JP4999333B2 - Rust prevention material - Google Patents

Description

  The present invention relates to a rust preventive material, and in particular, relates to a rust preventive material optimal for a steel sheet used in applications such as building materials, home appliances, and automobiles.

  Steel sheets with zinc-based coating layers, such as galvanized steel sheets, that have been chromated with a treatment liquid containing hexavalent chromium as the main component for the purpose of improving corrosion resistance have traditionally been used as automobiles and home appliances as steel sheets with high corrosion resistance. It has been widely used for building materials. However, hexavalent chromium is a pollution-controlling substance. In recent years, regulations for use in home appliances and automobiles are being strengthened, and replacement with chromate-free steel plates that do not contain hexavalent chromium is being promoted.

  As one of efforts to make chromate-free, surface-treated steel sheets with a pollution-free treatment film that does not use hexavalent chromium at all have been proposed. Among these, a method using an organic compound or an organic resin has been proposed (for example, Patent Document 1). Among them, there is an example in which silica supporting calcium in an organic film of a surface-treated steel sheet is added as a rust preventive material (for example, Patent Documents 2 and 3). This is presumed that the calcium ions eluted from the silica carrying calcium exhibit a rust preventive effect by forming a precipitation film.

JP 2005-154812 A Japanese Patent Laid-Open No. 9-12931 JP 2004-358743 A

  The surface-treated steel sheet coated with an organic resin containing silica loaded with calcium as a rust preventive material exhibits a considerable rust preventive effect, but in order to obtain the desired rust preventive effect, the type and composition of additives added separately. It was necessary to devise the above, and further, it was desired to improve its properties. As described above, the conventional silica loaded with calcium supports calcium by exchanging calcium ions with the surface silanol. Silanol has a weak acid point and has low ion releasing properties, and once calcium ions are present. When released, it is difficult to capture other ions therein, and it is presumed that the durability of the rust preventive effect is low.

  In order to improve this point, it is considered effective to introduce a cation exchange group that can easily carry and release metal ions into silica to carry the calcium ions. However, a desired functional group is introduced into silica. In the case of using a widely used silane coupling agent, sufficient effects cannot be obtained. That is, even if a cation exchange group is introduced into a silane coupling agent, this is reacted with silica, and calcium ions are supported on the cation exchange group, the resulting calcium ion-supporting silica is the silica of the silane coupling agent. The stability of bonding to the surface is not so high as to be satisfactory, and even when this was used as a rust preventive, a sufficient rust preventive effect could not be obtained. In particular, steel sheets are variously processed in applications such as home appliances, automobiles, and building materials, and are used for a long period of time. In these applications, harsh environments exposed to high temperatures, high humidity, and solvents, acids, etc. Since it may be used underneath, the above-mentioned problem of a decrease in the rust prevention effect occurred remarkably, and further improvement was necessary.

  In the background described above, the present invention is a rust preventive material composed of ion-exchangeable inorganic particles, which has a higher rust preventive property, and is highly superior in stability and sustainability of the rust preventive effect. The purpose is to develop.

  The present inventors have continued intensive studies to solve the above problems. As a result, it was found that the above problems can be solved by coating the surface of the inorganic particles with a polymer having a cation exchange group in which at least a part of the counter ions are metal ions, and using this as a rust preventive material. The invention has been completed.

That is, the present invention is selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphonic acid groups, phosphoric acid groups, phenolic hydroxyl groups, perfluoro tertiary alcoholic hydroxyl groups, arsenic acid groups, and selenic acid groups. Or coated with a polymer having two or more cation exchange groups, and at least a part of the counter ions in the cation exchange groups is Mg, Ca, Sr, Ba, Al, Ti, V, Mn, Fe, Consisting of metal ion-supporting inorganic particles that are one or more metal ions selected from the group consisting of Co, Ni, Cu, Zn, Zr, Mo, and W , and the inorganic particles are a single oxide of silicon, or It is a complex oxide containing silicon as a constituent element, and is a rust preventive material characterized in that the supported amount of the metal ions is 0.05 to 1.5 mmol / g.

  The rust preventive material of the present invention has an extremely high effect of the rust preventive material, and also has excellent stability and sustainability. In particular, even when used in harsh environments exposed to high temperatures, high humidity, solvents, acids, etc., rust prevention is unlikely to deteriorate, and it is extremely useful as a rust prevention material for steel sheets used under such severe conditions. Useful.

  The rust preventive material of the present invention comprises metal ion-supporting inorganic particles, which are core inorganic particles (hereinafter also referred to as core particles) coated with a polymer having a cation exchange group, and At least a part of the counter ion in the cation exchange group of the particle is a metal ion.

It said core particles, Ri Oh inorganic particles may be appropriately selected depending on the subject or the like to provide an anti-rust material of the present invention. Inorganic particles is excellent in-chemical stability and easily in terms available are various properties, alone oxides of silicon, or a composite oxide containing silicon as an element (hereinafter, silicon-based oxide ) . As the composite oxide, those containing an alkali metal or alkaline earth metal such as sodium, potassium, magnesium and calcium are also suitable.

  More specific examples of silicon-based oxides include silicas such as quartz, precipitated silica, fumed silica, sol-gel silica; silica-titania, silica-zirconia, silica-barium oxide, silica-alumina, silica-calcia, silica -Strontium oxide, silica-magnesia, silica-titania-sodium oxide, silica-titania-potassium oxide, silica-zirconia-sodium oxide, silica-zirconia-potassium oxide, silica-alumina-sodium oxide, or silica-alumina-potassium oxide And complex oxides such as calcium silicate, talc, zeolite, and montmorillonite.

  The polymer having a cation exchange group is not particularly limited, and may be a known polymer composed of a cation exchange group and a base resin, which is generally known as a cation exchange resin. Such a polymer may be a non-crosslinked product, but by using a crosslinked polymer, the solubility in a solvent or the like is lost, and the thermal stability, moisture resistance, acid / alkali resistance, etc. are excellent, under severe conditions. Even if it is used, it is preferable because the rust preventive effect can be further reduced. In addition, since the polymer has a cation exchange group, metal ions are easily retained and are less easily detached by washing with water or the like.

  In the present invention, not only an acid type (proton type) state but also a state (salt) in which a metal ion or other cation other than a proton is substituted is called a cation exchange group. Unless otherwise specified, the acid state or the salt state is simply referred to as “... acid group” (for example, when referred to as a sulfonic acid group, an acid type sulfonic acid group and Both salt type sulfonic acid groups are shown).

  Specific examples of the cation exchange group include a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, a phosphoric acid group, a phenolic hydroxyl group, a perfluoro tertiary alcoholic hydroxyl group, an arsenic acid group, and a selenic acid group. . Among these, the sulfonic acid group is superior in that it is excellent in chemical stability and not only easy to produce a metal ion as a counter ion but also easy to produce a polymer having the cation exchange group. A group derived from a strong acid having an acid dissociation constant (pKa) of 3.0 or less, such as a phosphoric acid group, is preferred, and a sulfonic acid group is most preferred. Moreover, you may have several different cation exchange groups as needed.

  The polymer skeleton portion (matrix resin) to which the cation exchange group is bonded is not particularly limited as long as it has a structure capable of bonding a cation exchange group. When used as a rust preventive material, in order to maintain long-term sustainability, the polymerization resistance needs to be high in heat resistance, solvent resistance, and weather resistance, so that the polymer is preferably crosslinked. In that case, the cross-linking of the cross-linked polymer indicates covalent cross-linking and does not include ionic cross-linking.

  The base resin may be any known resin such as polystyrene, (meth) acrylic, epoxy, polyester, polyamide, polyimide, polyurethane, polysulfone, polyether, and polyethersulfone. Among these, in terms of easy production of metal ion-carrying inorganic particles, polystyrene and (meth) acrylic are preferable, and particularly excellent in chemical stability such as hydrolysis resistance. It is preferably a polystyrene-based resin.

  The polymer having a cation exchange group coats the core particle. In the present invention, this coating means not only the state in which the polymer covers the outermost surface of the core particle, but also the core particle has pores. In the case of having, the state which covered the wall surface of this pore, the state which exists so that this pore may be filled, or the state which combined them is also included.

  In the present invention, the metal ions carried by the metal ion-carrying inorganic particles are not particularly limited. For example, even if the metal ions are monovalent metal ions such as Li, Na, and K, the obtained particles are Good rust prevention. However, in consideration of this high antirust property, metal ions having a valence of 2 or more are preferable. Specifically, Mg, Ca, Sr, Ba, Al, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, W, etc. are mentioned. Alkaline earth metals are most preferred due to their high rust prevention effect.

  In addition, what can take a different valence among the said metals means the valence in the carried state. In addition, the metal ion-carrying inorganic particles of the present invention may carry two or more kinds of metal ions having different element types and valences.

In the metal ion-carrying inorganic particles, the metal ion is present as a counter ion in the cation exchange group. That is, at least a part of the cation exchange group exists in the state (or complex) of the metal ion. Since cation exchange groups such as sulfonic acid groups and carboxylic acid groups are monovalent, when they form a salt with a polyvalent metal ion, usually one of the polyvalent metal ions and its valence A suitable number of cation exchange group residues (R—SO ₃ ⁻ , R—CO ₂ ^—, etc., R is the base resin) will be involved in the formation of a set of salts. Some may exist in the form of a half salt. For example, a cation exchange group sulfonic acid group, when the valence of the polyvalent metal ion is a _divalent, a state of the _{R-SO 3 -M-OSO 2} -R (M represents a metal atom) but, in _part, (the L ligand) -SO 3 -M-L may exist in the form of. Conversely, not all of the cation exchange groups need to exist in the form of a salt with a metal ion, and some of them exist in the form of an acid form or a salt with an ammonium ion or the like. Also good.

Carrying amount of the metal ions in the metal ion carrying inorganic particles of the present invention, the larger the tan Jiryou, corrosion protection is enhanced, while at more than a certain extent, to the effect obtained by carrying, It becomes too expensive or the process for carrying it becomes complicated. For these reasons, the supported amount of metal ions is 0 . 05~1.5mmol / g Ru der.

  As described above, in the metal ion-carrying inorganic particles used in the present invention, the metal ion is present as a counter ion in the cation exchange group. Accordingly, the polyvalent metal ions supported as counter ions can be supported in large amounts as the cation exchange capacity in the metal ion-supported inorganic particles increases, but those having an extremely large ion exchange capacity can be produced. In some applications, a cation exchange group that does not participate in counter ion formation with a metal ion may have an adverse effect. The cation exchange capacity (= number of cation exchange groups) in the metal ion-carrying inorganic particles of the present invention is preferably 0.005 to 4 mmol / g (weight of dry particles; the same applies hereinafter), and 0.1 to 3 mmol / g is more preferable. In addition, when a polymer having a cation exchange group of the present invention is produced by a production method as described later, generally, inorganic particles having a cation exchange capacity of Xmmmol / g are converted to N-valent metal ions. The amount carried is about 1.2 to 0.3 times (mmol / g) of X / N.

  The particle size, particle size distribution, shape, etc. of the metal ion-carrying inorganic particles are not particularly limited, and may be appropriately selected according to the application. These particle sizes, particle size distributions, shapes, and the like can be controlled by selection of core particles, the amount of polymerizable monomer used for coating, and the like by a manufacturing method as described later.

  The smaller the average particle size and the larger the specific surface area, the larger the contact area with the surroundings, the better the effect as a rust preventive, and the better dispersibility and coating properties when kneaded into organic resins, etc. The average particle diameter of the ion-carrying inorganic particles is preferably 0.005 to 100 μm, more preferably 0.005 to 10 μm, and particularly preferably 0.005 to 1 μm.

Furthermore, it is preferable that the average particle diameter of the primary particles constituting the particles is smaller because a dense rust preventive film can be formed. The average primary particle diameter of such particles is preferably 0.001 to 10 μm, more preferably 0.005 to 5 μm, and particularly preferably 0.005 to 1 μm. The specific surface area of the metal ion carrying inorganic particles is preferably from 1~400m ² / g, particularly preferably from 50 to 400 m ² / g. The shape is not particularly limited and may be any shape such as a spherical shape, a plate shape, a layer shape, a whisker shape, or an indefinite shape.

  In addition, the inorganic particles in the metal ion-carrying inorganic particles are obtained by coating the core particles with a polymer, and the ratio of both is not particularly limited. Usually, the higher the proportion of the polymer, the more cation exchange groups can be present, and thus the amount of supported metal ions also increases. Therefore, the average thickness of the polymer coating layer is preferably 1/10000 to 1/10 of the diameter of the core particle and 1000 nm or less. In addition, from the viewpoint of satisfactorily exhibiting rust prevention properties, the average thickness of the polymer coating layer is preferably 1/1000 to 1/100 of the diameter of the core particles and 100 nm or less.

  The method for producing the metal ion-carrying inorganic particles used in the present invention is not particularly limited. Preferably, the inorganic particles coated with the polymer having a cation exchange group contain metal ions. What is necessary is just to process with a solution, to carry out ion exchange, and to make it dry. According to this method, various metal ions can be selected as the metal ion solution used for the treatment, and therefore inorganic particles carrying any metal ions can be produced very easily.

  Also, the method for producing inorganic particles coated with a polymer having a cation exchange group is not particularly limited, but preferably, the inorganic particle powder is brought into contact with the polymerizable monomer under stirring. Then, the polymerizable monomer is adsorbed on the particles, then the adsorbed polymerizable monomer is polymerized, and further, a cation exchange group is introduced as necessary (this method is the present invention). Have already filed as Japanese Patent Application No. 2004-131877 and have already been published as Japanese Patent Application Laid-Open No. 2005-60668. In this prior application, the obtained particles can be used as a rust preventive. It is not described or suggested at all.) In general, when processing in a non-powder state such as a suspension or paste by dispersing the powder in a solvent, it is difficult to control the thickness and chemical composition of the coating layer, In some cases, a coalesced coating layer cannot be obtained. However, in this method, since the core particles are brought into a powder state when they are brought into contact with the polymerizable monomer, the above-described problems hardly occur. Hereinafter, these methods will be described more specifically.

  First, a method for producing inorganic particles coated with a polymer having a cation exchange group will be described. In this method, a powder comprising particles having a structure in which core particles are coated with a polymer is produced. The core particle is a core particle in the metal ion-carrying inorganic particles used in the present invention. Therefore, as described above, the particle size, particle size distribution, shape, and the like of the finally obtained metal ion-carrying inorganic particles greatly depend on which particles are used as the core particles.

  In this method, a polymerizable monomer is brought into contact with and adsorbed on the core particles. Since the core particles are not dispersed in the solvent, the phenomenon that the polymerizable monomer used remains dissolved in the solvent and hardly adsorbs hardly occurs, but in order to adsorb the polymerizable monomer efficiently, the polymerizable monomer It may be preferable to modify the surface of the core particle depending on the physical properties of the monomer.

  Specifically, the polymerizable monomer to be adsorbed (in the case of a mixture, the main component polymerizable monomer) is a carboxyl group, phosphonic acid group, phosphoric acid group, sulfonic acid group or the like. In the case of a compound having a cation exchange group and thereby having a solubility in water of 5% by mass or more, it is generally preferable to use particles having a water / n-hexane dispersibility tendency on the water side as the core particles. In particular, when the compound has a sulfonic acid group and has a solubility in water of 5% by mass or more and a solubility in n-hexane of 5% by mass or less, particles having a water / n-hexane dispersibility tendency on the water side are used. It is important to obtain coated particles having a uniform polymer layer.

  On the other hand, a polymerizable monomer having a solubility in water of less than 5% by mass is adsorbed because it has no cation exchange group or has a large influence of a hydrophobic group even if it has a cation exchange group. In this case, it is preferable to use particles having a water / n-hexane dispersibility tendency on the hexane side. In particular, when a polymerizable monomer having a solubility in water of less than 1% by mass such as styrene is to be adsorbed, not only the water / n-hexane dispersibility tends to be on the hexane side but also the modified hydrophobicity degree. It is preferable to use 40% by mass or more (particularly 50 to 90% by mass) of particles as core particles.

  The water / n-hexane dispersibility ratio was determined by adding almost equal amounts of water and n-hexane to a glass test tube or the like, adding a small amount of particle powder thereto, and shaking well so that the particles are on the water side. It can be judged by the distribution to the hexane side. The modified hydrophobization degree is a methanol concentration at which the amount of suspension obtained by a method of measuring the suspension ratio of the particle powder with respect to a solution with a changed water-methanol ratio is 50%.

  In general, inorganic particles such as inorganic oxide particles not subjected to any surface treatment have a water / n-hexane dispersibility tendency on the water side. The method for setting the dispersibility of such inorganic particles to the n-hexane side is not particularly limited, and a known surface treatment method may be employed. Specific examples include treatment with a silane coupling agent, a titanate coupling agent, silicone oil, cyclic siloxane, hexaalkyldisilazane, and the like. Among these, even when the amount of reactive groups such as silanol groups on the surface of the particle is small, it is uniformly processed, and since there are only one or two reaction ends, the treatment agent itself gels and fine particles are formed. An agglomerate generated by mixing or gelation does not adhere to the surface of the inorganic particles to form a non-uniform surface, and further, because it is highly reactive, it becomes an efficiently treated particle and is not immobilized. The treatment with cyclic siloxane or hexaalkyldisilazane is preferred in that the treatment agent is less likely to elute. Furthermore, in the case of particles treated with cyclic siloxane or hexaalkyldisilazane, the acid resistance and alkali resistance of the coated particles obtained by the production method of the present invention are higher than in the case of particles treated only with a silane coupling agent. Tend to be better.

  Among cyclic siloxanes, the following general formula is used because it is easy to obtain inorganic particles whose surface is uniformly coated due to large strain and easy cleavage.

(Wherein R ¹ is a monovalent hydrocarbon group having 1 to 18 carbon atoms, a hydrogen atom or a hydroxyl group, Me is a methyl group, and n is an integer of 3 to 6)
It is preferable to treat with a cyclic siloxane represented by

In the above formula, R ¹ is a hydrocarbon group having 1 to 18 carbon atoms. The hydrocarbon group is not particularly limited as long as it has 1 to 18 carbon atoms, and may be any known group. Specific examples of the hydrocarbon group include straight chain or branched alkyl groups having 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and an octadecyl group, a carbon such as a cyclopentyl group and a cyclohexyl group. A cyclic alkyl group having 4 to 6 carbon atoms; an alkenyl group having 2 to 18 carbon atoms such as vinyl group, allyl group, isopropenyl group, and octadecynyl group; phenyl group, naphthyl group, tolyl group, styryl group, xylyl group, mesityl group, etc. A substituted or unsubstituted aryl group having 6 to 18 carbon atoms; an aralkyl group having 7 to 9 carbon atoms such as a benzyl group and a phenethyl group;

  Among the hydrocarbon groups, a linear alkyl group having 1 to 3 carbon atoms, a phenyl group, a phenethyl group, or a vinyl group is particularly preferable. Moreover, in said formula, n is 3-6, Most preferably, it is 3-4.

  Specific examples of such cyclic siloxanes include octamethylcyclotetrasiloxane, hexamethylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, trimethyltrivinyl. Examples thereof include cyclotrisiloxane, tetramethylcyclotetrasiloxane, and trimethylcyclotrisiloxane.

  In the case of treatment with hexaalkyldisilazane, the following general formula

(In the above formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 18 carbon atoms.)
A hexaalkyldisilazane represented by In the above formula, examples of the alkyl group represented by R ^{2 to} R ⁷ include the same groups as those exemplified as R ¹ in the cyclic siloxane. In order to obtain high processing efficiency, the R ^{2 to} R ⁷ are preferably a linear alkyl group having 1 to 3 carbon atoms. R ^{2 to} R ⁷ may be different from each other, but are preferably the same group from the standpoint of availability and surface treatment efficiency.

  Specific examples of particularly preferred hexaalkyldisilazane include hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane and the like.

  The cyclic siloxane and hexaalkyldisilazane may be used alone or in combination with two or more different compounds. Moreover, you may use together with another surface treating agent.

  The method of surface treating and hydrophobizing inorganic particles using the surface treating agent as described above is not particularly limited as long as it is in accordance with a known technique, but aggregation is unlikely to occur during the treatment. A method using a dry process that does not use a solvent is preferable because it does not require time and effort such as removal.

  For example, when the treatment with hexaalkyldisilazane is performed, it is preferable to employ the methods described in Japanese Patent No. 2886037 and Japanese Patent No. 2886105. In this method, inorganic particles are introduced into a container, the container is sealed, and hexamethyldisilazane is introduced at a temperature of about 200 to 300 ° C. under an inert gas atmosphere so that the partial pressure is about 25 to 150 kPa. And it is carried out by holding for a certain time, preferably about 0.5 to 2 hours. At this time, water vapor is present in the container at a partial pressure of about 30 to 100 kPa, and a basic gas such as ammonia is allowed to coexist at a partial pressure of about 10 to 100 kPa as necessary.

  In the case of treating with cyclic siloxane, the liquid particles or gaseous cyclic siloxane is added to inorganic particles while stirring the inorganic particles, and then heated in a sealed reaction system. To describe this method more specifically, first, while stirring particles with a high-speed stirring device such as a Henschel mixer in an inert gas atmosphere such as nitrogen or argon, a cyclic siloxane or the like is added in a gaseous or liquid state thereto, It can be produced by heating to a predetermined temperature in a sealed reaction system. The method of adding cyclic siloxane or the like to the particles may be either liquid or gaseous, and when added in liquid form, it may be added dropwise or by spraying. It is particularly preferable to add it in the form of a gas from the viewpoint that it can be uniformly processed. The heating temperature is not particularly limited as long as the particle surface can be hydrophobized by cyclic siloxane or the like, but in general, it is preferably not less than the boiling point of the cyclic siloxane to be used, and usually about 100 to 300 ° C. It is. Further, the stirring speed and the like at the time of stirring are not particularly limited, and cannot be generally specified depending on the stirring device or the like to be used, but is generally about 100 to 3000 rpm.

  By adopting such a dry treatment, it is possible to prevent agglomeration in the surface treatment step of inorganic particles, and if necessary, it is possible to coat with a polymer in the same reaction vessel, which is industrially advantageous. is there.

  Next, the polymerizable monomer is adsorbed on the hydrophobic or hydrophilic particles as described above. The polymerizable monomer may be any polymer as long as it is polymerized and has a cation exchange group or can be introduced with a cation exchange group after polymerization. But you can. In general, a monofunctional polymerizable monomer having a cation exchange group or a functional group capable of introducing a cation exchange group is used. Moreover, it is preferable that it is a polymerizable monomer which has radically polymerizable unsaturated double bonds, such as a (meth) acryl group and a styryl group, at the point which is excellent in polymerizability.

  Specific examples of these polymerizable monomers include the following.

1. Monofunctional monomers having a cation exchange group Aromatic vinyl monomers such as styrene sulfonic acid and its salts, vinyl naphthalene sulfonic acid and its salts. (Meth) acrylic acid, maleic acid, 2- (meth) acryloyloxyethyl succinate and its salts, 2- (meth) acryloyloxyethyl maleate and its salts, 2- (meth) acryloyloxyethyl phthalate, etc. (Meth) acrylic monomers having a carboxyl group and salts thereof. (Meth) acrylic monomers having a phosphate group such as (meth) acryloxyethyl acid phosphate and salts thereof. (Meth) acrylic monomers having a sulfonic acid group such as 2- (meth) acrylamido-2-methylpropanesulfonic acid and 3-methacryloyloxypropanesulfonic acid, and salts thereof. Vinyl monomers having a phosphonic acid group such as vinylphosphonic acid and salts thereof.

2. Monomers having functional groups capable of introducing cation exchange groups Styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, p-tert-butylstyrene, chloromethylstyrene, p-chlorostyrene, vinylnaphthalene Aromatic vinyl monomers such as; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Trimethydecyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylic acid Monofunctional (meth) acrylic acid ester such as 2-methoxyethyl and 2-ethoxyethyl (meth) acrylate Lu monomer.

  The above polymerizable monomers are all single-tubular, and polymers polymerized using only these monomers are non-crosslinked. As described above, the polymer having a cation exchange group that coats the core particle has a higher stability and sustainability of the rust-preventing effect than the crosslinked product. It is preferable to use a polyfunctional polymerizable monomer as a crosslinking agent together with the monomer to obtain a crosslinked polymer. Examples of such polyfunctional polymerizable monomers include the following.

3. Polyfunctional polymerizable monomers that serve as crosslinking agents Aromatic vinyl monomers such as polyfunctional aromatic vinyl compounds such as divinylbenzene, divinylbiphenyl, trivinylbenzene, and divinylnaphthalene; ethylene glycol di ( (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolmethane tri (meth) acrylate, tetra Polyfunctional non-fluorine (meth) acrylic monomers such as methylolmethane tetra (meth) acrylate, methylenebis (meth) acrylamide, hexamethylenedi (meth) acrylamide; divinylsulfone, diallyl phthalate, etc.

  A monofunctional polymerizable monomer having a cation exchange group or a monofunctional polymerizable monomer having a functional group capable of introducing a cation exchange group, as well as a polyfunctional polymer serving as a crosslinking agent. When used in combination with a monomer, the polyfunctional polymerizable monomer is used in an amount of about 0.05 to 99% by mass, preferably 0.5% in the total polymerizable monomer. It is preferable to be about 30% by mass.

  The above polymerizable monomers may be used in combination with a plurality of different monomers as required.

  Further, in order to facilitate the adsorption of the polymerizable monomer as described above to the core particles, and to impart various other physical properties, it is also possible to use a mixture of polymerizable monomers other than those described above. . For example, when a monofunctional monomer having a cation exchange group or a monofunctional polymerizable monomer having a functional group capable of introducing a cation exchange group is solid at room temperature and normal pressure, the polymerization is performed. It is also preferable to dissolve in a liquid polymerizable monomer copolymerized with the polymerizable monomer. Such polymerizable monomers include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N-methylol (meth) ) (Meth) acrylic monomers having a hydroxyl group such as acrylamide; (meth) acrylonitrile, (meth) acrolein, vinyl acetate, N-vinylpyrrolidone, diacetone (meth) acrylamide, methyl vinyl ketone and the like.

  The polymerizable monomer (or a mixture thereof) may be brought into contact with the core particles alone, but is preferably added as a mixture with a polymerization initiator added in order to efficiently perform the polymerization step described later. .

  As a polymerization initiator to be used, a known polymerization initiator may be appropriately selected and used according to the polymerizable monomer to be used, and is not particularly limited. However, the polymerization initiator exhibits a polymerization initiation ability by heating. This is preferable because the operation is simpler. For example, when a vinyl monomer is used as the polymerizable monomer, octanoyl peroxide, lauroyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butyl peroxide Organic peroxides such as oxyisobutyrate, t-butylperoxylaurate, t-hexylperoxybenzoate, di-t-butylperoxide, 2,2, -azobisisobutyronitrile and 2,2 An azobis-based polymerization initiator such as, -azobis- (2,4, -dimethylvaleronitrile) can be cited as a suitable polymerization initiator.

  These polymerization initiators are generally used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymerizable monomer.

  Moreover, you may use what mix | blended other additives, such as a polymerization inhibitor, a polymerization inhibitor, and an ultraviolet absorber, as needed. Further, when the polymerizable monomer is a solid, it can be made liquid by using a small amount of a solvent.

  When contacting the above-mentioned polymerizable monomer and a mixture of optional components blended as necessary (hereinafter, polymerizable monomer mixture) with the powder of the core particles, the core particles are stirred. It is preferable to carry out below. Without stirring, the coating layer will be non-uniform. The stirring method is not particularly limited, and any known method may be used as long as particles can be floated by the stirring. For example, it may be directly mechanically stirred using a Henschel mixer or the like, or may be agitated by blowing a high-speed air stream, or a method of giving vibration or swinging from the outside. The stirring speed in the case of direct mechanical stirring cannot be generally specified depending on the material, shape, and particle diameter of the core particles, but generally it may be about 100 to 3000 rpm.

  The method for bringing the polymerizable monomer mixture into contact with the core particles is not particularly limited. Preferably, the polymerizable monomer mixture is gaseous or liquid in an inert gas atmosphere such as nitrogen or argon. More preferably, the liquid polymerizable monomer mixture is sprayed and added in an inert gas atmosphere. A known spray nozzle or the like can be suitably used for spraying. The addition rate is not particularly limited and may be determined according to various other conditions, but is generally 1 to 20 ml / min per 100 g of core particles. The temperature conditions for adding these are not particularly limited, and may be under cooling or under heating. However, since the monomer is polymerized before coating at an excessively high temperature, generally about −10 to 40 ° C. is preferable. .

The amount of the polymerizable monomer to be added is not particularly limited and may be appropriately set depending on the desired coating thickness. However, when the amount of the polymerizable monomer mixture used is too large, the particles are aggregated. In order to obtain the metal ion-carrying inorganic particles of the present invention, a pulverization step is required thereafter. When the amount is too large, the core particles are present in the polymer, and it is difficult to obtain the inorganic particles of the present invention. The amount of the polymerizable monomer used to form a coating layer having an appropriate thickness depends on the specific surface area and particle diameter of the core particles and cannot be generally stated, but in general, the specific surface area of the particles is 1 m. per ^2, the use of polymerizable monomer ^{2 × 10 -4 ~8 × 10 -4} g, since the coating layer having a thickness of about 1nm equivalent is formed, based on this value, the particle size Ya It can be appropriately determined according to the specific surface area. A typical use amount of the polymerizable monomer is 0.001 to 0.4 g per 1 g of core particles.

  Moreover, when adding the above-mentioned solvent or other optional components, if the amount of the solvent used is too large, the particles are likely to aggregate. Therefore, even when all the polymerizable monomers, solvents, and other components to be added are added, it is preferable that the amount of the polymerizable monomer, the solvent, and the other components be within the range that does not form a paste or dispersion and maintains the powder state. In order to avoid agglomeration between particles, generally the amount of polymerizable monomer, solvent and other components to be added is the amount of oil absorption of the powder composed of core particles (mixture of polymerizable monomer, solvent and other components). 3/4 or less, more preferably 1/2, further preferably 1/3 or less, particularly preferably 1/5 or less, and most preferably 1/10 or less.

  In this way, by adding the polymerizable monomer (and other optional components) to the stirred core particle, the polymerizable monomer (and other optional component) is adsorbed on the core particle. . In the production method of the present invention, the polymerizable monomer is then polymerized to form a polymer, and the powder is made of particles in a state where the core particles are covered with the polymer.

  As a method of polymerizing the polymerizable monomer thus adsorbed, a known method may be adopted as a polymerization method of the polymerizable monomer used, and it is not particularly limited. Is a method of initiating polymerization by heating. When the polymerizable monomer used is a vinyl monomer, it can be more efficiently polymerized by using a thermal polymerization initiator as described above. Moreover, the said heating temperature should just set suitably well-known conditions with the kind etc. of the polymerizable monomer and polymerization initiator which were used, and is generally 40-230 degreeC, Preferably it is about 50-180 degreeC.

  Further, when the polymerizable monomer used is a vinyl monomer, these operations are preferably performed in an inert gas atmosphere such as nitrogen or argon in order to prevent polymerization inhibition by oxygen.

  The pressure in the reaction vessel is not particularly limited, and may be pressurized, normal pressure, or reduced pressure. Depending on the type of polymerizable monomer used, pressurization is preferred among them. The pressure for pressurization is generally about 0.01 to 0.6 MPa. The polymerization time may be appropriately set according to the other conditions as described above, and is generally about 30 to 180 minutes.

  In addition, the manufacturing method of the particle | grains coat | covered with the said polymer is an example, and you may manufacture with a wet method. Moreover, when obtaining a crosslinked polymer, after coating with a non-crosslinked polymer, it may be produced by crosslinking by electron beam irradiation or the like.

  When the particles coated with the polymer obtained as described above are produced using a polymerizable monomer having a cation exchange group such as a sulfonic acid group or a carboxylic acid group, the metal described later is used as it is. What is necessary is just to use for the process of carrying ion.

  On the other hand, when a monomer having a functional group capable of introducing a cation exchange group is used, it is necessary to introduce a cation exchange group before carrying a metal ion, which is a cation exchange resin. This can be carried out in accordance with the method for introducing a cation exchange group in the production method.

  For example, when a polymerizable monomer such as styrene is used and the polymer has an aromatic hydrocarbon ring such as a benzene ring in its structure, it is known to react with fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, etc. Sulfonation or the like may be performed by a method. In the case of a polymer having an ester structure such as a methyl methacrylate polymer, an acid group can be introduced by hydrolysis of the ester. Furthermore, when it has an epoxy group or a chloromethyl group, it can be sulfonated by using sulfanilic acid, sodium sulfite or the like to introduce a sulfonic acid group.

  In addition, various ion exchange groups can be introduced by applying other known chemical reactions. When introducing these functional groups, it is necessary to select the introduction form and reaction conditions as appropriate so that the covering polymer is not lost due to peeling or the like. In general, a polymer of an aromatic vinyl monomer is chemically stable as compared with a (meth) acrylic monomer having an ester structure, and various functional groups can be easily introduced.

  In introducing such a functional group, a method of appropriately setting reaction conditions such as temperature and pressure without using a solvent and contacting the reactive agent in gaseous form with the coated particles in order to prevent aggregation of the resulting particles. Is preferably adopted. For example, when introducing a sulfonic acid group in the introduction of the cation exchange group, a method of contacting with a sulfur trioxide gas can be suitably employed.

  The inorganic particles coated with the polymer having a cation exchange group obtained by such a production method are obtained by exchanging a counter ion in the cation exchange group with a metal ion, whereby the metal ion-carrying inorganic particle of the present invention is used. Can do. As a method for exchanging the counter ion in the cation exchange group with a metal ion, various conventionally known methods can be adopted, and there is no particular limitation. Preferable examples include a method of mixing with a solution containing a target metal ion, followed by filtration and further washing with ion-exchanged water or the like, and a method of mixing with a solution containing the metal ion and then drying as it is.

  The metal ion source in the solution containing metal ions is not particularly limited as long as the solution can be adjusted. Specific examples include salts of inorganic acids such as nitrates, sulfates and hydrochlorides (chlorides), organic acid salts such as acetates, ammonium salts, hydroxides, and the like.

  The solvent for the solution is not particularly limited, and water or an organic solvent may be used. However, it is particularly preferable to use water from the viewpoints of economy, environment, and safety because adjustment of the solution containing metal ions is easy. If it is necessary to adjust the solubility when preparing a solution containing metal ions, an acid (sulfuric acid, nitric acid, hydrochloric acid, acetic acid, etc.) or alkali (ammonia, etc.) is added to the solution. May be.

  The concentration of the metal ion solution is not particularly limited, but a metal ion concentration of about 0.001 to 5 mol / L may be used in terms of easy preparation and excellent operability. Preferably it is about 0.01-1 mol / L.

  When mixing inorganic particles coated with a polymer having a cation exchange group and a metal ion solution, the mixing ratio depends on the ion exchange capacity of the inorganic particles, the concentration of the metal ion solution, and further the support. Depending on the amount of metal ions to be used, etc., it cannot be generally stated, but when performing filtration and washing, it is 1 time or more, preferably 1.5 times or more, more preferably 2 times the X / N. As described above, it is particularly preferable to use an excessive amount of metal ions so that the ratio is three times or more. On the other hand, if the amount is too large, there is a problem that a large amount of waste liquid containing metal ions is generated. On the other hand, when directly drying after mixing, the concentration and amount of the solution may be adjusted so as to be in the range of about 1.2 to 0.3 times the X / N.

  Further, it is preferable to mix the inorganic particles coated with the polymer having a cation exchange group and the metal ion solution with stirring. The mixing and stirring time is usually about 1 minute to 24 hours. The temperature at the time of mixing may be in the range from the freezing point to the boiling point of the solution, and usually at room temperature.

  When filtration and washing are performed, the filtration is not particularly limited as long as the target inorganic particles are retained, and a known filtration means may be selected as necessary. Further, centrifugal sedimentation or the like may be used instead of filtration.

  Washing is preferably performed with water that does not contain contaminating ions such as ion-exchanged water or distilled water. Washing may be performed until unnecessary components such as excess polyvalent metal ions and anion components eluted by ion exchange are washed away to a necessary level. The end point of washing can be confirmed by the metal ion concentration, pH, color tone, etc. in the filtrate.

  The drying may be performed under the condition that the polymer covering the core particles is not decomposed or the like, and any known drying method such as heat drying, air drying, or reduced pressure drying may be applied. When an aqueous solution is used, in order to save drying time, it may be dried after being replaced with a volatile organic solvent such as alcohol or acetone. When heating, the temperature is preferably 150 ° C. or lower, and more preferably 120 ° C. or lower. Note that in the case of metal ions whose valence changes when heated in the presence of oxygen, such as in the air, heating may be performed in an inert gas atmosphere such as nitrogen or argon. Conversely, in the production of the metal ion-carrying inorganic particles of the present invention, after the metal ions are carried by the above method, the target valence is actively oxidized or reduced. The metal ion can also be made.

  The dried product obtained as described above is usually a powder having the same particle size and particle size distribution as the inorganic particles coated with the polymer having a cation exchange group as described above. May be in a state of Such agglomeration is usually pulverized under use conditions (for example, mixed with a resin component), but may be pulverized and pulverized as necessary. Conversely, granulation can also be performed by a known method for the purpose of improving the handleability.

  The metal ion-carrying inorganic particles of the present invention that can be produced as in the above example are the mechanical strength of the core inorganic particles and the cation with the metal ions present in the coating layer of the polymer as counter ions. Various physical properties derived from exchange groups, and further, excellent powder having both physical properties of the polymer itself, in particular, the cation exchange group captures zinc ions and iron ions eluted from the steel sheet, Instead, it has a function of releasing a metal ion such as calcium that has been carried to form a rust-preventing film, so that it is excellent in rust prevention. Further, the cation exchange group exhibiting rust prevention property is excellent in the stability and sustainability of the rust prevention property because it is bonded to the polymer covering the core particles and has excellent resistance.

  In the present invention, as a method of using the metal ion-carrying inorganic particles as a rust preventive material, a known method of a rust preventive material in the form of inorganic particles used for a metal member can be employed without limitation. As a metal member, a well-known metal material can be used, For example, metal plates, such as a steel plate, a stainless steel plate, an aluminum plate, an aluminum alloy plate, a titanium plate, a copper plate, are mentioned. These metallic members may be made of an alloy.

  The surface of these materials may be plated, and examples of the type of plating include zinc plating, aluminum plating, copper plating, and nickel plating. These alloy platings may be used. In the case of steel plates, hot-dip galvanized steel plates, electrogalvanized steel plates, zinc-nickel alloy plated steel plates, hot-dip galvanized steel plates, aluminum-plated steel plates, aluminum-zinc alloyed steel plates, stainless steel plates, etc. Plated steel sheet can be applied. Among these, zinc-based plated steel sheets and aluminum-based plated steel sheets correspond to metal members that can be used particularly effectively.

  It is common to use such a metal member by coating the organic resin composition containing the rust preventive material of the present invention. In this case, examples of the organic resin include epoxy resins, modified epoxy resins, polyurethane resins, polyester resins, alkyd resins, acrylic copolymer resins, polybutadiene resins, phenol resins, and adducts or condensates of these resins. One of these can be used alone, or two or more can be mixed and used. Considering the dispersibility of the polymer-coated inorganic particles having ion exchange properties, an epoxy resin, a modified epoxy resin, and an acrylic copolymer resin are particularly preferable.

  Moreover, the compounding quantity of a rust preventive material is 1-100 weight part with respect to 100 weight part of organic resins, Preferably it is 10-60 weight part. Arbitrary methods, such as a coating method, a dipping method, and a spray method, are employable as the coating method to the surface of a metal member. The coating thickness of the organic resin composition is 0.1 to 5 μm after drying, preferably 0.5 to 3 μm, particularly preferably 0.5 to 1 μm.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these.

1. Measuring methods of physical properties Various physical properties of raw materials and products used in each example and comparative example were measured by the following methods.
-Average primary particle diameter High-definition image analysis software IP-1000PC (Asahi Engineering Co., Ltd.) using images of 1000 or more and less than 2000 images of particles taken with a scanning electron microscope (SEM) or transmission electron microscope (TEM). The average particle size of the primary particles was determined assuming that the particle shape was spherical.
-Specific surface area Using a specific surface area measuring device (manufactured by Shimadzu Corporation: Flowsorb 2-2300 type), nitrogen gas was used as an adsorbed gas, and the BET method was used.
Cation exchange capacity measurement Particle powder is dispersed in 1 mol / l HCl aqueous solution and stirred for 10 hours or more to form a hydrogen ion type, followed by filtration and washing, and the residue in 1 mol / l NaCl aqueous solution. The mixture was stirred for 10 hours or more to replace the sodium ion type. Subsequently, the liberated hydrogen ions contained in the solution obtained by filtration were quantified with a potentiometric titrator (COMTITE-900, manufactured by Hiranuma Sangyo Co., Ltd.) (A: mol).

Subsequently, the particles are dispersed in a 1 mol / l HCl aqueous solution, stirred for 4 hours or more, and the residue obtained by filtration is thoroughly washed with ion-exchanged water, dried at 60 ° C. for 5 hours, and its weight is measured. (W _C : g). Based on the above measurements, the following equation cation exchange capacity * cation exchange capacity _{= A × 1000 / W C [} mmol / g- dry weight]
Determined by
-Amount of metal ion supported The content of metal atoms was measured by a fluorescent X-ray analyzer (manufactured by Rigaku Corporation: X-ray spectrometer 3270) to determine the amount supported (mmol / g).

2. Production of metal ion-supporting inorganic particles Production Example 1
A stainless steel with a specific surface area of 200 m ² / g, an average primary particle size of 0.016 μm, and 50 g of silica powder (product name QS102; hereinafter referred to as QS102) manufactured by a thermal decomposition method and having an internal volume of 1000 ml The autoclave was charged. After the inside of the autoclave was replaced with nitrogen gas, 20 g of octamethylcyclotetrasiloxane (D4) was atomized with a two-fluid nozzle while rotating the stirring blade attached to the autoclave at 400 rpm and sprayed uniformly onto the silica powder. . After stirring for 30 minutes with nitrogen gas flowing, the autoclave was sealed and heated at 275 ° C. for 1 hour. Subsequently, the system was depressurized while being heated to remove unreacted D4. The obtained particle powder is hereinafter referred to as QS102-D4.

  50 g of QS102-D4 was charged into a stainless steel autoclave having an internal volume of 1000 ml. After the inside of the autoclave was replaced with nitrogen gas, the stirring blade attached to the autoclave was rotated at 800 rpm to polymerize 5 g of styrene, 0.5 g of divinylbenzene, and 0.3 g of t-butylperoxy-2-ethylhexanoate. The monomer mixed solution was atomized with a two-fluid nozzle for about 15 seconds and sprayed onto silica powder to wet the surface. After stirring for 30 minutes, the autoclave cock was closed and sealed, the temperature was raised from 20 ° C. to 80 ° C. over 1 hour, and kept at the same temperature for 1 hour to polymerize the polymerizable monomer.

  50 g of the obtained cross-linked polystyrene-coated silica is transferred to a pressure-resistant polytetrafluoroethylene container, solid sulfur trioxide is put into a flask directly connected to the container, and the vaporized sulfur trioxide is added with nitrogen gas to the cross-linked polystyrene. It is sent to a container containing coated silica for 15 minutes, the sulfur trioxide gas concentration in the system is set to 30 vol% or more, nitrogen gas is further introduced into the system, the pressure is increased to about 0.3 MPa, and stirring is performed in a sealed state. Then, it was sulfonated by heating at 80 ° C. for 1 hour. Subsequently, the system was evacuated to completely remove the unreacted sulfur trioxide gas and recover the powder. The obtained particles had a sulfonic acid group and had a cation exchange capacity of 0.48 meq / g.

50 g of the obtained crosslinked polystyrene-coated silica having sulfonic acid groups introduced therein is put in a glass container, and 700 ml of calcium nitrate aqueous solution having a calcium ion concentration of 0.1 mol / l is added and dispersed, and ion exchange treatment is performed at room temperature for 2 hours while stirring. went. Subsequently, filtration was performed, and washing was further performed 4 times with 300 ml of ion exchange water. After completion of washing, the particles were dried at 80 ° C. to obtain calcium ion-carrying particles. The average primary particle size was 0.016 μm, the specific surface area was 140 m ² / g, and the supported amount of calcium ions was 0.24 mmol / g.

Production Example 2
Using the same method as in Production Example 1, except that a polymerizable monomer mixed solution of 10 g of styrene, 1 g of divinylbenzene, and 0.5 g of t-butylperoxy-2-ethylhexanoate is used, Similarly, silica carrying calcium ions was produced. The average primary particle size was 0.018 μm, the specific surface area was 120 m ² / g, and the calcium ion loading was 0.65 mmol / g.

Production Example 3
In the same manner as in Production Example 1, except that a polymerizable monomer mixed solution of 5 g of styrene and 0.3 g of t-butylperoxy-2-ethylhexanoate was used, calcium was produced in the same manner as in Production Example 1. Non-crosslinked polystyrene-coated silica carrying ions was produced. The average primary particle size was 0.016 μm, the specific surface area was 120 m ² / g, and the calcium ion loading was 0.25 mmol / g.

Production Example 4
Magnesium ions produced in the same manner as in Production Example 1 except that the calcium nitrate aqueous solution used for the ion exchange treatment of the crosslinked polystyrene-coated silica having sulfonic acid groups introduced therein was changed to a magnesium nitrate aqueous solution. The silica which supported was manufactured. The average primary particle size was 0.016 μm, the specific surface area was 140 m ² / g, and the supported amount of magnesium ions was 0.22 mmol / g.

Production Example 5
Using the same method as in Production Example 1, an aqueous calcium nitrate solution used for the ion exchange treatment,
A silica carrying magnesium ions was produced in the same manner as in Production Example 1 except that the aqueous solution was changed to a magnesium nitrate aqueous solution. The average primary particle size was 0.016 μm, the specific surface area was 120 m ² / g, and the supported amount of magnesium ions was 0.44 mmol / g.

Production Examples 6-9
A calcium nitrate aqueous solution used for the ion exchange treatment of the crosslinked polystyrene-coated silica introduced with a sulfonic acid group, produced in the same manner as in Production Example 1, was used as a strontium nitrate aqueous solution (Production Example 5), a zinc nitrate aqueous solution (Production Example 6), Silica carrying various metal ions was produced in the same manner as in Production Example 1 except that the aqueous solution was changed to a titanium sulfate aqueous solution (Production Example 7) and a zirconium sulfate aqueous solution (Production Example 8). All the particles have an average primary particle diameter of 0.016 μm, a specific surface area of 120 m ² / g, and metal ion loadings of 0.12 mmol / g (Example 5) and 0.46 mmol / g (implementation), respectively. Example 6), 0.27 mmol / g (Production Example 7), and 0.40 mmol / g (Production Example 8).

Production Example 10
50 g of QS102 was charged into a glass separable flask having an internal volume of 2000 ml. After replacing the interior with nitrogen gas, 15 g of 2-acrylamido-2-methylpropanesulfonic acid (hereinafter abbreviated as AMPSH), 1 g of ethylene glycol dimethacrylate, 15 g of water, and 16 g while rotating the stirring blade at 800 rpm. A polymerizable monomer mixed solution composed of 2-hydroxyethyl methacrylate and 0.5 g of t-butylperoxy-2-ethylhexanoate was sprayed in the form of a mist with a two-fluid nozzle over about 15 seconds. . After stirring for 30 minutes, the temperature was raised from 20 ° C. to 90 ° C. over 1 hour, and kept at the same temperature for 1 hour to polymerize the monomer. The resulting particles have sulfonic acid groups and a cation exchange capacity of 0.8 meq / g.

50 g of the crosslinked AMPSH polymer-coated silica was put into a glass container, 700 ml of a calcium nitrate aqueous solution having a calcium ion concentration of 0.1 mol / l was added and dispersed, and ion exchange treatment was performed at room temperature for 2 hours with stirring. Subsequently, filtration was performed, and washing was further performed 4 times with 300 ml of ion exchange water. After the completion of washing, the product was dried at 100 ° C. to obtain calcium ion-supporting silica. The calcium ion-supporting silica had an average primary particle size of 0.016 μm, a specific surface area of 180 m ² / g, and a supported amount of metal ions of 0.4 mmol / g.

3. Verification of rust prevention effect Examples 1 to 10, Comparative Example 1
The antirust effect was implemented using the steel plate which coated the organic resin solution containing the metal ion carrying particle obtained by manufacture examples 1-10 on the galvanized steel plate. The composition of the organic resin solution was 100 parts by weight of epoxy resin (Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd.), 85 parts by weight of YH-300, a curing agent manufactured by the same company, and 1,4,7-diazabicyclo, a curing accelerator. 1 part by weight of undecaene and 30 parts by weight of the metal ion-supporting silica produced in Production Examples 1 to 10 were blended.

  This organic resin solution composition was kneaded, pulverized with a bead mill, defoamed, and coated on a hot dip galvanized steel sheet with a bar coater. The coated steel sheet was cured as it was at 150 ° C. for 5 hours to obtain a surface-treated steel sheet. The obtained surface-treated steel sheet was evaluated for rust prevention effect by a salt spray test.

A cross-cut reaching the coated plate surface with a cutter knife is put into a test plate of a surface-treated steel plate, and the sample is left in a salt spray test machine maintained at 35 ° C., and 5% sodium chloride aqueous solution is 1 kg / cm ^2. The coating film was sprayed for 7 days at a pressure of 5 to observe rust (rust) occurrence and evaluated based on the following evaluation criteria. In addition, the corrosion condition was evaluated according to the following criteria by observing the area where rust was generated on the flat surface.

Rust generation area of flat surface is less than 0.1%: ◎
0.1% or more and less than 5%: ○
5% or more and less than 20%: △
20% or more: ×

  As shown in Table 1, Examples 1 to 10 exhibited a high rust prevention effect with little rust generation.

Moreover, as a comparative example 1, in the composition of the organic resin solution applied to the steel sheet, a commercially available rust preventive material in which calcium ions are exchanged and supported on silica without coating with a polymer instead of metal ion-supporting silica. A comparative organic resin solution containing the same amount (specific surface area: 40 m ² / g) was also produced, and the antirust property was similarly evaluated. A result is (triangle | delta) and the high antirust property like the said Examples 1-10 was not obtained.

Claims (4)

One or more cations selected from the group consisting of sulfonic acid groups, carboxylic acid groups, phosphonic acid groups, phosphoric acid groups, phenolic hydroxyl groups, perfluoro tertiary alcoholic hydroxyl groups, arsenic acid groups, and selenic acid groups Coated with a polymer having an exchange group, and at least a part of the counter ion in the cation exchange group is Mg, Ca, Sr, Ba, Al, Ti, V, Mn, Fe, Co, Ni, Cu, It consists of metal ion-supporting inorganic particles that are one or more metal ions selected from the group consisting of Zn, Zr, Mo, and W , and the inorganic particles contain a single oxide of silicon or silicon as a constituent element A rust preventive material , which is a complex oxide and has a metal ion loading of 0.05 to 1.5 mmol / g.   The rust preventive material according to claim 1, wherein the polymer having a cation exchange group is a crosslinked polymer. The rust preventive material according to claim 2, wherein the metal ions are one or more metal ions selected from the group consisting of Mg, Ca, Sr, and Ba .   The average primary particle diameter of a metal ion carrying | support inorganic particle is 0.005-1 micrometer, The rust preventive material as described in any one of Claims 1-3.