-1).
Under a nitrogen atmosphere, 50 parts of methyl methacrylate, 2 parts of (A′-1) and 0.1 part of lauroyl peroxide were charged into a glass mold, and a polymer plate having a thickness of 2 mm was obtained in the same manner as in Example 1. After cooling, the polymer taken out from the mold was a glassy resin with good transparency. The surface resistivity of this resin plate was measured by the method of JIS K6911-1979 and found to be 5 × 10 ¹¹ Ω.

Examples 2-13
In a pressurized reaction vessel equipped with a stirrer, a dropping cylinder, a nitrogen gas inlet tube and a thermometer, water 102 parts, styrene 45 parts, methyl methacrylate 9 parts, methacrylic acid 4 parts, sodium persulfate 1 part, lauryl mercaptan 0.2 Parts and (A-1) to (G-1) of the number of parts described in Table 1 were added, and the system was replaced with nitrogen gas under stirring. Then, 37 parts of butadiene was injected from the dropping cylinder, and 30 hours at 50 ° C. The polymerization reaction was further carried out at 85 ° C. for 5 hours. By stripping unreacted monomers under reduced pressure and adjusting the pH to 9.5 with an aqueous sodium hydroxide solution, SBR polymer emulsions (P11-1) to (P11-12) having a solid content of 47.9% are obtained. It was.

Comparative Examples 2-4
As shown in Table 1, comparative SBR was performed in the same manner as in Example 2 except that only one of (A-1), (B-1) and Na dodecylbenzenesulfonate (DBS) was used. System polymer emulsions (P11′-1) to (P11′-3) were obtained.

  The performance of the obtained emulsion was evaluated by the following method. The results are shown in Table 2.

Polymerization stability test;
100 parts of each emulsion was filtered through a 150 mesh wire mesh, the residue on the wire mesh was washed 3 times with 30 parts of water, and the residue was dried at 130 ° C. for 45 minutes to obtain the dry residue weight. The weight percentage of the dry residue with respect to 100 parts of the emulsion was calculated. The smaller the drying residue, the better the polymerization stability.

Water resistance test of the dried coating;
Each emulsion was spread on a glass slide and dried at 60 ° C. for 8 hours and further at 20 ° C. for 24 hours to form a coating having a thickness of 0.2 mm. The water resistance of this coating was tested by the water drop test method of JIS K-6828. The case where the appearance of the coating after immersion for 240 hours was completely transparent was evaluated as “◯”, the case where it was slightly whitened, and the case where it was whitened ×.

Examples 14-25
In a container similar to Examples 2 to 13, 102 parts of water, 45 parts of styrene, 9 parts of methyl methacrylate, 4 parts of methacrylic acid, 1 part of sodium persulfate, 0.2 part of lauryl mercaptan and the number of parts of DBS described in Table 3 were charged. Under stirring, the inside of the system was replaced with nitrogen gas, and 37 parts of butadiene was injected from the dropping cylinder, and a polymerization reaction (polymerization reaction-1) was performed at 50 ° C. for 30 hours and further at 85 ° C. for 5 hours. By stripping unreacted monomers under reduced pressure and adjusting the pH to 9.5 with an aqueous sodium hydroxide solution, an SBR polymer emulsion (solid content 47.9%) was obtained. To this emulsion, the parts (A-1) to (G-1) shown in Table 3 and 1 part of sodium persulfate were further added, followed by polymerization reaction (polymerization reaction-2) at 75 ° C. for 3 hours. Combined emulsions (P2-1) to (P2-12) were obtained.

Comparative Examples 5-7
As shown in Table 3, in the polymerization reaction-2, a comparative SBR system was prepared in the same manner as in Example 6 except that only one of (A-1), (B-1) and DBS was used. Polymer emulsions (P2′-1) to (P2′-3) were obtained.

  The performance of the obtained emulsion was evaluated by the following method. The results are shown in Table 4.

Daily stability test;
Immediately after the production of each emulsion, the same polymerization stability test as described above was performed. Separately, 100 parts of each emulsion was placed in a 1.5 times volume glass bottle, sealed, and stored in a constant temperature bath at 40 ° C. for 6 months.
The emulsion after storage at 40 ° C. for 6 months was subjected to the same polymerization stability test as described above.
The larger the difference between the results of the polymerization stability test immediately after the production of each emulsion and after storage at 40 ° C. for 6 months, the lower the stability over time. The results are shown in Table 4.

  The vinyl polymer modifier of the present invention is used to modify various vinyl polymers, for example, for imparting antistatic properties such as ABS resin and acrylic resin, for paints, coating agents, adhesives and pressure-sensitive adhesives. It can be suitably used for the purpose of, for example, stability over time to the vinyl polymer emulsion and imparting water resistance to the dried film.

Claims (3)

A vinyl polymer modifier comprising a vinyl monomer (A) represented by the general formula (1) and a vinyl monomer (B) represented by the general formula (2), the vinyl polymer Is a nitrile group-containing monomer, unsaturated carboxylic acid or salt thereof, unsaturated carboxylic acid ester, unsaturated carboxylic acid amide, halogen atom-containing monomer, aromatic vinyl monomer, aliphatic hydrocarbon monomer And a vinyl polymer modifier comprising as a constituent monomer at least one member selected from the group consisting of a saturated carboxylic acid vinyl ester or (meth) allyl ester .
[In the formula (1), R ¹ is a hydrogen atom or a methyl group, A is an alkylene group having 2 to 4 carbon atoms, n is an integer of 2 to 50, M ¹ is a hydrogen atom or a monovalent or divalent cation, m Is 1 or 2, and represents the valence of M ¹ . ]
[In formula (2), R ² and R ³ are residues of an alcoholic hydroxyl group-containing compound, and at least one of R ² and R ³ is a residue of (meth) allyl alcohol or an oxyalkylene ether thereof. M ² is a hydrogen atom or a monovalent or divalent cation, p is 1 or 2, and represents the valence of M ² . ] Vinyl polymerization-body modifier according to claim 1 by weight ratio (A) / (B) is 99 / 1-30 / 70 of the monomer (A) and the monomer (B). The modifier for vinyl polymers according to claim 1 or 2 , wherein two or more of n A's in the monomer (A) are propylene groups.