JP5263749B2 - Polyamide composite particles, polyamic acid composite particles, polyimide composite particles, and production methods thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide composite particles from which a polyamide, a polyamic acid and a polyimide hardly drops and which have controlled polyamide, polyamic acid and polyimide mol. wts. and to provide a method for producing the same. <P>SOLUTION: This method for producing the composite particles comprising binding (1) the polyamic acid, (2) the polyamide, (3) the polyimide, or (4) monomers constituting the polymers or their oligomers to inorganic particles having Si-containing functional groups on their surfaces through the functional groups is characterized by involving a process for reacting the inorganic particles with a component capable of constituting the polyamide or polyimide. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to polyamide composite particles, polyamic acid composite particles, polyimide composite particles, and methods for producing them.

  Several methods have been proposed for producing polyamide, polyamic acid or polyimide particles.

  For example, Patent Document 1 discloses a method in which a polyamic acid varnish that is a polyimide precursor is prepared, this is dropped into a poor solvent, and particles are produced by a precipitation method.

  Patent Document 2 proposes a method in which a solution of a polyamic acid is placed in a polymer-insoluble solvent and heated to cause ring closure to perform imidization, and the produced particulate polymer is recovered.

  Patent Document 3 discloses an organic solvent (III) in which aromatic tetracarboxylic dianhydride (I) and aromatic diamine (II) are dissolved in (I) and (II) but not formed polyamic acid. Among them, a method for producing polyamic acid fine particles characterized by reacting the total amount of (I) and (II) at 10% by weight or less with respect to (III) is disclosed.

In Patent Document 4, after obtaining a fine particulate solid salt composed of diamine and dicarboxylic acid, a porous solid salt is prepared from the fine particulate solid salt, and polycondensation is always performed in a solid state using this porous solid salt. A method is disclosed.
Japanese Patent Publication No. 38-5997 Japanese Examined Patent Publication No. 39-30060 JP-A-9-302089 Japanese Patent Laid-Open No. 11-172006

  However, it is difficult to produce polyamide particles, polyamic acid particles or polyimide particles controlled to have a desired particle size or specific surface area by any method.

In addition, when polyamide, polyamic acid or polyimide particles are used in various applications, various functionalities (reactivity, etc.) are required depending on the application. Cannot be introduced or the type of functional group to be introduced is very limited.
Accordingly, the main object of the present invention is to produce polyamide composite particles, polyamic acid composite particles or polyimide composite particles that can be controlled to have a desired particle size or specific surface area and also have a functional group on an industrial scale. It is to provide a method that can.

  As a result of intensive studies in view of the problems of the prior art, the present inventor has found that the above object can be achieved by a specific method, and has completed the present invention.

  That is, the present invention relates to the following polyamide composite particles, polyamic acid composite particles, polyimide composite particles, and production methods thereof.

  Item 1. 1) Polyamic acid, 2) Polyamide, 3) Polyimide, or 4) Monomers constituting them or oligomers thereof are bonded to the inorganic particles having Si-containing functional groups on the surface through the functional groups. It is a method, Comprising: The manufacturing method of the composite particle including the process of making the component which can comprise a polyamide or a polyimide react with the said inorganic particle.

Item 2. The process according to item 1, wherein
(A) A step of obtaining polyamide composite particles by alternately polymerizing dicarboxylic acid chloride and diamine compound on the functional groups of inorganic particles having Si-containing functional groups
A method for producing composite particles.

Item 3. The process according to item 1, wherein
(B) The manufacturing method of the composite particle which is B process which obtains a polyamide composite particle by combining the polymer of a dicarboxylic acid chloride and a diamine compound to the said functional group of the inorganic particle which has Si containing functional group.

Item 4. The process according to item 1, wherein
(C) Step C for obtaining polyamic acid composite particles by alternately polymerizing tetracarboxylic anhydride and a diamine compound on the functional groups of inorganic particles having Si-containing functional groups
A method for producing composite particles.

Item 5. The process according to item 1, wherein
(D) A method for producing composite particles, which is a D step in which polyamic acid composite particles are obtained by bonding a polymer of tetracarboxylic anhydride and a diamine compound to the functional groups of inorganic particles having Si-containing functional groups.

Item 6. The process according to item 1, wherein
(E) A polyimide composite particle is obtained by alternately polymerizing tetracarboxylic anhydride and a diamine compound on the functional group of the inorganic particle having an Si-containing functional group, and further imidizing the obtained polyamic acid composite particle. E process
A method for producing composite particles.

Item 7. The process according to item 1, wherein
(F) A polyimide composite particle is obtained by bonding a polymer of tetracarboxylic anhydride and a diamine compound to the functional group of an inorganic particle having an Si-containing functional group, and further imidizing the obtained polyamic acid composite particle. The manufacturing method of the composite particle which is F process to obtain.

  Item 8. Item 8. The production method according to any one of Items 1 to 7, wherein the inorganic particles having a Si-containing functional group are obtained by bringing inorganic particles into contact with a solution in which a silane coupling agent is dissolved.

  Item 9. Item 4. The production method according to Item 2 or 3, wherein at least one of the dicarboxylic acid chloride and the diamine compound has a functional group.

  Item 10. Item 8. The production method according to any one of Items 4 to 7, wherein at least one of the tetracarboxylic anhydride and the diamine compound has a functional group.

  Item 11. Item 11. The method according to any one of Items 1 to 10, wherein the inorganic particles are porous particles having an average particle size of 10 nm to 1 mm.

  Item 12. 4. Polyamide composite particles obtained by the production method according to item 2 or 3.

  Item 13. 6. Polyamic acid composite particles obtained by the production method according to item 4 or 5.

  Item 14. Item 8. A polyimide composite particle obtained by the production method according to Item 6 or 7.

1. Production method of polyamide, polyamic acid and polyimide
1) Polyamic acid, 2) Polyamide, 3) Polyimide, or 4) Monomers constituting them or oligomers thereof are bonded to the inorganic particles having Si-containing functional groups on the surface through the functional groups. A method comprising a step of reacting the inorganic particles with a component capable of constituting polyamide or polyimide.

(1) Inorganic particles The material of the inorganic particles used in the present invention is not limited, and can be selected widely depending on the use of the final product. Examples thereof include silica, alumina, glass, zirconia, titania, ceria, zeolite, and the like.

  Among these, those containing an Si element, for example, silica, zeolite, and the like are preferable from the viewpoint of strong chemical bonding with a silane coupling agent described later.

  The shape of the inorganic particles is not limited, and may be appropriately determined according to the use of the final product such as a spherical shape, a plate shape, a film shape, a needle shape, a fiber shape, a flake shape, and a scale shape. For example, when it is spherical, the average particle size is usually about 5 nm to 1 cm, preferably about 10 nm to 1 mm.

In the present invention, the inorganic particles are preferably porous from the viewpoint of introducing a large number of Si-containing functional groups as the specific surface area increases. For example, silica gel, an alumina porous body, zeolite, etc. are mentioned. For example, in the case of silica gel, the specific surface area is usually about 10 to 4000 m ² / g (preferably about 20 to 2000 m ² / g). By appropriately selecting the material and specific surface area of these inorganic particles, the specific surface areas of the polyamide composite particles, polyamic acid composite particles and polyimide to be produced can be appropriately adjusted.

(2) Si-containing functional group The Si-containing functional group on the surface of the inorganic particles is not limited as long as it is a group containing Si. In the present invention, for example, those provided by a silane coupling agent are preferable.

  The silane coupling agent is not limited, and a known or commercially available one can be used. For example, vinyl type, epoxy type, styryl type, methacryloxy type, acryloxy type, amino type, ureido type, chloropropyl type, mercapto type, sulfide type, isocyanate type and the like can be mentioned.

  Of these, epoxy-based and amino-based are preferable. Specific examples include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxy. Silane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane , 3-glycidoxypropylmethyldiethoxysilane and the like.

  The inorganic particles having the Si-containing functional group can be obtained, for example, by bringing the inorganic particles into contact with a solution in which a silane coupling agent is dissolved.

  The method of contacting is not particularly limited, and examples thereof include a method of spraying and applying the solution to the inorganic particles. In the present invention, a method of immersing the inorganic particles in the solution is preferable.

  The solvent is not limited as long as the silane coupling agent is dissolved. For example, water; alcohols such as methanol, ethanol, butanol; ketones such as acetone, methyl ethyl ketone, cyclohexanone; ethyl acetate, butyl acetate, ethyl cellosolve acetate And esters such as methyl cellosolve acetate and butyrolactone; cyclic ethers such as dioxane, trioxane and tetrahydrofuran; and polyethers.

  The concentration of the silane coupling agent can be appropriately determined according to the type of the silane coupling agent, the inorganic particles, and the solvent, but is usually about 0.01 to 5 wt%, preferably about 0.05 to 1 wt%. That's fine.

  When immersed, if necessary, solid-liquid separation is performed by a known method such as centrifugation, and inorganic particles are collected. If necessary, the particles are washed with a solvent such as ethanol or acetone to be neutral. .

  The component that can constitute polyamide, polyamic acid, or polyimide refers to a monomer that can constitute polyamide, polyamic acid, or polyimide, and an oligomer and a polymer obtained by polymerizing the monomer. When there are two or more types of monomers that can be constituted, that is, in the case of a copolymer, a polymer obtained by polymerizing two or more types of monomers at least once is referred to as an oligomer or a polymer in the present invention. The oligomer usually refers to a polymer having a molecular weight of about 10,000 or less, and the polymer usually refers to a polymer having about 10,000 or more.

  Specific examples of preferred embodiments of the present invention are given below.

The first invention is a method for producing polyamide composite particles,
(A) A step of obtaining polyamide composite particles by alternately polymerizing a dicarboxylic acid chloride and a diamine compound on the functional groups of the inorganic particles having an Si-containing functional group.

The second invention is a method for producing polyamide composite particles,
(B) B process which obtains a polyamide composite particle by combining the polymer of the dicarboxylic acid chloride and a diamine compound with the said functional group of the inorganic particle which has Si containing functional group, It is characterized by the above-mentioned.

The third invention is a method for producing polyamic acid composite particles,
(C) It includes a C step of obtaining polyamic acid composite particles by alternately polymerizing tetracarboxylic anhydride and a diamine compound on the functional groups of the inorganic particles having Si-containing functional groups.

The fourth invention is a method for producing polyamic acid composite particles,
(D) including a D step of obtaining polyamic acid composite particles by bonding a polymer of tetracarboxylic anhydride and a diamine compound to the functional groups of the inorganic particles having Si-containing functional groups.

The fifth invention is a method for producing polyimide composite particles,
(E) A polyimide composite particle is obtained by alternately polymerizing tetracarboxylic anhydride and a diamine compound on the functional group of the inorganic particle having an Si-containing functional group, and further imidizing the obtained polyamic acid composite particle. E process is included.

The sixth invention is a method for producing polyimide composite particles,
(F) A polyimide composite particle is obtained by bonding a polymer of tetracarboxylic anhydride and a diamine compound to the functional group of an inorganic particle having an Si-containing functional group, and further imidizing the obtained polyamic acid composite particle. F process to be obtained.

  These are described in detail below.

1st invention 1st invention is a manufacturing method of polyamide composite particles,
(A) A step of obtaining polyamide composite particles by alternately polymerizing a dicarboxylic acid chloride and a diamine compound on the functional groups of the inorganic particles having an Si-containing functional group.

For example, the inorganic particles and the dicarboxylic acid chloride are bonded via the Si-containing functional group by immersing the inorganic particles having the Si-containing functional group in a solution in which the dicarboxylic acid chloride is dissolved. Next, the obtained dicarboxylic acid chloride-bonded inorganic particles are immersed in a solution in which the diamine compound is dissolved, so that the -COCl group and the diamine of the dicarboxylic acid chloride (the other end is the -COCl group bonded to the Si-containing functional group). An amide bond is formed between the compound and the —NH ₂ group. This process is repeated. In this way, composite particles to which a polyamide (oligomer) having a uniform molecular weight is imparted can be produced by immersing and reacting sequentially (alternatively) in a dicarboxylic acid chloride solution and a diamine compound solution. The molecular weight of the polyamide (oligomer) can be appropriately adjusted by adjusting the number of times of reaction. In addition, after immersing a dicarboxylic acid chloride solution as needed, you may make it wash | clean and dry before immersing a diamine compound solution. Further, the order of bonding to the Si-containing functional group is not limited, and may be performed from the bonding of the diamine compound first. What is necessary is just to determine these suitably by the functional group which Si containing functional group has.

In the present invention, at least one of the dicarboxylic acid chloride and the diamine compound may have a functional group. The functional group is not particularly limited as long as a desired function can be imparted on the surface of the obtained composite particle. For example, hydroxyl group (—OH), carboxyl group (—COOH), amino group (—NH ₂ ), alkenes (—CH═CH—), alkynes (—C≡C—), vinyl ethers (—CH═CH) -O-), amido (-CONH _2), a nitrile group (-C≡N), isocyanate group (-N = C = O), nitro group (-NO _2), sulfone group (-SO ₃ H), thiol group (-SH), other functional groups such as crown ether group, -CF ₃ group, -CCl ₃ group, can be exemplified -CBr _3, and the like. In addition, in the diamine compound and dicarboxylic acid chloride used as raw materials, each has a group —NH ₂ and a group —COCl, but these groups are present on the surface of the finally obtained composite particles. In some cases, it is included in the functional group of the present invention.

  The dicarboxylic acid chloride used in step A of the present invention is not particularly limited, and for example, the same ones used in conventional polyamide synthesis can be used. For example, aliphatic dicarboxylic acid dichlorides such as oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, fumaric acid dichloride, glutaric acid dichloride, adipic acid dichloride, muconic acid dichloride, sebacic acid dichloride, nonanoic acid dichloride, undecanoic acid dichloride; 1 , 2-cyclopropanedicarboxylic acid dichloride, 1,3-cyclobutanedicarboxylic acid dichloride, 1,3-cyclopentanedicarboxylic acid dichloride, 1,3-cyclohexanedicarboxylic acid dichloride, 1,4-cyclohexanedicarboxylic acid dichloride, etc. Dicarboxylic acid dichloride; phthalic acid dichloride, isophthalic acid dichloride, terephthalic acid dichloride, 1,4-naphthalenedicarboxylic acid dichloride, 1,5 -(9-oxofluorene) dicarboxylic acid dichloride, 1,4-anthracene dicarboxylic acid dichloride, 1,4-anthraquinone dicarboxylic acid dichloride, 2,5-biphenyldicarboxylic acid dichloride, 1,5-biphenylenedicarboxylic acid dichloride, 4,4 '-Biphenyldicarbonyl chloride, 4,4'-methylene dibenzoic acid dichloride, 4,4'-isopropylidene dibenzoic acid dichloride, 4,4'-bibenzyldicarboxylic acid dichloride, 4,4'-stilbene dicarboxylic acid dichloride 4,4'-transidicarboxylic acid dichloride, 4,4'-carbonyldibenzoic acid dichloride, 4,4'-oxydibenzoic acid dichloride, 4,4'-sulfonyldibenzoic acid dichloride, 4,4'-dithio Dichlori dibenzoate , P- phenylene diacetic acid dichloride, and aromatic dicarboxylic acid dichloride such as 3,3'-p-phenylene acid dichloride. These dicarboxylic acid chlorides can be used alone or in combination of two or more.

  When using the dicarboxylic acid chloride which has a functional group, what is the said dicarboxylic acid chloride and has the functional group hung up above can be used. For example, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic acid dichloride), 4-nitrophthalic acid dichloride, 3-nitrophthalic acid dichloride, 4-methylphthalic acid dichloride, tetrachlorophthalic acid dichloride, and the like. it can.

  In the present invention, a dicarboxylic acid chloride having a functional group and a dicarboxylic acid chloride having no functional group can be used in combination. Thereby, the characteristic of the polyamide composite particle obtained can be controlled arbitrarily. The ratio of both in this case can be appropriately set according to the type of functional group, the desired amount of functional group, and the like.

  Moreover, dicarboxylic acid chloride can be suitably selected according to the desired characteristic etc. of the polyamide composite particle obtained. For example, when aromatic dicarboxylic acid dichloride (in particular, at least one of terephthalic acid dichloride, 4,4′-biphenyldicarbonyl chloride and isophthalic acid dichloride) is used as the dicarboxylic acid chloride, the heat resistance of the resulting polyamide composite particles is improved. be able to.

  Tricarboxylic acid chlorides, tetracarboxylic acid chlorides and their anhydrides can also be used in place of dicarboxylic acid chlorides. When tetracarboxylic acid chloride or the like is used, it becomes polyamic acid composite particles obtained in the third and fourth steps described later, and this is also included in the polyamide composite particles obtained in the first step.

  Examples of the tricarboxylic acid chloride include trimellitic acid chloride and 1-carboxymethyl-2,3-5 cyclopentanetricarboxylic acid chloride. Examples of the tricarboxylic acid anhydride include trimellitic acid anhydride and 1-carboxymethyl-2,3-5 cyclopentanetricarboxylic acid anhydride.

  Examples of the tetracarboxylic acid chloride and the tetracarboxylic anhydride include those used in the present invention 3.

  The solvent for dissolving the dicarboxylic acid chloride is not particularly limited as long as it substantially dissolves the dicarboxylic acid chloride. For example, 2-propanone, 3-pentanone, tetrahydropyrene, epichlorohydrin, acetone, methyl ethyl ketone (MEK), tetrahydrofuran (THF), ethyl acetate, acetanilide, methanol, ethanol, isopropanol, toluene, xylene, N, Aprotic polar solvents such as N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP); cresol compounds and the like, including at least one of these A solvent can be used.

  The concentration of the solution may be appropriately set according to the type of dicarboxylic acid chloride to be used, but is usually about 0.001 to 2.0 mol / liter, preferably 0.01 to 1.0 mol / liter. To do.

  The diamine compound used in the step A is not particularly limited, and for example, the same ones used in conventional polyamic acid or polyimide synthesis can be used. For example, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 1,4 ′ -Bis (4-aminophenoxy) benzene, 1,3'-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, o-phenylenediamine, m-phenylenediamine, p-phenylene Diamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-methylene-bis (2-chloroaniline) 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino Diphenyl sulfide, 2,6′-diaminotoluene, 2,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 3,3′-diaminobenzophenone, 3,4-diaminobenzophenone, 4,4 '-Diaminobenzophenone, 4,4'-diaminobibenzyl, R (+)-2,2'-diamino-1,1'-binaphthalene, S (+)-2,2'-diamino-1,1'- 1, n-bis (4- (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy) alkane, etc. Aminophenoxy) alkane (n is 3 to 10), 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4- Minophenyl) fluorene, aromatic diamines such as 4,4′-diaminobenzanilide; 1,2-diaminomethane, 1,4-diaminobutane, tetramethylenediamine, 1,5-diaminopentane, 1,6-diaminohexane, Aliphatic diamines such as 1,8-diaminooctane, 1,10-diaminododecane, 1,11-diaminoundecane; 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 4 In addition to alicyclic diamines such as 4,4'-diaminodicyclohexylmethane, 3,4-diaminopyridine, 1,4-diamino-2-butanone, and the like can be used. These can use 1 type (s) or 2 or more types. In particular, it is preferable to use p-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, etc., since heat resistance and chemical resistance are improved.

  When using the diamine compound which has a functional group, it is the said diamine compound, Comprising: What has the functional group quoted above can be used. For example, 1,3-diamino-2-propyl alcohol, 2,2-bis (4-aminophenyl) hexafluoropropane, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 2,4,6- Triaminopyrimidine, 4,4′-diamino-3,3′-dihydroxybiphenyl, 2,4-diamino-6-hydroxypyrimidine, 4,5-diamino-2,6-dimercaptopyrimidine and the like can be used.

  In this invention, the diamine compound which has a functional group, and the diamine compound which does not have a functional group can also be used together. As a result, the characteristics and the like of the obtained polyamide composite particles can be changed. The ratio of both in this case can be appropriately set according to the type of functional group, the desired amount of functional group, and the like.

  Furthermore, in the present invention, other amine compounds (monoamine compounds, polyamine compounds, etc.) can be used in addition to the diamine compounds. By these, the characteristics of the obtained polyamide (the same applies in the case of polyamic acid and polyimide) can be changed. In particular, composite particles having not only a straight chain but also a branched polyamide can be produced by using a trivalent or higher polyvalent amine compound or the like.

  Examples of the monoamine compound include 2-aminothiophenol and 4-aminothiophenol.

  The solvent for dissolving the diamine compound is not particularly limited as long as the diamine compound is substantially dissolved. For example, 2-propanone, 3-pentanone, tetrahydropyrene, epichlorohydrin, acetone, methyl ethyl ketone (MEK), tetrahydrofuran (THF), ethyl acetate, acetanilide, methanol, ethanol, isopropanol, etc., N, N-dimethylformamide Aprotic polar solvents such as (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP); cresol compounds and the like, and a solvent containing at least one of these is used. be able to.

  The concentration of the solution may be appropriately set according to the type of the diamine compound to be used, but is usually about 0.001 to 2.0 mol / liter, preferably 0.01 to 1.0 mol / liter. .

2nd invention 2nd invention is a manufacturing method of polyamide composite particles,
(B) B process which obtains a polyamide composite particle by combining the polymer of the dicarboxylic acid chloride and a diamine compound with the said functional group of the inorganic particle which has Si containing functional group, It is characterized by the above-mentioned.

  The polymer of the dicarboxylic acid chloride and the diamine compound may be a polymer obtained by polymerizing at least one molecule of each of the dicarboxylic acid chloride and the diamine compound. That is, a polymer (dicarboxylic acid-diamine compound) in which one molecule of each is polymerized may be used. One polymer is polymerized in two molecules and the other is polymerized in one molecule (dicarboxylic acid-diamine compound-dicarboxylic acid) (diamine compound-). Dicarboxylic acid-diamine compound) may be used, and oligomers such as those obtained by polymerizing two molecules each (dimer in which the constitutional unit of the polymer is 2) and polymers polymerized by three molecules each (trimer) may be used. A polymer polymerized in a large amount may be used.

  In the present invention, the polyamide oligomer includes a polymer obtained by polymerizing dicarboxylic acid chloride and diamine one molecule at a time. The polyamide oligomer usually refers to a polymer having a molecular weight of about 10,000 or less, and the polymer usually refers to a polymer having about 10,000 or more. In the present invention, an oligomer is preferable from the viewpoint of good reactivity with other substances.

  The raw materials used in Step B, for example, dicarboxylic acid chloride and diamine compound, and compounds having these functional groups are the same as those described above in Step A (including preferred ones).

  In step B, for example, the dicarboxylic acid chloride solution and the diamine compound solution used in step A are mixed in advance before being immersed in inorganic particles, thereby polymerizing polyamide having a desired molecular weight (or emulsion). To prepare. Then, the polyamide and the inorganic particles may be bonded via Si-containing functional groups by immersing (or dispersing) the inorganic particles in the obtained polyamide solution (or emulsion).

  The molecular weight (degree of polymerization) of the polyamide (oligomer) can be adjusted by appropriately adjusting the concentration, mixing ratio, time and the like of the dicarboxylic acid chloride solution and the diamine compound solution.

  The mixing ratio of the two solutions can be appropriately changed depending on the type of dicarboxylic acid chloride / diamine compound and the concentration of each solution, but is usually about dicarboxylic acid chloride: diamine compound = 1: 0.5 to 1.5 (molar ratio). And it is sufficient.

  In mixing, stirring or the like may be appropriately performed by a known method.

3rd invention 3rd invention is a manufacturing method of a polyamic-acid composite particle, Comprising:
(C) It includes a C step of obtaining polyamic acid composite particles by alternately polymerizing tetracarboxylic anhydride and a diamine compound on the functional groups of the inorganic particles having Si-containing functional groups.

The present invention is the same as Step A except that tetracarboxylic anhydride is used in place of dicarboxylic acid chloride in Step A above.
The tetracarboxylic anhydride is not particularly limited, and for example, the same tetracarboxylic anhydride as that used in conventional polyimide synthesis can be used. For example, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4 ′ -Biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (2,3-dicarboxyphenoxy) benzene Dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′- Biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, anthracene-2,3,6 , 7-Tetracarboxylic dianhydride Aromatic tetracarboxylic anhydrides such as phenanthrene-1,8,9,10-tetracarboxylic dianhydride; aliphatic tetracarboxylic anhydrides such as butane-1,2,3,4-tetracarboxylic dianhydride Alicyclic tetracarboxylic anhydrides such as cyclobutane-1,2,3,4-tetracarboxylic dianhydride; thiophene-2,3,4,5-tetracarboxylic dianhydride, pyridine-2, Heterocyclic tetracarboxylic acid anhydrides such as 3,5,6-tetracarboxylic dianhydride can be used. These can use 1 type (s) or 2 or more types. In the present invention, BTDA, pyromellitic dianhydride and the like are particularly preferable.

  Moreover, when using the tetracarboxylic anhydride which has a functional group, the functional group quoted at the A process is mentioned for the said functional group. Examples of the tetracarboxylic acid having this functional group include bicyclo (2.2.2) oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis ( 3,4-anhydrodicarboxyphenyl) hexafluoropropane and the like can be used. In the present invention, a tetracarboxylic acid having a functional group can be used in combination with a tetracarboxylic acid having no functional group. Thereby, the characteristic of the polyamic acid composite particle obtained can be arbitrarily controlled. The ratio of both in this case can be appropriately set according to the type of functional group, the desired amount of functional group, and the like.

  Furthermore, in this invention, what substituted a part of tetracarboxylic anhydride with the acid chloride can be used. By substituting with acid chloride, effects such as increasing the reaction rate depending on conditions can be obtained. As the acid chloride, for example, diethyl pyromellitate diacyl chloride and the like can be used.

  The solvent for dissolving the tetracarboxylic anhydride is not particularly limited as long as it substantially dissolves the tetracarboxylic anhydride, and examples thereof include the same solvents as those for dissolving the dicarboxylic acid chloride.

  The concentration of the solution may be appropriately set according to the type of tetracarboxylic anhydride to be used, but is usually about 0.001 to 2.0 mol / liter, preferably 0.01 to 1.0 mol / liter. And

  Examples of the diamine compound and the solution thereof are the same as those used in step A above. The same applies to diamine compounds having functional groups.

4th invention 4th invention is a manufacturing method of a polyamic-acid composite particle, Comprising:
(D) including a D step of obtaining polyamic acid composite particles by bonding a polymer of tetracarboxylic anhydride and a diamine compound to the functional groups of the inorganic particles having Si-containing functional groups.

  The present invention is the same as the B process except that tetracarboxylic anhydride is used in place of the dicarboxylic acid chloride in the B process.

  The kind of tetracarboxylic anhydride, the solvent to be used, and the like are the same as those described above in Step C (including preferred ones).

  In the present invention, the polyamic acid oligomer (also the polyimide oligomer) includes those obtained by polymerizing a tetracarboxylic anhydride and a diamine compound one molecule at a time. The polyamic acid oligomer usually refers to a polymer having a molecular weight of about 10,000 or less, and the polymer usually refers to a polymer having about 10,000 or more. In the present invention, an oligomer is preferable from the viewpoint of good reactivity with other substances.

5th invention and 6th invention 5th invention is the manufacturing method of a polyimide composite particle, Comprising:
(E) A polyimide composite particle is obtained by alternately polymerizing tetracarboxylic anhydride and a diamine compound on the functional group of the inorganic particle having an Si-containing functional group, and further imidizing the obtained polyamic acid composite particle. E process is included.

  That is, a step of imidizing is further added to the polyamic acid composite particles obtained in the above step C.

The sixth invention is a method for producing a polyimide composite particle,
(F) A polyimide composite particle is obtained by bonding a polymer of tetracarboxylic anhydride and a diamine compound to the functional group of an inorganic particle having an Si-containing functional group, and further imidizing the obtained polyamic acid composite particle. F process to be obtained.

  That is, the step of imidizing is further added to the polyamic acid composite particles obtained in the step D.

  The imidization method is not particularly limited as long as the polyimide particles can be obtained as they are from the polyamic acid composite particles. In the present invention, in particular, (i) a method of imidizing by heating in an organic solvent (wet thermal ring closure), ( It is desirable to employ a method of ii) imidization by a chemical reaction in an organic solvent (chemical ring closure) or (iii) a method of imidization by heating in a dry mode (without solvent) (dry thermal ring closure). Among these, the method according to (iii) is more preferable.

  In the method (i) by heating, for example, polyamic acid composite particles may be dispersed in an organic solvent and heated at a temperature of usually 130 ° C. or higher, preferably about 130 to 250 ° C. As an organic solvent, if it has a boiling point more than the temperature required for imidation reaction, it will not be restrict | limited. In particular, in the present invention, the organic solvent preferably contains a solvent capable of forming an azeotrope with water (hereinafter also referred to as “azeotropic solvent”). That is, in the present invention, it is preferable to use an azeotropic solvent as a part or all of the organic solvent. As the azeotropic solvent, for example, xylene, ethylbenzene, octane, cyclohexane, diphenyl ether, nonane, pyridine, dodecane and the like can be used. These can use 1 type (s) or 2 or more types. In the present invention, the azeotropic solvent is preferably contained in the organic solvent in an amount of 10% by volume or more. By using an azeotropic solvent, water produced as a by-product (mainly condensed water) can be azeotropically removed and removed from the reaction system by refluxing, etc., thereby suppressing hydrolysis of unreacted amide bonds, Decrease in molecular weight can be prevented.

  The proportion of the polyamic acid composite particles dispersed in the organic solvent may be set as appropriate according to the type of the organic solvent, but is usually about 1 to 50 g / liter, preferably 5 to 10 g / liter.

  In the method based on the chemical reaction (ii), a known chemical ring closure method can be applied. For example, the polyamic acid composite particles may be dispersed in an organic solvent composed of pyridine and acetic anhydride and heated at a temperature of usually about 15 to 115 ° C. for about 24 hours while stirring. What is necessary is just to set the mixture ratio of both solvents suitably.

  In the method according to the above (iii), for example, polyamic acid composite particles may be recovered and heated while flowing the composite particles in an atmosphere such as air, vacuum, or inert gas. The heating temperature may generally be about 130 to 300 ° C. Further, the flow method can be carried out by using a known stirring flow device or the like. Also by this method, it is possible to imidize without agglomerating particles. In particular, in this method, since imidization is performed under a condition in which a solvent is not substantially present, heating efficiency is good and safety is advantageous.

  The polyimide composite particles produced in the E step and the F step may be collected by a known method and washed with an organic solvent such as petroleum ether, methanol, acetone, etc. as necessary.

2. Polyamide composite particles The polyamide composite particles of the present invention can be obtained by the above-described A process or B process. Specifically, polyamide oligomers or polyamides are bonded to the inorganic particle surfaces via Si-containing functional groups.

  The molecular weight of the polyamide oligomer and the polyamide bonded per Si-containing functional group can be appropriately set according to the use of the final product, but is usually about 100 to 10000, preferably about 300 to 8000. . The polyamide oligomer and the polyamide may be linear or branched.

The specific surface area (BET method) of the polyamide composite particles of the present invention is usually about 10 to 4000 m ² / g, preferably about 20 to 2000 m ² / g.

  The polyamide composite particles may have a functional group, and the type and the presence ratio of the functional group may be appropriately set according to the use of the final product.

3. Polyamic acid composite particles The polyamic acid composite particles of the present invention are obtained in the above-described C step or D step. Specifically, polyamide oligomers or polyamides are bonded to the inorganic particle surfaces via Si-containing functional groups.

  The molecular weight of the polyamic acid oligomer and the polyamic acid bonded to each Si-containing functional group can be appropriately set according to the use of the final product, but is usually about 100 to 10000, preferably about 300 to 8000. It is. The polyamic acid oligomer and the polyamic acid may be linear or branched.

The specific surface area (BET method) of the polyamic acid composite particles of the present invention is usually about 10 to 4000 m ² / g, preferably about 20 to 2000 m ² / g.
Further, the polyamic acid composite particles may have a functional group, and the type and the presence ratio of the functional group may be appropriately set according to the use of the final product.

4). Polyimide composite particles The polyimide composite particles of the present invention are obtained in the above-mentioned E process or F process. Specifically, a polyimide oligomer or a polyimide is bonded to the inorganic particle surface via a Si-containing functional group.

  The molecular weight of the polyimide oligomer and polyimide bonded per Si-containing functional group can be appropriately set according to the use of the final product, etc., but is usually about 100 to 10000, preferably about 300 to 8000. . The polyimide oligomer and polyimide may be linear or branched.

The specific surface area (BET method) of the polyimide composite particles of the present invention is usually about 10 to 4000 m ² / g, preferably about 20 to 2000 m ² / g.

  Moreover, the polyimide composite particle may have a functional group, and the type and the presence ratio of the functional group may be appropriately set according to the use of the final product.

According to the production method of the present invention, polyamide composite particles, polyamic acid composite particles, or polyimide composite particles controlled to have a desired particle size or specific surface area can be industrially produced.
According to the production method of the present invention, it is also possible to provide polyamide composite particles, polyamic acid composite particles, or polyimide composite particles that can also have functionality.
According to the production method of the present invention, the molecular weight of polyamide, polyamic acid and polyimide to be bonded can be freely controlled. Therefore, it is also possible to produce functional polyamide composite particles having high reactivity, low molecular weight (oligomer), functional polyamic acid composite particles, functional polyimide composite particles, and the like.
In the polyamide composite particles, polyamic acid composite particles or polyimide composite particles of the present invention, the inorganic particles and the resin component such as polyamide are chemically bonded via Si-containing functional groups. Is hard to fall off.

  Therefore, the composite particles of the present invention are chromatographed (separation and purification of pharmaceuticals, metal ions, organic compounds, etc.); diagnostic agents; ion exchange (production of pure water, removal of ions in liquid, ion exchange membrane of fuel cell); Gas and liquid purification (deodorization, decolorization, impurity removal); building materials (heat insulation, sound insulation, sound absorption, chemical substance removal); plastic molding materials and films (gas separation, insulation, light diffusibility, strength, toughness, heat resistance) , Improvement of flame retardancy); additives to plastics, rubber and the like (improvement of strength, toughness, heat resistance, flame retardancy); and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following embodiment.

Silane coupling treatment 1
Silica coupling agent KBE-903 (3-aminopropyltrimethoxysilane (C ₂ H ₅ O) ₃ SiC ₃ H ₆ NH ₂ , manufactured by Shin-Etsu Chemical Co., Ltd.) in a solution of 0.5 g in ion-exchanged water 625 ml 50 g (Wakosil C-300, specific surface area 412 m ² / g by BET method, manufactured by Wako Pure Chemical Industries, Ltd.) was dispersed and stirred at room temperature for 24 hours, followed by filtration to separate silica gel. The separated silica gel was washed with water, dried and then heat-treated at 110 ° C. for 2 hours.

Silane coupling treatment 2
The same procedure as in the above treatment 1 was performed except that KBM-403 (3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent.

The following solutions were used as solutions used in the solution examples.

Solution 1: 0.05 mol / L of 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride in DMF solution 2: 0.05 mol / L of 4,5-diamino-2,6-dimercaptopyrimidine DMF solution solution 3: 0.05 mol / L 4-aminothiophenol in DMF solution 4: 0.05 mol / L 2,4,6-triaminopyrimidine in DMF solution 5: 0.05 mol / L 4,4 ' -Diaminodiphenyl ether in DMF solution 6: 0.05 mol / L 3,5-diaminobenzoic acid in DMF solution 7: 0.05 mol / L terephthalic acid chloride in DMF solution

Example 1
After 20 g of silica gel particles treated with silane coupling (treatment 1) were dispersed in solution 1 (100 ml) and stirred for 24 hours at room temperature, the silica gel was filtered and washed with DMF. Next, the silica gel washed with DMF is dispersed in solution 2 (100 ml), stirred for 24 hours at room temperature, filtered, washed with DMF, and then dispersed again in solution 1 (100 ml) for 24 hours. After stirring at room temperature, it was filtered and washed in the same manner. Further, the silica gel particles are dispersed in solution 3 (100 ml), stirred for 24 hours at room temperature, filtered, washed with DMF and acetone, dried, and heated at 160-180 ° C. for 4 hours under reduced pressure. And imidized. As a result, polyimide composite particles of the following formula 1 were obtained (in addition, the spherical substance in the formula represents silica gel particles). The specific surface area measured by the BET method was 400 m ² / g.

When the difference spectrum of the infrared absorption spectrum of the obtained composite particles and silica gel particles was measured, characteristic absorption based on the imide skeleton was observed in the vicinity of 1780 cm ^-1 and 720 cm ^-1 . The thermal decomposition temperature of the polyimide layer measured by TGA (thermogravimetric apparatus) was about 450 ° C., and the resin content was about 2 wt%. The amount of SH supported was quantified using 2,2′-dipyridyl disulfide and found to be about 0.005 μmol / mg.

Example 2
Solution 1 (100 ml), solution 2 (50 ml) and solution 3 (50 ml) were mixed and stirred for 24 hours to obtain an oligomeric amide acid varnish. 20 g of silica gel particles treated with silane coupling treatment (treatment 1) were dispersed in this oligomer varnish, stirred for 24 hours, filtered, washed with DMF, dried and then heated at 160-180 ° C. for 4 hours under reduced pressure. Treated and imidized. As a result, polyimide composite particles represented by the following formula 2 were obtained (the spherical substance in the formula represents silica gel particles). The specific surface area measured by BET method was 390 m ² / g.

When the difference spectrum of the infrared absorption spectrum of the obtained composite particles and silica gel particles was measured, characteristic absorption based on the imide skeleton was observed in the vicinity of 1780 cm ^-1 and 720 cm ^-1 . The thermal decomposition temperature of the polyimide layer measured by TGA was about 480 ° C., and the resin content was about 3 wt%. The amount of SH supported was determined using 2,2'-dipyridyl disulfide and found to be 0.006 μmol / mg.

Example 3
After 20 g of silica gel particles treated with silane coupling (treatment 1) were dispersed in solution 1 (100 ml) and stirred for 24 hours at room temperature, the silica gel was filtered and washed with DMF. Next, the silica gel washed with DMF is dispersed in solution 4, stirred for 24 hours at room temperature, filtered, washed with DMF, then dispersed again in solution 1 (100 ml) and stirred for 24 hours at room temperature. Then, it was filtered and washed in the same manner. Further, the silica gel particles are dispersed in solution 3 (100 ml), stirred for 24 hours at room temperature, filtered, washed with DMF and acetone, dried, and heated at 160-180 ° C. for 4 hours under reduced pressure. And imidized. As a result, polyimide composite particles represented by the following formula (3) were obtained (the spherical substance in the formula represents silica gel particles). The specific surface area measured by BET method was 401 m ² / g.

When the difference spectrum of the infrared absorption spectrum of the obtained composite particles and silica gel particles was measured, characteristic absorption based on the imide skeleton was observed in the vicinity of 1780 cm ^-1 and 720 cm ^-1 . The thermal decomposition temperature of the polyimide layer measured by TGA was about 480 ° C., and the resin content was about 3.5 wt%. The amount of SH supported was quantified using 2,2′-dipyridyl disulfide and found to be about 0.005 μmol / mg.

Example 4
Solution 1 (90 ml) and solution 4 (30 ml) were mixed and the solution stirred for 24 hours was added with solution 3 (60 ml), and further stirred for 24 hours to obtain an amic acid oligomer. 20 g of silica gel particles treated with silane coupling treatment (treatment 1) were dispersed in this oligomer varnish, stirred for 24 hours, filtered, washed with DMF, dried and then heated at 160-180 ° C. for 4 hours under reduced pressure. Treated and imidized. As a result, polyimide composite particles represented by the following formula (4) were obtained (the spherical substance in the formula represents silica gel particles). The specific surface area measured by the BET method was 392 m ² / g.

When the difference spectrum of the infrared absorption spectrum of the obtained composite particles and silica gel particles was measured, characteristic absorption based on the imide skeleton was observed in the vicinity of 1780 cm ^-1 and 720 cm ^-1 . The thermal decomposition temperature of the polyimide layer measured by TGA was about 480 ° C., and the resin content was about 4 wt%. The amount of SH supported was quantified using 2,2'-dipyridyl disulfide and found to be 0.005 μmol / mg.

Example 5
After 20 g of silica gel particles treated with silane coupling (treatment 1) were dispersed in solution 1 (100 ml) and stirred for 24 hours at room temperature, the silica gel was filtered and washed with DMF. Silica gel washed with DMF is dispersed in solution 4 (100 ml), stirred for 24 hours at room temperature, filtered, washed with DMF, then dispersed again in solution 1 (100 ml) and stirred for 24 hours at room temperature. Then, it was filtered and washed in the same manner. Next, after dispersing in solution 2 and stirring for 24 hours at room temperature, filtering, washing with DMF, dispersing again in solution 1 (100 ml) and stirring for 24 hours at room temperature. Filtered and washed. Further, the silica gel particles are dispersed in solution 3 (100 ml), stirred for 24 hours at room temperature, filtered, washed with DMF and acetone, dried, and heated at 160-180 ° C. for 4 hours under reduced pressure. And imidized. As a result, polyimide composite particles of the following formula (5) were obtained (in this case, the spherical substance represents silica gel particles). The specific surface area measured by BET method was 390 m ² / g.

When the difference spectrum of the infrared absorption spectrum of the obtained composite particles and silica gel particles was measured, characteristic absorption based on the imide skeleton was observed in the vicinity of 1780 cm ^-1 and 720 cm ^-1 . The thermal decomposition temperature of the polyimide layer measured by TGA was about 450 ° C., and the resin content was about 5 wt%. The amount of SH supported was quantified using 2,2'-dipyridyl disulfide and found to be about 0.007 μmol / mg.

Example 6
Solution 1 (90 ml) and solution 4 (30 ml) were mixed and stirred for 24 hours, and solution 1 (60 ml), solution 2 (60 ml) and solution 3 (60 ml) were mixed and stirred for 24 hours. The mixture was further stirred for 24 hours to obtain an amide acid oligomer varnish. 20 g of silica gel particles treated with silane coupling treatment (treatment 1) were dispersed in this oligomer varnish, stirred for 24 hours, filtered, washed with DMF, dried and then heated at 160-180 ° C. for 4 hours under reduced pressure. Treated and imidized. As a result, polyimide composite particles of the following formula (6) were obtained (in addition, spherical substances in the formula indicate silica gel particles). The specific surface area measured by the BET method was 387 m ² / g.

When the difference spectrum of the infrared absorption spectrum of the obtained composite particles and silica gel particles was measured, characteristic absorption based on the imide skeleton was observed in the vicinity of 1780 cm ^-1 and 720 cm ^-1 . The thermal decomposition temperature of the polyimide layer measured by TGA was about 480 ° C., and the resin content was about 5.5 wt%. The amount of SH supported was quantified using 2,2'-dipyridyl disulfide and found to be 0.007 μmol / mg.

Example 7
Solution 1 (100 ml) and solution 5 (90 ml) were mixed and stirred for 24 hours, 20 g of silica gel particles treated with silane coupling (treatment 1) were dispersed, stirred for 24 hours, filtered, and then washed with DMF. After drying, it was imidized by heat treatment at 160 to 180 ° C. for 4 hours under reduced pressure. As a result, polyimide composite particles represented by the following formula (7) were obtained (the spherical substance in the formula represents silica gel particles). The specific surface area measured by the BET method was 396 m ² / g.

When the difference spectrum of the infrared absorption spectrum of the obtained composite particles and silica gel particles was measured, characteristic absorption based on the imide skeleton was observed in the vicinity of 1780 cm ^-1 and 720 cm ^-1 . The thermal decomposition temperature of the polyimide layer measured by TGA was about 500 ° C., and the resin content was about 6 wt%.

Example 8
After 20 g of silica gel particles treated with silane coupling (treatment 2) were dispersed in solution 2 (100 ml) and stirred for 24 hours at room temperature, the silica gel was filtered and washed with DMF. Next, silica gel washed with DMF is dispersed in solution 1 (100 ml), stirred for 24 hours at room temperature, filtered, washed with DMF, and then dispersed again in solution 2 (100 ml) for 24 hours. The mixture was stirred at room temperature, filtered and washed in the same manner, and once again dispersed in Solution 1 (100 ml), stirred at room temperature for 24 hours, filtered, and washed with DMF. Further, the silica gel particles are dispersed in Solution 3 and stirred for 24 hours at room temperature, filtered, washed with DMF and acetone, dried, and then heated at 160 to 180 ° C. for 4 hours under reduced pressure to imidize. did. As a result, polyimide composite particles represented by the following formula (8) were obtained (the spherical substance in the formula represents silica gel particles). The specific surface area measured by the BET method was 395 m ² / g.

When the difference spectrum of the infrared absorption spectrum of the obtained composite particles and silica gel particles was measured, characteristic absorption based on the imide skeleton was observed in the vicinity of 1780 cm ^-1 and 720 cm ^-1 . The thermal decomposition temperature of the polyimide layer measured by TGA was about 450 ° C., and the resin content was about 2 wt%. The amount of SH supported was quantified using 2,2′-dipyridyl disulfide and found to be about 0.006 μmol / mg.

Example 9
Solution 1 (100 ml) and solution 6 (90 ml) were mixed and stirred for 24 hours, 20 g of silica gel particles treated with silane coupling (treatment method 1) were dispersed, stirred for 24 hours, filtered, and then washed with DMF. After drying, the mixture was heat-treated at 160 to 180 ° C. for 4 hours under reduced pressure to be imidized. As a result, polyimide composite particles represented by the following formula (9) were obtained (the spherical substance in the formula represents silica gel particles). The specific surface area measured by the BET method was 403 m ² / g.

The resulting composite particles and based on the imide skeleton was measured difference spectrum of infrared absorption spectrum characteristic absorption of the silica gel particles were observed in the vicinity of and around 720 cm ^-1 1780cm ^-1. The thermal decomposition temperature of the polyimide layer measured by TGA was about 480 ° C., and the resin content was about 5 wt%.

Example 10
20 g of silica gel particles subjected to silane coupling treatment (treatment 1) were dispersed in solution 7 (100 ml) and stirred for 24 hours at room temperature, after which the silica gel was filtered and washed with DMF. Next, the silica gel washed with DMF was dispersed in solution 2 (100 ml), stirred for 24 hours at room temperature, filtered, washed with DMF, and then dispersed again in solution 7 (100 ml) for 24 hours. After stirring at room temperature, it was filtered and washed in the same manner. Further, the silica gel particles were dispersed in solution 3 (100 ml), stirred for 24 hours at room temperature, filtered, washed with DMF and acetone, and dried under reduced pressure. As a result, polyamide composite particles represented by the following formula (10) were obtained (the spherical substance in the formula represents silica gel particles). The specific surface area measured by BET method was 401 m ² / g.

The resulting composite particles and silica gel particles amide characteristic absorption 3300 cm ^-1 peripheral based on binding was measured difference spectrum of infrared absorption spectrum ^{of, 2850 cm -1, 1640 cm -1} , observed in the vicinity of 1540 cm ^-1 It was. The thermal decomposition temperature of the polyamide layer measured by TGA was about 380 ° C., and the resin content was about 1.5 wt%. The amount of SH supported was quantified using 2,2′-dipyridyl disulfide and found to be about 0.005 μmol / mg.

Example 11
Solution 7 (100 ml), solution 2 (50 ml) and solution 3 (50 ml) were mixed and stirred for 24 hours to obtain an amide oligomer varnish. 20 g of silica gel particles subjected to silane coupling treatment (treatment method 1) were dispersed in this oligomer varnish, stirred for 24 hours, filtered, washed with DMF and acetone, and dried under reduced pressure. As a result, polyamide composite particles represented by the following formula (11) were obtained (the spherical substance in the formula represents silica gel particles). The specific surface area measured by the BET method was 395 m ² / g.

When the difference spectrum of the infrared absorption spectrum of the obtained composite particles and silica gel particles was measured, the characteristic absorption based on the amide bond was around 3300 cm ^-1, around 2850 cm ^-1 , 1640 cm ^-1 and 1540 cm ^-1 . Admitted. The thermal decomposition temperature of the polyamide layer measured by TGA was about 380 ° C., and the resin content was about 2 wt%. The amount of SH supported was quantified using 2,2′-dipyridyl disulfide and found to be 0.006 μmol / mg.

Evaluation Since both the polyamide and the polyimide bonded to the composite particles of Examples 1 to 11 are low-molecular oligomers, according to this production method, the molecular weight of the polyamide or the like to be bonded to the composite particles can be controlled and uniform. It can be seen that the molecular weight can be reduced.

Claims (7)

2) made of Polyamide or inorganic particles having a Si-containing functional groups on the surface 4) monomer or oligomer thereof to configure this is a process for producing composite particles formed by bonding via the functional group, wherein the inorganic particles is at least one porous particles selected from the group consisting of silica gel and zeolite, a manufacturing method of composite particles comprising the step of reacting the ingredients may constitute made of polyamide on the inorganic particles. The process according to claim 1,
(A) A step of obtaining polyamide composite particles by alternately polymerizing dicarboxylic acid chloride and diamine compound on the functional groups of inorganic particles having Si-containing functional groups
A method for producing composite particles. The process according to claim 1,
(B) The manufacturing method of the composite particle which is B process which obtains a polyamide composite particle by combining the polymer of a dicarboxylic acid chloride and a diamine compound to the said functional group of the inorganic particle which has Si containing functional group. The manufacturing method according to any one of claims 1 to 3 , wherein the inorganic particles having the Si-containing functional group are obtained by bringing the inorganic particles into contact with a solution in which a silane coupling agent is dissolved.   The production method according to claim 2 or 3, wherein at least one of the dicarboxylic acid chloride and the diamine compound has a functional group. The average particle diameter of the inorganic particles is 10 nm to 1 mm, the manufacturing method according to any one of claims 1-5.   Polyamide composite particles obtained by the production method according to claim 2 or 3.