JP4466945B2 - Cationic polymer particles and method for producing the same - Google Patents

Description

  The present invention relates to cationic polymer particles and a method for producing the same.

  It is known that polymer particles having a functional group capable of imparting a cation (hereinafter referred to as a cationic group) on the surface, so-called cationic polymer particles, are used as reactive particles having the cationic group as a reactive group. It has been. For example, an adsorbent that adsorbs proteins on the surface of the particles, a cross-linking agent that is added to a film such as a resin and reacts with an anionic reaction site to form a uniform and strong cross-linked structure in the film, In addition to being used as a surface modifier that attaches to the surface of a film such as a resin or a fiber such as cellulose and imparts slipperiness, matteness, etc., substrate particles for plating with various metals (based on conductive particles) (Material particles). The cationic polymer particles are generally used in the form of a cationic latex or as a powder.

  As the cationic polymer particles, those having more cationic groups on the particle surface are demanded as being excellent as reactive fine particles. Conventionally, as a method for obtaining such cationic polymer particles, a cationic group is positively imparted to the surface of the polymer particles by emulsion polymerization of the monomer component using an emulsifier having a cationic group to form particles. There was a way. However, in the technique using the cationic emulsifier, for example, when it is added to a film such as a resin, the film physical properties are lowered such as being present in the film together with the polymer particles and reducing water resistance. However, there are problems such as weak adhesion when used as a surface modifier.

  Therefore, unlike the method using the cationic emulsifier, a technique has been proposed in which a cationic group is fixed to the polymer particle by introducing a cationic group into the polymer particle itself. Specifically, there is a method in which a monomer having a cationic group (cationic monomer) and a nonionic vinyl monomer are emulsion-polymerized using an emulsifier to form particles (for example, see Patent Document 1). In such a technique, if the amount of the cationic group introduced into the polymer particle can be increased, the amount of the cationic group present on the particle surface can be increased accordingly. However, in this method, if the amount of the cationic monomer used is increased, the polymerization stability at the time of particle synthesis becomes poor, so that a large amount of the cationic monomer cannot be used and added. For this reason, in the obtained polymer particles, the amount of cationic groups introduced into the polymer particles is not sufficient in view of the amount of cationic groups on the particle surface, and since the emulsifier is used, There was a problem similar to the case of using an emulsifier.

As a method for solving the above problem, a technique for introducing a cationic group into the polymer particle itself without using an emulsifier has been proposed. Specifically, a method of copolymerizing a cationic monomer and a nonionic vinyl monomer without using an emulsifier in an aqueous medium to form particles (for example, see Patent Document 2), or using an emulsifier in an aqueous medium. First, a part of the mixture of the cationic monomer and the nonionic vinyl monomer is polymerized in advance to produce seed polymer particles, and the remaining monomer is added to this production system to further polymerize (seed polymerization) to form particles (core -Shell type particles) (for example, see Patent Document 3).
Japanese Patent Laid-Open No. 62-263211 JP-A-11-209417 Japanese Examined Patent Publication No. 7-10883

  However, in the method using no emulsifier, the problem due to the emulsifier can be solved, but when a large amount of cationic monomer is used, the polymerization stability during particle synthesis is still poor. Further, for example, in the seed polymerization method, the operation becomes complicated, and it is necessary to delicately control the polymerization rate and the amount of added monomer, and so-called polymerization control is difficult. As described above, after all, a sufficient amount of a cationic monomer cannot be used and added, and there remains a problem that particles must be synthesized while suppressing the amount used. From the point of view of whether the actually obtained polymer particles are more excellent in their function as reactive particles, the amount of cationic groups introduced into the polymer particles is still not sufficiently large, In addition, it has been desired that further development efforts be made in view of the high level required by technological progress in recent years.

  Therefore, the problem to be solved by the present invention is to provide a cationic polymer particle in which more cationic groups are introduced into the polymer particle, and a method for producing such a cationic polymer particle.

  The following reason can be considered about not being able to introduce a sufficient amount of cationic groups into the polymer particles. That is, in general, a cationic monomer has high hydrophilicity and is preferentially present in an aqueous solvent, is unlikely to form monomer droplets in an aqueous medium, and is not preferentially incorporated into polymer particles in the polymerization process, and is preferential in an aqueous medium. Polymerization will proceed. If the cationic monomer is in excess, most of it will be present in the aqueous solvent, and it will be polymerized in the aqueous medium to form a water-soluble polymer, which is difficult to be taken into the particles. Further, the produced water-soluble polymer causes problems such as a decrease in the colloidal stability of the particles and the generation of a large amount of aggregates. Therefore, in the above conventional method, in order to avoid the above problem, the amount of the cationic monomer used must inevitably be suppressed to a predetermined amount or less, and a sufficient introduction amount of the cationic group can be ensured. There was no.

  Based on the above technical analysis, the present inventor has intensively studied a new method for solving the above-described problems. And as a result of repeating trial and error and experiment for the method of introducing more cationic groups into the polymer particles, a polymer having a cationic group (cationic polymer) is separately prepared in advance, in an aqueous medium, Conventionally, in order to obtain polymer particles by polymerizing a non-cationic radical polymerizable monomer using a radical polymerizable initiator, the cationic polymer prepared in advance is present in the aqueous medium. Then we focused on the method that was not seen at all. If the cationic monomer is polymerized in advance, the above-mentioned problems caused by the use of the cationic monomer can be prevented, and the polymerization reaction can proceed stably, and the polymerized product is synthesized. He thought that it was easily incorporated into the polymer particles, and as a result, a sufficiently large number of cationic groups could be introduced into the resulting polymer particles. Furthermore, due to the hydrophilicity / hydrophobicity balance between the polymer synthesized by the polymerization reaction and the aqueous medium, the cationic polymer incorporated in the polymer particles is more likely to be unevenly distributed near the particle surface, and as a result, there are sufficiently many particles on the particle surface. It was also considered that the cationic group can be present.

In fact, when the cationic polymer particles were produced by the above method, surprisingly, a cationic polymer in which a sufficiently large amount of cationic groups was introduced into the polymer particles at a level that could not be realized in the past. It was confirmed that particles were obtained.
The present invention has been completed based on these findings.
That is, in the cationic polymer particles according to the present invention, the polymer (A) having at least one cationic group selected from the group consisting of an alkyleneimine polymer, a vinylamine polymer, and an allylamine polymer has a cationic group. And a cationic polymer particle having a functional group (a) capable of reacting with the amino group and / or imino group of the polymer (A), mixed in the polymer (B), In at least a part of the particles, the amino group and / or imino group of the polymer (A) reacts with the functional group (a) of the polymer (B), whereby the polymer (B) is polymer (A ) And the amount of cationic groups on the particle surface is 0.05 meq. / G or more, and the polymer (B) is obtained by polymerizing a non-cationic radical polymerizable monomer having a solubility in water of 0.01 to 10% by weight, and the polymer (B In the polymer particles, the content of the functional group (a) is 1 to 40 mol% with respect to the amino group and / or imino group in the polymer (A).

  The method for producing cationic polymer particles according to the present invention includes an aqueous medium in which a polymer (A) having at least one cationic group selected from the group consisting of an alkyleneimine polymer, a vinylamine polymer, and an allylamine polymer is present. A method for producing cationic polymer particles, wherein the non-cationic radical polymerizable monomer is polymerized using a radical polymerization initiator in a state where a dispersion state of the non-cationic radical polymerizable monomer is formed. The non-cationic radical polymerizable monomer has a water solubility of 0.01 to 10% by weight, and at least one of the non-cationic radical polymerizable monomers is an amino group contained in the polymer (A). And / or a functional group (a) that can react with an imino group, Characterized in that with respect to the amino group and / or imino group content in the polymer (A) of the functional groups (a) of the polymerizable monomer component, 1 to 40 mol%.

  ADVANTAGE OF THE INVENTION According to this invention, the cationic polymer particle by which many cationic groups are introduce | transduced into the polymer particle, and the manufacturing method of such a cationic polymer particle can be provided.

Hereinafter, although the cationic polymer particle concerning this invention and its manufacturing method are demonstrated in detail, the range of this invention is not restrained by these description and does not impair the meaning of this invention except the following illustrations. Changes can be made as appropriate within the range.
[Cationic polymer particles]
<Polymer (A)>
The polymer (A) referred to in the present invention is a polymer having a cationic group (cationic polymer), and specifically includes an alkyleneimine polymer (polyalkyleneimines), a vinylamine polymer (polyvinylamines), and allylamine. At least one selected from the group consisting of polymer polymers (polyallylamines) is used. These polymers have an amino group or an imino group as a cationic group.

The alkyleneimine-based polymer (polyalkyleneimine) generally refers to a compound obtained by polymerizing a saturated hydrocarbon having a nitrogen atom as a constituent unit. For example, polyethyleneimine, polypropyleneimine, Examples thereof include polybutadieneimine, polybutadieneimine, and copolymers thereof. Moreover, when represented by the general formula, for example, (—CH ₂ CH ₂ NH—) _n , (—CH ₂ CH ₂ CH ₂ NH—) _n , (—CH ₂ CH ₂ CH ₂ CH ₂ NH—) _n , _{(-CH 2 CH 2 n (CH} 2 NH 2) CH 2 CH 2 NH-) n, (- CH 2 CH 2 n (CH 2 CH 2 NH 2) CH 2 CH 2 NH-) n, (- CH 2 _{CH 2 n (CH 2 CH 2} CH 2 NH 2) CH 2 CH 2 NH-) n, (- CH 2 CH 2 CH 2 n (CH 2 NH 2) CH 2 CH 2 CH 2 NH-) n, (- _{CH 2 CH 2 CH 2 n (} CH 2 CH 2 NH 2) CH 2 CH 2 CH 2 NH-) n, (- CH 2 CH 2 CH 2 n (CH 2 CH 2 CH 2 NH 2) CH 2 CH 2 CH _{2 NH-)} polymers _n are preferable ani It is. These may be used alone or in combination of two or more.

In the alkyleneimine polymer, the alkylene group preferably has 2 to 8 carbon atoms, and the repeating unit number n is preferably 10 or more, more preferably 10 to 45. Further, it may be a linear structure, a branched structure having a side chain, or a cyclic structure, and is not limited. However, a branched structure is preferable, and a polyethyleneimine having a branched structure is particularly preferable. .
Examples of the monomer that can be used in the production of the alkyleneimine polymer include ethyleneimine, propyleneimine, N-hydroxyethylethyleneimine, N-cyanoethylethyleneimine, N-methylethyleneimine, N-ethylethyleneimine, and N-phenyl. Ethyleneimine, N-acetylethyleneimine, N-methacryloylaziridine, β-aziridinylmethylpropionate, β-aziridinylethyl methacrylate, hexamethylene-bis-1,6-N, N′-diethyleneurea, diphenylmethane -Using at least one of monomers such as -bis-4,4'-N, N'-diethyleneurea, 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate] as essential, Heavy by known polymerization methods It is preferable to combine them.

  As the vinylamine polymer (polyvinylamines), generally, a polyvinylamine obtained by hydrolyzing a polymer having a structural unit derived from a monomer classified as vinylamine is preferable. For example, European Patent Publication No. 0071050 And polyvinylamines described in JP-A-0216387. Specifically, a homopolymer obtained by polymerizing by a known polymerization method using N-vinylformamide having a hydrolysis degree of 1 to 100%, preferably 80 to 100% as a monomer, and partially or Examples thereof include copolymers obtained by polymerization by a known polymerization method using N-vinylformamide and vinyl formate or vinyl acetate that are completely hydrolyzed as monomers. The structural unit derived from N-vinylformamide in the copolymer is preferably 80 to 100% hydrolyzed. In addition, the structural unit derived from vinyl formate or vinyl acetate in the copolymer can be partially or completely hydrolyzed to be a structural unit derived from vinyl alcohol. Examples of other monomers that can be used in the production of the copolymer include monoethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic acid, N-vinylpyrrolidone, and acrylonitrile. These may be used alone or in combination of two or more.

As the allylamine-based polymer (polyallylamines), for example, known polyallylamine, polymethallylamine, polyalkylallylamine, polyalkylmethallylamine and derivatives thereof obtained by radical polymerization of monomers classified as allylamine, and Preferred are copolymers of these (including derivatives). These may be used alone or in combination of two or more.
As the polyallylamine derivatives, various known polyallylamine derivatives can be preferably used. For example, (i) salts of polyallylamines and acids (for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, and methanesulfonic acid, toluenesulfonic acid, acetic acid, propionic acid, cinnamic acid And one or more selected from organic acids such as (meth) acrylic acid, etc. The amino groups in the polyallylamines may be all or partly reacted with an acid. (Ii) Copolymers of polyallylamines and monomers copolymerizable therewith (examples of monomers copolymerizable with polyallylamines include (meth) acrylic acid esters, styrenes, (meta ) Acrylamides, acrylonitriles, vinyl esters, etc.), (iii) polymers composed of repeating structural units represented by the following general formulas (1) to (5) And the like.

(In the above general formulas (1) to (5), R ^{1 to} R ⁴ may represent an organic group which may have a substituent, and R ⁵ and R ⁶ may have a hydrogen atom or a substituent. R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents —COOR ⁹ , —CN and —CONR ¹⁰ R ¹¹ (wherein R ^{9 to} R ¹¹ represent a hydrogen atom, an aliphatic group) and represents an aromatic group) G ^-.. represents a counter anion).
Examples of the organic group that can be employed as R ^{1 to} R ⁶ include groups containing a hydrocarbon moiety and / or a hydrogen halide moiety, and these groups are further substituted with hydrogen, carbon, nitrogen, oxygen, sulfur, phosphorus, It may contain atoms such as silicon, boron and halogen, and / or a functional group composed of these atoms. Examples of this functional group include an alkyl group, an aralkyl group, an aryl group, an acyl group, a sulfonyl group, and heterocycles which may have a substituent.

In particular, examples of organic groups that can be employed as R ^{1 to} R ⁴ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n- Alkyl groups such as hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-decyl, n-dodecyl, octadecyl, 1,3-butadienyl and 1,3-pentadienyl; benzyl, phenylethyl Aralkyl groups such as vinylbenzyl, 1-phenylvinyl and 2-phenylvinyl; aryl groups such as phenyl group, naphthyl group, tolyl group and vinylphenyl group; Examples of these organic groups having further substituents include, for example, fluoroethyl group, trifluoroethyl group, methoxyethyl group, phenoxytyl group, hydroxyphenylmethyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, bromophenyl. Group, iodophenyl group, fluorophenyl group, hydroxyphenyl group, methoxyphenyl group, acetoxyphenyl group, cyanophenyl group and the like.

Examples of the counter anion that can be employed as G ⁻ include halogen ions (Cl ⁻ , Br ⁻ , I ^{− and the} like), sulfonate ions, alkyl sulfonate ions, aryl sulfonate ions, aryl sulfonate ions, alkyl carboxylate ions, and the like. An aryl carboxylate ion etc. are mentioned.
As the polymer (A), a polymer further hydrophobized can also be used. When the polymer (A) is further hydrophobized, effects such as easier incorporation by the polymer particles obtained during the polymerization reaction can be obtained. The method for obtaining the polymer (A) that has been further hydrophobized is not limited. Specifically, (a) the polymer (A) is prepared from a compound having a hydrophobic group such as a phenyl group, an alkyl group and a vinyl group. And (b) a method of copolymerizing with a monomer having a hydrophobic group in the synthesis step of the polymer (A). When an alkyleneimine polymer is used as the polymer (A), the type of monomer (alkyleneimine) used for the synthesis, specifically the type of alkylene group in the monomer (carbon number, etc.) should be appropriately selected. The method of adjusting so that the hydrophobization degree of the polymer (A) obtained may become large may be mentioned.

  Preferred examples of the method (a) include a method of alkylating a polyalkyleneimine such as polyethyleneimine. Specifically, it is a method of reacting a polyalkyleneimine with an alkylating agent such as an alkyl halide (see, for example, US Pat. No. 3,251,778 and European Patent No. 0379161). As the alkyl halide, for example, an alkyl halogen compound having an alkyl group having 1 to 30 carbon atoms can be preferably used, and these may be used alone or in combination of two or more. In this method, the degree of alkylation of the polyalkyleneimines is a ratio of the number of the above-mentioned alkylated repeating structural units to the total number of repeating structural units derived from the alkyleneimine constituting the polyalkyleneimines, for example, The content is preferably 1 to 50%, more preferably 1 to 30%.

Preferred examples of the method (a) include a method in which an alkylene oxide is reacted with a polyalkyleneimine such as polyethyleneimine. Specifically, it is a method of performing an alkoxylation reaction of polyalkyleneimines in the presence of a base as a catalyst. The alkylene oxide is preferably an alkylene oxide having 2 to 22 carbon atoms, and examples thereof include ethylene oxide, propylene oxide, and long-chain alkylene oxides having an alkylene group having 10 to 22 carbon atoms. Those obtained by epoxidizing are preferred. These may be used alone or in combination of two or more.
Examples of the method (a) also include polyalkyleneimines such as polyethyleneimine, epoxides, base esters, aldehydes, formaldehyde, ketones, isocyanates, organic acids, urea, anhydrides, acyl halides, chloroformates, A method of reacting a compound classified into acrylonitrile, acrylate, methacrylate, dialkyl carbonate, thioisocyanate, dialkyl sulfate, cyanamide, haloformate, melamine formaldehyde and the like is preferable. These may be used alone or in combination of two or more. In this method, the above compound is reacted with the imino group in the polyalkyleneimine as a reaction site.

As the method of (a), for example, a polyalkyleneimine such as polyethyleneimine is reacted with ethylene oxide or the like, followed by addition of propylene oxide or the like, so as to be alkoxylated as a so-called block copolymer. A method for obtaining the polyalkyleneimines is also preferred.
As the method of (b) above, for example, a copolymer having a hydrophobic group in the preparation stage of polyallylamines or polyvinylamines, that is, in the reaction of radical polymerization (polyallylamines) or hydrolysis (polyvinylamines). Preferred is a method of reacting (copolymerizing) with other possible monomers. Examples of the other monomer having a hydrophobic group include vinyl acetate, 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, and 1,3-pentadiene. Conjugated diene monomers; aromatic vinyl compounds such as styrene, α-methylstyrene, monochlorostyrene, vinyltoluene, divinylbenzene; unsaturated nitrile compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile; methyl (meth) Acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, propyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate , Lauryl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) ) Unsaturated monocarboxylic acid esters such as acrylates; Unsaturated dicarboxylic acid diesters such as dimethyl fumarate, dimethyl maleate, diethyl itaconate; (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) Unsaturated amides such as acrylamide and N-substituted derivatives thereof; In this method, the usage-amount of the other monomer which has the said hydrophobic group is not specifically limited, In the range which does not impair the desired physical property as a polymer (A), it can set suitably.

Although the weight average molecular weight (Mw) of a polymer (A) is not limited, For example, it is preferable that it is 500-5,000,000, More preferably, it is 1,000-1,000,000, More preferably, it is 2 , 000 to 500,000. If the Mw is less than 500, the polymer particles may not be stably incorporated into the polymer particles, and aggregates may be generated in the aqueous medium. If the Mw exceeds 5,000,000, the viscosity is in a state of being dissolved in the aqueous medium. May be high and difficult to handle.
<Polymer (B)>
The polymer (B) referred to in the present invention is a polymer having no cationic group (cationic functional group). Specifically, unlike the polymer (A), the polymer does not have a cationic group such as an amino group or an imino group. Specifically, the polymer has an anionic group (anionic polymer) or an ionic group. Examples thereof include a polymer having no group (nonionic polymer). The polymer (B) is preferably a polymer having higher hydrophobicity than the polymer (A) to be used, and the polymer (A) incorporated during the synthesis of the particles of the polymer (B) is more preferentially near the particle surface. It tends to exist.

The method for synthesizing the polymer (B) is not limited, but for example, a method of polymerizing a non-cationic radical polymerizable monomer (non-cationic monomer) by a known polymerization method is preferable.
The non-cationic monomer is not particularly limited as long as it is a compound having at least one ethylenically unsaturated group in the molecule. For example, acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, silica C3-C8 unsaturated monocarboxylic acids such as cinnamate; C3-C8 unsaturated dicarboxylic acids such as maleic acid, itaconic acid, fumaric acid, citraconic acid, chloromaleic acid and their anhydrides; Monoesters of unsaturated dicarboxylic acids having 3 to 8 carbon atoms such as monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate and their derivatives Styrene sulfonic acid, 2-acrylamido-2-methylpropane (Meth) acrylamide-alkanesulfonic acid such as sulfonic acid; sulfonic acid group-containing polymerizable unsaturated monomer such as sulfoalkyl (meth) acrylate such as 2-sulfoethyl (meth) acrylate; vinyl acetate, 1,3-butadiene, 2 -Conjugated diene monomers such as methyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene; styrene, α-methylstyrene, monochlorostyrene, vinyltoluene, divinylbenzene, etc. Aromatic vinyl compounds; unsaturated nitrile compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl ( (Meth) acrylate Propyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) Unsaturated monocarboxylic acid esters such as acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate; dimethyl fumarate, dimethyl maleate, diethyl itaconate, etc. Saturated dicarboxylic acid diesters; unsaturated amides such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-substituted derivatives thereof Body; and the like preferably.

  When synthesizing the polymer (B), the non-cationic monomer to be used is preferably adjusted so that the total solubility in water is, for example, 0.01 to 10% by weight. Preferably it is 0.02-7 weight%, More preferably, it is 0.03-5 weight%. By using a non-cationic radically polymerizable monomer whose solubility in water satisfies the above range, the polymer (A) incorporated into the particles of the polymer (B) is more particles due to the hydrophilicity / hydrophobicity balance with the polymer (A). The effect of being easily present near the surface is obtained. Further, when the solubility in water is less than 0.01% by weight, the polymerization rate is extremely lowered when a water-soluble polymerization initiator is used, and coarse when a hydrophobic polymerization initiator is used. There is a possibility that polymer particles may be formed. When the amount exceeds 10% by weight, the colloidal stability of the polymer particles may be lowered during the polymerization reaction, and aggregates may be formed.

The polymer (B) is preferably a polymer having a functional group (a) that can react with the amino group and / or imino group of the polymer (A). When such a polymer (B) is used, a larger amount of the polymer (A) can be taken into the obtained cationic polymer particles, and an effect that a larger number of cationic groups can be introduced can be obtained. Further, structurally, cationic polymer particles obtained by grafting the polymer (A) onto the polymer (B) may be obtained.
Examples of the functional group (a) include, but are not limited to, epoxy group, isocyanate group, carboxyl group, halogen group, aldehyde group, carbonyl group, acid anhydride group, acid halide group, N-chloroformyl group, chloro Examples include a formate group, an imide ether group, and an amidinyl group. Of these, an epoxy group, an isocyanate group, a carboxyl group, and a halogen group are preferable.

  When the polymer (B) is a polymer having the functional group (a), the content of the functional group (a) in the polymer (B) is not limited, but an amino group in the polymer (A) and / or It is preferable that it is 1-40 mol% with respect to an imino group, More preferably, it is 2-30 mol%, More preferably, it is 3-20 mol%. If the content of the functional group (a) is less than 1 mol%, the effect may not be sufficiently obtained due to the functional group (a), and if it exceeds 40 mol%, the resulting cationic property In the polymer particles, the reaction between the polymer (A) and the polymer (B) becomes excessive, and the polymer (A) may not be preferentially present on the particle surface.

  Examples of a method for obtaining the polymer (B) having the functional group (a) that brings about the above-described effect include (i) a non-cationic monomer that further has a functional group (a), and a non-cationic monomer. Although the method of superposing | polymerizing using a part or all in the whole usage-amount of a monomer can be mentioned, It does not limit. Further, as an embodiment that brings about the same effect as the effect described above, (ii) reacting the functional group (a) of the monomer having the functional group (a) with the amino group and / or imino group of the polymer (A). The polymer (A) is incorporated during the synthesis of the polymer (B) particles, and the polymerizable reactive group of the monomer having the functional group (a) is copolymerized with the monomer for synthesizing the polymer (B). However, the method is not limited.

The monomer having the functional group (a) that can be used in the method (i) is not limited, and examples thereof include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, acrylic acid, methacrylic acid, maleic acid, 2 Preferred examples include -methacryloxyethyl succinic acid and 2-chloro-hydroxypropyl methacrylate. Of these, glycidyl methacrylate and allyl glycidyl ether are more preferable. The usage-amount of the monomer which also has the said functional group (a) is not limited, It is preferable to set suitably so that the range of content of the functional group (a) mentioned above may be satisfy | filled.
Although the weight average molecular weight (Mw) of a polymer (B) is not limited, For example, it is preferable that it is 500-5,000,000, More preferably, it is 1,000-2,000,000, More preferably, it is 2 , 1,000 to 1,000,000. If the Mw is less than 500, the polymer particles may not be used.

<Cationic polymer particles>
The cationic polymer particles of the present invention are polymer particles in which the polymer (A) is mixed in the polymer (B).
In the cationic polymer particles of the present invention, the mixed state may be, for example, a state where the polymer (A) is uniformly present in the polymer (B), or is present in the form of particles of any size. It may be in a state where it is formed, or it may be in a band-like state at random, and is not limited.
In the cationic polymer particles of the present invention, the mixing ratio of the polymer (A) which is an essential component is not limited, but is preferably 1% by weight or more, more preferably 2% with respect to the cationic polymer particles. % By weight or more, more preferably 3% by weight or more, more preferably 4% by weight or more. Cationic polymer particles having a polymer (A) mixing ratio of 1% by weight or more are used as various functions as reactive particles, particularly crosslinking reactivity in a film, and when used as carrier particles or substrate particles. Reactivity with protein or metal is very excellent. On the other hand, if it is less than 1% by weight, the above excellent functions may not be sufficiently exhibited.

In the cationic polymer particles of the present invention, it is preferable that the mixed polymer (A) is sufficiently present near the particle surface in order to sufficiently exhibit the above-described excellent functions.
In the cationic polymer particle of the present invention, since the polymer (A) is introduced in a sufficiently large amount in the particle, the amount of the cationic group (amino group and / or imino group) on the particle surface is also sufficient. Many particles. Specifically, the cationic polymer particle of the present invention has an amount of cationic groups on the particle surface of 0.05 meq. / G or more, more preferably 0.10 meq. / G or more, more preferably 0.20 meq. / G or more, particularly preferably 0.30 meq. / G or more, most preferably 0.40 meq. / G or more. The amount of cationic groups on the particle surface is 0.05 meq. If it is less than / g, the above-described excellent functions as reactive particles may not be sufficiently exhibited. In addition, the abundance of the cationic group on the particle surface is measured and evaluated by the method described in Examples described later.

  In the cationic polymer particles of the present invention, the polymer (B) is preferably a polymer having the functional group (a) described above, and at least one of the cationic polymer particles (particle surface and inside of the particles) of the present invention. In part, the polymer (B) is grafted to the polymer (A) by the reaction of the amino group and / or imino group of the polymer (A) with the functional group (a) of the polymer (B). Is preferred. If this graft structure is present in at least a part of the particles, the particle properties are further improved in terms of strength and the like, and excellent effects such as being able to stably exist a cationic group for a long period of time are expected. it can. In the cationic polymer particle of the present invention, more preferably, the graft structure is present on at least a part of the particle surface, and the same effect as described above can be expected on the particle surface.

The average particle diameter of the cationic polymer particles of the present invention is not limited, but is preferably 0.01 to 10 μm, more preferably 0.02 to 8 μm, and further preferably 0.03 to 5 μm. When the average particle diameter exceeds 10 μm, the specific surface area becomes small, and a cationic group sufficient for the amount of the polymer (A) used (and the amount of the polymer (A) taken into the polymer particles) is formed on the particle surface. There is a possibility that it cannot be sufficiently present.
Although the method for producing the cationic polymer particles of the present invention is not limited, for example, it is preferable to obtain them by the production method of the present invention described later.
The use of the cationic polymer particles of the present invention is not limited, and as in the past, for example, an adsorbent that adsorbs proteins on the particle surface or a film such as a resin is added to react with an anionic reaction site. In addition to a cross-linking agent that forms a uniform and strong cross-linked structure in the film, and a surface modifier that attaches to the surface of a film such as a resin or a fiber such as cellulose to impart slipperiness or matting properties. In addition, it can be suitably used as substrate particles for plating with various metals or the like (substrate particles of conductive particles).

[Method for producing cationic polymer particles]
The production method of the present invention is a method of polymerizing a non-cationic radically polymerizable monomer using a radical polymerization initiator in an aqueous medium in which the polymer (A) is present. The details of the polymer (A) and the non-cationic radical polymerizable monomer (non-cationic monomer) are as described above.
In carrying out the production method of the present invention, means and conditions in a known polymerization technique for obtaining a particulate polymer can be appropriately selected and employed except for the conditions described below.

In the production method of the present invention, it is important to carry out the polymerization reaction of the non-cationic monomer in a state where the polymer (A) is present in the aqueous medium. The cationic polymer particles according to the present invention can be easily obtained.
In the production method of the present invention, the polymerization method is not limited, and any method can be adopted as long as the non-cationic monomer to be used can be polymerized as a particulate polymer. For example, in addition to a suspension polymerization method, an emulsion polymerization method, a dispersion polymerization method, a microsuspension polymerization method (miniemulsion polymerization method), and the like, a seed polymerization method in which the polymer (A) plays a role as a seed particle is also included.

In the production method of the present invention, the amount of the non-cationic monomer used is not limited, but for example, it is preferably 1 to 70% by weight, more preferably 2 to 60% by weight, based on the aqueous medium. More preferably, it is 3 to 50% by weight. If the amount of the non-cationic monomer used is less than 1% by weight, the polymerization rate may decrease and the productivity of the polymer particles may be greatly reduced. If it exceeds 70% by weight, the polymer particles in the polymerization reaction may be reduced. Colloidal stability may be reduced and agglomerate.
The non-cationic monomer is preferably a monomer having a functional group (functional group (a)) that can react with the amino group and / or imino group of the polymer (A). Is as described above. In the production method of the present invention, the non-cationic monomer has the functional group (a), so that the polymer (A) can be more taken into the obtained cationic polymer particles during the polymerization reaction. become.

In the production method of the present invention, the use amount (blending amount) of the polymer (A) is not limited, but it is, for example, 1 to 300% by weight with respect to the total use amount of the non-cationic monomer. More preferably, it is 2-250 weight%, More preferably, it is 3-200 weight%. When the amount of the polymer (A) used (blending amount) is less than 1% by weight, sufficient cationic groups cannot be introduced into the resulting polymer particles, and the function and characteristics as reactive particles are sufficient. If the amount exceeds 300% by weight, an effect commensurate with the blending amount cannot be obtained, and a large amount of the polymer (A) may remain in the aqueous medium.
The aqueous medium used in the production method of the present invention is not limited, and an aqueous medium used in a known suspension polymerization method or emulsion polymerization method can be preferably used. For example, water is preferable, but a hydrophilic organic solvent and water may be used in combination.

  Examples of the hydrophilic organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and allyl alcohol; ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, pentanediol, hexanediol, and heptane. Glycols such as diol and dipropylene glycol; Ketones such as acetone, methyl ethyl ketone, and methyl propyl ketone; Esters such as methyl formate, ethyl formate, methyl acetate, and methyl acetoacetate; Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dipropylene glycol Ethers such as monomethyl ether; and the like preferably. These may be used alone or in combination of two or more.

In the production method of the present invention, it is preferable that, for example, substantially no emulsifier is used in the polymerization of the non-cationic monomer, but there is no limitation, and the amount usually used in known emulsion polymerization methods. Emulsifiers can also be used. Note that the fact that no emulsifier is substantially used is not limited to the fact that no emulsifier is used, and includes cases where the emulsifier is used slightly. In particular, in the case where a problem of physical properties can occur due to the use of a large amount of emulsifier, the polymerization may be performed using the emulsifier in a small amount range in which the problem cannot occur. As an emulsifier, the well-known emulsifier which can be used for an emulsion polymerization method can be used.
In the production method of the present invention, the non-cationic monomer and the polymer (A) are charged into a predetermined reactor together with the aqueous solvent, and then sufficiently stirred, so that the polymer (A) is present in the aqueous solvent. It is preferable to form a dispersion state of the non-cationic monomer in the above state, but there is no limitation. The state in which the polymer (A) is present in the aqueous solvent is not limited, but specifically, the state in which the polymer (A) is dissolved in the aqueous solvent or the polymer (A) as a latex polymer. And the like in a water-based medium. For the stirring, a conventionally known stirring technique can be employed. For example, stirring by a stirrer, stirring by a homomixer, stirring by a high-speed stirrer, stirring by ultrasonic waves, and the like can be mentioned. Thereafter, the temperature of the charged contents (reaction system) is heated to a predetermined reaction temperature, and a radical polymerization initiator is added to initiate the polymerization reaction, preferably with stirring.

  In the production method of the present invention, a generally known radical polymerization initiator can be used as the radical polymerization initiator. For example, hydroperoxides such as potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, t-butyl-hydroperoxide, diisopropylbenzene hydroperoxide and cumene hydroperoxide; azobisisobuty Such as rhonitrile, 2,2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2,4-dimethylvaleronitrile) and 4,4'-azobis (4-cyanovaleric acid) Preferred examples include aliphatic azo compounds; redox initiators in which polymerization initiators of the hydroperoxides are combined with reducing agents such as ascorbic acid, polyvalent metal salts, and sodium formaldehyde sulfoxylate. These may be used alone or in combination of two or more.

The radical polymerization initiator is a radical polymerization initiator having a functional group (functional group (a)) capable of reacting with the amino group and / or imino group of the polymer (A), similarly to the non-cationic monomer described above. It is preferable that it is an agent. By using the radical polymerization initiator having such a functional group (a), more cationic polymer particles can be incorporated into the polymer (A) during the suspension polymerization reaction.
In the production method of the present invention, the amount of the radical polymerization initiator used is not limited, but is preferably 0.01 to 10% by weight with respect to the total amount of non-cationic radical polymerizable monomer used. More preferably, it is 0.05-8 weight%, More preferably, it is 0.1-5 weight%. The radical polymerization initiator is preferably added after the reaction system is heated, but is not limited thereto.

In the production method of the present invention, the temperature of the polymerization reaction is preferably, for example, 20 to 190 ° C, more preferably 20 to 120 ° C, and further preferably 40 to 95 ° C.
In the production method of the present invention, the polymerization reaction time is not limited, but for example, it is preferably 1 to 30 hours, more preferably 2 to 24 hours, still more preferably 3 to 20 hours.
In the production method of the present invention, the pH of the reaction system is not limited, but in order to increase the amount of the cationic group on the surface of the obtained cationic polymer particles, for example, it is adjusted to a range of 4 to 11. Is more preferable, and 3 to 12 is more preferable.

In the production method of the present invention, the embodiment of the polymerization reaction may be either a batch type or a continuous type, and is not limited.
In the production method of the present invention, an aging period may be provided as necessary after the suspension polymerization reaction is completed.
By carrying out the production method of the present invention as described above, the cationic polymer particles are obtained in the state of a dispersion formed by dispersing in an aqueous medium. The cationic polymer particles obtained by the production method of the present invention may be used for a desired application as it is in the above dispersion, or once only the cationic polymer particles are separated from the dispersion and used for a desired application. Well, it is not limited. At this time, as a method for separating only the cationic polymer particles from the dispersion, a known separation technique can be appropriately employed. For example, a centrifugal separation method, a filtration method, a decantation method, and the like are preferable.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, for convenience, “part by weight” may be simply referred to as “part”, and “liter” may be simply referred to as “L”. In addition, “wt%” may be described as “wt%”.
Measurement methods and evaluation methods in Examples and Comparative Examples are shown below.
<Polymerization rate of monomer>
A part of the dispersion obtained after the polymerization is sampled, and after adding an appropriate amount of 2 wt% hydroquinone aqueous solution as a polymerization inhibitor, the residual monomer amount is calculated by a calibration curve method by gas chromatography (GC) measurement. The total residual monomer amount was also converted and the polymerization rate relative to the total monomer amount used in the polymerization reaction was determined.

<Average particle diameter of polymer particles>
About the average particle diameter of the obtained polymer particle, it measured using the particle size distribution meter (Horiba Ltd. make, product name: LA-910).
<Amount of cationic polymer introduced into polymer particles>
"When polymer (A) is used"
A part of the dispersion obtained after the polymerization reaction is sampled, and centrifuged at 30,000 G for 1 hour using an ultracentrifuge to obtain polymer particles (precipitate) and other aqueous medium, etc. (Supernatant) was completely separated and the supernatant was recovered. The obtained supernatant was subjected to GPC measurement. Moreover, after water | moisture content of the obtained supernatant was evaporated with the hotplate heated at 150 degreeC, the weight of the residual solid substance was measured and this was made into the residual weight of the polymer (A) in the aqueous medium in the said sample. The residual weight of the polymer (A) in the entire dispersion was also determined by conversion.

The weight obtained by subtracting the remaining weight from the total use weight of the polymer (A) is calculated, and the ratio to the weight of the obtained polymer particles is determined. This value is the mixture ratio (wt%) of the polymer (A) in the polymer particles. did.
However, when a polymerization initiator or a non-cationic monomer having a functional group capable of reacting with the cationic group (amino group and / or imino group) of the polymer (A) is used, the non-cationic monomer is polymerized. A part of the polymer (B) obtained in this manner may be bonded to the polymer (A) remaining in the aqueous medium. Even in such a situation, in the calculation of the mixing ratio, the measured residual weight is assumed to be the residual weight of the polymer (A) (which is estimated more). Therefore, the calculated mixing ratio of the polymer (A) is a value (lower limit value) when estimated to be the smallest.

“When polymer (A) is not used and cationic monomer is used”
Even when a cationic monomer is used, the presence of residual solids in a part (sample) of the dispersion obtained after the polymerization reaction can be confirmed and confirmed in the same manner as when the polymer (A) is used. In this case, this was regarded as the residue of the polymer derived from the cationic monomer in the aqueous medium. Only the presence or absence is shown in the table.
However, when the presence of the residue is confirmed, the residue is not limited to a polymer derived from only a cationic monomer, but may be a copolymer derived from both a cationic monomer and a non-cationic monomer. In any case, the thing derived from the cationic monomer remains in the aqueous medium. Therefore, the mixing ratio of the polymer derived from the cationic monomer is lower than the value (upper limit value) when all the cationic monomers contribute to the synthesis of the polymer particles.

<Amount of cationic group on polymer particle surface>
The amount of cationic groups on the surface of the polymer particles (for example, the amount of amine) is “conductivity titration method by Kawaguchi et al. (H. Kawagucni, et.al., J. Appl. Polymer Sci., Vol 26, 2015 (1981))”. The relative value was evaluated from the value measured by Specifically, latex in which polymer particles are dispersed in water is placed in a cellulose tube (UCC, product name: Seamless Cellulose Tubing, size: 36/32) and dialyzed in running water for 10 days to obtain a solid content concentration. Take 50 g of 4% latex by weight in a 100 ml beaker, add 1 ml of 20% aqueous solution of Emulgen 147 (manufactured by Kao Soap), adjust pH to 12 with N / 5 NaOH, Conductivity titration with 10 HCl (product name: CM-117, manufactured by Kyoto Electronics Industry Co., Ltd. is used as the conductivity meter), and measure the amount required for titration from the second bending point to the third bending point This value (meq./g) was relatively evaluated as the amount of cationic groups on the surface of the polymer particles .

[Example 1]
  A 2 L four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was mixed with 50 g of a 30 wt% aqueous solution of polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., product name: P-1000), methyl methacrylate (water Solubility in water: 1.76 wt%) 197 g, allyl glycidyl ether 3 g and ion-exchanged water were added to make a total of 1900 g.
  While vigorously stirring the contents of the flask, the inside of the flask was purged with nitrogen, heated to 60 ° C., and maintained at the same temperature, 2,2′-azobis (2-aminodipropane) hydrochloric acid as a polymerization initiator. A milky white dispersion (1) in which 100 g of a 4 wt% aqueous solution of a salt (product name: VA-50, manufactured by Wako Pure Chemical Industries, Ltd.) is added and polymerized for 8 hours to disperse the cationic polymer particles (1). ) The polymerization rate was 99% or more. The average particle diameter of the cationic polymer particles (1) in the dispersion (1) was 0.26 μm.

[Comparative Example 1]
In a flask similar to that in Example 1, 2 g of diethylaminoethyl methacrylate (cationic colloid equivalent value: 0.51 meq./g as dimethyl sulfate quaternized product), 198 g of methyl methacrylate (solubility in water: 1.76 wt%) and ions Exchange water was added to make 1900 g in total.
While vigorously stirring the contents of the flask, the inside of the flask was purged with nitrogen, heated to 60 ° C., and maintained at the same temperature, 2,2′-azobis (2-aminodipropane) hydrochloric acid as a polymerization initiator. A milky white dispersion (c1) obtained by adding 100 g of a 4 wt% aqueous solution of a salt (product name: VA-50, manufactured by Wako Pure Chemical Industries, Ltd.) and performing polymerization for 8 hours to disperse the cationic polymer particles (c1). ) The polymerization rate was 97%.

The average particle diameter of the cationic polymer particles (c1) in the dispersion (c1) was 0.61 μm.
[Comparative Example 2]
In Comparative Example 1, polymerization was carried out in the same manner as in Comparative Example 1 except that 2 g of diethylaminoethyl methacrylate and 198 g of methyl methacrylate were used, except that 10 g of diethylaminoethyl methacrylate and 190 g of methyl methacrylate were used. After about 2 hours from the start, aggregates were formed and a stable dispersion could not be obtained.
Similarly, in Comparative Example 1, polymerization was carried out in the same manner as in Comparative Example 1 except that 3 g of diethylaminoethyl methacrylate and 197 g of methyl methacrylate were used. And a stable dispersion could not be obtained.

[Comparative Example 3]
To the same flask as in Example 1, 200 g of methyl methacrylate (water solubility: 1.76 wt%) and ion-exchanged water were added to make a total of 1900 g.
While vigorously stirring the contents of the flask, the inside of the flask was purged with nitrogen, heated to 60 ° C., and maintained at the same temperature, 2,2′-azobis (2-aminodipropane) hydrochloric acid as a polymerization initiator. A milky white dispersion (c2) in which 100 g of a 4 wt% aqueous solution of a salt (product name: VA-50, manufactured by Wako Pure Chemical Industries, Ltd.) is added and polymerized for 8 hours to disperse polymer particles (c2) is obtained. Obtained. The polymerization rate was 96%.
The average particle diameter of the polymer particles (c2) in the dispersion (c2) was 0.70 μm.
The obtained dispersion in the above Examples and Comparative Example (1) Contact and (c1) ~ (c2), the amount of polymer remaining in the aqueous medium (other than polymer particles), the average particle size of the polymer particles, and polymer The amount of the cationic group on the particle surface (amine amount) was measured. The results are shown in Table 1.

Cationic polymer particles according to the present invention are adsorbents that adsorb proteins on the particle surface, and are added to a film such as a resin to react with anionic reaction sites, thereby forming a uniform and strong cross-linked structure in the film. In addition to a cross-linking agent that forms a surface, a surface modifier that is attached to the surface of a film such as a resin or a fiber such as cellulose to impart slipperiness or matte properties, etc., as well as substrate particles for plating with various metals (conductive Can be suitably used as the base particles of the conductive particles.
The production method according to the present invention can be preferably applied when, for example, the cationic polymer particles of the present invention are obtained.

Claims (3)

A polymer (A) having at least one cationic group selected from the group consisting of an alkyleneimine polymer, a vinylamine polymer, and an allylamine polymer,
Not be have a cationic group, and having the polymer (A) can react with an amino group and / or imino group having a functional group (a), becomes mixed into the polymer (B), a cationic polymer Particles ,
In at least part of the particles, the amino group and / or imino group of the polymer (A) reacts with the functional group (a) of the polymer (B), so that the polymer (B) is polymer (A )
The amount of cationic groups present on the particle surface is 0.05 meq. / G or more,
The polymer (B) is obtained by polymerizing a non-cationic radical polymerizable monomer having a water solubility of 0.01 to 10% by weight,
The content of the functional group (a) in the polymer (B) before the reaction is 1 to 40 mol% with respect to the amino group and / or imino group in the polymer (A).
Cationic polymer particles. Dispersion state of a non-cationic radical polymerizable monomer in an aqueous medium in which a polymer (A) having at least one cationic group selected from the group consisting of an alkyleneimine polymer, a vinylamine polymer and an allylamine polymer is present. In the state of forming a non-cationic radically polymerizable monomer using a radical polymerization initiator, a method for producing cationic polymer particles ,
The water solubility of the non-cationic radical polymerizable monomer is 0.01 to 10% by weight,
At least one of the non-cationic radical polymerizable monomers has a functional group (a) capable of reacting with the amino group and / or imino group of the polymer (A), and the non-cationic radical polymerizable property The content of the functional group (a) in the monomer component is 1 to 40 mol% with respect to the amino group and / or imino group in the polymer (A).
A method for producing cationic polymer particles. The radical polymerization initiator is an initiator having a functional group capable of reacting with an amino group and / or imino groups the polymer (A) has, a manufacturing method of the cationic polymer particles of claim 2.