JPS63223007A - Disintegration type crosslinked resin particle and production thereof - Google Patents

Abstract

PURPOSE:To obtain particles capable of being disintegrated from not only the surface but also the interior in an ionic atmosphere and releasing metallic ions with an organic acid having biological activity and ions, by polymerizing a mixture consisting of a metallic ester type polyfunctional polymerizable monomer and polyfunctional polymerizable monomer. CONSTITUTION:The aimed particles, obtained by polymerizing a mixture consisting of 5-100wt.% metallic ester type polyfunctional polymerizable monomer expressed by formula I or II [X is -CO-, -SO2- or -PO(OH)-; Y is organic acid residue; R2 is H or CH3; R1 is monofunctional organic acid residue having biological activity; M is tri- or polyvalent metallic atom; m>=2; n>=1; m+n is equal to the valence of the metal M] and 95-0wt.% mono- and/or polyfunctional polymerizable monomer having alpha,beta-ethylenically unsaturated bond in a solvent without dissolving the formed polymer, as necessary, using a dispersion stabilizer and removing the solvent, containing groups having metallic ester bond expressed by the formula in crosslinked point and having 0.01-250mu average particle diameter.

Description

[Detailed Description of the Invention] Industrial Application Field The present invention relates to collapsible crosslinked resin particles and a method for producing the same.
More specifically, it is a novel collapsible cross-linked resin that completely disintegrates on the surface and inside to such an extent that it cannot maintain its particle shape in an ionic atmosphere, and also releases organic acids and metal ions with biological activity. This article relates to particles and their manufacturing method.

Prior Art In the field of antifouling paints for ships, etc., technology that uses resins that are hydrolyzed and gradually eluted in an ionic atmosphere such as weak alkalinity as a resin vehicle has greatly improved fuel efficiency due to antifouling performance and borizing effect. Recently, it has been receiving a lot of attention from the viewpoint of improvements.

Such resins include, for example, acrylic resins into which acyl bonds having halogenated fatty acid bonding units or electron-withdrawing groups are introduced (Japanese Patent Application Nos. 58-101463 and 56-198).
No. 240), acrylic resin containing organic tin salt (Japanese Patent Application Laid-open No. 5
No. 7-98570), polyester m resin containing metal ester bonds in the polymer main chain (Japanese Patent Application No. 165911/1983)
Various resins have been proposed, such as No. 56-165922). However, all of these have been developed as resin vehicles for antifouling paints, and are required to have not only hydrolysis ability but also film-forming ability and film properties, and therefore have their own limitations in terms of molecular weight, metal content, etc. It was to be done. In the field of paints, many attempts have been made to add resin particles to film-forming resin varnishes in order to increase the solid content concentration and improve workability without increasing the viscosity. Therefore, in the field of antifouling paints, the use of hydrolyzable resin particles without film-forming ability is also being considered. For example, special public service in 1986-
No. 3830 discloses a polymeric film-forming composition comprising a polyacrylate having the basic unit represented by M is Cu or Zn, which polyacrylate is film-forming. It is disclosed that the film-forming property may be used as a film-forming material, or it may be a film-forming film-forming film-forming film.

In the same patent, regarding the molecular weight of polyacrylates.

5,000 to 1×10 1 , it seems that crosslinked resins that do not have the so-called hydrolyzable film-forming ability are also included. However, in producing such a resin, the patent discloses a method in which a polymer or copolymer having acrylic acid groups is ion-exchanged with a metal salt solution, and the polyacrylic acid metal salt is precipitated in an aqueous medium. This precipitate is separated and added to a solvent or film-forming resin varnish. Naturally, therefore, this crosslinked resin is an amorphous precipitate, and since it gradually precipitates once it becomes water-insoluble, the acid groups of acrylic acid or methacrylic acid remain in the resin. If such resin is included in the coating, the water absorption rate is too high, so the antifouling effect will not last long due to hydrolysis.

It is easy to cause whitening of the paint film, and since the resin precipitate is not controlled as particles with a clear interface, it is not colloidally stabilized in the paint and has poor dispersion stability. was also extremely inadequate.

Therefore, it can be added to antifouling paints as resin particles, which can be disintegrated from the surface and inside in an ionic atmosphere, release antifouling metal ions as desired, and increase water absorption rate or hydrolysis rate. Research continued in order to provide disintegrating vinyl resin particles that are easy to control and extremely easy to adjust for coatings, and the present inventors first discovered the formula % formula % (wherein R2 is hydrogen or a methyl group; X is 10-11~1
0 hydrocarbon; M is a polyvalent metal atom with a valence of 2 or more; Y is an organic residue; m and n are 2≦m≦p, n=p−m, P': the valence relationship of the metal M 5 to 1 metal ester type polyfunctional polymerizable monomers represented by
00% by weight and 95-0% by weight of monofunctional and/or polyfunctional polymerizable monomers having α,β-ethylenically unsaturated bonds
An average compound having crosslinking points containing metal ester bonds obtained by polymerizing a monomer mixture consisting of the following in a solvent that does not dissolve the resulting polymer.

Collapsible vinyl resin particles having a particle diameter of 0.01 to 250 μm were discovered and a patent application was filed on August 26, 1986 under the title of the invention ``Collapsible Vinyl Resin Particles''.

The present invention further develops the above invention to obtain novel collapsible crosslinked resin particles.

The problem that the invention aims to solve is that it can be stably dispersed and contained as resin particles in a resin liquid such as a paint, and that it cannot be disintegrated from the surface or inside in an ionic atmosphere such as acidic or basic. ,
Organic acids that release metal ions and impart desired properties biologically or scientifically, such as organic acids with biological activity or organic acids that modify the coating surface, such as hydrophilicity or lipophilicity. It is an object of the present invention to provide novel collapsible crosslinked resin particles that can also release .

Means for Solving the Problems According to the present invention, the above object is achieved when the crosslinking point has the formula -X
-Osum-M-yaR,)n -・-(1)-p-
A bond represented by; R1 is a monovalent organic acid residue having biological activity; M is a polyvalent metal atom with a valence of 3 or more; m is an integer of 2 or more; n is an integer of 1 or more, provided that m+n is a metal M This can be achieved by using collapsible crosslinked resin particles containing a group having a metal ester bond represented by (equal to the valence of ) and having an average particle size of 0.01 to 250μ.

The collapsible resin particles according to the present invention are novel resin particles discovered by the present inventors.

R.

(CH,=C-X-0 surface-M-tRx) n
”・(n) Or Ryo (CH,=C-Y-X-○ force “M→R1)n...(■
)-p- bond; Y is an organic residue R2 is hydrogen or a methyl group; R8 is a monovalent organic acid residue having biological activity; M is a polyvalent metal atom with a valence of 3 or more; (an integer of 2 or more, n is an integer of 1 or more, where m+n is equal to the valence of the metal M) 5 to 1 metal ester type polyfunctional polymerizable monomers
00% by weight and monofunctional and/or polyfunctional polymerizable monomers having α, β-ethylenically unsaturated bonds 95~o′Wi
% of a monomer mixture is polymerized in a solvent that does not dissolve the produced polymer, optionally using a dispersion stabilizer, and the solvent is removed.

Alternatively, a resin having an acid group represented by the formula -X-OH or its alkali metal salt ○ -P-) and a resin having an acid group represented by the formula -X-OH (-P-) and a resin having an acid group represented by the formula -X-OH (where Rz is a monovalent organic acid residue having biologically active ability) An organic acid is reacted with a hydroxide, halide, sulfide (including sulfate and nitrate), or oxide of a trivalent or higher polyvalent metal at a temperature below the decomposition point of the metal compound. Grind the product.

It can be produced industrially advantageously by a classification method.

In the first method for producing resin particles of the present invention, the polymerizable unsaturated organic acid of the metal ester type polyfunctional polymerizable monomer represented by formula (n) or formula (m) used as a raw material Or hydroxides, halides, sulfides, or oxides of trivalent or higher valent metal atoms for their alkali metal salts.

It can be easily produced by reacting it with an organic acid having a monovalent biological activity represented by COOH, if desired, in an appropriate solvent at a temperature below the decomposition temperature of the metal salt.

The polymerizable unsaturated organic acids used in the above method include:
For example, methacrylic acid, acrylic acid, p-styrenesulfonic acid, 2-methyl-2-acrylamidopropanesulfonic acid, acidophosphooxypropyl methacrylate, 3-chloro-2-acidophosphooxypropyl methacrylate, acidophosphooxyethyl methacrylate , itaconic acid (anhydride), maleic acid (anhydride), monoalkyl itaconate (e.g. methyl, ethyl, butyl, 2-ethylhexyl, etc.), monoalkyl maleate (e.g. methyl).

(ethyl, butyl, 2-ethylhexyl, etc.); haphazard combinations of OH group-containing polymerizable unsaturated monomers and acid anhydrides, such as 2-hydroxyethyl (meth)acrylate, succinic anhydride, maleic anhydride, phthalic anhydride, etc. Hafestel and the like can be used alone or in combination of two or more.

Examples of trivalent or higher valent metals include Group IIb of the periodic table (e.g. A1, Ga, TI), Group IVa (e.g. Ti, Z
r), rVb group (e.g. Si, Ge, Sn, Pb),
One or more metals of the Va group (e.g. V), the VIa group (e.g. Cr, Mo) and iron are used, and these metals include hydrates, halides, especially chlorides, sulfides (sulfates, nitrates). ) or in oxide form.

Furthermore, organic acids with monovalent biological activity represented by R1C0OH are useful as medicines, agricultural chemicals, repellents, bactericidal agents, antibacterial agents, antifungal agents, in vitro substances, antibiotics, fragrances, preservatives, etc. Various aliphatic, aromatic, alicyclic, and heterocyclic organic acids are used.

Typical examples include alicyclic carboxylic acids such as thiaram-bric acid and hydronocarpic acid, salicylic acid, cresotic acid, naphthoic acid, p-oxybenzoic acid, mandelic acid, dibromosalcylic acid, cinnamic acid, and caprochlorone. acid, nitrobenzoic acid,
Aromatic carboxylic acids such as 2,4-dichlorophenoxyacetic acid, 2,4.5-trichlorophenoxyacetic acid, nitronaphthalenecarboxylic acid, aspirin and nicotinic acid, lactone carboxylic acids such as purpic acid and purpicic acid,
Uracil-4-carboxylic acid, 5-fluorinated uracil-4-
Carboxylic acids, uracil derivatives such as uracil-5-carboxylic acid, penicillin U, ampicillin, penicillin B
Carboxylic acids having a penicillin skeleton such as Benicillanic acid, Benicillinic acid, Penicillin O, and others such as sarcomycin, chloramphenicol, variotin, and tripalazine.

Examples include rifamycin B and lusonsomycin.

Biologically active substances containing alcoholic hydroxyl groups are also acid anhydrides (e.g. succinic anhydride, maleic anhydride).

Carboxylic acids can be introduced and used by halfesterification with phthalic anhydride, tetrahydrophthalic anhydride). These alcoholic hydroxyl-containing biologically active substances include testosterone, uridine, thymidine, lementhol, cinnamic alcohol, benzyl alcohol, maltol, linalool, dimethylbenzyl carbinol, lonol, and the like.

There are dithiocarbamates such as methyldithiocarbamate.

(3) ○ Those having -0-S- bonds include 1-nato-4-sulfonic acid, paraphenylbenzenesulfonic acid,
Examples include sulfur-containing aromatic compounds such as β-naphthalenesulfonic acid and quinolinesulfonic acid.

Examples include triethylpyrophosphate, dimethylamino phosphate, and various other organic phosphoric acid compounds.

(5) As having a -9- bond.

Examples include compounds having groups.

Examples include ocarboxylic acids.

(7) Those having a -0- bond include phenol,
Cresol, xylenol, thymol, carvacrol, eugenol, phenylphenol, benzylphenol, guaiacol, butylstilbene, (di)nitrophenol, nitrocresol, methyl salicylate, benzyl salicylate, (mono, di, tri, tetra, penta) Chlorophenol, chlorocresol, chloroxylenol, chlorothymol, p-chloro-0-cyclohexylphenol, p-chloro-0-cyclopentylphenol, p-chloro-0-n-hexylphenol, p
-chloro-0-benzylphenol, p-chloro-0-
In addition to phenols such as benzyl-m-cresol,
Examples include β-naphthol and 8-hydroxyquinoline.

These are typical examples of organic acids that can be used, but the present invention is not limited to such organic acids. , any organic acid can be used.

Further, α, β-
As the ethylenically unsaturated compound, any monofunctional or polyfunctional polymerizable monomer used in the production of ordinary acrylic resins or vinyl resins can be used, and these are usually divided into the following groups.

(2) Carboxyl group-containing monomers, such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc.

(2) Hydroxyl group-containing monomers, such as 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, furyl alcohol, methalyl alcohol, etc.

(2) Nitrogen-containing alkyl acrylates or methacrylates, such as dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate.

■) Polymerizable amides, such as acrylamide and methacrylic acid amide.

■) Polymerizable nitriles, such as acrylonitrile and methacrylate trile.

(2) Alkyl acrylates or methacrylates, such as methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, etc.

(2) Polymerizable aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, etc.

■) α-olefins, such as ethylene and propylene.

(2) Vinyl compounds 5 such as vinyl acetate and vinyl propionate.

X) Diene compounds 1 such as butadiene, isoprene, etc.

Xt) Metal-containing-functional compounds, such as vinylferrocentrickyltin(meth)acrylate, γ-methacroyloxytrimethoxysilane, etc.

Furthermore, if desired, polyfunctional polymerizable monomers having two or more radically polymerizable ethylenically unsaturated groups in the molecule may also be used, specific examples of which include ethylene glycol diacrylate and ethylene glycol dimethacrylate. , triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1 ,6-
Hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate, glycerol diacrylate, glycerol allyloxy dimethacrylate, 1 , 1.1-trishydroxymethylethane diacrylate, 1゜1, l-trishydroxymethylethane triacrylate, 1,1.1-trishydroxymethylethane dimethacrylate, i, it 1-
Trishydroxymethylethane trimethacrylate, 1
゜1.1-Trishydroxymethylpropane diacrylate, 1,1.1-trishydroxymethylpropane triacrylate, 1,1.1-trishydroxymethylpropane dimethacrylate, 1゜1.1-trishydroxymethylpropane trimethacrylate , triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate, and divinylbenzene.

The above metal ester type polyfunctional polymerizable monomer and α, β-
A monomer mixture consisting of a monofunctional and/or polyfunctional polymerizable monomer having an ethylenically unsaturated bond is polymerized according to a conventional method in a solvent that does not dissolve the resulting polymer,
Collapsible vinyl resin particles having an average particle diameter o of 01 to 250μ are produced.

In this case, the metal ester type polyfunctional polymerizable monomer can account for 5 to 100% by weight of the total monomers, but the proportion is appropriately selected in consideration of desired effects, economical efficiency, etc.

The present inventors have determined that in the crosslinked resin particles of the present invention, the crosslinking points by groups having metal ester bonds are expressed as the number of moles of organic acid involved in the crosslinking of the crosslinking points having metal ester bonds/the weight of the crosslinked resin particles (g). The crosslinking density expressed as 0.000
It has been found that when the amount is selected within the range of 0.03 to 0.1 mol/g, it is particularly useful in terms of production method or effect.

As the polymerization method, any method such as ordinary emulsion polymerization, NAD method, suspension polymerization method, or precipitation polymerization method can be used. Also, ordinary polymerization initiators can be used, such as benzoyl peroxide, t- Organic peroxides such as butyl peroxide and cumene hydroperoxide, azobiscyanovaleric acid,
organic azo compounds such as azobisisobutyronitrile, azobis-(2,4-dimethyl)valeronitrile, azobis-(2-amidinopropane) hydrochloride;
Inorganic water-soluble radical initiators such as potassium persulfate, ammonium persulfate, sodium persulfate, and hydrogen peroxide, and combinations of these inorganic water-soluble radical initiators with sodium pyrosulfite, sodium bisulfite, divalent iron ions, etc. A redox initiator such as that obtained from the above method can be conveniently used.

Further, if desired, a suitable amount of a conventional chain transfer agent such as lauryl mercaptan or hexyl mercaptan can be used in combination.

When obtaining fine particles with an average particle size of about 0.01 to 40 μm, the particles are produced by an emulsion polymerization method in an aqueous medium containing water or an organic solvent in the presence of a compound, resin, etc. having an appropriate surfactant ability. Separation of the resin particles from the emulsion is preferably carried out by spray drying the emulsion, solvent displacement, azeotroping,
Centrifugation, filtration.

This is done by removing water by a combination of drying and the like.

The resin particles of the present invention can also be produced by polymerizing monomers in an organic solvent 1 such as an aliphatic hydrocarbon such as hexane, heptane, or octane that does not dissolve the produced polymer.
In order to control the zero particle size, which is produced by the AD method and can also be obtained by the usual suspension polymerization method or precipitation polymerization method, pulverization and sieving may be performed.

Alternatively, the resin particles of the present invention can also, as already mentioned,
It is also extremely easy to react directly with a -X-OH group-containing organic acid and a hydroxide, halide, sulfide, or oxide of a trivalent or higher valent metal atom. Moreover, it can be produced industrially with advantage. In this case, the resin having an -X-OH group includes an acrylic resin having an acid group, a polyester resin, an alkyd resin,
Any coating resin can be used, such as polyether resins, epoxy resins, etc., and they can also be used in the form of alkali metal salts. The bioactive organic acid and metal salt are as already described in the first method. These can be reacted simply by mixing and heating, but in that case,
It is necessary to carry out the reaction at a temperature below the decomposition temperature of the metal salt.

In addition, when selecting a monovalent organic acid with a low boiling point and using a reaction format that involves a dehydration reaction, the monovalent organic acid will distill out of the system together with water, and metal ester bonds will be formed between the resins, resulting in an increase in viscosity. Alternatively, since there is a risk of gelation, it is preferable to use an excessive amount of organic acid to control such an increase in viscosity.

The novel crosslinked particles of the present invention can be produced very advantageously by any of the above methods, and these particles are easily hydrolyzed in an ionic atmosphere.

It is extremely useful in a wide range of applications such as paints, pesticides, etc., since it causes total disintegration of particles and releases metal ions and organic acids with bioactive potential.

The collapsible crosslinked resin particles of the present invention can be used alone or mixed with a film-forming resin varnish together with an antifouling agent to prepare an excellent antifouling paint, and the average particle size is also optimal for paints. This is particularly useful in the paint field, particularly in the antifouling paint field.

The present invention will be explained below with reference to Examples. Parts and percentages are by weight unless otherwise specified.

1-Holding type example, 1 side rush side 1 800 parts of isopropyl alcohol, 26 parts of aluminum hydroxide, and 43 parts of methacrylic acid in a four-bottle flask equipped with a reflux condenser, a stirrer, and a nitrogen introduction tube.

Add 111 parts of 2.4-dichlorophenoxyacetic acid.

A metal-containing monomer was synthesized by reacting at 50°C. 3 parts of azobisisobutyronitrile was added to this solution, and a polymerization reaction was carried out at 75°C for 4 hours.

As the reaction proceeded, the polymer precipitated. The precipitate is filtered,
After repeated washing with deionized water and acetone, it was dried.

The average particle size of the obtained particles P-1 was 2.4 μ.

Example 2 Using the same reaction apparatus as in Example 1, 800 parts of isopropyl alcohol, 65 parts of tin tetrachloride, 43 parts of methacrylic acid, and 4 parts of 2,4-dichlorophenoxyacetic acid were placed in four flasks.
4 parts and 94 parts of oleic acid were added and reacted at 50°C to synthesize a metal-containing monomer. 3 parts of azobisisobutyronitrile was added to this solution, and a polymerization reaction was carried out at 80° C. for 4 hours.

As the reaction proceeded, the polymer precipitated. Thereafter, the precipitate was filtered, washed, and dried in the same manner as in Example 1.

The average particle diameter of the obtained particles P-2 was 4.5 μ.

Example 3 Using the same reaction apparatus as in Example 1, 1000 parts of isopropyl alcohol and 6 parts of chromium trichloride were placed in a four-loaf flask.
89 parts of water salt, 45 parts of sorbic acid.

Add 63 parts of phosphoxypropyl methacrylate acid,
A metal-containing monomer was synthesized by reacting at 50°C. 5 parts of 2-hydroxyethyl acrylate, 10 parts of methyl methacrylate, and 3 parts of azobisisobutyronitrile were added to this solution, and a polymerization reaction was carried out at 80°C for 4 hours.

As the reaction proceeded, the polymer precipitated. Thereafter, the precipitate was filtered, washed, and dried in the same manner as in Example 1.

The average particle diameter of the obtained particles P-3 was 2.2μ.
It was.

Example 4 Using the same reaction apparatus as in Example 1, 800 parts of isopropyl alcohol and 54.2 parts of pig iron trichloride were placed in four flasks.
-Methyl 2-acrylamidopropanesulfonic acid (72 parts), 2,4-dichlorophenoxyacetic acid (44 parts), and sorbic acid (45 parts) were added and reacted at 50°C to synthesize a metal-containing monomer. 3 parts of azobisisobutyronitrile was added to this solution, and a polymerization reaction was carried out at 80° C. for 4 hours.

As the reaction proceeded, the polymer precipitated. Thereafter, the precipitate was filtered, washed, and dried in the same manner as in Example 1.

The average particle diameter of the obtained particles P-4 was 1.8 μ.

Example 5 Using the same reaction apparatus as in Example 1, 1000 parts of isopropyl alcohol, 26 parts of aluminum hydroxide, 25 parts of nicotinic acid, and 61 parts of methacrylic acid were added to a four-bottle flask, and the mixture was reacted at 50°C to form a metal-containing monomer. synthesized a polymer. 30 parts of methyl methacrylate and 3 parts of azobisisobutyronitrile were added to this solution, and a polymerization reaction was carried out at 80° C. for 4 hours.

As the reaction proceeded, the polymer precipitated. Thereafter, the precipitate was filtered, washed, and dried in the same manner as in Example 1.

The average particle diameter of the obtained particles P-5 was 1.1 μ.

Example 6 Using the same reaction apparatus as in Example 1, 800 parts of isopropyl alcohol, 71 parts of tetraisopropioxytitanate, 110 parts of 2,4-dichlorophenoxyacetic acid, and 43 parts of methacrylic acid were added to a fourth flask. A metal-containing monomer was synthesized by reacting at ℃. 3 parts of azobisisobutyronitrile was added to this solution, and a polymerization reaction was carried out at 80° C. for 4 hours.

As the reaction proceeded, the polymer precipitated. Thereafter, the precipitate was filtered, washed, and dried in the same manner as in Example 1.

The average particle diameter of the obtained particles P-6 was 1.6 μ.

Example 7 Using the same reaction apparatus as in Example 1, 1000 parts of isopropyl alcohol, 1-85 parts of tetra-n-butyrolooxytitane, 90 parts of 2゜4-dichlorophenoxyacetic acid, and methacrylic acid were placed in four flasks. 60 parts were added and reacted at 50°C to synthesize a metal-containing monomer. In this solution, 5 parts of styrene, 1 part of ethyl acrylate, n.
15 parts of -butyl and 3.5 parts of azobisisobutyronitrile were added, and a polymerization reaction was carried out at 75°C for 5 hours.

As the reaction proceeded, the polymer precipitated. Thereafter, the precipitate was filtered, washed, and dried in the same manner as in Example 1.

The average dimensional diameter of the obtained particles P-7 was 1.1μ. Example 8 (1) Preparation of emulsifier having amphoteric group Stirrer, nitrogen introduction tube, temperature control device, condenser, decanter - Bishydroxyethyltaurine 13 to 2Q Kolben with
4 parts, 130 parts of neopentyl glycol, 236 parts of azelaic acid, 186 parts of phthalic anhydride and 27 parts of xylene were charged and the temperature was raised. Water produced by the reaction is azeotroped with xylene and removed.

The temperature was raised to 190°C over about 2 hours from the start of refluxing, stirring and dehydration were continued until the acid value equivalent to carboxylic acid reached 145, and then the mixture was cooled to 140°C.

Next, the temperature was maintained at 140°C, and the "Cardura E1o"
314 parts of persatic acid glycidyl ester (manufactured by Shell) were added dropwise over 30 minutes, and stirring was continued for 2 hours to complete the reaction. The resulting polyester resin has an acid value of 5
9, hydroxyl number 90, M n = 1054. This is called emulsifier A.

(2) Production of metal-containing monomer Using the same reaction apparatus as in Example 1, 200 parts of isopropyl alcohol, 72 parts of tetraisopropioxytitanate, 87 parts of trimethylpyrophosphoric acid,
42 parts of methacrylic acid was added and reacted at 50°C. Thereafter, isopropyl alcohol was removed under reduced pressure to obtain metal-containing monomer A.

(3) Production of resin particles 380 parts of deionized water, 2 parts of emulsifier As, and 5 parts of dimethylethanolamine were charged into a 2Q reaction vessel equipped with a stirrer, a nitrogen inlet tube, and a temperature control device, and the temperature was raised to 80°C while stirring.
℃, and add 2. azobiscyanovaleric acid to this.
5 parts of deionized water and 1 part of dimethylethanolamine
．． A mixed solution consisting of 6 parts of methyl methacrylate, 100 parts of methyl methacrylate, and 35 parts of ethyl acrylate, and a solution of 65 parts of metal-containing monomer A dissolved in 250 parts of deionized water were added dropwise over 90 minutes. After that, stirring was continued for another 90 minutes to obtain an aqueous dispersion of fine resin particles having an average dimensional diameter of 52 mμ. By freeze-drying this fine resin dispersion, fine resin particle powder could be obtained. This resin powder is referred to as P-8.6 Example 9 After charging 100 parts of deionized water and 30 parts of polyvinyl alcohol with an average molecular weight of 1500 into an IQ reaction vessel equipped with a stirrer, a cooler, and a temperature control device, LOOORPM was added.
35 parts of methyl methacrylate and 2-acrylic acid were heated to 60°C while thoroughly purging with N2 gas while stirring.
2 parts of hydroxyethyl and 2,2'-azobis-(2
, 4-dimethylvaleronitrile) (trade name v-65, manufactured by Wako Pure Chemical Industries, polymerization agent) and Example 8.
25 parts of metal-containing monomer A used in and 250 parts of deionized water
After the completion of the dropwise addition, the temperature inside the reaction vessel was raised to 70°C.

The reaction was further carried out for 5 hours to obtain a fine resin particle suspension.

The suspension was centrifuged to separate the supernatant into resin particles, and only the resin particles were dispersed in deionized water. After repeating this process three times, fine resin particle powder could be obtained. The average dimensional diameter of the resin particles was 7.1 microns. This resin dispersion is freeze-dried to obtain fine resin powder P-9.

Comparative Example 1 Isopro alcohol 800 was added to the same reaction apparatus as in Example 1.
1 part, 50 parts of ethylene glycol dimethacrylate, and 3 parts of azobisisobutyronitrile were added, and polymerization was carried out in the same manner as in Example 1. The obtained particles are referred to as Comparative Particles 1.

Comparative Example 2 Comparative particles 2 were obtained in the same manner as in Example 1, except that 124 parts of oleic acid was used instead of 111 parts of 2,4-dichlorophenoxyacetic acid.

Comparative Example 3 800 parts of deionized water, 50 parts of nickel dimethacrylate, and 2 parts of azobiscyanovaleric acid were added to the same reaction apparatus as in Example 1, and a polymerization reaction was carried out at 80° C. for 4 hours. Thereafter, the same treatment as in Example 1 was carried out to obtain Comparative Particles 3.

Particles P-1 to 9 of Examples 1 to 9, Comparative Examples to 3, and Comparative Particles 1 to 3 (1100 II) were each placed in a 500 oct Meyer, and about 1 g (wet weight) of the diatom Navicula sp. A biological activity test was conducted by adding 300 oc of filtered seawater and keeping it at 25°C for 7 days. Biological activity was evaluated based on whether the diatoms were alive or dead and changes in the weight of the diatoms.

The results are shown in Table 1.

(Leaving space below) 1st Table of beans (1 g each of particles P-1 to 9 of Examples 1 to 9 and Comparative Examples 1 to 3 and Comparative particles 1 to 3 were placed in a 500 cc Meyer,
In this, ■ Tetrahydrofuran (THF) ■ Deionized water ■ Alkaline aqueous solution (OH aqueous solution PH = 10.2) 2
The disintegration property was examined after 120 hours under penetration at 25°C with addition of 00mα. The disintegration property was evaluated by measuring the suspended/transparent state of the test solution and the metal concentration in the solution after filtration by atomic absorption spectrometry.

The results are shown in Table 2.

(Leaving space below) Table 2 From the results of the biological activity test and disintegration test, the particles of the present invention disintegrate after hydrolysis even in a slightly alkaline atmosphere such as seawater, and at the same time release biologically active substances. It is an epoch-making particle.

Claims (5)

[Claims] (1) At the crosslinking point, the formula -X-O)-_mM-(R_1)_n...(I)
(X in the formula is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼
A bond represented by; R_1 is a monovalent organic acid residue with biological activity; M is a polyvalent metal atom with a valence of 3 or more; m is an integer of 2 or more; n is an integer of 1 or more, provided that m+n is a metal M Collapsible crosslinked resin particles containing a group having a metal ester bond represented by (2) The crosslinking density by the group having a metal ester bond represented by formula I is 0. 00003 to 0.01 mol/g. (3) M is IIIb, IVa, IVb, Va, VIa of the periodic table
Particles according to claim 1 selected from the group consisting of group metals and Fe. (4) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (II) Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (III) (In the formula, X is ▲ Mathematical formulas, chemical formulas, tables, etc. There are▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼Or▲There are mathematical formulas, chemical formulas, tables, etc.▼
A bond represented by; Y is an organic residue; R_2 is hydrogen or a methyl group; R_1 is a monovalent organic acid residue with biological activity; M is a polyvalent metal atom with a valence of 3 or more; m is an integer of 2 or more ,
Metal ester type polyfunctional polymerizable monomers 5 to 1 (n is an integer of 1 or more, provided that m+n is equal to the valence of metal M)
00% by weight and 95-0% by weight of monofunctional and/or polyfunctional polymerizable monomers having α,β-ethylenically unsaturated bonds
-X-O)-_mM-(R_1) is characterized in that a monomer mixture consisting of )＿n・・・(I
) (in the formula, X, M, R_1, m, and n are respectively as described above)
A method for producing collapsible crosslinked resin particles containing a group having a metal ester bond represented by the following at a crosslinking point and having an average particle size of 0.01 to 250μ. (5) Acid group or its alkali metal salt represented by the formula -X-OH (where X is ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas, There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
), an organic acid represented by R_1-COOH (R_1 is a monovalent organic acid residue having biologically active ability), and hydroxides, halides, and sulfides of trivalent or higher polyvalent metals ( (including sulfates and nitrates) or oxides at a temperature below the decomposition point of the metal compound, and the reaction product is pulverized and classified. R_1)_n (in the formula, X, M, R_1, m and n are respectively as described above)
A method for producing collapsible crosslinked resin particles containing a group having a metal ester bond represented by the following at a crosslinking point and having an average particle size of 0.01 to 250μ.