JP2015214708A - Phase separation structure and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phase separation structure having a resin phase and a particulate phase in a phase separation state.SOLUTION: A resin composition including particles is prepared through mixing: a resin; and organic inorganic composite particles having an organic group on a surface of an inorganic particle and having a shape preventing inorganic particles to have contact with each other by steric hindrance of the organic group. A phase separation sheet 1 including a resin phase 2 and a particulate phase 3 neighboring the resin phase 2 and formed of the organic inorganic composite particles is formed from the resin composition including particles.

Description

  The present invention relates to a phase separation structure and a method for producing the same.

  In recent years, a phase separation structure composed of a particle phase formed from a resin phase and inorganic particles is expected to be applied in various industrial applications.

  For example, a phase separation sheet has been proposed in which a fine particle phase is formed on the surface of a sheet by applying a dispersion liquid in which inorganic fine particles are dispersed in an organic solvent to the surface of a resin sheet and volatilizing the solvent. (For example, refer to Patent Document 1).

JP 2008-6817 A

  However, in the conventional phase separation structure, when the inorganic particles are partially dispersed or compatible with the resin, the phase separation between the resin phase and the particle phase becomes insufficient.

  An object of the present invention is to provide a phase separated structure in which a resin phase and a particle phase are phase separated.

  To achieve the above object, the phase separation structure of the present invention comprises a resin phase and a particle phase containing organic-inorganic composite particles adjacent to the resin phase and having an organic group on the surface of the inorganic particles, The organic-inorganic composite particles in the particle phase have at least a shape in which the inorganic particles do not contact each other due to steric hindrance of the organic group.

  In the phase separation structure of the present invention, it is preferable that the particle phase is formed in a layer shape.

  In the phase separation structure of the present invention, it is preferable that the particle phase is unevenly distributed on one side or both sides of the phase separation structure.

  In the phase-separated structure of the present invention, it is preferable that the particle phase is formed in a layer form by arranging the organic-inorganic composite particles in three dimensions.

  In the phase separation structure of the present invention, it is preferable that the organic-inorganic composite particles have an average particle size of 400 nm or less.

  The method for producing a phase separation structure of the present invention includes a step of preparing a particle-containing resin composition by blending a resin and organic-inorganic composite particles having an organic group on the surface of the inorganic particles, and It is characterized by comprising a step of molding a phase-separated structure comprising a resin phase and a particle phase adjacent to the resin phase and formed from the organic-inorganic composite particles from a particle-containing resin composition.

  In the method for producing a phase separation structure, it is preferable that the organic-inorganic composite particles are produced in a high-temperature solvent.

  In the method for producing a phase separation structure of the present invention, it is preferable that the organic-inorganic composite particles are produced in high-temperature and high-pressure water.

  In the method for producing a phase-separated structure according to the present invention, it is preferable that the organic-inorganic composite particles are manufactured so as to have at least a shape in which the inorganic particles do not contact each other due to steric hindrance of the organic group. is there.

  In the phase separation structure of the present invention, the resin layer and the particle phase are phase-separated depending on the affinity between the resin and the organic group of the organic-inorganic composite particles. That is, regardless of the kind of inorganic particles, the resin layer and the particle phase are phase-separated by the selection of the organic group.

  Therefore, such a phase separation structure can be applied to various industrial uses.

  In addition, according to the method for producing a phase separation structure of the present invention, a simple method of molding from a particle-containing resin composition is used to produce a phase separation structure composed of a resin phase and a particle phase, which are phase-separated. can do.

FIG. 1 is a phase separation sheet which is an embodiment of the phase separation structure of the present invention, in which (a) shows an enlarged cross-sectional view and (b) shows an enlarged plan view. FIG. 2 is a production process diagram for producing the phase separation sheet shown in FIG. 1, wherein (a) is a step of applying a particle-containing resin composition onto a release sheet to form a coating film. (B) shows the process of drying a coating film and shape | molding a phase-separation sheet. FIG. 3 is an image processing diagram of a TEM photograph of the organic-inorganic composite particles of Preparation Example 1. FIG. 4 shows an image processing diagram (250,000 times) of a TEM photograph of a cross section of the phase separation sheet of Example 1. FIG. 5 is an image processing diagram (250,000 times) of a TEM photograph of a cross section of the phase separation sheet of Example 2. FIG. 6 shows an image processing diagram (250,000 times) of a TEM photograph of a cross section of the phase separation sheet of Example 3. FIG. 7 is an image processing diagram of a TEM photograph of a cross section of the phase separation sheet of Example 4, wherein (a) is an image processing diagram of 50,000 times, and (b) an image processing diagram of 250,000 times. Show. FIG. 8 shows an image processing diagram of a TEM photograph (250,000 times) of a cross section of the phase separation sheet of Example 5. FIG. 9 is an image processing diagram of a TEM photograph (1,000,000 times) of a cross section of the phase separation sheet of Example 9. FIG. 10 shows an image processing diagram of a TEM photograph (1,000,000 times) of a cross section of the phase separation sheet of Example 12. FIG. 11 shows an image processing diagram of a TEM photograph (250,000 times) of a cross section of the phase separation sheet of Example 13. FIG. 12 shows an image processing diagram of a TEM photograph (250,000 times) of a cross section of the phase separation sheet of Example 14.

  FIG. 1 is a phase separation sheet as an embodiment of the phase separation structure of the present invention, and FIG. 2 is a production process diagram for producing the phase separation sheet shown in FIG.

  In FIG. 1A, this phase separation sheet 1 is composed of a resin phase 2 and a particle phase 3. Specifically, the phase separation sheet 1 is formed in a flat plate shape, and includes a resin phase 2 formed in a layer shape and a particle phase 3 formed in a layer shape on the resin phase 2.

  The resin phase 2 is formed in a sheet shape. In addition, the resin phase 2 is formed in a layer shape by the particle phase 3 being unevenly distributed (described later) in the phase separation sheet 1.

  The particle phase 3 is substantially formed only from organic-inorganic composite particles.

  The thickness of the resin phase 2 is not particularly limited, and is, for example, 1 nm to 1000 μm, preferably 5 nm to 100 μm, and more preferably 10 nm to 10 μm.

  The particle phase 3 is adjacent to the upper side (one side) of the resin phase 2. In other words, the particle phase 3 is unevenly distributed on the upper surface of the resin phase 2 on the upper side of the phase separation sheet 1.

  In addition, the particle phase 3 is formed in a layered manner on the upper surface of the resin phase 2 by arranging the organic-inorganic composite particles in a substantially three-dimensional alignment. That is, in the particle phase 3, the organic-inorganic composite particles are aligned and arranged in the thickness direction and the surface direction (direction orthogonal to the thickness direction) of the phase separation sheet 1.

  Specifically, in the particle phase 3, there are at least organic-inorganic composite particles arranged in a three-dimensional substantially regular manner. Specifically, such organic-inorganic composite particles are stacked in a close-packed manner. Yes. The organic-inorganic composite particles described above are stacked in a close-packed structure such as a hexagonal close-packed structure or a cubic close-packed structure.

  The thickness of the particle phase 3 is, for example, 1 nm to 1000 μm, preferably 10 nm to 100 μm.

  It does not specifically limit as resin which forms the resin phase 2, For example, a thermosetting resin, a thermoplastic resin, etc. are mentioned.

  Examples of the thermosetting resin include polycarbonate resin, epoxy resin, thermosetting polyimide resin, phenol resin, urea resin, melamine resin, diallyl phthalate resin, silicone resin, thermosetting urethane resin, and the like.

  Examples of the thermoplastic resin include olefin resin, acrylic resin, polystyrene resin, polyester resin, polyacrylonitrile resin, maleimide resin, polyvinyl acetate resin, ethylene / vinyl acetate copolymer, polyvinyl alcohol resin, polyamide resin, polyvinyl chloride. Resin, polyacetal resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, polyallyl sulfone resin, thermoplastic polyimide resin, thermoplastic urethane resin, polyetherimide resin, polymethylpentene Examples thereof include resins, cellulose resins, liquid crystal polymers, and ionomers.

  These resins can be used alone or in combination of two or more.

  Among the above-mentioned resins, preferably, a thermoplastic resin, more preferably, a highly oriented resin having high orientation is mentioned, specifically, an olefin resin, an acrylic resin, a polystyrene resin, a polyester resin, a polyvinyl alcohol resin. , Thermoplastic polyimide resin, polyetherimide resin and the like.

  Examples of the olefin resin include a cyclic olefin resin and a chain olefin resin. Preferably, cyclic olefin resin is mentioned.

  Examples of the cyclic olefin resin include polynorbornene, ethylene-norbornene copolymer, or derivatives thereof.

  Examples of the chain olefin resin include polyethylene, polypropylene, and ethylene / propylene copolymer.

  Examples of the acrylic resin include polymethyl methacrylate and polyethyl methacrylate.

  Examples of the polystyrene resin include polystyrene, poly (α-methylstyrene), styrene / (α-methylstyrene) copolymer, styrene / butadiene copolymer, and the like. Preferably, polystyrene is used.

  Examples of the polyester resin include polyarylate, polyethylene terephthalate, and polyethylene naphthalate.

  The polyvinyl alcohol resin can be obtained by, for example, complete or partial saponification of a polyvinyl acetate resin obtained by polymerizing a vinyl monomer containing vinyl acetate as a main component by an appropriate method. The saponification degree of polyvinyl alcohol resin is 70-100 mol%, for example, Preferably, it is 70-99.99 mol%, More preferably, it is 80-99.9 mol%.

  The organic-inorganic composite particles are particles that can be dispersed as a primary in a solvent (described later) and / or a resin and have an organic group on the surface of the inorganic particles. Specifically, organic-inorganic composite particles are obtained by subjecting inorganic particles to surface treatment with an organic compound. The organic-inorganic composite particles can be used singly or in combination of two or more.

  Examples of inorganic substances forming inorganic particles include metals composed of metal elements such as typical elements and transition elements, for example, nonmetals composed of nonmetal elements such as boron and silicon, for example, inorganic compounds containing metal elements and / or nonmetals. Etc.

  Examples of the metal element or nonmetal element include, for example, boron (B) in Group IIIB-silicon (Si) in Group IVB-arsenic (As) in Group VB-tellurium in Group VIB in the long-period periodic table ( Te) -Astatine of group VIIB (At) as a boundary, these elements and elements on the left side and the lower side of the long-period periodic table from the boundary are mentioned. Specifically, for example, Sc, Y Group IIIA elements such as, for example, Group IVA elements such as Ti, Zr and Hf, for example Group VA elements such as V, Nb and Ta, for example Group VIA elements such as Cr, Mo and W, for example, Mn, Re VIIA group elements such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, etc., Group VIII elements such as Cu, Ag, Au, etc., such as Zn, Cd, H Group IIB elements such as, for example, Group IIIB elements such as B, Al, Ga, In, Tl, for example, Group IVB elements such as Si, Ge, Sn, Pb, for example, VB elements such as As, Sb, Bi, Examples include VIB group elements such as Te and Po, for example, lanthanide series elements such as La, Ce, Pr, and Nd, and actinium series elements such as Ac, Th, and U.

  Examples of inorganic compounds include hydrogen compounds, hydroxides, nitrides, halides, oxides, carbonates, sulfates, nitrates, metal complexes, sulfides, carbides, phosphorus compounds, and the like. The inorganic compound may be a complex compound, and examples thereof include oxynitrides and complex oxides.

  Of the inorganic substances described above, inorganic compounds are preferable, and oxides, composite oxides, carbonates, sulfates, and the like are more preferable.

Examples of the oxide include metal oxide, and preferably titanium oxide (titanium dioxide, titanium oxide (IV), titania: TiO ₂ ), cerium oxide (cerium dioxide, cerium oxide (IV), ceria: CeO ₂ ). Etc.

  The oxides can be used alone or in combination of two or more.

  The composite oxide is a compound of oxygen and a plurality of elements, and the plurality of elements are selected from elements other than oxygen, a group I element, and a group II element in the oxide described above. The combination of at least 2 or more types is mentioned.

  Examples of the first element include alkali metals such as Li, Na, K, Rb, and Cs. Examples of Group II elements include alkaline earth metals such as Be, Mg, Ca, Sr, Ba, and Ra.

  The combination of a plurality of elements is preferably at least Group II, such as a combination of Group II elements and Group IVb elements, a combination of Group II elements and Group VIIIb elements, a combination of Group II elements and Group IVa elements, and the like. Examples include combinations containing a genus element.

  Examples of the composite oxide containing at least a Group II element include alkaline earth metal titanates, alkaline earth metal zirconates, alkaline earth metal ferrates, alkaline earth metal stannates, and the like. .

  As the complex oxide oxide, an alkaline earth metal titanate is preferably used.

The alkaline earth metal titanate, for example, titanate beryllium (BeTiO _3), magnesium titanate (MgTiO _3), calcium titanate (CaTiO _3), strontium titanate (SrTiO _3), barium titanate (BaTiO ₃ ) And radium titanate (RaTiO ₃ ).

  Complex oxides can be used alone or in combination of two or more.

  In the carbonate, examples of the element that combines with carbonic acid include alkali metals and alkaline earth metals. Examples of the alkali metal and alkaline earth metal are the same as described above.

  Among the elements that combine with carbonic acid, an alkaline earth metal is preferable.

  Specifically, the carbonate preferably includes a carbonate containing an alkaline earth metal. Examples of such a carbonate include beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, Examples include radium carbonate. These carbonates can be used alone or in combination of two or more.

The sulfate is a compound of sulfate ion (SO ₄ ²⁻ ) and a metal cation (more specifically, a compound in which a hydrogen atom of sulfuric acid (H ₂ SO ₄ ) is substituted with a metal), Examples of the metal contained in the metal include alkali metals and alkaline earth metals. Examples of the alkali metal and alkaline earth metal are the same as described above.

  Among metals, an alkaline earth metal is preferable.

  Specifically, the sulfate preferably includes a sulfate containing an alkaline earth metal. Examples of such sulfate include beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, Examples thereof include radium sulfate, and preferably, barium sulfate is used.

  These sulfates can be used alone or in combination of two or more.

  The organic compound is, for example, an organic group-introducing compound that introduces (arranges) an organic group on the surface of the inorganic particle, and specifically includes a bonding group that can be bonded to the surface of the inorganic particle and an organic group. It is out.

The bonding group is appropriately selected depending on the type of inorganic particles, and examples thereof include a carboxyl group, a phosphate group (—PO (OH) ₂ , a phosphono group), an amino group, a sulfo group, a hydroxyl group, a thiol group, and an epoxy group. , Functional groups such as isocyanate group (cyano group), nitro group, azo group, silyloxy group, imino group, aldehyde group (acyl group), nitrile group, vinyl group (polymerizable group). Preferably, a carboxyl group, a phosphoric acid group, an amino group, a sulfo group, a hydroxyl group, a thiol group, an epoxy group, an azo group, a vinyl group and the like are mentioned, and more preferably, a carboxyl group and a phosphoric acid group are mentioned.

  One or more of these bonding groups are contained in the organic compound. Specifically, the bonding group is bonded to the terminal or side chain of the organic group.

  The organic group includes, for example, a hydrocarbon group such as an aliphatic group, an alicyclic group, an araliphatic group, and an aromatic group.

  Examples of the aliphatic group include a saturated aliphatic group and an unsaturated aliphatic group.

  As a saturated aliphatic group, a C1-C20 alkyl group etc. are mentioned, for example.

  Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 3, 3, Linear or branched having 1 to 20 carbon atoms, such as 5-trimethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl An alkyl group (paraffin hydrocarbon group) etc. are mentioned. Preferably, a C4-C18 linear or branched alkyl group is mentioned.

  Examples of the unsaturated aliphatic group include an alkenyl group having 2 to 20 carbon atoms and an alkynyl group.

  Examples of the alkenyl group include alkenyl groups having 2 to 20 carbon atoms such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl (oleyl), icocenyl and the like (olefin carbonization). Hydrogen group).

  Examples of the alkynyl group include alkynyl groups having 2 to 20 carbon atoms such as ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl and the like (acetylene) Hydrocarbon group).

  Examples of the alicyclic group include a cycloalkyl group having 4 to 20 carbon atoms and a cycloalkenyl alkylene group having 7 to 20 carbon atoms.

  Examples of the cycloalkyl group include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, and the like.

  Examples of the cycloalkenylalkylene group include norbornene decyl (norbornyl decyl, bicyclo [2.2.1] hept-2-enyl-decyl) and the like.

  Examples of the araliphatic group include aralkyl groups having 7 to 20 carbon atoms such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl, and diphenylmethyl.

  Examples of the aromatic group include aryl groups having 6 to 20 carbon atoms such as phenyl, xylyl, naphthyl, and biphenyl.

  The organic group described above is a hydrophobic group for imparting hydrophobicity to the surface of the inorganic particles.

  Therefore, the organic compound containing a hydrophobic group described above is provided as a hydrophobic organic compound for subjecting inorganic particles to a hydrophobic treatment.

  Specific examples of such hydrophobic organic compounds include saturated aliphatic group-containing carboxylic acids (saturated fatty acids) such as hexanoic acid, decanoic acid, and dodecanoic acid (lauric acid), and oleic acid, for example. Examples thereof include aliphatic group-containing carboxylic acids such as unsaturated aliphatic group-containing carboxylic acids (unsaturated fatty acids). Examples of the hydrophobic organic compound include an alicyclic group-containing carboxylic acid (alicyclic carboxylic acid) such as cyclohexane monocarboxylic acid, and an araliphatic group-containing carboxylic acid (aromatic such as 6-phenylhexanoic acid). Aliphatic carboxylic acid), for example, aromatic group-containing carboxylic acid (aromatic carboxylic acid) such as benzoic acid and toluene carboxylic acid. Moreover, saturated aliphatic group-containing phosphonic acids such as decylphosphonic acid, and saturated aliphatic group-containing phosphoric acid esters such as diethyl decylphosphonate, ethyl decylphosphonate, and ethyl octylphosphonate are also included.

  On the other hand, the organic compound can also be provided as a hydrophilized organic compound for hydrophilic treatment of inorganic particles. In that case, the organic group in the hydrophilized organic compound includes the above-described hydrocarbon group and a hydrophilic group bonded thereto. And have.

  That is, the hydrophilic group is bonded to the end of the above-described hydrocarbon group (the end (one end) bonded to the binding group and the other end (the other end)) or the side chain in the hydrophilic organic compound.

  The hydrophilic group is a functional group having polarity (that is, a polar group), for example, carboxyl group, hydroxyl group, phosphate group, amino group, sulfo group, carbonyl group, cyano group, nitro group, aldehyde group, thiol. Group and the like. One or more of these hydrophilic groups are contained in the hydrophilic organic compound.

  Examples of the organic group containing a carboxyl group (carboxyl group-containing organic group) include carboxy saturated aliphatic groups such as 3-carboxypropyl, 4-carboxybutyl, 6-carboxyhexyl, 8-carboxyoctyl, 10-carboxydecyl, and the like. Carboxy aliphatic groups such as carboxy unsaturated aliphatic groups such as carboxybutenyl. Examples of the organic group containing a carboxyl group include a carboxy alicyclic group such as carboxycyclohexyl, a carboxy aromatic aliphatic group such as carboxyphenyl hex, and a carboxy aromatic group such as carboxyphenyl. It is done.

  Examples of the organic group containing a hydroxyl group (hydroxyl group-containing organic group) include hydroxy-saturated aliphatic groups (hydroxy-aliphatic groups) such as 4-hydroxybutyl, 6-hydroxyhexyl, and 8-hydroxyoctyl. Hydroxyaromatic groups such as hydroxybenzyl, 2- (4-hydroxyphenyl) ethyl, 3- (4-hydroxyphenyl) propyl, 6- (4-hydroxyphenyl) hexyl, for example, hydroxyaromatic groups such as hydroxyphenyl Etc.

  Examples of the organic group containing a phosphoric acid group (phosphoric acid group-containing organic group) include, for example, a phosphono saturated aliphatic group (phosphonoaliphatic group) such as 6-phosphonohexyl, and a phosphonoaromatic fat such as 6-phosphonophenylhexyl. Family groups and the like.

  Examples of the organic group containing an amino group (amino group-containing organic group) include an amino saturated aliphatic group (amino aliphatic group) such as 6-aminohexyl and an aminoaromatic aliphatic group such as 6-aminophenylhexyl. Can be mentioned.

  Examples of the organic group containing a sulfo group (sulfo group-containing organic group) include a sulfo-saturated aliphatic group (sulfoaliphatic group) such as 6-sulfohexyl, a sulfoaromatic group such as 6-sulfophenylhexyl, and the like. Can be mentioned.

  Examples of the organic group containing a carbonyl group (carbonyl group-containing organic group) include an oxo saturated aliphatic group (oxo aliphatic group) such as 3-oxopentyl.

  Examples of the organic group containing a cyano group (cyano group-containing organic group) include a cyano saturated aliphatic group (cyano aliphatic group) such as 6-cyanohexyl.

  Examples of the organic group containing a nitro group (nitro group-containing organic group) include a nitro saturated aliphatic group (nitroaliphatic group) such as 6-nitrohexyl.

  Examples of the organic group containing an aldehyde group (aldehyde group-containing organic group) include aldehyde saturated aliphatic groups (aldehyde aliphatic groups) such as 6-aldehyde hexyl.

  Examples of the organic group containing a thiol group (thiol group-containing organic group) include thiol saturated aliphatic groups (thiol aliphatic groups) such as 6-thiol hexyl.

  Specifically, as the organic compound containing a hydrophilic group, for example, a carboxyl group-containing organic compound, a hydroxyl group-containing organic compound, a phosphate group-containing organic compound, an amino group-containing organic compound, a sulfo group-containing organic compound, a carbonyl group-containing Examples include organic compounds, cyano group-containing organic compounds, nitro group-containing organic compounds, aldehyde group-containing organic compounds, and thiol group-containing organic compounds.

  Examples of the carboxyl group-containing organic compound include dicarboxylic acid. Examples of such dicarboxylic acid include propanedioic acid (malonic acid), butanedioic acid (succinic acid), and hexanedioic acid (adipic acid). , Aliphatic dicarboxylic acids such as saturated aliphatic dicarboxylic acids such as octanedioic acid (sebacic acid), unsaturated aliphatic dicarboxylic acids such as itaconic acid, alicyclic dicarboxylic acids such as cyclohexyl dicarboxylic acid, for example 6 -Aroaliphatic dicarboxylic acids such as carboxyphenylhexanoic acid, for example, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid. In addition, examples of the carboxyl group-containing organic compound include a carboxyl group-containing phosphate ester, and specifically, carboxylic acid ethyl decyl phosphate, carboxylic acid octyl phosphate, and the like.

  Examples of the hydroxyl group-containing organic compound include monohydroxylcarboxylic acid, and specific examples of such monohydroxylcarboxylic acid include 4-hydroxybutanoic acid, 6-hydroxyhexanoic acid, and 8-hydroxyoctanoic acid. 4-hydroxyphenylacetic acid, 3- (4-hydroxyphenyl) propionic acid, 6- (4-hydroxyphenyl) hexanoic acid, hydroxybenzoic acid and the like.

  Examples of the phosphoric acid group-containing organic compound include monophosphonocarboxylic acid, and specific examples include 6-phosphonohexanoic acid and 6-phosphonophenylhexanoic acid.

  Examples of the amino group-containing organic compound include monoaminocarboxylic acid, and specific examples include 6-aminohexanoic acid and 6-aminophenylhexanoic acid.

  Examples of the sulfo group-containing organic compound include monosulfocarboxylic acid, and specific examples include 6-sulfohexanoic acid and 6-sulfophenylhexanoic acid.

  Examples of the carbonyl group-containing organic compound include monocarbonyl carboxylic acid, and specific examples include 4-oxovaleric acid.

  Examples of the cyano group-containing organic compound include monocyanocarboxylic acid, and specific examples include 6-cyanohexanoic acid.

  Examples of the nitro group-containing organic compound include mononitrocarboxylic acid, and specific examples include 6-nitrohexanoic acid.

  Examples of the aldehyde group-containing organic compound include monoaldehyde carboxylic acid, and specific examples include 6-aldehyde hexanoic acid.

  Examples of the thiol group-containing organic compound include monothiolcarboxylic acid, and specific examples include 6-thiolhexanoic acid.

  The organic groups described above may be the same or different from each other.

  When the organic groups are different, that is, when the organic group includes a plurality of different organic groups, the organic groups include a plurality of organic groups of the same family and / or a plurality of organic groups of different groups.

  Examples of the homologous organic group include a combination of a plurality of aliphatic groups, a combination of a plurality of alicyclic groups, a combination of a plurality of araliphatic groups, and a combination of a plurality of aromatic groups. In addition, as a homologous organic group, for example, a combination of a plurality of carboxyaliphatic groups, a combination of a plurality of carboxyalicyclic groups, a combination of a plurality of carboxyaromatic groups, a plurality of carboxyaromatic groups A combination, a combination of a plurality of hydroxy aliphatic groups, a combination of a plurality of hydroxy aromatic aliphatic groups, a combination of a plurality of hydroxy aromatic groups, a combination of a plurality of phosphono aliphatic groups, a plurality of phosphono aromatic aliphatic groups A combination of a plurality of amino aliphatic groups, a combination of a plurality of amino araliphatic groups, a combination of a plurality of sulfo aliphatic groups, a combination of a plurality of sulfo araliphatic groups, a plurality of oxo aliphatic groups A combination of groups, a combination of a plurality of cyano aliphatic groups, a combination of a plurality of nitro aliphatic groups, a combination of a plurality of aldehyde aliphatic groups, A combination between the thiol aliphatic group having can be mentioned.

  The organic group of the same family preferably includes a combination of a plurality of aliphatic groups, more preferably a combination of a plurality of saturated aliphatic groups, and particularly preferably a saturated aliphatic group having less than 10 carbon atoms. A combination of a group and a saturated aliphatic group having 10 or more carbon atoms, specifically, a combination of hexyl and decyl.

  If the organic group includes a plurality of homologous organic groups, the organic group includes a plurality of organic groups having different sizes (length or / and size, that is, the number of carbon atoms). Therefore, between the adjacent large organic groups, resin molecules enter the voids (pockets) formed corresponding to the small organic groups, and the interaction between the large organic groups and the resin molecules Can be improved. As a result, the dispersibility of the organic-inorganic composite particles can be improved.

  Examples of organic groups of different groups include aliphatic groups, alicyclic groups, araliphatic groups, aromatic groups, carboxyaliphatic groups, carboxyalicyclic groups, carboxyaromatic aliphatic groups, carboxyaromatic groups, Hydroxy aliphatic group, hydroxy aromatic aliphatic group, hydroxy aromatic group, phosphono aliphatic group, phosphono aromatic aliphatic group, amino aliphatic group, amino aromatic aliphatic group, sulfo aliphatic group, sulfo aromatic aliphatic group, oxo Examples include a combination of at least two different groups selected from the group consisting of an aliphatic group, a cyano aliphatic group, a nitro aliphatic group, an aldehyde aliphatic group, and a thiol aliphatic group.

  The organic group of different groups preferably includes an araliphatic group and a combination of aromatic groups, and more preferably a combination of an araliphatic group having 7 to 15 carbon atoms and an aromatic group having 6 to 12 carbon atoms. Specifically, a combination of phenylhexyl and phenyl can be mentioned.

  Further, the organic group of different groups preferably includes a combination of an aliphatic group and a hydroxy aliphatic group, more preferably a combination of a saturated aliphatic group and a hydroxy saturated aliphatic group, and particularly preferably A combination of a saturated aliphatic group having 10 or more carbon atoms and a hydroxy saturated aliphatic group having less than 10 carbon atoms is exemplified, and specifically, a combination of decyl and 6-hydroxyhexyl is exemplified.

  If the organic group contains a plurality of different groups of organic groups, when the resin is prepared as a mixture of a plurality of resin components, the organic groups are those of each resin component that are highly compatible with the organic groups of each group. Excellent compatibility with the resin molecules can be exhibited. Therefore, the interaction between the organic group and the resin molecule of the resin component can be improved. As a result, the dispersibility of the organic-inorganic composite particles can be improved.

  The organic group described above is present on the surface of the inorganic particle in the organic-inorganic composite particle. Specifically, the organic group extends from the surface of the inorganic particle toward the outside of the inorganic particle through the bonding group.

  The organic-inorganic composite particles described above are produced by subjecting an inorganic substance and an organic compound to a reaction treatment, preferably a high temperature treatment.

  The high temperature treatment is performed in a solvent. Examples of the solvent include water, for example, the organic compounds described above.

  Specifically, inorganic materials and organic compounds are treated at high pressure in water at high pressure (hydrothermal synthesis: hydrothermal reaction), or inorganic materials are treated at high temperature in organic compounds (high temperature treatment in organic compounds). Thus, organic-inorganic composite particles are obtained. That is, organic-inorganic composite particles are obtained by surface-treating the surface of inorganic particles formed of an inorganic substance with an organic compound.

  In hydrothermal synthesis, for example, the above-described inorganic substance and organic compound are reacted in the presence of water at a high temperature and high pressure (first hydrothermal synthesis).

  As the inorganic substance used for the first hydrothermal synthesis, carbonates, sulfates, and oxides are preferable. Preferably, an oxide is used.

  That is, first, an inorganic substance, an organic compound, and water are put into a pressure-resistant sealed container and heated to prepare a reaction system at high temperature and high pressure.

  The compounding ratio of each component is, for example, 1 to 1500 parts by weight, preferably 5 to 500 parts by weight, and more preferably 5 to 250 parts by weight with respect to 100 parts by weight of the inorganic substance. For example, it is 50-8000 mass parts, Preferably, it is 80-6600 mass parts, More preferably, it is 5-4500 mass parts.

  In addition, since the density of an organic compound is 0.8-1.1 g / mL normally, the compounding ratio of an organic compound is 1-1500 mL with respect to 100 g of inorganic substances, Preferably, 5-500 mL, More preferably, it is 5-250 mL.

  Moreover, the compounding mole number of an organic compound is 0.01-1000 mol with respect to 1 mol of inorganic substances, Preferably, it is 0.02-50 mol, Furthermore, more preferably, it sets to 0.1-10 mol You can also

  When the organic compound contains a plurality of (for example, two) organic groups of different types, specifically, the molar ratio of the organic compound containing one organic group and the organic compound containing the other organic group Is, for example, 10:90 to 99.9: 0.1, preferably 20:80 to 99: 1.

  Moreover, since the density of water is about 1 g / mL normally, the compounding ratio of water is 50-8000 mL with respect to 100 g of inorganic substances, for example, Preferably, it is 80-6600 mL, More preferably, it is 5-4500 mL It is.

  As for the reaction conditions in the hydrothermal reaction, specifically, the heating temperature is, for example, 100 to 500 ° C, preferably 200 to 400 ° C. Moreover, a pressure is 0.2-50 Mpa, for example, Preferably, it is 1-50 Mpa, More preferably, it is 10-50 Mpa. The reaction time is, for example, 1 to 200 minutes, preferably 3 to 150 minutes. On the other hand, the reaction time when a continuous reaction apparatus is used can be set to 1 minute or less.

  In the above reaction, the obtained reaction product mainly includes a precipitate that precipitates in water and a deposit that adheres to the inner wall of the sealed container.

  The precipitate is obtained, for example, by sedimentation separation in which the reactants are sedimented by gravity or a centrifugal field. Preferably, it is obtained as a precipitate of the reaction product by centrifugal sedimentation (centrifugation) in which sedimentation is caused by a centrifugal force field.

  Further, the deposit is collected by, for example, a spatula.

  Thereby, organic-inorganic composite particles having an organic group on the surface of the inorganic particles are obtained.

  In the first hydrothermal synthesis, the inorganic material before the reaction and the inorganic material forming the inorganic particles after the reaction are the same.

  On the other hand, an organic-inorganic composite particle containing inorganic particles formed from an inorganic material different from the inorganic material that is the charged raw material can also be obtained by hydrothermal synthesis of the inorganic material (charged raw material) and the organic compound (second water) Thermal synthesis).

  Examples of the inorganic substance used for the second hydrothermal synthesis include hydroxides, metal complexes, nitrates, sulfates, and the like. Preferably, a hydroxide and a metal complex are used.

In the hydroxide, examples of the element contained in the hydroxide (an element constituting a cation that combines with hydroxyl ion (OH ⁻ )) are the same as those in the oxide described above.

Specific examples of the hydroxide include titanium hydroxide (Ti (OH) ₄ ) and cerium hydroxide (Ce (OH) ₄ ).

  In the metal complex, the metal element contained in the metal complex is a metal element constituting a composite oxide with the metal contained in the above-described hydroxide, and examples thereof include titanium, iron, tin, and zirconium. Preferably, titanium is used.

  Examples of the ligand of the metal complex include monohydroxycarboxylic acids such as 2-hydroxyoctanoic acid.

  Examples of the metal complex include 2-hydroxyoctanoic acid titanate. The metal complex can be obtained from the above metal element and ligand by a known method.

  Examples of the organic compound include the same organic compounds used in the first hydrothermal synthesis described above.

  In the second hydrothermal synthesis, the inorganic substance and the organic compound are reacted in the presence of water at high temperature and high pressure.

  The compounding ratio of each component is, for example, 1 to 1500 parts by mass, preferably 5 to 500 parts by mass, and more preferably 5 to 250 parts by mass with respect to 100 parts by mass of the inorganic compound. Is, for example, 50 to 8000 parts by mass, preferably 80 to 6600 parts by mass, and more preferably 80 to 4500 parts by mass.

  Moreover, the compounding ratio of the organic compound is, for example, 0.9 to 1880 mL, preferably 4.5 to 630 mL, and more preferably 4.5 to 320 mL with respect to 100 g of the hydroxide. The number of moles can be set, for example, to 0.01 to 10000 moles, preferably 0.1 to 10 moles with respect to 1 mole of hydroxide.

  Moreover, the mixture ratio of water is 50-8000 mL with respect to 100 g of hydroxides, Preferably, it is 80-6600 mL, More preferably, it is 5-4500 mL.

  The reaction conditions in the second hydrothermal synthesis are the same as the reaction conditions in the first hydrothermal synthesis described above.

  Thereby, the organic-inorganic composite particle which has an organic group on the surface of the inorganic particle formed from the inorganic substance different from the preparation inorganic raw material is obtained.

  In the second hydrothermal synthesis formulation described above, a carbonic acid source or a hydrogen source can be further blended with each component.

  Examples of the carbonic acid source include carbon dioxide (carbon dioxide gas), for example, formic acid and / or urea.

  Examples of the hydrogen source include hydrogen (hydrogen gas), for example, acids such as formic acid and lactic acid, and hydrocarbons such as methane and ethane.

  The compounding ratio of the carbonic acid source or the hydrogen source is, for example, 5 to 140 parts by mass, preferably 10 to 70 parts by mass with respect to 100 parts by mass of the inorganic substance.

  In addition, the mixing | blending ratio of a carbonic acid source can also be 5-100 mL with respect to 100 g of inorganic substances, Preferably, it can also be 10-50 mL. The number of moles of the carbonic acid source is, for example, 0.4 to 100 moles, preferably 1.01 to 10.0 moles, and more preferably 1.05 to 1.30 moles with respect to 1 mole of the inorganic substance. Can also be set.

  Moreover, the mixing | blending ratio of a hydrogen source can be 5-100 mL with respect to 100 g of inorganic substances, Preferably, it can be 10-50 mL. Moreover, the compounding mole number of a hydrogen source is 0.4-100 mol with respect to 1 mol of inorganic substances, Preferably, it is 1.01-10.0 mol, More preferably, it is 1.05-2.0 mol Can also be set.

  In the high temperature treatment in an organic compound, an inorganic substance and an organic compound are blended and, for example, they are heated under normal pressure. The organic compound is subjected to high-temperature treatment while serving also as an organic group-introducing compound and a solvent for dispersing or dissolving the inorganic substance.

  The compounding ratio of the organic compound is, for example, 10 to 10,000 parts by mass, preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the inorganic substance. Moreover, the mixing ratio of the organic compound based on volume is, for example, 10 to 10000 mL, preferably 100 to 1000 mL with respect to 100 g of the inorganic substance.

  The heating temperature is, for example, a temperature exceeding 100 ° C., preferably 125 ° C. or more, more preferably 150 ° C. or more, and usually, for example, 300 ° C. or less, preferably 275 ° C. or less. The heating time is, for example, 1 to 60 minutes, preferably 3 to 30 minutes.

  The shape of the organic-inorganic composite particles (primary particles) thus obtained is not particularly limited, and may have, for example, an anisotropy or an isotropic property. In this case, the maximum length) is, for example, 200 μm or less, preferably 1 nm to 200 μm, more preferably 3 nm to 50 μm, and particularly preferably 3 nm to 10 μm.

  The average particle diameter of the organic-inorganic composite particles will be described in detail in the examples below, but is measured by dynamic light scattering (DLS) and / or transmission electron microscope (TEM) or scanning electron microscope (SEM). It is calculated by image analysis.

  If the average particle diameter is less than the above range, the ratio of the volume of the organic group to the surface of the organic-inorganic composite particles becomes high, and it may be difficult to obtain the function of the inorganic particles.

  Moreover, when an average particle diameter exceeds the above-mentioned range, it may be crushed when mixing with resin.

  The organic-inorganic composite particles obtained in this manner are less likely to aggregate in the dry state. Even if apparently aggregated in the dry state, the particles are aggregated in the particle-dispersed resin composition and the particle-dispersed resin molded body ( Formation of secondary particles) is prevented, and the particles are dispersed almost uniformly as primary particles in the resin.

  That is, the organic-inorganic composite particles have at least a shape in which the inorganic particles do not contact each other due to steric hindrance of the organic group.

  Thereafter, the organic-inorganic composite particles obtained by the above-described first or second hydrothermal synthesis or high-temperature treatment in an organic compound are washed and / or wet classified as necessary.

  In order to wash the organic / inorganic composite particles, for example, a solvent is added to the organic / inorganic composite particles obtained by the first or second hydrothermal synthesis or high-temperature treatment in the organic compound to wash the unreacted organic compound. (That is, the organic compound is dissolved in a solvent), and then the solvent is removed and recovered (separated).

  Examples of the solvent include alcohols such as methanol, ethanol, propanol and isopropanol (hydroxyl group-containing aliphatic hydrocarbons), for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone and cyclopentanone (carbonyl group-containing aliphatic hydrocarbons), For example, aliphatic hydrocarbons such as pentane, hexane, heptane (specifically, alkanes), halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, trichloroethane, and halogenated aromatics such as chlorobenzene and dichlorobenzene Examples include aromatic hydrocarbons such as ethers such as tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene, and xylene, and aqueous pH adjusting solutions such as water and ammonia water. Preferably, alcohol and water are used.

  The organic-inorganic composite particles after washing are separated and recovered from the solvent (supernatant liquid), for example, by filtration, decantation, or the like. Thereafter, if necessary, the recovered material is dried by, for example, heating or airflow.

  In order to wet-classify the organic-inorganic composite particles, for example, the organic-inorganic composite particles obtained by the first or second hydrothermal synthesis or the high-temperature treatment in the organic compound, or the above-described washing A solvent is added to the organic-inorganic composite particles, and they are stirred and then allowed to stand, or separated into a supernatant and a precipitate by centrifugal sedimentation. Examples of the solvent include those similar to the above, and specifically, halogenated aliphatic hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons, hydroxyl group-containing aliphatic hydrocarbons, carbonyl group-containing aliphatic hydrocarbons. And pH adjusting aqueous solution.

  Thereafter, the top is collected.

  In wet classification, the supernatant after recovery can be further filtered. For the filtration, for example, a filter having an opening diameter of 500 nm or less, preferably 400 nm or less, and usually 1 nm or more is used.

  Thereafter, the solvent is removed from the recovered material to obtain organic-inorganic composite particles.

  Organic-inorganic composite particles having a small size can be obtained by wet classification.

  The shape of the organic-inorganic composite particles (primary particles) thus obtained is not particularly limited, and is, for example, a substantially rectangular parallelepiped shape such as a substantially cubic shape, for example, a substantially spherical shape, for example, a substantially long sphere (or a spindle shape). ), A spheroidal shape such as a substantially oblate ball, for example, a needle-like shape or a rod-like shape. Preferably, it has a substantially cubic shape or a substantially spherical shape. If it is a substantially cubic shape or a substantially spherical shape, the organic-inorganic composite particles can be reliably and easily packed in a close-packed state in the particle phase 3.

  The average particle diameter of the organic-inorganic composite particles is, for example, 400 nm or less, preferably 300 nm or less, more preferably 200 nm or less, and particularly preferably 100 nm or less. Usually, for example, 1 nm or more, preferably 2 nm or more. is there. The average particle diameter of the organic-inorganic composite particles is measured by a known method, and specifically, as will be described in detail in later Examples, measurement by DLS, and / or transmission electron microscope (TEM) or scanning type It is measured by image analysis with an electron microscope (SEM).

  When the average particle diameter of the organic-inorganic composite particles exceeds the above-described specific range, each particle (one particle) becomes heavy, and it may be difficult to form the phase separation sheet 1.

  The organic-inorganic composite particles obtained in this way are difficult to aggregate in the dry state, and even if apparently aggregated in the dry state, the particle dispersion and the particle-containing resin composition solution (varnish, described later) , Aggregation (formation of secondary particles) is prevented, and the particles are dispersed almost uniformly as primary particles in the solvent.

  The organic-inorganic composite particles have at least a shape in which the inorganic particles do not contact each other due to steric hindrance of the organic group.

  Further, in the organic-inorganic composite particle, the ratio of the surface area of the organic group to the surface area of the inorganic particle, that is, the surface coverage of the organic group in the organic-inorganic composite particle (= (surface area of the organic group / surface area of the inorganic particle) × 100) Is, for example, 30% or more, preferably 60% or more, and usually 200% or less.

  In calculating the surface coverage, first, the shape of the inorganic particles is confirmed by a transmission electron microscope (TEM), the average particle size is further calculated, and the specific surface area of the particles is calculated from the shape of the inorganic particles and the average particle size. calculate. Moreover, the ratio of the organic group which occupies for an organic inorganic composite particle is computed from the weight change when an organic inorganic composite particle is heated to 800 degreeC with a differential thermal balance (TG-DTA). Thereafter, the amount of the organic group in one particle is calculated from the molecular weight of the organic group, the density of the particle, and the average volume. And surface coverage is calculated | required from them.

  In addition, at least when the surface coverage is high and the organic group of the organic-inorganic composite particles has a length that cancels the charge of the inorganic particles, the type of the solvent (medium) in which the organic-inorganic composite particles are dispersed Can be controlled (designed or managed) by the type of organic group.

  In addition, the resin and the organic-inorganic composite particles can be selected so that their solubility parameters (SP values) satisfy a predetermined relationship.

  Next, a method for producing the phase separation sheet 1 will be described with reference to FIG.

  In this method, first, a particle-containing resin composition is prepared by blending a resin and organic-inorganic composite particles.

  Specifically, the particle-containing resin composition is prepared by, for example, blending a solvent, organic-inorganic composite particles, and a resin and stirring them (solution preparation). The particle-containing resin composition thus prepared is a varnish containing a solvent.

  In the particle-containing resin composition, organic-inorganic composite particles are dispersed as primary particles in a solvent and a resin.

  Examples of the solvent include, but are not limited to, solvents used in the above-described washing, and, in addition, alicyclic hydrocarbons such as cyclopentane and cyclohexane (specifically, cycloalkyl). ), For example, esters such as ethyl acetate, polyols such as ethylene glycol, glycerin, etc., nitrogen-containing compounds such as N-methylpyrrolidone, pyridine, acetonitrile, dimethylformamide, such as isostearyl acrylate, lauryl acrylate, isoboro Nyl acrylate, butyl acrylate, methacrylate, acrylic acid, tetrahydrofurfuryl acrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxye Le acrylate, acrylic monomers such as acryloyl morpholine, e.g., styrene, vinyl group-containing monomers such as ethylene, for example, an epoxy group-containing monomers such as bisphenol A type epoxy and the like.

  These solvents can be used alone or in combination of two or more. Preferably, halogenated aliphatic hydrocarbon and aromatic hydrocarbon are used.

  To prepare the particle-containing resin composition, specifically, first, the solvent and the resin described above are blended, and the resin is dissolved in the solvent to prepare a resin solution. Thereafter, the resin solution and the organic-inorganic composite particles are blended and stirred to prepare a particle-containing resin composition (first preparation method).

  The blending ratio of the resin is, for example, 40 parts by mass or less, preferably 35 parts by mass or less, more preferably 30 parts by mass or less, and usually 0.1 parts by mass with respect to 100 parts by mass of the resin solution. As mentioned above, Preferably, it is 0.5 mass part or more, More preferably, it is 1 mass part or more. When the blending ratio of the resin exceeds the above range, the resin solubility may be lowered.

  The blending ratio of the organic-inorganic composite particles is, for example, 1 to 1000 parts by mass, preferably 5 to 800 parts by mass, and more preferably 10 to 600 parts by mass with respect to 100 parts by mass of the solid content (resin) of the resin solution. It is.

  Also, for example, a solvent and organic-inorganic composite particles are blended, and the organic-inorganic composite particles are dispersed in the solvent to prepare a particle dispersion, and then the particle dispersion and resin are blended, The particle-containing resin composition can also be prepared by stirring (second preparation method).

  In the particle dispersion, the organic-inorganic composite particles are dispersed as primary particles in a solvent.

  The blending ratio of the organic / inorganic composite particles is, for example, 0.1 to 70 parts by weight, preferably 0.2 to 60 parts by weight, and more preferably 0.5 to 50 parts by weight with respect to 100 parts by weight of the particle dispersion. Part by mass.

  The blending ratio of the resin is, for example, 1 to 10,000 parts by weight, preferably 10 to 2,000 parts by weight, more preferably 100 parts by weight of the solid content (organic-inorganic composite particles) of the particle dispersion. 20 to 1,000.

  Furthermore, for example, a particle-containing resin composition can be prepared by first preparing a resin solution and a particle dispersion, and then mixing and stirring the resin solution and the particle dispersion (first). 3).

  The blending ratio of the resin in the resin solution is the same as the blending ratio exemplified in the first preparation method described above.

  The blending ratio of the organic-inorganic composite particles in the particle dispersion is the same as the blending ratio exemplified in the second preparation method.

  The resin solution and the particle dispersion are, for example, 99: 1 to 10:90, preferably in a mass-based blending ratio of resin and organic-inorganic composite particles (mass number of resin: mass number of organic-inorganic composite particles), preferably 95: 5 to 20:80, more preferably 90:10 to 30:70.

  Furthermore, for example, a particle-containing resin composition can be prepared by blending a solvent, organic-inorganic composite particles, and a resin at a time and stirring them (fourth preparation method).

  The blending ratio of each component is, for example, 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight, more preferably, organic / inorganic composite particles with respect to 100 parts by weight of the total amount of the particle-containing resin composition. It is 3-30 mass parts, and is 40 mass parts or less with a resin, Preferably, it is 35 mass parts or less, and is 0.1 mass part or more normally. Moreover, the compounding ratio of the solvent is the remainder excluding the organic-inorganic composite particles and the resin in the particle-containing resin composition.

  Furthermore, for example, without blending a solvent, the resin can be melted by heating and blended with organic-inorganic composite particles to prepare a particle-containing resin composition (fifth preparation method).

  The particle-containing resin composition thus prepared is a melt of the particle-containing resin composition that does not contain a solvent.

  When the resin is made of a thermoplastic resin, the heating temperature is equal to or higher than the melting temperature, specifically 200 to 350 ° C. Moreover, when resin consists of thermosetting resins, it is the temperature which resin will be in a B-stage state, Comprising: For example, it is 85-140 degreeC.

  The blending ratio of the resin and the organic-inorganic composite particles is the blending ratio of the resin and the organic-inorganic composite particles based on the mass (the mass number of the resin: the mass number of the organic-inorganic composite particles). Preferably, it mix | blends so that it may become 95: 5-15: 85, More preferably, it will be 90: 10-20: 80.

  Of the first to fifth preparation methods described above, the first to fourth preparation methods are preferable, and the third and fourth preparation methods are more preferable.

  In the particle-containing resin composition obtained by each of the preparation methods described above, the organic-inorganic composite particles are uniformly dispersed in the resin. Specifically, in the particle-containing resin composition, organic-inorganic composite particles are dispersed as primary particles (without substantially agglomerating) in the resin.

  Thereafter, the obtained particle-containing resin composition is applied onto, for example, a release sheet 5 to produce a coating film 4, and the coating film 4 is dried to form the phase separation sheet 1.

  The release sheet 5 is formed in a sheet shape made of a resin material such as polyethylene, polypropylene, and polyethylene terephthalate, for example, a metal material such as copper, iron, and stainless steel. Preferably, a resin material is used.

  In the application of the particle-containing resin composition, for example, a coating method such as a spin coater method, a bar coater method, or a brush coating method is used. In the application of the particle-containing resin composition, the solvent is removed by volatilization simultaneously with or immediately after the application. If necessary, the solvent can be dried by heating after coating.

  And by drying (specifically, volatilization of the solvent) of the coating film 4 described above, the organic-inorganic composite particles are three-dimensionally arranged on the upper side of the phase separation sheet 1, whereby the particle phase 3 becomes It is formed in layers on the upper side. Thereby, since the particle phase 3 is unevenly distributed on the upper side of the phase separation sheet 1, the resin phase 2 is formed in a layered manner on the lower side. That is, the phase separation sheet 1 is composed of a resin phase 2 formed in a layer on the lower side and a particle phase 3 formed in a layer on the upper side of the resin phase 2.

  In the phase separation sheet 1 thus obtained, the resin phase and the particle phase are phase-separated depending on the affinity between the resin and the organic group of the organic-inorganic composite particles. That is, regardless of the kind of inorganic particles, the resin phase 2 and the particle phase 3 are phase-separated by the selection of the organic group.

  Therefore, the phase separation sheet 1 can be applied to various industrial uses.

  When the phase separation sheet 1 is actually used, the release sheet 5 is peeled off from the phase separation sheet 1 (resin phase 2) as shown by the phantom line in FIG.

  Further, according to the above-described method, the resin phase 2 and the particle phase 3 are formed by a simple method of molding from the particle-containing resin composition, that is, a simple method of applying the resin-containing resin composition. The separated phase separation sheet 1 can be manufactured.

  In the above-described method, the phase-separated structure of the present invention is formed as the phase-separated sheet 1 by applying the particle-containing resin composition. For example, the phase-separated structure is injected into a mold or the like (casting, potting), Then, if necessary, the phase separation structure of the present invention can be formed as a phase separation block (lumps) by thermoforming with a hot press or the like.

  In the particle phase 3 described above, the organic-inorganic composite particles are arranged three-dimensionally. For example, although not shown, two-dimensionally, specifically, in the plane direction of the phase separation sheet 1 It can also be arranged. In that case, in the particle phase 3, the organic-inorganic composite particles are formed in one layer without overlapping each other in the thickness direction, and the thickness of the particle phase 3 is substantially equal to the average particle diameter of the organic-inorganic composite particles. Are the same.

  Preferably, the organic-inorganic composite particles are aligned in a three-dimensional manner.

  Further, the particle phase 3 can be unevenly distributed on the lower side of the phase separation sheet 1, that is, on the lower surface of the resin phase 2.

  In this case, although not shown, in the phase separation sheet 1, the resin phase 2 is formed on the upper side, and the particle phase 3 is formed thereunder. That is, the particle phase 3 is laminated on the upper surface of the release sheet 5, and the resin phase 2 is exposed to air.

  Furthermore, as shown in FIG. 11, the particle phase 3 can be unevenly distributed on both the upper and lower sides of the phase separation sheet 1, that is, both the upper and lower surfaces of the resin layer 2.

  In this case, in the phase separation sheet 1, the resin phase 2 is formed on the upper side and the lower side, and the particle phase 3 is formed therebetween. That is, the particle phase 3 is disposed so as to sandwich the resin layer 2.

  Preparation Examples, Comparative Preparation Examples, Examples and Comparative Examples are shown below to further illustrate the present invention, but the present invention is not limited to them.

In addition, the evaluation method of an organic inorganic composite particle and a phase separation sheet is described below.
(1) X-ray diffraction method (XRD)
Organic-inorganic composite particles are filled in glass folders, respectively, and X-ray diffraction is performed under the following conditions. Then, the component of an inorganic particle is attributed by database search from the obtained peak.

X-ray diffractometer: D8 DISCOVER with GADDS, manufactured by Bruker AXS (incident side optical system)
-X-ray source: CuKα (λ = 1.542 mm), 45 kV, 360 mA
Spectrometer (monochromator): Multilayer mirror Collimator diameter: 300 μm
(Receiving side optical system)
Counter: Two-dimensional PSPC (Hi-STAR)
・ Distance between organic / inorganic composite particles and counter: 15 cm
・ 2θ = 20, 50, 80 degrees, ω = 10, 25, 40 degrees, Phi = 0 degree, Psi = 0 degrees ・ Measurement time: 10 minutes ・ Attribution (semi-quantitative software): FPM EVA, manufactured by Bruker AXS ( 2) Fourier transform infrared spectrophotometry (FT-IR)
The Fourier transform infrared spectrophotometric measurement of the organic-inorganic composite particles is performed by the KBr method using the following apparatus.

Fourier transform infrared spectrophotometer: FT / IRplus, manufactured by JASCO (3) Measurement of average particle diameter by dynamic light scattering (DLS) Organic / inorganic composite particles are used as solvents (for example, cyclohexane, chloroform, hexane, toluene, ethanol) A sample (solid content concentration of 1% by mass or less) is prepared by dispersing in a good solvent in which organic-inorganic composite particles are dispersed as primary particles, such as ammonia water, and the average particle size of the organic-inorganic composite particles in the sample is changed. Measured with an automatic light scattering photometer (model number “ZEN3600” manufactured by Sysmex Corporation).
(4) Observation with Transmission Electron Microscope (TEM) The phase separation sheet of each Example was cut along the thickness direction, and the cut surface was measured with a transmission electron microscope (TEM, H-7650, manufactured by Hitachi High-Technologies Corporation). Observe and observe the phase separation state of the resin phase and the particle phase, observe the shape of the organic-inorganic composite particles, and measure the thickness of the resin phase and the particle phase.

The state of phase separation is evaluated based on the following evaluation criteria.
◯: The particle phase (segregation phase) is entirely formed at least on the surface side.
Δ: A particle phase (segregation phase) is partially formed on at least one surface side.
X: Particle phase (segregation phase) is not formed.

  In order to clarify the cut surface of the film, in TEM observation, the film is embedded in an epoxy resin and cut (cut).

  Separately, a particle dispersion (solid content concentration of 1% by mass or less) of organic-inorganic composite particles diluted with a solvent is dropped on a TEM grid (collodion membrane, carbon support membrane), dried, and transmission electron microscope (TEM) ), The average particle size of the organic-inorganic composite particles is calculated by image analysis.

(Preparation of organic-inorganic composite particles)
Preparation Example 1
A 5-mL high-pressure reactor (manufactured by AKICO) was charged with 1.09 g of cerium hydroxide (Ce (OH) ₄ : manufactured by Wako Pure Chemical Industries, Ltd.), 1.0362 mL of decanoic acid, and 1.010 mL of pure water. .

  Next, the lid of the high-pressure reactor is closed, heated to 400 ° C. in a shaking-type heating furnace (manufactured by AKICO), the inside of the high-pressure reactor is pressurized to 40 MPa, and shaken for 10 minutes, thereby hydrothermal synthesis. (Second hydrothermal synthesis).

  Thereafter, rapid cooling was performed by putting the high-pressure reactor into cold water.

Next, ethanol was added and stirred, and the mixture was centrifuged at 12000 G for 20 minutes in a centrifuge (trade name: MX-301, manufactured by Tommy Seiko Co., Ltd.) to separate the precipitate (reactant) from the supernatant (washing step) ). This washing operation was repeated 5 times. Thereafter, ethanol in the precipitate was heated and dried at 80 ° C. to obtain organic-inorganic composite particles having a decyl group on the surface of cerium oxide (CeO ₂ ).

  Next, the centrifuge tube was charged with the organic-inorganic composite particles obtained above and chloroform, and centrifuged at 4000 G for 5 minutes using a centrifuge (trade name: MX-301, manufactured by Tommy Seiko Co., Ltd.). And precipitates (wet classification).

  Next, the supernatant was taken out and dried to obtain organic-inorganic composite particles having a small particle size.

  Thereafter, for the obtained organic-inorganic composite particles, (1) XRD, (2) FT-IR, (3) DLS (average particle diameter), (4) TEM (dispersed state and average particles of organic-inorganic composite particles) (Diameter) was evaluated.

As a result, in (1) XRD, inorganic compound forming the inorganic particles were confirmed to be CeO _2.

  In (2) FT-IR, it was confirmed that a saturated aliphatic group (decyl group) was present on the surface of the inorganic particles.

  Furthermore, in (3) DLS, the average particle diameter of the organic-inorganic composite particles was 7 nm, and in (4) TEM, the average particle diameter of the organic-inorganic composite particles was 3-9 nm.

  Further, (4) the image processing diagram of the TEM photograph of Preparation Example 1 is shown in FIG.

As can be seen from FIG. 3, there are gaps between the inorganic particles, and the organic-inorganic composite particles have a shape in which the inorganic particles (CeO ₂ ) do not come into contact with each other due to steric hindrance of the organic group (decyl group). I understand.

Preparation Examples 2-9 and Comparative Preparation Examples 1-3
Based on the description of Table 1, organic-inorganic composite particles were prepared in the same manner as in Preparation Example 1, except that the formulation of the inorganic substance, organic compound, and water was changed, and subsequently wet-classified.

  In addition, the preparation example of Ti complex described in Table 1 is shown below.

(Preparation of titanium complex)
To a 500 mL beaker, 100 mL of 30% by volume hydrogen peroxide solution and 25 mL of 25 wt% ammonia were added under ice cooling. Further, 1.5 g of titanium powder was added to them, and the mixture was stirred for 3 hours under ice-cooling until completely dissolved. Next, 15.5 g of 2-hydroxyoctanoic acid dissolved in 25 mL of ethanol was added and stirred. After all the components were dissolved, stirring was stopped and the mixture was allowed to stand overnight. Then, the water-soluble titanium complex (2-hydroxyoctanoic acid titanate) was obtained by making it dry at 75 degreeC with a dryer for 3 hours.

The inorganic particles of Comparative Example Preparation Example 3 (TiO ₂₎ were titanium oxide particles (untreated) and subjected as it is.

(Preparation of phase separation sheet)
Example 1
(Preparation of particle dispersion)
Polystyrene was blended in chloroform, and they were mixed by stirring to prepare a resin solution having a solid content concentration of 10% by mass in which polystyrene was dissolved in chloroform.

  Separately, the organic-inorganic composite particles of Preparation Example 1 were blended in chloroform, and these were stirred and mixed to prepare a particle dispersion having a solid content concentration of 1% by mass in which the organic-inorganic composite particles were dispersed in chloroform. .

  Next, the resin solution and the particle dispersion are blended so that the blending ratio of the resin and the organic-inorganic composite particles based on mass is 99: 1 (= mass number of polystyrene: mass number of the organic-inorganic composite particles). The mixture was stirred and mixed to prepare a particle-containing resin composition (varnish). The solid content (polystyrene and organic-inorganic composite particles) concentration in the varnish of the particle-containing resin composition was 9.2% by mass.

  Specifically, 99 parts by mass of a resin solution having a solid content concentration of 10% by mass and 10 parts by mass of a particle dispersion having a solid content concentration of 1% by mass were blended.

  Thereafter, the prepared particle-containing resin composition was applied onto a polyethylene terephthalate sheet (release sheet) by a spin coating method to form a coating film (5) (see FIG. 2A). In addition, chloroform volatilized immediately after formation of the coating film (5).

  Thus, a phase separation sheet (1) having a thickness of 4.7 μm was produced (see FIG. 2B).

Examples 2-14 and Comparative Examples 1-3
A particle-containing resin composition is prepared based on the formulation of the resin solution and the organic-inorganic composite particles (specifically, the mixing ratio based on the mass of the resin and the organic-inorganic composite particles) in Tables 2 to 5 A phase separation sheet (1) was produced in the same manner as in Example 1 except that.

  That is, in Examples 6 to 12 and Comparative Examples 1 to 3 shown in Table 3, a particle-containing resin composition is obtained from a resin (polystyrene) solution having a solid content concentration of 10% by mass and a particle dispersion having a solid content concentration of 1% by mass. A product varnish was prepared, and then a phase separation sheet was prepared.

  In Example 13 shown in Table 4, a varnish of a particle-containing resin composition was prepared from a resin (polymethyl methacrylate) solution having a solid content concentration of 10% by mass and a particle dispersion having a solid content concentration of 1% by mass. Subsequently, a phase separation sheet was produced.

  Furthermore, in Example 14 shown in Table 5, a varnish of a particle-containing resin composition was prepared from a resin (polyethyl methacrylate) solution having a solid content concentration of 10% by mass and a particle dispersion having a solid content concentration of 1% by mass. Subsequently, a phase separation sheet was produced.

(Evaluation)
The phase separation sheets of Examples 1 to 14 were observed by (4) TEM.

  The image processing figures of the TEM photograph of the cross section of the phase-separation sheet | seat of Examples 1-5, 9, 12-14 are shown in FIGS. 4-12, respectively.

  As a result, as shown in FIG. 1 (a) and FIG. 1 (b), the phase separation sheets (1) of Examples 1 to 12 and 14 have a resin layer (2) formed on the lower side, Only the organic-inorganic composite particles formed such that they are phase-separated from the particle layer (3) formed on the upper side of the resin layer (2), and the particle layer (3) is arranged three-dimensionally. It was confirmed that it was formed from. Each organic-inorganic composite particle has a substantially cubic shape and is filled with a hexagonal close-packed structure.

  Moreover, as can be seen from FIG. 11, the phase separation sheet (1) of Example 13 includes a resin layer (2), and a particle layer (3) formed on both the upper and lower sides of the resin layer (2). Thus, it was confirmed that they were formed so as to be phase-separated, and the particle layer (3) was formed only from organic-inorganic composite particles arranged three-dimensionally. Each organic-inorganic composite particle has a substantially cubic shape and is filled with a hexagonal close-packed structure.

  Further, the thicknesses of the resin phase (2) and the particle phase (3) in the phase separation sheets of Examples 1 to 5 were measured. Moreover, the result of the phase-separation state in the phase-separation sheet of each Example and a comparative example is shown in Table 2-Table 5.

  Moreover, the organic-inorganic composite particles had a substantially cubic shape.

1 Phase separation sheet 2 Resin phase 3 Particle phase

FIG. 1 is a phase separation sheet which is an embodiment of the phase separation structure of the present invention, in which (a) shows an enlarged cross-sectional view and (b) shows an enlarged plan view. FIG. 2 is a production process diagram for producing the phase separation sheet shown in FIG. 1, wherein (a) is a step of applying a particle-containing resin composition onto a release sheet to form a coating film. (B) shows the process of drying a coating film and shape | molding a phase-separation sheet. FIG. 3 is an image processing diagram of a TEM photograph of the organic-inorganic composite particles of Preparation Example 1. 4 is an image processing diagram (250,000 times) of a TEM photograph of a cross section of the phase separation sheet of Reference Example 1. FIG. FIG. 5 is an image processing diagram of a TEM photograph (250,000 times) of a cross section of the phase separation sheet of Reference Example 2 . FIG. 6 shows an image processing diagram (250,000 times) of a TEM photograph of a cross section of the phase separation sheet of Example 3. FIG. 7 is an image processing diagram of a TEM photograph of a cross section of the phase separation sheet of Example 4, wherein (a) is an image processing diagram of 50,000 times, and (b) an image processing diagram of 250,000 times. Show. FIG. 8 shows an image processing diagram of a TEM photograph (250,000 times) of a cross section of the phase separation sheet of Example 5. FIG. 9 is an image processing diagram of a TEM photograph (1,000,000 times) of a cross section of the phase separation sheet of Example 9. FIG. 10 shows an image processing diagram of a TEM photograph (1,000,000 times) of a cross section of the phase separation sheet of Example 12. FIG. 11 shows an image processing diagram of a TEM photograph (250,000 times) of a cross section of the phase separation sheet of Example 13. FIG. 12 shows an image processing diagram of a TEM photograph (250,000 times) of a cross section of the phase separation sheet of Example 14.

Further, in the organic-inorganic composite particle, the ratio of the surface area of the organic group to the surface area of the inorganic particle, that is, the surface coverage of the organic group in the organic-inorganic composite particle (= (surface area of the organic group / surface area of the inorganic particle) × 100) Is, for example, 30% or more, preferably 60% or more .

Preparation Examples, Comparative Preparation Examples, Examples , Reference Examples and Comparative Examples are shown below to further illustrate the present invention, but the present invention is not limited to them.

Fourier transform infrared spectrophotometer: FT / IRplus, manufactured by JASCO (3) Measurement of average particle diameter by dynamic light scattering (DLS) Organic / inorganic composite particles are used as solvents (for example, cyclohexane, chloroform, hexane, toluene, ethanol) A sample (solid content concentration of 1% by mass or less) is prepared by dispersing in a good solvent in which organic-inorganic composite particles are dispersed as primary particles, such as ammonia water, and the average particle size of the organic-inorganic composite particles in the sample is changed. Measured with an automatic light scattering photometer (model number “ZEN3600” manufactured by Sysmex Corporation).
(4) Observation by Transmission Electron Microscope (TEM) The phase separation sheet of each Example and each Reference Example was cut along the thickness direction, and the cut surface was taken by a transmission electron microscope (TEM, H-7650, Hitachi High-Technologies Corporation). The phase separation of the resin phase and the particle phase is observed, the shape of the organic-inorganic composite particles is observed, and the thickness of the resin phase and the particle phase is measured.

(Preparation of phase separation sheet)
Reference example 1
(Preparation of particle dispersion)
Polystyrene was blended in chloroform, and they were mixed by stirring to prepare a resin solution having a solid content concentration of 10% by mass in which polystyrene was dissolved in chloroform.

Reference Example 2, Examples 3-14 and Comparative Examples 1-3
A particle-containing resin composition is prepared based on the formulation of the resin solution and the organic-inorganic composite particles (specifically, the mixing ratio based on the mass of the resin and the organic-inorganic composite particles) in Tables 2 to 5 A phase separation sheet (1) was produced in the same manner as in Reference Example 1 except that.

(Evaluation)
The phase separation sheets of Reference Examples 1-2 and Examples 3-14 were observed by (4) TEM.

Image processing diagrams of TEM photographs of cross sections of the phase separation sheets of Reference Examples 1 and 2 and Examples 3 to 5, 9, and 12 to 14 are shown in FIGS. 4 to 12, respectively.

As a result, as shown in FIGS. 1 (a) and 1 (b) , the phase separation sheets (1) of Reference Examples 1-2 and Examples 3-12 and 14 were formed on the lower side. The layer (2) and the particle layer (3) formed on the upper side of the resin layer (2) are formed so as to be phase-separated, and the particle layer (3) is arranged in a three-dimensional manner. It was confirmed that it was formed only from organic-inorganic composite particles. Each organic-inorganic composite particle has a substantially cubic shape and is filled with a hexagonal close-packed structure.

Further, the thicknesses of the resin phase (2) and the particle phase (3) in the phase separation sheets of Reference Examples 1-2 and Examples 3-5 were measured. Moreover, the result of the phase-separation state in the phase-separation sheet of each Example , each reference example, and a comparative example is shown in Table 2-Table 5.

Claims (9)

A resin phase;
Adjacent to the resin phase, comprising a particle phase containing organic-inorganic composite particles having an organic group on the surface of the inorganic particles,
The phase-separated structure according to claim 1, wherein the organic-inorganic composite particles in the particle phase have at least a shape in which the inorganic particles do not contact each other due to steric hindrance of the organic group.   The phase separation structure according to claim 1, wherein the particle phase is formed in a layer shape.   The phase separation structure according to claim 1 or 2, wherein the particle phase is unevenly distributed on one side or both sides of the phase separation structure.   The phase-separated structure according to any one of claims 1 to 3, wherein the particle phase is formed into a layer by arranging the organic-inorganic composite particles in a three-dimensional alignment.   The phase separation structure according to any one of claims 1 to 4, wherein an average particle size of the organic-inorganic composite particles is 400 nm or less. A step of preparing a particle-containing resin composition by blending a resin and organic-inorganic composite particles having an organic group on the surface of the inorganic particles; and
Characterized in that it comprises a step of molding a phase-separated structure comprising a resin phase and a particle phase adjacent to the resin phase and formed from the organic-inorganic composite particles from the particle-containing resin composition. The manufacturing method of a phase-separation structure.   The method for producing a phase separation structure according to claim 6, wherein the organic-inorganic composite particles are produced in a high-temperature solvent.   The method for producing a phase separation structure according to claim 6 or 7, wherein the organic-inorganic composite particles are produced in high-temperature and high-pressure water.   The phase according to any one of claims 6 to 8, wherein the organic-inorganic composite particles are manufactured so as to have at least a shape in which the inorganic particles do not contact each other due to steric hindrance of the organic group. A method for manufacturing a separation structure.