CN102256695A - Process for producing hollow microspheres and process for producing porous molded ceramic - Google Patents

Process for producing hollow microspheres and process for producing porous molded ceramic Download PDF

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CN102256695A
CN102256695A CN2009801507805A CN200980150780A CN102256695A CN 102256695 A CN102256695 A CN 102256695A CN 2009801507805 A CN2009801507805 A CN 2009801507805A CN 200980150780 A CN200980150780 A CN 200980150780A CN 102256695 A CN102256695 A CN 102256695A
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heat
solid material
microsphere
manufacture method
expandable microsphere
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CN102256695B (en
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江尻哲男
佐竹义克
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Kureha Corp
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Kureha Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
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    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B16/04—Macromolecular compounds
    • C04B16/08—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons
    • C04B16/085—Macromolecular compounds porous, e.g. expanded polystyrene beads or microballoons expanded in situ, i.e. during or after mixing the mortar, concrete or artificial stone ingredients
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    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0016—Granular materials, e.g. microballoons
    • C04B20/002—Hollow or porous granular materials
    • C04B20/0024—Hollow or porous granular materials expanded in situ, i.e. the material is expanded or made hollow after primary shaping of the mortar, concrete or artificial stone mixture
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
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    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/0615—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
    • C04B38/062—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles the burned-out substance being formed in situ, e.g. by polymerisation of a prepolymer composition containing ceramic powder
    • C04B38/0625—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles the burned-out substance being formed in situ, e.g. by polymerisation of a prepolymer composition containing ceramic powder involving a foaming step of the burnable material
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K3/00—Materials not provided for elsewhere
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms

Abstract

The invention provides a process for producing hollow microspheres which comprises: a step (1) in which heat-expandable microspheres having a microcapsular structure comprising a shell formed from a thermoplastic resin and, encapsulated therein, a blowing agent capable of gasifying or generating a gas and a solid material having an average particle diameter or average major-axis length smaller than the average particle diameter of the heat-expandable microspheres are dispersed in a liquid dispersion medium to prepare a slurry; and a step (2) in which the heat-expandable microspheres are heated in the slurry to soften and thermally expand the shells thereof, thereby forming hollow microspheres having the solid material adherent to the surface of the softened shells.

Description

The manufacture method of the manufacture method of hollow microsphere and porous ceramic formed body
Technical field
The present invention relates to the manufacture method that solid materials such as particulate, microfibre are attached to the hollow microsphere of case surface securely.In addition, the invention still further relates to the manufacture method that this hollow microsphere is formed the porous ceramic formed body of agent use as porous matter.
Background technology
Heat-expandable microsphere has has enclosed the gasifiable microcapsule structure that maybe can produce the blowing agent of gas and get in the shell that is formed by thermoplastic resin.Heat-expandable microsphere is also referred to as heat-expandable macrosphere or thermal expansivity microcapsules.If heat-expandable microsphere is heated to the temperature more than the softening point of the thermoplastic resin that forms shell, then because the thermal decomposition gas of the gasification of blowing agent itself or blowing agent and thermal expansion.By the thermal expansion of heat-expandable microsphere, formed hollow microsphere as the ducted body particle.
The thermal expansion that is caused by the heating of heat-expandable microsphere is commonly referred to as foamable or foaming.Heat-expandable microsphere also can be used as separately independently the foaming body particle and forms hollow microsphere after foaming.Relative therewith, the foamable polystyrene particle that has flooded liquid blowing agent is to make its foamable in the mould by being filled in, thereby forms the expanded moldings that the foaming body particle merges incorporate regulation shape, rather than heat-expandable microsphere.
Hollow microsphere is also referred to as baton round or plastic hollow pearl.Heat-expandable microsphere can form low-gravity hollow microsphere by thermal expansion.Therefore, for lightweight, give purposes such as design, heat-expandable microsphere is added in the various base materials such as China ink, coating, plastics.
If the purposes field of heat-expandable microsphere enlarges, and require the high performance in each purposes field, then the level that requires to heat-expandable microsphere also can improve.As to heat-expandable microsphere require one of characteristic, in the time of can being set forth in foamable and after the foaming, the cohesion that is caused by the fusion between the foaming body particle is few, even cohesion hardly.
Heat-expandable microsphere not only can be fitted in the base materials such as China ink, coating, plastics under the state of not foaming, and usually cooperates under the state after the foaming.Foaming body particle (hollow microsphere) utmost point light weight that the heat-expandable microsphere foaming forms for example, if it is included in the coating, then can realize the lightweight of coated object.Yet,, be difficult to sometimes mix, even when mixing, can destroy the foaming body particle with base material such as coating if the foaming body particle condenses each other.
As the method that prevents to condense between the foaming body particle, considered by be covered the not method of case surface of heat-expandable microsphere of foaming of solia particles such as inorganic particles, organic fine particles.Yet, make solia particle equably attached to the case surface of heat-expandable microsphere, and then strictly to control its adhesion amount be extremely difficult.If can not make solia particle equably attached to the case surface of heat-expandable microsphere, then be difficult to uniform foaming.If the adhesion amount of solia particle is very few, the fusion in the time of then can not preventing foamable fully.If the adhesion amount of solia particle is too much, then be difficult to foaming, in the worst case, can not foam sometimes.
The foaming body particle (hollow microsphere) of heat-expandable microsphere is because therefore utmost point light weight is difficult to be applicable to new purposes sometimes.For example, as disclosed in the TOHKEMY 2007-39333 communique (patent documentation 1), the porous ceramic formed body is made by the following method: the mixture that will contain ceramic raw material and porous matter formation agent is shaped to the formed body of regulation shape, then, this formed body is burnt till.If use the foaming body particle (hollow microsphere) of heat-expandable microsphere to form agent, then can obtain to have the porous ceramic formed body of required porous structure accordingly with the size of foaming body particle as porous matter.
Yet, because as low-gravity hollow microsphere of foaming body particle and excessive as the difference in specific gravity between the hyperbaric ceramic raw material of inorganic material, it is extremely difficult therefore disperseing equably.Therefore, if use hollow microsphere to form agent, then be difficult to obtain to have the porous ceramic formed body of uniform porous structure as porous matter.The porous ceramic formed body can be for example as diesel particulate filter device (the Diesel Particulate Filter of the particle-like substance that exhaust comprised that is used to reduce diesel engine; DPF) use in the purposes, if but porous structure is inhomogeneous, then can not bring into play sufficient performance as filter.
In aqueous dispersion medium, make under the situation of heat-expandable microsphere by suspension polymerization, if use the aqueous dispersion medium as dispersion stabilizer such as the inorganic particles that contains colloidal silica, then the case surface of the heat-expandable microsphere that is generated will be adhered to inorganic particles.Yet,, therefore be difficult to make the case surface of the strong firm attachment of inorganic particles of the amount that is enough to prevent that the foaming body particle from merging each other at heat-expandable microsphere because the adhesive force between inorganic particles and the heat-expandable microsphere is little.
If in the recovery process after polymerization finishes, the reactant mixture that will contain the heat-expandable microsphere that generates to some extent filters, washs, and then the inorganic particles that uses as dispersion stabilizer comes off in a large number.Small amounts of inorganic particulate attached to the case surface of the heat-expandable microsphere that reclaims also breaks away from treatment process thereafter easily simply.
If increase the amount of dispersion stabilizers such as colloidal silica, then can increase the adhesion amount of inorganic particles, and this proportion is increased to a certain degree to the case surface of heat-expandable microsphere.Yet in the method, the disengaging problem of the inorganic particles in washing procedure, the treatment process thereafter can't solve.And if adopt such method that inorganic particles is increased the adhesion amount of the case surface of heat-expandable microsphere, the average grain diameter that then can produce the heat-expandable microsphere of gained diminishes, particle diameter distributes becomes big such problem.
Is effective in order to give various functions to hollow microsphere, make solia particle with various functions attached to the method for its case surface.Yet, make solia particle securely attached to the case surface of hollow microsphere, and it is extremely difficult problem that its adhesion amount is controlled in the required scope with various functions.
In the past, the method as making solia particle attached to the case surface of heat-expandable microsphere had proposed Several Methods.In TOHKEMY 2002-363537 communique (patent documentation 2), proposed, in the water system decentralized medium, the polymerism mixture that will contain polymerizable monomer and blowing agent carries out suspension polymerisation in the presence of the organo-silicon compound with polymerisable reactive group, thereby makes the method for heat-expandable microsphere.According to the method for patent documentation 2,, can make the case surface of various solia particles such as colloidal silica attached to heat-expandable microsphere by the effect of organo-silicon compound.In the method, need to use expensive organo-silicon compound, and will to make a large amount of hyperbaric solia particles be difficult attached to the case surface of the foaming body particle after the foaming securely.
TOHKEMY 2003-112039 communique (patent documentation 3), international disclosing in No. 2005/049698 brochure (patent documentation 4) and the TOHKEMY 2006-213930 communique (patent documentation 5) disclose, and heat-expandable microsphere and solia particle are mixed the method that case surface is attached with the heat-expandable microsphere of solia particle that is manufactured on.Yet, in simple mixed method, can not make solia particle securely attached to the case surface of heat-expandable microsphere, solia particle comes off simply in treatment process thereafter.
About making the method for solia particle, Several Methods has been proposed also attached to the case surface of the foaming body particle (hollow microsphere) of heat-expandable microsphere.In the Japanese kokai publication hei 3-273037 communique (patent documentation 6) following method being disclosed: mixes granular or fibrous solid in the moist press cake of heat-expandable microsphere, carry out drying and become less than 1 weight % until moisture content, carry out foamable then.Yet the heat-expandable microsphere that disclosed method is difficult to suppress in the drying process in the patent documentation 6 condenses and premature expansion.
Proposed in the TOHKEMY 2001-98079 communique (patent documentation 7), made colloid shape calcium carbonate with surface conditioning agent or dispersant method attached to the foaming body particle surface of heat-expandable microsphere.According to disclosed method in the patent documentation 7, disperse in air though can suppress the foaming body particle, be difficult to make solia particle securely attached to the case surface of foaming body particle.
Proposed in the TOHKEMY 2006-35092 communique (patent documentation 8), the aqueous dispersion of heat-expandable microsphere is mixed with inorganic particles, carry out Separation of Solid and Liquid then and carry out drying after forming filter cake or Separation of Solid and Liquid and form powder, then, make heat-expandable microsphere add the method for thermal expansion.According to disclosed method in the patent documentation 8, disperse though can prevent the foaming body particle, be difficult to suppress heat-expandable microsphere cohesion and premature expansion.
Proposed in the TOHKEMY 2006-137926 communique (patent documentation 9), the acrylic acid series polymeric compounds that uses dispersion stabilizer particle such as colloidal silica and obtain is not being carried out under the dry situation, adding the method that hollow microsphere is made in thermal expansion as the moisture filter cake of the heat-expandable microsphere of shell.Therefore disclosed method in the patent documentation 9 owing to do not need drying process, can suppress that hollow microsphere merges each other, premature expansion, and if in moisture filter cake the hybrid solid particulate, then can obtain the mixture of hollow microsphere and solia particle.Yet, in order to make moisture filter cake foamable, need to use the powder mixer under mechanical shearing, to heat, cause easily that therefore heat-expandable microsphere, hollow microsphere merge, breakage.In addition, in the method for patent documentation 9, the dispersion stabilizer particle therefore be difficult to make other solia particle to adhere to securely, and the dispersion stabilizer particle that adheres to comes off easily attached to the case surface of heat-expandable microsphere during owing to polymerization.
Patent documentation 1: TOHKEMY 2007-39333 communique
Patent documentation 2: TOHKEMY 2002-363537 communique
Patent documentation 3: TOHKEMY 2003-112039 communique
Patent documentation 4: the international brochure that discloses No. 2005/049698
Patent documentation 5: TOHKEMY 2006-213930 communique
Patent documentation 6: Japanese kokai publication hei 3-273037 communique
Patent documentation 7: TOHKEMY 2001-98079 communique
Patent documentation 8: TOHKEMY 2006-35092 communique
Patent documentation 9: TOHKEMY 2006-137926 communique
Summary of the invention
Problem of the present invention provides does not need complicated operations, do not need to use expensive compound and heat-expandable microsphere does not take place and merge each other and premature expansion, and the solid materials such as particulate, microfibre of making organic or inorganic are securely attached to the method for the hollow microsphere of case surface.
Another problem of the present invention provides hollow microsphere forms agent etc. as porous matter purposes.More specifically, another problem of the present invention provides hollow microsphere that use obtains by said method forms the porous ceramic formed body of agent as porous matter manufacture method.
Present inventors further investigate in order to realize above-mentioned problem, found that, if employing is dispersed in heat-expandable microsphere and solid material and forms slurry in the liquid dispersion medium, be blown into methods such as adding the hot steam and make heat-expandable microsphere foamable (thermal expansion) in this slurry, then the solid material case surface of having softened when foamable is adhered to securely.
By selecting adhesion amount, the kind of solid material, the hollow microsphere that can obtain to have various functions.For example, the hollow microsphere that hyperbaric solid material is got attached to case surface, because particle integral body is high specific gravity, the porous matter that therefore can be suitable as the manufacturing raw material of porous ceramic formed body forms agent and uses.
Can think that the slurry that is dispersed with heat-expandable microsphere and solid material is not suitable for foaming by the heating under the hot conditions, but can distinguish: be blown into the method that adds the hot steam by employing and wait and make the heat-expandable microsphere foamable, at this moment, the case surface of having softened can be adhered to fine solid material securely.The present invention is based on these understanding and finishes.
According to the present invention, providing a kind of has the manufacture method of the hollow microsphere of solid material in the shell surface attachment, and described manufacture method is characterised in that, comprises following operation 1 and operation 2:
(1) operation 1, following heat-expandable microsphere and average grain diameter or average major diameter are dispersed in the liquid dispersion medium less than the solid material of the average grain diameter of this heat-expandable microsphere, thereby modulation slurry, described heat-expandable microsphere have in the shell that forms by thermoplastic resin, has enclosed the gasifiable blowing agent that maybe can produce gas and microcapsule structure, and can carry out thermal expansion by heating and form hollow microsphere; And
(2) operation 2, and this heat-expandable microsphere of heating makes its shell softening in this slurry, and the gasification by this blowing agent or the gas that produced by this blowing agent and thermal expansion, thus, are formed on the hollow microsphere that the case surface of having softened is attached with this solid material.
In addition,, provide a kind of manufacture method of porous ceramic formed body, it is characterized in that, comprise following operation a～c according to the present invention:
Operation a forms agent with ceramic raw material and porous matter and mixes to come modulating mixture;
Operation b is shaped to this mixture the formed body of regulation shape; And
Operation c carries out maintenance with this formed body or burns till,
In described manufacture method, form agent as this porous matter, use obtains by above-mentioned manufacture method, case surface is attached with the hollow microsphere of solid material.
Manufacturing method according to the invention, the compound that does not need complicated operations, do not need to use costliness can be provided, and, do not cause that heat-expandable microsphere merges each other, premature expansion, make solid materials such as particulate, microfibre securely attached to the method for the hollow microsphere of case surface.
The method according to this invention, owing to make the heat-expandable microsphere foaming that freely disperses in slurry, the heat-expandable microsphere when therefore foaming is difficult to merge each other, the hollow microsphere that obtains after the foaming also is difficult to merge each other.The method according to this invention, because therefore softening case surface when making solid material attached to foamable can not suppress the heat-expandable microsphere foaming, and, can make solid material securely attached to the case surface of having softened.Be dispersed in amount, the kind of the solid material in the slurry by change, can at random control amount, kind attached to the solid material of case surface.
If as solid material, use hyperbaric inorganic particles, and by stirring slurry each composition is disperseed equably on one side, make the heat-expandable microsphere foamable on one side, then adhere to hyperbaric inorganic particles securely in case surface, thus, can obtain the high hollow microsphere of the whole proportion of particle.The hollow microsphere that proportion has improved can mechanically evenly mix with the such hyperbaric particle of ceramic raw material.Therefore, if the hollow microsphere that uses case surface to be attached with the high specific gravity solid material forms agent as porous matter, then can make porous ceramic formed body with even porous structure.
Description of drawings
Fig. 1 is the key diagram that shows the thermal expansion of heat-expandable microsphere.
Fig. 2 shows that case surface of the present invention is attached with the key diagram of manufacture method of the hollow microsphere of solid material.
Description of reference numerals
1 heat-expandable microsphere
2 shells
3 blowing agents
101 hollow microspheres
102 shells
103 hollows
21 containers
22 liquid dispersion mediums
23 solid materials
The specific embodiment
As the heat-expandable microsphere that uses among the present invention, in the shell that forms by thermoplastic resin, enclosed the gasifiable microcapsule structure that maybe can produce the blowing agent of gas and get so long as have, and can carry out the heat-expandable microsphere that thermal expansion forms hollow microsphere by heating and get final product, can obtain by any manufacture method.
Shown in Fig. 1 (a), heat-expandable microsphere 1 has the structure of having enclosed blowing agent 3 by the shell of being made by thermoplastic resin 2.If heat-expandable microsphere 1 is heated to the temperature more than the softening point of the thermoplastic resin that constitutes its shell 2, then shown in Fig. 1 (b), because the gasification of blowing agent 3 or thermal expansion, thereby be the hollow microsphere 101 of hollow 103 in the shell 102 after having obtained to expand by the gas of blowing agent generation.
Generally speaking, heat-expandable microsphere can carry out the polymerizable monomer mixture that contains blowing agent and polymerizable monomer at least the method for suspension polymerisation and make by in aqueous dispersion medium.By suspension polymerisation, the polymer that is generated by the polymerization of polymerizable monomer (thermoplastic resin) forms shell, generates to have the heat-expandable microsphere of having enclosed the structure of blowing agent in this shell.
As polymerizable monomer, use free-radical polymerised polymerizable monomer usually.As the concrete example of polymerizable monomer, can enumerate nitriles such as acrylonitrile, methacrylonitrile, α-Lv Bingxijing, α-ethoxy propylene nitrile, anti-maleic nitrile is monomer; Carboxylic monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid; Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, isobornyl acrylate, cyclohexyl acrylate, benzyl acrylate, β-acrylic ester monomers such as carboxy acrylic ester; Methyl methacrylate, EMA, n-BMA, isobutyl methacrylate, metering system tert-butyl acrylate, isobornyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, β-methacrylate ester monomers such as carboxyl methacrylate; Vinylidene chloride; Vinyl acetate; Styrenic monomers such as styrene, AMS, chlorostyrene; Acrylamide such as acrylamide, Methacrylamide monomer; Maleimides such as N-phenylmaleimide, N-(2-chlorphenyl) maleimide, N-cyclohexyl maleimide, N-lauryl maleimide are monomer.
For heat-expandable microsphere, the polymer that forms shell is a thermoplastic resin, and, preferably have gas barrier property.From these viewpoints, preferred vinylidene chloride (being total to) polymer and (methyl) acrylonitrile (being total to) polymer, but be not limited thereto.Should " (being total to) polymer " mean homopolymers and/or copolymer.Should " (methyl) acrylonitrile " mean acrylonitrile and/or methacrylonitrile.
As vinylidene chloride (being total to) polymer, can enumerate as polymerizable monomer and use independent vinylidene chloride or vinylidene chloride and can obtain (being total to) polymer with the mixture of the ethene base system monomer of its copolymerization.As can with the monomer of vinylidene chloride copolymerization, for example can enumerate acrylonitrile, methacrylonitrile, methacrylate, acrylate, styrene, vinyl acetate etc.
As 1,1-dichloroethylene (being total to) polymer, at least a monomer 0～70 quality % that preferably uses vinylidene chloride 30～100 quality % as polymerizable monomer and be selected from acrylonitrile, methacrylonitrile, acrylate, methacrylate, styrene and the vinyl acetate obtains (being total to) polymer.If the copolymerization ratio of vinylidene chloride is less than 30 quality %, then gas barrier property is low excessively, and is therefore not preferred.
As 1,1-dichloroethylene (being total to) polymer, more preferably use vinylidene chloride 40～80 quality %, be selected from least a monomer 0～60 quality % in acrylonitrile and the methacrylonitrile and be selected from acrylate and methacrylate in the copolymer of at least a monomer 0～60 quality %.By forming the copolymer of such composition, design blowing temperature easily, and, realize high foamability easily.
Under the situation of expectation solvent resistance, high temperature foaminess, preferably form shell by (methyl) acrylonitrile (being total to) polymer.As (methyl) acrylonitrile (being total to) polymer,, can enumerate and use independent (methyl) acrylonitrile or (methyl) acrylonitrile and can obtain (being total to) polymer with the ethene base system monomer of its copolymerization as polymerizable monomer.As can with the ethene base system monomer of (methyl) acrylonitrile compolymer, can enumerate vinylidene chloride, acrylate, methacrylate, styrene, vinyl acetate etc.
As (methyl) acrylonitrile (being total to) polymer, preferably use at least a monomer 0～70 quality % that is selected from least a monomer 30～100 quality % in acrylonitrile and the methacrylonitrile and is selected from vinylidene chloride, acrylate, methacrylate, styrene and the vinyl acetate to obtain (being total to) polymer as polymerizable monomer.If the copolymerization ratio of (methyl) acrylonitrile is less than 30 quality %, then solvent resistance, hear resistance are insufficient.
(methyl) acrylonitrile (being total to) polymer can be divided into: (being total to) polymer that the usage ratio of (methyl) acrylonitrile is big, blowing temperature is high; (being total to) polymer that the usage ratio of (methyl) acrylonitrile is little, blowing temperature is low.As big (being total to) polymer of the usage ratio of (methyl) acrylonitrile, can enumerate as polymerizable monomer uses at least a monomer 0～20 quality % that is selected from least a monomer 80～100 quality % in acrylonitrile and the methacrylonitrile and is selected from vinylidene chloride, acrylate, methacrylate, styrene and the vinyl acetate to obtain (being total to) polymer.
As little (being total to) polymer of the usage ratio of (methyl) acrylonitrile, can enumerate as polymerizable monomer and use more than at least a monomer 30 quality % be selected from acrylonitrile and the methacrylonitrile and less than 80 quality % and be selected from least a monomer in vinylidene chloride, acrylate, methacrylate, styrene and the vinyl acetate greater than 20 quality % and below the 70 quality % and (being total to) polymer that obtains.
As (methyl) acrylonitrile (being total to) polymer, preferred use be selected from least a monomer 51～100 quality %, vinylidene chloride 0～40 quality % in acrylonitrile and the methacrylonitrile and be selected from acrylate and methacrylate at least a monomer 0～48 quality % obtain (being total to) polymer.
Polymer as shell, do not comprise 1 being contemplated to be, under the situation of (being total to) polymer of 1-dichloroethylene, preferably as polymerizable monomer use be selected from least a monomer 30～100 quality % in acrylonitrile and the methacrylonitrile and be selected from acrylate and methacrylate at least a monomer 0～70 quality % obtain (methyl) acrylonitrile (being total to) polymer.
As not comprising 1, other of 1-dichloroethylene (being total to) polymer, preferably use acrylonitrile 1～99 quality %, methacrylonitrile 1～99 quality % as polymerizable monomer and be selected from acrylate and methacrylate at least a monomer 0～70 quality % and the copolymer that obtains.
In order to obtain excellent especially heat-expandable microsphere such as processability, foaminess, gas barrier property, solvent resistance, (methyl) acrylonitrile (being total to) polymer of shell preferably use acrylonitrile 20～80 quality %, methacrylonitrile 20～80 quality % and be selected from acrylate and methacrylate in the copolymer that obtains as polymerizable monomer of at least a monomer 0～20 quality %.
In order to improve foam characteristics, processing characteristics, solvent resistance, hear resistance, can merge the use cross-linkable monomer with polymerizable monomer.As cross-linkable monomer, can use compound usually with 2 above carbon-to-carbon double bonds.As cross-linkable monomer, for example can enumerate, divinylbenzene, the divinyl naphthalene, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol (DEG) two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, 1,10-decanediol two (methyl) acrylate, two (methyl) acrylic acid glyceride, dihydroxymethyl tristane two (methyl) acrylate, PEG#200 two (methyl) acrylate, PEG#400 two (methyl) acrylate, two sense cross-linkable monomers such as PEG#600 two (methyl) acrylate; Trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, isocyanic acid triallyl, 1,3,5-triacryl six hydrogen-1,3,5-triazines trifunctional cross-linkable monomers such as (triacrylformal); The multifunctional cross-linkable monomer that trifunctionals such as pentaerythrite four (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, dipentaerythritol six (methyl) acrylate are above; Or the like.The usage ratio of cross-linkable monomer is that benchmark is preferably 0.05～5 quality % with the total amount of polymerizable monomer, more preferably 0.1～3 quality %.
As blowing agent, use can be by heating the material that gasifies or produce gas.As blowing agent, preferred gasifiable compound under the temperature below the softening point of the polymer (thermoplastic resin) that forms shell.As such blowing agent, low boiling point organic solvent is preferred, for example can enumerate ethane, ethene, propane, propylene, normal butane, iso-butane, butylene, isobutene, pentane, isopentane, neopentane, 2,2,4-trimethylpentane, n-hexane, isohexane, normal heptane, 2,2,4,6, hydrocarbon such as 6-five methylheptane (that is Permethyl 99A), benzinum; CCl 3F, CCl 2F 2, CClF 3, CClF 2-CClF 2Deng Chlorofluorocarbons; Tetraalkyl silane such as tetramethylsilane, trimethyl ethylsilane, trimethyl isopropyl silane, trimethyl n-pro-pyl silane; Or the like.These blowing agents can use separately respectively or be used in combination more than 2 kinds.
Wherein, preferred iso-butane, normal butane, pentane, isopentane, n-hexane, isohexane, heptane, 2,2,4-trimethylpentane, Permethyl 99A, benzinum and their mixture more than 2 kinds.The blowing agent that can produce gas by heating is that Celogen Az etc. carries out the compound that thermal decomposition produces gas by heating.
The content of the blowing agent of enclosing in heat-expandable microsphere is preferably 5～50 quality %, more preferably 7～40 quality %.The usage ratio of polymerizable monomer and blowing agent is preferably regulated according to the mode that at polymerization rear casing polymer and blowing agent is aforementioned proportion.
As polymerization initiator, preferably in polymerizable monomer the oil-soluble polymerization initiator of solubility.As polymerization initiator, for example can enumerate dialkyl, peroxidating diacyl, peroxyester, peroxy dicarbonate and azo-compound.Polymerization initiator is generally comprised within the monomer mixture, but suppress at needs under the situation of premature polymerization, can part or all add in the aqueous dispersion medium with it in granulating working procedure or after the granulating working procedure, move it in the drop of polymerism mixture.Polymerization initiator is that benchmark uses with the ratio of 0.0001～3 quality % usually with the aqueous dispersion medium.
Suspension polymerisation is carried out in containing the aqueous dispersion medium of dispersion stabilizer usually.As dispersion stabilizer, for example can enumerate inorganic particles such as silica, magnesium hydroxide.In addition,, for example can use the condensation product of diethanol amine and aliphatic dicarboxylic acid, polyvinylpyrrolidone, polyethylene glycol oxide, various emulsifying agents etc. as auxiliary stabilizer.Dispersion stabilizer uses with the ratio of 0.1～20 mass parts usually with respect to polymerizable monomer 100 mass parts.
The aqueous dispersion medium that contains dispersion stabilizer is usually by being engaged in dispersion stabilizer, auxiliary stabilizer in the deionized water and modulating.The pH value of water is suitably determined according to the kind of employed dispersion stabilizer, auxiliary stabilizer during polymerization.For example, under the situations of silica as dispersion stabilizer such as use colloidal silica, under sour environment, carry out polymerization.In order to make aqueous dispersion medium is acid, adds acid as required, and the pH value of system is adjusted into below 7, is preferably below the pH6, is preferably especially about pH3～4.Under sour environment, be dissolved under the situation of the dispersion stabilizer in the aqueous dispersion medium at magnesium hydroxide, calcium phosphate etc., under alkaline environment, carry out polymerization.
As one of preferred compositions of dispersion stabilizer, the combination of colloidal silica and condensation product is arranged.As the condensation product, be preferably the condensation product of diethanol amine and aliphatic dicarboxylic acid, the condensation product of condensation product, diethanol amine and the itaconic acid of preferred especially diethanol amine and adipic acid.The acid number of condensation product is preferably more than 60 and less than 95, and more preferably 65～90.In addition, if add inorganic salts such as sodium chloride, sodium sulphate, then obtain heat-expandable microsphere easily with more even shape of particle.As inorganic salts, the preferred usually salt that uses.
The use amount of colloidal silica changes according to its particle diameter, is 0.5～20 mass parts, is preferably in the scope of 1～15 mass parts with respect to polymerizable monomer 100 mass parts usually.The condensation product uses with the ratio of 0.05～2 mass parts usually with respect to polymerizable monomer 100 mass parts.Inorganic salts are with respect to polymerizable monomer 100 mass parts to be the ratio use of 0～100 mass parts.
As reagent and additive in polymerization, can make to have at least a compound that is selected from nitrite alkali slaine, stannous chloride, stannic chloride, water dissolvable ascorbic acid class and the boric acid in the aqueous dispersion medium.If in the presence of these compounds, carry out suspension polymerisation, can not take place when polymerization then that polymer particles condenses each other, polymer can stably not make heat-expandable macrosphere simultaneously attached to removing the heat release that is produced by polymerization under the situation on the polymeric kettle wall effectively.
In the nitrite alkali slaine, natrium nitrosum and potassium nitrite in the easiness that obtains, be preferred in price.As the ascorbic acid class, can enumerate the slaine of ascorbic acid, ascorbic acid, the ester of ascorbic acid etc., wherein preferably use the ascorbic acid class of water dissolvable.Water dissolvable ascorbic acid class means that the dissolubility to 23 ℃ water is 1g/100cm 3Above material, preferred ascorbic acid and its alkali metal salt.Wherein, preferred L-ascorbic acid (vitamin C), sodium ascorbate and potassium ascorbate.Reagent and additive in polymerization uses with the ratio that is generally 0.001～2 mass parts with respect to polymerizable monomer 100 mass parts, is preferably 0.01～1 mass parts.
The order of adding each composition in aqueous dispersion medium is arbitrarily, add entry and dispersion stabilizer usually, add stabilization aid, reagent and additive in polymerization etc. as required, thereby modulation contains the aqueous dispersion medium of dispersion stabilizer.On the other hand, can respectively polymerizable monomer and blowing agent be joined in the aqueous dispersion medium, integrated formation polymerizable monomer mixture (oily mixture) in aqueous dispersion medium, but will add in the aqueous dispersion medium again after polymerizable monomer and the blowing agent mixing in advance usually.Polymerization initiator can add in the polymerizable monomer in advance and uses, but avoid at needs under the situation of premature polymerization, for example, the mixture of polymerizable monomer and blowing agent can be added in the aqueous dispersion medium, add polymerization initiator while stirring, integrated in aqueous dispersion medium.Can make in the other container of being blended in of polymerism mixture and aqueous dispersion medium and carry out, mix, join in the polymeric kettle then with mixer, dispersion machine with high shear force.
By polymerizable monomer mixture and aqueous dispersion medium are mixed, thereby in aqueous dispersion medium, form the drop of polymerizable monomer mixture.The average grain diameter of the drop preferably average grain diameter with the target heat-expandable microsphere is roughly consistent.Suspension polymerisation is normally with the degassing in the reactive tank or use inert gas replacement, and the temperature that is warmed up to 30～100 ℃ is again carried out.
After suspension polymerisation, water is removed by for example filtration, centrifugation, sedimentation.Heat-expandable microsphere is carried out drying after filtering, washing.Heat-expandable microsphere does not carry out drying under the lower temperature of gasification degree at blowing agent.
The average grain diameter of heat-expandable microsphere of the present invention is generally 0.5～150 μ m, is preferably 1～130 μ m, and more preferably 3～100 μ m are preferably in the scope of 5～50 μ m especially.The content of the blowing agent of heat-expandable microsphere of the present invention is generally 5～50 quality %, is preferably 7～40 quality %.The blowing temperature of heat-expandable microsphere changes according to the difference of the kind of the thermoplastic resin (polymer) that constitutes shell, thickness etc.
Manufacture method of the present invention be comprise following operation 1 and operation 2 in the shell surface attachment manufacture method of the hollow microsphere of solid material is arranged.
(1) operation 1, following heat-expandable microsphere and average grain diameter or average major diameter are dispersed in the liquid dispersion medium less than the solid material of the average grain diameter of this heat-expandable microsphere, thereby modulation slurry, described heat-expandable microsphere have in the shell that forms by thermoplastic resin, has enclosed the gasifiable blowing agent that maybe can produce gas and microcapsule structure, and can carry out thermal expansion by heating and form hollow microsphere; And
(2) operation 2, and this heat-expandable microsphere of heating makes its shell softening in this slurry, and the gasification by this blowing agent or the gas that produced by this blowing agent and thermal expansion, thus, are formed on the hollow microsphere that the case surface of having softened is attached with this solid material.
With reference to Fig. 2 the summary of manufacture method of the present invention is described.Shown in Fig. 2 (a), in container 21, be added in disperseed heat-expandable microsphere 1 and solid material 23 in the liquid dispersion medium 22 and slurry.For heat-expandable microsphere 1 and solid material 23 are disperseed equably, preferably stir.Make the heat-expandable microsphere foamable by in this slurry, being blown into heating means such as adding the hot steam, then shown in Fig. 2 (b), generate foaming body (hollow microsphere) 101, and a plurality of solid materials 23 are arranged in its surface attachment.
The solid material that uses in the operation 1 is to be solid, average grain diameter or the average major diameter micro-solid material less than the average grain diameter of heat-expandable microsphere down at normal temperature (25 ± 15 ℃).The shape of solid material is granular, spherical, cubic, spindle shape, bar-shaped, tabular, needle-like, fibrous etc., has no particular limits.The material of solid material both can be that inorganic matter also can be an organic matter.
As solid inorganic material, for example can enumerate silica, lime stone, quartz, apatite, magnetic iron ore, zeolite, clay natural goodses such as (montmorillonite, hectorite, saponite, vermiculite, talcum, mica, micas (mica) etc.); Carbonic acid metal salts such as calcium carbonate; Metal sulfates such as barium sulfate, aluminum sulfate, cobaltous sulfate, copper sulphate, nickelous sulfate; Metal oxides such as titanium oxide, zinc oxide, aluminium oxide, tin oxide, vanadium oxide, indium oxide, chromium oxide, tungsten oxide, iron oxide; Metal hydroxides such as aluminium hydroxide, magnesium hydroxide; Metal sulfide such as copper sulfide, vulcanized lead; Metal borate such as aluminium borate, Firebrake ZB; Metal nitrides such as aluminium nitride, chromium nitride, cobalt nitride; Glass such as glass flake, bead; Potteries such as ceramic bead; The particulate of metal or alloy; Carbide such as carbon black, CNT, graphite, active carbon, fullerene; Powder bodies such as crystal pearl, mica, ネ Off エ リ Application シ Na イ ト, hydrotalcite, synthetic silicic acid, silica flour, Cab-O-sil, diatomite, ground pumice, other inorganic pigment.
As the solid inorganic material of colloid shape, for example can enumerate colloidal silica, colloid shape calcium carbonate, magnesium hydroxide colloid, calcium phosphate colloid etc.As needle-like or fibrous solid inorganic material, can enumerate glass fibre, carbon fiber, alumina fibre, potassium titanate crystal whisker, aluminium borate whisker, wollastonite (ウ オ ラ ス Na イ ト) etc.
As organic solid material, for example can enumerate the particulate of organic resins such as polystyrene bead, polymethyl methacrylate pearl, polytetrafluoroethylene (PTFE) pearl, cotton fiber, Fypro etc.Comprise the organic resin particulate that has imported cross-linked structure, the organic resin particulate that has imported functional group or polar group etc. in the particulate of organic resin.
These solid materials can be distinguished use separately, or are used in combination more than 2 kinds.Solid material can be to have implemented surface-treated materials such as hydrophobization processing.By the kind of selection, can control proportion or give functions such as thermal insulation, sliding, sound insulation, electric conductivity, magnetic, piezoelectricity, bactericidal properties, ultraviolet-absorbing attached to the solid material of the case surface of hollow microsphere.
The average grain diameter of inorganic and/or organic solid material or average major diameter are preferred to be generally below the 10 μ m fully less than the average grain diameter of heat-expandable microsphere, is preferably below the 3 μ m, more preferably below the 1 μ m, is preferably especially below the 0.1 μ m.The lower limit of this average grain diameter or average major diameter is about 0.001 μ m from the viewpoint of effect and operability.The average grain diameter of solid material is to measure the average diameter or the average major diameter of the primary particle that obtains by the observation counting method of having used electron microscope or light microscope.
As solid material, using average grain diameter is below the 3 μ m, is preferably below the 1 μ m, and more preferably below the 0.1 μ m, and proportion (true specific gravity) is 1.5～6.0g/cm 3, be preferably 2.0～6.0g/cm 3, 2.5～5.8g/cm more preferably 3Scope at least a inorganic matter, thereby can improve the proportion of hollow microsphere.As such inorganic matter, for example can enumerate calcium carbonate (for example, proportion=about 2.70g/cm 3Powdered whiting, proportion=about 2.60g/cm 3Lightweight and colloid shape calcium carbonate), crystallinity silica (proportion=2.6g/cm 3), aluminium oxide (proportion=3.98g/cm 3), kaolin (clay) (proportion=2.5～2.6g/cm 3), titanium oxide (for example, proportion=3.9g/cm 3Detitanium-ore-type or proportion=4.2g/cm 3Rutile-type), barium sulfate (proportion=4.50g/cm 3), zinc oxide (proportion=5.70g/cm 3Common zinc oxide or proportion=5.78g/cm 3Four-needle-like zinc oxide) etc.
The content of solid material (adhesion amount) can suitably be determined according to the kind of required function and solid material, total amount with the hollow microsphere that is attached with solid material is a benchmark, be generally 1～99.9 quality %, be preferably 10～99.5 quality %, more preferably 15～99.3 quality % are preferably in the scope of 20～99.0 quality % especially.Yet, in the adhesion amount of the dispersion stabilizer (for example, inorganic particles such as silica, magnesium hydroxide) that uses for the particle diameter of controlling heat-expandable microsphere is not included in.
Solid material generally can be based on of poor quality calculating the between each hollow microsphere that obtains in the presence of solid material and not to the adhesion amount of the case surface of hollow microsphere.At solid material is under the situation of inorganic matter, can measure the method for the amount of the ash content after burning again by making the hollow microsphere burning that is got attached to case surface by solid material, calculates the adhesion amount of solid material.
If the content of solid material is very few, then be difficult to preventing to bring into play various functions fully when heat-expandable microsphere from condensing each other.If the content of solid material is too much, then heat-expandable microsphere is difficult to foaming.
In above-mentioned operation 1, heat-expandable microsphere and average grain diameter or average major diameter are dispersed in the liquid dispersion medium less than the solid material of the average grain diameter of this heat-expandable microsphere, thus the modulation slurry.
As liquid dispersion medium, be preferably formed the medium that thermoplastic resin does not dissolve or solubility is little of the shell of heat-expandable microsphere.Liquid dispersion medium does not preferably make the thermoplastic resin of the shell that forms heat-expandable microsphere decompose or the low medium of degree of decomposition.
As the concrete example of liquid dispersion medium, can enumerate water; Isopropyl alcohol, ethylene glycol, glycerine, phthalic acid ester, silicone oil, paraffin wet goods organic solvent; Water/ethylene glycol mixture, water/mixed solvents such as glycerine mixed liquor; Or the like.Wherein, preferred water and the aqueous dispersion mediums such as mixed solvent that contain water, special preferred water.Can add surfactant, dispersion stabilizer etc. as required in the liquid dispersion medium.
The concentration of the heat-expandable microsphere in the liquid dispersion medium is generally 0.1～10 quality %, is preferably 0.1～8 quality %, and more preferably 0.2～7 quality % is preferably in the scope of 0.3～5 quality % especially.If its excessive concentration, then the addition that heat merges, maybe must reduce solid material takes place in foaming body each other easily when the foamable of heat-expandable microsphere.If its concentration is low excessively, then production efficiency reduces.
At heat-expandable microsphere is that the polymerizable monomer mixture that will contain polymerizable monomer and blowing agent in aqueous dispersion medium carries out suspension polymerisation and under the situation about forming, by before suspension polymerisation, in the suspension polymerisation process or after the suspension polymerisation, in aqueous dispersion medium, add solid material, thus can modulate that heat-expandable microsphere and solid material are dispersed in the aqueous dispersion medium and slurry.In this case, can be before the front and back of suspension polymerisation, suspension polymerisation and the suspension polymerisation process medium, add solid material several times.At solid material is under the situation of the such dispersion stabilizer of colloidal silica, usually in the suspension polymerisation process, add after the suspension polymerisation.In order to adjust the concentration of the heat-expandable microsphere in the slurry, can add liquid dispersion medium such as water or with the part of aqueous dispersion medium by filtering or tilting to remove.
At heat-expandable microsphere is to be undertaken by the polymerizable monomer mixture that will contain polymerizable monomer and blowing agent in aqueous dispersion medium under the situation that suspension polymerisation forms, the heat-expandable microsphere that reclaims from aqueous dispersion medium can be dispersed in the decentralized medium of liquid with solid material, thus the modulation slurry.
In above-mentioned operation 2, in slurry, heat heat-expandable microsphere, make its shell softening, and the gasification by blowing agent or the gas that produces from blowing agent and thermal expansion, thus, be formed on the hollow microsphere that the case surface of having softened is attached with solid material.
Owing to have difference in specific gravity between heat-expandable microsphere and the solid material usually, the therefore preferred slurry that adds in possessing the container of agitating device (jar, polymeric kettle etc.) stirs, and heat-expandable microsphere and solid material are evenly dispersed in the slurry.The foamable of heat-expandable microsphere also preferably carries out while stirring slurry.
As the foamable method, have the heating slurry method, in slurry, be blown into the method that adds the hot steam, dielectric heating etc.Using aqueous dispersion medium etc. under the situation of evaporated liquid as liquid dispersion medium under the lower temperature, can heat pressurization.Wherein, being blown into the method that adds the hot steam in slurry, owing to can make the heat-expandable microsphere foamable in the short time at the utmost point, is particularly preferred therefore.The temperature that adds the hot steam depends on the blowing temperature of heat-expandable microsphere, is generally 100～200 ℃, is preferably 110～190 ℃, more preferably in 120～180 ℃ the scope.Pressure when adding the hot steam and being blown into is generally 0.1～1.56MPa, is preferably 0.14～1.26MPa, more preferably in the scope of 0.2～1.0MPa.
Behind foamable in slurry, filter slurry, the method for washing foaming body particle reclaims solid material securely attached to the hollow microsphere of case surface.Hollow microsphere of the present invention, because the shell that is formed by thermoplastic resin during foamable is softening, the case surface of the state that this has softened is adhered to solid material, so by common washing step the solid material that adheres to is come off.
The average grain diameter of hollow microsphere of the present invention is preferably 2～200 μ m, and more preferably 5～100 μ m are preferably in the scope of 10～60 μ m especially.If the average grain diameter of hollow microsphere is too small, then using this hollow microsphere to form under the situation of agent as porous matter, the formation of porous structure is insufficient easily.On the other hand, if the average grain diameter of this hollow microsphere is excessive, then carrying out when mixing with the raw material that constitutes porous matter formed body such as porous ceramic formed body and/or during in the mixture moulding by mixing acquisition, this hollow microsphere breaks easily, consequently, the formation of porous structure may be insufficient.
Hollow microsphere of the present invention because its case surface is attached with solid material, therefore can prevent to merge each other, and, disperse in air in the time of can being suppressed at its operation.By adjusting kind and amount, can give hollow microsphere with various functions attached to the solid material of case surface.
Hollow microsphere of the present invention by making hyperbaric solid material attached to its case surface, can improve the proportion (apparent specific gravity) of particle integral body, thus, evenly mixes easily with high inorganic material of proportion etc.Hyperbaric hollow microsphere is suitable as the porous matter of using in the manufacturing process of porous ceramic formed body for example and forms agent.The porous ceramic formed body that has used porous matter to form agent can be made by disclosed manufacture method in for example TOHKEMY 2007-39333 communique (patent documentation 1).
Particularly, in the manufacture method of the porous ceramic formed body that comprises following operation a～c, form agent as this porous matter, the case surface that use obtains by above-mentioned manufacture method is attached with the hollow microsphere of solid material, described operation is: operation a forms agent with ceramic raw material and porous matter and mixes to come modulating mixture; Operation b is shaped to this mixture the formed body of regulation shape; And operation c, this formed body is burnt till.
As ceramic raw material, can enumerate mixture, carborundum, metallic silicon of potteries such as talcum, kaolin, aluminium oxide, aluminium hydroxide, silica etc.Case surface is attached with the usage ratio of the hollow microsphere of solid material and can suitably determines according to required porous structure.Firing temperature is about 1400～2000 ℃.
Generally speaking, the material group who is called as pottery is extremely widely, and its characteristic also is various.The kind of pottery comprises pottery chinaware, glass, cement, gypsum, enamel, fine ceramics (new system pottery) etc.
Hollow microsphere of the present invention, for example, the porous matter that also can be used as lightweight aerated concrete (ALC) forms agent and uses.Contain the ALC that this porous matter forms agent, inside comprises separated foam, unusual light weight, but can bring into play the higher such excellent specific property of intensity.ALC is light weight but also intensity is higher, fire resistance, thermal insulation, application property are also excellent not only, therefore is extensive use of as the construction material on the wall of building, floor etc.
In the manufacturing of ALC, generally use silicic acid raw material such as silica and calcareous raw materials such as cement, lime as main material, use gypsum and operation to repeat raw material etc. as auxiliary material.In the micropowder of these raw materials, add entry and porous matter forming agent is made slurry, then this slurry is added to making its semi-solid preparation in the mould.Next, by adopting autoclave to carry out the high-temperature high-pressure steam maintenance semi-solid preparation thing, thereby can obtain ALC.
Make the operation of ALC in this wise, comprise following operation a～c: operation a, ceramic raw material and porous matter are formed agent mix to come modulating mixture as the porous ceramic formed body; Operation b is shaped to this mixture the formed body of regulation shape; And operation c, this formed body is carried out maintenance.Using cement, gypsum etc. to make in the technology of porous ceramic formed body, carry out maintenance sometimes and replace burning till as ceramic raw material.In the present invention, form agent, use hollow microsphere of the present invention as the porous matter of ALC etc.
Embodiment
More specifically the present invention will be described below to enumerate embodiment and comparative example, but the present invention is not limited only to these embodiment.In the present invention, the assay method of rerum natura and characteristic is as follows.
(1) expansion ratio
Heat-expandable microsphere 0.7g is put into gill formula baking oven, and heating made its foaming (thermal expansion) in 2 minutes under the blowing temperature of regulation.The hollow microsphere of gained is put into graduated cylinder, measure its volume.The volume of hollow microsphere divided by the volume of the heat-expandable microsphere of foaming not, is calculated expansion ratio.At this moment, blowing temperature is heated up since 70 ℃ with per 5 ℃, make it in foaming at each temperature.Will be at the expansion ratio under the temperature that obtains maximum expansion ratio under this condition as maximum expansion ratio.
(2) average grain diameter
Use Nikkiso Company Limited's system " マ イ Network ロ ト ラ Star Network MT3300EX " (registration mark), measured the average grain diameter (median diameter) of heat-expandable macrosphere and foaming body particle.
(3) proportion
The proportion of heat-expandable microsphere and hollow microsphere means the proportion of particle integral body, according to the use of stipulating among the JIS Z8807 determination method of specific gravity bottle measure.
(4) content of solid material
Heat-expandable microsphere and calculate by the quality of measuring the ash content after the burning attached to the content of the solid material of the case surface of hollow microsphere.Its concrete steps are as follows.
＜blowing agent quantitatively
The amount and the ratio of the remaining blowing agent that air-dry back preservation 1 in drier having carried out round the clock dry hollow microsphere (drying sample) is comprised adopt following steps to measure.
A) by the about 0.2g of drying sample being joined in the aluminum cup (diameter 6cm, height 3cm).At this moment, the quality of the cup before the sample is put in weighing, after having put into sample weighing comprise cup quality, calculate the poor of them, thereby measure the exact mass of drying sample.
B) then, to the loam cake of aluminum on the bowl cover, 200 ℃ of following heat treated 10 minutes, the sample (following sample after the heat treated is called " sample of having removed blowing agent ") of heat treated was passed through in weighing afterwards in order to make blowing agent gasification.
C) here, obtain of poor quality before and after the heat treated, this amount with the blowing agent that particle from drying sample volatilizes is consistent.Use this numerical computations to go out the ratio (f: quality %) of remaining blowing agent with respect to drying sample integral body.Quantitative experiment respectively carries out 2 times.
＜ash content quantitatively
D) will adopt with the made sample 1.5～1.7g weighing of having removed blowing agent of above-mentioned " blowing agent quantitatively " same steps as on medical packing paper, with this weighing value as Wdf (g).
E) the accurate empty quality of weighing magnetic crucible, with this weighing value as Wa (g).
F) the magnetic crucible is put in the each a small amount of gradation of the sample of having removed blowing agent after the weighing, adopted electric heater to repeat the such operation of pre-carbonization, after all the sample carbonization finishes, adopt 930 ℃ electric furnace to make its ashing more than 3 hours.
G) after cooling, weighing comprises the quality of calcination at interior magnetic crucible, with this weighing value as Wb (g).
H) ash amount Ws (g) obtains according to following formula.
Ws(g)＝Wb(g)-Wa(g)
I) with in the following calculating formula of these numerical value substitutions, calculate the value of ash amount with respect to drying sample integral body (quality %).Quantitative experiment respectively carries out 2 times, calculates mean value.
[several 1]
Figure BDA0000068965360000211
[modulation example 1]
(1) modulation of aqueous dispersion medium
The colloidal silica 22g that adds solid constituent 40 quality % in deionized water 770g makes its dispersion.Then, in dispersion liquid, add diethanol amine-adipic acid condensation product 0.8g and natrium nitrosum 0.13g and make its dissolving.Then, in dispersion liquid, add hydrochloric acid, thereby modulate the aqueous dispersion medium of pH3.5.
(2) modulation of polymerizable monomer mixture
With vinylidene chloride 123g, acrylonitrile 86g, methyl methacrylate 11g, diethylene glycol (DEG) two (methacrylate) 0.33g, 2,2 '-azo is two-and methyl pentane nitrile 1.1g and normal butane 35g mix, thereby modulate the polymerizable monomer mixture.The quality % of each polymerizable monomer in the polymerizable monomer mixture is vinylidene chloride/acrylonitrile/methyl methacrylate=56/39/5.
(3) formation of drop
Aqueous dispersion medium and above-mentioned (2) middle polymerizable monomer mixture of modulating of adopting homogenizer to modulate in above-mentioned (1) mix, thereby have formed the fine droplet of polymerizable monomer mixture in aqueous dispersion medium.
(4) suspension polymerisation
The aqueous dispersion medium that has disperseed the drop of polymerizable monomer mixture is joined in the polymeric kettle that has mixer of 1.5 liters of capacity.By this polymeric kettle is put into tepidarium, kept 22 hours down at 50 ℃, make the polymerizable monomer mixture carry out polymerisation.By this polymerisation, formed have the normal butane of in the shell that forms by vinylidene chloride-acrylonitrile methyl meth acrylat copolymer, having enclosed blowing agent and the heat-expandable microsphere of microcapsule structure.After polymerisation, the reactant mixture in the polymeric kettle is filtered washing.Then, will wash and filter and repeat 2 times, carry out drying then, reclaim heat-expandable microsphere.
(5) heat-expandable microsphere
The average grain diameter of the heat-expandable microsphere that obtains like this is 14 μ m, and the maximum expansion ratio under 130 ℃ of the blowing temperatures is 50 times, and proportion is 0.02g/cm 3This heat-expandable microsphere contains the colloidal silica that uses as dispersion stabilizer with the content of 3.3 quality %.
[comparative example 1]
In the heat-expandable microsphere that modulation example 1 is obtained, add deionized water, thereby modulate the water paste 500g of the concentration 1 quality % of this heat-expandable microsphere.This water paste is joined in the polymeric kettle that has mixer of 1.5 liters of capacity.While stir water paste with pressure 0.48MPa to the steam that wherein is blown into 150 ℃ of temperature, heat-expandable microsphere heating is made its foaming.The foaming body particle (hollow microsphere) that foaming by heat-expandable microsphere forms floats to top, the particle that wherein has heat to merge on all.
[comparative example 2]
In the heat-expandable microsphere that modulation example 1 is obtained, add deionized water, thereby modulate the water paste 500g of the concentration 1 quality % of this heat-expandable microsphere.This water paste is joined in the polymeric kettle that has mixer of 1.5 liters of capacity.Stirred 1 hour down in room temperature (23 ℃) while stirring water paste, the colloidal silica that the result owing to dissociating makes the water paste gonorrhoea.
This water paste filtered reclaims heat-expandable microsphere, results verification the content of colloidal silica be reduced to 2.4 quality % from 3.3 initial quality %.This heat-expandable microsphere is heated to 130 ℃ makes its foaming, the result has observed between the foaming body particle and has merged strongly.Maximum expansion ratio under 130 ℃ of the blowing temperatures of this heat-expandable microsphere is 50 times.
[embodiment 1]
Add deionized water in the heat-expandable microsphere that in modulation example 1, obtains, thereby modulate the water paste 500g of the concentration 1 quality % of this heat-expandable microsphere.In this water paste, add colloid shape calcium carbonate (average grain diameter 50nm) 40g, join then in the polymeric kettle that has mixer of 1.5 liters of capacity.While stir this water paste with pressure 0.48Mpa to wherein being blown into the steam that is heated to 150 ℃ of temperature, make the heat-expandable microsphere foamable.In the water paste after foaming is handled, foaming body particle (hollow microsphere) disperses, and can not form agglomerate.
Foaming body particle in the water paste is filtered washing.Then, will wash and filter and repeat 2 times, carry out drying then, reclaim foaming body particle (hollow microsphere).The average grain diameter of this foaming body particle is 50 μ m, and proportion is 0.095g/cm 3The total content of the inorganic matter that this foaming body particle is comprised is 80 quality %.The hollow microsphere that obtains has like this suppressed the dustability that disperses significantly in air, and, with the Combination excellence of the high inorganic matter of proportion.
[embodiment 2]
Beyond use colloidal silica (solid constituent 40 quality %, average grain diameter 12nm) 100g replacement colloid shape calcium carbonate 40g, make foaming body particle (hollow microsphere) similarly to Example 1.The average grain diameter of this foaming body particle is 53 μ m, and proportion is 0.10g/cm 3The total content of the inorganic matter that this foaming body particle is comprised is 85 quality %.The hollow microsphere that obtains has like this suppressed the dustability that disperses significantly in air, and, with the Combination excellence of the high inorganic matter of proportion.
The industry utilizability
The hollow microsphere that case surface of the present invention is attached with solid material can make lightweights such as plastics, coating, various materials, porous materialization, give various functions and use in wide technical.The high specific gravity change the hollow microsphere porous matter that also can be used as the porous ceramic formed body form agent and use.

Claims (15)

1. one kind has the manufacture method of the hollow microsphere of solid material in the shell surface attachment, and described manufacture method is characterised in that, comprises following operation 1 and operation 2:
(1) operation 1, following heat-expandable microsphere and average grain diameter or average major diameter are dispersed in the liquid dispersion medium less than the solid material of the average grain diameter of this heat-expandable microsphere, thereby modulation slurry, described heat-expandable microsphere has to enclose in the shell that is formed by thermoplastic resin the gasifiable microcapsule structure that maybe can produce the blowing agent of gas, and can carry out thermal expansion, formation hollow microsphere by heating; And
(2) operation 2, and this heat-expandable microsphere of heating makes its shell softening in this slurry, and the gasification by this blowing agent or the gas that produced by this blowing agent and thermal expansion, thus, are formed on the hollow microsphere that the case surface of having softened is attached with this solid material.
2. manufacture method according to claim 1, in described operation 1, the concentration of modulating this heat-expandable microsphere is the interior slurry of scope of 0.1～10 quality %.
3. manufacture method according to claim 1, this solid material be selected from have granular, spherical, cubic, spindle shape, bar-shaped, tabular, needle-like or the inorganic matter of fibrous shape and at least a solid material in the organic matter.
4. manufacture method according to claim 1, this solid material are that average grain diameter is below the 3 μ m and proportion is 1.5～6.0g/cm 3Scope at least a inorganic matter.
5. manufacture method according to claim 1, this solid material are at least a inorganic matters that is selected from calcium carbonate, crystallinity silica, aluminium oxide, kaolin, titanium oxide, barium sulfate and the zinc oxide.
6. manufacture method according to claim 1, this heat-expandable microsphere have the interior average grain diameter of scope of 0.5～150 μ m.
7. manufacture method according to claim 1, this liquid dispersion medium is an aqueous dispersion medium.
8. manufacture method according to claim 1, this heat-expandable microsphere is to carry out suspension polymerisation by the polymerizable monomer mixture that will contain polymerizable monomer and blowing agent in aqueous dispersion medium to form, and, described operation 1 is as follows: by before suspension polymerisation, in the suspension polymerisation process or after the suspension polymerisation, in this aqueous dispersion medium, add solid material, thereby be modulated at the slurry that is dispersed with heat-expandable microsphere and solid material in the aqueous dispersion medium.
9. manufacture method according to claim 1, this heat-expandable microsphere obtains by following method: the polymerizable monomer mixture that will contain polymerizable monomer and blowing agent in aqueous dispersion medium carries out suspension polymerisation and forms, then, from this aqueous dispersion medium, reclaim
And, in described operation 1, this heat-expandable microsphere is dispersed in the decentralized medium of liquid with solid material, thus the modulation slurry.
10. manufacture method according to claim 1 in described operation 2, is blown in this slurry and adds the hot steam and heat this heat-expandable microsphere, makes its thermal expansion.
11. manufacture method according to claim 1, in described operation 2, the total amount that the formation case surface is attached with this hollow microsphere is the hollow microsphere of the solid material of benchmark in the scope of 1～99.9 quality %.
12. manufacture method according to claim 1, this hollow microsphere have the interior average grain diameter of scope of 2～200 μ m.
13. the manufacture method of a porous ceramic formed body is characterized in that, comprises following operation a～c:
Operation a forms agent with ceramic raw material and porous matter and mixes to come modulating mixture;
Operation b is shaped to this mixture the formed body of regulation shape;
Operation c carries out maintenance or burns till this formed body,
In described manufacture method, form agent as this porous matter, use obtains by the described manufacture method of claim 1, case surface is attached with the hollow microsphere of solid material.
14. manufacture method according to claim 13, this solid material are average grain diameters is below the 3 μ m and proportion is 1.5～6.0g/cm 3Scope at least a inorganic matter.
15. manufacture method according to claim 13, this solid material are at least a inorganic matters that is selected from calcium carbonate, crystallinity silica, aluminium oxide, kaolin, titanium oxide, barium sulfate and the zinc oxide.
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