JPH02265943A - Polymer dispersion and its production - Google Patents

Abstract

PURPOSE:To obtain a polymer dispersion useful as, e.g. a mordant for fixing a dye for antiirradiation and antihalation in a photographic field by adding a polymer having an anionic functional group to an aqueous dispersion of a polymer having a quat. ammonium salt. CONSTITUTION:The title polymer dispersion is an aqueous dispersion containing a polymer having a quat. ammonium salt represented by the formula (wherein A is a unit derived from a monomer having at least two copolymerizable, ethylenically unsaturated groups one of which is contained in the side chain; B is a unit derived by copolymerizing an ethylenically unsaturated monomer; R<1> is H, an alkyl or an aralkyl; L is a bivalent 1-20C bonding group; R<2>, R<3> and R<4> are each a 1-20C alkyl or au aryl, X<-> is an anion, m is 0 or 1 ; x, y and z are molar percentages; x is 0-60; y is 0-95; and z is 5-100) and a polymer having an anionic functional group.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a polymer dispersion and a polymer in which an aqueous dispersion of a polymer having a quaternary ammonium salt and a polymer having a 7-ionic group coexist. Regarding the method for producing a dispersion, mordants for dyes, especially mordants for fixing round dyes for preventing irradiation or preventing halation in the photographic field;
A mordant for fixing dyes in diffusion transfer photography;
and conductive materials (e.g. 5solid 5tate
Ionics/J 24iLJ (/Yl@), and polymer dispersions and polymer dispersions useful as antistatic agents, especially antistatic agents in the photographic field), etc. Concerning methods of manufacturing things.

(Prior Art) Conventionally, the production of a crosslinked polymer dispersion (latex) having a quaternary ammonium salt structure has been described, for example, in US Pat. Ris
r, Tata J, Tokukaisho! J-303J1, same jter λ
/ri7≠! No., same tλ-30, 2≠2, same 6-ko 3≠
As described in Publication No./J, etc., a copolymerizable monomer containing at least two ethylenically unsaturated groups, an ethylenically unsaturated monomer 1, and a vinyl monomer having a quaternary ammonium salt structure. - is emulsified in water using a surfactant and emulsion polymerized using a polymerization initiator. Emulsifying a monomer (for example, vinylbenzyl chloride) having a group in the molecule that reacts with the sexually unsaturated monomer 1 and a tertiary amine to form a quaternary ammonium salt using a surfactant, There are known methods such as emulsion polymerization using a polymerization initiator, followed by a polymer reaction (sometimes using an auxiliary solvent), and then reacting with a tertiary aban to form a crosslinked dispersion polymer. It is being

Furthermore, a non-crosslinked polymer dispersion can also be synthesized by using the same method.

By these methods, a polymer dispersion having good dispersion stability can be obtained. However, it has been extremely difficult to prepare a dispersion in which a polymer having an anionic functional group is added to these polymer dispersions so that they coexist.

That is, when a polymer having an anionic functional group is added to an aqueous dispersion of a polymer having a quaternary ammonium salt, which is a cationic group, aggregation occurs due to strong interaction between the cationic and anionic groups. It is extremely difficult to re-disperse the aggregates that have formed, and in most cases, polymers with anionic functional groups have a salt structure (e.g. C00N a , C00K , S O
3N a.

-8O□K), this was not possible.

(Problems to be Solved by the Invention) An object of the present invention is to provide a polymer dispersion in which a polymer dispersion having a quaternary ammonium salt and a polymer having an anionic functional group coexist, and a polymer dispersion as described above. The object of the present invention is to provide a method for stably producing the same without the formation of aggregates.

(Means for Solving the Problems) As a result of intensive studies, the present inventors found that (1) a polymer dispersion having at least one kind of quaternary ammonium salt as a constituent component and a polymer having an anionic functional group; Coexisting aqueous polymer dispersion. (2) after adding at least/glaze ethylenically unsaturated monomers having at least one anionic functional group to a polymer dispersion containing repeating units having at least one quaternary ammonium salt; ,
It has been found that the above object can be achieved by a method for producing an aqueous polymer dispersion obtained by carrying out a polymerization reaction.

In addition, in this application, a polymer dispersion (A) having a quaternary ammonium salt and a polymer (B) having an anionic functional group
coexistence means that the molecules of (A) and (B) are in a mixed state; some of the molecules of (A) and (B) are in a mixed state; and the molecules of (A) and (B) are in a mixed state. Refers to a state in which the two exist separately or in a mixture.

The polymer dispersion obtained by the present invention will be explained in detail below.

First, the polymer dispersion having at least seven quaternary ammonium salts in the present invention can be prepared by the following general formula [13
It is expressed as

General formula [I] In the formula, A is a monomer unit copolymerized with a copolymerizable monomer having at least one copolymerizable ethylenically unsaturated group and containing at least l-') in the side chain. represents. B represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. R1 represents a hydrogen atom, a lower alkyl group or an aralkyl group. L is 7-20
represents a divalent linking group having 5 carbon atoms. R, R, R
' may be the same or different, each with 7
It represents an alkyl group having ~20 carbon atoms, a substituted alkyl group, an aryl group having 6 to 20 carbon atoms, and a substituted aryl group.

Any λ or more groups among R2, R, and R%L may be mutually connected to form a cyclic structure together with a base atom.

Xθ represents a gap ion. m represents Q or /.

X%Ys" represents the mole percentage of each component, X is O or Shibuo"1, and y is O or Shiri! , 2 represents a value from j to 100.

To explain the above general formula (N) in detail, examples of monomers in A include divinylbenzene, ethylene glycol dimethacrylate-1, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol Diacrylate %'l'-hequinanediol diacrylate, neonitylglycol dimethacrylate, tetramethynonodimethacrylate, etc., and this P
) Ticyhinylben-y/, ethylene glycol dimethacrylate is particularly preferred.

Examples of ethylenically unsaturated heptamers in B are ethylene, propylene, i-butene, imbutene, styrene, α
-Methylstyrene, vinyl lactone.

Monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), esters or amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n -hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, 1) -hexyl acrylate% coethyl hexyl acrylate L/-t,
acrylamide, N-methylacrylamide), monoethylenically unsaturated compounds (e.g. acrylonitrile) or dienes (e.g. butadiene, isoprene), including styrene, 1)-butyl methacrylate,
Particularly preferred are methyl methacrylate. B may contain two or more types of the above-mentioned heptad units.

In addition, as B, a monomer having a group in the molecule that reacts with a tertiary amine to produce a quaternary ammonium salt (e.g., vinylbenzyl chloride) or a hydrolyzate thereof (e.g., hydroxymethylstyrene) can be used. etc. are included. these are.

It is an unreacted product or by-product when performing a polymer reaction with a tertiary amine.

R is a hydrogen atom or a lower alkyl group (e.g. methyl, ethyl, n-propyl, n-, butyl, n-aval, n-hexyl) or an aralkyl group (e.g. tF
ibe/zyl) is preferred, and among these, a hydrogen atom or a methyl group is particularly preferred.

L represents a divalent linking fund having l to about Q carbon atoms, specifically fX"+ (-J"-X2+O2-X"-1)+J3-
X”)-e, J'3-.

p q r
Represented by s. X %X %X ,X
may be the same or different, -COO--OCO-
l -CON- (R represents a hydrogen atom, an alkyl group having a carbon number/-j, or a substituted alkyl group having a carbon number/--), -
co--so□ has the same meaning as above, R6 has the same meaning as alkylene having 7 to about 100 carbon atoms, RFi hydrogen atom, alkyl group (carbon number 1 to t),
It may be a substituted alkyl group (representing carbon number (7 to 6)), and represents an alkyl group, a substituted alkylene group, an arylene group, a substituted arylene group, an aralkylene group, or a mearalkylene group.

p%q% 1% S and t represent O or /.

These do not become O at the same time.

Examples of the substituents that may be further substituted include a halogen atom, a nitro group, a cyan group, an alkyl group,
Substituted alkyl group, alkoxy group, substituted alkoxy group, -
A group represented by NHCOR (R8 represents an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, an aralkyl group, a substituted aralkyl group), -NH8O2R (R is the same as above), -8OR (R is the same as above) ), -8O,
! Examples include R (R is the same as above, -COR8 (R and R are the same as above), and the like.

Jl, J, J, J may be the same or different groups (R9, RIG may be the same or different from each other, hydrogen atom, alkyl group, substituted alkyl 17x2#i
, an R-substituted phenyl group, an aralkyl group, (R9 and RIO have the same meanings as above), an amine group (which may be substituted with an alkyl group), a hydroxyl group, and a group that forms a hydroxyl group by hydrolysis.

Of the linking groups represented by L, alkylene/
groups (e.g. methylene group, ethylene group, trimethylene group,
hexamethylene group, etc.), phenylene group (e.g., 0-phenylene &, p-phenylene group, m-phenylene group, etc.), arylene group, etc. However, R represents an alkylene group having 1 to about 1 carbon atoms. ), -Co□--Co2-R1
2- (However, R represents an alkylene group, a phenylene group, or an arylene alkylene group.), -CONH-R12-(
However, LR represents the same as above, ), -CON-R1
2- (However, R and R are the same as above -CONH--CO-C
I(2-CH2-CO2-CH2CH2CH2--CO
NHCH□-CONHCHCH--CONHCI(2C
Particularly preferred are H2CH2 and the like. R, TL, R are
Alkyl group having 7 to 20 carbon atoms or 6 to 20 carbon atoms
an aryl group having Q carbon atoms or from 7 to 20
Preference is given to aralkyl groups having 5 carbon atoms, each of which may be the same or different. These alkyl groups, aryl groups, and aralkyl groups include substituted alkyl groups,
Includes substituted aryl groups and substituted aralkyl groups.

The alkyl group is an unsubstituted alkyl group (for example, methyl,
Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 1-butyl, n-amyl, isoamyl, n-
1=xyl, cyclohexyl, n-heptyl, n-octyl, -1ethylhexyl, n-nonyl, n-decyl,
n-dodecyl); the carbon atom of the alkyl group is preferably /
-/, 2 pieces. More preferably 1 to 10 carbon atoms
It is individual. Examples of substituted alkyl groups include alkoxyalkyl groups (e.g. methoxymethyl, methoxyethyl,
Methoxybutyl, ethoxyethyl, ethoxypropyl,
Methoxybutyl, butoxyethyl, butoxypropyl,
butoxybutyl, vinylodiethyl), cyanoalkyl groups (e.g., λ-cyanoethyl, 3-siarabrubyl,
≠-cyanobutyl), halogenated alkyl groups (e.g., cofluoroethyl, cochloroethyl, 3-fluoropropyl), alkoxycarbonylalkyl groups (e.g., ethoxycarbonylmethyl), allyl groups, coptenyl groups, propargyl groups, and the like.

Examples of the aryl group include unsubstituted aryl groups (e.g. phenyl, naphthyl); examples of substituted aryl groups include alkylaryl groups (e.g. comethylphenyl, 3-methylphenyl, Hiro-methylphenyl, ≠-ethylphenyl,
F-propylphenyl, ≠-term-butylphenyl), alkoxyaryl groups (e.g. ≠-methoxyphenyl, 3-methoxy7ale, Hiro-ethoxyphenyl), aryloxyaryl groups (e.g. term-phenoxyphenyl), etc. It will be done. The aryl group preferably has 6 to 10 carbon atoms, more preferably 6 to 70 carbon atoms. Particularly preferred is a phenyl group.

Examples of the aralkyl group include unsubstituted aralkyl groups (e.g. benzyl, phenethyl, diphenylmethyl, naphthylmethyl); substituted aralkyl groups such as alkylaralkyl groups (e.g. V-methylbenzyl, co-, j-dimethylbenzyl, ≠-in propylbenzyl)S alkoxyaralkyl group, (e.g. Eva 4=-methoxybenzyl, san-ko)-+shibe/zyl), cyanoaralkyl group, (e.g. Hiro-77/benzyl), per70roalkoxyaralkyl group
4, (e.g., tif4'--? metafluoropropoquin benzyl group, Hiro-undecafluorohexyloxypenzyl group, etc.), no-rogenated aralkyl group, (e.g., Eva, ≠-
chlorobenzyl group, Hiro-bromobenzyl group, 3-chlorobenzyl group, etc.).

The number of carbon atoms in the aralkyl group is preferably 7 to /J,
Preferably the number is 7 to ii. Among these, benzyl group, 7
Particularly preferred is the enethyl group.

xeF! , s ion, such as... rogane ion (e.g. chloride ion, bromide ion), alkyl or aryl sulfonate ion (e.g. meta/sulfonic acid,
Ethanesulfo/acid, benzenesulfo'Ms p -toluenesulfonic acid), acetate ion, sulfate ion, nitrate ion/etc., and chlorine ion.

Acetate ion and sulfate ion are particularly preferred.

Further, it is also preferable that two or more arbitrary groups of L, R2, R3, and R4 are bonded to each other to form a cyclic structure together with the nitrogen atom. Preferred cyclic structures to be formed include pyrrolidines, a piperidine ring, a morpholine ring, a pyridine ring, an ibadazole ring, and a quinuclidine ring. Particularly preferred are biC1 lysine ring 1 morpholine ring, piperidine ring, imidazole ring, and pyridine ring.

m represents 0 or /'ft, preferably l.

X can be from 0 to Q mol, preferably from Q to 4 co mol, more preferably from Q to 3 Q mol.

y is from O to yz mol%, preferably from 0 to mol%, more preferably from O to 4/-Omol%.

2 is! to 100% by mole, preferably 10 to 100% by mole, more preferably ≠0 to 100% by mole
It's morchi.

Next, the ethylenically unsaturated monomer having at least one anionic functional group used in the present invention will be explained below.

Examples of anionic functional groups include -COOH group, -8o
Examples include H group, -8o2H group, -op(OH)2 group (or its monoalkyl ester group), -0803H group, and the like. These anionic groups may be in the form of respective salts, such as alkali metal salts (eg, Na salts), ammonium salts (eg, salts with ammonia, methylamine, dimethylamine, etc.).

Examples of ethylenically unsaturated monomers having a strong anionic functional group are shown below in non-dissociated form, but are not limited thereto.

HOCOCHri CHCOOH.

As mentioned above, each of these monomers may be used in the form of a salt structure.

In the present invention, the ethylenically unsaturated monomer having at least/more anionic groups added to the polymer dispersion may be 2is or more.

Moreover, at that time, an ethylenically unsaturated monomer having no anionic group may be used in combination.

Examples of the ethylenically unsaturated monomer that may be used in combination include compounds selected from the same group as the ethylenically unsaturated monomer represented by B, as described above.

In the present invention, the amount of the ethylenically unsaturated monomer having an anionic functional group to be added can be changed depending on the amount of the quaternary ammonium salt in the polymer dispersion, but preferably / to 100 molti, particularly preferably! to 100 molti.

However, when a monomer having an anionic group is used in the form of a salt structure, the amount added is preferably / or less relative to the quaternary ammonium salt in the polymer dispersion. ! molty, particularly preferably 3 to 70 molty.

In addition, the ethylenically unsaturated monomer that does not have an anionic group and is used in combination can be added in any amount as required, but the monomer that has an anionic group
The amount added is preferably about 200 to 200 moles, and particularly preferably 0 to 100 moles.

Below, regarding the polymer dispersion used in the present invention, a polymer (a) having a quaternary ammonium salt and an ethylenically unsaturated monomer having an anionic group are included at least /a! The polymer (b) obtained by polymerizing the monomers contained in the polymer (b) will be specifically exemplified in this order, but the present invention is not limited thereto. (The ratio of (a) and (b) represents the molar percentage of the amount of quaternary ammonium salt and the anionic group in the monomer having anionic functional group.)
The method for synthesizing the polymer dispersion according to the invention is described in detail below.

First, a monomer dispersion having at least one kind of quaternary ammonium salt represented by the general formula [1] is prepared, for example, by JP-A-Shoj.
1) It can be synthesized by a known method as described in No. 97≠j.

The polymer represented by the general formula [1] of the present invention is:

Copolymerizable monomers, ethylenically unsaturated monomers generally containing at least four ethylenically unsaturated groups as described above;
and tertiary amines having the general formula (e.g. trimethylamine, triethylabane, trilobylamine, NiN-dimethylbenzylamine, N-methylpiperidine, N-methylmorpholine, pyridine, Hiro-methylpyridine, etc.)
It can be obtained by quaternizing it.

In addition, the polymer represented by the general formula CI) of the present invention includes a copolymerizable monomer containing at least one ethylenically unsaturated group, an ethylenically unsaturated monomer, and the following general formula (where B, i%L , m%X is the same as shown above)
, R2, R3, L, m are the same as those shown above) and are unsaturated (e.g., N,N-dimethylanoethyl, methacrylate), N,N-diethylabanoethyl methacrylate), N,N-dimethylaminoethyl acrylate-4,N,N-diethylaminoethyl acrylate, N-(N,N-dimethylaminopropyl)acrylamide, N-(N,N-dihexylaminomethyl)acrylamide , 3-(≠-pyridyl)propyl acrylate, N-ethylaminomethylstyrene% N, N-dimethylaminomethylstyrene, N,N-diethylaminomethylstyrene% N IN-dipropylaminomethylstyrene, N-vinylbe/ After polymerization with a compound having the structure R'-X (in the formula, R', X are (same as shown above) (e.g., p-)luenesulfo/methyl acid, dimethyl sulfate, diethyl sulfate, ethyl bromide, n-propyl bromide, allyl chloride, n-butyl bromide, chloro-λ-butene, ethyl chloroacetate) f-t, n-hexyl bromide% n-octyl bromide; aralkylating agents such as benzyl chloride, benzyl bromide, p-nitrobenzyl chloride, p-chlorobenzyl chloride, p-methylbenzyl chloride, p-isopropylbenzyl chloride, dimer such as delbenzyl chloride, p-methoxybenzyl chloride, p--'</tafluoropropenyloxypenzyl chloride, naphthyl chloride, or diphenylmethyl chloride, preferably N p
) It can also be obtained by quaternization with methyl luenesulfonate, dimethyl sulfate, diethyl sulfate, benzyl chloride).

Furthermore, the polymer represented by the general formula (I) of the present invention can be used in JP-A-42-Jul! It can be synthesized using a method similar to the method described in No. 2, or the method described in JP-A No. 6 JJJJ.

In this case, the polymer represented by the general formula (1) is a copolymerizable monomer having at least λ of the above ethylenically unsaturated groups, an ethylenically unsaturated monomer, and the general formula % is as shown above. unsaturated monomers (e.g., ttj:, N-hinylbenzyl-N).

N, N-1J methyl ammonium chloride IJ)", N-vinyl be/zil-N, N, N-17 engineering fk77 monium chloride % N-vinyl be/zil-N, N.

N-tributylammonium chloride, N-vinylbenzyl-N,N,N-to'Jhexylammonium chloride, N-vinylbenzyl-N-dodecylhydridinium chloride, N-vinylbe/zyl-N-methylmorpholinicum Chloride, N'-vinylbenzyl-N-benzylimip'yv':ymucro17, &-vinyl-N
-hexylpyridinium bromide, N(λ-acryloyloxyethyl)-N,N,N-)riethera/monium chloride, N+3-acrylamidopropyl)-N,
It can also be obtained by polymerization with N,N-triethylammonium chloride (%N, 3-acrylamidopropyl)-N,N,N-)butylammonium bromide, etc.).

The above polymerization reaction is performed using a generally known emulsion polymerization method.

In emulsion polymerization, a radical polymerization initiator is emulsified in water or a mixed solvent of water and a water-miscible organic solvent (e.g., methanol, ethanol, acetone, etc.) using at least one emulsifier. Generally used to range from JOoC to about 100'C, preferably from +00C to about 100'C.
It is carried out at a temperature of 'C. Amount of water-miscible organic solvent: Q~ioo% by volume, preferably 0~ioo% with respect to Hirosui
jO%.

The polymerization reaction is usually carried out at 0°0! relative to the monomer to be polymerized. −
j, lji% of a radical polymerization initiator and, if necessary, 0.
It is carried out using an emulsifier having a weight rating of 7 to IQ. Examples of polymerization initiators include azobis compounds, peroxides, hydro/R-oxides, redox catalysts, such as potassium persulfate, ammonium persulfate, tert-butyl peroctoate, benzoyl oxide, isopropyl perphonate, 2. Examples include ≠-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydrono-hair oxide, dicumyl peroxide, azobisisobutyronitrile, and JJ'-azobis(coamidinopropane) hydrochloride.

Emulsifiers are anionic, cationic, and amphoteric.

In addition to nonionic surfactants, there are also water-soluble polymers. Nine examples are Lauri/#! Soda, sodium dodecyl sulfate, sodium l-octoxycarbonylmethyl-7-octoxycarbonyl meta/sulfonate, sodium laurylnaphthalene sulfonate, laurylben+! ! /
Sodium sulfonate, sodium lauryl phosphate, cetyltrimethylammonium chloride, dodecyltrimethylammonium chloride, N-2-ethylhexylpyridinium chloride, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, polyvinyl alcohol, Tokusho! J-A
Examples include emulsifiers and water-soluble polymers described in No.

In emulsion polymerization, depending on the purpose, a polymerization initiator,
It goes without saying that the concentration, % polymerization temperature, reaction time, etc. can be varied widely and easily.

The above reaction to form a quaternary ammonium salt generally takes about j0C
It is carried out at a temperature of 0 to 30°C, but especially +CJ
o 'C-r o c'C Kaho 1 L i.

Next, the polymerization of an ethylenically unsaturated monomer containing an anionic columnar monomer in the present invention will be explained.

First, an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer having an anionic functional group of at least /m is added to the polymer dispersion having the quaternary ammonium salt. The entire amount may be added instantly, or may be added dropwise over several minutes to about an hour. There are no particular restrictions on the temperature when adding the monomer, but it is preferably
The range is from ec to tOoC. Further, it is preferable to stir the polymer dispersion during addition. When adding the ethylenically unsaturated monomer, the monomer itself may be added as is, or if necessary, an auxiliary solvent (e.g., water or an organic solvent such as methanol, ethanol, proponol-resistant, acetate, ethyl acetate, acetonitrile, etc.) may be added. The solution may be diluted or dissolved with a solvent or a mixed solvent thereof.

Polymerization of these post-added ethylenically unsaturated monomers can be carried out using a method similar to that used in conventional solution polymerization reactions.

Polymerization reactions generally range from about JOOC to TOOOC.

Preferably, it is carried out at a temperature of about 4 Ao'c to about 0°C.

Moreover, the polymerization reaction is 0.0! with respect to the ethylenically unsaturated monomer to be polymerized. -j Polymerization can be carried out using a radical initiator. As the radical initiator that can be used, those selected from the same group as those mentioned above can be used. This radical initiator may be added after the addition of the ethylenically unsaturated monomer is completed, or may be added simultaneously with the ethylenically unsaturated monomer or before addition.

(9) In the polymerization reaction, the above-mentioned emulsifier may be further added as necessary.

It goes without saying that in the polymerization reaction of ethylenically unsaturated monomers of the present invention, the polymerization initiator, concentration, polymerization temperature, reaction time, etc. can be varied widely and easily.

The higher the polymerization rate of the polymer dispersion when adding the ethylenically unsaturated monomer of the present invention, the better, preferably 10% to 16%! ~ioo%
It is.

As mentioned above, in the present invention, the amount of the ethylenically unsaturated monomer having an anionic functional group to be added is as follows:
The am of the quaternary ammonium salt in the polymer dispersion can be varied as necessary, but is preferably from 1 to 100 mol, particularly preferably! No, 20
It is 0 morti.

However, when using a monomer having an anionic group in the form of a salt structure, the amount added is preferably/or not relative to the quaternary ammonium salt in the polymer dispersion. molti, particularly preferably 3 to 70 molti.

In addition, the ethylenically unsaturated monomer having no anionic group that is used in combination can be added in any amount as required, but the amount added is about O to QQ molar relative to the monomer having an anionic group. are preferred, and particularly preferred are Q to ioo morti.

The production method of the present invention is characterized in that an anionic monomer is first added to a cationic polymer dispersion in order to coexist with the anionic polymer, and then polymerization is carried out.

As a result, a stable polymer dispersion can be obtained even if an anionic polymer is coexisting.

Here, "1 stable" means that there is no coarse particles due to agglomeration etc. (size of several microns or more) or sedimentation of particles during the production of the polymer dispersion, and the produced polymer dispersion is It means that the particle size does not easily change over time and does not cause precipitation.

Ninth, the polymer dispersion of the present invention can be manufactured very easily since all the manufacturing steps can be carried out in one container, and there is no need to use a large amount of solvent.

The polymer dispersion obtained according to the present invention is usefully used as a mordant or an antistatic agent in the photographic field.

The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 (Synthesis of Exemplary Compound 1) Synthesis of O polymer dispersion (/-a) /7jOd of distilled water was placed in a reaction vessel, degassed with nitrogen gas, and Nirasantrax H-μj (JθChi aqueous solution )lh
Oxl, chloromethylstyrene λ 06oy (i, 2 mol), divinylbenzea/j, 0p (o, i mol) were added and heated to 0c.

700 yd of distilled water degassed with nitrogen gas plus potassium persulfate, If, and 0.2 yd of degassed distilled water plus 0.2 yd of sodium bisulfite! jI was added at the same time, and the mixture was heated and stirred for 2 hours. Roughly add the same amount of potassium persulfate and sodium sulfite mixture as above, raise the temperature to 700C, and continue heating and stirring for 3 hours.

The resulting latex was cooled to room temperature and diluted with distilled water 100x.
1737 (7.7 mol) of N-methylmorpholine was added. Then slowly raise the temperature to 7o 0C,
The mixture was heated and stirred for 2 hours. After cooling to room temperature, it was filtered, and the remaining inorganic salt and N-methylmorpholine were removed by ultrafiltration to obtain a polymer dispersion mordant (exemplified compound/-a).

The obtained polymer had a solid concentration of t and y% by weight, and the cationized nitrogen atom gold cap was determined to have a concentration of 73×10 by titration.
(mol/lP latex). The average particle diameter of the latex was 127 nm (measured using a Coulter submicron particle analyzer Nikka Kiki ■).

Polymerization of acrylic acid in Q polymer dispersion (/-a) The synthesized polymer dispersion (/-a) JOOP was placed in a reaction vessel and while stirring at room temperature under a nitrogen stream, acrylic acid Hiroshi, J
'Yl! (-COOH/'total nitrogen atoms = '/
4c) was dissolved in distilled water tjy and added dropwise over a period of 2 minutes. After dropping, heat to 70°C and
．． -'-azobis(2-amidinopropane) hydrochloride (commercially available from Wako Tsumugi Pharmaceutical ■ under the name y-to) o,
A solution prepared by dissolving arp in 10 g of distilled water was added a total of λ times every hour, and the temperature was further raised to ro 0c and stirring was continued for 3 hours.

After cooling, the mixture was filtered to obtain a polymer dispersion having a solid content r and a weight average particle size ii nm (measured by the same method as above).

In this experiment, no deposits due to agglomeration of particles were observed on the flask wall or stirring blade, and the resulting dispersion had low viscosity and was extremely stable even after several months.

Synthesis was carried out in exactly the same manner as in Examples λ to Koji Series 1, except that the same polymer (/-a) was used and the amount of acrylic acid added was changed. The amount of acrylic acid added and the polymerized red are summarized in Table 1 below.

Also in this experiment, for the flask wall and stirring.

No deposits due to agglomeration of particles were observed, and the series of dispersions obtained had low viscosity and remained extremely stable even after 7 months.

Examples J to 7 The polymer dispersion (/-a) λoop of Example 1 was placed in a reaction vessel, and while stirring at room temperature under a stream of oxygen, various amounts of potassium styrene sulfinate (Table 1) were added. )
was dissolved in distilled water (2Q1) and added dropwise over 2 minutes. fI! After completing the fourth step, heat to 700CK,
-Azobis(coamidinopropa/)hydrochloride (commercially available from Wako Tsumugi Pharmaceutical ■ under the name V-tO) o, 01
A solution dissolved in ft-distilled water was added a total of times every 7 hours, and the temperature was further raised to 100℃ and stirring was continued for 3 hours. After cooling, the desired polymer was dispersed by heating. A series of synthesis results (Examples!, 6, 7) with different amounts of potassium styrene sulfinate added are shown in Table 1.

In this experiment as well, 7. No deposits due to agglomeration of particles were observed on the walls or for stirring, and the resulting dispersion had a low viscosity and was extremely stable even after several months.

Example r? The polymer dispersion (/-a) of Example / and Zθo1 were placed in a reaction vessel, and while stirring at room temperature under a steady stream of air, acrylic acid and sodium hydroxide in an amount of /10 equivalent of the added acrylic acid were added to distilled water≠ The solution dissolved in OP was added dropwise over 2 minutes. (Amount of acrylic acid added, see Table λ) liii
After completing step I, heat to 70°C, 2. ．． 2'-Azobis(,2-7midinoprononin)hydrochloride (
V-j (Wako Tsumugi Yoshi commercially available under the name 7) 0.0jp with distilled water! - add the solution dissolved in λ a total of λ times every hour,
Furthermore, the temperature was raised to 0c and stirring continued for J hours.

After cooling, it was filtered to obtain the desired polymer dispersion. Results of each synthesis performed by changing the amount of acrylic acid added (Example 1)
? ) is shown in Table 1.

In this experiment, no deposits due to agglomeration of particles were observed on the flask wall or stirring surface, and the resulting dispersion had low viscosity and was extremely stable even after one month.

Examples 10 to /J 0 Synthesis of polymer dispersion (A-a) / 7 j Od of distilled water was placed in a reaction vessel, degassed with nitrogen gas, and Nirasantrax) l-41-1 (,30
% water full liquid) a oty, divinylbenzene is,
oy (0.7 mol)% styrene 1. lyco, 5 mol), chloromethylstyrene, oy (o.

23 mol) was added to 700 d of distilled water heated to AO0C and degassed with nitrogen gas, potassium persulfate,!
and degassed distilled water 2! Sodium bisulfite (O, DI) was added to the mixture, and nine components were added at the same time, and the mixture was heated and stirred for 4 hours.

Furthermore, a mixed solution of potassium persulfate and sodium sulfite in exactly the same amount as above was added, the temperature was raised to 70°C, and heating and stirring were continued for 3 hours.

The obtained latex was cooled to room temperature and diluted with distilled water toQ-
was added, and N-methylpiperidine (2v, 2pco, 5mol) was added. Thereafter, the temperature was slowly raised to 700C, and the mixture was heated and stirred for 4 hours. After cooling to room temperature, the mixture was filtered, and the remaining inorganic salt and N-methylpiperidine were removed by ultrafiltration to obtain a polymer dispersion mordant (exemplified compound 4-a).

The dead polymer obtained had a solid content of 2.2% by weight, and the content of cationized nitrogen atoms in the polymer was determined by titration.1. was J x 10-' (mol/ly latex).

Polymerization of potassium styrene sulfinate in O polymer dispersion (,la -a) Example except that the amount of potassium styrene sulfinate was varied and (≦-a) was used as the polymer dispersion! The desired polymer dispersion was obtained in exactly the same manner as above. Table 3 shows a series of synthesis results for different potassium styrene sulfinate addition lids (Examples 101l/, /, 2).

In this experiment, no deposits due to particle collection were observed on the flask wall or stirring blade, and the obtained dispersion had low viscosity and was extremely stable even during the evening hours. Ta.

Example/J (synthesis of exemplified compound t) J! Add Oxl distilled water, degassed with nitrogen gas, and prepare Nira Santrax) (-17 (j 0% aqueous solution)/
Jxl, divinylbe/ze/ko, 6ri (o.

0-mol), styrene (0, phthalamole), chloromethylstyrene λde, oy (o, phthalmol) were added and heated to to'c. Distilled water degassed with NX gas, 20 m of potassium persulfate 0. j2 and 1 ml of degassed distilled water with sodium bisulfite o,
The mixture was added at the same time, and the mixture was heated and stirred for - hours. Furthermore, add exactly the same amount of potassium persulfate and sodium sulfite mixture as above, raise the temperature to 70°C, and
Heating and stirring were continued for an hour.

The resulting latex was cooled to room temperature and mixed with distilled water/t
(Add Ntd, triethylamine/ri 0.2) (o,
iy mole) was added. Thereafter, the temperature was slowly raised to 7 cm, and the mixture was heated and stirred for several hours. After cooling to room temperature, it was filtered, and the remaining inorganic salts and triethylamine were removed by ultrafiltration. a) was obtained.

What is the solid content concentration of the obtained polymer? , j weight 1t%, the cationized nitrogen atom content in the polymer is determined by titration to λ, 0
0x10 (mol//p latex).

-i Polymerization of acrylic acid and sodium acrylate in a combined dispersion r
ry (-COOH/a nitrogen atom content-'/7 amount)
9. Dissolve 0.32 g of sodium hydroxide in distilled water and dropwise over 2 minutes. 700C after completion of dripping
1,2'-azobis(dinopropane) hydrochloride (commercially available from Wako Tsumugi Pharmaceutical ■ under the name %I'-10) o, oty dissolved in distilled water jd every 7 hours. The mixture was added a total of λ times, and the temperature was raised to ro 0c and stirring was continued for 3 hours. After cooling, a polymer dispersion (exemplary compound t) having a solid content concentration of 70.3% by weight and an average particle size/θt nm (measured by the same method as above) was obtained.

In this experiment, no deposits due to agglomeration of particles were observed on the flask wall or stirring blade, and the resulting dispersion had low viscosity and remained extremely stable even after one month.

Comparative Example For the polymer (a) Jooy used in Examples /~/j, an aqueous solution of each acid polymer was added to the same acid content as in the example (Table 4t below) at room temperature while stirring. The mixture was added dropwise over 70 minutes. (Comparative Examples/-/3) Due to the addition of the acid polymer, coarse aggregates were formed in any of the polymer dispersions, resulting in a viscous liquid. Further, even after heating or stirring for a long time (7 hours), it was no longer possible to reconstitute #1.Stable dispersion without fruit.

The synthesis method of the present invention produces a stable polymer dispersion in which a polymer dispersion having a quaternary ammonium salt and a polymer having an anionic functional group coexist. It is clear that this is an excellent method.

ζ Target of correction “Detailed description of the invention” in the specification of- & Contents of correction The description in the “Detailed Description of the Invention” section of the 8A specification is below 1° Display of incidents Heisei 1st Year Poetry Request No. t7744I In 2゜ name of invention Polymer dispersions and polymer dispersions Production method [ 3゜ person who makes corrections relationship with the matter

Claims (3)

[Claims] (1) An aqueous polymer dispersion in which a polymer dispersion containing at least one quaternary ammonium salt and a polymer having an anionic functional group coexist as constituent components. (2) An aqueous polymer dispersion in which a polymer dispersion having at least one quaternary ammonium salt and a polymer having an anionic functional group coexists as a constituent component is mixed with at least one quaternary ammonium salt. It is obtained by adding at least one ethylenically unsaturated monomer having at least one anionic functional group to a polymer dispersion containing a repeating unit having a salt, and then carrying out a polymerization reaction. A method for producing a characteristic aqueous polymer dispersion. (3) The method for producing an aqueous polymer dispersion according to claim (2), wherein the polymer having a quaternary ammonium salt is a polymer represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A has at least one copolymerizable ethylenically unsaturated group, and a copolymerizable group containing at least one of the copolymerizable ethylenically unsaturated groups is included. represents a monomer unit copolymerized with monomers. B represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer. R^1 represents a hydrogen atom, a lower alkyl group or an aralkyl group. L represents a divalent linking group having 1 to 20 carbon atoms. R^2, R^
3. R^4 may be the same or different, and each represents an alkyl group or substituted alkyl group having 1 to 20 carbon atoms, or an aryl group or substituted group having 6 to 20 carbon atoms. Represents an aryl group. Any two or more groups among R^2, R^3, R^4, and L may be interconnected to form a cyclic structure together with the nitrogen atom. X^■ represents an anion. m represents 0 or 1. x, y, z represent the mole percentage of each sensitivity, x is 0 to 6
0, y represents a value from 0 to 95, and z represents a value from 5 to 100.