CN102159625A - Method for producing hydrophilized microparticles, and hydrophilized microparticles produced by same - Google Patents

Abstract

Provided is a method for producing vinyl polymer microparticles each having a highly hydrophilized surface without deteriorating excellent physical properties including mechanical properties and other properties including particle-size-controlling properties inherent in vinyl polymer microparticles. Also provided are the hydrophilized particles. Specifically disclosed is a method for producing hydrophilized microparticles, which is characterized by comprising contacting a mixed gas essentially comprising a fluorine gas and a gas of a compound containing an oxygen atom with base particles to render the surfaces of the base particles hydrophilic, wherein the base particles comprise vinyl polymer microparticles having a mass average particle diameter of 1000 microns or less and the mixed gas contains the fluorine gas at a concentration of 0.01 to 1.0 vol%.

Description

The preparation method of hydrophilization particulate and the hydrophilization particulate that utilizes this method to obtain

Technical field

The present invention relates to a kind of surface in substrate particle carries out wetting ability and gives processing to prepare the method for hydrophilization particulate.

Background technology

Ethene base system (being total to) polymer particles, usually, by being that raw material carries out the incompatible preparation of radical polymerization with (methyl) acrylic monomer or polystyrene ethene base system monomer composition as polymer raw, can be by selecting the monomeric kind of employed ethene base system, combination etc., perhaps, by in described ethene base system monomer composition, adding inorganic set member or the non-polymerization various rerum naturas such as the physical strength of controlling particulate, thermotolerance, optical characteristics, surface shape, porousness that become to grade.In addition,, can suitably select suspension polymerization, letex polymerization, seeding polymerization, dispersion polymerization etc. as polymerization process, can in the scope of broad, prepare particle dia, size-grade distribution Be Controlled vinyl based polymer particulate.Vinyl based polymer particulate, even in high molecular particle, also easy above-mentioned various rerum naturas of control from meaningful property consideration economically, are used to paint additive, film additive etc. widely in the industrial field.

In recent years, being background based on water systemization of the coating of environmental problem etc., in addition, be target with carrying out of new purposes field to the good characteristic of applying flexibly vinyl based polymer particulate, carried out trial with the surface hydrophilic of vinyl based polymer particulate.

As the hydrophilicity-imparting treatment of such particulate, known following method.For example, in patent documentation 1, putting down in writing and a kind ofly have the cross-linked polymer particle of reactive functional groups, making to have and with these functional groups the modification of reactive group of chemical reactions or the method for non-modified poly (ethylene glycol) reaction to take place with respect to the surface.In this technology, when making the reaction of modification or non-modified poly (ethylene glycol), the secondary aggegation easily takes place in particulate.In addition; the reactive functional groups of cross-linked polymer particle; be introduced in the polymkeric substance by (methyl) acrylic monomer with reactive functional groups; but; when the monomer that contains this functional group is high density; there is following problem: easily cause the generation, the generation of secondary agglutinative of particulate or coarse particle etc., the control of the size-grade distribution difficulty that becomes, the mechanical characteristics of particle reduces.Therefore, it is difficult introducing reactive functional groups with high density at microparticle surfaces.In addition, owing to be the surface treatment method of chemical, therefore, can not get equably by the particulate of hydrophilization.There is the problem of the particulate can not get having equably and to high-density hydrophilic group in its result.

In patent documentation 2, putting down in writing a kind of adsorption surface promoting agent with technology with the surface hydrophilic of fluoro-resin particle.Therefore this technology, is difficult to keep unvaryingly the hydrophilization state owing to only make SURFACTANT ADSORPTION on the fluoro-resin particle surface, and hydrophilic degree is also low.

In patent documentation 3, putting down in writing and a kind ofly making ozone gas be dissolved in the water and make microparticulate in ozone water, carry out the method for hydrophilicity-imparting treatment.In the method, when carrying out hydrophilization fully, there are the intensity of particle and the problem that thermotolerance reduces.

Above patent documentation 1-3, therefore the secondary aggegation of particulate, easily takes place in the processing owing to being in liquid phase, can not handle uniformly, therefore, is difficult to obtain the high particulate of hydrophilic degree.

In patent documentation 4,5, putting down in writing a kind of method of using ozone gas to carry out hydrophilicity-imparting treatment.In patent documentation 6, putting down in writing a kind of method of utilizing the Low Temperature Plasma Treating of having used argon gas to come microparticle surfaces is carried out hydrophilicity-imparting treatment.Therefore these methods, easily produce the static aggegation owing to be processing in having the gas of electric charge, are difficult to equably particle surface be carried out hydrophilicity-imparting treatment.

The prior art document

Patent documentation

Patent documentation 1: the spy opens flat 5-1106 communique

Patent documentation 2: the spy opens the 2005-336241 communique

Patent documentation 3: the spy opens the 2007-326935 communique

Patent documentation 4: the spy opens the 2001-212447 communique

Patent documentation 5: the spy opens the 2005-239915 communique

Patent documentation 6: the spy opens the 2007-184278 communique

Summary of the invention

In the present invention, be that problem is described with preparation method and the such hydrophilization particulate that the high vinyl based polymer particulate of a kind of hydrophilization degree that idiocratically obtains the surface such as controlled that is used for not damaging various rerum naturas such as favorable mechanical characteristic that above-mentioned vinyl based polymer particulate had, thermotolerance, particle dia is provided.

The present inventor is in order to address the above problem, hydrophilization methods to vinyl based polymer particulate has been carried out deep research, it found that, by under specific atmosphere, handling vinyl based polymer particulate, can not damage mechanical characteristics that vinyl based polymer particulate had etc. good idiocratically obtain the high particle of wetting ability, thereby finish the present invention.

The preparation method of the hydrophilization particulate of the present invention that can address the above problem, it is processing by the mixed gas that must contain the fluorine gas and the gas of the compound that contains Sauerstoffatom is contacted with substrate particle, make the surface hydrophilic of substrate particle, thereby the method for preparing the hydrophilization particulate, it is characterized in that, with the quality average particle diameter is that vinyl based polymer particulate below the 1000 μ m is a substrate particle, and the concentration of the fluorine gas in the mixed gas is 0.01-1.0 volume %.

As the above-mentioned gas that contains the compound of Sauerstoffatom, preferred oxygen.In addition, after making above-mentioned mixed gas and processing that substrate particle contacts, the preferably processing that substrate particle is contacted with moisture.As this moisture, be preferably alkaline aqueous solution and/or, water and/or water vapour.

Comprise the hydrophilization particulate that obtains by above-mentioned preparation method in the present invention.

In preparation method of the present invention, can not damage ground such as favorable mechanical characteristic that vinyl based polymer particulate had, evenly and to heavens hydrophilization be carried out on the surface of vinyl based polymer particulate.And this preparation method is easy method, can carry out the hydrophilicity-imparting treatment of height in the short period of time, and therefore, economy is good.Thus, by preparation method of the present invention, can provide a kind of at an easy rate and have evenly and the vinyl based polymer particulate of the hydrophilic surface of height.

Embodiment

Preparation method of the present invention is by the processing that the mixed gas that must contain the fluorine gas and the gas of the compound that contains Sauerstoffatom is contacted with substrate particle, makes the method for the surface hydrophilic of substrate particle.Consider to handle by this, the hydrogen that is combined on the carbon is replaced to oxygen and fluorine, becomes-C (F)=O, and afterwards, part or all of-C (F)=O is converted into carboxyl.Therefore, near surface generation a plurality of-C (the F)=O and/or the carboxyl of hydrophilization particulate, wetting ability significantly improves.In addition, in the time of with the generation of above-mentioned-C (F)=O or carboxyl, the reaction of CF key has also taken place to be transformed in the CH key in the part particle skeleton.In addition, the existence of these functional groups or key can be confirmed by x-ray photoelectron spectroscopy (ESCA) etc.

After making above-mentioned mixed gas and processing that substrate particle contacts, the processing that the substrate particle after the processing is contacted with moisture.By with the contacting of moisture ,-C (F)=O more effectively is converted into carboxyl.As moisture, preferred alkaline aqueous solution and/or, water and/or water vapour.

Surface at the hydrophilization particulate that obtains by preparation method of the present invention has-C (F)=O and/or carboxyl, still, and further, in particle surface or inside, except these groups,, can also have and the covalently bound fluorine composition of the carbon of hydrocarbon (being also referred to as the covalent attachment fluorine) as the fluorine composition.The covalent attachment fluorine by with-C (F)=O and/or carboxyl coexistence, have the effects such as secondary aggegation that suppress between the particle, therefore, even also preferably there is the covalent attachment fluorine in trace.

In addition, by the hydrophilization particulate that preparation method of the present invention obtains, be attached with hydrogen fluoride (HF) sometimes as the fluorine composition.This HF may become harmful on operation hydrophilization particulate of the present invention, therefore preferred its content is few more good more.More preferably do not adhere to HF fully.

These fluorine compositions can be divided into the content of solvability fluorine and the content of non-solubility fluorine.That is, in solubility test described later, the fluorine that ionization is dissolved in the solvent is called the solvability fluorine, its content is called the content of solvability fluorine.In the solvability fluorine, contain the fluorine that comes from hydrofluoric fluorine and coming from of above-mentioned adhering to (dissociating)-C (F)=O.

On the other hand, in solubility test, failing the dissolved fluorine is the non-solubility fluorine, and its content is the amount of non-solubility fluorine.The non-solubility fluorine is equivalent to described covalent attachment fluorine usually, also comprises sometimes being directed to undissolvable free fluorine composition in the particle.

The content of the content of solvability fluorine and non-solubility fluorine is represented with the content (mg/g) that fluorine atom contained in every 1g particle converts.

According to the security of having studied the hydrophilization particulate and the result of characteristic, preferably have the non-solubility fluorine to a certain extent.Particularly, during for the scope of 0.1-50mg/g, show and suppress above-mentioned secondary agglutinative effect, therefore preferred.But, in the time of too much, have wetting ability to become possibility that the mechanical characteristics of insufficient or particle reduces.More preferably the content of non-solubility fluorine is 1-40mg/g, more preferably 2-20mg/g.

On the other hand, the content of solvability fluorine, aspect operation hydrophilization particulate, preferably its content is few or do not have the solvability fluorine, particularly, preferred not enough 1mg/g.More preferably below the 0.5mg/g, more preferably below the 0.2mg/g, further be preferably below the 0.1mg/g, be preferably below the 0.01mg/g especially.

The degree of hydrophilization can be with acid number (KOH dosis neutralisata: mgKOH/g) represent.The acid number of hydrophilization particulate of the present invention is preferably more than the 0.05mgKOH/g.During less than 0.05mgKOH/g, the dispersed insufficient possibility in water-medium is arranged.Acid number is more preferably more than the 0.1mgKOH/g, more preferably more than the 1mgKOH/g.During the acid number of hydrophilization particulate is defined as and the amount (mg) of the required KOH of 1g particle, determined by method described later.In addition, the hydrophobicity height of substrate particle, nonwetting in water, therefore, can not be dispersed in the aqueous medium, can not carry out the mensuration of acid number.In addition, under the situation of having carried out neutralizing treatment described later, the hydrogen atom of the carboxyl that has generated on substrate particle is replaced by alkali metal atom.Therefore, in the hydrophilization particulate behind neutralizing treatment, can not estimate hydrophilic degree by acid number.

The hydrophilization degree of particle also can represent with hydrophobic deg, utilizes the hydrophobic deg of the particle that method of the present invention obtains to be preferably below 10, most preferably is 0.Hydrophobic deg can be obtained by following method.

[hydrophobic deg]

In being placed with the glass beaker of 200cc of stirrer, the bottom adds ion exchanged water 50cc, after the particle of 0.2g swims on the water surface, the top of drop-burette is sunk in the water in beaker, gently rotating under the stirrer, adding described particle certainly after 5 minutes, gently import methyl alcohol simultaneously by drop-burette.Continue the importing of methyl alcohol, up to the complete submerged of all particles of the water surface, the import volume (cc) of the methyl alcohol when measuring the complete submerged of particle is obtained hydrophobic deg according to following formula.

The import volume (cc) of amount (the cc)+methyl alcohol of import volume (the cc) * 100/{ water of hydrophobic deg (%)=methyl alcohol }

At this, before adding methyl alcohol, swim in the situation of the complete submerged of particle of the water surface by drop-burette, judge that hydrophobic deg is 0%.

In addition, the CV value of the shape of hydrophilization particulate, average particle diameter, particle dia, the preferred mode and the scope of mechanical characteristics are identical with preferred mode and scope in the explanation of substrate particle described later.

[hydrophilicity-imparting treatment]

Hydrophilicity-imparting treatment, substrate particle contact with mixed gas and get final product, and there is no particular limitation for its method, preferably import mixed gas and handle the time method (sealing contact process) of defined in the container that can keep substrate particle under sealed state; Perhaps in the container that can keep substrate particle, make the mixed gas circulation, the method for supplying with continuously (supplying with method continuously).

During processing, preferably improve the contact efficiency of mixed gas and substrate particle, carry out hydrophilization at short notice equably.For improving contact efficiency, preferably mixed gas is diffused in the processing vessel, can enumerate that whipping apptss such as using blower carries out to mixed gas that air-flow stirs or on supporting plate etc., apply the method etc. of substrate particle thinly.In addition, also can stir substrate particle, can enumerate and use roller revolver etc. to make the processing vessel rotation or utilize whipping appts to make substrate particle mobile method etc.The method that these improve contact efficiency can also several different methods be used in combination.

On supporting plate etc., apply thinly under the situation of full substrate particle, for the ground of zero deflection between particle equably and carry out hydrophilicity-imparting treatment in the short period of time, preferably in processing vessel, load, make that the thickness of substrate particle layer is below the 2mm.The thickness of preferred particle layer is below the 0.5mm.

The concentration of the fluorine gas in the mixed gas is 0.01-1.0 volume %.When the concentration of fluorine gas is less than 0.01 volume %, the possibility that has the inadequate particle of hydrophilicity-imparting treatment to exist.Consider that from this point that has good uniformity of hydrophilicity-imparting treatment the concentration of preferred fluorine gas is more than the 0.08 volume %.The concentration of fluorine gas is 1.0 volume % when following, though adularescent or painted also seldom.More preferably the concentration of fluorine gas is below the 0.3 volume %.

In mixed gas, with fluorine gas, the gas that contains the compound of Sauerstoffatom also is must composition.As the gas of the compound that contains Sauerstoffatom, can preferably enumerate gases such as oxygen, sulfurous gas, carbonic acid gas, carbon monoxide, nitrogen peroxide.Wherein, even on the effective this point of hydrophilicity-imparting treatment under the treatment condition in gentleness, preferred oxygen.Except the gas of fluorine gas and the compound that contains Sauerstoffatom, can also in mixed gas, use rare gas elementes such as nitrogen, helium, argon gas.In addition, the outburst of dust from prevent the processing gas phase, consider, preferably use nitrogen as rare gas element in viewpoint industrial and that carry out hydrophilicity-imparting treatment safely.Therefore, the mixed gas of composition that preferably has the gas of the compound that contains fluorine gas, contains Sauerstoffatom and rare gas element further, more preferably contains the mixed gas of fluorine gas, oxygen and nitrogen as mixed gas.

As long as the concentration of the gas of the compound that contains Sauerstoffatom in the mixed gas is 0.1 volume %-99.99 volume %, just can carry out hydrophilization as the substrate particle of purpose of the present invention.The concentration of gas of compound that contains Sauerstoffatom has the possibility that has the inadequate particle of hydrophilization during less than 0.1 volume %.For the uniform particle of the degree that obtains hydrophilization (powder), in addition, for the particle that has obtained at short notice by the highly-hydrophilic change, the gas concentration that contains the compound of Sauerstoffatom is preferably more than the 0.1 volume %, more preferably more than the 0.5 volume %.On the other hand, the concentration height of gas that contains the compound of Sauerstoffatom, can not give the bad influence of hydrophilization of particle, but, the generation that dust from the inhibition hydrophilicity-imparting treatment breaks out, the reason that can carry out hydrophilicity-imparting treatment are safely considered, the gas concentration that preferably contains the compound of Sauerstoffatom is below the 10 volume %, more preferably below the 5 volume %.

Use the situation of rare gas element as the composition of mixed gas, there is no particular limitation for the concentration of rare gas element, suitably selects to get final product in the scope of the effect of not damaging the wetting ability processing that is brought by fluorine gas and the gas that contains the compound of Sauerstoffatom.Usually, be preferably below the 99 volume %.When surpassing 99 volume %, the possibility that has the inadequate particle of hydrophilization is arranged.In addition, the generation that the dust from the inhibition hydrophilicity-imparting treatment breaks out, the reason that can carry out hydrophilicity-imparting treatment safely consider that the concentration of preferred rare gas element is more than the 90 volume %, more preferably more than the 94 volume %.

The dividing potential drop of the fluorine gas in the mixed gas is 8Pa (0.06Torr) when above, and having good uniformity of hydrophilicity-imparting treatment is therefore preferred.More preferably more than the 24Pa (0.18Torr), more preferably more than the 64Pa (0.48Torr).Consider that from the decomposition of the vinyl based polymer skeleton that suppresses to bring and painted viewpoint the dividing potential drop of preferred fluorine gas is below the 1000Pa (7.5Torr), more preferably below the 700Pa (5.25Torr) by hydrophilicity-imparting treatment.

The dividing potential drop of the oxygen with oxygen during as the composition of mixed gas is considered from the viewpoint of carrying out hydrophilicity-imparting treatment equably, is preferably 70Pa (0.53Torr)～85000Pa (637.6Torr).In addition, consider, be preferably 70Pa-7998Pa (60Torr), more preferably 70Pa-3999Pa (30Torr) from viewpoint industrial and that carry out hydrophilicity-imparting treatment safely.About the dividing potential drop of the compound that contains Sauerstoffatom, preferred range also is same.

The dividing potential drop of the nitrogen with nitrogen during as the composition of mixed gas, consider from viewpoint industrial and that carry out hydrophilicity-imparting treatment safely, be preferably 3199Pa (24Torr)～79180Pa (594Torr), more preferably 71918Pa (540Torr)～79180Pa (594Torr).About the situation of the rare gas element that uses other, the preferred range of the dividing potential drop of other rare gas element also is same.

In order to carry out hydrophilicity-imparting treatment safely, the stagnation pressure of mixed gas is preferably below the 101.3kPa (760Torr).When surpassing 101.3kPa, there is mixed gas to drain to the outer possibility of container.

The ratio of mixed gas and substrate particle under the situation of sealing contact, with respect to the substrate particle of 1kg, converts with normal temperature and pressure, preferably supplies with 30L-4000L, more preferably supplies with the mixed gas of 1000L-3000L.Under the situation of continuous supply type, with respect to the substrate particle of 1kg, convert with normal temperature and pressure, the preferred total flux of supplying with is 30L-15000L, more preferably the total flux of Gong Geiing is 1000L-10000L.

Particularly, the situation of sealing contact is directly put into the chamber that can seal with substrate particle, perhaps will be placed on substrate particle in the container put into can be airtight the chamber, after the decompression, importing mixed gas, the time of handling defined.Residual when moisture is arranged, produce HF, therefore danger, during decompression, preferably carry out vacuum exhaust fully.The situation of supply type imports mixed gas in the time of defined and gets final product continuously.

The situation of sealing contact can also be before importing mixed gas, in advance to carrying out preheating in the chamber.Temperature of reaction is preferably about-20 ℃ to 200 ℃, more preferably about 0 ℃ to 100 ℃, and more preferably 10 ℃ to 40 ℃.When temperature of reaction surpasses 200 ℃, the possibility that has the vinyl polymer particle to decompose; On the other hand, when temperature of reaction was lower than-20 ℃, hydrophilicity-imparting treatment became insufficient sometimes.In addition, the meaning of so-called temperature of reaction is meant the temperature of the gas in the chamber.

When importing mixed gas, can in the chamber, import the gas of the compound that contains Sauerstoffatom or the gas beyond other the fluorine gas earlier, import fluorine gas afterwards, also can import the gas that has been pre-mixed.

The duration of contact of substrate particle and mixed gas (treatment time), there is no particular limitation, handles desirable hydrophilization degree and get final product, and roughly handles about 10 minutes to 60 minutes and finish.After the processing, preferably reduce pressure about 0.13Pa (0.001Torr) once more, import the operation of nitrogen afterwards.When this operation finishes, open into normal atmosphere.

In the preparation method of hydrophilization particulate of the present invention, preferably after the contact undertaken by above-mentioned mixed gas is handled, further make the processing that contacts with moisture again with particle after mixed gas contacts.By being formed on the particle surface with contacting of mixed gas-C (F)=O,, more effectively converted to carboxyl by contacting with moisture.In addition, can also remove the HF that generates this moment and the HF or the F that are adsorbed on the particle surface effectively ₂Above-mentioned moisture be preferably alkaline aqueous solution and/or, water and/or water vapour.

As the mode that the particle that makes after mixed gas contacts contacts with moisture, use the mode of alkaline aqueous solution as moisture; Make water and/or water vapour mode as moisture; Use alkaline aqueous solution and water and/or water vapour all can as the mode of moisture.Wherein, be preferably alkaline aqueous solution and water and/or water vapour the mode of using as moisture.In addition, there is no particular limitation for engagement sequence, from removing HF or the F that is adsorbed on the particle surface effectively ₂Deng viewpoint consider, after preferably making particle and alkaline aqueous solution contacting, the mode that contacts with water and/or water vapour again.When contacting, on particle surface, form an alkali metal salt or the amine salt (the following carboxylate salt that is called sometimes) of carboxylic acid with alkaline aqueous solution.This carboxylate salt further improves the wetting ability of particle, and is therefore preferred, afterwards, contacts with water and/or water vapour by making particle, can wash unnecessary alkaline aqueous solution.In addition, in this manual, below sometimes particle will be contacted with alkaline aqueous solution situation be called alkaline purification, the situation that particle is contacted with water is called warm water washing.

Carry out effectively changing, remove in addition, effectively HF or the F that is adsorbed on the particle surface as being used for to carboxyl or carboxylate salt ₂, reduce fluorine and the treatment process that contacts water of solvability, there is no particular limitation, for example can enumerate to be used for water vapour being sent in the chamber method that particle is contacted with water with after the chamber that contacts of gas opens into normal atmosphere; With after the chamber that contacts of gas opens into normal atmosphere water vapour is sent in the chamber will being used for, after making particle and water contacting, further, taken out particle and make it to be dispersed in the water, utilize water or contain the method that the solvent of water washs; After gas contacts, in the chamber, take out particle, the particle that takes out is immersed in other the water vapour atmosphere or utilize water or contain the method that the solvent of water washs; After gas contacts, in the chamber, take out particle, make the particle of taking-up be dispersed in the method for carrying out alkaline purification in the alkaline aqueous solution; After gas contacts, in the chamber, take out particle, after the particle of taking-up being dispersed in carry out alkaline purification in the alkaline aqueous solution, further take out particle, make it to be dispersed in the water, utilize water or contain method that the solvent of water washs etc.Be preferably 1 minute about-600 minutes with the duration of contact of moisture.

For carry out effectively-C (F)=O is to the conversion of carboxyl or carboxylate salt, in addition, in order to remove the HF that generates this moment effectively or to be adsorbed on HF or F on the particle surface ₂, the temperature of moisture (alkaline aqueous solution and/or, water and/or water vapour) is preferably more than 20 ℃, more preferably more than 40 ℃, more preferably more than 60 ℃, most preferably is more than 80 ℃.

In addition, utilize alkaline aqueous solution or water or contain the solvent treatment of water, the situation of washing particle, adding up among the 100 quality % of solvent and particle, the concentration of particle is preferably 0.5 quality %-50 quality %.During the concentration less than 0.5 quality % of particle, the amount of the fluoride waste that produces during the particle of washing defined amount increases, therefore, and the possibility that has industrial cost to raise.When the concentration of particle surpasses 50 quality %, have and wash the inadequate possibility that becomes.In order to carry out the washing of particle effectively, go back under the state of preferably in solvent, having put into particle and carry out ultrasonic dispersing.

As mentioned above, attached to the solvability fluorine that becomes to grade of the fluorine on the particle surface, have the security that causes particle or by problem such as corrosion with contacting of other material may, therefore, preferably remove the solvability fluorine as far as possible, when enforcement is used as the alkaline purification of above-mentioned moisture with alkaline aqueous solution, can more effectively remove the solvability fluorine that is adsorbed on the particle surface.

As alkaline aqueous solution, the preferred aqueous solution that uses water-soluble amines such as ammonia, monoethanolamine, diethanolamine, with alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxides, or alkali metal compounds such as alkaline carbonate such as Quilonum Retard, yellow soda ash, salt of wormwood, rubidium carbonate, cesium carbonate are dissolved in the aqueous solution that contains alkalimetal ion that forms in the water.In above-mentioned alkaline aqueous solution, preferably contain the aqueous solution of alkalimetal ion, further, more preferably contain the aqueous solution of sodium, preferred especially aqueous sodium hydroxide solution.

The concentration of alkaline aqueous solution is preferably 0.01N-5N.More preferably 0.05N-2N, more preferably 0.1N-1N.There is no particular limitation for the concrete method of alkaline purification, for example can enumerate: after the contacting of gas, after making the particle that from the chamber, takes out be dispersed in the alkaline aqueous solution of above-mentioned concentration, under the temperature more than 80 ℃, make particle contact 1 minute-600 minutes method with alkaline aqueous solution.

The amount (content of solvability fluorine) of the amount (total fluoro quantity) of contained fluorine atom in the hydrophilization particulate that obtains, ionization and free fluorine atom and by chemical bond be introduced in the particle skeleton, the amount (content of non-solubility fluorine) of unionized fluorine atom, can adopt following method to measure.

[total fluoro quantity: oxygen flask combustion method]

The particle of weighing 2mg on the filter paper of 3cm * 2cm, particle does not wrap up with dispersing.Utilize Bunsen burner to heat, continue the red heat state about 5 seconds being attached to platinum gauze on the Molotov cocktail (platinum pull バ ス ケ Star ト).Behind the cooling platinum gauze, the filter paper that has wrapped up particle is installed in the platinum gauze.In capacity is the Molotov cocktail of 500ml, put into the distilled water of 15ml, behind the wetting Molotov cocktail inwall, enclose being replaced into oxygen atmosphere in the Molotov cocktail.Then, to the igniting of the filter paper in the platinum gauze, it is promptly inserted in the flask.After the burning, rock flask 2,3 times, place after 30 minutes, the content of Molotov cocktail is moved in the polypropylene system beaker that capacity is 100ml, add distilled water again, be adjusted to and add up to 50ml.Add the 5ml damping fluid, regulate pH, under the use magnetic stirring apparatus stirs, use ionometer to measure the concentration of fluorion, obtain total fluoro quantity (mg/g) to certain value.At this, ionometer uses " Orion11150004-Star " (サ one モ Off イ Star シ ヤ one サ イ エ Application テ イ Off イ Star Network society system), and electrode uses " Orion9609BNWP " (same companies system)

[content of solvability fluorine: fluoride ion electrode method]

At capacity is the distilled water that drops into 50ml in the polypropylene system beaker of 100ml, adds the damping fluid of 5ml again.Under the use magnetic stirring apparatus stirs, fluoride ion electrode is immersed in the solution.Drop into the particle of 0.2g, measure the concentration that drops into back 360 minutes fluorion, as the content (mg/g) of solvability fluorine.Ionometer and electrode identical ionometer and electrode when using mensuration with total fluoro quantity.

[content of non-solubility fluorine]

The content of non-solubility fluorine (mg/g) utilizes following formula to obtain.

The content of non-solubility fluorine=(total fluoro quantity)-(content of solvability fluorine)

In addition, having or not of the generation of the carboxyl on the particle surface after the hydrophilicity-imparting treatment, measure by using x-ray photoelectron spectroscopy (ESCA: for example the manipulation type x-ray photoelectron spectroscopy " PHI Quantera SXM (registered trademark) " of ア Le バ Star Network Off ア イ society system).In the present invention, judge by the having or not of peak of 288eV.

Then, substrate particle is described.Employed substrate particle among the present invention, just there is no particular limitation so long as contain the particle of vinyl based polymer, only the particle that is formed by the vinyl based polymer and all can be used by the organism inorganics composite particles that the material that is compounded with organism and inorganics forms.In addition, in vinyl of the present invention, also comprise (methyl) acryl.As vinyl based polymer particulate, particularly, can enumerate the particle that only forms by vinyl based polymers such as (methyl) acrylic acid series (being total to) polymkeric substance, (methyl) acrylic acid series-styrene based copolymers; Perhaps polymerizability (the meaning that contains vinyl; Below identical) free radical polyalcohol of organoalkoxysilane and/or the organism inorganics composite particless such as multipolymer of polycondensate, polymerizability organoalkoxysilane and vinyl monomer.The meaning when being called in the following description, " vinyl polymer " is meant: only polymerization the monomeric organic polymkeric substance of ethene base system.In addition, the meaning of so-called in the present invention " vinyl based polymer particulate " is meant: contain the composition that formed by " vinyl polymer " or the particle of skeleton.The preparation method's of these vinyl based polymer particulates details can adopt letex polymerization, suspension polymerization, seeding polymerization, sol-gel method etc. as described later, and wherein, seeding polymerization and sol-gel method can reduce size-grade distribution and preferred.In addition, the composition of particulate can utilize GC-MS etc. to confirm.

[vinyl polymer particle]

The vinyl polymer particle obtains by the monomer composition polymerization that will contain the monomeric monomer mixture of ethene base system.As the ethene base system monomer that is contained in the monomer mixture, have the cross-linkable monomer that has plural vinyl in the non-crosslinked monomer of a vinyl, the molecule in molecule and all can use.

As described non-crosslinked monomer, for example can enumerate (methyl) vinylformic acid; (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) dodecylacrylate, (methyl) glycidyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid stearyl, (methyl) esters of acrylic acids such as (methyl) 2-EHA; (methyl) acrylic monomers such as (methyl) vinylformic acid hydroxyalkyl acrylate class such as (methyl) vinylformic acid 2-hydroxyethyl ester, (methyl) vinylformic acid 2-hydroxy-propyl ester, (methyl) vinylformic acid 2-hydroxybutyl ester; Vinylbenzene, o-methyl styrene, a vinyl toluene, p-methylstyrene, vinyl xylene, ethyl vinyl benzene, alpha-methyl styrene, to methoxy styrene, to t-butyl styrene, to styryl phenyl, chloro styrene, m-chlorostyrene, to styrenic monomers such as chloro-styrene, para hydroxybenzene ethene; 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether etc. contain the vinyl ethers of hydroxyl; 2-hydroxyethyl allyl ethers, 4-hydroxybutyl allyl ethers etc. contain the allyl ether series of hydroxyl etc.In addition, (methyl) vinylformic acid is being used as under the monomeric situation of described non-crosslinked, can also carrying out the part neutralization with basic metal.These non-crosslinked monomers may be used alone, used in two or more.In these non-crosslinked monomers, preferably use intramolecularly not have the necessary composition of monomer conduct of ester bond, wherein, optimization styrene is a monomer, special optimization styrene, alpha-methyl styrene, vinyl xylene, ethyl vinyl benzene etc.

As cross-linkable monomer, for example can enumerate Viscoat 295, ethylene glycol dimethacrylate, the Diethylene Glycol dimethacrylate, the triethylene glycol dimethacrylate, ten ethylene glycol dimethacrylates, ten five ethylene glycol dimethacrylates, 56 ethylene glycol dimethacrylates, dimethacrylate 1,3-divinyl ester, 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, allyl methacrylate(AMA), trimethylolpropane trimethacrylate, polyfunctionalities such as tetramethylol methane tetraacrylate (methyl) acrylate; Polyalkylene glycol two (methyl) acrylate such as polyoxyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate; Vinylstyrene, divinyl naphthalene and their divinyl aromatic compounds such as derivative; N, linking agents such as N-divinyl aniline, divinyl ether, vinyl thioether, divinyl sulfonic acid; Polyhutadiene unsaturated polyester, polyisoprene unsaturated polyester etc.These cross-linkable monomers may be used alone, used in two or more.Wherein, preferably use monomer that intramolecularly do not have an ester bond as must composition, wherein, optimization aromatic divinyl compound, preferred especially Vinylstyrene.

Used styrenic monomers as the non-crosslinked monomer, used under the situation of divinyl aromatic compound as cross-linkable monomer, the hydrophilic effect of the particle that brings by method of the present invention of being easy to get, therefore preferred.

In addition, the content of the cross-linkable monomer in the described monomer mixture is preferably more than the 1 quality %, more preferably more than the 5 quality %, more preferably more than the 10 quality %; Be preferably below the 50 quality %, more preferably below the 40 quality %, more preferably below the 30 quality %.By the content that makes the cross-linkable monomer in the described monomer mixture is more than the 1 quality %, the solvent resistance of vinyl polymer particle and thermotolerance height; In addition, be that it is suitable to make as the hardness of particle below the 50 quality % by the content that makes the cross-linkable monomer in the described monomer mixture.

In addition, when polymeric monomer composite, as required, can also use polymerization starter or dispersion stabilizer.As polymerization starter, usually, the polymerization starter that uses in polymerization all can use, and for example, can use superoxide series initiators or azo series initiators etc.As described superoxide series initiators, can enumerate hydrogen peroxide, peracetic acid, benzoyl peroxide, lauroyl peroxide, peroxidation decoyl, adjacent chlorobenzoyl peroxide, O-methoxy benzoyl peroxide, 3,5,5-trimethyl acetyl superoxide, peroxide-2-ethyl hexanoic acid tert-butyl, ditertiary butyl peroxide, 1, two (tert-butyl peroxide)-3 of 1-, 3,5-trimethyl-cyclohexane, methyl ethyl ketone peroxide, di-isopropyl peroxydicarbonate, hydrogen phosphide cumene, cyclohexanone peroxide, tertbutyl peroxide, di-isopropylbenzene hydroperoxide etc.

As the azo series initiators, can enumerate dimethyl 2, the 2-Diisopropyl azodicarboxylate, azo two cyclohexanenitriles, 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (2, the 3-nitrile dimethyl), 2,2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2,3,3-trimethylammonium butyronitrile), 2,2 '-azo two (2-isopropyl butyronitrile), 1,1 '-azo two (hexanaphthene-1-nitrile), 2,2 '-azo two (4-methoxyl group-2, the 4-methyl pentane nitrile), 2-(carbamyl azo) isopropyl cyanide, 2,2 '-azo two (2-amidine propane) dihydrochloride, 4,4 '-azo two (4-cyanopentanoic acid), 4,4 '-azo two (4-cyanopentanoic acid) (4,4 '-ア ゾ PVC ス (acid of 4-シ ア ノ バ レ リ Application)), 2,2 '-azo-bis-iso-dimethyl etc.

These polymerization starters may be used alone, used in two or more.In addition, the addition of these polymerization starters with respect to the monomer mixture of 100 mass parts, is preferably more than 0.1 mass parts, more preferably more than 1 mass parts; Be preferably below 5 mass parts, more preferably below 3 mass parts.

Dispersion stabilizer is, using suspension polymerization etc. to make under the monomer composition polymeric situation, and the stabilization of the droplet dia of monomer composition is used when seeking polyreaction.In addition, dispersion stabilizer can also not be included in the monomer composition, but dissolving or be dispersed in the solvent (for example water solvent) as dispersion medium.As dispersion stabilizer, anionic surfactant, nonionic surfactant, cationic surfactant, amphoterics all can use.Dispersion stabilizer may be used alone, used in two or more.Wherein, be preferably fatty acid oils such as sodium oleate, Viscotrol C potassium; Alkyl sulfuric ester such as sodium lauryl sulphate, ammonium lauryl sulfate salt; Polyoxyethylene diphenylethyllene phenyl ether sulfuric acids such as polyoxyethylene diphenylethyllene phenyl ether sulfuric ester ammonium salt, polyoxyethylene diphenylethyllene phenyl ether sodium sulfovinate salt; Alkylbenzene sulfonates such as Sodium dodecylbenzene sulfonate; Anionic surfactants such as sulfonated alkyl naphathalene, alkane sulfonate, dialkyl sulfosuccinates, alkyl phosphate salt, naphthalene sulfonic acidformaldehyde condensation product, polyoxyethylene alkyl phenyl ether sulfuric acid, polyoxyethylene alkyl sulfuric ester salt.

Dispersion stabilizer is suitably regulated its addition according to the size of desirable vinyl polymer particle and is got final product.For example, if expect average particle diameter is the situation of the following vinyl based polymer particle of the above 30 μ m of 3 μ m, monomer mixture with respect to 100 mass parts, the addition of dispersion stabilizer is preferably more than 0.1 mass parts, more preferably more than 0.5 mass parts, more preferably more than 1 mass parts; Be preferably below 10 mass parts, more preferably below 5 mass parts, more preferably below 3 mass parts.

In addition, can also in monomer composition, add pigment, softening agent, polymerization stabilizer, white dyes, magnetic powder, UV light absorber, antistatic agent, fire retardant etc.The consumption of these additives with respect to the monomer mixture of 100 mass parts, is preferably more than 0.01 mass parts, more preferably more than 0.1 mass parts, more preferably more than 0.5 mass parts; Be preferably below 10 mass parts, more preferably below 5 mass parts, more preferably below 3 mass parts.

[preparation method of vinyl polymer particle]

The preparation method of vinyl polymer particle is to make the monomer composition polymerization that contains above-mentioned monomer mixture.In addition,, known polymerization processs such as suspension polymerization, seeding polymerization, letex polymerization be can adopt, wherein, suspension polymerization, seeding polymerization are preferably as polymerization process.

Under the situation that adopts suspension polymerization, as employed solvent, so long as not exclusively the solvent of dissolved monomer composition preferably uses water solvent with regard to there is no particular limitation.With respect to the monomer composition of 100 mass parts, these solvents can suitably use in the scope below 10000 mass parts more than 20 mass parts usually.As the preparation method of vinyl polymer particle, preferably make the monomer composition that contains monomer mixture and polymerization starter be suspended in dissolving or be dispersed with in the water solvent of dispersion stabilizer and carry out the polymeric method.

The polymerization temperature of suspension polymerization is preferably more than 50 ℃, more preferably more than 55 ℃, more preferably more than 60 ℃; Be preferably below 95 ℃, more preferably below 90 ℃, more preferably below 85 ℃.In addition, polymerization reaction time was preferably more than 1 hour, more preferably more than 2 hours, more preferably more than 3 hours; Be preferably below 10 hours, more preferably below 8 hours, more preferably below 5 hours.In addition, for the particle dia of the vinyl polymer of controlling generation, while polyreaction preferably after the restriction of the droplet dia that has carried out monomer composition or the restriction of carrying out droplet dia react.The restriction of the droplet dia of this monomer composition for example can be undertaken by utilizing high speed stirrers such as T.K. clarifixator, line mixer that the suspension that monomer composition is dispersed in form in the aqueous medium is stirred.And, by the vinyl based polymer particle that polyreaction generates, in the operations such as classification that can also supply to drying, further are provided with as required.In addition, drying is preferably being carried out below 150 ℃, is more preferably carrying out below 120 ℃, is further preferably carrying out below 100 ℃.

Adopt the situation of seeding polymerization method,, preferably use polystyrene, (methyl) acrylic ester polymer, more preferably the little particulate of non-crosslinked or degree of crosslinking as seed particles.In addition, the average particle diameter of seed particles is preferably 0.1 μ m-10 μ m, and is preferably below 10 with the value (CV value) that 100 * particle dia standard deviation/average particle diameter is represented.The preparation method of such seed particles can adopt the method for known use, for example can enumerate emulsifier-free emulsion polymerization, dispersion polymerization etc.

The add-on of the monomer composition in the seeding polymerization with respect to the seed particles of 1 mass parts, is preferably 0.5 mass parts～50 mass parts.When the add-on of monomer composition was very few, the increase of the particle dia that is brought by polymerization diminished; In addition, in the time of too much, have monomer composition do not absorbed in the seed particles fully, in medium alone polymerization generate unusual particle may.In addition, about the drying conditions of polymerization temperature, can be suitable for the condition same with described suspension polymerization with the particle that obtains.

[the compound particle of organic-inorganic]

The compound particle of organic-inorganic is to contain organism part and the inorganics particle partly that comes from vinyl polymer.As the mode of the compound particle of described organic-inorganic, can enumerate inorganics particulates such as metal oxides such as silicon-dioxide, aluminum oxide, titanium dioxide, metal nitride, metallic sulfide, metallic carbide and be disperseed to be included in the mode that forms in the vinyl polymer; The mode that (organic) polysiloxane, poly-titanoxane metal oxygen alkane (メ タ ロ キ サ Application) chains (molecular chain that contains " metal-oxygen-metal " key) such as (Port リ チ タ ノ キ サ Application) and organic molecule are composited on molecular level; The particle that obtains as the polyreaction of organoalkoxysilane generation hydrolysis-condensation reaction by having the vinyl that can form vinyl based polymers such as vinyltrimethoxy silane or vinyl or make with silane compound to be the particle that obtains of polysiloxane and the reactions such as polymerizable monomer of raw material, to comprise the mode of the organism inorganics composite particles that contains vinyl polymer skeleton and polysiloxane skeleton etc. with vinyl with water-disintegrable silyl.Wherein, preferably include the mode of the organism inorganics composite particles that contains vinyl polymer skeleton and polysiloxane skeleton especially.

Below, the organism inorganics composite particles (following only be called sometimes " composite particles ") that contains vinyl polymer skeleton and polysiloxane skeleton is described in detail.

Described vinyl polymer skeleton can also have side chain, has branched structure, further have crosslinking structure for having the vinyl polymer of the main chain that is made of the repeating unit with following chemical formula (1) expression.Can suitably control the hardness of composite particles.

[Chemical formula 1]

In addition, the polysiloxane skeleton is defined as, and the siloxane unit continuity ground of representing with following chemical formula (2) carries out Chemical bond, has constituted the part of the network of eyed structure.

[Chemical formula 2]

Constitute the SiO of polysiloxane skeleton ₂Amount, with respect to the quality of composite particles, be preferably more than the 0.1 quality %, more preferably more than the 1 quality %; Be preferably below the 25 quality %, more preferably below the 10 quality %.SiO in the polysiloxane skeleton ₂Amount when being above-mentioned scope, it is easy that the control of the hardness of composite particles becomes.In addition, constitute the SiO of polysiloxane skeleton ₂Amount be, by being determined at the quality percentage that the quality before and after the roasting temperature particle more than 800 ℃ is obtained in the oxidisability atmosphere such as air.

Composite particles about each mechanical characteristicies such as its hardness or strength at breaks, can be regulated arbitrarily by the ratio of suitable variation polysiloxane skeleton part or vinyl polymer skeleton part.Polysiloxane skeleton in the composite particles is preferably by obtaining the silane compound hydrolysis-condensation reaction with hydrolization group.

As having water-disintegrable silane compound, there is no particular limitation, for example can enumerate with the silane compound of following general formula (3) expression and derivative thereof etc.

R’ _mSiX _4-m (3)

(in the formula, R ' can also have substituting group, and expression is selected from least a group in alkyl, aryl, aralkyl and the unsaturated aliphatic group, and X represents to be selected from least a group in hydroxyl, alkoxyl group and the acyloxy, and m is the integer of 0-3.)

As the silane compound with general formula (3) expression, there is no particular limitation, for example as the silane compound of m=0, can enumerate four functionality silane such as tetramethoxy-silicane, tetraethoxysilane, tetraisopropoxysilan, four butoxy silanes; Silane compound as m=1, can enumerate methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, the hexyl Trimethoxy silane, the decyl Trimethoxy silane, phenyltrimethoxysila,e, the benzyl Trimethoxy silane, the naphthyl Trimethoxy silane, methyl triacetoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidyl ether oxygen base propyl trimethoxy silicane, vinyltrimethoxy silane, 3-(methyl) acryloxy propyl trimethoxy silicane, 3,3, three-functionality-degree silane such as 3-trifluoro propyl Trimethoxy silane; As the silane compound of m=2, can enumerate two functionality silane such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, diacetoxy dimethylsilane, diphenyl silanodiol; As the silane compound of m=3, can enumerate single functionality silane such as trimethylammonium methoxy silane, trimethylethoxysilane, trimethyl silicane alkanol etc.

As the derivative of silane compound with general formula (3) expression, there is no particular limitation, for example can enumerate: the compound that group that part X can be formed chelate compound by carboxyl, beta-dicarbonyl etc. has replaced; Described silane compound partial hydrolysis and low-shrinkage thing of obtaining etc.

Have water-disintegrable silane compound, can only use a kind of, also can the two or more uses of appropriate combination.In addition, in general formula (3), only use the silane compound of m=3 and derivative thereof, can not get composite particles as the situation of raw material.

The polysiloxane skeleton of composite particles is the situation of the mode of the organosilicon atom that directly is combined with Siliciumatom on having at least one carbon atom in vinyl based polymer skeleton at intramolecularly, have a water-disintegrable silane compound as described, be necessary to use silane compound with the organic group that contains vinyl bonds.

As the organic group that contains vinyl bonds, for example can enumerate with the organic group of following general formula (4), (5) and (6) expression etc.

CH ₂＝C(-R ^a)-COOR ^b- (4)

(in the general formula, R ^aExpression hydrogen atom or methyl, R ^bCan also have substituting group, the expression carbonatoms is the organic group of the divalence of 1-20.)

CH ₂＝C(-R ^c)- (5)

(in the general formula, R ^cExpression hydrogen atom or methyl.)

CH ₂＝C(-R ^d)-R ^e- (6)

(in the general formula, R ^dExpression hydrogen atom or methyl, R ^eCan also have substituting group, the expression carbonatoms is the organic group of the divalence of 1-20.)

As the organic group of general formula (4), for example can enumerate (methyl) acryloxy etc.; Silane compound as the general formula with (methyl) acryloxy (3), for example can enumerate γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxyl silane, γ-acryloxy propyl trimethoxy silicane, γ-acryloxy propyl-triethoxysilicane, γ-methacryloxypropyl triacetoxysilane, γ-methacryloxy ethoxycarbonyl propyl Trimethoxy silane (perhaps, being also referred to as γ-trimethoxy-silylpropyl-Beta-methyl acryloyl-oxy benzyl ethyl ether), γ-methacryloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl methyldiethoxysilane, γ-acryloxy propyl group methyl dimethoxysilane etc.They can only use a kind of, also can two or more and usefulness.

Organic group as described general formula (5), for example can enumerate vinyl, pseudoallyl etc., as the silane compound of described general formula (3), for example can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, vinyltriacetoxy silane, vinyl methyl dimethoxysilane, vinyl methyldiethoxysilane, vinyl methyl diacetoxy silane etc. with these organic groups.These can only use a kind of, also can two or more and usefulness.

Organic group as described general formula (6), for example can enumerate 1-alkenyl or ethenylphenyl, different alkenyl or pseudoallyl phenyl etc., as the silane compound of described general formula (3), for example can enumerate 1-hexenyl Trimethoxy silane with these organic groups, 1-hexenyl triethoxyl silane, 1-octenyl Trimethoxy silane, 1-decene base Trimethoxy silane, γ-trimethoxy-silylpropyl vinyl ether, ω-trimethoxysilyl undecanoic acid vinyl acetate, to trimethoxysilyl vinylbenzene, 1-hexenyl methyl dimethoxysilane, 1-hexenyl methyldiethoxysilane etc.These can only use a kind of, also can two or more and usefulness.

Contained vinyl polymer skeleton in the composite particles, can make ethene base system monomer component absorb in the particle that the hydrolysis-condensation reaction by silane compound obtains by (I) with polysiloxane skeleton after, make it polymerization and obtain.In addition, especially described silane compound has hydrolization group, is having under the situation of the organic group that contains vinyl bonds simultaneously, also can by (II) behind the hydrolysis-condensation reaction of silane compound its polymerization be obtained.

Described composite particles is had no particular limits, can be (i) polysiloxane skeleton has the mode (Chemical bond type) that direct chemical at least one carbon atom in vinyl based polymer skeleton is combined with the organosilicon atom of Siliciumatom at intramolecularly, also can be the mode (IPN type) that does not (ii) have such organosilicon atom, but be preferably the mode of (i) at intramolecularly.In addition, utilize the method for described (I) to obtain the situation of polysiloxane skeleton and vinyl polymer skeleton, can access composite particles with mode (ii), especially as long as described silane compound has hydrolization group and the organic group that contains vinyl bonds, the composite particles that just can be had described (i) and mode (ii) simultaneously.In addition, as according to as described in the method for (II) obtained the situation of polysiloxane skeleton and vinyl polymer skeleton, the composite particles that can be had the mode of (i).

In described (I) and method (II), as the monomer that can absorb in the particle with polysiloxane skeleton, can enumerate described ethene base system monomer, can suitably select according to the rerum natura of desirable composite particles.These can only use a kind of, also can two or more and usefulness.

For example, hydrophobic ethene base system monomer, in the time of in monomer component being absorbed have the particle of polysiloxane skeleton and since can generate make the monomer component emulsion dispersion stable emulsion, therefore preferred.In addition, when using described cross-linkable monomer, the adjusting of the mechanical characteristics of the composite particles that can easily obtain in addition, can also make the solvent resistance of composite particles improve.As cross-linkable monomer, can use illustration as being used for the cross-linkable monomer of described vinyl polymer particle cross-linkable monomer.

The preparation method of composite particles preferably includes hydrolytic condensation operation and polymerization process, the absorption operation that more preferably is included in after hydrolysis, the condensation operation and polymerizable monomer is absorbed.By comprising the absorption operation, can regulate the specific refractory power of the content and the contained vinyl polymer skeleton of the vinyl polymer framework ingredient in the composite particles.In addition, the silane compound that is used for the hydrolytic condensation operation does not have key element that can constitute the polysiloxane skeleton structure and the situation that constitutes the key element of vinyl polymer skeleton simultaneously, with described absorption operation is necessary, forms the vinyl polymer skeleton in the polymerization process of following after this absorption operation.

So-called described hydrolytic condensation operation is, silane compound is hydrolyzed and the operation of the reaction of polycondensation.By the hydrolytic condensation operation, can access particle (polysiloxane particle) with polysiloxane skeleton.Hydrolysis and polycondensation can be adopted once, gradation, arbitrary method such as continuous.Be hydrolyzed, during polycondensation, can preferably use basic catalysts such as ammonia, urea, thanomin, Tetramethylammonium hydroxide, alkali metal hydroxide, alkaline-earth metal oxyhydroxide as catalyzer.

Except water and catalyzer, can in the described solvent that contains water, contain organic solvent.As organic solvent, for example can enumerate methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, ethylene glycol, propylene glycol, 1, alcohols such as 4-butyleneglycol; Ketone such as acetone, methylethylketone; Ester classes such as ethyl acetate; Octane-iso, hexanaphthene etc. (ring) paraffin class; Benzene, toluene etc. are aromatic hydrocarbon based etc.These may be used alone, used in two or more.

In the hydrolytic condensation operation, in addition, can also and use anionic property, cationic, nonionic surfactant; Or macromolecule dispersing agents such as polyvinyl alcohol, polyvinylpyrrolidone.These may be used alone, used in two or more.

Hydrolytic condensation, can by will as described silane compound, the catalyzer of raw material and contain water and the solvent of organic solvent after, in temperature be more than 0 ℃ below 100 ℃, be preferably stir below 70 ℃ more than 0 ℃ more than 30 minutes 100 hours with under carry out.Thus, can access the polysiloxane particle.In addition, can also be hydrolyzed condensation reaction after desirable degree prepares particle, it as seed particles, is further added silane compound seed particles is grown up in reaction system.

Absorb operation, so long as in the presence of the polysiloxane particle, the absorption operation of under the state that monomer component is existed, carrying out, just there is no particular limitation.Therefore, can in the solvent that has disperseed the polysiloxane particle, add monomer component, also can in containing the solvent of monomer component, add the polysiloxane particle.Wherein, preferably, in the solvent that has disperseed the polysiloxane particle in advance, add monomer component as described in the former.Especially from reaction solution (polysiloxane particle dispersion), do not take out the polysiloxane particle ground that in hydrolysis, condensation operation, obtains, the method for in this reaction solution, adding monomer component, have the advantage that operation is uncomplicated, productivity is good, therefore preferred.

In addition, in absorbing operation, monomer component is absorbed in the polysiloxane morphology of particles, but, in order to carry out the absorption of monomer component apace, temperature and time when the preferred ratio of mixture of suitably setting polysiloxane particle and monomer component concentration, polysiloxane and monomer component separately, blended treatment process, device, mixing, mixed treatment process, device etc., and under this condition, carry out.

These conditions, according to kind of employed polysiloxane particle and monomer component etc., with due regard to its necessity gets final product.In addition, these conditions can only suitably be used a kind of, also can make up two or more suitable uses.

The addition of the monomer component in the described absorption operation with respect to the quality as the silane compound of the raw material of polysiloxane particle, in mass, is preferably more than 0.01 times below 100 times.More preferably more than 0.5 times below 30 times, more preferably more than 1 times below 20 times.The situation of the not enough described scope of addition, the absorbed dose of the monomer component of polysiloxane particle can tail off sometimes, and it is insufficient that the mechanical characteristics of the composite particles of generation can become; The situation that surpasses described scope has to make the monomer component that has added absorb the trend of the difficulty that becomes in the polysiloxane particle fully because unabsorbed monomer component is residual, have in follow-up polymerization stage, easily produce interparticle agglutinative may.

In described absorption operation, the opportunity of the interpolation of monomer component, there is no particular limitation, can once add, and also can be divided into several times adding, can also be so that speed is reinforced arbitrarily.In addition, when adding monomer component, monomer component can be only added, also the solution of monomer component can be added, but, be mixed into method in the polysiloxane particle with making monomer component emulsification be distributed to the emulsion that forms in water or the aqueous solvent with emulsifying agent in advance, can more effectively absorb in the polysiloxane particle, therefore preferred.

There is no particular limitation for described emulsifying agent, for example, as described dispersion stabilizer and illustration the anionic surfactant; Or polyethylene oxide alkyl ethers, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid esters, sorbitan-fatty acid ester, polyoxygenated sorbitan-fatty acid ester, polyoxyethylene alkylamine, glycerol fatty acid ester, oxyethylene group-nonionic surfactants such as oxypropylene group block polymer.Nonionic surfactant can make the polysiloxane particle, absorbed the polysiloxane particle behind the monomer component and the dispersion state stabilization of composite particles, and is therefore preferred.These emulsifying agents, can only use a kind of, also can be two or more and use.

There is no particular limitation for the consumption of emulsifying agent, particularly, with respect to 100 mass parts will the emulsive monomer component total mass, be preferably more than 0.01 mass parts, more preferably more than 0.05 mass parts, more preferably more than 1 mass parts; Be preferably below 10 mass parts, more preferably below 8 mass parts, more preferably below 5 mass parts.The situation of less than 0.01 mass parts can not get stable emulsion sometimes; The situation that surpasses 10 mass parts, what concurrent letex polymerization as side reaction etc. arranged may.For obtaining emulsion, as long as use clarifixator and ultrasonic homogenizer etc. to make monomer component and emulsifying agent in water, become the latex state.

In addition, when utilizing emulsifying agent that monomer component emulsification is disperseed,, preferably use water below 10 times or water-miscible organic solvent more than 0.3 times with respect to the quality of monomer component.As described water-miscible organic solvent, can enumerate methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, amylalcohol, ethylene glycol, propylene glycol, 1, alcohols such as 4-butyleneglycol; Ketone such as acetone, methylethylketone; Ester classes such as ethyl acetate etc.

Absorb operation, preferably in the temperature range below 60 ℃ more than 0 ℃, under agitation carry out more than 5 minutes below 720 minutes.These conditions are suitably set according to employed polysiloxane particle and monomeric kind etc. and are got final product, and it is a kind of that these conditions can only adopt, and perhaps also can make up two or more employings.

In absorbing operation, whether be absorbed into judgement in the polysiloxane particle about monomer component, for example, can be by before adding monomer component and after the absorption stage end, utilize the microscopic examination particle, confirming making particle dia become big, thereby easily judge by the absorption of monomer component.

Polymerization process is for making the monomer component polyreaction, obtains having the operation of the particle of vinyl polymer skeleton.Particularly, used the silane compound that possesses organic group situation as silane compound with vinyl bonds, for the vinyl bonds polymerization that makes this organic group to form the operation of vinyl polymer skeleton; Through the situation that absorption operation, the vinyl bonds polymerization that monomer component that absorbs for making or the monomer component that is absorbed and polysiloxane skeleton are had is to form the operation of vinyl (being) polymer backbone, but, the situation that is equivalent to the two all can become the operation that forms vinyl (being) polymer backbone by reaction arbitrarily.

Polyreaction, there is no particular limitation, can in the process of hydrolytic condensation operation or absorption operation, carry out, also can carry out after both operations arbitrarily or after both operations, but, usually, in (carried out absorbing the situation of operation yes absorbing operation after) beginning after the hydrolytic condensation operation.

There is no particular limitation for polymerization process, for example uses the method for method, irradiation ultraviolet radiation or the radioactive rays of radical polymerization initiator, the method for heating etc. all can adopt.As described radical polymerization initiator, there is no particular limitation, for example can enumerate the polymeric radical polymerization initiator that is used for described vinyl polymer particle.These radical polymerization initiators may be used alone, used in two or more.

The consumption of radical polymerization initiator, the total mass with respect to the monomer component of 100 mass parts is preferably more than 0.001 mass parts, more preferably more than 0.01 mass parts, more preferably more than 0.1 mass parts; Be preferably below 20 mass parts, more preferably below 10 mass parts, more preferably below 5 mass parts.The situation of usefulness quantity not sufficient 0.001 mass parts of radical polymerization initiator can not improve the polymerization degree of monomer component sometimes.Addition means for the solvent of radical polymerization initiator, there is no particular limitation, methods that all add in initial (before the reaction beginning) (make in advance radical polymerization initiator with monomer component emulsification dispersive mode, absorbed the mode of adding radical polymerization initiator behind the monomer component); In an initial part, the method for adding remainder continuously of adding earlier; Perhaps, carry out the method that pulse is added intermittently; Perhaps, the method etc. that makes up these in the past known method all can adopt.

Fashionable temperature of reaction is preferably more than 40 ℃ to carry out radical polymerization, more preferably more than 50 ℃; Be preferably below 100 ℃, more preferably below 80 ℃.Spend under the low situation in reaction temperature, the mechanical characteristics that can not fully improve the polymerization degree, the composite particles inadequate trend that becomes is arranged; On the other hand, under the too high situation of temperature of reaction, having becomes in polymerization, and interparticle agglutinative trend easily takes place.In addition, carry out the fashionable reaction times of radical polymerization, according to the kind of employed polymerization starter suitably change get final product, still common, be preferably more than 5 minutes, more preferably more than 10 minutes; Be preferably below 600 minutes, more preferably below 300 minutes.Under too short situation of reaction times, can not fully improve the polymerization degree sometimes; Under long situation of reaction times, become agglutinative trend easily takes place between particle.

According to above-mentioned preparation method, what can obtain having the preferred characteristic of aftermentioned (mechanical characteristics and particle size distribution characteristics etc.) forms substrate particle by vinyl based polymer particulate.

There is no particular limitation for the shape of the substrate particle of using among the present invention, for example, spherical, ellipsoid of revolution shape, quartzy candy shape (the flat sugared shape of gold), lamellar, needle-like, dumbbell shaped all can, the shape of particle surface also is that level and smooth shape, pleated, vesicular all can.Wherein, on the many this point of industrial purposes, be preferably spherical.The size of substrate particle is counted below the 1mm (1000 μ m) with the quality average particle diameter.Surpass the particle of 1mm, purposes is limited, utilizes the field also few in industrial.The quality average particle diameter is preferably 0.05-500 μ m, more preferably 0.1-100 μ m, more preferably 0.5-30 μ m.The meaning of quality average particle diameter is, in known particle size distribution method in the past, the value of obtaining as the volume averaging particle dia, particularly, be the value of measuring by the accurate particle size distribution device (for example, trade name is " コ one Le タ one マ Le チ サ イ ザ one III type ", ベ Star Network マ Application コ one Le タ one Co., Ltd.'s system) that has used Coulter principle.

In addition, the particle size dispersion coefficient on the particle dia of the substrate particle of using among the present invention (CV value) is preferably below 40%.The CV value surpasses at 40% o'clock, has the deviation of particle dia excessive, the uneven possibility of appearance in hydrophilicity-imparting treatment is arranged.In addition, the CV value is, the quality average particle diameter of the substrate particle that will measure by the accurate particle size distribution device that has used Coulter principle, is applied to the value obtained in the following formula with the standard deviation of the particle dia of substrate particle.

The standard deviation of the particle size dispersion coefficient of substrate particle (%)=100 * particle dia/quality average particle diameter

The quality average particle diameter of hydrophilization particulate and the preferable range of particle size dispersion coefficient also are the scopes identical with substrate particle.

Substrate particle utilizes described method by hydrophilicity-imparting treatment.Substrate particle is preferably identical degree with dispersiveness, mechanical characteristics, form and aspect, the particle size distribution characteristics (CV value) of hydrophilization particulate, preferably at the front and back of hydrophilicity-imparting treatment no change.In addition, so-called dispersiveness is the character of the adhesion or the fusion of no particle.

Mechanical characteristics for example, can be estimated with elasticity of compression rate, fail in compression load, response rate etc.Elasticity of compression rate of the present invention is applying load on particle, the spring rate (N/mm during 10% distortion ²: MPa); The fail in compression load is to strengthen the load (mN) that is compressed to when destroying; Response rate is the response rate (%) after the compression.Measuring method about them is elaborated in an embodiment.Even in substrate particle, hydrophilic particulate, elasticity of compression rate is preferably 1000N/mm ²More than, 2000N/mm more preferably ²More than, 3000N/mm more preferably ²More than.Similarly, the fail in compression load is preferably more than the 1mN, more preferably more than the 3mN, more preferably more than the 5mN.In addition, response rate is preferably more than 0.5%, more preferably more than 1%, more preferably more than 5%.

Embodiment

The present invention will be described in more detail by the following examples.In addition, the present invention is not limited by following embodiment, as long as change enforcement in the scope that does not break away from aim of the present invention, all within the scope of the present invention.In addition, in the following, if not special explanation, the meaning of " part " is " mass parts ", and the meaning of " % " is " quality % ".

Synthesis example 1

In four-hole boiling flask, put into 400 parts of ion exchanged waters, 25% 6 parts of ammoniacal liquor, 180 parts of methyl alcohol with prolong, thermometer, liquid droping port, under agitation, to this solution, add 100 parts of 3-methacryloxypropyl trimethoxy silane from liquid droping port, carry out the hydrolysis-condensation reaction of 3-methacryloxypropyl trimethoxy silane, the emulsion of preparation polysiloxane particle.

Then, in dissolved 0.35 part of solution that forms of polyoxyethylene vinylbenzene phenyl ether sulfuric ester ammonium salt as emulsifying agent (the first industrial pharmacy society system: " Ha イ テ ノ one Le (registered trademark) NF-08 ") with 175 parts of ion exchanged waters, add and dissolved 70 parts of Vinylstyrenes, 2,2 '-azo two (2, the 4-methyl pentane nitrile) (with the pure pharmaceutical worker of light industry society system: " V-65 ") 3.4 parts solution, make it emulsification by TK clarifixator (special machine chemical industry society system) with the speed of 6000rpm and disperseed the emulsion of preparation monomer component 5 minutes.

The emulsion that obtains is added in the emulsion of polysiloxane particle, further stir.Add emulsion after 2 hours, reaction solution is taken a sample, the result who utilizes microscope to observe has confirmed that the polysiloxane particle absorbs monomer component and hypertrophyization.

Then, under nitrogen atmosphere, make reaction solution be warmed up to 65 ℃, kept 2 hours down, carry out the radical polymerization of monomer component at 65 ℃.With the emulsion solid-liquid separation after the radical polymerization, utilize ion exchanged water, methyl alcohol that the filter cake that obtains is washed after, under 80 ℃, made it vacuum-drying 12 hours, obtain substrate particle 1 (organism inorganics composite particles).Utilize コ one Le タ one マ Le チ サ イ ザ one III type (ベ Star Network マ Application コ one Le タ one society's system) to measure the particle dia of this substrate particle 1, the outcome quality average particle diameter is that 3.8 μ m, particle size dispersion coefficient (CV value) are 2.9%.In addition, the average particle diameter of substrate particle is measured the particle dia of 30000 particles by コ one Le タ one マ Le チ サ イ ザ one III type (ベ Star Network マ Application コ one Le タ one society's system), obtains average particle diameter.The CV value (%) of particle dia is obtained according to following formula.

[mathematical expression 1]

$\mathrm{CV}=\frac{\mathrm{\σ}}{\stackrel{\‾}{X}}\×100$

σ represents the standard deviation of particle dia,

The expression average particle diameter.

Synthesis example 2

The amount of the 3-methacryloxypropyl trimethoxy silane in being added on flask is 50 parts, with synthesis example 1 similarly, the emulsion of preparation polysiloxane particle.

Then, in dissolved described " Ha イ テ ノ one Le NF-08 " 0.75 part of solution that forms with 175 parts of ion exchanged waters, adding is by 125 parts of vinylbenzene, 1, the solution of 25 parts of 6-hexanediol dimethacrylate and described " V-65 " 4 parts of compositions, make it emulsification by TK clarifixator (special machine chemical industry society system) with the speed of 6000rpm and disperseed the emulsion of preparation monomer component 5 minutes.Afterwards with synthesis example 1 similarly, obtain substrate particle 2 (organism inorganics composite particles).

The emulsion that obtains is added in the emulsion of polysiloxane particle, further stir.Add emulsion after 2 hours, reaction solution is taken a sample, the result who utilizes microscope to observe has confirmed that the polysiloxane particle absorbs monomer component and hypertrophyization.

Then, under nitrogen atmosphere, make reaction solution be warmed up to 65 ℃, kept 2 hours down, carry out the radical polymerization of monomer component at 65 ℃.With the emulsion solid-liquid separation after the radical polymerization, utilize ion exchanged water, methyl alcohol that the filter cake that obtains is washed.By under 80 ℃, making it vacuum-drying 12 hours, obtain substrate particle 2.The quality average particle diameter of this substrate particle 2 is that 3.8 μ m, CV value are 3.3%.

Synthesis example 3

The amount of the ammoniacal liquor except 25% is 20 parts, vinylbenzene is 75 parts, 1 when the emulsion preparation of carrying out monomer component, and the 6-hexanediol dimethacrylate is beyond 75 parts, similarly obtains substrate particle 3 (organism inorganics composite particles) with synthesis example 2.The quality average particle diameter of this substrate particle 3 is that 2.1 μ m, CV value are 5.2%.

Synthesis example 4

The amount of the ammoniacal liquor except 25% is 20 parts, similarly obtains substrate particle 4 (organism inorganics composite particles) with synthesis example 1.The quality average particle diameter of this substrate particle 4 is that 2.0 μ m, CV value are 5.3%.

Synthesis example 5

In four-hole boiling flask, add and dissolved as 150 parts of the ion-exchange aqueous solution of described " the Ha イ テ ノ one Le NF-08 " of dispersion stabilizer 2 parts with prolong, thermometer, liquid droping port.Append 100 parts of Vinylstyrenes and described " V-65 " 2 parts, make it emulsification by described TK clarifixator (special machine chemical industry society system) with the speed of 5000rpm and disperseed the preparation suspension liquid 5 minutes.

In this suspension liquid, add 250 parts of ion exchanged waters, under nitrogen atmosphere, be warmed up to 65 ℃, kept 2 hours down, carry out radical polymerization at 65 ℃.With the emulsion solid-liquid separation after the radical polymerization, utilize ion exchanged water, methyl alcohol that the filter cake that obtains is washed, further carry out progressive operation.By the particle vacuum-drying after making classification under 80 ℃ 12 hours, obtain substrate particle 5 (vinyl polymer particle).The quality average particle diameter of this substrate particle 5 is that 2.1 μ m, CV value are 25.0%.

Synthesis example 6

Except having used by 30 parts of vinylbenzene and 1, the monomer mixture of 70 parts of compositions of 6-hexanediol dimethacrylate replaces similarly obtaining substrate particle 6 (vinyl polymer particle) with synthesis example 5 beyond 100 parts of the Vinylstyrenes.The quality average particle diameter of this substrate particle 6 is that 2.8 μ m, CV value are 19.0%.

Synthesis example 7

Except having used by 70 parts of vinylbenzene and 1, the monomer mixture of 30 parts of compositions of 6-hexanediol dimethacrylate replaces similarly obtaining substrate particle 7 (vinyl polymer particle) with synthesis example 5 beyond 100 parts of the Vinylstyrenes.The quality average particle diameter of this substrate particle 7 is that 2.3 μ m, CV value are 23.5%.

Synthesis example 8

Replace similarly obtaining substrate particle 8 (vinyl polymer particle) with synthesis example 5 100 parts of the Vinylstyrenes except having used by 70 parts of methyl methacrylates and 30 parts of monomer mixtures of forming of ethylene glycol dimethacrylate.The quality average particle diameter of this substrate particle 8 is that 3.2 μ m, CV value are 30.0%.

Synthesis example 9

The amount of the ammoniacal liquor except 25% is 10 parts, similarly obtains substrate particle 9 (organism inorganics composite particles) with synthesis example 1.The quality average particle diameter of this substrate particle 10 is that 3.0 μ m, CV value are 2.5%.

Synthesis example 10

The amount of the ammoniacal liquor except 25% is 10 parts, in emulsion when preparation 1 of carrying out monomer component, the 6-hexanediol dimethacrylate is beyond 100 parts, similarly obtains substrate particle 10 (organism inorganics composite particles) with synthesis example 1.The quality average particle diameter of this substrate particle 10 is that 3.0 μ m, CV value are 2.7%.

Embodiment 1

The substrate particle that obtains in synthesis example 11 of 120g is put into the cavate processing vessel that capacity is 500L.The thickness of particle layer is 0.5mm.Behind the 1Pa that reduces pressure in the chamber, import fluorine gas (F ₂) and oxygen (O ₂), make F ₂: 13.33Pa (0.1Torr), O ₂: 80kPa (600Torr).F ₂Be 0.017 volume %, remain and be O ₂Afterwards, after handling 60 minutes under 30 ℃,, turn back to normal atmosphere then to carrying out nitrogen replacement in the chamber.Particle 7g after the gas processing is encased in the separating flask (セ パ ラ Block Le Off ラ ス コ) of 500ml, adds ion exchanged water, total amount is 350g (particle concentration is 2 quality %), carries out ultrasonic dispersing 10 minutes under normal temperature (about 25 ℃).Then, be heated to 85 ℃, heat-treat 3 hours after, carry out the washing (with the processing that contacts of moisture) of particle.Behind the cool to room temperature, filtered particles after according to the order of ion exchanged water, methyl alcohol the filter cake that obtains being washed, is carried out vacuum-drying 12 hours under 80 ℃, obtains the related hydrophilization particulate 1 of embodiment 1.

Embodiment 2

Except with F ₂Change to beyond 133.3Pa (1Torr), the 0.17 volume %, carry out hydrophilicity-imparting treatment similarly to Example 1, obtain the related hydrophilization particulate 2 of embodiment 2.

Embodiment 3

Except having used substrate particle 2 to replace the substrate particle 1, obtain the related hydrophilization particulate 3 of embodiment 3 similarly to Example 2.

Embodiment 4

Except with F ₂Change to beyond 0.67kPa (5Torr), the 0.83 volume %, obtain the related hydrophilization particulate 4 of embodiment 4 similarly to Example 1.

Embodiment 5-11

Except having used the substrate particle 2-8 that in synthesis example 2-8, obtains to replace obtaining the related hydrophilization particulate 5-11 of embodiment 5-11 similarly to Example 4 the substrate particle 1.

Comparative example 1

Except with F ₂Change to beyond 1.33kPa (10Torr), the 1.64 volume %, carry out hydrophilicity-imparting treatment similarly to Example 1, obtain comparative example 1 related relatively use hydrophilization particulate 1.

Comparative example 2

Get the substrate particle 1 that 5g obtains in synthesis example 1, make it to be dispersed among the methyl alcohol 45g, add 3-aminopropyl trimethoxysilane 0.5g, stir down, heated 2 hours down at 100 ± 2 ℃.Behind the cool to room temperature, filter the filter cake that utilizes methanol wash to obtain.Under 80 ℃, carry out vacuum-drying 12 hours, obtain comparative example 2 related relatively use hydrophilization particulate 2.

Comparative example 3

Get the substrate particle 1 that 0.5g obtains in synthesis example 1, join among the oxide treatment mixed solution 100ml that is mixed with sulfuric acid 200ml/L, chromic acid 400g/L in advance, under 70 ℃, carried out heat treated 5 minutes.Behind the cool to room temperature, filter the particulate that utilizes water washing to obtain.Under 80 ℃, carry out vacuum-drying 12 hours, obtain comparative example 3 related relatively use hydrophilization particulate 3.

＜evaluating characteristics 〉

For substrate particle that in each synthesis example, obtains and the hydrophilization particulate that in embodiment and comparative example, obtains, estimate following characteristic, be illustrated in table 1～table 3.

[quality average particle diameter, CV value]

Quality average particle diameter and CV value are utilized with the same method of described synthesis example 1 and are measured.

[particle shape]

Use electron microscope to carry out the observation of particle, visual predicting shape.

[dispersiveness in water]

Ion exchanged water 30g is put into the screwed pipe that capacity is 50cc, add particle 0.1g, the dispersion state of visual observation particle in water.Estimate as follows: the fused substantially fully situation to water of particle is designated as " zero "; Most of particle is fused in water, but existing the part particle directly to swim in situation waterborne is designated as " △ "; Most particle is swum in situation waterborne be designated as " * ".

[hydrophobic deg]

In being placed with the glass beaker of 200cc of stirrer, the bottom drops into ion exchanged water 50cc, after the particle that makes 0.2g swims on the water surface, in water in beaker is sunk on the top of drop-burette, gently rotating under the stirrer, adding described particle certainly after 5 minutes, gently import methyl alcohol simultaneously by drop-burette.Continue the importing of methyl alcohol, up to the complete submerged of all particles of the water surface, the import volume (cc) of the methyl alcohol when measuring the complete submerged of particle is obtained hydrophobic deg according to following formula.In addition, before adding methyl alcohol by described drop-burette, when swimming in the complete submerged of the particle of the water surface, hydrophobic deg is 0%.

The import volume (cc) of amount (the cc)+methyl alcohol of import volume (the cc) * 100/{ water of hydrophobic deg (%)=methyl alcohol }

[variation of tone]

Estimate the tone of the particle of hydrophilicity-imparting treatment front and back by visual observation.The situation note of the variation of no tone is done " zero ", and the xanchromatic situation note that will have trace is made " △ ", with complete variable color the situation note do " * ".

[content of the content of total fluoro quantity, solvability fluorine, non-solubility fluorine]

Utilize described method to obtain the content of total fluoro quantity and solvability fluorine, with the content of its difference as the non-solubility fluorine.

[acid number (KOH dosis neutralisata)]

In weighing the sample particle of 0.5g in add ultrapure water (utilizing オ Le ガ ノ society's system " PURELITE " PRA-0015-000 type to prepare, below 18.2M Ω cm), total amount is adjusted to 50g after, carried out ultrasonication 10 minutes.Then, use automatic titration device (flat natural pond industry society system, COM-1600) to carry out neutralization titration, the addition of the titrating solution when obtaining the potential variation amount and becoming maximum calculates acid number by following formula.In addition, the titrating solution working concentration is the KOH aqueous solution of 0.005M.

[mathematical expression 2]

[affirmation of carboxyl and carboxylate salt]

Use x-ray photoelectron spectroscopy (ESCA: ア Le バ Star Network Off ア イ Co., Ltd. system; The sweep type x-ray photoelectron spectroscopy; PHI Quantera SXM ^TM(Scanning X-ray Microprobe)), confirm the having or not of generation of lip-deep carboxyl of substrate particle after the hydrophilicity-imparting treatment and carboxylate salt.

[there is rate in the surface of C, O, F atom]

Use x-ray photoelectron spectroscopy (ESCA; JEOL society system; JPS-9000MC), that measures C, O on substrate particle and the hydrophilization microparticle surfaces and F atom exists rate (mole %), and there is rate (%) in the apparent surface who calculates each atom by following formula.

The apparent surface of C atom exist rate (%)=100 * [the C atom exist rate (mole %)/(the C atom exist rate (mole %)+O atom have rate (mole %)+F atom have a rate (mole %))]

The apparent surface of O atom exist rate (%)=100 * [the O atom exist rate (mole %)/(the C atom exist rate (mole %)+O atom have rate (mole %)+F atom have a rate (mole %))]

The apparent surface of F atom exist rate (%)=100 * [the F atom exist rate (mole %)/(the C atom exist rate (mole %)+O atom have rate (mole %)+F atom have a rate (mole %))]

[10% elasticity of compression rate (10%K value: hardness)]

By Tianjin, island slight compression trier (society of Shimadzu Seisakusho Ltd. system, " MCTW-500 "), under room temperature (25 ℃), be dispersed in sample table (material: the sample particle the SKS flat board) for one, using diameter is the circular dull and stereotyped (material: diamond) of 50 μ m, with the center position applying load of certain loaded speed (2.275mN/ second) to particle, mensuration makes particle be deformed into 10% o'clock load and the displacement (mm) that compression displacement is a particle dia.In the radius substitution following formula with the compression displacement of the compression load measured, particle, particle, the value of calculating.Three different particles are carried out this operation, with 10% elasticity of compression rate of its mean value as substrate particle.

[mathematical expression 3]

$E=\frac{3\×F}{2^{1/2}\×S^{3/2}\×R^{1/2}}$

(at this, E: elasticity of compression rate (N/mm ²), F: compression load (N), S: compression displacement (mm), R: the radius of particle (mm).)

[fail in compression load]

With elasticity of compression rate applying load on particle similarly, with particle by deformation failure the time load (mN) load as fail in compression.

[compression set response rate (response rate)]

Compression set response rate (response rate) is to use slight compression trier (Shimadzu Seisakusho Ltd.'s system: " MCTW-500 "), and sample particle is compressed to conversion load for behind the 9.8mN, measures the relation of load value when reducing load and compression displacement and the value that obtains; Be to be initial point load value 0.098mN, to be 1.486mN/ when measuring second with load and compression (answers) speed in the load removed with the terminal point of removing when load, as to the displacement (L1) of the point of conversion, with ratio (L1/L2) from the point of conversion to the displacement (L2) of the point that obtains the initial point load value (%) and the value of representing.

[table 1]

In table 4, the measurement result of the various rerum naturas of reference example 1 expression substrate particle 9.

According to table 4, the particulate that obtains in embodiment 12-17 is by hydrophilicity-imparting treatment, and hydrophobic deg becomes 0.That is, as can be seen,, similarly carry out hydrophilicity-imparting treatment, also can obtain the hydrophilization particulate even in mixed gas, contain under the situation of rare gas element.In addition, the physical strength of each particulate does not almost change before and after handling.In addition, use XPS (ESCA), analyze the result of the hydrophilization microparticle surfaces of embodiment 12-17, observe the peak of the carbon that is equivalent to carboxyl at the 288eV place.Further, the result who has a rate (%) from the apparent surface of each atom and compares before the hydrophilicity-imparting treatment as can be seen, and the amount of the Sauerstoffatom of the substrate particle after the hydrophilicity-imparting treatment has increased relatively, can confirm to have generated carboxyl.

In addition, measuring the result of the amount of solvability fluorine, is 1.83mg/g in hydrophilization particulate 12, is 1.50mg/g in hydrophilization particulate 14.

Embodiment 18-21

Except the temperature with mixed gas changes to-20 ℃ (embodiment 18), 0 ℃ (embodiment 19), 20 ℃ (embodiment 20), 40 ℃ (embodiment 21) respectively, carry out gas processing similarly to Example 16, obtain hydrophilization particulate 18-21.The washing of being undertaken by ion exchanged water after in embodiment 18-21, not carrying out gas processing.

Use XPS (ESCA), carry out the result who has quantitative analysis of various atoms on the substrate particle surface after the hydrophilicity-imparting treatment, observe the peak of the carbon that is equivalent to carboxyl at the 288eV place.In addition, can confirm that be accompanied by the rising of the temperature of the mixed gas when carrying out hydrophilicity-imparting treatment, relatively the amount of Sauerstoffatom has increased, the amount of fluorine atom has reduced (table 5).

[table 5]

Embodiment 22,23

The hydrophilization particulate 12 of 7g is immersed in 85 ℃ the ion exchanged water, under agitation, 85 ℃ of 3 hours (concentration of particle are 6.3 quality %) of washing down.Afterwards, wash, further, under 80 ℃, carry out vacuum-drying 12 hours, obtain hydrophilization particulate 22 according to the order of ion exchanged water, methyl alcohol.

Hydrophilization particulate 14 is also carried out same warm water washing, obtain hydrophilization particulate 23.

Embodiment 24,25

The hydrophilization particulate 12 of 7g is immersed in the aqueous sodium hydroxide solution of 0.25N (concentration of particle is 2 quality %), under agitation, under 85 ℃, carry out alkaline purification 3 hours.After the filtered particles, particle is immersed in 85 ℃ the ion exchanged water (concentration of particle is 6.3 quality %), under identical temperature, carried out carrying out washing treatment 3 hours.Behind the cool to room temperature, filtered particles is washed according to the order of ion exchanged water, methyl alcohol, further, carries out vacuum-drying 12 hours under 80 ℃, obtains hydrophilization particulate 24.

Hydrophilization particulate 14 is also carried out the washing of same alkaline purification and warm water, obtain hydrophilization particulate 25.

Measure the amount of the solvability fluorine of hydrophilization particulate 12,14 and 22-25.The result is illustrated in the table 6.

[table 6]

The amount of solvability fluorine (mg/g)

Embodiment 12	1.83
		Embodiment 14	1.50
Embodiment 22	0.65
		Embodiment 23	0.60
Embodiment 24	0.04
		Embodiment 25	0.13

According to table 6 as can be seen, the amount of solvability fluorine at most, is washed the amount that can reduce the solvability fluorine by carrying out alkaline purification and warm water in the embodiment 12,14 that does not carry out the washing of alkaline purification and warm water.In addition, as can be seen, according to the order of warm water washing, alkaline purification and warm water washing, the reduction effect of the amount of solvability fluorine can uprise.

Embodiment 26-28

The substrate particle that obtains in synthesis example 10 10 of 120g is put into the cavate processing vessel that capacity is 500L.Except the temperature of the composition of mixed gas and the gas in the chamber is the condition of expression in the table 7, carry out gas processing similarly to Example 1, obtain hydrophilization particulate 26-28.In addition, in embodiment 26-28, do not carry out the carrying out washing treatment of being undertaken by ion exchanged water after the gas processing.

In the table 7, the measurement result of the various rerum naturas of reference example 2 expression substrate particle 10.

According to table 7, the particulate that obtains in embodiment 26-28 is by hydrophilicity-imparting treatment, and hydrophobic deg becomes 0.That is, as can be seen,, similarly carry out hydrophilicity-imparting treatment, also can obtain the hydrophilization particulate even in mixed gas, contain under the situation of rare gas element.In addition, the physical strength of each particulate does not almost change before and after handling.Use XPS (ESCA), analyze the result of the hydrophilization microparticle surfaces that in embodiment 26-28, obtains, observe the peak of the carbon that is equivalent to carboxyl at the 288eV place.In addition, the result who has a rate (%) from the apparent surface of each atom and compares before the hydrophilicity-imparting treatment as can be seen, and the amount of the Sauerstoffatom of the substrate particle after the hydrophilicity-imparting treatment has increased relatively, can confirm to have generated carboxyl.In addition, the amount of the solvability fluorine of hydrophilization particulate 26 is 3.76mg/g.

According to embodiment 15,16 (tables 4), embodiment 27, the XPS of 28 (tables 7) (ESCA) analytical results, as can be seen, with monomer component is that the substrate particle of acrylic ester is compared, monomer component is the substrate particle of polystyrene (divinyl aromatic compound), under identical hydrophilicity-imparting treatment condition, with respect to substrate particle (before the hydrophilicity-imparting treatment) originally, the increase degree that has rate of the O atom after the hydrophilicity-imparting treatment is big, and, the F atom have a rate height, monomer component is the reactive height of the substrate particle of polystyrene with respect to mixed gas, easily by hydrophilicity-imparting treatment.

Embodiment 29

The hydrophilization particulate 26 of 7g is immersed in 85 ℃ the ion exchanged water (concentration of particle is 6.3 quality %), under agitation, under 85 ℃, carried out carrying out washing treatment 3 hours.Afterwards, wash, further, under 80 ℃, carry out vacuum-drying 12 hours, obtain hydrophilization particulate 29 according to the order of ion exchanged water, methyl alcohol.

Embodiment 30

The hydrophilization particulate 26 of 7g is immersed in the aqueous sodium hydroxide solution of 0.25N (concentration of particle is 2 quality %), under agitation, under 85 ℃, carry out alkaline purification 3 hours.After the filtered particles, particle is immersed in 85 ℃ the ion exchanged water (concentration of particle is 6.3 quality %), under identical temperature, carried out carrying out washing treatment 3 hours.Behind the cool to room temperature, filtered particles is washed according to the order of ion exchanged water, methyl alcohol, further, carries out vacuum-drying 12 hours under 80 ℃, obtains hydrophilization particulate 30.

The amount of hydrophilization particulate 26,29 that mensuration obtains and 30 solvability fluorine.The result is illustrated in the table 8.

[table 8]

	The amount of solvability fluorine (mg/g)
		Embodiment 26	3.76
Embodiment 29	0.77
		Embodiment 30	0.10

According to table 8 as can be seen, the amount of solvability fluorine can reduce by carrying out washing treatment, in addition, as can be seen, the situation that contains styrenic monomers with substrate particle is the same, and according to the order of carrying out the warm water washing, carrying out alkaline purification and warm water washing, the fluorine reduction effect of being brought by carrying out washing treatment uprises.

In addition,, utilize XPS (ESCA) to carry out the result that surface-element is analyzed, confirmed the existence of Na about each particle that in embodiment 24,25,30, obtains.

Industrial applicibility

Method of the present invention is not damage the useful method that the simple method of the good ground utilizations such as mechanical property that particle has improves the hydrophiling degree of particle surface. The hydrophily of the hydrophiling particulate that obtains by method of the present invention is high, the various particulates of the field of electronic materials such as the additive that can use as aqueous coating or conducting particles base material.

Claims (6)

1. the preparation method of a hydrophilization particulate, this method is by the processing that the mixed gas that must contain the fluorine gas and the gas of the compound that contains Sauerstoffatom is contacted with substrate particle, makes the surface hydrophilic of substrate particle, thereby prepares the method for hydrophilization particulate, it is characterized in that

With the quality average particle diameter is that vinyl based polymer particulate below the 1000 μ m is a substrate particle, and the concentration of the fluorine gas in the mixed gas is 0.01-1.0 volume %.

2. the preparation method of hydrophilization particulate according to claim 1, wherein, the described gas that contains the compound of Sauerstoffatom is oxygen.

3. the preparation method of hydrophilization particulate according to claim 1 and 2, wherein, after making described mixed gas and processing that described substrate particle contacts, the processing that substrate particle is contacted with moisture.

4. the preparation method of hydrophilization particulate according to claim 3, wherein, described moisture is alkaline aqueous solution.

5. according to the preparation method of claim 3 or 4 described hydrophilization particulates, wherein, described moisture is water and/or water vapour.

6. a hydrophilization particulate is characterized in that, this hydrophilization particulate obtains by any described preparation method among the claim 1-5.