WO2006095567A1

WO2006095567A1 - Method of recovering encapsulated substance and novel microsphere obtainable by the method

Info

Publication number: WO2006095567A1
Application number: PCT/JP2006/303106
Authority: WO
Inventors: Toshiaki Masuda; Takashi Fujie; Katsushi Miki; Takayuki Aoki
Original assignee: Matsumoto Yushi-Seiyaku Co., Ltd.
Priority date: 2005-03-08
Filing date: 2006-02-15
Publication date: 2006-09-14
Also published as: JP4970245B2; JPWO2006095567A1

Abstract

A method of recovering an encapsulated substance which includes a contact step in which a microsphere constituted of a shell comprising a thermoplastic resin and an encapsulated substance enclosed in the shell and having a boiling point not higher than the softening point of the thermoplastic resin is brought into contact with a solvent. Also provided is a novel microsphere which can be obtained through the contact step in the method of encapsulated-substance recovery. This microsphere comprises the thermoplastic resin as a shell.

Description

Method for recovery of inclusion substance and novel microspheres obtainable by the method

The present invention relates to a method for recovering an inclusion substance from microspheres composed of an outer shell made of a thermoplastic resin and an inclusion substance contained therein, and novel microspheres obtainable by carrying out the method.

Background art

book

In recent years, along with the strengthening of regulations on chemical substances and the promotion of resource recycling from used electric appliances and automobiles, it has been required to recover substances and useful substances that affect the natural environment. In particular, chlorofluorocarbons (chlorofluorocarbons) are the causative agents of ozone depletion and global warming, and when released into the atmosphere and reach the stratosphere, they are ^^ by strong ultraviolet light from the sun, and chlorine generated thereby Radicals break the ozone layer in the stratosphere, create ozone holes, etc., and restore the environmental status of the stratosphere. In addition, since fluorocarbons remaining in the troposphere of the earth are stable compounds that are extremely difficult to be absorbed, they are not decomposed and cause a greenhouse effect like carbon dioxide, thereby promoting global warming and living organisms. Reminiscent of a suitable global environment. Therefore, releasing fluorocarbons to the atmosphere has a tremendous impact on the life on earth and humanity.

At present, recovery of fumigant gas is a global issue that human beings should work on, and technology for recovering fluorocarbon gas from resin materials containing fluorocarbon gas as a foaming agent is attracting attention.

For example, according to Patent Document 1, a fractured material containing a mixture of a thermosetting urethane foam resin containing fluorocarbon gas and fragments of a thermoplastic resin is supplied to a vented extruder, and the broken material is finely crushed or broken in the parelle. After the fluorocarbon gas which has been melted and separated from the waste material is recovered in the vent section, the fractured material from which the fluorocarbon gas has been removed is pushed out from the nozzle connected to the barrel, and the separated fluorocarbon gas is separated in communication with the vent section. Discloses a method of recovering fluorocarbon after separating futon gas. In Patent Document 2, the outer plate or the inner plate of a heat insulating box filled with a foamed heat insulating material is peeled, and the foamed heat insulating material is peeled from the outer plate or the inner plate while framed by a peeling device. Separate the exfoliated body and the exfoliated foamed heat insulating material from each other by separation, pulverize the separated foamed insulating material with a crusher, and release the foam encapsulated in the internal bubbles, There is disclosed a method of recovering the fluorocarbon gas in the foamed heat insulating material by liquefying and recovering the released fluorocarbon with a fluorocarbon recovery device.

All of these methods require large-scale equipment because they recover the waste using physical means such as powder and melting. Also, due to the nature of the equipment, it is difficult to maintain airtightness, so there is a problem that high recovery rates can not be expected.

A thermally expandable microcapsule is known as a kind of resin material containing the above-mentioned foaming agent, and has a structure in which a thermoplastic resin is used as an outer shell and an inclusion substance as the foaming agent is enclosed therein. ing. When such a thermally expandable microcapsule is heated, a part or all of the inner packaging material is vaporized and the volume of the whole inclusion material is expanded, and further, an outer shell softened by heating is generated by the volume expansion of the inclusion material. By the pressure, it is pushed outward and a lightweight hollow particle is obtained.

Patent Document 3 discloses a novel thermal expansion! "A micro micro capsule which solves the defect of fumigant gas. This thermally expandable microcapsule has a smaller load on the environment instead of fluorocarbon gas. It is characterized in that it contains a fluorine-containing ether compound as a blowing agent.

Patent Document 1: Japanese Patent Application Laid-Open No. 20002-1942

Patent Document 2: Japanese Patent Application Laid-Open No. 2 00 0 1 0 2 9 2 3

Patent Document 3: International Publication No. 2 0 0 4/0 7 4 3 9 6 Panfleet

As fluorine-containing ether compounds are more expensive than chlorofluorocarbons, recovery and reuse are desired from the viewpoint of resource recycling. Also, it has not been thought conventionally that the encapsulated substances contained in the thermal expansion I “raw microcapsules or hollow particles had a significant effect on the natural environment. Now that the cause of urban air pollution is listed as a cause of the urban air pollution, we can not deny the possibility of enforcing restrictions on the recovery and reuse of substances that are suspected even if there are only a few negative effects on the global environment. For any reason like this, no matter what kind of substance the contained substance is, how to recover it Disclosure of inventions that are urgently needed to be established

An object of the present invention is to provide a simple and efficient method for efficiently recovering an entrapped substance from microspheres composed of an outer shell made of a thermoplastic resin and an encapsulated substance contained therein. Also, another object of the present invention is to provide novel microspheres which can be obtained after recovering the inclusion substance.

When the methods disclosed in Patent Documents 1 and 2 are applied to microspheres, the device is large and difficult to operate, high recovery rate of the contained substance can not be expected, and a large amount of energy such as powder melting is consumed. Problems such as the necessity of physical means are expected. As a result of various investigations in consideration of these problems, the inventors of the present invention have made it clear that (1) the microspheres are already fine and fine and have a large surface area, so that the microspheres and the solvent are contacted. By using this method, it is possible to efficiently transfer the encapsulated substance inside the shell to the solvent outside the shell and recover it using a concentration gradient without damaging the shell, and (2) the microspheres obtained after recovery Found that they are novel microspheres etc., and reached the present invention.

That is, the method for recovering the inclusion substance according to the present invention comprises: an outer shell made of a thermoplastic resin; and microspheres composed of an inclusion substance which is contained therein and has a boiling point lower than the soft point of the thermoplastic resin. A method comprising the step of contacting with a solvent. The method for recovering the inclusion substance of the present invention is preferably a method further comprising a separation step of recovering the inclusion substance from the mixture obtained in the contacting step, and it is more preferable to carry out the separation step together with the contacting step. .

The novel microspheres according to the present invention can be obtained after the above-mentioned transversal step in the above-mentioned method for recovering an inclusion substance, and the thermoplastic resin is used as an outer shell. BEST MODE FOR CARRYING OUT THE INVENTION

First, a microsphere containing an inclusion substance used in the present invention will be described.

[Microsphere]

The microspheres used in the present invention are microspheres composed of an outer shell made of a thermoplastic resin and an inclusion substance contained therein and having a boiling point lower than the soft softening point of the thermoplastic resin. Ru.

The inclusion rate of the inclusion substance contained in the microspheres is not particularly limited, but it is preferably 5% or more, more preferably 15% or more, from the viewpoint of enhancing the working efficiency when recovering the inclusion substance. , Particularly preferably 30% or more.

The inclusion rate of the inclusion substance (hereinafter also referred to as the inclusion rate of the foaming agent) is a value representing the percentage of the weight of the inclusion substance contained in the microspheres to the weight of the microspheres.

The microspheres used in the present invention are roughly classified into thermally expandable microspheres and thermally expanded microspheres (obtained by thermally expanding the thermally expandable microspheres). These are described in detail below. a. Thermally expandable microspheres

The thermally expandable microspheres are composed of an outer shell made of a thermoplastic resin and an inclusion substance which is contained therein and has a boiling point lower than the softening point of the thermoplastic resin, and the inclusion substance acts as a foaming agent. The thermally expandable microspheres are thermally expandable as a whole.

(The property in which the whole microsphere swells due to the heat of calorific) is shown. In the following description, the inclusion substance and the foaming agent are used synonymously.

The blowing agent is not particularly limited as long as it is a substance having a boiling point equal to or lower than the softening point of the thermoplastic resin, and, for example, hydrocarbons having 1 to 12 carbons and their halides; fluorine-containing compounds; And compounds which generate a gas by thermal decomposition by heating such as azodicarbonamide. These foaming agents may be used alone or in combination of two or more.

Carbon number :! Examples of the hydrocarbon of 1 to 12 include pronone, cyclopropane, propylene, butane, normal butane, isobutane, cyclobutane, normolepentene, cyclopentane, isopentane, pentane, nonolemanolehexane, isohexane, and the like. Examples thereof include hydrocarbons such as sun, cyclohexane, heptane, cycloheptane, octane, isooctane, cyclooctane, 2-methylpentane, 2,2-dimethylbutane, and petroleum ether. These hydrocarbons may be linear, branched or alicyclic and are preferably aliphatic.

Examples of the halide of hydrocarbon having 1 to 12 carbon atoms include methyl chloride, methylene chloride, chloroform, carbon tetrachloride and the like. These halides are the above-mentioned charcoal It is preferable that it is a halide of fluoride (fluoride, chloride, bromide, fluoride, etc.).

The fluorine-containing compound is not particularly limited. For example, a compound having an ether structure, containing no chlorine atom and bromine atom, and having 2 to 2 carbon atoms: L 0 is preferred. Specifically, C ₃ H ₂ F ₇ OCF ₂ H, C ₃ HF ₆ OCH ₃ , C ₂ HF ₄ OC ₂ H ₂ F ₃ , C ₂ H ₂ F ₃ CC ₂ H ₂ JT ₃ ,

C ₃ H ₂ F ₅ O ₂ H ₃ JT ₂ , ₃ HF ₆ O ₂ H ₂ r ₃ , C ₃ H ₃ F ₄ OCHF ₂ , C ₃ HF ₆ O C ₃ H ₂ F ₅ , C ₄ H ₃ F ₆ o CHF ₂ , C ₃ H ₃ F ₄ o C ₂ HF ₄ , C ₃ HF ₆ OC ₃ H ₃ F ₄ , C ₃ F ₇ OCH ₃ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ and Hyde-mouth fluoroethers such as C ₇ F ₁₅ OC ₂ H _{5 and the} like. The (fluoro) alkyl group of the hydrofluoroether may be linear or branched.

The foaming agent may be composed, for example, of a fluorine-containing compound in total, but together with the fluorine-containing compound, a substance other than a fluorine-containing compound having a boiling point lower than the softening point of thermoplasticity is used in combination. It is also good. Such substances are not particularly limited, and can be selected from those exemplified as the above-mentioned blowing agents, for example. Substances other than fluorine-containing compounds can be selected as appropriate depending on the thermal expansion region of the thermal expansion I “raw microspheres”.

The proportion of the fluorine-containing compound in the blowing agent is preferably more than 50% by weight of the entire blowing agent, 80% by weight. It is more preferable that the ratio is more than ₀ , particularly preferably more than 95% by weight. As the weight proportion of the fluorine-containing compound in the foaming agent is higher, the physical properties of the fluorine-containing compound are reflected on the thermally expandable microspheres, and the physical properties such as flame retardancy and non-combustibility are imparted to the thermally expandable microspheres. it can.

The thermally expandable microspheres are made of, for example, a thermoplastic resin obtained by polymerizing a monomer mixture containing a radical polymerizable monomer, and by appropriately blending a polymerization initiator with the monomer mixture, The outer shell of thermally expanded green microspheres can be formed.

Examples of radically polymerizable monomers include, but are not particularly limited to, ditrinotrile monomers such as atalilonitrile, methatalilonitrile, α-chloroacrylonitrile, α-ethoxyacrylonitrile, fumaronitrile etc. Body: Carboxyl group-containing monomers such as atalic acid, metatthallic acid, itaconic acid, maleic acid, fumaric acid and citraconic acid; Vinylidene chloride; Bielyl acetate; Methyl (meth) acrylate, ethyl (meth) aq relay N-Butyl (meth) acrylate, isobutyl (meth) acrylate, t-butynore (meth) acrylate, isobornyl (meth) atalylate, vicinal hexyl (meth) atalylate, benzyl (meth) acrylate, 3 -(Meth) atalinoleate based monomers such as carboxy ethyl acrylate; styrene based monomers such as styrene, α-methylstyrene, crorostyrene and the like; acrylamides, substituted acrylamides, methacrylates, substituted methacrylamides Acrylamide-based monomers such as, for example, maleimide-based monomers such as フ -phenyl- maleimide, Ν- (2 _ 口口 -bi-no-le) maleimide, Ν-cyclohexyl maleimide, Ν- lauryl maleimide and the like Can be mentioned. With respect to the carboxyl group-containing monomer, part or all of the carboxyl groups may be neutralized during polymerization.

These radically polymerizable monomers may be used alone or in combination of two or more. Among these, the monomer mixture is a 2-tolyl monomer, a (meth) atalinoleic acid ester monomer, a carboxyl group-containing monomer, a styrenic monomer, acetate, and vinyl chloride and vinyl chloride. A monomer mixture containing at least one radically polymerizable monomer selected from diidene is preferred. In particular, heat resistance can be imparted when the monomer mixture is a monomer mixture containing a tolyl monomer as an essential component, and thus preferred. The weight ratio of the nitrile monomer is preferably 80% by weight or more, more preferably 90% by weight or more, particularly preferably 9% by weight or more, in consideration of the heat resistance with respect to the monomer mixture. It is 5% by weight or more.

In addition, when the monomer mixture is a monomer mixture containing a carboxyl group-containing monomer as an essential component together with the tolyl monomer, heat resistance can be imparted and the thermally expandable microspheres can be expanded. The thermally expanded microspheres obtained by the present invention can be produced so as to have a residual power capable of re-expansion, and 90.degree. C. or higher (preferably 100.degree. C. or higher, more preferably 1). It is further preferable because re-expansion can be set to start at a temperature of 20 ° C. or higher). The weight ratio of the tolyl monomer is to adjust the retention and foamability of the encapsulated foaming agent, and to adjust the re-expansion start temperature of the thermally expanded microspheres, and to evaluate the internal pressure high-speed running performance etc. considering, for the monomer mixture, preferably 2 0-9 5 weight ^_0/0, more preferably from 2 0 to 8 0 wt ^_0/0, more preferably 2 0-6 0 weight ⁰ / ₀ , particularly preferably 20 to 50 double %, Most preferably from 20 to 40% by weight. In addition, the weight ratio of the carboxyl group-containing monomer can be adjusted by adjusting the re-expansion start temperature of the thermally expanded microspheres, normal internal pressure high-speed running performance evaluation, and the inclusion retention rate of the incorporated foaming agent and TO foam In view of the properties and the like, it is preferably 5 to 80% by weight, more preferably 20 to 80% by weight, based on the monomer mixture. / ₀ , more preferably 40 to 80 weight. / _0, a 5 0-8 0 weight ^_0/0 properly favored particularly, most preferably 6 0-8 0 weight ^_0/0.

When the monomer mixture contains a carboxyl group-containing monomer as an essential component, it reacts with the carboxyl group of the carboxyl group-containing monomer as a monomer other than the carboxyl group-containing monomer contained in the monomer component. Containing monomers to be Examples of the monomer that reacts with the carboxyl group-containing monomer include: N-methylol nore (meth) acrylic amide, N, N-dimethyoleaminoethynole (meth) acrylic acid, N, N -Dimethylaminopropyl (meth) acrylate, magnesium mono (meth) atalylate, zinc mono (meth) atarylate, bulidyl glycidyl ether, propanyl dalysicinole ether, glycidyl (meth) atalylate, 2-hydroxyethyryl (Meth) atalylate, 2-hydroxypropyl (meth) atarylate, 2-hydroxyl-peptil (meth) atalylate, 2-hydroxy-1-phenoxypropyl (meth) acrylate and the like. The weight ratio of the monomer reactive to the carboxyl group of the carboxyl group-containing monomer, the monomer mixture is preferably from 0.1 to 1 0 weight ^_0/0, more preferably 1-8 weight ^_0/0, most preferably 3-5 wt ^_0/0.

The monomer mixture may contain, in addition to the above-mentioned radically polymerizable monomer, a polymerizable monomer (crosslinking agent) having two or more polymerizable double bonds. By polymerization using a crosslinking agent, the content of the microspheres contained in the thermally expanded microspheres obtained by the present production method is reduced, and the retention of the encapsulated foam after thermal expansion (including The decrease in retention rate is suppressed, and thermal expansion can be performed effectively.

In the present invention, the retention ratio (%) of the foaming agent after thermal expansion is the thermal expansion obtained by thermal expansion, with the inclusion rate of the foaming agent encapsulated in the thermally expandable microspheres before expansion. were the encapsulation efficiency of the microspheres contained a blowing agent When G _2, defined by G s / G ^ 1 0 0 . The crosslinking agent is not particularly limited, but, for example, aromatic diaryl compounds such as dibutylbenzene and divinylnaphthalene; metatalinoaryl acid, triarylthiomalonole, triarylisocyanate, ethylene glycol di (meth) arylates Diethylene diglycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) atalylate, 1, 9 nonandiol di (meth) atalylate, 1, 10- Decanediol di (meth) atalylate, PEG # 200 di (meth) acrylate, PEG # 400 di (meth) acrylate, PEG # 600 di (meth) acrylate, neopentyl glycol di (meth) acrylate 1, 4-butanedioresi methacrylate, 1, 6, 1-hexanedio reg ) Athalylate, 1,9 Nonanediol Di (meth) atalylate, Trimethylolpropane Trimethacrylate, Glycerin Dimetatalylate, Dimethylolone Noltricyclodecandylate Acrylate, Pentaerythritol Tonoretotri (Meth) Acrylate, Pentaerythritol Tritetramer Clearate, Dipentaerythritol Hexaacrylate, Neopentyl Glycol Benzoate, Trimethylol Propane Linoleate Benzoate, 2-Hydroxy- 1-Acryloyl xylpropyl methacrylate, Hydroxypipalic Acid Di (Meth) atari such as neopentyl glycol diacrylate, ditrimethylolpropane tetraatarylate, 2-butynore 2-ethynore 1, 3-propanediol diatalylate, etc. As possible de be given over door compound. These crosslinking agents may be used alone or in combination of two or more.

The weight ratio of the crosslinking agent is not particularly limited, but in view of the degree of crosslinking, the retention rate of the blowing agent contained in the outer shell, the heat resistance! Preferably, it is 0.01 to 5% by weight, and more preferably 0.5 to 3% by weight.

There is no particular limitation on the polymerization initiator, and known polymerization initiators can be used. For example, t-butylperoxyisobutyrate, t-butylperoxydi-2-ethylenediethyl, t-hydroxynoroxy-2-ethyl-nophenol, 2,5-dimethinole-2,5-bis (2-Ethyl hexano reperoxy) Hexane, 1,1,3,3-Tetramethylbutyl propoxy 2-diethyle-hexanoate, t-Putyl peroxide pivalate, t-Hexyl peroxy Oxy bivalate, t-butyl Peroxyneodecanoate, t-hydroxyle peroxyneodecanoate, 1-hydroxyl-hydroxylone 1-methylethylperoxyneo-decanoate, 1,1,3,3-tetra Methinolole peroxyneodecanoate, Cuminole peroxyneodecanoate, di-n-propylperoxydicarbonate, di-sopropio-lepoxydicarbonate, bis (4 _ 1-butynorexic port Hexylene) peroxydicarbonate, di-sec-butynoleno, o-oxydicarbonate, di-2-ketoxeno-le-poxy dicarbonate, di 2-echinole hexoleno, Oxy dicarbonate, di-3_ methoxybutylperoxydicarbonate 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl oleooxide, stearyl paxide, Peroxyacids such as succinic acid peroxide, benzoyl peroxide and the like; 2, 2'-azobis (4-methoxy-l, 4-dimethylvaleronitrile), 2, 2'-azobisiso Butyronitrile, 2,2'-azobis (2, 4-dimethyl valeronitrinole), 2,2 'monoazobis (2-methinolepropionate), 2,2'-azobis (2-methylbutyronitrile) Aso compounds and the like can be mentioned. The polymerization initiator is preferably an oil-soluble polymerization initiator that is soluble in the radically polymerizable monomer.

The thermally expandable microspheres can be produced using various techniques used in the conventionally known method of producing thermally expandable microcapsules.

That is, a monomer mixture essentially containing a radically polymerizable monomer, optionally containing a crosslinking agent, a polymerization initiator, and a foaming agent, and the resulting mixture being a water-based compound containing an appropriate dispersion stabilizer etc. For example, a method of suspension polymerization in a suspension. · · Dispersion stabilizers in aqueous systems include colloidal silica, colloidal carbonate, magnesium hydroxide, calcium phosphate, aluminum hydroxide, ferric hydroxide, calcium sulfate, sodium sulfate, calcium borate, calcium carbonate, Examples include barium carbonate, magnesium carbonate, and alumina sol. Dispersion stabilizers are preferably used in a proportion of 0.1 to 20% by weight, based on the monomer mixture. In addition, dispersion stabilization aid for dispersion type polymers such as condensation products of diethanolamine and aliphatic dicarboxylic acid, gelatin, polyvinylinolepyrollidone, methyl cellulose, polyethylene oxide, polyvinyl alcohol etc. Agent, Kanolekiltrimethylan chloride Cationic surfactants such as monium and sodium dialkyldimethyl ammonium, anionic surfactants such as alkyl sulfate sodium and the like, alkyl dimethyl amino acetate betaine, alkyl dihydroxy amino acetate betaine and the like It is also possible to use various emulsifying agents such as organic surfactants. Dispersion stabilizers are preferably used in a proportion of 0.5 to 5% by weight, based on the monomer mixture.

The aqueous suspension containing the dispersion stabilizer is prepared by blending the dispersion stabilizer, the dispersion stabilizer adjuvant and the like in water (for example, ion exchanged water). The pH of the aqueous suspension at the time of polymerization is appropriately determined depending on the type of dispersion stabilizer and dispersion stabilizer adjuvant used. In addition, a water-soluble reducing agent may be added to the aqueous suspension to suppress the formation of aggregated microspheres during polymerization. Examples of the zk-soluble reducing agent include sodium nitrite, lithium nitrite and other metal salts such as lithium nitrite, stannous chloride, stannous chloride, ferrous chloride, ferric chloride, and sulfuric acid. Iron, water-soluble ascorbic acid and the like can be mentioned. Among these, alkali metal nitrites are preferable in terms of stability in water. The addition amount thereof is preferably from 0. 0 0 0 !! to 1% by weight, more preferably from 0. 0 0 0 3 to 0. 1% by weight with respect to the monomer mixture. The polymerization temperature may be set freely according to the type of polymerization initiator, preferably in the range of 40 to 100 ° C., more preferably 4 to 90 ° C., particularly preferably 50 to 85 ° C. Controlled by The initial pressure of polymerization is in the range of 0 to 5.0 MPa, more preferably 0.1 to 3.0 MPa, and particularly preferably 0.2 to 2.O MPa in gauge pressure. The obtained thermally expandable microspheres have good foaming performance, can be filled into an assembly of a tire and a rim, and can exhibit sufficient performance of ^ used as a tire internal pressure imparting material. From the viewpoint that the thickness of the thermoplastic resin which is the shell of the green and green microspheres can secure the inclusion retention rate of the incorporated foaming agent, the foaming agent is 2 to 8 of the whole of the thermally expandable microspheres. % By weight, preferably 5 to 60% by weight. It is adjusted to be / ₀ , more preferably 7 to 50% by weight. In particular, ^^ foaming agent comprises fluorine-containing compound, preferably 1 0-6 0% by weight, more preferably 1 5-5 0 weight ^_0/0.

The average particle size of the thermally expandable microspheres is not particularly limited because it can be freely designed according to the application, and is preferably 1 to 100 μπμ, more preferably 2 to 8 It is μμπ 特に, particularly preferably 5 to 60μπι.

In addition, the coefficient of variation cv of the thermal expansion! ■ raw microspheres particle size distribution is not particularly limited, but is preferably Or 30% or less, more preferably 27% or less, and particularly preferably 25% or less. The coefficient of variation CV is calculated by the following formulas (1) and (2).

CV = (s / <X »X 1 0 0 (%) · · · (1) s = {∑ (x-<x» V (n-1)) ^1/2 ·, · (2) (wherein formula , S is the standard deviation of particle size, x> is the average particle size, xi-th particle size, n is the number of particles.)

The thermally expandable microspheres may be added or modified with components other than the shell and the inclusion substance. For example, it is preferable to use a fine particle filler attached to the outer surface of the outer shell of the thermally expandable microspheres from the viewpoint of improving the dispersibility and the flowability at the time of use.

The fine particle filler may be either an organic or inorganic filler, and the type and amount thereof are appropriately selected according to the purpose of use.

Examples of organic fillers include: metal stearates such as magnesium stearate, stearic acid strength / resium, stearic acid narrow mouth, barium stearate, lithium stearate and the like; polyethylene wax, lauric acid amide, myristic acid amide, normitin And synthetic powders such as acid amide, stearic acid amide and hydrogenated castor oil; resin powder such as polyacrylamide, polyimide, nylon, polymethyl methacrylate, polyethylene, polytetrafluoroethylene and the like.

As the inorganic filler, those having a layered structure, for example, talc, myon, bentonite, sericite, carbon black, molybdenum disulfide, tungsten disulfide, graphite fluoride, calcium fluoride, boron nitride, Etc .; Other, Silica, Anolemina, Cloud Mother, Carbonate Licum, Hydroxide Hydroxide, Calcium Phosphate, Magnesium Hydroxide, Magnesium Phosphate, Magnesium Sulfate, Parium Sulfate, Titanium Dioxide, Zinc Oxide, Ceramic Beads, Glass Beads, Crystal Beads Can be mentioned.

These particulate fillers may be used alone or in combination of two or more.

Among the above, the particulate filler attached to the outer surface of the outer shell has a melting point of 90 ° C. or higher (preferably 100 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 12 ° C.). With a melting point of at least 0 ° C., particularly preferably at least 150 ° C., most preferably at least 200 ° C. Organic compounds or inorganic compounds having a layered structure (preferably at least one selected from carbon black, molybdenum disulfide, tungsten disulfide, fluorinated graphite and boron nitride), that is, It is preferable that it is a thermal adhesion inhibitor. Here, the thermal fusion preventing agent prevents thermal fusion of the shell resin of the thermally expandable microspheres and Z or the thermally expanded microspheres, and further, the thermal expansion adjacent to the thermally expanded [] green microspheres And prevent thermal fusion with Z or thermally expanded microspheres, thereby reducing foaming performance, thereby serving to expand the thermally expandable microspheres, for example. When a thermally expanded microsphere having a re-expanding capacity is filled inside the assembly of a tire and a rim, even if the tire is injured and the tire internal pressure is reduced, the tire injured portion is rapidly sealed. The tire can exert a high internal tire pressure application function, and as a result, it is possible to travel the necessary distance even in a damaged tire.This effect is particularly remarkable when the foaming agent contains a fluorine-containing compound: ^ is there.

Also, in the case of thermally expandable microspheres using a thermoplastic resin obtained by polymerizing a monomer mixture containing, as essential components, a tolyl monomer and a force propoxy group-containing monomer as the outer shell, In addition to being able to exhibit good performance in heat resistance and flame retardancy (incombustibility), it is obtained by expanding the raw microspheres, and it is obtained by expanding the raw microspheres, and it has thermal expansion that has the ability to re-expand. The microspheres can be re-expanded at a temperature of 90 ° C. or more (preferably 100 ° C. or more, more preferably 120 ° C. or more), and the above-mentioned effect becomes remarkable.

The average particle size of the particulate filler is preferably not more than 1/10 of the thermal expansion before adhesion [· and the average particle size of the raw microspheres. Here, the average particle size means the average particle size of one flame particle.

The amount of adhesion of the particulate filler to the thermally expandable microspheres is not particularly limited, but the function of the particulate filler can be sufficiently exerted, and in consideration of the size of the true specific gravity of the thermally expandable microspheres, etc. Preferably 0.1 to 95% by weight, more preferably 0.5 to 60% by weight, based on the weight of the heat-expandable microspheres. / _0, and particularly preferably 5 to 5 0 wt%, and most preferably 8-3 0% by weight.

Thermal expansion 1. The adhesion of the particulate filler to the outer surface of the green microspheres can be carried out by mixing the green microspheres and the particle filler. Thermal mixing is not particularly limited. Can be carried out using an apparatus with a very simple mechanism such as a container and a stirring panel. Can. Moreover, you may use the powder mixer which can perform general rocking | fluctuation or stirring. As a powder mixer, for example, a powder mixer capable of rocking stirring or stirring such as a ribbon mixer, a vertical screw mixer and the like can be mentioned. Also, in recent years, a combination of stirring devices has made it possible to use a highly efficient powder mixer, such as Spir permixer (Kata Co., Ltd.) and Hi-Speed Mixer (Fukae Co., Ltd.). Neugram Machine (manufactured by Seishin Enterprise Co., Ltd.) may be used.

The thermally expandable microspheres are, for example, filled in the inside of an assembly of a tire and a rim as it is, and are expanded by heating at a temperature higher than the expansion start temperature of the thermally expandable microspheres, and used as a volume retaining material. be able to. In addition, it may be used as a filler for reducing the weight of paints in automobiles, etc., foam particles for foam ink for wallpaper and clothes decoration, or foam material for resin compositions for light weight.

Next, thermally expanded microspheres will be described.

b. Thermally expanded microspheres

Thermally expanded microspheres are obtained by thermally expanding the thermally expandable microspheres described above. There is no particular limitation on the method of producing the thermally expanded microspheres! / As long as it is a manufacturing method including the step of heating and thermally expanding I "raw microspheres, there is no particular limitation, and conventionally known methods may be used. Among the methods S that can be applied, in particular, the following two methods can be mentioned as preferred methods.

(A) A gaseous fluid containing the heat-expanded microspheres (raw material) described above is allowed to flow through a gas introduction pipe provided with a dispersion nozzle at the outlet and installed inside a hot air flow, and jetted from the dispersion nozzle. And (dispersion step) of causing the gas fluid to collide with the collision plate installed at the downstream portion of the dispersion nozzle to disperse the heat expansion microspheres in the hot air flow of ttrts (dispersion step); A step of heating and expanding thermally expandable microspheres in the hot air stream at a temperature higher than the expansion start temperature (expansion step).

(B) A gaseous fluid containing the thermally expandable microspheres (raw material) described above is allowed to flow through at least one gas introduction pipe provided with a dispersion nozzle at the outlet and installed outside the hot air flow, from the tfits dispersion nozzle A step of dispersing the thermally expandable microspheres into the hot air flow by spraying (dispersion step), and a step of causing the dispersed thermally expandable microspheres to heat and expand in the hot air flow above the expansion start temperature (expansion (expansion) A manufacturing method comprising the steps of In the above manufacturing method, energy efficiency is high, temperature control is easy, and almost the same thermal history can be continuously given to any of the thermal expansion microspheres serving as the raw material, and dispersion in the air flow is possible. Sex is high. For this reason, the variation of the coefficient of variation of the particle size distribution before and after S stretching is small, and the uniformity of the quality of the obtained thermally expanded microspheres (particularly, the particle size distribution and the distribution of true specific gravity) is high. That is, the formation of aggregated microspheres contained in the obtained thermally expanded microspheres can be suppressed as much as possible, and furthermore, the content of the raw material and the microspheres expanded by the force can be extremely reduced.

Further, in the above manufacturing method, by controlling the expansion condition, the obtained thermally expanded microspheres can be made to have or not have the re-expansion start temperature. It should be noted that the fact that the microspheres have a re-expansion start temperature means that the once-expanded thermally expanded microspheres have the property of still expanding thermally, and when the thermally expanded microspheres are heated, they are again thermally expanded. Means to be seen. And the temperature which starts the heat expansion is called re-expansion start temperature. Also, the fact that the thermally expanded microspheres have a re-expansion start is synonymous with the fact that the expansion rate at the maximum (re) expansion temperature is more than 100%. On the other hand, the microspheres do not have a re-expansion start temperature, which means that the microspheres are almost completely thermally expanded.

There is no particular limitation on the control of expansion conditions. For example, first, parameters such as the raw material supply rate, the hot air flow rate, and the raw material dispersion gas amount are fixed, and the hot air flow temperature (hereinafter sometimes referred to as "hot air temperature") is changed. Next, the hot air flow is changed stepwise, and while the other parameters are fixed, the raw material microspheres are expanded at each temperature, and the true specific gravity of the obtained microspheres is measured, and the hot air temperature is measured. Create a graph that plots the relationship between (X axis) and true specific gravity (y axis). In this graph, by setting a temperature range corresponding to the lowest true specific gravity (minimum value in the graph) to hot air, it is possible to manufacture the obtained thermally expanded microspheres so as not to have a re-expansion start temperature. .

Further, when producing expanded microspheres having a desired true specific gravity, the temperature is set to the hot air temperature corresponding to the desired true specific gravity in the graph. As a result, control of the S tension conditions is performed, and it is possible to produce thermally expanded microspheres having a residual power capable of re-expansion as desired.

Furthermore, when changing the raw material supply amount and z or the amount of powdery powder, the hot air flow The expansion condition is controlled by changing the temperature of the hot air or the like in consideration of the amount of heat supplied by the heat source and the total heat capacity of the thermal expansion microspheres as the raw material. For example, increase the amount of raw material dispensation and the amount of raw material dispersed air: ^ raises the hot air temperature. If you want to reduce the amount of raw material supply and the amount of dispersed gas, lower the temperature of the hot air.

According to the above manufacturing method, energy efficiency is high, temperature control is easy, and substantially the same heat history can be continuously given to any thermally expandable microspheres as a raw material. Dispersion in the Therefore, the variation of the coefficient of variation of the particle size distribution before and after expansion is small, and the uniformity of the quality of the obtained thermally expanded microspheres (particularly, the particle size distribution and the distribution of true specific gravity) is high. That is, the formation of the aggregated microspheres contained in the obtained thermally expanded microspheres can be suppressed as much as possible, and the content of the raw material and the slightly expanded microspheres can be extremely reduced.

The thermally expanded microspheres thus obtained can be used, for example, as a main member of a run flat tire. That is, by filling the thermally expanded microspheres inside the assembly of the tire and the rim, when the tire is damaged and the tire internal pressure decreases, the tire scratch seal and the Z or tire internal pressure application are applied. It can be used as a material. The average particle size of the thermally expanded microspheres is not particularly limited, and can be freely designed according to the application. For example, in consideration of the retention of the foaming agent by the outer shell, the durability of the thermally expanded microspheres, etc., preferably:! It is preferably from 10 to 100 μm, more preferably from 5 to 800 μπι, particularly preferably from 10 to 500 μι.

The content (25 ° C) of microspheres with a true specific gravity of 0.79 gZ cc or more contained in the thermally expanded microspheres can be used to recover the encapsulated substance with high efficiency, considering the uniformity of the true specific gravity, In order to obtain novel microspheres having a good shape, the content is preferably 5% by weight or less, more preferably 3% by weight or less, still more preferably 2% by weight or less, particularly preferably 1% by weight or less. The content of microspheres of 0.79 g / cc or more is determined by quantifying the sedimented component after differential gravity separation using isopropinole alcohol (specific gravity at 25 ° C .: 0.79). In the present invention, the true specific gravity is measured, for example, by using a liquid replacement method (Archimedes method) using isopropyl alcohol at a temperature of 25 ° C. for samples 0.5 to 2.O g. Here, the true specific gravity is not a value obtained by measuring the true specific gravity of one of the thermally expanded microspheres, but the true specific gravity is measured on an assembly of the thermally expanded microspheres. Mean specific gravity.

The thickness of the shell of the thermally expanded microspheres is not particularly limited, but in order to recover the encapsulated material with high efficiency and obtain novel microspheres with a good shape, it is preferable to use 0.1 to 2 0 0 preferably. More preferably 0.2 to 10 μπ, even more preferably 0.2 to 5 μπ, and particularly preferably 0.2 to 1 μm. The thickness of the outer shell is calculated from the average particle diameter of the thermally expanded microspheres, the inclusion rate of the foaming agent, and the true specific gravity measured by the liquid replacement method (Archimedes method). The calculation method is as follows.

(1) First, consider one thermally expanded microsphere having an average particle size, calculate the total volume from the average particle size, calculate the total weight from the true specific gravity, and obtain the total weight obtained and the foaming agent. The blowing agent gas weight is calculated from the inclusion rate.

(2) Then, the difference between the total weight and the blowing agent gas weight is used as the weight of the outer shell, and the volume of the outer shell is calculated from the weight of the outer shell and the specific gravity of the outer shell.

(3) Furthermore, the difference between the total volume and the volume of the shell is taken as the volume inside the shell, and the volume inside the shell is calculated from the volume inside the shell.

(4) Finally, the average particle size is divided by 2 to calculate an average particle size, and the difference between the average particle size and the size of the outer shell is calculated to calculate the thickness of the outer shell.

The thermally expanded microspheres may or may not have a re-expansion start temperature. In particular, when the thermally expanded microspheres do not have the re-expansion start 3⁄J, or even when they have the re-expansion start temperature, the re-expansion magnification of the thermally expanded microspheres is in the range of 100 to 500%. In this case, the thickness of the thermoplastic resin constituting the outer shell is small, and the inclusion substance can easily permeate the outer shell, and the inclusion substance can be recovered with high efficiency.

As the microspheres used in the present invention, the thermal expansion [the raw microspheres and the thermally expanded microspheres may be used as they are, but from the viewpoint of recovery and reuse of resources, thermal expansion Preferred are used microspheres in which the raw microspheres or the thermally expanded microspheres are used for an application.

The application is not particularly limited as long as it is an application utilizing various properties possessed by thermally expandable microspheres or thermally expanded microspheres. The above properties include, for example, design, porosity, bulkiness, anti-slipping ability, anti-shrinkage (dimensional stability), weight reduction (cost reduction), heat insulation (heat retention, cold storage), shock absorption ( Resilient resilience), soundproofness, vibration control, okada, surface modification (dampening, soft feeling added), concealability, easy peelability, etc. Can. As a specific application, when the tire is injured and the tire internal pressure is lowered by filling the thermally expanded microspheres inside the main components of the lamb rat tire (the tire-rim assembly), Additives for rubber and resin internals (add to rubber and resin, for example, foams during heat molding, etc.) Can be mentioned. Next, the method of recovering the inclusion substance in the microspheres described above will be described in detail.

[Method for recovering contained substances]

The method for recovery of the inclusion substance of the present invention is a method including a contacting step of bringing the microspheres and the solvent described above into contact with each other.

The solvent used in this contact step is not particularly limited as long as it is a liquid, but generally, the degree of polarity of the solvent, the type of thermoplastic resin constituting the outer shell of the microspheres, and the operability in the separation step described later It is selected in consideration of etc.

Examples of the solvent include: water; alcohols such as methanol, ethanol, propanol, ethylene glycol and glycerol; ethers such as propyl ether, butyl ether, pentyl ether and hexenoare tenoleate; methyl formate, ethyl formate and propyl formate And esterones such as butyl formate, methyl acetate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate; acetone, methyl ethyl ketone, sic anhydride, pinacolin And ketones such as mesithioxide; hexane, heptane, octan, nonane, decane, undecane, dodecane, dodecane, cyclohexane, and aliphatic hydrocarbons such as methylcyclohexane; benzene, tonoleene, xylene, Aromatic hydrocarbons such as norebenzene and pheninole acetylene; nitriles such as acetonitrile and propiodiitol; amides such as dimethylformamide (DMF); sulfoxides such as dimethyl sulfoxide (DMSO) It can be mentioned. These solvents may be used alone or in combination of two or more.

In the recovery method of the present invention, it is preferable to use a polar solvent because the contained substance can be recovered with high efficiency. Examples of polar solvents include 7 alcohols, ethers, esters, ketones, ditolyls, amides, sulfoxides and the like. Of these polar solvents, water and alcohols are preferred, and Water is even more preferred in light of the fact that the novel microspheres obtained by the bright recovery method retain a good shape and the isolation of inclusions is easy!

The polar solvent may be a solvent that exhibits acidity or alkalinity, but the thermoplastic resin constituting the shell of the microsphere is a monomer mixture containing an acidic monomer such as a carboxyl group-containing monomer. Tj ^ is preferably obtained when the polar solvent exhibits alkalinity, and it is further preferred that the polar solvent is water and / or alcohols (especially ethanol etc.) exhibiting alkalinity, and the recovery method of the present invention is preferred. From the viewpoint that the resulting novel microspheres retain a good shape and the isolation of the inclusion substance is easy, water showing al- toricity is particularly preferred. The polar solvent exhibits alkalinity: ^, and the pH of the polar solvent is particularly preferably 9 to 14 and more preferably 11 to 13 with respect to pH 7 of the polar solvent.

In the contacting step, the microspheres and the solvent are mixed to cause an insect. The mixing ratio of the microspheres and the solvent is not particularly limited, but in consideration of the improvement of recovery efficiency, economy and the like, the number of microspheres per liter of solvent is 0.1 to 300 g. And more preferably 10 to 200 g, and particularly preferably 10 to 100 g.

The contact time between the microspheres and the solvent in the contact step is appropriately set in consideration of the solvent, the inclusion substance, the thermoplastic resin that constitutes the outer shell of the microspheres, the workability, etc. 1 to 1000 hours.

The contact time between the microspheres and the solvent in the contacting step is appropriately set similarly to the contacting time, and is not particularly limited. However, in view of the fact that contacting the two at too low temperature is not advantageous in operation and that the boiling point of the inclusion substance is usually room temperature or slightly higher in many cases, the contact temperature is For example, −50 to: 100 ° C. The contact temperature is preferably equal to or lower than the boiling point of the contained substance.

The infestation time and contact temperature in the contacting step may be appropriately set in consideration of the thickness of the outer shell of the microspheres.

In the case where the thickness of the outer shell of the microspheres is 2 μm or more (for example, when the microspheres are heat-expandable microspheres), the contact time in the contacting step is:! The time is preferably 100 hours, more preferably 10 to 100 hours, and particularly preferably 10 to 100 hours. It is preferable that the temperature of the insects in the kneading step is 30 to 100 ° C., more preferably 50 to 100 ° C., 70 to 1 It is particularly preferable that the temperature is o o ° c. The solvent used in this case is preferably one having a boiling point equal to or higher than the contact temperature of the microspheres and the solvent, and among the solvents exemplified above, a solvent having a boiling point of 50 ° C. or more can be mentioned.

Next, in the case where the thickness of the outer shell of the microspheres is less than 2 μm (for example, in the case of the microspheres being thermally expanded microspheres), the contact time in the contacting step is The time is preferably 0.1 to 500 hours, and more preferably 0.1 to 100 hours. The contact temperature in the contact step is preferably 0 to 80 ° C. In this case, as the solvent to be used, one having a boiling point higher than the contact temperature between the microspheres and the solvent is desirable. Among the solvents exemplified above, a solvent having a boiling point of 20 ° C. or higher may be mentioned. it can.

In the method of the present invention for recovering an encapsulated substance, the encapsulated substance encapsulated in the microspheres can be recovered by bringing the microspheres into contact with the solvent. Although the action is not confirmed, it is presumed that the thermoplastic resin constituting the outer shell swells or is degraded by the solvent, and the encapsulated substance in the inner shell permeates and diffuses in the solvent according to the concentration gradient. It is preferable that the recovery method of the inclusion substance of the present invention further includes a separation step. The separation step is a step of recovering the inclusion substance from the mixture containing the microspheres and the solvent obtained in the contact step.

The separation step may be performed together with the insecticidal step or may be performed after the contact step, but by carrying out the separation step together with the contact step, the inclusion substance can be separated and recovered in a short time.

The specific means for carrying out the separation step is not particularly limited, and examples thereof include distillation separation, extraction separation, centrifugation, adsorption separation and the like of the inclusion substance.

Distillation is a method of separating and recovering an encapsulated substance using the difference in boiling point between the encapsulated substance and a solvent. The difference in boiling point is preferably larger in order to increase the working efficiency. The boiling point difference is, for example, preferably 5 ° C. or more, more preferably 10 ° C. or more, and particularly preferably 20 ° C. or more. In distillative separation, the inclusion substance is once steamed and liquefied and separated by a cooling device, but in consideration of the fact that the boiling point of the inclusion substance is usually at room temperature or slightly higher, the cooling device It is preferable to control the temperature of the refrigerant used for the shellfish β of the inclusion substance contained in the solution low. The temperature of the refrigerant and the boiling point of the substance contained The degree difference is, for example, preferably 30 ° C. or more, more preferably 50 ° C. or more, and particularly preferably 100 ° C. or more.

Extraction separation and centrifugation are methods of separation and recovery using the property that phase difference between the inclusion substance and the solvent occurs. In the case of extraction separation or centrifugation, as the solvent, one having a property of phase separation when mixed with the inner packing material is preferable. Examples of the solvent include water; alcohols such as methanol and ethanol, and the like. The phase is not easily separated by extraction and separation, and centrifugation may be performed to separate the inclusion substance and the solvent from each other. The inclusion substances separated in phase by extraction separation and centrifugation are separated and recovered through a separation operation such as decantation.

P and separation is a method of capturing and recovering airborne substances by adsorption duet using an adsorbent such as activated carbon. The substance trapped in the adsorption unit is desorbed by steam and regenerated, and it is recovered by freezing and cooling.

In the contacting step and the separating step, the mixture containing the microspheres and the solvent may or may not be stirred, but when stirred, the contact efficiency of the microspheres and the solvent increases. it is conceivable that. The stirrer used for the stirring is not particularly limited, and examples thereof include common stirrers such as homomixers and line mixers. There is also no particular limitation on the stirring speed.

There are no particular limitations on the pressure atmosphere in carrying out the contact step and the separation step, and the reaction may be carried out under reduced pressure, normal pressure, or calo pressure.

Next, novel microspheres that can be obtained after the contacting step are described.

Invisible Microspheres]

The novel microspheres (hereinafter also referred to as microspheres a) of the present invention are microspheres which can be obtained after the insecticidal step in the above-mentioned recovery method, and have a thermoplastic resin as an outer shell.

Microsphere a is a novel microsphere in which a solvent is included in its outer shell instead of the inclusion substance. At least a solvent is contained in the microsphere a. The encapsulated substance remaining without being recovered may be contained together with the solvent.

Although the solvent may be removed from the mixture after the insecticidal step to dry the microspheres a, the microspheres may be handled in a liquid-wet state, considering that aggregation and fusion do not occur. Is preferred.

As the above-mentioned liquid, the solvent described in the above-mentioned recovery method can be used as it is, but depending on the use of the microsphere a, dibutyl phthalate, di-hydroxy phthalate, di-octyl azide, tricycle / le-phosphate, tri-ethyl citrate Plasticizers such as asetil ripyl citrate, octyl alcohol (when used for plastics, elastomers, sealants, paints, etc.) Monomers such as dicyclopentadiene (light-weight foams and adhesives When used for the purpose); Non-ionic surfactant, alkylene glycol alcohol, polyalkylene glycol, glycerin, silicone oil, liquid paraffin, fats and oils, etc. may be used as a liquid. By replacing the solvent in the mixture after the contacting step with a liquid, it is possible to make the microspheres a in a liquid-wetted state.

There is no particular limitation on the average particle size of the microspheres a, but when the microspheres a are in a wet state, preferably:! It is -1000 m, more preferably 5 to 800 μm, particularly preferably 10 to 500 πι, and most preferably 1 to 150 μπι.

The true specific gravity of the microsphere a! There is no particular limitation, but when the microspheres a are in a dried state, they are preferably in the range of 0.51 to 1.5 g Zcc, more preferably in the range of 0.10 to 1. O g / cc, particularly preferably 0. It is 0.001 to 0.8 g / cc.

For the application of the microsphere a, the application utilizing the various properties possessed by the above-mentioned thermally expandable microspheres and the thermally expanded microspheres, and the application utilizing the fact that the microspheres a are in the form of minute particles There is no particular limitation as long as The microsphere a may be used as a filler for resin and other materials, for example, for fillers such as extruded cement-molded articles, sealants, resin clay fillers, and ceramic siding. Reinforcing Filler, Reinforcing Filler of Wood Plate 研磨, Abrasive for hand-washing stone and detergent for business use, Anti-blocking agent, Smoothing agent, Lightweight aggregate substitute, Pore-forming agent, Fluidizer, Dust prevention Agents, greening accelerators, and anti-forensic agents. Example

The present invention will be described in detail by the following examples and comparative examples, but the present invention is not limited to these examples. (Measurement method and definition)

[Measurement of average particle size and particle size distribution]

A laser diffraction ^ degree distribution measuring apparatus (SYMPATEC 3⁄4 MH EROS & RODOS) was used as a measuring apparatus. The dispersion pressure of the dry dispersion unit was 5. O bar, the degree of vacuum was measured by the dry measurement method at 5.0 mbar, and the D50 value was defined as the average particle size. [Measurement of true specific gravity]

The true specific gravity was measured by a liquid replacement method (Archimedes method) using isopropinole alcohol at a temperature of 25 ° C.

[Measurement of moisture content of thermally expandable microspheres]

As a measurement device, measurement was performed using a Karl Fischer moisture meter (MKA-5 10 N, Kyoto Electronics Co., Ltd. ± 3⁄4).

[Measurement of inclusion rate of foaming agent enclosed in thermally expandable microspheres]

1. 0 g of thermally expandable microspheres were placed in a stainless steel evaporation dish with a diameter of 80 mm and a depth of 15 mm, and their weight D was measured. After 30 ml of acetonitrile, the mixture was dispersed uniformly and allowed to stand at room temperature for 30 minutes, and then heated at 120 ° C. for 2 hours to measure the weight after drying (W ₂ ). The inclusion rate of the blowing agent is calculated by the following equation.

Encapsulation efficiency _{_{(wt%) = (W x -W 2}} ) (g) / 1. 0 (g) X 1 00- ( water content) (Weight ^_0/0)

(In the formula, the moisture content is measured by the above method.)

[Inclusion retention rate]

The encapsulation retention rate of the foaming agent is a ratio of the encapsulation rate of the foaming agent before expansion (GJ to the encapsulation rate (G ₂ ) of the foaming agent after expansion, and is calculated by the following equation.

Inclusion retention rate (%) = Q ₂ / G _X 1 00

[Measurement of (re) expansion start and maximum (re) expansion]

As a measuring device, DMA (DMA Q 800, manufactured by TA instr ume nts) was used. Thermal expansion I “raw microspheres are thermally expanded microspheres) 0.5 mg in an aluminum cup with a diameter of 6. O mm, depth of 4. 8 mm, and a diameter of 5.6 mm, a thickness of 0.1 mm on it. The sample lid was placed with an aluminum lid, and the sample height was measured while applying a force of 0.10 N from the top of the sample by a calo indenter. The sample was heated from 20 to 300 ° C. at a heating rate of 10 ° C./min, and the amount of displacement of the calo indenter in the vertical direction was measured. The displacement start temperature in the positive direction was taken as the (re) expansion start temperature, and the temperature at which the maximum displacement (H ₂ ) was shown was taken as the maximum (re) expansion temperature. The (re) expansion coefficient (E) at the maximum (re) expansion temperature is calculated by the following formula.

E (%) = H ₂ / H ₁ x 100

Production Example 1

After adding 150 g of sodium chloride, 3. 3 g of adipic acid-diethanol amine condensate, 20 g of colloidal silica (active ingredient: 20%) and 0.15 g of sodium nitrite to 500 g of ion-exchanged water It was mixed uniformly to make it the water phase.

200 g of Atarilonitrinole, 45 g of Methacrylonitrile, 75 g of Methacrylic Acid, 1.2 g of Trimethylolpropane trimethacrylate, 2.0 g of Azabisisobutyronitril and C ₃ F ₇ OCH ₃ The substance and the foaming agent (150 g) were mixed, stirred and dissolved to obtain an oil phase.

The aqueous phase and the oil phase were mixed, premixed at 3,000 rpm for 2 minutes with a homomixer, and stirred at 10,000 rpm for 2 minutes to obtain a suspension. It was transferred to a reactor, purged with nitrogen and then polymerized at 61 ° C. for 20 hours while stirring. After polymerization, the polymerization product was filtered and dried to obtain the obtained thermal expansion [Mixed microspheres as microspheres 1. The ignition source was brought close to the thermally expandable microspheres but it did not burn.

Production Example 2

The microspheres 1 obtained in Production Example 1 were thermally expanded by the method for producing the thermally expanded microspheres described above (production method (A) to produce the thermally expanded microspheres. The small spheres were filled in the hollow portion of the assembly of the tire and the rim, and used as a member of a run flat tire The running test of the run flat tire was carried out, and the thermally expanded microspheres after the test (thermal expansion after running test) The obtained microspheres are hereinafter referred to simply as “microspheres 2” and their physical properties are measured. The average particle diameter is 90 μm, true specific gravity 0.228 g Zcc, inclusion rate 32%, inclusion retention rate 98%, re-expansion start 132 ° C, maximum re-expansion temperature 202 ° C, re-expansion ratio 211%, true specific gravity 0.79 g / cc or more of content of microspheres (25 ° C) is 0.8 weight ./.Met. Production Example 3

The heat-expanded microspheres obtained by polymerizing in the same manner as in Preparation Example 1 were changed to microspheres 3 except that 64 g of isopentane was used as the inclusion substance in place of C ₃ F ₇ OCH ₃ 15 Og in Preparation Example 1. .

Production Example 4

The microspheres 3 obtained in Production Example 3 were thermally expanded in the same manner as in Production Example 2 to produce thermally expanded microspheres (microspheres 4).

Production Example 5

Production Example 1 A super mixer (micro mixer 1) was prepared with Microsphere 1 and carbon black (Lion stock company ring, product name: Ketjen black ECP 600 JD, average particle size: 34 nm) in a weight ratio of 9: 1. The mixture was uniformly mixed using Kaita Co., Ltd. to obtain thermally expanded microspheres in which carbon black adhered to the outer surface. The obtained thermally expandable microspheres were thermally expanded in the same manner as in Production Example 2 to produce thermally expanded microspheres (microspheres 5). [Example 1]

The microsphere 2 obtained in Production Example 2 was weighed out at 0.05 g, mixed and dispersed in 20 mL of ethanol. The resulting mixture was left overnight in a refrigerator and then extracted with hexane. The obtained hexane phase was analyzed by gas chromatography (GC 17 A, manufactured by Shimadzu Corporation), and C ₃ F ₇ OCH ₃ was detected.

The same operation as described above was performed by replacing the ethanol used above with acetonitrile, toluene, dimethylformamide, weakly alkaline water (pH 9) and strongly alkaline water (pH 12), respectively. In each, C ₃ F ₇ OCH ₃ was detected.

[Example 2]

40 g of the microspheres 2 obtained in Production Example 2 were weighed, and 1 L of ethanol was mixed and dispersed for 10 minutes using a homomixer. The resulting mixture was supplied to a 2 L eggplant-shaped flask and distilled under atmospheric pressure with the heat source for heating the flask set to 40 ° C. This distillation operation is carried out for 30 minutes, and the distillate (7.7 mL) collected in a condenser cooled with liquid nitrogen is analyzed by gas chromatography to confirm that it is C ₃ F ₇ OCH ₃ and recovered. The rate was 90%. In addition, new microspheres were obtained after recovery.

[Example 3] A C ₃ F ₇ OCH ₃ was recovered in the same manner as in Example 2 except that strong alkaline water (p H 12) was used instead of ethanol in Example 2 above. The recovery rate was 90%. In addition, the new microspheres obtained after recovery retained spherical shape, and strongly alkaline water was contained in the outer shell.

[Example 4]

40 g of the microspheres 3 obtained in Production Example 3 were weighed, and 1 L of ethanol was mixed and dispersed for 10 minutes using a homomixer. The resulting mixture was supplied to a 2 L eggplant-shaped flask and distilled under atmospheric pressure with the heat source for heating the flask set to 30 ° C. This distillation operation was carried out for 30 minutes, and the distillate (22 mL) collected in a condenser cooled with liquid nitrogen was analyzed by gas chromatography to confirm that it was isopentane, and the recovery rate was 91%. In addition, new microspheres were obtained after recovery.

[Example 5]

The same procedure as in Example 4 was repeated except that strong alkaline water (p H 12) was used instead of ethanol in Example 4 above to recover isopentane. The recovery rate was 91%. In addition, the new microspheres obtained after recovery retained spherical shape, and strong Alkaline water was contained in the outer shell.

[Example 6]

200 g of the microspheres 1 obtained in Production Example 1 were weighed, and mixed with a homomixer and mixed and dispersed for 10 minutes with strong water (pH12). The resulting mixture was fed to a 2 L eggplant flask, and the flask was subjected to pressure distillation while setting the temperature to 80 ° C. This distillation operation is carried out for 120 minutes, and the distillate (37 mL) accumulated in the cooling tube cooled with liquid nitrogen is analyzed by gas chromatography to confirm that it is C ₃ F ₇ CHCH ₃ and recovered. The rate was 88%. In addition, the new microspheres obtained after recovery retained spherical shape, and strongly alkaline water was contained in the outer shell.

[Example 7]

200 g of the microspheres 3 obtained in Production Example 3 were weighed, mixed with a homomixer, and mixed and dispersed for 10 minutes with strong water (pHl 2). The resulting mixture was fed to a 2 L eggplant flask, and the flask was heated at a temperature of 80 ° C. and heated under atmospheric pressure. This distillation operation is carried out for 120 minutes, and the distillate collected in the cooling pipe cooled with liquid nitrogen (9 OmL) was analyzed by gas chromatography to find that it was C ₃ F ₇ OCH ₃ , and the recovery rate was 90%. In addition, the new microspheres obtained after recovery retained spherical shape, and strongly alkaline water was contained in the outer shell. The novel microspheres were dried at 40 ° C. for 20 hours, and the true specific gravity of the unframed flakes was measured and found to be 0.97 g / cc. [Example 8]

40 g of the microspheres 5 obtained in Production Example 5 were weighed, and 1 L of ethanol was mixed and dispersed for 10 minutes using a homomixer. The resulting mixture was supplied to a 2 L eggplant-shaped flask and distilled under atmospheric pressure with the heat source for heating the flask set to 40 ° C. This distillation operation is carried out for 30 minutes, and the distillate (7.7 mL) collected in a condenser cooled with liquid nitrogen is analyzed by gas chromatography to confirm that it is C ₃ F ₇ CHCH ₃ , The recovery rate was 90%. In addition, new microspheres were obtained after recovery.

[Example 9]

C ₃ F ₇ OCH ₃ was recovered in the same manner as in Example 2 except that strong alkaline water (pH 12) was used instead of ethanol in Example 8 above. The recovery rate was 91%. In addition, the new microspheres obtained after recovery retained spherical shape, and strongly alkaline water was contained in the outer shell. Industrial applicability

According to the method of the present invention for recovering the inclusion substance of the present invention, the inclusion substance can be recovered simply and efficiently from the microspheres constituted of the outer shell made of a thermoplastic resin and the inclusion substance entrapped therein.

The novel microspheres of the present invention are novel microspheres which can be obtained after recovering the inclusion substance in the above-mentioned recovery method, and which have not been known so far.

Claims

The scope of the claims

1 includes a contact step in which a solvent is brought into contact with microspheres constituted of an outer shell made of a thermoplastic resin and an inclusion substance contained therein and having a boiling point lower than the soft softening point of the thermoplastic resin. , How to recover contained substances.

2. The method for recovering the inclusion substance according to claim 1, further comprising a separation step of recovering the self-contained substance from the mixture containing the microspheres and the solvent obtained in the step of helminth.

3. The method for recovering contained substances according to claim 2, wherein the separation step is performed together with the insecticidal step.

4. The method for recovering contained substances according to claim 2 or 3, wherein the separation step is a step for separating the contained substances by distillation.

5. The method for recovering contained substances according to claim 2 or 3, wherein the separation step is a step for extracting and separating the contained substances from the mixture.

6. The method for recovering contained substances according to any of claims 5 to 6, wherein the microspheres further comprise a particulate filler attached to the outer surface of the outer shell.

7. Claim: The inclusion rate of the inclusion substance is 5% or more. A method of recovering an internal packaging material according to any one of to 6.

.. 8 the contained in microspheres, a true specific gravity of 2 5 ° C is 0 7 9 _§ Bruno <<least in § Ru microspheres content is 5 wt% or less, according to claim! A method of recovering the inclusion according to any one of 7 to 7 above.

9. The thermoplastic resin is at least one selected from a tolyl monomer, a (meth) acrylic acid ester monomer, a carboxyl group-containing monomer, a styrenic monomer, butyl acetate and vinylidene chloride. The method for recovering an encapsulated substance according to any one of claims 1 to 8, which is a resin obtained by polymerizing a monomer mixture containing one kind of radical polymerizable monomer.

10. The inner packing material according to claim 9, wherein the thermoplastic resin is a resin obtained by polymerizing a monomer mixture containing a tolyl monomer and a carboxyl group-containing monomer as essential components. Recovery method.

1 1 · The inclusion substance has an ether structure and contains chlorine and bromine atoms, The method for recovering contained substances according to any one of claims 1 to 10, wherein the method comprises at least a fluorine-containing compound having 2 to 10 carbon atoms.

1 2. Claim: The solvent is a polar solvent! A method of recovering an encapsulated substance according to any one of 1 to 11.

13. The method for recovering an inner packing material according to claim 12, wherein said polar solvent is ethanol and / or water.

14. The method for recovering an encapsulated substance according to claim 12, wherein the polar solvent is a solvent exhibiting alkalinity.

The method for recovering the inclusion material according to any one of claims 1 to 14, wherein the microspheres are microspheres filled in the hollow portion of an assembly of a tire and a rim.

1 6 Claim:! 15. The method for recovering an encapsulated substance according to any one of 15 to 15, which can be obtained after the contacting step, and the thermoplastic resin is an outer shell, novel microspheres.

17. The novel microspheres of claim 16, wherein the solvent is contained within the shell.

18. The novel microspheres according to claim 16 or 17 which are in a liquid-wetted state.