CN116635478A - Polycarbonate-containing slurry composition - Google Patents

Polycarbonate-containing slurry composition Download PDF

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Publication number
CN116635478A
CN116635478A CN202280008586.9A CN202280008586A CN116635478A CN 116635478 A CN116635478 A CN 116635478A CN 202280008586 A CN202280008586 A CN 202280008586A CN 116635478 A CN116635478 A CN 116635478A
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solvent
slurry composition
polycarbonate
inorganic material
oxide
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小暮望
藤野匠
高桥直子
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Sumitomo Seika Chemicals Co Ltd
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Sumitomo Seika Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63464—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62625—Wet mixtures
    • C04B35/6264—Mixing media, e.g. organic solvents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention provides a slurry composition comprising polycarbonate that exhibits high inorganic material dispersibility. More specifically, provided is a slurry composition comprising an inorganic material (A), a polycarbonate (B), a dispersant (C) and a solvent (D), wherein the solvent (D) is separated from the inorganic material (A) by a Hansen solubility parameter distance of 1 to 11MPa 0.5 The distance between the solvent (D) and the polycarbonate (B) is 4-8 MPa 0.5 。

Description

Polycarbonate-containing slurry composition
Technical Field
The present invention relates to a polycarbonate-containing composition (preferably a slurry composition) and the like. The contents of all documents described in the present specification are incorporated into the present specification by reference.
Background
In recent years, various products have been produced by molding and sintering slurry compositions containing inorganic materials such as conductive particles, ceramics, glass, and phosphors and a molding binder. The properties required for the binder include: to obtain a slurry composition excellent in dispersibility and storage stability of an inorganic material; the molded article produced using the slurry composition is not fragile; and the amount of carbon residue after sintering is small; etc. As the binder, polyvinyl butyral, ethylcellulose, carboxymethyl cellulose, polyvinyl alcohol, polyacrylate, polyethylene oxide, and the like are generally used. If the binder remains in the sintered body, the performance may be affected, and therefore, the degreasing step takes a lot of time and energy. Therefore, the degreasing step becomes a bottleneck in the efficiency of the production of the inorganic sintered body. Accordingly, as a binder having excellent thermal decomposition properties, polycarbonates such as polyethylene carbonate and polypropylene carbonate have been studied in recent years (for example, patent documents 1 and 2).
In addition, along with the multifunction, miniaturization, and flexibility of electronic devices, attempts have been made to make multilayer ceramic capacitors (thin ceramic green sheets) and thin metal wiring, for example, and along with this, inorganic materials have been made to be finer. As the inorganic material is miniaturized, the packing density and the surface area are increased, and thus the viscosity of the slurry composition is also easily increased, and if the viscosity is increased, the following problems are easily caused: when a molded article (for example, a sheet) is produced using the slurry composition, molding becomes difficult or dispersion failure occurs. Accordingly, development of a dispersant having more excellent dispersibility of an inorganic material and development of a slurry composition exhibiting high dispersibility of an inorganic material have been desired. In addition to designing a slurry composition, a method using an index of affinity between substances such as solubility parameter has been studied (for example, patent documents 3 and 4).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2004-010453
Patent document 2: japanese patent laid-open publication 2016-199423
Patent document 3: japanese patent laid-open publication No. 2005-116504
Patent document 4: japanese patent laid-open No. 2009-238978
Disclosure of Invention
Problems to be solved by the invention
When a slurry composition is prepared using a polycarbonate as a binder, it is difficult to obtain a good slurry composition exhibiting high dispersibility because the solvent solubility of polycarbonate is significantly different from that of conventional binders. Accordingly, a slurry composition comprising polycarbonate as a binder and exhibiting high dispersibility of inorganic materials is desired. In particular, a slurry composition exhibiting high dispersibility of an inorganic material even if a fine (e.g., submicron-sized) inorganic material is used as the inorganic material is preferred.
The present inventors have studied to provide a slurry composition containing a polycarbonate and exhibiting high dispersibility of an inorganic material, and a molded article and a sintered article produced using the slurry composition.
Means for solving the problems
The present inventors have found that a slurry composition comprising an inorganic material, a polycarbonate, a dispersant and a solvent, that is, a slurry composition having a solubility parameter between the materials in a specific range can be used as a slurry composition exhibiting high dispersibility of the inorganic material, and further repeated improvements have been made.
The present invention includes, for example, the subject matter described in the following items.
Item 1.
A slurry composition comprising an inorganic material (A), a polycarbonate (B), a dispersant (C) and a solvent (D),
the solvent (D) and the inorganic material (A) have a Hansen solubility parameter distance of 1-11 MPa 0.5 ，
The distance between the solvent (D) and the Hansen solubility parameter of the polycarbonate (B) is 4-8 MPa 0.5 。
Item 2.
The slurry composition according to item 1, wherein the solvent (D) is HanThe value of the Sendai solubility parameter is 18-25 MPa 0.5 。
Item 3.
The slurry composition according to item 1 or 2, wherein the above solvent (D) is a solvent comprising at least one compound containing a hydroxyl group.
Item 4.
The slurry composition according to any one of items 1 to 3, wherein the polycarbonate (B) is an aliphatic polycarbonate.
Item 5.
The slurry composition according to item 4, wherein,
aliphatic polycarbonates are copolymers of epoxides with carbon dioxide,
the epoxide is at least one selected from the group consisting of ethylene oxide, propylene oxide, 1, 2-butylene oxide, and cyclohexane oxide.
Item 6.
The slurry composition according to any one of items 1 to 5, wherein the dispersant (C) has a Hansen solubility parameter value of 23 to 32MPa 0.5 。
Item 7.
The slurry composition according to any one of items 1 to 6, wherein the dispersant (C) is a compound having an alkylene oxide chain structure.
Item 8.
The slurry composition according to any one of items 1 to 7, wherein the inorganic material (A) has a median diameter of 0.01 to 20 μm as measured by a laser diffraction/scattering method.
Item 9.
The slurry composition according to any one of items 1 to 8, wherein the inorganic material (A) is a ceramic.
Item 10.
The slurry composition according to item 1 to 9, wherein the polycarbonate is 1 to 30 parts by mass, the dispersant is 0.1 to 10 parts by mass, and the solvent is 10 to 400 parts by mass, based on 100 parts by mass of the inorganic material.
Item 11.
A molded article obtained by molding the slurry composition according to any one of items 1 to 10.
Item 12.
A sintered body obtained by sintering the molded article according to item 11.
Effects of the invention
It is possible to provide a composition (preferably a slurry composition) which contains an inorganic material and is excellent in thermal decomposition properties (thus enabling a sintered body to be obtained at a low energy cost) stably dispersed.
Detailed Description
Hereinafter, embodiments included in the present invention will be described in more detail. The invention preferably comprises: a slurry composition comprising an inorganic material (a), a polycarbonate (B), a dispersant (C) and a solvent (D); a molded body obtained by molding the slurry composition; and a sintered body obtained by sintering the slurry composition or the molded body. In the present specification, the slurry composition may be referred to as a slurry composition of the present invention, the molded article may be referred to as a molded article of the present invention, and the sintered article may be referred to as a sintered article of the present invention. The present invention is not limited thereto, and includes all aspects disclosed in the present specification that can be recognized by those skilled in the art.
As described above, the slurry composition of the present invention contains the inorganic material (a), the polycarbonate (B), the dispersant (C), and the solvent (D). These components contained in the slurry composition of the present invention are sometimes referred to as the inorganic material of the present invention, the polycarbonate of the present invention, the dispersant of the present invention, and the solvent of the present invention, respectively.
The Hansen solubility parameter (hereinafter also referred to as HSP) includes a dispersion term (dD), a polarity term (dP), and a hydrogen bond term (dH), and can be obtained by Hansen dissolution ball method based on the results of evaluating affinities (solubility, wettability, etc.) with a plurality of solvents, for example, using values described in Hansen Solubility Parameters:a user' shandbook, second edition, boca Raton, fla:crc press (Hansen, charles (2007)), and the like. In the present invention, the value of this document is used for the solvent, and the value obtained by hansen dissolution ball method is used for the other substances.
In the present invention, unless otherwise specified, the value calculated by the formula (1) is referred to simply as hansen solubility parameter value.
HSP＝(dD 2 +dP 2 +dH 2 ) 0.5 (1)
The hansen solubility parameter distance (hereinafter also referred to as Ra) of different substances (for example, substance 1 and substance 2) refers to a value calculated from formula (2).
Ra＝(4×(dD 2 -dD 1 ) 2 +(dP 2 -dP 1 ) 2 +(dH 2 -dH 1 ) 2 ) 0.5 (2)
In the formula, dD 1 、dP 1 、dH 1 Is a dispersion term (dD), a polar term (dP), a hydrogen bond term (dH), dD of the substance 1 2 、dP 2 、dH 2 Is a dispersion term (dD), a polar term (dP), a hydrogen bond term (dH) of substance 2.
In the present invention, the hansen solubility parameter of a substance is obtained by hansen dissolution ball method, specifically, the method is as follows. The substance (test substance) solving the hansen solubility parameters was thoroughly mixed with each test solvent. The concentration was set to 10% by volume in the case where the test substance was polycarbonate, and to 0.5% by volume in the case where the test substance was an inorganic material. After standing for 24 hours, the polycarbonate solution was visually judged as being in a dissolved state or an undissolved state, and the inorganic material solution was visually judged as being cloudy or precipitated. The "affinity" is set in the dissolved state or cloudiness, and the "no affinity" is set in the undissolved state or precipitation. Then, the respective test solvents dD, dP, dH were plotted in a three-dimensional space, and the spheres (hansen dissolved spheres) were determined so as to include a plot of the test solvent having affinity and a plot of the test solvent not having affinity, and the center points (coordinates of dD, dP, dH in the three-dimensional space) were set as values of hansen solubility parameters of the test substances. The test solvents (solvents) used and dD, dP, dH and HSP are shown in the following table (Hansen Solubility Parameters: A user's handbook, second edition. Boca Raton, fla: CRC Press (Hansen, charles (2007)).
[ Table 1A ]
Solvent name dD dP dH HSP
Hexane 14.9 0.0 0.0 14.9
Toluene (toluene) 18.0 1.4 2.0 18.2
1, 4-Dioxacyclohexane 17.5 1.8 9.0 19.8
Decyl alcohol 17.6 2.7 10.0 20.4
Acetic acid isobutyl ester 15.1 3.7 6.3 16.8
Propyl acetate 15.3 4.3 7.6 17.6
Tetrahydrofuran (THF) 16.8 5.7 8.0 19.5
Methyl isobutyl ketone 15.3 6.1 4.1 17.0
Diethylene glycol monoethyl ether acetate 16.8 6.3 15.7 23.9
N-propanol 16.0 6.8 17.4 24.6
Benzaldehyde 19.4 7.4 5.3 21.4
Ethanol 15.8 8.8 19.4 26.5
Methyl ethyl ketone 16.0 9.0 5.1 19.1
Propylene glycol 16.8 9.4 23.3 30.2
Acetone (acetone) 15.5 10.4 7.0 19.9
Ethylene glycol 17.0 11.0 26.0 33.0
Methanol 15.1 12.3 22.3 29.6
N-methyl-2-pyrrolidone 18.0 12.3 7.2 23.0
N, N-dimethylformamide 17.4 13.7 11.3 24.9
Water and its preparation method 15.5 16.0 42.3 47.8
Dimethyl sulfoxide (DMSO) 18.4 16.4 10.2 26.7
Acetonitrile 15.3 18.0 6.1 24.4
Epsilon-caprolactone 19.7 15.0 7.4 25.8
Dipropylene glycol 16.0 20.2 18.4 31.7
Thioglycollic acid 16.0 13.5 20.0 29.0
Diethylene glycol 16.6 12.0 20.7 29.1
1, 3-butanediol 16.6 10.0 21.5 28.9
Lactic acid 17.0 8.3 28.4 34.1
Lactic acid ethyl ester 16.0 7.6 12.5 21.7
Ethylene glycol dimethyl ether 15.4 6.3 6.0 17.7
The inorganic material (a) of the present invention is not particularly limited, and the median diameter (D) measured by a laser diffraction/scattering method is preferably 50 ) Inorganic material of 0.01-20 mu m. From the viewpoint of obtaining a dense sintered body, it is more preferably 0.01 to 10. Mu.m, still more preferably 0.01 to 5. Mu.m.
The type of the inorganic material is not particularly limited, and examples thereof include: ceramics, conductor powder, glass powder, phosphor particles, and the like. These may be used alone or in combination of two or more.
Examples of the ceramics include: ceramics such as aluminum oxide, zirconium oxide, titanium oxide, barium titanate, strontium titanate, zirconium titanate, lead zirconate titanate, lanthanum vanadate, ferrite, zinc oxide, magnesium oxide, beryllium oxide, aluminum nitride, silicon nitride, boron nitride, gallium nitride, silicon carbide, zirconium carbide, magnesium fluoride, tin-doped indium oxide, antimony-doped tin oxide, and aluminum-doped zinc oxide.
Examples of the conductive powder include: metals such as copper, iron, nickel, palladium, platinum, gold, silver, aluminum, tungsten, and tin, alloys thereof, carbon materials such as graphite, carbon black, and carbon nanotubes, and the like.
Examples of the glass powder include: caO-Al 2 O 3 -SiO 2 Of MgO-Al system 2 O 3 -SiO 2 Tied, liO 2 -Al 2 O 3 -SiO 2 Glass powders such as various kinds of silicon oxides, bismuth oxide glass, silicate glass, lead glass, zinc glass, boron glass, and the like.
Examples of the phosphor particles include: y is Y 2 SiO 5 ：Ce、CaWO 4 ：Pb、BaMgAl 14 O 23 ：Eu、Y 2 O 3 ：Eu、Y 2 SiO 5 ：Eu、Y 3 A l5 O 12 ：Eu、Zn 3 (PO 4 ) 2 ：Mn、YBO 3 ：Eu、GdBO 3 ：Eu、ScBO 3 ：Eu、LuBO 3 ：Eu、Zn 2 SiO 4 ：Mn、BaAl 12 O 19 ：Mn、CaAl 12 O 19 ：Mn、YBO 3 ：Tb、BaMgAl 14 O 23 ：Mn、LuBO 3 ：Tb、BaMgAl 12 O 23 : eu, etc.
In the present invention, from the viewpoint of easy availability of a slurry composition exhibiting high dispersibility, ceramics are preferred, and oxide ceramics are more preferred. More specifically, for example, alumina, titania, barium titanate, zinc oxide, magnesium oxide, and the like are particularly preferable.
These inorganic materials may be modified on the surface by plasma treatment, coupling agent treatment, or the like.
The polycarbonate (B) of the present invention is not particularly limited, and aromatic polycarbonates such as bisphenol a polycarbonate, aliphatic polycarbonates such as polyethylene carbonate and polytrimethylene carbonate can be used. From the viewpoint of excellent thermal decomposability, aliphatic polycarbonates are preferred, and aliphatic polycarbonates obtained by copolymerizing an epoxide with carbon dioxide are particularly preferred.
The epoxide is not particularly limited, and examples thereof include: ethylene oxide, propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, isobutylene oxide, 1, 2-pentane oxide, 2, 3-pentane oxide, 1, 2-hexane oxide, 1, 2-octane oxide, 1, 2-decane oxide, cyclopentane oxide, cyclohexane oxide, styrene oxide, vinyl cyclohexane oxide, 3-phenyl propylene oxide, allyl glycidyl ether, methyl glycidyl ether, phenyl glycidyl ether, epichlorohydrin, and the like. Among them, ethylene oxide, propylene oxide, 1, 2-butylene oxide, and cyclohexene oxide are preferable from the viewpoint of having high reactivity. These epoxides may be used alone or in combination of two or more. In the case where the epoxide comprises ethylene oxide, the resulting polycarbonate comprises polyethylene carbonate; in the case where the epoxide is propylene oxide, the resulting polycarbonate comprises polypropylene carbonate; in the case of epoxides comprising 1, 2-epoxybutane, the resulting polycarbonate comprises polybutylenecarbonate. In addition, where the epoxide comprises cyclohexene oxide, the resulting polycarbonate comprises polycyclohexenyl carbonate.
In the case of combining two or more epoxides, for example in the case of using propylene oxide and cyclohexane oxide as epoxide, the resulting polycarbonate is poly (propylene/cyclohexene) carbonate. In this case, the copolymer may be a random copolymer or a block copolymer. More preferably random copolymers.
The polycarbonate of the present invention may have other structural units in addition to the polycarbonate within a range that does not hinder the effects of the present invention, and the terminal groups may be modified. Examples of the other structural unit include structural units such as polyether, polyester, polyamide, and polyacrylate, and structural units having a polar group such as carboxyl group, hydroxyl group, and amino group. Examples of the modification of the terminal group include modification with an acid anhydride, a cyclic acid anhydride, an acyl halide, an isocyanate compound, and the like. When the polycarbonate has other structural units, the content thereof is preferably 10 mol% or less, more preferably 5 mol% or less, further preferably 3 mol% or less, and particularly preferably 1 mol% or less, based on the total structural units of the polycarbonate.
In the case where the polycarbonate of the present invention has other structural units, the structural units may be contained in the polycarbonate in the form of a random or block polymer or a graft polymer.
In addition, two or more polycarbonates having different structures may be used in combination.
The mass average molecular weight (Mw) or molecular weight distribution (Mw/Mn) of the polycarbonate of the present invention is not particularly limited. For example, from the viewpoint of excellent moldability, the mass average molecular weight (Mw) of the polycarbonate is preferably 5000 or more, more preferably 10000 or more, and further preferably 100000 or more. Further, from the viewpoint of excellent handling, the mass average molecular weight (Mw) of the polycarbonate is preferably 1000000 or less, more preferably 750000 or less, and further preferably 500000 or less. The mass average molecular weight (Mw) described in the present invention is a value calculated by measurement (using standard polystyrene as a reference) in a tetrahydrofuran solution at 40 ℃ using a gel permeation chromatograph (for example, a Waters2695 separation module manufactured by Waters, japan).
The molecular weight distribution (Mw/Mn) of the polycarbonate of the present invention is preferably, for example, 1 to 15 from the viewpoint of excellent handleability. The upper or lower limit of this range may be exemplified by: 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10, 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14 or 14.5. For example, the range may be 1.1 to 10 or 1.5 to 8.
The polycarbonate of the present invention can be produced, for example, by copolymerizing the epoxide with carbon dioxide in the presence of a catalyst.
Examples of the catalyst include: zinc-based catalysts, aluminum-based catalysts, chromium-based catalysts, cobalt-based catalysts, boron-based catalysts, and the like. Among them, zinc-based catalysts or cobalt-based catalysts are preferable from the viewpoint of having high polymerization activity in the polymerization reaction of epoxide and carbon dioxide.
Examples of the zinc-based catalyst include: diethyl zinc-water based catalyst, diethyl zinc-pyrogallol based catalyst, bis ((2, 6-diphenyl) phenoxy) zinc, N- (2, 6-diisopropylphenyl) -3, 5-di-tert-butyl salicylaldimine zinc, 2- ((2, 6-diisopropylphenyl) amide) -4- ((2, 6-diisopropylphenyl) imino) -2-pentenoacetic acid zinc, adipic acid zinc, glutaric acid zinc, and the like.
The cobalt-based catalyst may be: cobalt acetate-acetic acid catalyst, cobalt N, N ' -bis (3, 5-di-t-butylsalicylidene) -1, 2-cyclohexyldiamine acetate, cobalt N, N ' -bis (3, 5-di-t-butylsalicylidene) -1, 2-cyclohexyldiamine pentafluorobenzoate, cobalt N, N ' -bis (3, 5-di-t-butylsalicylidene) -1, 2-cyclohexyldiamine chloride, cobalt N, N ' -bis (3, 5-di-t-butylsalicylidene) -1, 2-cyclohexyldiamine nitrate, cobalt N, N ' -bis (3, 5-di-t-butylsalicylidene) -1, 2-cyclohexyldiamine 2, 4-dinitrobenzene oxide, cobalt tetraphenylporphyrin chloride, cobalt tetraphenylporphyrin acetate, cobalt N, N ' -bis [2- (ethoxycarbonyl) -3-oxobutylene ] -1, 2-cyclohexyldiamine chloride, cobalt N, N ' -bis [2- (ethoxycarbonyl) -3-oxobutylene ] -1, 2-cyclohexyldiamine pentafluorobenzoate, and the like.
In the case of cobalt catalysts, a promoter is preferably used. As cocatalysts, there may be mentioned: pyridine, N-4-dimethylaminopyridine, N-methylimidazole, tetrabutylammonium chloride, tetrabutylammonium acetate, triphenylphosphine, bis (triphenylphosphine) ammonium chloride, bis (triphenylphosphine) ammonium acetate, and the like.
The amount of the catalyst (co-catalyst if necessary) used in the polymerization reaction is preferably 0.001 mol or more, more preferably 0.005 mol or more, based on 1 mol of the epoxide, from the viewpoint of promoting the progress of the polymerization reaction. In addition, from the viewpoint of obtaining an effect corresponding to the amount used, the amount of the metal catalyst (co-catalyst if necessary) used in the polymerization reaction is preferably 0.2 mol or less, more preferably 0.1 mol or less, based on 1 mol of the epoxide.
The polymerization reaction may be carried out using a reaction solvent as required. The reaction solvent is not particularly limited, and various organic solvents can be used. Examples of the organic solvent include: aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, cyclohexane, etc.; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; halogenated hydrocarbon solvents such as methylene chloride, chloroform, 1-dichloroethane, 1, 2-dichloroethane, chlorobenzene, bromobenzene, etc.; ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, 1, 4-dioxane, 1, 3-dioxolane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, anisole, and the like; ester solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, and the like; amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; and carbonate solvents such as dimethyl carbonate, diethyl carbonate and propylene carbonate.
The amount of the reaction solvent to be used is preferably 100 to 10000 parts by mass based on 100 parts by mass of the epoxide, for example, from the viewpoint of allowing the reaction to proceed smoothly.
The method for polymerizing the epoxide and carbon dioxide in the presence of the catalyst is not particularly limited, and examples thereof include a method in which the epoxide, the catalyst, and if necessary, a cocatalyst, a reaction solvent, and the like are charged into an autoclave, mixed, and then carbon dioxide is introduced thereinto to react.
The amount of carbon dioxide used in the polymerization reaction is preferably 0.5 to 10 moles, more preferably 0.6 to 5 moles, and even more preferably 0.7 to 3 moles, based on 1 mole of epoxide.
The pressure of use of the carbon dioxide used in the polymerization reaction is not particularly limited, but is preferably 0.1MPa or more, more preferably 0.2MPa or more, further preferably 0.5MPa or more from the viewpoint of smoothly proceeding the reaction, and is preferably 20MPa or less, more preferably 10MPa or less, further preferably 5MPa or less from the viewpoint of obtaining an effect according to the pressure of use.
The polymerization temperature in the polymerization reaction is not particularly limited, but is preferably 0℃or higher, more preferably 20℃or higher, further preferably 30℃or higher from the viewpoint of shortening the reaction time, and is preferably 100℃or lower, more preferably 80℃or lower, further preferably 60℃or lower from the viewpoint of suppressing side reactions and improving the yield.
The reaction time varies depending on the polymerization conditions, and thus, it cannot be said that it is usually preferably about 1 hour to about 40 hours.
The polycarbonate produced may be purified and dried as needed.
Examples of the dispersant (C) of the present invention include: polycarboxylic acids such as polymers containing unsaturated carboxylic acids such as acrylic acid and methacrylic acid (e.g., polyacrylic acid and polymethacrylic acid) and salts thereof (e.g., sodium salt and potassium salt); copolymers of monomers such as ethylene, isobutylene, styrene, butadiene, and the like with maleic anhydride and derivatives thereof; organic acids such as citric acid, tartaric acid, oleic acid, and acetic acid; fatty acid esters such as glycerin fatty acid ester, sucrose fatty acid ester and polyoxyethylene sorbitan fatty acid ester; phosphate esters such as isopropyl phosphate and polyoxyethylene alkyl ether phosphate; polyethers such as polyethylene glycol, polyethylene glycol monostearate, polyethylene glycol monophenyl ether, and polyethylene glycol-polypropylene glycol copolymer; amine compounds such as oleylamine, polyethyleneimine, and poly-N-ethylethyleneimine; quaternary ammonium salts such as stearyl trimethyl ammonium chloride and cetyl trimethyl ammonium chloride; higher alcohols such as dodecanol and oleyl alcohol. Examples of the commercial products include: the ECODIS series manufactured by the company square, the fanning series manufactured by the company square コ, the fanning series a one-year family of the access, manufactured by Tobang chemical industry Co., ltd a low-level alloy series manufactured by east Asia Synthesis company, a high-level alloy series manufactured by daily oil company to one, DIPERBYK series manufactured by Pick chemical company, i, e.g., one manufactured by Sanyo chemical company, b, e.g., b, c the "mountain" series, and the "mountain" series, etc. manufactured by the fine chemical company of taste are made by the company of the nux fine chemistry.
The dispersant of the present invention preferably has a hansen solubility parameter (HSP value) of 22 to 31MPa 0.5 . The upper or lower limit of this range may be, for example, 22.1, 22.2, 22.3, 22.4, 22.5, 22.6, 22.7, 22.8, 22.9, 23, 23.1, 23.2, 23.3, 23.4, 23.5, 23.6, 23.7, 23.8, 23.9, 24, 24.1, 24.2, 24.3, 24.4, 24.5, 24.6, 24.7, 24.8, 24.9, 25, 25.1, 25.2, 25.3, 25.4, 25.5, 25.6, 25.7, 25.8, 25.9, 26, 26.1, 26.2, 26.3, 26.4, 26.5, 26.6, 26.7, 26.8, 26.9, 27, 27.1, 27.2, 27.3, 27.4, 27.5, 27.6, 27.7, 27.8, 27.9, 28, 28.1, 28.2, 28.3, 28.4, 28.5, 28.6, 28.7, 28.8, 28.9, 29, 29.1, 29.2, 29.3, 29.4, 29.5, 29.6, 29.7, 29.8, 29.9, 30, 30.1, 30.2, 30.3, 30.4, 30.5, 30.6, 30.7, 30.8 or 30.9MPa 0.5 . For example, the range may be 22.5 to 30.5MPa 0.5 . The range is more preferably 25 to 30.5MPa 0.5 Particularly preferably 27 to 30.5MPa 0.5 。
In addition, the dispersants of the present invention preferably contain at least one or more acidic functional groups. As the acidic functional group, there may be mentioned: carboxyl, hydroxyl, phosphate, sulfonate, phenol, thiol, anhydride, and the like. Examples of such a dispersant include: the fluxjfil family of ecocis series and fan コ, respectively, and the faco industry company, respectively, and the faco family of faco, respectively the low-level alloy is manufactured by east Asia synthetic company, the Mega-line alloy manufactured by daily oil company, the cover-line, the DISERBYK-line manufactured by Pick chemical company, and the like.
The dispersant may be suitably used singly or in combination of two or more. When two or more of the above-mentioned dispersants are used in combination, a dispersant which does not satisfy the above-mentioned conditions may be used in combination as long as the HSP value as a mixture falls within the above-mentioned range. When two or more dispersants are used in combination, the HSP values of the dispersants used are preferably all within the above-mentioned range.
As the solvent (D) of the present invention, an organic solvent is preferable. More specifically, for example, it is possible to use: alcohols such as methanol, ethanol, isopropanol, n-propanol, isopropanol, benzyl alcohol, phenethyl alcohol, and α -terpineol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.: hydrocarbons such as hexane, cyclohexane, heptane, α -pinene, limonene, benzene, toluene, xylene, and the like; halogenated hydrocarbons such as methylene chloride, 1, 2-dichloroethane, chloroform, chlorobenzene, etc.; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, (particularly n-propyl acetate, n-butyl acetate), ethyl lactate, butyl lactate, ethyl salicylate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, terpineol acetate, dihydroterpineol acetate, isobornyl acetate, gamma-butyrolactone, epsilon-caprolactone, and the like; carbonates such as dimethyl carbonate, diethyl carbonate, and propylene carbonate; ethers such as tetrahydrofuran, 1, 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, anisole, and the like; nitriles such as acetonitrile, propionitrile, isobutyronitrile, and benzonitrile; amides such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and tetramethylurea; or water, etc. Among them, at least one selected from the group consisting of amide solvents, ester solvents, ether solvents, and carbonate solvents is preferable. These may be used singly or in combination of two or more.
Although not particularly limited, the solvent preferably has a hansen solubility parameter value of 18 to 25MPa from the viewpoint of affinity with the polycarbonate of the present invention and the dispersant of the present invention 0.5 . The upper or lower limit of this range may be, for example, 18.1, 18.2, 18.3, 18.4, 18.5, 18.6, 18.7, 18.8, 18.9, 1.9, 19.1, 19.2, 19.3, 19.4, 19.5, 19.6, 19.7, 19.8, 19.9, 20, 20.1, 20.2, 20.3, 20.4, 20.5, 20.6, 20.7, 20.8, 20.9, 21, 21.1, 21.2, 21.3, 21.4, 21.5, 21.6, 21.7, 21.8, 21.9, 22, 22.1, 22.2, 22.3, 22.4, 22.5, 22.6, 22.7, 22.8, 22.9, 23.1, 23.2, 23.3, 23.4, 23.5, 23.6, 23.7, 23.8, 24.24.9, 24.24.4, 24.9, 24.4, 24.5, 24.9, 24.7, 24.9, 24.5, 24.9, 4, 4.9, or 3.9 0.5 . For example, the range may be 19 to 24MPa 0.5 Or 20-23 MPa 0.5 . As described above, the Hansen solubility parameter values of the solvent were Hansen Solubility Parameters, A user's handbook, second edition, boca Raton, fla, CRC Press (Hansen, charles (2007)). However, the hansen solubility parameter was obtained for a solvent not described in the manual according to the method for determining hansen solubility parameter.
Further, for a solvent (mixed solvent) obtained by mixing two or more solvents, the respective items (dD, dP, dH) of each solvent to be mixed are obtained, and then the volume fraction in the respective items and the mixed solvent is obtained. Specifically, the HSP of the mixed solvent is obtained by multiplying the term of each solvent to be mixed by the volume fraction (weighted average) in the mixed solvent to obtain the term of each solvent to be mixed, and substituting the value of each term of the mixed solvent into the following formula.
HSP＝(dD 2 +dP 2 +dH 2 ) 0.5
For example, when the hansen solubility parameters are solved for a mixed solvent of solvents A, B and C containing (a) vol% of solvent a, (B) vol% of solvent B, and (C) vol% of solvent C, dD, dP, dH of the respective solvents are set as:
solvent a: dDa, dPa, dHa
Solvent B: dDb, dPb, dHb
Solvent C: dDc, dPc, dHc the number of the individual pieces of the plastic,
each item (dDm, dPm, dHm) of the mixed solvent was calculated as follows.
dDm＝dDa×(a)％+dDb×(b)％+dDc×(c)％
dPm＝dPa×(a)％+dPb×(b)％+dPc×(c)％
dHm＝dHa×(a)％+dHb×(b)％+dHc×(c)％
Then, the total hansen solubility parameter HSPm of the mixed solution was determined as follows:
HSPm＝(dDm 2 +dPm 2 +dHm 2 ) 0.5 。
in addition, the solvent (D) of the present invention preferably contains at least one compound containing a hydroxyl group in the molecule. Examples of the solvent containing a hydroxyl group in a molecule include: alcohols such as methanol, ethanol, and n-propanol; hydroxy acid esters such as ethyl lactate and butyl lactate. The amount of the solvent containing a hydroxyl group in the molecule to be used is, for example, preferably 1 to 100% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 30% by mass, relative to the total amount of the solvent (D) from the viewpoint of the workability of the slurry composition.
The solvent (D) of the present invention and the inorganic material (A) of the present invention have a Hansen solubility parameter distance (Ra) of 1 to 11MPa 0.5 . The upper limit or lower limit of the range may be, for example, 1.1,1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8 or 10.9MPa 0.5 . For example, the range may be 2 to 10.5MPa 0.5 Or 3-10 MPa 0.5 . By setting the hansen solubility parameter distance of the solvent (D) and the inorganic material (a) to the above range, a slurry composition exhibiting high dispersibility can be preferably obtained.
In addition, the Hansen solubility parameter distance (Ra) between the solvent (D) of the present invention and the polycarbonate (B) of the present invention is 4 to 8MPa 0.5 . The upper or lower limit of the range may be, for example, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8 or 7.9MPa 0.5 . For example, the range is 5 to 7.8MPa 0.5 Or 6 to 7.5MPa 0.5 . By setting the hansen solubility parameter distance (Ra) between the solvent (D) and the polycarbonate (B) to the above range, a slurry composition having particularly excellent moldability can be obtained.
In the slurry composition of the present invention, the amount of the polycarbonate (B) varies depending on the use of the slurry composition and the like, and therefore cannot be generally said, but is preferably 1 to 30 parts by mass relative to 100 parts by mass of the inorganic material (a). The upper or lower limit of the range may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, or 29 parts by mass. For example, the range may be 3 to 25 parts by mass or 5 to 20 parts by mass. When the amount of the polycarbonate (B) is in this range, a dense sintered body having more excellent moldability can be easily obtained.
In the slurry composition of the present invention, the amount of the dispersant (C) varies depending on the kind of the inorganic material (a) and the like, and therefore cannot be generally said, but is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the inorganic material (a). The upper or lower limit of the range may be, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8 or 9.9. The range may be, for example, 0.5 to 8 parts by mass, and 1 to 5 parts by mass. When the amount of the dispersant (C) is within this range, a slurry composition exhibiting higher dispersibility is easily obtained.
In the slurry composition of the present invention, the amount of the solvent (D) varies depending on the use of the slurry composition, the molding method, etc., and therefore cannot be generally said, but is preferably 10 to 400 parts by mass relative to 100 parts by mass of the inorganic material (a). The upper or lower limit of the range may be, for example, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, or 390 parts by mass. The range may be, for example, 20 to 350 parts by mass or 50 to 300 parts by mass. When the amount of the solvent (D) is within this range, a slurry composition having higher dispersibility and excellent handleability can be easily obtained.
The slurry composition of the present invention may contain, in addition to the inorganic material (a), the polycarbonate (B), the dispersant (C) and the solvent (D), known additives such as an adhesion promoter, an adhesion imparting agent, an antifoaming agent, a sintering aid, a lubricant, a plasticizer, an antistatic agent and a rheology modifier, if necessary. Further, a binder other than the polycarbonate (B) may be contained as long as the effect of the present invention is not impaired.
Examples of the adhesion promoter include: n-2- (aminoethyl) -3-aminopropyl methyldimethoxy silane, N-2- (aminoethyl) -3-aminopropyl trimethoxy silane, 3-glycidoxypropyl methyldiethoxy silane, dimethyl dimethoxy silane, tetramethoxy silane, and the like.
Examples of the adhesion imparting agent include: rosin derivatives, terpene resins, terpene phenol resins, rosin-indene resins, alkylphenol resins, styrene resins, and the like.
As the sintering aid, for example, there may be mentioned: lithium silicate, magnesium oxide, calcium oxide, yttrium oxide, barium oxide, calcium aluminate, and the like.
Examples of the thermal decomposition accelerator include: dioctylamine, diazabicycloundecene, triethanolamine, tetrabutylammonium acetate, potassium hydroxide, and the like.
As the lubricant, for example, there may be mentioned: hydrocarbons such as paraffin wax and liquid paraffin wax; fatty acid amides such as erucamide and ethylene bis-stearamide; fatty acids such as stearic acid and behenic acid; higher alcohols such as stearyl alcohol and oleyl alcohol; esters such as glycerol monostearate, glycerol monooleate and butyl stearate.
As the plasticizer, there may be mentioned: phthalate esters such as dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, and butyl benzyl phthalate; aliphatic dibasic acid esters such as dibutyl adipate, dibutyl sebacate, diethyl succinate and glyceryl triacetate; cyclic carbonates such as propylene carbonate and glycerol carbonate; polyethers such as polyethylene glycol and polypropylene glycol; phosphoric acid esters such as trimethyl phosphate, tributyl phosphate, triphenyl phosphate, and tricresyl phosphate; epoxidized vegetable oils such as epoxidized soybean oil, epoxidized castor oil, and epoxidized linseed oil.
As the antistatic agent, for example, there may be mentioned: dinonylnaphthalene sulfonic acid, sodium dodecyl sulfonate, polyethylene glycol, ionic liquids, and the like.
Examples of the binder other than polycarbonate include: vinyl polymers such as polyvinyl butyral, polyacrylate, polyvinyl alcohol, polyvinyl acetate, and polystyrene, cellulose polymers such as ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and cellulose acetate, and ester polymers such as polycaprolactone and polylactic acid.
The amount of these known additives and the binder other than the polycarbonate (B) is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the inorganic material (a) in total.
Examples of the method for producing the polymer composition of the present invention include a method of mixing the components (a), (B) and (C) and other additives as needed by a known method, and for example, a melt kneading method using an extruder or the like, a solution mixing method using a solvent, and the like can be used.
The method for producing the slurry composition is not particularly limited. For example, the method can be used as follows.
As a first method, a prescribed amount of a solvent (D) and a dispersant (C) are added to an inorganic material (a) to obtain a dispersion of the inorganic material (a). Further, the polycarbonate (B) is dissolved in the solvent (D), and the dispersant (C) and the additives as needed are added to the solution, followed by stirring to produce a uniform composition. Next, the above composition is added to the dispersion liquid of the inorganic material (a), and further dispersed, to obtain a slurry composition.
As a second method, a uniform composition is produced by dissolving the polycarbonate (B) in the solvent (D), adding the dispersant (C) and the additives as needed to the solution, and stirring the mixture. After adding the inorganic material (a) to the composition, it is dispersed to obtain a slurry composition.
As a third method, a predetermined amount of the solvent (D) is added to the inorganic material (a) to obtain a dispersion of the inorganic material (a). Further, the polycarbonate (B) is dissolved in the solvent (D), and the dispersant (C) and the additives as needed are added to the solution, followed by stirring to produce a uniform composition. Next, the above composition is added to the dispersion liquid of the inorganic material (a), and further dispersed, to obtain a slurry composition.
In the case where the dispersing operation is performed a plurality of times as in the first and third methods, the dispersing conditions may be the same or different.
As a method for performing the dispersion, various methods such as a method using a medium type dispersing machine such as a bead mill, a ball mill, an attritor, a paint stirrer, a sand mill, a dry mixing method using a kneader or the like, a method using three rolls, a method using a planetary stirrer, and the like can be used.
As described above, a molded article (molded article of the present invention) obtained by using the slurry composition of the present invention is also provided. By using the slurry composition of the present invention, a compact and smooth-surfaced molded article can be obtained.
As a method for forming the slurry composition, various methods can be used depending on the purpose of the slurry composition, and examples thereof include: doctor blade method, die coating method, slurry casting method, screen printing method, gravure printing method, offset printing method, gravure offset printing method, inkjet printing method, die casting method, cast molding method, and the like.
The slurry composition formed by various methods can be preferably used for manufacturing a formed body. For example, the slurry composition may be a green body, a degreased body, a sintered body, or the like. For example, the slurry composition or the green body may be degreased to prepare a degreased body. In addition, for example, a slurry composition, a green body, or a degreased body may be sintered to prepare a sintered body.
For example, the slurry composition can be formed into a green body by removing the solvent through a drying process, and is preferable. The drying method is not particularly limited, and examples thereof include known drying methods such as a hot air dryer, a reduced pressure dryer, a far infrared ray dryer, and a microwave dryer. The drying conditions are not particularly limited, and may be appropriately set according to the kind and amount of the solvent in the molded body, the thickness of the molded body, and the like.
Alternatively, for example, the solvent (D) may be removed from the slurry composition to prepare a dried product or a granulated product, and then a green body may be prepared by a known method. Examples of the method for preparing the slurry composition into a dried product or a granulated product include a spray drying method and a freeze drying method. Examples of the molding method of the dried product or granulated product include a hydraulic method, a cold isostatic method, an extrusion molding method, an injection molding method, and a casting molding method.
The molded body (green body) may be subjected to cutting, lamination, and other processing as necessary, and the polycarbonate (B) is removed by a degreasing step to obtain a degreased body. The degreasing conditions are not particularly limited, and may be appropriately set according to the type and amount of the polycarbonate (B) in the molded article, the thickness of the molded article, and the like. For example, the reaction may be carried out at about 200℃to about 800℃in an inert atmosphere such as nitrogen or argon or in an oxygen-containing atmosphere containing oxygen.
The present invention also includes a sintered body (sintered body of the present invention) obtained by using the above slurry composition or a molded body (green body or degreased body).
The sintering method is not particularly limited, and for example, vacuum sintering, normal pressure sintering, microwave sintering, plasma sintering, or the like may be used.
The sintering atmosphere may be appropriately set according to the type of the inorganic material (a). For example, the reaction may be carried out under vacuum, under an inert atmosphere such as nitrogen or argon, under an oxidizing atmosphere such as air, oxygen, ozone or nitrogen dioxide, or under a reducing atmosphere such as hydrogen or carbon monoxide.
The sintering temperature may be at least a temperature at which the inorganic material (a) can be sintered, and may be, for example, 200 to 2000 ℃.
In The present specification, "including" includes "consisting essentially of … …", "… …" (The term "comprising" includes "consisting essentially of" and "establishing of."). The present invention includes all arbitrary combinations of the constituent elements described in the present specification.
In addition, when the subject matter encompassed by the present invention is specified, various characteristics (properties, structures, functions, and the like) described above with respect to the embodiments of the present invention may be arbitrarily combined. That is, the present invention also includes a subject matter composed of all combinations of the characteristics described in the present specification that can be combined.
Examples
Hereinafter, embodiments of the present invention will be described more specifically by way of examples, but the embodiments of the present invention are not limited to the following examples.
The physical properties of each component used were measured by the following methods.
[ mass average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of polycarbonate ]
The mass average molecular weight (Mw) and the molecular weight distribution (Mw/Mn) were determined by measurement in a tetrahydrofuran solution at 40℃using a gel permeation chromatograph (manufactured by Waters, waters 2695 separation module, japan) based on standard polystyrene.
[ determination of hansen solubility parameters ]
The material to be measured was evaluated for the solubility, wettability, and the like of the solvent, and the hansen solubility parameter of the solvent, for which the solubility was determined to be good, was plotted as a minimum radius sphere, which falls inside the sphere and outside the sphere, and the center of the sphere was defined as the value of the hansen solubility parameter. More specifically, as described below.
The substance (test substance) solving the hansen solubility parameters was thoroughly mixed with each test solvent. The concentration was set to 10% by volume in the case where the test substance was polycarbonate, and to 0.5% by volume in the case where the test compound was an inorganic material. After standing for 24 hours, whether the polycarbonate solution was in a dissolved state or an undissolved state was visually judged, and whether the inorganic material solution was cloudy or precipitated was visually judged. The "affinity" is set in the dissolved state or cloudiness, and the "no affinity" is set in the undissolved state or precipitation. Then, the respective test solvents dD, dP, dH were plotted in a three-dimensional space, and the spheres (hansen dissolved spheres) were determined so as to include a plot of the test solvent having affinity and a plot of the test solvent not having affinity, and the center points (coordinates of dD, dP, dH in the three-dimensional space) were set as values of hansen solubility parameters of the test substances. The test solvents (solvents) used and their dD, dP, dH and HSP are shown in the following table (Hansen Solubility Parameters: A user's handbook, second edition. Boca Raton, fla: CRC Press (Hansen, charles (2007)).
[ Table 1B ]
Solvent name dD dP dH HSP
Hexane 14.9 0.0 0.0 14.9
Toluene (toluene) 18.0 1.4 2.0 18.2
1, 4-Dioxacyclohexane 17.5 1.8 9.0 19.8
Decyl alcohol 17.6 2.7 10.0 20.4
Acetic acid isobutyl ester 15.1 3.7 6.3 16.8
Propyl acetate 15.3 4.3 7.6 17.6
Tetrahydrofuran (THF) 16.8 5.7 8.0 19.5
Methyl isobutyl ketone 15.3 6.1 4.1 17.0
Diethylene glycol monoethyl ether acetate 16.8 6.3 15.7 23.9
N-propanol 16.0 6.8 17.4 24.6
Benzaldehyde 19.4 7.4 5.3 21.4
Ethanol 15.8 8.8 19.4 26.5
Methyl ethyl ketone 16.0 9.0 5.1 19.1
Propylene glycol 16.8 9.4 23.3 30.2
Acetone (acetone) 15.5 10.4 7.0 19.9
Ethylene glycol 17.0 11.0 26.0 33.0
Methanol 15.1 12.3 22.3 29.6
N-methyl-2-pyrrolidone 18.0 12.3 7.2 23.0
N, N-dimethylformamide 17.4 13.7 11.3 24.9
Water and its preparation method 15.5 16.0 42.3 47.8
Dimethyl sulfoxide (DMSO) 18.4 16.4 10.2 26.7
Acetonitrile 15.3 18.0 6.1 24.4
Epsilon-caprolactone 19.7 15.0 7.4 25.8
Dipropylene glycol 16.0 20.2 18.4 31.7
Thioglycollic acid 16.0 13.5 20.0 29.0
Diethylene glycol 16.6 12.0 20.7 29.1
1, 3-butanediol 16.6 10.0 21.5 28.9
Lactic acid 17.0 8.3 28.4 34.1
Lactic acid ethyl ester 16.0 7.6 12.5 21.7
Ethylene glycol dimethyl ether 15.4 6.3 6.0 17.7
From the obtained hansen solubility parameters, hansen solubility parameter values (HSP values) of the respective substances and hansen solubility parameter distances (Ra) between the different substances were calculated.
The hansen solubility parameter values (HSP values) obtained for the following inorganic materials a-1 to A5, polycarbonates B-1 to B-4, and dispersants C-1 to C-4, and the center point coordinates (i.e., the values of dD, dP, and dH) of hansen dissolution balls obtained when these values were solved are shown in the following table.
TABLE 2
[ particle size distribution of inorganic Material in slurry composition ]
The particle size distribution was measured using a laser diffraction type particle size distribution measuring apparatus (SALD-7100 manufactured by Shimadzu corporation). More specifically, 0.1g of the slurry composition was diluted 30 times with the solvent used for dispersion (i.e., used for preparation of the slurry composition), mixed with shaking thoroughly, and the sample was further diluted with the same solvent so that the absorbance was 0.1 to 0.2, and the particle size distribution was measured.
The evaluation of dispersibility was determined by the following criteria.
Score 5: the particle size distribution is unimodal and narrow.
Score 4: the particle size distribution was unimodal, narrow, but distorted.
Score 3: the particle size distribution is unimodal but broad.
Score 2: the particle size distribution is multimodal.
Score 1: obvious aggregation and gelation were observed.
[ mechanical Properties of molded article ]
The slurry composition obtained in several examples was applied to a PET film (MFA of multireel, manufactured by dorry corporation) using a beck type applicator manufactured by An Tian refiner, and dried at room temperature for 15 hours, thereby forming a sheet having a thickness of about 10 μm.
From the sheet-like molded body, a JIS No. 1 dumbbell was cut, and the sheet-like molded body was subjected to JIS K6251: 2017, a tensile TEST was performed at 23℃at a strain rate of 6cm per minute using a bench type precision tester (zef-TEST manufactured by Shimadzu corporation), and the maximum stress and strain at break were measured.
Production example 1
Into a 1L-volume four-necked flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, a dean-Stark tube and a reflux condenser were charged 77.3g (0.95 mol) of zinc oxide, 123g (1 mol) of glutaric acid, 1.14g (0.02 mol) of acetic acid and 760g of toluene. Then, nitrogen gas was introduced into the reaction system at a flow rate of 50 mL/min, and the temperature was raised to 55℃and the mixture was stirred at that temperature for 4 hours to react. Then, the temperature was raised to 110℃and stirred at that temperature for 2 hours to conduct azeotropic dehydration, and after removing the water, the mixture was cooled to room temperature to obtain a slurry containing the organozinc catalyst.
Production example 2
After the inside of a 1L-volume autoclave equipped with a stirrer, a gas introduction tube and a thermometer was replaced with a nitrogen atmosphere, 8.0mL (containing 1.0g of the organozinc catalyst), 131g of hexane and 46.5g (0.80 mol) of propylene oxide were charged into the reaction solution containing the organozinc catalyst obtained in production example 1. Then, carbon dioxide was added with stirring, the inside of the reaction system was replaced with a carbon dioxide atmosphere, and carbon dioxide was filled until the inside of the reaction system became 1.5 MPa. Then, the temperature was raised to 60℃and the polymerization was carried out for 8 hours while supplementing the carbon dioxide consumed by the reaction.
After the reaction was completed, the autoclave was cooled, depressurized, and after removing the catalyst, the autoclave was dried under reduced pressure to obtain 80.8g of polypropylene carbonate. The Mw of the resulting polypropylene carbonate was 341000 and the Mw/Mn was 7.8.
Production example 3
The same operation as in production example 2 was conducted except that 57.7g (0.80 mol) of propylene oxide was changed to 1, 2-butylene oxide, to obtain 91.5g of polybutylene carbonate. The Mw of the resulting polybutene carbonate was 400000 and the Mw/Mn was 9.3.
Production example 4
The same operations as in production example 2 were conducted except that 78.5g (0.80 mol) of propylene oxide was changed to cyclohexene oxide, to obtain 37.5g of polycyclohexenyl carbonate. The obtained polycyclohexenyl carbonate had Mw of 233900 and Mw/Mn of 6.9.
Production example 5
The same operations as in production example 2 were conducted except that 46.5g (0.80 mol) of propylene oxide and 2.5g (0.025 mol) of cyclohexene oxide were used, to obtain 83.5g of poly (propylene/cyclohexene) carbonate. The Mw of the resulting poly (propylene/cyclohexene) carbonate was 283000 and the Mw/Mn was 6.4.
Examples 1 to 22 and comparative examples 1 to 2
As the inorganic material (a), the following was used.
A-1: manufactured by light metals company of japan, aluminum oxide C20 (D 50 ＝13.1μm)
A-2: titanium oxide SSP-20 (D) 50 ＝1.69μm)
A-3: manufactured by Sakai chemical industry Co., ltd., barium titanate BT-01 (D) 50 ＝0.18μm)
A-4: made by Sakai chemical industry Co., ltd., first zinc oxide (D 50 ＝1.31μm)
A-5: yu's Xing productManufactured by Co., ltd., magnesia 1000A (D) 50 ＝0.77μm)
As polycarbonate (B), the following was used.
B-1: the polypropylene carbonate obtained in production example 2
B-2: polybutylene carbonate obtained in production example 3
B-3: polycyclohexene carbonate obtained in production example 4
B-4: poly (propylene/cyclohexene) carbonate obtained in production example 5
As the dispersant (C), the following was used.
C-1: one RS-610 manufactured by Tobang chemical industry Co., ltd
C-2: sun oil company manufacturing, cartridge SC-0505K
C-3: the seal S-80 manufactured by Sanyo chemical industry Co Ltd
C-4: a super-group PN411 manufactured by Weisu Fine chemical Co
The soybean RS-610 is polyoxyethylene alkyl (12 to 15) ether phosphoric acid. The MAXUAN flame SC-0505K is composed of a polymer having an ionic group in the main chain and a polyoxyalkylene chain in the graft chain. And b-off S-80 is sorbitan monooleate. The higher-fatty PN411 is higher fatty acid ester.
[ preparation of slurry, method 1: examples 1 to 13, 15, 18 to 19, 22 and comparative examples 1 to 6]
According to the composition of Table 3, the solvent (D) was added to the inorganic material (A) so that the solid content concentration was 50% by mass, and dispersion treatment was performed for 20 hours using a bench ball mill (V-2M manufactured by Kogyo Co., ltd.). Then, 3.0 parts by mass of polycarbonate (B), dispersant (C), dibutyl phthalate and the remaining solvent (D) were added and further dispersed for 3 hours to obtain a slurry composition. In the case where the number of solvents described in table 3 is two or more, the solvent (D) is a mixed solution (mixed solvent) of the two or more solvents. In example 8, the polycarbonate (B) was a mixed polycarbonate composition of B-1 and B-3 shown in Table 3.
[ preparation of slurry, method 2: examples 14, 16, 17, 20, 21]
According to the compositions shown in Table 3, the inorganic material (A) was added with the solvent (D) so that the solid content concentration was 50% by mass, the dispersant (C) and the polycarbonate (B) was added thereto in a predetermined amount of 10% by mass, and the dispersion treatment was performed for 20 hours using a bench ball mill (V-2M manufactured by Kogynecomastia Co., ltd.). Then, 3.0 parts by mass of the remaining polycarbonate (B), dibutyl phthalate and the remaining solvent (D) were added and further dispersed for 3 hours to obtain a slurry composition. In the case where the number of solvents described in table 3 is two or more, the solvent (D) is a mixed solution (mixed solvent) of the two or more solvents.
The evaluation results of dispersibility of the obtained slurry composition are shown in table 4 together with HSP values of the solvent (D) and the dispersant (C), and HSP distances (Ra) of the inorganic material (a) and the solvent (D) and HSP distances (Ra) of the polycarbonate (B) and the solvent (D). The results of the study on the mechanical properties of the molded articles are shown in Table 5.
In the case where the solvents described in table 3 are two or more, the hansen solubility parameter of the solvent (D) shown in table 4 is the hansen solubility parameter of a mixed solution (mixed solvent) of the two or more solvents.
For hansen solubility parameters of the mixed solvent, the terms of each solvent to be mixed are multiplied by the volume fraction (weighted average) in the mixed solvent, and the terms in terms of the mixed solvent are obtained.
For example, in the case of solving hansen solubility parameters for a mixed solvent of solvents A, B and C containing (a) volume% of solvent a, (B) volume% of solvent B, and (C) volume% of solvent C, if dD, dP, dH of each solvent are respectively:
solvent a: dDa, dPa, dHa
Solvent B: dDb, dPb, dHb
Solvent C: dDc, dPc, dHc the number of the individual pieces of the plastic,
each item (dDm, dPm, dHm) of the mixed solvent is calculated as follows.
dDm＝dDa×(a)％+dDb×(b)％+dDc×(c)％
dPm＝dPa×(a)％+dPb×(b)％+dPc×(c)％
dHm＝dHa×(a)％+dHb×(b)％+dHc×(c)％
The total hansen solubility parameter thsm of the mixed solution was obtained as follows:
tHSPm＝(dDm 2 +dPm 2 +dHm 2 ) 0.5 。
TABLE 4
The aliphatic polycarbonate in comparative example 6 was not dissolved.
TABLE 5
In comparative examples 1 to 5, sheet formation was not performed.

Claims (12)

1. A slurry composition comprising an inorganic material (A), a polycarbonate (B), a dispersant (C) and a solvent (D),
the Hansen solubility parameter distance between the solvent (D) and the inorganic material (A) is 1-11 MPa 0.5 ，
The Hansen solubility parameter distance between the solvent (D) and the polycarbonate (B) is 4-8 MPa 0.5 。
2. The slurry composition according to claim 1, wherein the solvent (D) has a hansen solubility parameter value of 18 to 25MPa 0.5 。
3. Slurry composition according to claim 1 or 2, wherein the solvent (D) is a solvent comprising at least one hydroxyl containing compound.
4. The slurry composition according to any one of claims 1 to 3, wherein the polycarbonate (B) is an aliphatic polycarbonate.
5. The slurry composition according to claim 4, wherein,
aliphatic polycarbonates are copolymers of epoxides with carbon dioxide,
the epoxide is at least one selected from the group consisting of ethylene oxide, propylene oxide, 1, 2-butylene oxide, and cyclohexane oxide.
6. The slurry composition according to any one of claims 1 to 5, wherein the dispersant (C) has a hansen solubility parameter value of 23 to 32MPa 0.5 。
7. The slurry composition according to any one of claims 1 to 6, wherein the dispersant (C) is a compound having an alkylene oxide chain structure.
8. The slurry composition according to any one of claims 1 to 7, wherein the median diameter of the inorganic material (a) is 0.01 to 20 μm as measured by a laser diffraction/scattering method.
9. The slurry composition according to any one of claims 1 to 8, wherein the inorganic material (a) is a ceramic.
10. The slurry composition according to claim 1 to 9, wherein the polycarbonate is 1 to 30 parts by mass, the dispersant is 0.1 to 10 parts by mass, and the solvent is 10 to 400 parts by mass, based on 100 parts by mass of the inorganic material.
11. A molded article obtained by molding the slurry composition according to any one of claims 1 to 10.
12. A sintered body obtained by sintering the molded body according to claim 11.
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