JP2006052412A - Organic polymer porous body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic polymer porous body having uniform pores and excellent formability and provide a porous carbon material capable of being formed into a variety of shapes, such as a massive, fibrous, sheet-like, and film-like shape and having uniform pores. <P>SOLUTION: A micelle-containing organic polymer has at least one peak in a X-ray diffraction pattern, wherein at least one pair of a diffraction angle (2θ) and a lattice spacing (d) of the peak satisfies the following equation: 2θ=2sin<SP>-1</SP>(λ/2d) [λ is a wavelength in nm of a characteristic X-ray Kα1], and d comprises one or more values selected from a range of 0.8 to 150 nm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a porous organic polymer. More specifically, the present invention relates to a three-dimensional structure and manufacturing method of organic materials useful for electrodes and adsorbents.

Conventionally, as mesoporous materials, inorganic mesoporous materials composed of a three-dimensional structure made of silica and having relatively uniform pores of 1.5 to 10 nm, and uniform pores of organic / inorganic composite polymers There are known mesoporous materials and the like (for example, Patent Documents 1 and 2).
Note that the mesoporous mentioned here means that “a hole having a diameter of about 2 to 50 nm is opened”.

JP-A-8-67578 JP 2000-17102 A

  Also, after polymerizing furfuryl alcohol using a siliceous mesoporous powder called SBA-15 as a mold and carbonizing by sintering, the mesoporous powder as a mold is dissolved and removed with hydrofluoric acid. A carbon material having uniform pores obtained by transferring the mesoporous structure is known (for example, Non-Patent Document 1).

NATURE, Volume 412, 12 pages, issued in July 2002

However, since the former mesoporous material is an inorganic or organic / inorganic composite porous material, it is brittle and easily cracked. Therefore, there is a problem that molding processability is extremely poor, and only a powder form can be obtained, and a form such as a lump, fiber, sheet, or film cannot be obtained.
Moreover, the carbon material obtained by using the former mesoporous powder as the latter mold can only obtain a powder having a very small particle size, and it should be in the form of a lump, fiber, sheet or film. There is a problem that can not be.
Further, when obtaining a carbon material having uniform pores, it is necessary to remove the mesoporous powder as a template, and there is a problem that dangerous hydrofluoric acid or the like must be used at that time. .
That is, an object of the present invention is to provide a porous body having uniform pores and excellent moldability, and further, various forms such as a lump, fiber, sheet, or film, and uniform An object of the present invention is to provide a porous carbon material having various pores.

As a result of intensive studies, the present inventors have found that the above object can be achieved by using a specific micelle-containing organic polymer, and have reached the present invention.
That is, the present invention has at least one peak in the X-ray diffraction pattern, and at least one set of the diffraction angle (2θ) and the lattice spacing (d) of the peak satisfies the following relational expression (1). And d is one or more values within the range of 0.8 nm or more and 150 nm or less; and a method for producing the same.
2θ = 2sin ⁻¹ (λ / 2d) (1)
(Λ represents the wavelength (nm) of Kα1 of characteristic X-rays.)

  The present invention also provides that the total pore volume of pores corresponding to a diameter within a range of ± 40% of the pore diameter showing the maximum peak in the pore diameter distribution curve is 50% by volume based on the total pore volume. An organic polymer porous body, a porous carbon material characterized by the above, and a method for producing the same.

Since the micelle-containing organic polymer of the present invention is an organic material, it can be easily processed and has excellent film properties. Since the organic polymer porous material and porous carbon material produced using this can retain the shape at the time of producing the micelle-containing organic polymer as they are, they can be formed into various shapes such as a lump, fiber, sheet, or film. That is, in the micelle-containing organic polymer of the present invention, micelles having a uniform particle diameter have a uniform shape or are regularly arranged, and this shape can be maintained as it is. Therefore, in the organic polymer porous material and the porous carbon material obtained from the micelle-containing machine polymer, the pores having a uniform pore diameter have a uniform shape or are regularly arranged. And from such uniformity and regularity, the micelle-containing organic polymer, organic polymer porous body and porous carbon material of the present invention exhibit excellent performance such as heat insulation, separation ability and adsorption ability. Further, when the porous carbon material is used for the electrode of the electric double layer capacitor, since the pores have a uniform diameter, the effective electrode area can be increased and the electric double layer can have a high capacity.
Furthermore, since the organic polymer porous body and porous carbon material of the present invention do not require the use of dangerous hydrofluoric acid, the organic polymer porous body and porous carbon material can be provided extremely safely and simply.

The X-ray diffraction pattern in the present invention is obtained, for example, by a small angle scattering measurement method which is a kind of X-ray diffraction method.
The X-ray diffraction method uses the principle of Thomson scattering in which a part of X-rays incident on a substance is scattered without changing the wavelength. The small-angle scattering measurement method utilizes the fact that if there are fine particles of about 1 to 150 nm or non-uniform regions of density, diffuse scattering occurs in the incident X-ray direction. This scattering exists regardless of whether it is crystalline or amorphous, and has the property that the smaller the diameter of the internal structure, the wider the structure, regardless of the internal structure of the particle and the region where the density is not uniform.
The X-ray diffraction patterns obtained by these methods are obtained by plotting the scattering intensity of the measurement substance at each diffraction angle with the vertical axis representing the scattering intensity and the horizontal axis representing the diffraction angle (2θ). Note that λ is the wavelength of Kα1 of the characteristic X-ray of the metal used during measurement.
The X-ray diffraction pattern has at least one peak, and at least one set of the diffraction angle (2θ) and the lattice spacing (d) of the peak is substantially the above relational expression (1) excluding measurement errors. Satisfactory satisfaction indicates a structure in which the lattice spacing (d) is regularly arranged at intervals of 0.8 nm to 150 nm.
That is, the substance having the characteristics of such an X-ray diffraction pattern satisfies any of the following (1) to (3).
(1) The micelle diameter Dm or the pore diameter Dp is uniform, and the micelle or pore shape is uniform.
(2) The shape of the pores or micelles is uniform, and the arrangement structure of the micelles or pores is regular.
(3) The micelle diameter Dm or Dp pore diameter is uniform, and the micelle or pore arrangement structure is regular.

In the present invention, “micelle” in terms of micelle-containing organic polymer, micelle diameter and the like indicates an aggregate of surfactants.
As an example of the micelle-containing organic polymer of the present invention, there can be mentioned a structure in which a surfactant (A) or the like forms micelles in the organic polymer (B) forming the polymer matrix.

The lattice spacing (d) is related to the micelle diameter or the pore diameter.
[1] When the space group can be specified, the micelle diameter (Dm) can be estimated by the following procedure.
(1) First, the space group of the micelle-containing polymer is specified. X-ray diffraction measurement of the micelle-containing polymer is performed to determine the value of the lattice spacing (d1) of the micelle-containing polymer. The lattice constant (r1) of the space group of the micelle-containing polymer is determined from the identified space group and the value of the lattice spacing (d1) obtained as a result of the measurement.
(2) The space group of the organic polymer porous body obtained by removing micelles by the method described later is specified. X-ray diffraction measurement of the organic polymer porous material is performed to determine the value of the lattice spacing (d2) of the organic polymer porous material. The lattice constant (r2) of the space group of the organic polymer porous body is obtained from the space group of the specified organic polymer porous body and the value of the lattice spacing (d2) obtained as a result of the measurement.
(3) The pore diameter (Dp) of the organic polymer porous material excluding micelles is determined using a pore distribution curve as described later.
(4) The micelle diameter (Dm) is calculated from the following equation (2).
(Dm) = (Dp) × (r1) / (r2) (2)
[2] When the space group of the micelle-containing polymer cannot be specified, the micelle diameter cannot be specified, but the lattice spacing (d) can be used as an index of the micelle diameter.
[3] When the space group of the organic polymer porous body or the porous carbon material cannot be specified, the pore diameter cannot be specified, but the lattice spacing (d) can be used as an index of the pore diameter.

The lattice spacing (d) (nm) of the micelle-containing organic polymer of the present invention is preferably 0.8 or more, more preferably 1 or more, particularly preferably 2 or more, and preferably 150 or less, more preferably 100. Hereinafter, it is particularly preferably 50 or less.
If the lattice spacing (d) (nm) of the micelle-containing organic polymer of the present invention is less than 0.8, the micelle diameter or pore diameter (nm) will inevitably be less than 0.8. When used for an electric double layer capacitor, a catalyst carrier, etc., it is not preferable because ink, ions, molecules and the like tend to hardly enter the pores.
On the other hand, if it exceeds 150, it is not preferable from the viewpoint of reduction in surface area, adsorption capacity, and electrical characteristics when used in an ink jet receiving layer, an electric double layer capacitor or a catalyst carrier.

Examples of the micelle shape of the micelle-containing organic polymer of the present invention include a rod shape, a spherical shape, and a layer shape.
The micelle arrangement of the micelle-containing organic polymer of the present invention may have regularity or no regularity, but preferably has regularity.
The fact that the arrangement of micelles has regularity means that the arrangement structure of micelles has a symmetry indicated by a space group.
A space group refers to a group created by a set of symmetrical elements.
The symmetry element means the symmetry that occurs when atoms, particles, vacancies, micelles, etc. are regularly arranged in three dimensions in an infinite manner. Five types of rotation axes, symmetry centers, mirror surfaces, reflection axes, translations, Examples include a helical axis and a projection surface. There are 230 possible combinations of symmetry elements, and all regular arrangements can be explained here. Detailed descriptions and diagrams of all space groups can be found in International Table of Crystallography, Vol. A (D. Reidel, 1987).
Examples of such space groups include those shown in Table 1.

  FIG. 1 is a perspective sectional view schematically showing a state in which micelles or pores and an organic polymer, or pores and carbon form a space group “2-d hexagonal p6 mm”. In this cross section, the hatched portion represents an organic polymer or carbon, and the open portion represents a pore or a micelle. That is, micelles or pores are regularly present in the organic polymer or carbon. FIG. 1 shows one unit of a space group, and the micelle-containing organic polymer, organic polymer porous body or porous carbon material of the present invention has such a continuous shape (others). It is the same for the figure in Fig.).

  FIG. 2 is a perspective transmission diagram schematically illustrating a state in which micelles or pores and an organic polymer, or pores and carbon form a space group “cubic Ia3d”. Cylindrical three-dimensionally connected micelles or pores represented by dotted lines are regularly present in the organic polymer or carbon.

FIG. 3 is a perspective cross-sectional view schematically showing that micelles or pores and an organic polymer, or pores and carbon form a space group “cubic Pm3n”. The hatched portion is a cross section of the organic polymer or carbon, and is regularly present so as to enclose the squirrel-like or tetrapod-like spherical micelles or pores.
FIG. 4 is a perspective cross-sectional view schematically showing that micelles or pores and an organic polymer, or pores and carbon form a space group “3-d hexagonal P6 ₃ / mmc”. is there. The shaded area is a cross section of the organic polymer or carbon, and regularly exists so as to enclose spherical micelles or pores.

As the micelle-containing organic polymer of the present invention, for example, the surfactant (A) may have a structure in which micelles are formed in the organic polymer (B) forming the polymer matrix. The structure is not particularly limited as long as it has two peaks and the diffraction angle (2θ) and the lattice spacing (d) of one of the peaks satisfy the relational expression (1).
Although it does not specifically limit as surfactant (A), Well-known anionic surfactant (A1), cationic surfactant (A2), nonionic surfactant (A3), and amphoteric surfactant (A4) Can be used.

  Examples of the anionic surfactant (A1) include carboxylic acid and its salt (A1a), sulfate ester and its salt (A1b), carboxymethylated product and its salt (A1c), sulfonic acid and its salt (A1d), and phosphate ester And salts thereof (A1e) and the like can be used.

  Carboxylic acid and its salt (A1a) include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and other saturated or unsaturated fatty acids having 8 to 22 carbon atoms; naturally derived higher fatty acids An aromatic carboxylic acid having 8 to 22 carbon atoms such as 4-methylsalicylic acid, and a salt thereof can be used.

Moreover, as these salts, the salt which combines the anion which consists of said carboxylic acid, and the following cations can be used.
As a cation forming the salt, alkali metal, alkaline earth metal, ammonium ion, or the like can be used.

  Examples of the alkali metal include lithium, sodium and potassium. Examples of the alkaline earth metal include barium and calcium.

Examples of sulfates and salts thereof (A1b) include higher alcohol sulfates such as sulfuric monoesters of aliphatic alcohols having 8 to 22 carbon atoms such as octyl alcohol, decyl alcohol, lauryl alcohol; alkylenes of alcohols having 8 to 22 carbon atoms Higher alkyl ether sulfates such as sulfuric acid monoesters of oxide (hereinafter referred to as AO) adducts (addition mole number 1 to 20); sulfated oils of natural fats and oils having carboxylic acid residues having 8 to 22 carbon atoms; oleic acid Sulfated fatty acid esters of unsaturated fatty acid esters having 8 to 30 carbon atoms such as butyl, butyl ricinoleate and butyl linoleate; Sulfated olefins of olefins having 8 to 22 carbon atoms such as octene, dodecene and octadecene; and salts thereof Etc. can be used.
As AO, one having 2 to 4 carbon atoms can be used, and ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 2,3- and 1,3-butylene. Examples thereof include oxide and tetrahydrofuran. Moreover, you may add independently and may add 2 or more types of AO at random addition or block addition.

  As the carboxymethylated product and a salt thereof (A1c), a carboxymethylated product of an aliphatic alcohol having 8 to 22 carbon atoms; a carboxymethylated product of an AO adduct of an aliphatic alcohol, or a salt thereof can be used.

Examples of the sulfonic acid and its salt (A1d) include alkyl benzene sulfonic acids such as octyl benzene sulfonic acid, dodecyl benzene sulfonic acid and octadecyl benzene sulfonic acid; alkyl naphthalene sulfonic acids such as octyl naphthalene sulfonic acid; sulfo-2-succinic acid di-2-ethylhexyl ester Sulfo fatty acid esters such as dioctadecyl sulfosuccinic acid ester; α-olefin sulfonic acid; Igepon T-type sulfonic acid; and salts thereof can be used.
As these salts, a salt formed by combining an anion composed of sulfonic acid and a cation exemplified in (A1a) can be used.

  As phosphate ester and its salt (A1e), higher alcohol phosphate ester such as lauryl alcohol phosphate monoester and lauryl alcohol phosphate diester; higher alcohol AO adduct phosphate ester and salts thereof can be used.

As the cationic surfactant (A2), a quaternary ammonium salt type cationic surfactant (A2a), an amine salt type cationic surfactant (A2b) and the like can be used.
Examples of the quaternary ammonium salt type cationic surfactant (A2a) include tetraalkylammonium cations such as lauryltrimethylammonium chloride and didecyldimethylammonium chloride (the carbon number of each alkyl group is preferably 1 to 18); lauryldimethylbenzyl An ammonium cation having a benzyl group and an alkyl group (preferably having 1 to 18 carbon atoms) such as ammonium chloride (benzalkonium chloride); a pyridinium cation such as cetylpyridinium chloride and oleylpyridinium chloride; a polyoxyalkylene group and an alkyl group A quaternary ammonium salt composed of an ammonium cation having a carbon number of preferably 1 to 18 can be used.
As anions constituting these quaternary ammonium salts, hydroxide ions, halogen ions (for example, fluorine ions, chlorine ions, bromine ions, iodine ions), nitrate ions, nitrite ions, methosulphate ions, carbon number 1 ~ 8 carboxyl anions (for example, anions derived from formic acid, acetic acid, propionic acid, 2-ethylhexanoic acid, lactic acid, malic acid, gluconic acid, etc.) and the like can be used.

  As the amine salt type cationic surfactant (A2b), primary amine salts such as laurylamine chloride, stearylamine bromide, cetylamine methosulfate; laurylmethylamine chloride, stearylethylamine bromide, dilaurylamine methosulfate, laurylpropyl Secondary amine salts such as amine acetate; tertiary amine salts such as lauryl diethylamine chloride and laurylethylmethylamine bromide can be used.

As the nonionic surfactant (A3), an AO addition type nonionic surfactant (A3a), a polyvalent alcohol type nonionic surfactant (A3b) and the like can be used.
As the AO addition type nonionic surfactant (A3a), a saturated or unsaturated higher alcohol AO addition having 8 to 22 carbon atoms such as 2-ethylhexyl alcohol, dodecyl alcohol, oleyl alcohol, linoleic alcohol, obtusyl alcohol, etc. (Addition mole number 3 to 100); stearic acid EO adduct (addition mole number 10 to 50 mol), oleic acid EO adduct (addition mole number 10 to 50 mol), polyethylene glycol (molecular weight 400 to 2000) laurin C8-22 saturated or unsaturated carboxylic acid AO adducts such as acid diesters; ethylene glycol, propylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, neopentyl alcohol, pentaerythritol, dipentaerythritol , Sorbitan, Seo AO adduct of polyhydric alcohol having 2 to 22 carbon atoms such as bitol and sucrose (addition mole number 10 to 120); trimethylolpropane monostearate EO (addition mole number 10 to 50 mole) ) PO (addition mol number 10-50 mol) random adduct, sorbitan monostearate EO adduct (addition mol number 10-50 mol), sorbitan dilaurate EO (addition mol number 10-50 mol) PO (addition mol number 10) ˜50 mol) polyhydric alcohol carboxylate AO adduct such as random adduct; sorbitan monostearyl ether EO adduct (addition mole number 10-50 mol), methyl glycoside EO (addition mole number 10-50 mol) PO ( Addition mole number 10-50 moles) Random adduct, lauryl glycoside EO adduct (addition mole number 10-50 moles) Nonalkylphenol EO (addition mole number 10-50 mol) PO (addition mole number 10-50 mol) block adduct, octylphenol EO adduct (addition mole number 10-50 mol), bisphenol AEO adduct Alkylphenol AO adducts such as (addition mole number 10-50 mol); higher alkylamines such as laurylamine EO adduct (addition mole number 10-50 mol), stearylamine EO adduct (addition mole number 10-50 mol) AO adduct; EO adduct of hydroxypropyl oleic acid amide (addition mole number: 10 to 50 mol), EO adduct of dihydroxyethyl lauric acid amide (addition mole number: 10 to 50 mol), etc. Can be used.

  Examples of the polyhydric alcohol type nonionic surfactant (A3b) include polyhydric alcohol carboxylates such as pentaerythritol monooleate and sorbitan monolaurate; polyhydric alcohols such as pentaerythritol monolauryl ether, sorbitan monomethyl ether and lauryl glycoside. Alkyl ethers can be used.

As the amphoteric surfactant (A4), amino acid type amphoteric surfactant (A4a), betaine type amphoteric surfactant (A4b), imidazoline type amphoteric surfactant (A4c) and the like can be used.
The amino acid type amphoteric surfactant (A4a) is an amphoteric surfactant having an amino group and a carboxyl group in its molecule, and an alkylaminopropionic acid type amphoteric interface such as sodium stearylaminopropionate or potassium laurylaminopropionate. Activators; alkylaminoacetic acid type amphoteric surfactants such as sodium laurylaminoacetate and ammonium stearylaminoacetate.

  The betaine type amphoteric surfactant (A4b) is an amphoteric surfactant having a quaternary ammonium salt type cation moiety and a carboxylic acid type anion moiety in its molecule, such as stearyldimethylaminoacetic acid betaine and lauryl. Examples thereof include alkyl dimethyl betaines such as dimethylaminoacetic acid betaine; amide betaines such as coconut oil fatty acid amidopropyl betaine; alkyldihydroxyalkyl betaines such as lauryl dihydroxyethyl betaine.

  Examples of the imidazoline type amphoteric surfactant (A4c) include 2-undecyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine and 2-heptadecenyl-hydroxyethyl imidazoline.

Of these surfactants (A), the cationic surfactant (A2) is preferable, and the quaternary ammonium salt type cationic surfactant (A2a) is more preferable. Particularly preferred are quaternary ammonium salts composed of tetraalkylammonium cations and quaternary ammonium salts composed of ammonium cations having a benzyl group and an alkyl group.
(A) can use the commercial item as it is, and what was manufactured by the well-known method may be used for it. Moreover, you may use 2 or more types of mixtures.

  The amount of (A) used (parts by weight) is preferably 0.5 or more, more preferably 10 or more, particularly preferably 30 or more, and most preferably based on 100 parts by weight of the organic polymer (B) forming the polymer matrix. Is 50 or more, preferably 200 or less, more preferably 150 or less, particularly preferably 120 or less, and most preferably 100 or less.

  The amount of (A) used (parts by weight) is preferably 0.5 or more, more preferably 10 or more, particularly preferably 30 or more, and most preferably based on 100 parts by weight of the organic polymer (B) forming the polymer matrix. Is 50 or more, preferably 200 or less, more preferably 150 or less, particularly preferably 120 or less, and most preferably 100 or less.

The shape of the micelle and the space group of the micelle arrangement are mainly influenced by the chemical structure of the surfactant (A). This is also affected by the amount of surfactant, temperature, media type, and the like.
The shape of the micelle can be controlled by the balance between the size of the hydrophilic group and the size of the hydrophobic group of the surfactant (A). Details are described in the literature (Supramolecular Science, Tokyo Science Doujin, 1998).
For example, in an aqueous system, generally, as the volume occupied by a hydrophobic group increases with respect to the length of the hydrophobic group, the volume changes from a spherical micelle to a rod-like micelle and from a rod-like micelle to a layered micelle (for example, the shape of a surfactant Is a triangular pyramid, and the bottom part is a hydrophilic group, the volume of the triangular pyramid is the volume occupied by the hydrophobic group, and the height is the length of the hydrophobic group. If the height of the pyramid is short, it will become a triangular pyramid with a large bottom area, and if it is arranged, it will be easily spherical, whereas if the height of the triangular pyramid is long, it will become a triangular pyramid with a small bottom area, forming a spherical micelle. I think it will be difficult.)

The space group that can be formed is determined by the shape of the micelle.
As a space group that can be taken when a surfactant capable of forming spherical micelles is used, for example, 3-d hexagonal P6 ₃ / mmc, cubic Pm3n, and the like are used. Also, a surfactant that forms rod-like micelles is used. Examples of the space group that can be taken include 2-d hexagonal p6 mm, cubic Ia3d, and the like.
Examples of the space group that can be taken when a surfactant that forms layered micelles is used include Lamella L1.

Although it does not specifically limit as an organic polymer (B) which forms a polymer matrix, A well-known thermoplastic resin (B1), a thermosetting resin (B2), these mixtures, etc. can be used.
Examples of the thermoplastic resin (B1) include vinyl resin (B1-1), polyester (B1-2), polyamide (B1-3), polyurethane (B1-4), and polycarbonate (B1-5).

The vinyl resin (B1-1) can be obtained by polymerizing one or more of the non-crosslinkable vinyl monomers (b1).
As the vinyl monomer (b1), vinyl hydrocarbon (b1-1), epoxy group-containing vinyl monomer (b1-2), vinyl ester (b1-3), vinyl ether (b1-4), vinyl ketone (b1-5), Alkyl (meth) acrylate (b1-6), vinyl monomer (b1-7) having a polyoxyalkylene group, carboxyl group-containing vinyl monomer (b1-8), sulfo group-containing vinyl monomer (b1-9), phosphono group-containing Vinyl monomer (b1-10), hydroxyl group-containing vinyl monomer (b1-11), nitrogen-containing vinyl monomer (b1-12), halogen element-containing vinyl monomer (b1-13) and other vinyl monomers (b1-14) Used.

As the vinyl hydrocarbon (b1-1), an aliphatic vinyl hydrocarbon (b1-1a), an alicyclic vinyl hydrocarbon (b1-1b), an aromatic vinyl hydrocarbon (b1-1c), or the like is used.
As the aliphatic vinyl hydrocarbon (b1-1a), alkene or alkadiene having 2 to 50 carbon atoms (preferably 2 to 22) can be used. For example, ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene. Octene, dodecene, octadecene, butadiene, isoprene, 1,4-pentadiene and the like.

  As the alicyclic vinyl hydrocarbon (b1-1b), an alicyclic vinyl hydrocarbon having 5 to 50 carbon atoms (preferably 5 to 22) can be used. For example, cyclohexene, cyclopentadiene, dicyclopentadiene, pinene , Limonene, indene, vinylcyclohexene, and ethylidenebicycloheptene.

  As the aromatic vinyl hydrocarbon (b1-1c), aromatic vinyl hydrocarbons having 8 to 50 carbon atoms (preferably 8 to 22) can be used. For example, styrene, α-methylstyrene, vinyl toluene, 2, Examples include 4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, and phenylstyrene.

  As the epoxy group-containing vinyl monomer (b1-2), a monomer containing an epoxy group and a vinyl group (having 6 to 50 (preferably 6 to 20) carbon atoms) can be used. For example, glycidyl (meth) acrylate, etc. Is mentioned.

  As the vinyl ester (b1-3), a monomer containing a vinyl group and an ester bond (4 to 50 (preferably 6 to 20) carbon atoms) can be used. For example, vinyl acetate, vinyl butyrate, propionic acid Vinyl, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, vinyl methoxyacetate, vinyl benzoate, dialkyl fumarate (two alkyl groups are linear, branched or And a dialkyl maleate (the two alkyl groups are linear, branched or cyclic groups having 2 to 8 carbon atoms) and the like.

  As the vinyl ether (b1-4), a vinyl group-containing monomer having an ether bond (3 to 50 (preferably 6 to 20) carbon atoms) can be used. For example, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether , Vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro 1,2-pyran, 2-butoxy-2′-vinyl Examples include roxydiethyl ether and vinyl 2-ethylmercaptoethyl ether.

  As vinyl ketone (b1-5), a C6-C50 vinyl ketone etc. can be used, For example, vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone, etc. are mentioned.

  As the alkyl (meth) acrylate (b1-6), an alkyl (meth) acrylate having an alkyl group having 1 to 50 (preferably 1 to 20) carbon atoms can be used. For example, methyl (meth) acrylate, ethyl ( (Meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, cyclohexyl methacrylate , Benzyl methacrylate, and phenyl (meth) acrylate.

The vinyl monomer (b1-7) having a polyoxyalkylene group is a (meth) acrylate having a polyoxyalkylene group having a weight average molecular weight (hereinafter abbreviated as Mw) of 100 to 10,000 (preferably 300 to 5,000). For example, polyethylene glycol mono (meth) acrylate having a number average molecular weight (hereinafter abbreviated as Mn) of 300, polypropylene glycol (Mn500) monoacrylate, methyl alcohol EO 10 mol adduct (meth) acrylate and lauryl alcohol EO 30 mol addition Examples include (meth) acrylates.
In the above or below, Mn and Mw are a number average molecular weight and a weight average molecular weight, respectively, in terms of polystyrene measured by a gel permeation chromatography method (hereinafter abbreviated as GPC method).

  As the carboxyl group-containing vinyl monomer (b1-8), a monomer having 3 to 50 carbon atoms (preferably 3 to 20) containing a carboxyl group and a vinyl group and a salt thereof can be used. For example, (meth) acrylic Acid, (anhydrous) maleic acid, monoalkyl maleate (alkyl group having 1 to 10 carbon atoms) ester, fumaric acid, monoalkyl fumarate (alkyl group having 1 to 10 carbon atoms) ester, crotonic acid, itaconic acid, itacone Acid monoalkyl (alkyl group having 1 to 10 carbon atoms) ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester (alkyl group having 1 to 10 carbon atoms), cinnamic acid and alkali metal salts thereof (for example, , Sodium salts, potassium salts, etc.), alkaline earth metal salts (eg calcium salts, magnesium salts) ), Amine salts or ammonium salts.

As the sulfo group-containing vinyl monomer (b1-9), vinyl sulfate, vinyl sulfate, vinyl sulfate and the like can be used.
As the vinyl sulfuric acid, a monomer having 2 to 50 carbon atoms (preferably 2 to 20) containing a vinyl group and a sulfo group can be used. For example, vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, α -Methylstyrenesulfonic acid, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloylamino-2,2 -Dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid .

As the vinyl sulfate, a salt formed by combining the above-mentioned anion made of vinyl sulfate and the cation exemplified in (A1a) can be used. For example, sodium vinyl sulfonate, 2- (meth) acrylamide-2-methylpropane Examples thereof include calcium sulfonate and sodium 3- (meth) acryloyloxy-2-hydroxypropanesulfonate.
As vinyl sulfate ester, what consists of said vinyl sulfate and C2-C50 (preferably 3-22) alcohol etc. can be used.
As alcohols, saturated or unsaturated aliphatic alcohols (3 to 22 carbon atoms) can be used, and primary alcohols (3 to 22 carbon atoms), secondary alcohols (3 to 22 carbon atoms), and tertiary alcohols. Alcohol (C3-C22) etc. can be used.

  Examples of the vinyl sulfate ester include methyl vinyl sulfonate and sulfopropyl (meth) acrylate.

  As the phosphono group-containing vinyl monomer (b1-10), a monomer having 4 to 50 carbon atoms (preferably 5 to 20) containing a phosphono group and a vinyl group can be used. For example, hydroxyalkyl (meth) acrylate (Hydroxyalkyl group having 1 to 20 carbon atoms) Phosphoric acid monoester, 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, 2-acryloyloxyethanephosphonic acid and the like.

  As the hydroxyl group-containing vinyl monomer (b1-11), a monomer having 4 to 50 carbon atoms (preferably 4 to 20) containing a hydroxyl group and a vinyl group can be used. For example, hydroxystyrene, hydroxyethyl (meta ) Acrylate, hydroxypropyl (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol , Propargyl alcohol, 2-hydroxyethyl propenyl ether, sucrose allyl ether, and the like.

  As nitrogen-containing vinyl monomer (b1-12), amino group-containing vinyl monomer (b1-12a), amide group-containing vinyl monomer (b1-12b), nitrile group-containing vinyl monomer (b1-12c), quaternary ammonio group-containing A vinyl monomer (b1-12d) and a nitro group-containing vinyl monomer (b1-12e) can be used.

  As the amino group-containing vinyl monomer (b1-12a), a monomer having 4 to 50 carbon atoms (preferably 5 to 20) containing an amino group and a vinyl group can be used. For example, aminoethyl (meth) acrylate, Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine N, N-dimethylaminostyrene, methyl α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, Mino indole, aminopyrrole, and the like amino imidazole and amino mercaptothiazole is.

As the amide group-containing vinyl monomer (b1-12b), a monomer having 3 to 50 carbon atoms (preferably 3 to 20) containing an amide group and a vinyl group can be used. For example, (meth) acrylamide, N-methyl (Meth) acrylamide, N-butylacrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide, N, N-dimethylacrylamide, N, N— Examples include dibenzylacrylamide, methacrylformamide, N-methyl N-vinylacetamide, and N-vinylpyrrolidone.

As the nitrile group-containing vinyl monomer (b1-12c), a monomer having 3 to 50 carbon atoms (preferably 3 to 20) containing a nitrile group and a vinyl group can be used, for example, (meth) acrylonitrile and cyanostyrene. Etc.

  As the quaternary ammonio group-containing vinyl monomer (b1-12d), a quaternized product of a tertiary amino group-containing vinyl monomer having 6 to 50 carbon atoms (preferably 8 to 20) (for example, methyl chloride, dimethyl sulfate, benzyl). And the like quaternized with a quaternizing agent such as chloride and dimethyl carbonate). Examples of the tertiary amino group-containing vinyl monomer include trimethylaminoethyl (meth) acrylate, triethylaminoethyl (meth) acrylate, trimethylaminoethyl (meth) acrylamide, triethylaminoethyl (meth) acrylamide, and tetraallylamine. It is done.

  As the nitro group-containing vinyl monomer (b1-12e), a monomer having 6 to 50 carbon atoms (preferably 6 to 20) containing a nitro group and a vinyl group can be used, and examples thereof include nitrostyrene and dinitrostyrene. Can be mentioned.

  As the halogen-containing vinyl monomer (b1-13), a vinyl group-containing hydrocarbon having 2 to 50 carbon atoms (preferably 2 to 20) having a halogen atom can be used, and examples thereof include vinyl chloride, vinyl bromide, and vinylidene chloride. , Allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

  Other vinyl monomers (b1-14) include acetoxystyrene, phenoxystyrene, ethyl α-ethoxy acrylate, isocyanatoethyl (meth) acrylate, cyanoacrylate, m-isopropenyl-α, α-dimethylmethylbenzyl isocyanate and the like. Can be mentioned.

(B1) is a known method and can be obtained by reacting (b1) with a polymerization initiator and, if necessary, a solvent.
As a polymerization initiator for polymerizing the monomer, a radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator can be used.
Any radical polymerization initiator may be used as long as it is used for the polymerization of known vinyl monomers. Typical examples include peroxide polymerization initiators and azo polymerization initiators. Moreover, you may use the redox polymerization initiator which uses a peroxide polymerization initiator and a reducing agent together. Further, two or more of these may be used in combination.

  As the peroxide polymerization initiator, a water-soluble peroxide polymerization initiator can be used, and examples thereof include hydrogen peroxide, peracetic acid, and ammonium salts, potassium salts, and sodium salts of persulfuric acid.

Examples of the azo polymerization initiator include azobisamidinopropane salt, azobiscyanovaleric acid (salt), and 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide].
Examples of the redox polymerization initiator include water-soluble peroxides such as persulfate, hydrogen peroxide and hydroperoxide (the ones exemplified above can be used) and water-soluble inorganic or organic reducing agents (ferrous iron Salt, sodium hydrogen sulfite, alcohol, polyamine and the like) and a water-based redox polymerization initiator.

As the anionic polymerization initiator, known ones can be used. For example, strong alkaline substances such as strontium, calcium, potassium, sodium and lithium, weak alkaline substances such as pyridine, and the like can be used.
As the cationic polymerization initiator, known ones can be used, for example, proton acids such as sulfuric acid, phosphoric acid and perchloric acid, and Lewis such as boron trifluoride, aluminum chloride, titanium tetrachloride and tin tetrachloride. An acid or the like can be used.
Among these polymerization initiators, radical polymerization initiators, anionic polymerization initiators and redox polymerization initiators are preferred, more preferably redox polymerization initiators, and particularly preferably redox polymerization initiators using potassium persulfate and a reducing agent in combination. It is.

  The amount (parts by weight) of the polymerization initiator used is preferably 0.1 or more, more preferably 0.2 or more, particularly preferably 0.3 or more, and 20 or less with respect to 100 parts by weight of (b1). More preferably, it is 10 or less, and particularly preferably 5 or less.

  Polyester (B1-2) is a dehydration-condensation of diol (b2-2) and dicarboxylic acid (b2-1) or its ester-forming group derivative (an acid anhydride, acid halide, lower alkyl ester having 4 or less carbon atoms). The oxycarboxylic acid (b2-3) is subjected to dehydration condensation, and the lactone (b2-4) is subjected to ring-opening polymerization.

  As the dicarboxylic acid (b2-1), a dicarboxylic acid having 4 to 20 carbon atoms can be used, and examples thereof include adipic acid, maleic acid, terephthalic acid, and phthalic acid. As the diol (b2-2), a diol having 2 to 18 carbon atoms can be used. For example, ethylene glycol, diethylene glycol, 2,2-dimethylpropanediol, 1,4-butanediol, 1,18-octadecanediol and Examples include alkylene oxide adducts of bisphenol A.

  As the oxycarboxylic acid (b2-3), an oxycarboxylic acid having 2 to 12 carbon atoms can be used. For example, hydroxyacetic acid, ω-oxycaproic acid, ω-oxyenanthic acid, ω-oxycaprylic acid, ω- Examples include oxypelargonic acid, ω-oxycapric acid, 11-oxyundecanoic acid, and 12-oxidedecanoic acid.

  As the lactone (b2-4), a lactone having 6 to 12 carbon atoms can be used, and examples thereof include caprolactone, enanthlactone, laurolactone, and undecanolactone.

By dehydrating and condensing the diol (b2-2) with the dicarboxylic acid (b2-1) or its ester-forming group derivative (an acid anhydride, an acid halide, a lower alkyl ester having 4 or less carbon atoms) (B1-2) Can be manufactured. The molar ratio of (b2-1) / (b2-2) is preferably 1.1 / 1 to 1 / 1.1, and more preferably 1.05 / 1 to 1 / 1.05.
Examples of esterification catalysts include inorganic acids (sulfuric acid, hydrochloric acid, etc.), organic acids (p-toluenesulfonic acid, methanesulfonic acid, polyphosphate esters, etc.), antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin). Oxide), titanium catalyst (tetrabutyl titanate, etc.), zirconium catalyst (tetrabutyl zirconate, etc.), zirconium organic acid salt (zirconyl acetate), organic acid metal salt catalyst (zinc acetate, etc.), and the like.

When using a catalyst, the usage-amount of a catalyst is 0.1-5 weight part normally with respect to 100 weight part of monomers (the total weight of two when (b2-1) and (b2-2) are used). .
Polyester (B1-2) is produced by a known method, for example, by reacting (b2-1) and (b2-2) in the presence of an esterification catalyst at 1 torr and 200 ° C. for 18 hours.

Polyamide (B1-3) is a method of dehydrating condensation of dicarboxylic acid (b2-1) and diamine (b3-1), a method of dehydrating condensation of aminocarboxylic acid (b3-2), and a lactam (b3-3). It can be obtained by a ring polymerization method.
As the diamine (b3-1), diamines having 2 to 18 carbon atoms can be used. For example, ethylenediamine, 1,3-propanediamine, 2,2-dimethylpropanediamine, 1,4-butanediamine, isophoronediamine, Examples include 1,18-octadecanediamine and phenylenediamine.

  As the aminocarboxylic acid (b3-2), an aminocarboxylic acid having 2 to 12 carbon atoms can be used. For example, glycine, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargon Examples include acid, ω-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

  As the lactam (b3-3), a lactam having 6 to 12 carbon atoms can be used, and examples thereof include caprolactam, enantolactam, laurolactam, and undecanolactam.

When (b2-1) and (b3-1) are subjected to dehydration condensation to obtain (B1-3), the molar ratio of (b2-1) / (b3-1) is 1.1 / 1 to 1/1. .1 is preferable, and 1.05 / 1 to 1 / 1.05 is more preferable.
Polyamide (B1-3) is produced by a known method, for example, by reacting (b2-1) and (b3-1) at 1 torr and 200 ° C. for 12 hours.

Polyurethane (B1-4) can be obtained by polyaddition reaction of diisocyanate (b4-1) and diol (b2-2).
As the diisocyanate (b4-1), a diisocyanate having 6 to 20 carbon atoms (excluding carbon in the isocyanate group; hereinafter the same) can be used. For example, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 2,4'- or 4,4'-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) , Dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), methylcyclohexadiene diisocyanate (hydrogenated TDI), 2,5- or 2,6-norbornene diisocyanate, m- or p-xylylene diisocyanate (XDI) Beauty α, α, α ', α'- tetramethylxylylene diisocyanate (TMXDI), and the like.

When (b4-1) and (b2-2) are reacted to obtain (B1-4), the molar ratio of (b4-1) / (b2-2) is 1.1 / 1 to 1/1. .1 is preferable, and 1.05 / 1 to 1 / 1.05 is more preferable.
As the urethanization catalyst, known catalysts can be used, such as metal catalysts such as tin-based catalysts and lead-based catalysts; triethylenediamine, tetramethylethylenediamine, N-ethylmorpholine, triethylamine, diethylethanolamine, and carbonates or organic thereof. Amine-based catalysts such as acid salts are used.

When using a catalyst, the usage-amount of a catalyst is 0.1-5 weight part normally with respect to 100 weight part of monomers (total weight of (b4-1) and (b2-2)).
The polyurethane (B1-4) is produced by a known method, for example, by reacting (b4-1), (b2-2) and a urethanization catalyst at 60 ° C. in a nitrogen atmosphere.

Polycarbonate (B1-5) can be obtained by condensation of diol (b2-2) and phosgene or carbonic acid diester.
When (B1-5) is obtained by condensing diol (b2-2) with phosgene or carbonic acid diester, the molar ratio of (b2-2) / phosgene or carbonic acid diester is 1.1 / 1 to 1/1. .1 is preferable, and 1.05 / 1 to 1 / 1.05 is more preferable.
Polycarbonate (B1-5) is produced by a known method, for example, by reacting (b2-2) and phosgene at 1 torr and 120 ° C.

  The Mn of the thermoplastic resin (B1) is preferably 10,000 or more, more preferably 20,000 or more, particularly preferably 30,000 or more, most preferably 40,000 or more, and 1,000,000 or less. Is more preferably 500,000 or less, particularly preferably 400,000 or less, and most preferably 300,000 or less.

  As the thermosetting resin (B2), a crosslinked cured product (B2-1) of a thermosetting resin (B1a) in which a crosslinking reactive group is introduced into the thermoplastic resin (B1), a constituent monomer of the thermoplastic resin (B1). And a crosslinked resin (B2-2), an epoxy resin (B2-3), a phenol resin (B2-4), a furan resin (B2-5) and the like derived from a crosslinking monomer can be used.

The cross-linked cured product (B2-1) is a thermosetting resin (B1a) having a cross-linking reactive group introduced into the thermoplastic resin (B1), if necessary, in the presence of a curing agent, a catalyst and / or a solvent. It can be obtained by carrying out an epoxidation reaction, a urethanization reaction and / or a urealation reaction.
Examples of the crosslinking reactive group include an epoxy group, a hydroxyl group, a carboxyl group, an amino group, and an isocyanate group.

Examples of the method for obtaining (B1a) include a method of (co) polymerizing a vinyl monomer having a crosslinking reactive group when the vinyl monomer (b1) is polymerized.
Examples of the vinyl monomer having a crosslinking reactive group include (b1-2), (b1-7), (b1-8), (b1-11), and (b1-12).
(B1a) The amount (parts by weight) of the vinyl monomer having a crosslinking reactive group used in the synthesis is preferably 5 or more, more preferably 10 or more, particularly preferably 100 parts by weight of (B1a). Is 15 or more, preferably 100 or less, more preferably 70 or less, and particularly preferably 50 or less.

  Examples of the curing agent include diol, diamine, diisocyanate, and diepoxide.

When the curing agent is used, the amount (parts by weight) of the curing agent is preferably 0.1 or more, more preferably 1 or more, particularly preferably 5 or more, with respect to 100 parts by weight of (B1a). 50 or less is preferable, More preferably, it is 30 or less, Most preferably, it is 25 or less.
In the urethanization reaction and urea reaction, a urethanization catalyst may be used as necessary. As the urethanization catalyst, the above can be used.
When using a catalyst, the usage-amount of a catalyst is 0.1-5 weight part normally with respect to 100 weight part of resin.

The crosslinked resin (B2-2) can be obtained by replacing a part of the constituent monomer of the thermoplastic resin (B1) with a crosslinking monomer and polymerizing it.
Crosslinkable monomers include 2-8 or more polyfunctional vinyl monomers containing non-conjugated double bonds; and high functionality carboxylic acids, high functionality alcohols, high functionality having 3-8 or more functional groups Functional amines and high functional isocyanates can be used.
Examples of the polyfunctional vinyl monomer include polyhydric alcohol {2 to 50 (preferably 2 to 20) carbon atoms, 2 to 8 (preferably 2 to 4)} poly (meth) acrylates and aromatic polyfunctional vinyl compounds. For example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and polyethylene glycol di (meth) acrylate; divinyl Examples include benzene, divinyltoluene, divinylxylene, divinylketone, and trivinylbenzene.

  The use amount (parts by weight) of the polyfunctional vinyl monomer is preferably 0.1 or more, more preferably 1 or more, particularly preferably with respect to 100 parts by weight of the total weight of the vinyl monomer (b1) and the polyfunctional vinyl monomer. 5 or more, preferably 50 or less, more preferably 30 or less, particularly preferably 25 or less.

As the highly functional carboxylic acid, a polyfunctional (3 to 5 valent) carboxylic acid having 4 to 50 carbon atoms can be used. For example, trimellitic acid, 1,2,4,5-benzenetetracarboxylic acid, benzenehexacarboxylic acid Examples include acids and naphthalene tetracarboxylic acids.
The use amount (parts by weight) of the high-functional carboxylic acid is based on 100 parts by weight of the total weight of the dicarboxylic acid (b2-1), oxycarboxylic acid (b2-3), lactone (b2-4) and high-functional carboxylic acid. And preferably 0.1 or more, more preferably 1 or more, particularly preferably 5 or more, and 50 or less, more preferably 30 or less, particularly preferably 25 or less.

As the highly functional alcohol, a polyfunctional (3 to 5 valent) alcohol having 3 to 50 carbon atoms can be used, and examples thereof include glycerin, diglycerin, trimethylolpropane, pentaerythritol and dipentaerythritol.
The amount of polyfunctional alcohol used (parts by weight) is 0 with respect to 100 parts by weight of the total weight of the diol (b2-2), oxycarboxylic acid (b2-3), lactone (b2-4) and polyfunctional alcohol. Is preferably 1 or more, more preferably 1 or more, and particularly preferably 5 or more, and is preferably 50 or less, more preferably 30 or less, and particularly preferably 25 or less.

As the high-functional amine, a polyfunctional (3-5 pentavalent) amine having 3 to 50 carbon atoms can be used, for example, diethylenetriamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc. Is mentioned.
The use amount (parts by weight) of the high-functional amine is 0 with respect to 100 parts by weight of the total weight of the diamine (b3-1), aminocarboxylic acid (b3-2), lactam (b3-3) and polyfunctional amine. Is preferably 1 or more, more preferably 1 or more, and particularly preferably 5 or more, and is preferably 50 or less, more preferably 30 or less, and particularly preferably 25 or less.

  As the high-functional isocyanate, polyfunctional (3- to 6-valent) isocyanate having 3 to 60 carbon atoms can be used. For example, HDI trimer, IPDI trimer, TDI trimer, 2-isocyanatoethyl-2,6-diisocyanate Examples include caproate, HDI 3 mol adduct of glycerol, HDI 4 mol adduct of pentaerythritol, and HDI 6 mol adduct of dipentaerythritol. The amount (parts by weight) of the high-functional isocyanate is preferably 0.1 or more, more preferably 1 or more, particularly preferably 5 with respect to 100 parts by weight of the total weight of the diisocyanate (b4-1) and the polyfunctional isocyanate. Or more, preferably 50 or less, more preferably 30 or less, and particularly preferably 25 or less.

The crosslinked resin (B2-2) is produced in the same manner as a known method, for example, the production method of the thermoplastic resin (B1).
When the crosslinked resin (B2-2) is a polyester, the ratio of the number of moles of carboxyl groups to the number of moles of hydroxyl groups is 1.1 / 1 to 1 / 1.1, preferably 1.05 / 1 to 1/1 /. It is preferable to set the usage amount of dicarboxylic acid, polyfunctional carboxylic acid, diol, polyfunctional alcohol, oxycarboxylic acid and lactone so as to be 1.05).

  When the crosslinked resin (B2-2) is a polyamide, the ratio of the number of moles of carboxyl groups to the number of moles of amino groups is 1.1 / 1 to 1 / 1.1, preferably 1.05 / 1 to 1/1 /. It is preferable to set the usage-amount of dicarboxylic acid, polyfunctional carboxylic acid, diamine, polyfunctional amine, aminocarboxylic acid, and lactam so that it may become 1.05).

  When the crosslinked resin (B2-2) is polyurethane, the ratio of the number of moles of isocyanate groups to the number of moles of hydroxyl groups is 1.1 / 1 to 1 / 1.1, preferably 1.05 / 1 to 1/1 /. It is preferable to set the use amount of diisocyanate, polyfunctional isocyanate, diol and polyfunctional alcohol so as to be 1.05).

The epoxy resin (B2-3) can be obtained by reacting a polyepoxide with a polyamine and / or polycarboxylic acid (or acid anhydride).
At this time, in order to make the epoxy resin (B2-3) a thermosetting resin, one of the polyepoxides, polyamines, and polycarboxylic acids to be used has a functional group number in which any one component has three or more functions. To do. Moreover, you may use monofunctional epoxide, monofunctional amine, and monofunctional carboxylic acid in the range which does not impair a physical property.

  As the epoxide having 1 functional group, an epoxide having 2 to 50 carbon atoms can be used, and examples thereof include EO, PO, styrene oxide, phenyl glycidyl ether and allyl glycidyl ether.

As the polyepoxide having 2 functional groups, polyepoxide having 4 to 50 carbon atoms can be used, and examples thereof include ethylene glycol diglycidyl ether, 1,4 epoxycyclohexane and bisphenol A diglycidyl ether.
As the polyepoxide having 3 to 6 functional groups, polyepoxide having 6 to 50 carbon atoms can be used, and examples thereof include glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether and dipentaerythritol hexaglycidyl ether.
Polyepoxy may be used alone or a mixture may be used.

As the polyamine, diamine (b3-1), a highly functional amine, or the like can be used. Polyamines may be used alone or in a mixture.
The amount of polyamine used (parts by weight) is preferably 20 or more, more preferably 25 or more, particularly preferably 30 or more, and preferably 100 or less, more preferably 60 or less, with respect to 100 parts by weight of epoxide. Especially preferably, it is 50 or less.

As polycarboxylic acid, dicarboxylic acid (b2-1), highly functional carboxylic acid, etc. can be used. The polycarboxylic acid may be used alone or a mixture may be used.
The use amount (parts by weight) of the polycarboxylic acid is preferably 50 or more, more preferably 50 or more, particularly preferably 60 or more, and preferably 150 or less, more preferably 100 with respect to 100 parts by weight of the epoxide. Hereinafter, it is particularly preferably 90 or less.

As the phenol resin (B2-4), a resole resin, a novolac resin, or the like can be used, and it can be obtained by reacting phenol with formaldehyde.
The resole resin can be obtained by reacting phenol and formaldehyde in the same amount or in excess of formaldehyde in the presence of a base catalyst such as sodium hydroxide, ammonia or organic amine.
The phenol / formaldehyde molar ratio is preferably 1/1 to 1/2, and more preferably 1 / 1.1-1 to 1 / 1.9.
The amount (parts by weight) of the base catalyst used is preferably 0.5 or more, more preferably 0.7 or more, particularly preferably 1 or more, with respect to 100 parts by weight of the total weight of phenol and formaldehyde. The following is preferable, more preferably 15 or less, and particularly preferably 10 or less.

The novolak resin can be obtained by reacting phenol and formaldehyde in the same amount or in excess of phenol in the presence of an acid catalyst such as oxalic acid.
The molar ratio of phenol / formaldehyde is preferably 1/1 to 1 / 0.7, more preferably 1 / 0.9 to 1 / 0.75.
The amount (parts by weight) of the acid catalyst used is preferably 0.5 or more, more preferably 0.7 or more, particularly preferably 1 or more, with respect to 100 parts by weight of the total weight of phenol and formaldehyde. The following is preferable, more preferably 15 or less, and particularly preferably 10 or less.

Furan resin (B2-5) can be obtained by reaction of furan and / or a derivative thereof with formaldehyde.
The molar ratio of furan and furan derivative / formaldehyde is preferably from 1 / 0.7 to 1/2, more preferably from 1 / 0.7 to 1 / 0.9 and from 1 / 1.1 to 1 / 1.9. It is.

Further, as other furan resins, compounds produced by replacing a part of furan and furan derivatives with melamine, urea or the like can be used.
When replacing furan with melamine or urea, the amount thereof is preferably 0.1 or more, more preferably 1 or more, particularly preferably 5 or more, and preferably 50 or less with respect to 100 parts by weight of furan. More preferably, it is 30 or less, and particularly preferably 25 or less.

  Examples of other thermosetting resins include known thermosetting resins such as xylene resin, petroleum resin, urea resin, melamine resin, alkyd resin, and silicone resin.

Of these organic polymers (B), the thermosetting resin (B2) is preferable, and more preferably, a crosslinked cured product of a thermosetting resin (B1a) in which a crosslinking reactive group is introduced into the thermoplastic resin (B1) ( B2-1); a cross-linked resin (B2-2) derived from a constituent monomer and a cross-linking monomer of the thermoplastic resin (B1); a phenol resin (B2-4) and a furan resin (B2-5). Particularly preferred are (B2-4) and (B2-5), and most preferred is (B2-4).
The organic polymer (B) may be used alone or in combination of two or more thereof.

Other additives for resin (E) can be arbitrarily added to the micelle-containing organic polymer of the present invention within a range that does not impair the characteristics depending on various uses.
Additives for resins (E) include pigments, dyes, fillers (organic and / or inorganic fillers), nucleating agents, glass fibers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, UV absorbers And antibacterial agents.
When the resin additive (E) is added, the amount of (E) used (parts by weight) is preferably 0.1 or more, more preferably 0.2 or more, relative to 100 parts by weight of (B). Especially preferably, it is 0.3 or more, most preferably 0.4 or more, and 30 or less is preferable, More preferably, it is 20 or less, Especially preferably, it is 10 or less, Most preferably, it is 5 or less.

The method for producing the micelle-containing organic polymer is not particularly limited.
(1) Constituent monomer of organic polymer (B), surfactant (A), solvent and resin additive (E) as necessary, and then micelle of surfactant is formed in the constituent monomer A method of obtaining a micelle-containing organic polymer by polymerizing and curing the constituent monomers, and then removing the solvent if necessary.
(2) Dissolve the prepolymer in a solvent, add (A) and (E) as necessary to form micelles of (A) in the prepolymer, polymerize and cure the prepolymer After removing the solvent, to obtain a micelle-containing organic polymer,
(3) The organic polymer (B) is dissolved in a solvent, (A) and, if necessary, a solvent and (E) are added, and (A) micelles are formed in (B). A method of obtaining a micelle-containing organic polymer by removing the solvent, if necessary, can be mentioned.

Here, the prepolymer means an organic polymer (B) of Mn 1000 to 100,000 having a crosslinking reactive group.
Although there is no limitation in particular as a solvent which can be used at the time of manufacture of a micelle containing organic polymer, For example, water; C1-C12 hydrocarbons, such as pentane, hexane, cyclohexane, toluene, xylene, mesitylene; Methanol, ethanol, isopropanol 1-butanol, ethylene glycol, glycerin and other C1-C10 alcohols; ethyl acetate, butyl acetate and other C2-C12 esters; acetone, methyl ethyl ketone and other C3-C12 ketones; diethyl ether, C2-C12 ethers such as butyl ethyl ether; C2-C12 amides such as N, N-dimethylformamide and N-diethylacetamide; C2-C12 sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide; Can be mentioned.

  Of these, water, hydrocarbons, alcohols and esters, and ketones are preferable, and water, toluene, xylene, mesitylene, methanol, ethanol, isopropanol, 1-butanol, ethyl acetate, and acetone are more preferable.

  When a solvent is used during the production of the micelle-containing organic polymer, the amount of the solvent used (parts by weight) is not particularly limited, but is preferably 1 or more, more preferably 5 per 1 part by weight of the surfactant (A). Above, particularly preferably 10 or more, most preferably 15 or more, and preferably 100 or less, more preferably 50 or less, particularly preferably 40 or less, most preferably 30 or less.

  The micelle-containing organic polymer of the present invention can be processed into various shapes. For example, it can be made into a shape such as a block shape, a fiber shape, a sheet shape, or a film shape by a method such as injection molding or extrusion molding.

  In the case of molding, the molding temperature may be a temperature at which the organic polymer can be molded, but is preferably 200 ° C. or lower, more preferably 150 ° C. or lower.

  The micelle-containing organic polymer of the present invention can be used as a raw material for the organic polymer porous material and porous carbon material described below, and also as an ink receiving layer (especially effective when a cationic surfactant is used). Can be used.

Next, the organic polymer porous body of the second invention will be described.
In the organic polymer porous material of the present invention, the total pore volume of the pores corresponding to the diameter within the range of ± 40% of the pore diameter showing the maximum peak in the pore diameter distribution curve is based on the total pore volume. It is 50 volume% or more, preferably 60 volume% or more, more preferably 70 volume% or more, particularly preferably 75 volume% or more, and most preferably 80 volume% or more.
Here, the pore diameter distribution curve is a value obtained by differentiating pore volume (V) by pore diameter (D) (dV / dD) on the vertical axis and pore diameter (D) on the horizontal axis. Means a curve.
The pore diameter showing the maximum peak means the pore diameter at which the dV / dD value of the pore diameter distribution curve is maximized.
The pore diameter distribution curve is calculated from an adsorption isotherm obtained by measuring the adsorption amount of argon or nitrogen gas. It can also be obtained from the pore distribution curve obtained from the mercury intrusion method.
From the adsorption isotherm, a pore diameter and a pore volume of 0.3 to 50 nm are determined, and from a mercury intrusion method, a pore diameter and a pore volume of 10 to 1000 nm are determined. Usually, 50 nm or less is measured by an adsorption isotherm, and 50 nm or more is measured by a mercury intrusion method. By using both methods, it is possible to measure all the preferable pore diameter ranges.

The method of calculating from the adsorption isotherm is exemplified below.
The measurement sample is cooled to liquid nitrogen temperature (−196 ° C.), nitrogen gas is introduced, and the adsorption amount is obtained by a constant volume method or a weight method. An adsorption isotherm is created by gradually increasing the pressure of the introduced nitrogen gas and plotting the amount of nitrogen gas adsorbed against each equilibrium pressure.
From this adsorption isotherm, calculation of Cranston-Inklay method (for example, Adv. Catalysis, Vol. 9, 143, 1957) or BJH method (J. Catalysis, Vol. 4, 649, 1965), etc. The pore diameter distribution curve is obtained from the equation.

The mercury intrusion method is a measurement method based on the principle that mercury does not cause capillary action unless external pressure is applied. When a porous sample is immersed in mercury and external pressure is applied, mercury penetrates into the sample. At this time, the applied external pressure and the diameter of the smallest pore through which mercury can permeate have the relationship of the following formula (3).
D = −4γcos θ / P (3)
(D represents the pore diameter (cm), γ represents the surface tension of mercury (480 dyne / cm), θ represents the contact angle (140 °), and P represents the measurement pressure (kg / cm ² ).)
Further, the total volume of pores having pores having a pore diameter (D) or more corresponding to the pressure is determined from the amount of mercury that has penetrated.
The obtained results are plotted with the pore volume on the vertical axis and the pore diameter on the horizontal axis, and the curve obtained by differentiating the obtained curve is the pore distribution curve.
For details on the mercury intrusion method, see J.H. Amer. Inst. Chem. Engrs. 2, 307, published in 1956.

The organic polymer porous body of the present invention has a structure in which a large number of pores are formed in an organic polymer. Examples of the pore shape of the organic polymer porous material of the present invention include a cage shape, a one-dimensional tunnel shape, and a three-dimensional tunnel shape.
The arrangement of the pores of the organic polymer porous material of the present invention may or may not have regularity, but preferably has regularity.

The organic polymer porous material of the present invention has at least one peak in the X-ray diffraction pattern, and at least one set of the diffraction angle (2θ) and the lattice spacing (d) of the peak is represented by the following relational expression (1 ) And d is preferably one or more values within a range of 0.8 nm to 150 nm. That is, there are one or more pairs satisfying 2θ and d, but one pair with d of 0.8 to 150 nm is sufficient.
2θ = 2sin ⁻¹ (λ / 2d) (1)
(Λ represents the wavelength (nm) of Kα1 of characteristic X-rays.)
The lattice spacing (d) (nm) is preferably 0.8 or more, more preferably 1 or more, particularly preferably 2 or more, and is preferably 150 or less, more preferably 100 or less, particularly preferably 50 or less. is there.

The pore arrangement of the organic polymer porous material of the present invention that satisfies the above conditions may or may not have regularity, but preferably has regularity.
The fact that the arrangement of the pores has regularity means that the arrangement structure of the pores has symmetry indicated by a space group.
As such a space group, the same thing as a micelle containing organic polymer can be illustrated.

Further, the porous organic polymer of the present invention preferably has a pore diameter (nm) showing a maximum peak in the pore diameter distribution curve of 0.3 or more, more preferably 0.4 or more, particularly preferably 0.00. It is 5 or more, most preferably 1 or more, and preferably 100 or less, more preferably 50 or less, particularly preferably 40 or less, and most preferably 30 or less.
When the pore diameter (nm) showing this maximum peak is less than this range, for example, when the organic polymer porous material of the present invention is used for an ink jet receiving layer or a catalyst carrier, ink, ions, etc. are contained in the pores. Or it may be difficult for molecules to enter. On the other hand, when the amount exceeds this range, the surface area may be decreased, the adsorption ability may be decreased, or the electrical characteristics may be decreased when used in the above-described application.

Although the manufacturing method of an organic polymer porous body is not specifically limited, It can obtain by removing surfactant (A) from a micelle containing organic polymer.
Examples of the method for removing the surfactant (A) from the micelle-containing organic polymer include a method by baking and a method of treating with an extraction solvent.

  In the method by baking, the organic polymer porous body can be obtained by heating the micelle-containing organic polymer to a constant temperature and decomposing and removing the surfactant.

The atmosphere at the time of thermal decomposition may be an atmosphere of an inert gas such as neon, argon, nitrogen or carbon dioxide, air or a mixture thereof, and among these, air is preferable. In addition, it is preferable to use a thermal decomposition apparatus equipped with inlets and outlets for inflow gas and outflow gas so that decomposition products can be removed. An example of such an apparatus is an electric furnace that can vent gas.
When removing by this method, it is necessary to pay attention to the softening temperature of the resin. For example, if the organic polymer is a thermoplastic resin, the formed pores may disappear due to softening when heated to a softening temperature or higher.

In the method of treating with an extraction solvent, the organic polymer porous material can be obtained by extracting and removing the surfactant (A) in the micelle-containing organic polymer with an extraction solvent.
As the extraction solvent, it is preferable to use a solvent that has high solubility in a surfactant and has as low an affinity as possible for the resin. If the affinity with the resin is high, the resin dissolves in the extraction solvent, and the formed pores may disappear.
Examples of such an extraction solvent include hydrophilic solvents such as water, ethanol, methanol, and acetone, and mixed solutions thereof (50% by volume ethanol aqueous solution, 80% by volume methanol aqueous solution, 40% by volume acetone aqueous solution, etc.); pentane, Examples include lipophilic solvents such as hexane, heptane, toluene, and xylene.

  The use amount (parts by weight) of the extraction solvent is preferably 10 or more, more preferably 15 or more, particularly preferably 20 or more, and most preferably 30 or more, with respect to 1 part by weight of the micelle-containing organic polymer. Or less, more preferably 150 or less, particularly preferably 120 or less, and most preferably 100 or less.

When a cationic surfactant is used, extraction may be facilitated by adding a strong acid (for example, hydrochloric acid) to the extraction solvent, because the cation of the cationic surfactant is ion-exchanged with protons. When an anionic surfactant is used, extraction may be facilitated by adding a strong base (for example, potassium hydroxide) to the extraction solvent.
The addition amount of the acid or base is preferably 1 mol or more, more preferably 2 mol or more, particularly preferably 5 mol or more, and preferably 100 mol or less, more preferably 1 mol with respect to 1 mol of the surfactant. 80 mol or less, particularly preferably 50 mol or less.

When the micelle-containing organic polymer is treated with a solvent, the extraction solvent to which an acid or a base is added as necessary is kept at the extraction temperature, the micelle-containing organic polymer is added thereto, and if necessary, (1) ultrasonic waves are used. Extraction by irradiation, (2) extraction by repeated pressurization-normal pressure, (3) extraction by repeated decompression-normal pressure, (4) extraction by repeated pressurization-depressurization, etc.
After the extraction is completed, the organic solvent porous body is obtained by washing 1 to 5 times with a small amount of extraction solvent and drying the attached extraction solvent (reduced pressure). In addition, in order to omit a drying process, you may substitute with the other low boiling-point solvent which can be used when using an organic polymer porous body.
When drying under reduced pressure, the degree of reduced pressure is preferably 1 to 100 torr, more preferably 1 to 75 torr, and particularly preferably 1 to 50 torr.
The drying time (hour) is preferably 1 to 24, more preferably 1 to 18, and particularly preferably 1 to 12.
The organic polymer porous material of the present invention can be used as a raw material for the porous carbon material described below, and also includes an ink jet receiving layer, an electric double layer capacitor electrode material carrier, a catalyst carrier, a medical separation membrane, clean water or waste water. It can also be used as a processing adsorbent, a GPC column filler, and the like.

Next, the porous carbon material of the third invention will be described.
In the porous carbon material of the present invention, the total pore volume (volume%) of the pores with respect to the diameter within the range of ± 40% of the pore diameter showing the maximum peak in the pore diameter distribution curve is based on the total pore volume. Or more, preferably 60 or more, more preferably 70 or more, particularly preferably 75 or more, and most preferably 80 or more.

The porous carbon material of the present invention has a structure in which a large number of pores are formed in carbon. In addition, examples of the pore shape of the porous carbon material of the present invention include a cage shape, a one-dimensional tunnel shape, and a three-dimensional tunnel shape.
The arrangement of the pores of the porous carbon material of the present invention may or may not have regularity, but preferably has regularity.

The porous carbon material of the present invention also has at least one peak in the X-ray diffraction pattern as well as the micelle organic-containing polymer and organic polymer porous body of the present invention, and the diffraction angle (2θ) of the peak and the lattice plane It is preferable that at least one set of the intervals (d) satisfies the following relational expression (1), and d is one or more values within the range of 0.8 nm to 150 nm.
2θ = 2sin ⁻¹ (λ / 2d) (1)
(Λ represents the wavelength (nm) of Kα1 of characteristic X-rays.)
The lattice spacing (d) (nm) is preferably 0.8 or more, more preferably 1 or more, particularly preferably 2 or more, and is preferably 150 or less, more preferably 100 or less, particularly preferably 50 or less. is there.

The arrangement of pores of the porous carbon material of the present invention that satisfies the above conditions may or may not have regularity, but preferably has regularity. The fact that the arrangement of the pores has regularity means that the arrangement structure of the pores has the symmetry indicated by the space group, and examples of such a space group are the same as those of the micelle-containing organic polymer. it can.

Furthermore, the porous carbon material of the present invention also preferably has a pore diameter (nm) showing a maximum peak in the pore diameter distribution curve of 0.3 nm or more, more preferably 0.4 or more, particularly preferably 0.5. In addition, it is preferably 100 or less, more preferably 50 or less, and particularly preferably 30 or less.
When the pore diameter (nm) showing the maximum peak is less than this range, for example, when the porous carbon material of the present invention is used for an electrode material for an electric double layer capacitor or a catalyst carrier, ions are present in the pores. Or it may be difficult for molecules to enter. On the other hand, when the amount exceeds this range, the surface area may be decreased, the adsorption ability may be decreased, or the electrical characteristics may be decreased when used in the above-described application.

Although the manufacturing method of a porous carbon material is not specifically limited, For example, it can obtain by carrying out baking carbonization of the micelle containing organic polymer directly, or baking an organic polymer porous body.
The firing carbonization atmosphere is preferably performed in an inert gas atmosphere such as nitrogen, helium, neon, argon, carbon dioxide, or a mixed gas thereof.

  Moreover, it is preferable to perform aging (preheating) before baking carbonization.

The aging atmosphere may be an atmosphere of an inert gas such as neon, argon, nitrogen or carbon dioxide, air, or a mixture thereof. Of these, air is preferable.
When the organic polymer is a thermoplastic resin, the disappearance or deformation of pores at the calcination carbonization temperature above the softening point can be prevented by partially oxidizing the surface of the organic polymer by aging. In this case, it is preferable to partially oxidize the surface of the organic polymer at a temperature rising rate of 30 ° C./min or higher at a temperature of softening point + 100 ° C. or higher in an oxygen-containing atmosphere.
In addition, it is preferable to use a thermal decomposition apparatus equipped with inlets and outlets for the inflowing gas and the outflowing gas so that decomposition products can be removed during calcination carbonization and aging. As such an apparatus, a carbonization furnace, an electric furnace or the like can be used. For example, a rotary kiln furnace, a carbonization furnace such as a multistage stirred moving bed furnace and a multistage fluidized bed furnace, other special carbonization furnaces, and an electric furnace capable of venting gas. Etc.

  Since the organic polymer porous body and the porous carbon material derived from the micelle-containing organic polymer can maintain the shape of the micelle-containing organic polymer, by forming the micelle-containing organic polymer into a desired shape in advance, A porous carbon material can be made into a desired shape. For example, a corresponding organic polymer porous body or porous carbon material can be obtained from a powder, film, sheet-like or fibrous micelle-containing organic polymer.

  Thus, the obtained organic polymer porous body and porous carbon material can form various shapes, have a uniform pore diameter, and have a regular pore shape and / or pore arrangement. Furthermore, the porous carbon material obtained by firing the micelle-containing organic polymer and the organic polymer porous body does not need to use dangerous hydrofluoric acid or the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples. In the following, “part” means “part by weight” and “%” means “% by weight”.
<Example 1>
A stainless steel autoclave was charged with 10 parts of phenol, 16 parts of 36% formalin and 1.5 parts of 10% sodium hydroxide and stirred until uniform. After the inside of the autoclave was replaced with nitrogen gas, the mixture was stirred at 75 ° C. for 3 hours under normal pressure to obtain a prepolymer. Next, 7 parts of octyltrimethylammonium chloride, 1.8 parts of 85% lactic acid and 1.5 parts of glycerin were added and stirred until uniform. Thereafter, water and unreacted monomers were removed under reduced pressure. The obtained viscous resin was put into a mold and formed into a sheet (4 cm × 5 cm, thickness 1 mm), and then cured at 70 ° C. for 120 hours to obtain a sheet-like micelle-containing organic polymer (G1).

This micelle-containing organic polymer (G1) was subjected to X-ray diffraction measurement under the following conditions to determine the diffraction angle (°) of the detected maximum peak. The results are shown in Table 2.
X-ray diffraction conditions: using a RINT2200 powder X-ray diffractometer (manufactured by Rigaku Denki Co., Ltd.), Cu-Kα ₁ (λ = 0.154056 nm), 40.0 KV tube voltage, 30 mA tube current, divergence slit 1/2 °, Measurement was carried out under the condition of scattering slit 1/2 light reception 0.15 mm.
Note that (G1) was dried as a measurement sample at 25 ° C. and 1 torr for 2 hours as a pretreatment.

<Example 2>
A micelle-containing organic polymer (G2) was obtained in the same manner as in Example 1, except that 7 parts of cetyltrimethylammonium chloride was used instead of octyltrimethylammonium chloride.
For this micelle-containing organic polymer (G2), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 2.

<Example 3>
Example 1 is different from Example 1 except that 7 parts of EO ₂₀ PO ₇₀ EO ₂₀ (ethylene oxide / propylene oxide block copolymer; Pluronic P123 (manufactured by BASF)) is used in place of octyltrimethylammonium chloride. Similarly, a sheet-like micelle-containing organic polymer (G3) was obtained.
For this micelle-containing organic polymer (G3), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 2.

<Example 4>
190 parts of ethanol and 9 parts of 35% concentrated hydrochloric acid were added to a glass container and stirred until uniform. Next, 3 parts of the micelle-containing organic polymer (G1) obtained in Example 1 was charged, and the temperature was raised to 40 ° C. Extraction was performed at 40 ° C. for 7 hours while irradiating ultrasonic waves (frequency: 15 kHz), then the sheet was taken out, washed 3 times with 10 parts of ethanol, and dried at 25 ° C. and 1 torr for 2 hours to form a sheet-like organic polymer A porous material (GE4) was obtained.

For this organic polymer porous material (GE4), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 3.
In addition, the pore distribution curve of the organic polymer porous material was measured by a nitrogen adsorption method (measured from 0.3 nm to 50 nm) and a mercury intrusion method (measured from 50 nm to 500 nm), and the pore diameter showing the maximum peak V / Vmax (the ratio of the total pore volume of the pores to the diameter within the range of ± 40% of the pore diameter showing the maximum peak in the total pore volume). The results are shown in Table 3.
Nitrogen adsorption method apparatus: AUTOSORB-1 GAS / SORPTION SYSTEM (manufactured by Quantachrome Corporation).
Mercury intrusion apparatus: MERCURY PRESURER POROSOMETER MOD220 (manufactured by Carlo Erba).
In addition, when measuring a pore distribution curve, it pre-processed like the X-ray-diffraction measurement of Example 1, and was set as the measurement sample.
Moreover, V / Vmax is calculated | required by +/- 40% of the total pore volume / total pore volume x100 of the pore diameter which shows the maximum peak. The total pore volume was the sum of the volumes of pores having a pore diameter of 0.3 nm to 500 nm.

<Example 5>
In Example 4, a hollow columnar organic polymer was used in the same manner as in Example 4 except that 3 parts of the micelle-containing organic polymer (G2) obtained in Example 2 was used instead of the micelle-containing organic polymer (G1). A porous material (GE5) was obtained.
For this organic polymer porous material (GE5), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 3.
Moreover, it carried out similarly to Example 4, and calculated | required the pore diameter which shows a maximum peak, and V / Vmax about the organic polymer porous body (GE5). The results are shown in Table 3.

<Example 6>
Example 4 is the same as Example 4 except that 35% concentrated hydrochloric acid is not used and 3 parts of the micelle-containing organic polymer (G3) obtained in Example 3 is used instead of the micelle-containing organic polymer (G1). Thus, a sheet-like organic polymer porous body (GE6) was obtained.
For this organic polymer porous material (GE6), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 3.
Moreover, it carried out similarly to Example 4, and calculated | required the pore diameter which shows a maximum peak, and V / Vmax about the organic polymer porous body (GE6). The results are shown in Table 3.

<Example 7>
The micelle-containing organic polymer (G1) obtained in Example 1 was placed in an electric furnace capable of nitrogen flow, air was allowed to flow in advance at a rate of 10 L / min, and the temperature was raised to 250 ° C. over 30 minutes. Time aging was performed. Thereafter, nitrogen was flowed at a rate of 10 L / min and held at 250 ° C. for 30 minutes. The temperature was raised to 650 ° C. over 1 hour, and calcination was performed at this temperature for 3 hours. Furthermore, it heated up to 800 degreeC over 1 hour, baked for 5 hours, and obtained the sheet-like porous carbon material (MCG7). The shape was a sheet.
For the sheet-like porous carbon material (MCG7), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 4.
Further, in the same manner as in Example 4, the pore diameter showing the maximum peak and V / Vmax were determined for the porous carbon material (MCG7). The results are shown in Table 4.

<Example 8>
A sheet-like porous carbon material (MCG8) was prepared in the same manner as in Example 7 except that the micelle-containing organic polymer (G2) obtained in Example 2 was used instead of the micelle-containing organic polymer (G1) in Example 7. Obtained.
For the porous carbon material (MCG8), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 4.
Further, in the same manner as in Example 4, the pore diameter showing the maximum peak and V / Vmax were determined for the porous carbon material (MCG8). The results are shown in Table 4.

<Example 9>
A porous carbon material (MCG9) was obtained in the same manner as in Example 7 except that the organic polymer porous material (GE6) obtained in Example 6 was used instead of the micelle-containing organic polymer (G1) in Example 7. The shape was a sheet.
For this porous carbon material (MCG9), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 4.
Further, in the same manner as in Example 4, with respect to the porous carbon material (MCG9), the pore diameter showing the maximum peak and V / Vmax were obtained. The results are shown in Table 4.

<Example 10>
Glass Kolben 1 was charged with 10 parts of phenol, 16 parts of 36% formalin and 1.5 parts of 10% sodium hydroxide, and stirred until uniform. After replacing the inside of Kolben with nitrogen gas, the mixture was stirred at 75 ° C. for 3 hours under a normal pressure hermetically sealed to obtain a prepolymer. Next, 7 parts of stearyltrimethylammonium chloride, 120 parts of ion-exchanged water and 2 parts of 35% hydrochloric acid were added to Kolben 2 and stirred at room temperature until uniform. The contents of Kolben 1 were added thereto and stirred at room temperature until uniform. Then, it heated up at 95 degreeC and stirred for 1.5 hours. The precipitated solid was collected by filtration and washed twice with 50 parts of ion exchange water to obtain a powdered micelle-containing organic polymer (G10).

  For the micelle-containing organic polymer (G10), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 2.

<Example 11>
In Example 1, micelle-containing organic polymer ( G11) was obtained.
For the micelle-containing organic polymer (G11), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 2.

<Example 12>
In Example 1, a viscous resin was obtained in the same manner as in Example 1 except that glass Kolben was used in place of the stainless steel autoclave and 7 parts of stearyltrimethylammonium chloride was used in place of octyltrimethylammonium chloride. It was. Add 0.85 parts of hexamethylenetetramine to 13.1 parts of viscous resin and stir until uniform, then put the resin into a mold and mold it into a sheet (4 cm x 5 cm, thickness 1 mm), then at 70 ° C Curing was performed for 120 hours to obtain a sheet-like micelle-containing organic polymer (G12).
For the micelle-containing organic polymer (G12), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 2.

<Example 13>
In Example 4, a powdery organic polymer was used in the same manner as in Example 4 except that 3 parts of the micelle-containing organic polymer (G10) obtained in Example 10 was used instead of the micelle-containing organic polymer (G1). A porous material (GE13) was obtained.
For the organic polymer porous material (GE13), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 3.
Moreover, it carried out similarly to Example 4, and calculated | required the pore diameter which shows a maximum peak, and V / Vmax about the organic polymer porous body (GE13). The results are shown in Table 3.

<Example 14>
In Example 4, an organic polymer porous material (GE14) was prepared in the same manner as in Example 4 except that 3 parts of the micelle-containing organic polymer (G11) obtained in Example 11 was used instead of the micelle-containing organic polymer (G1). )
For the organic polymer porous material (GE14), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 3.
Moreover, it carried out similarly to Example 4, and calculated | required the pore diameter which shows a maximum peak, and V / Vmax about the organic polymer porous body (GE14). The results are shown in Table 3.

<Example 15>
In Example 4, an organic polymer porous material (GE15) was prepared in the same manner as in Example 4 except that 3 parts of the micelle-containing organic polymer (G12) obtained in Example 12 was used instead of the micelle-containing organic polymer (G1). )
For the organic polymer porous material (GE15), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 3.
Moreover, it carried out similarly to Example 4, and calculated | required the pore diameter which shows a maximum peak, and V / Vmax about the organic polymer porous body (GE15). The results are shown in Table 3.

<Example 16>
In the same manner as in Example 7 except that the micelle-containing organic polymer (G10) obtained in Example 10 was used instead of the micelle-containing organic polymer (G1) in Example 7, a powdery porous carbon material (MCG16) was obtained. Obtained.
For the porous carbon material (MCG16), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 4.
Further, in the same manner as in Example 4, for the porous carbon material (MCG16), the pore diameter showing the maximum peak and V / Vmax were obtained. The results are shown in Table 4.

<Example 17>
A sheet-like porous carbon material (MCG17) is obtained in the same manner as in Example 7 except that the micelle-containing organic polymer (G11) obtained in Example 11 is used instead of the micelle-containing organic polymer (G1) in Example 7. It was.
For the porous carbon material (MCG17), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 4.
Further, in the same manner as in Example 4, for the porous carbon material (MCG17), the pore diameter showing the maximum peak and V / Vmax were obtained. The results are shown in Table 4.

<Example 18>
A porous carbon material (MCG18) was obtained in the same manner as in Example 7 except that the micelle-containing organic polymer (G12) obtained in Example 12 was used instead of the micelle-containing organic polymer (G1) in Example 7. The shape was a sheet.
For the porous carbon material (MCG18), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 4.
Further, in the same manner as in Example 4, for the porous carbon material (MCG18), the pore diameter showing the maximum peak and V / Vmax were obtained. The results are shown in Table 4.

<Comparative Example 1>
In Example 1, a sheet-like phenol resin (G19) was obtained in the same manner as in Example 1 except that octyltrimethylammonium chloride was not used.
For the sheet-like phenol resin (G19), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 2.

<Comparative Example 2>
After firing at 650 ° C. for 3 hours in the same manner as in Example 7 except that the sheet-like phenol resin (G19) obtained in Comparative Example 1 was used instead of the micelle-containing organic polymer (G1) in Example 7, The temperature was raised to 800 ° C. over 1 hour and firing was performed for 5 hours. Finally, steam activation was performed to form pores to obtain a carbon material (MCG19). As for the shape, a part of the sheet collapsed.
For the carbon material (MCG19), the diffraction angle (°) of the maximum peak was determined in the same manner as in Example 1. The results are shown in Table 4.
Further, in the same manner as in Example 4, for the carbon material (MCG19), the pore diameter showing the maximum peak and V / Vmax were obtained. The results are shown in Table 4.

  The micelle-containing organic polymers of Examples 1 to 3 and 10 to 12 have a diffraction angle, and the polymer of Comparative Example 1 does not diffract. That is, it can be seen that the micelle-containing organic polymer of the present invention has regularity in at least two of the micelle diameter, the micelle shape, and the micelle arrangement. Furthermore, since the pore diameter of the organic polymer porous material described below is uniform, it can be seen that it has a uniform micelle diameter. That is, it can be seen that the micelle-containing organic polymer of the present invention contains micelles having a uniform diameter in the polymer matrix, and the micelle shape is uniform or the micelles are regularly arranged.

  It can be seen that the organic polymer porous bodies of Examples 4 to 6 and 13 to 15 have a uniform pore diameter because the value of V / Vmax is large. Further, since the X-ray diffraction angle exists and d is obtained, it can be seen that the pore shape is uniform or the pores are regularly arranged.

In Examples 7-9 and 16-18, the shape was maintained even after the calcination carbonization step.
Moreover, it turns out that the porous carbon material of Examples 7-9 and 16-18 has a uniform pore diameter from the value of V / Vmax being large. Further, since an X-ray diffraction angle exists and d is obtained, it can be seen that the shape of the pores is uniform or the pores are regularly arranged.
On the other hand, in the carbon material of Comparative Example 2, although the pore diameter is relatively uniform, the uniformity of the pore diameter is inferior to that of the example because V / Vmax is smaller than that of the example. In addition, since X-ray diffraction does not occur, it can be seen that the shape of the pores is not uniform and the arrangement of the pores is not regular.

The organic polymer porous body and porous carbon material of the present invention have excellent performance such as electrical insulation, heat insulation, separation ability and adsorption ability.
Accordingly, the porous carbon material includes various battery electrodes, electric double layer capacitor electrodes, capacitor electrodes, and other electrode materials; canister adsorbents, adsorbents for water or wastewater treatment, adsorbents for water purifiers or deodorizers, Adsorption materials such as adsorbents for food refining and adsorbents for gases; semiconductor insulating materials, electronic component materials such as solid electrolytes, medical separation membranes, and catalyst carriers.

It is a perspective sectional view showing typically a mode that a micelle or a pore, and an organic polymer, or a pore and carbon form space group "2-d hexagonal p6mm". FIG. 5 is a perspective transmission diagram schematically illustrating a state in which micelles or pores and an organic polymer, or pores and carbon form a space group “cubic Ia3d”. FIG. 5 is a perspective cross-sectional view schematically showing a state in which micelles or pores and an organic polymer, or pores and carbon form a space group “cubic Pm3n”. It is a perspective sectional view showing typically a mode that a micelle or a pore, and an organic polymer, or a pore and carbon form space group "3-d hexagonal P6 < ₃ > / mmc".

Claims (7)

The total pore volume of the pores corresponding to the diameter within the range of ± 40% of the pore diameter Dmax showing the maximum peak in the pore diameter distribution curve is 50% by volume or more based on the total pore volume. An organic polymer porous material. The X-ray diffraction pattern has at least one peak, and at least one set of the diffraction angle (2θ) and the lattice spacing (d) of the peak satisfies the following relational expression (1), and d is 0. The organic polymer porous body according to claim 1, wherein the porous organic polymer has one or more values within a range of 8 nm or more and 150 nm or less.
2θ = 2sin ⁻¹ (λ / 2d) (1)
(Λ represents the wavelength (nm) of Kα1 of characteristic X-rays.) The organic polymer porous material according to claim 1 or 2, wherein a pore diameter Dmax showing a maximum peak in the pore diameter distribution curve is 0.3 nm or more and 100 nm or less. The organic polymer porous body according to any one of claims 1 to 3, wherein the organic polymer is a thermosetting resin. Crosslinked cured body (B2-1) of thermosetting resin (B1a) in which organic polymer (B) has introduced a crosslinking reactive group into thermoplastic resin (B1); Constituent monomer and crosslinking monomer of thermoplastic resin (B1) 2 or more thermosetting resins (B2) selected from the group consisting of a phenol resin (B2-4) and a furan resin (B2-5). The organic polymer porous body in any one of -4. After forming micelles of the surfactant (A) in the monomer and / or prepolymer, the monomer and / or prepolymer is polymerized and cured to form a micelle-containing organic polymer, and the surfactant (A) It removes, The manufacturing method of the organic polymer porous body in any one of Claims 1-5 characterized by the above-mentioned. The method for producing a porous organic polymer according to claim 6, wherein the removal of the surfactant (A) is performed by calcination and / or solvent extraction.

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