JP7372517B2 - Composite materials, their manufacturing methods, and their uses - Google Patents
Composite materials, their manufacturing methods, and their uses Download PDFInfo
- Publication number
- JP7372517B2 JP7372517B2 JP2019082822A JP2019082822A JP7372517B2 JP 7372517 B2 JP7372517 B2 JP 7372517B2 JP 2019082822 A JP2019082822 A JP 2019082822A JP 2019082822 A JP2019082822 A JP 2019082822A JP 7372517 B2 JP7372517 B2 JP 7372517B2
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- JP
- Japan
- Prior art keywords
- pigment particles
- carbon
- white pigment
- composite material
- polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002131 composite material Substances 0.000 title claims description 71
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000002245 particle Substances 0.000 claims description 103
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 80
- 239000003575 carbonaceous material Substances 0.000 claims description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 58
- 239000002041 carbon nanotube Substances 0.000 claims description 47
- 238000000576 coating method Methods 0.000 claims description 47
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 46
- 239000011248 coating agent Substances 0.000 claims description 43
- 239000000049 pigment Substances 0.000 claims description 42
- 125000005372 silanol group Chemical group 0.000 claims description 40
- 229920002635 polyurethane Polymers 0.000 claims description 38
- 239000004814 polyurethane Substances 0.000 claims description 38
- 239000004408 titanium dioxide Substances 0.000 claims description 36
- 239000012463 white pigment Substances 0.000 claims description 33
- 239000008199 coating composition Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 25
- 238000000926 separation method Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 239000004020 conductor Substances 0.000 claims description 12
- 239000002612 dispersion medium Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
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- 239000003973 paint Substances 0.000 description 37
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- 239000000463 material Substances 0.000 description 11
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- 238000005119 centrifugation Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
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- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 3
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- 235000010755 mineral Nutrition 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
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- 239000002562 thickening agent Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、無機顔料粒子とカーボン材料を含む複合材料及びその製造方法、並びに該複合材料を含む導電性材料、塗料組成物、塗膜に関する。 The present invention relates to a composite material containing inorganic pigment particles and a carbon material, a method for producing the same, and a conductive material, coating composition, and coating film containing the composite material.
カーボン材料は、炭素原子で構成される種々の形状を有する材料であり、カーボンブラック、カーボンナノチューブ、グラフェン、カーボンナノコイル、カーボンナノホーン、フラーレン、ダイヤモンドライクカーボン等がよく知られている。例えば、カーボンナノチューブ(CNT)は、六角網目状の炭素原子配列のグラファイトシートが円筒状に巻かれた構造を有する物質である。通常、カーボンナノチューブとしては、層数の少ない単層CNTや2層CNTが高グラファイト構造を有しているために導電性等の特性が特に高いことが知られている。 Carbon materials are materials that are composed of carbon atoms and have various shapes, and carbon black, carbon nanotubes, graphene, carbon nanocoils, carbon nanohorns, fullerenes, diamond-like carbon, and the like are well known. For example, carbon nanotubes (CNTs) are materials that have a structure in which graphite sheets in which carbon atoms are arranged in a hexagonal network are wound into a cylindrical shape. Generally, as carbon nanotubes, it is known that single-walled CNTs and double-walled CNTs, which have a small number of layers, have particularly high properties such as electrical conductivity because they have a highly graphite structure.
このようなカーボン材料を無機粒子と複合化させ、カーボン材料が有する導電性、熱伝導性等の性能を無機粒子に付与させる試みが行われている。例えば、特許文献1には、複数のカーボンナノチューブが、互いに直接接続されたネットワーク構造を形成し、それが母粒子表面に直接固定されている複合粒子が開示されている。母粒子として、金属粒子、例えば、窒化アルミニウムや酸化アルミニウム、窒化チタン、窒化ケイ素、窒化ホウ素、酸化クロム、ニッケル、酸化ニッケル、酸化マグネシウム、ケイ素、炭化ケイ素、窒化ケイ素、二酸化ケイ素、チタン、酸化チタン、炭化チタン、タングステン、炭化タングステン、亜鉛、酸化亜鉛、酸化スズ、スズ等が挙げられている。この複合粒子を製造するには、カーボンナノチューブが分散した液に母粒子を浸漬し、母粒子表面においてカーボンナノチューブの分散状態と凝集状態との可逆的反応状態を生じさせて、母粒子表面にカーボンナノチューブを固定させている。 Attempts have been made to combine such carbon materials with inorganic particles to impart properties such as electrical conductivity and thermal conductivity possessed by carbon materials to the inorganic particles. For example, Patent Document 1 discloses a composite particle in which a plurality of carbon nanotubes form a network structure in which they are directly connected to each other, and the network structure is directly fixed to the surface of a base particle. As base particles, metal particles such as aluminum nitride, aluminum oxide, titanium nitride, silicon nitride, boron nitride, chromium oxide, nickel, nickel oxide, magnesium oxide, silicon, silicon carbide, silicon nitride, silicon dioxide, titanium, titanium oxide are used. , titanium carbide, tungsten, tungsten carbide, zinc, zinc oxide, tin oxide, tin, etc. To produce these composite particles, the base particles are immersed in a liquid in which carbon nanotubes are dispersed, and a reversible reaction state between the dispersed state and the agglomerated state of the carbon nanotubes is generated on the surface of the base particle. The nanotubes are fixed.
また、特許文献2には、セラミック原料粒子表面に0.001重量%以上0.1重量%以下のカーボンナノチューブを含有し、1.0×108Ω・cm以下の体積抵抗率を有する複合セラミックス材料粒子を開示している。前記セラミック原料粒子として、アルミナ、ジルコニア、窒化珪素、窒化アルミニウム、窒化ホウ素、炭化珪素、フェライト、酸化亜鉛、酸化チタン等が挙げられている。この複合セラミックス材料粒子を製造するには、少なくともセラミック原料粒子と、カーボンナノチューブと、該カーボンナノチューブを分散させる合成ポリマー、界面活性剤等の分散剤と、溶媒とを含む混合スラリーを作製する工程と、耐圧容器内に前記混合スラリーを供給した後、前記混合スラリーを撹拌しながら前記耐圧容器内に二酸化炭素を供給する二酸化炭素供給工程による方法を開示している。 Further, Patent Document 2 describes a composite ceramic containing 0.001% by weight or more and 0.1% by weight or less of carbon nanotubes on the surface of ceramic raw material particles and having a volume resistivity of 1.0×10 8 Ω・cm or less. Material particles are disclosed. Examples of the ceramic raw material particles include alumina, zirconia, silicon nitride, aluminum nitride, boron nitride, silicon carbide, ferrite, zinc oxide, titanium oxide, and the like. To produce these composite ceramic material particles, there is a step of preparing a mixed slurry containing at least ceramic raw material particles, carbon nanotubes, a synthetic polymer for dispersing the carbon nanotubes, a dispersant such as a surfactant, and a solvent. discloses a method using a carbon dioxide supply step of supplying the mixed slurry into a pressure-resistant container and then supplying carbon dioxide into the pressure-resistant container while stirring the mixed slurry.
更に、特許文献3には、未処理のカーボンナノチューブを窒素原子含有極性溶媒に分散させ、当該分散液中に、アミノ基、カルボキシル基、ヒドロキシ基の極性官能基を有するシランカップリング剤等で表面が修飾されたシリカゲル粒子、酸化チタン粒子又は酸化亜鉛粒子を撹拌して、その粒子表面にカーボンナノチューブをコーティングする方法を開示している。 Furthermore, Patent Document 3 discloses that untreated carbon nanotubes are dispersed in a nitrogen atom-containing polar solvent, and the surface of the dispersion is treated with a silane coupling agent having a polar functional group such as an amino group, a carboxyl group, or a hydroxyl group. discloses a method of coating carbon nanotubes on the surface of modified silica gel particles, titanium oxide particles, or zinc oxide particles by stirring the particles.
カーボン材料と無機顔料粒子とを複合化させることにより、溶媒分散体や塗料組成物等の溶媒中に配合した際にいわゆる「色分かれ」現象を防止することができると期待される。「色分かれ」現象とは、カーボンナノチューブ等のカーボン材料と二酸化チタン等の無機顔料粒子との比重差等によって溶媒中で両者が分離する現象をいう。「色分かれ」現象が生ずると、両者の分布が不均一になるため、塗膜とした際の特性(顔料特性、導電性、熱伝導性等)にムラが生じてしまう。 By combining a carbon material and inorganic pigment particles, it is expected that the so-called "color separation" phenomenon can be prevented when the carbon material is blended into a solvent such as a solvent dispersion or a paint composition. The "color separation" phenomenon refers to a phenomenon in which a carbon material such as a carbon nanotube and an inorganic pigment particle such as titanium dioxide are separated in a solvent due to a difference in specific gravity between the two. When the "color separation" phenomenon occurs, the distribution of both becomes uneven, resulting in uneven properties (pigment properties, electrical conductivity, thermal conductivity, etc.) when formed into a coating film.
しかしながら、特許文献1の方法では、ファンデルワールス力によりカーボン材料が無機顔料粒子の表面に直接固定しているために強度が十分ではなく、溶媒に配合した際に両者が分離してしまい、前記の色分かれ現象が生じる。また、特許文献2の方法でも、超臨界状態において、分散剤及び溶媒が二酸化炭素中に溶け込むことによって、カーボン材料は不安定な分散状態となり、ファンデルワールス力を主体とした力によって無機顔料粒子の表面に吸着し安定な状態となるが、吸着力だけでは強度が十分ではなく、溶媒に配合した際に両者が分離してしまい、「色分かれ」現象が生じる。更に、特許文献3の方法では、官能基を有するシランカップリング剤等で表面が修飾された粒子を用いてカーボン材料を固定しているが、溶媒に配合した際に両者の固定が不十分となって分離してしまい、「色分かれ」現象が生じるという問題が解決されていない。 However, in the method of Patent Document 1, the strength is not sufficient because the carbon material is directly fixed to the surface of the inorganic pigment particles by van der Waals force, and when mixed in a solvent, the two separate, resulting in the A color separation phenomenon occurs. Furthermore, in the method of Patent Document 2, the dispersant and solvent dissolve in carbon dioxide in a supercritical state, resulting in an unstable dispersion state of the carbon material, and a force mainly based on van der Waals forces causes the inorganic pigment particles to However, the adsorption force alone is not strong enough, and when mixed in a solvent, the two separate, resulting in a "color separation" phenomenon. Furthermore, in the method of Patent Document 3, carbon materials are immobilized using particles whose surfaces are modified with a silane coupling agent having a functional group, but when they are mixed in a solvent, the immobilization of both is insufficient. The problem of the "color separation" phenomenon occurring due to the separation of the two colors remains unsolved.
本発明は、上述の課題に鑑みてなされたものであり、無機顔料粒子とカーボン材料とを強固に固定し、溶媒に配合した際に「色分かれ」現象を抑制することを目的とする。 The present invention has been made in view of the above-mentioned problems, and aims to firmly fix inorganic pigment particles and carbon materials and suppress the "color separation" phenomenon when blended with a solvent.
本発明者らは、上記の課題を解決すべく鋭意検討した結果、両末端にシラノール基を有するポリウレタンを使用することで、無機顔料粒子とカーボン材料とを強固に固定できること、こうして得た複合材料を溶媒に配合した際に「色分かれ」現象を十分に抑制できることを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors found that by using polyurethane having silanol groups at both ends, inorganic pigment particles and carbon material can be firmly fixed, and the composite material obtained in this way The present invention was completed based on the discovery that the "color separation" phenomenon can be sufficiently suppressed when the compound is blended with a solvent.
すなわち、本発明は、以下の(1)から(10)の発明を含む。
(1) 無機顔料粒子とカーボン材料と両末端にシラノール基を有するポリウレタンとを含む、複合材料。
(2) 無機顔料粒子とカーボン材料とが、両末端にシラノール基を有するポリウレタンで固定された、(1)に記載の複合材料。
(3) 無機顔料粒子が無機白色顔料粒子である、(1)又は(2)に記載の複合材料。
(4) 無機白色顔料粒子が二酸化チタン顔料である、(3)に記載の複合材料。
(5) カーボン材料がカーボンナノチューブである、(1)乃至(4)の何れか一項に記載の複合材料。
(6) (1)乃至(5)の何れか一項に記載の複合材料を含む導電性材料。
(7) (1)乃至(5)の何れか一項に記載の複合材料又は(6)に記載の導電性材料と、樹脂とを含む、塗料組成物。
(8) (1)乃至(5)の何れか一項に記載の複合材料又は(6)に記載の導電性材料を含む、塗膜。
(9) 少なくとも無機顔料粒子とカーボン材料と両末端にシラノール基を有するポリウレタンとを水性分散媒中で混合する工程を含む、複合材料の製造方法。
(10) (9)に記載の混合工程で得られた混合液を固液分離する工程、次いで、得られた固形分を30℃以上180℃以下の温度で加熱する工程を含む、複合材料の製造方法。
That is, the present invention includes the following inventions (1) to (10).
(1) A composite material containing inorganic pigment particles, a carbon material, and a polyurethane having silanol groups at both ends.
(2) The composite material according to (1), wherein the inorganic pigment particles and the carbon material are fixed with polyurethane having silanol groups at both ends.
(3) The composite material according to (1) or (2), wherein the inorganic pigment particles are inorganic white pigment particles.
(4) The composite material according to (3), wherein the inorganic white pigment particles are titanium dioxide pigments.
(5) The composite material according to any one of (1) to (4), wherein the carbon material is a carbon nanotube.
(6) A conductive material containing the composite material according to any one of (1) to (5).
(7) A coating composition comprising the composite material according to any one of (1) to (5) or the conductive material according to (6), and a resin.
(8) A coating film comprising the composite material according to any one of (1) to (5) or the conductive material according to (6).
(9) A method for producing a composite material, including the step of mixing at least inorganic pigment particles, a carbon material, and a polyurethane having silanol groups at both ends in an aqueous dispersion medium.
(10) A composite material comprising a step of solid-liquid separation of the mixed liquid obtained in the mixing step described in (9), and a step of heating the obtained solid content at a temperature of 30°C or higher and 180°C or lower. Production method.
本発明によれば、無機顔料粒子とカーボン材料とを強固に固定することができるため、溶媒に配合した際の「色分かれ」現象を抑制でき、安定した塗膜特性(顔料特性、導電性、熱伝導性等)を保持することができる。 According to the present invention, since the inorganic pigment particles and the carbon material can be firmly fixed, the phenomenon of "color separation" when blended with a solvent can be suppressed, and stable coating film properties (pigment properties, conductivity, thermal conductivity, etc.).
本発明の複合材料は、無機顔料粒子とカーボン材料と両末端にシラノール基を有するポリウレタンとを含む。両末端にシラノール基を有するポリウレタンの接着作用により、無機顔料粒子とカーボン材料とを固定することができる。そのメカニズムは定かではないが、シラノール基が無機顔料粒子の表面と何らかの結合をし、もう一方のシラノール基もカーボン材料の表面と何らかの結合をするとともに、ポリウレタンの接着作用の働きにより両者の固定強度を高めることができると考えられる。 The composite material of the present invention includes inorganic pigment particles, a carbon material, and a polyurethane having silanol groups at both ends. The adhesive action of polyurethane having silanol groups at both ends can fix the inorganic pigment particles and the carbon material. The mechanism is not clear, but the silanol group has some kind of bond with the surface of the inorganic pigment particle, and the other silanol group also has some kind of bond with the surface of the carbon material, and the adhesive action of polyurethane strengthens the bond between the two. It is thought that it is possible to increase the
前記の無機顔料粒子は、化学的に無機質の顔料粒子のことをいい、天然鉱物でもよいし、亜鉛、チタン、鉛、鉄、銅、クロム等の化合物を原料として造るものでもよい。例えば、白色顔料 (亜鉛華(酸化亜鉛)、二酸化チタン、鉛白等)、赤色顔料 (べんがら、朱、カドミウム赤等)、黄色顔料 (黄鉛、黄土、カドミウム黄等)、緑色顔料 (エメラルド緑、酸化クロム緑等)、青色顔料 (紺青、コバルト青等)、紫色顔料 (マンガン・バイオレット、マース・バイオレット等)、黒色顔料 (チタンブラック、鉄黒等)、透明性白色顔料 (体質顔料ともいう。シリカ白、アルミナ白、白土、炭酸カルシウム等) があり、これらに限定されない。また、酸化チタン微粒子、酸化スズ微粒子等の透明性顔料も無機顔料粒子に含まれ、更に、アルミニウム、金、銀、銅等の金属顔料も含まれる。本発明では、白色顔料(無機白色顔料粒子)が好ましく、二酸化チタン、亜鉛華(酸化亜鉛)が更に好ましい。 The above-mentioned inorganic pigment particles refer to chemically inorganic pigment particles, and may be natural minerals or may be produced from compounds such as zinc, titanium, lead, iron, copper, and chromium. For example, white pigments (zinc oxide, titanium dioxide, lead white, etc.), red pigments (red, vermilion, cadmium red, etc.), yellow pigments (yellow, yellow ocher, cadmium yellow, etc.), green pigments (emerald green, etc.). , chromium oxide green, etc.), blue pigments (dark blue, cobalt blue, etc.), violet pigments (manganese violet, mars violet, etc.), black pigments (titanium black, iron black, etc.), transparent white pigments (also called extender pigments) (silica white, alumina white, white clay, calcium carbonate, etc.), but are not limited to these. Inorganic pigment particles also include transparent pigments such as titanium oxide fine particles and tin oxide fine particles, and metal pigments such as aluminum, gold, silver, and copper. In the present invention, white pigments (inorganic white pigment particles) are preferred, and titanium dioxide and zinc white (zinc oxide) are more preferred.
無機顔料粒子の平均一次粒子径は電子顕微鏡法にて測定することができる。具体的には、透過型電子顕微鏡(日立製作所製 H-7000)を用いて無機顔料粒子を撮影し、自動画像処理解析装置(ニレコ製 ルーゼックス(登録商標)AP)を用いて画像処理を行い、2000個の粒子について一次粒子径を測定し、その平均値を平均一次粒子径とする。 The average primary particle diameter of inorganic pigment particles can be measured by electron microscopy. Specifically, inorganic pigment particles were photographed using a transmission electron microscope (Hitachi H-7000), and image processing was performed using an automatic image processing and analysis device (Nireco Luzex (registered trademark) AP). The primary particle size of 2000 particles is measured, and the average value is defined as the average primary particle size.
無機顔料粒子の形状は特に限定されず、球状、棒状、針状、紡錘状、板状等の任意の形状のものを用いることができる。球状以外の形状の場合の上記平均一次粒子径については、棒状、針状、紡錘状粒子の場合は短軸側の長さの平均で規定し、板状の場合は面の対角線長さの平均で規定する。 The shape of the inorganic pigment particles is not particularly limited, and any shape such as spherical, rod-like, needle-like, spindle-like, or plate-like shape can be used. The above average primary particle diameter for shapes other than spherical is defined by the average length of the minor axis for rod-shaped, needle-shaped, and spindle-shaped particles, and the average diagonal length of the surface for plate-shaped particles. stipulated by.
二酸化チタン白色顔料は、平均一次粒子径が0.1μm以上1.0μm以下程度の二酸化チタン粒子であり、塗膜の白色度及び隠蔽性等の観点から、平均粒子径は0.15μm以上0.6μm以下であることが好ましく、0.2μm以上0.4μm以下であることが好ましい。二酸化チタン白色顔料の結晶構造についても特に限定されず、アナターゼ型、ルチル型、ブルッカイト型等を用いることができるが、塗料樹脂の劣化を抑制する観点から、ルチル型が好ましい。 The titanium dioxide white pigment is titanium dioxide particles with an average primary particle size of about 0.1 μm or more and 1.0 μm or less, and from the viewpoint of the whiteness and hiding property of the coating film, the average particle size is about 0.15 μm or more and 0.1 μm or more. It is preferably 6 μm or less, and preferably 0.2 μm or more and 0.4 μm or less. The crystal structure of the titanium dioxide white pigment is not particularly limited either, and anatase type, rutile type, brookite type, etc. can be used, but rutile type is preferable from the viewpoint of suppressing deterioration of paint resin.
二酸化チタン白色顔料は、いわゆる硫酸法、塩素法の何れの方法で製造したものも用いることができる。また、二酸化チタン白色顔料の粒子表面を、各種の無機化合物や有機化合物で被覆したものを用いてもよい。無機化合物としては、例えばケイ素、アルミニウム、チタン、ジルコニウム、スズ、アンチモン等の金属酸化物及び/又は金属含水酸化物等が挙げられる。また、有機化合物としては、ポリオール系、アミン系、カルボン酸系等の有機化合物(具体的には、トリメチロールメタン、トリメチロールエタン、トリメチロールプロパン、ペンタエリスリトール、ジメチルエタノールアミン、トリエタノールアミン、ステアリン酸、オレイン酸等)が挙げられる。二酸化チタンの粒子表面を、上記の無機化合物で被覆した後、更に上記の有機化合物で被覆したものを用いてもよい。 As the titanium dioxide white pigment, those produced by either the so-called sulfuric acid method or the chlorine method can be used. Further, titanium dioxide white pigment whose particle surface is coated with various inorganic compounds or organic compounds may be used. Examples of the inorganic compound include metal oxides and/or metal hydrated oxides such as silicon, aluminum, titanium, zirconium, tin, and antimony. Examples of organic compounds include polyol-based, amine-based, and carboxylic acid-based organic compounds (specifically, trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, dimethylethanolamine, triethanolamine, and stearin). acid, oleic acid, etc.). The particle surface of titanium dioxide may be coated with the above-mentioned inorganic compound and then further coated with the above-mentioned organic compound.
前記のカーボン材料は、炭素原子で構成される種々の形状を有する材料であり、カーボンブラック、カーボンナノチューブ、グラフェン、カーボンナノコイル、カーボンナノホーン、フラーレン、ダイヤモンドライクカーボン等を用いることができ、カーボンナノチューブ等のカーボンナノ粒子が好ましい。 The above-mentioned carbon material is a material having various shapes composed of carbon atoms, and carbon black, carbon nanotubes, graphene, carbon nanocoils, carbon nanohorns, fullerenes, diamond-like carbon, etc. can be used. Carbon nanoparticles such as the following are preferred.
カーボンナノチューブとしては、その構造において特に限定されるものではなく、シングルウォールカーボンナノチューブ及びダブルウォールカーボンナノチューブ等のマルチウォールカーボンナノチューブの何れも用いることができる。カーボンナノチューブは、平均長さが5μm以上であることが好ましい。こうすることで、少ない配合量であっても複合材料の表面において導電パスを良好に形成し、複合材料の導電性を十分に高めることができる。また、カーボンナノチューブは、平均直径が1nm以上3nm以下であることが好ましい。こうすることで、複合材料の導電性をより良好なものとすることができる。カーボンナノチューブの平均長さは、透過型電子顕微鏡(TEM)を用いて粒子を観察したときの100個の粒子の長さの平均値を意味する。平均直径についても同様である。 The carbon nanotubes are not particularly limited in their structure, and either single-wall carbon nanotubes or multi-wall carbon nanotubes such as double-wall carbon nanotubes can be used. It is preferable that the carbon nanotubes have an average length of 5 μm or more. By doing so, even with a small amount of compounding, a conductive path can be formed well on the surface of the composite material, and the conductivity of the composite material can be sufficiently increased. Moreover, it is preferable that the carbon nanotubes have an average diameter of 1 nm or more and 3 nm or less. By doing so, the conductivity of the composite material can be improved. The average length of carbon nanotubes means the average length of 100 particles when the particles are observed using a transmission electron microscope (TEM). The same applies to the average diameter.
カーボンナノチューブは、ラマン分光分析によるGバンドとDバンドの強度比(G/D比)が15以上であることが好ましく、30以上であることがより好ましく、50以上であることが更に好ましい。ラマン分光分析法により得られるラマンスペクトルにおいて1,590cm-1付近に見られるラマンシフトは、グラファイト由来のGバンドと呼ばれ、1,350cm-1付近に見られるラマンシフトはアモルファスカーボンやグラファイトの欠陥に由来のDバンドと呼ばれる。このGバンド、Dバンドの強度比、すなわちG/D比が高いカーボンナノチューブほどグラファイト化度が高く、高品質であること、すなわち高結晶性であり高い導電性を有していることを示している。 The carbon nanotube preferably has an intensity ratio of G band to D band (G/D ratio) determined by Raman spectroscopy of 15 or more, more preferably 30 or more, and even more preferably 50 or more. The Raman shift seen around 1,590 cm -1 in the Raman spectrum obtained by Raman spectroscopy is called the G band derived from graphite, and the Raman shift seen around 1,350 cm -1 is caused by defects in amorphous carbon and graphite. It is called the D band derived from Carbon nanotubes with a higher intensity ratio of the G band and D band, that is, a higher G/D ratio, have a higher degree of graphitization and are of higher quality, indicating that they are highly crystalline and have high conductivity. There is.
カーボンナノチューブは、化学気相成長(CVD)法、アーク放電法、レーザー蒸着法等の任意の製法にて得ることができる。また、カーボンナノチューブは、各種の市販品を用いることもできる。例えば、単層カーボンナノチューブとしては、TUBALLTM(OCSiAl社製)、ZEONANO(登録商標)SG101(日本ゼオン社製)、NC1100(NANOCYL社製)、MEIJO eDIPS(名城ナノカーボン社製)、HipcoTM(NanoIntegris社製)等を用いることができ、多層カーボンナノチューブとしては、VGCF(登録商標)-H(昭和電工社製)等を用いることができる。 Carbon nanotubes can be obtained by any method such as chemical vapor deposition (CVD), arc discharge, and laser deposition. Furthermore, various commercially available carbon nanotubes can also be used. For example, single-walled carbon nanotubes include TUBALL TM (manufactured by OCSiAl), ZEONANO (registered trademark) SG101 (manufactured by Nippon Zeon), NC1100 (manufactured by NANOCYL), MEIJO eDIPS (manufactured by Meijo Nano Carbon), and Hipco TM (manufactured by Meijo Nano Carbon). NanoIntegris), etc. can be used, and as the multi-walled carbon nanotube, VGCF (registered trademark)-H (manufactured by Showa Denko), etc. can be used.
前記の「両末端にシラノール基を有するポリウレタン」とは、ポリウレタン(分子内にウレタン結合を有する重合体)の両末端に、任意の手法によってシラノール基を導入したものである。シラノール基とは、少なくとも1つのヒドロキシル基を有するケイ素原子からなる基のことを意味しており、アルコキシ基等の置換基を有していてもよい。 The above-mentioned "polyurethane having silanol groups at both ends" is one in which silanol groups are introduced at both ends of polyurethane (a polymer having urethane bonds in the molecule) by any method. A silanol group means a group consisting of a silicon atom having at least one hydroxyl group, and may have a substituent such as an alkoxy group.
ポリウレタンの両末端にシラノール基を導入する方法としては公知の方法を用いることができ、例えば、特開2009-235257号に記載のような方法を用いることができる。この方法では、まず、ポリオールとポリイソシアネートとを反応させて、両末端にイソシアネート基を有する高分子(ウレタンプレポリマー)を作製する。このウレタンプレポリマーに、イソシアネート基との反応性を有する官能基をもつアルコキシシラン化合物(シリル化剤)を反応させることで、両末端にアルコキシシリル基を有するポリウレタンが得られる。更に、両末端のアルコキシシリル基の少なくとも1つを、加水分解反応等によってシラノール基に変換(水性化)することによって、ポリウレタンの両末端にシラノール基を導入することができる。以下ではこのようにして得られる高分子化合物のことを、水性シラノール化ウレタンポリマーと呼ぶことがある。 As a method for introducing silanol groups to both ends of polyurethane, a known method can be used, for example, a method described in JP-A No. 2009-235257 can be used. In this method, first, a polyol and a polyisocyanate are reacted to produce a polymer (urethane prepolymer) having isocyanate groups at both ends. By reacting this urethane prepolymer with an alkoxysilane compound (silylating agent) having a functional group that is reactive with isocyanate groups, a polyurethane having alkoxysilyl groups at both ends can be obtained. Furthermore, silanol groups can be introduced at both ends of the polyurethane by converting at least one of the alkoxysilyl groups at both ends into a silanol group (hydrogenization) by a hydrolysis reaction or the like. Hereinafter, the polymer compound obtained in this manner may be referred to as an aqueous silanated urethane polymer.
両末端にシラノール基を有するポリウレタンは、各種公知の方法で製造できるほか、市販品を用いることができる。例えば、水性シリル化ウレタン系樹脂組成物(アクアリンカー(登録商標)SU500:コニシ社製)等を使用することができる。 Polyurethane having silanol groups at both ends can be produced by various known methods, and commercially available products can also be used. For example, an aqueous silylated urethane resin composition (Aqualinker (registered trademark) SU500: manufactured by Konishi Co., Ltd.) can be used.
本発明の複合材料は、両末端にシラノール基を有するポリウレタンの接着作用によって無機顔料粒子とカーボン材料とが溶媒に配合した際に分離しにくくなるように固定されたものである。ここで、本発明における「固定」とは、溶媒に配合した際に分離しにくい状態で複合していることをいい、どのような力が影響してもかまわない。両末端にシラノール基を有するポリウレタンを媒介として、化学的な力、物理的な力又はその両者によって無機顔料粒子とカーボン材料とが結合した状態を想定しているが、それに限定されない。本発明の複合材料の電子顕微鏡写真を図1に示す。 In the composite material of the present invention, the inorganic pigment particles and the carbon material are fixed to each other by the adhesive action of polyurethane having silanol groups at both ends so that they are difficult to separate when mixed in a solvent. Here, "fixed" in the present invention refers to a composite state in which it is difficult to separate when blended in a solvent, and it does not matter what kind of force may be applied. Although it is assumed that the inorganic pigment particles and the carbon material are bonded by chemical force, physical force, or both through polyurethane having silanol groups at both ends, the present invention is not limited thereto. An electron micrograph of the composite material of the present invention is shown in FIG.
本発明の複合材料においては、無機顔料粒子とカーボン材料との溶媒中の固定強度を例えば下記の方法によって評価することができる。 In the composite material of the present invention, the fixation strength of the inorganic pigment particles and the carbon material in a solvent can be evaluated, for example, by the method below.
まず、塩素化ポリオレフィン樹脂をバインダー樹脂として、水を溶媒として用いて、複合材料の顔料質量濃度(PWC)を60%として、塗料組成物を調製する。塩素化ポリオレフィン樹脂としては、例えば、水系塩素化ポリオレフィン樹脂として市販されている日本製紙社製のスーパークロン(登録商標)E-480Tを用いることができる。塗料化直後の塗料組成物の一部を採取し、サンプル1とする。 First, a coating composition is prepared using a chlorinated polyolefin resin as a binder resin, water as a solvent, and a pigment mass concentration (PWC) of the composite material of 60%. As the chlorinated polyolefin resin, for example, Superchron (registered trademark) E-480T manufactured by Nippon Paper Industries, Ltd., which is commercially available as a water-based chlorinated polyolefin resin, can be used. A portion of the coating composition immediately after being made into a coating material was collected and designated as Sample 1.
次に、塗料化直後の塗料組成物を3000Gで10分間、遠心分離し、遠心分離後の液面近傍の塗料組成物を採取して、サンプル2とする。「液面近傍」とは、遠心分離に用いる遠沈管の容積にもよるが、通常は液面から3mm程度の深さまでの範囲を意味する。上記の遠心分離操作は、塗料組成物を長期保管した時の状況を短時間で再現するための操作である。 Next, the paint composition immediately after being made into a paint is centrifuged at 3000G for 10 minutes, and the paint composition near the liquid surface after centrifugation is collected and used as sample 2. "Near the liquid surface" usually means a range up to a depth of about 3 mm from the liquid surface, although it depends on the volume of the centrifuge tube used for centrifugation. The above-mentioned centrifugation operation is an operation for reproducing in a short time the situation when the coating composition is stored for a long period of time.
続いて、サンプル1、2の各々について、分光測色計を用いてL*a*b*表色系における値を測定する。分光測色計としては、エックスライト社製のX-Rite eXact等を用いることができる。サンプル1のL*値、a*値、b*値をL1、a1、b1とし、サンプル2のL*値、a*値、b*値をL2、a2、b2として、L1とL2との差(L1-L2)からΔL、a1とa2との差(a1-a2)からΔa、b1とb2との差(b1-b2)からΔbを算出する。 Subsequently, for each of Samples 1 and 2, values in the L * a * b * color system are measured using a spectrophotometer. As the spectrophotometer, X-Rite eXact manufactured by X-Rite, etc. can be used. Let L * value, a * value, b * value of sample 1 be L1, a1 , b1, and let L * value, a * value, b * value of sample 2 be L2 , a2 , b2 , ΔL from the difference between L 1 and L 2 (L 1 - L 2 ), Δa from the difference between a 1 and a 2 (a 1 - a 2 ), and Δa from the difference between b 1 and b 2 (b 1 - b 2 ) to calculate Δb.
ここで、複合材料における無機顔料粒子とカーボン材料との固定強度が小さい場合又は無機顔料粒子とカーボン材料とが固定しておらず、単に混合状態にある場合、上記の遠心分離操作によって、無機顔料粒子とカーボン材料が分離して無機顔料粒子(又は複合材料)の大部分は沈降するとともに、液面近傍に遊離のカーボン材料が集合することになる。一方で、無機顔料粒子とカーボン材料との固定強度が大きい場合、上記の遠心分離操作によっても無機顔料粒子とカーボン材料がほとんど分離しないことから、複合材料の大部分は沈降して、液面近傍には遊離のカーボン材料が少量しか存在しないことになる。 Here, if the fixation strength between the inorganic pigment particles and the carbon material in the composite material is small, or if the inorganic pigment particles and the carbon material are not fixed and are simply in a mixed state, the inorganic pigment can be removed by the above centrifugation operation. The particles and the carbon material separate and most of the inorganic pigment particles (or composite material) settle, and free carbon material collects near the liquid surface. On the other hand, if the fixation strength between the inorganic pigment particles and the carbon material is high, the inorganic pigment particles and the carbon material will hardly be separated even by the above centrifugation operation, and most of the composite material will settle and remain near the liquid surface. There will be only a small amount of free carbon material present.
このように、無機顔料粒子とカーボン材料との固定強度に応じて、上記遠心分離操作後の液面近傍の遊離のカーボン材料の存在量が変化し、これが上述のΔL、Δa、Δbのうち少なくとも一つに反映される。従って、無機顔料粒子とカーボン材料との固定強度についての間接的な指標として、ΔL、Δa、Δbのうち少なくとも一つを用いることができる。ΔL、Δa、Δbの何れを用いるかは、顔料の種類(色)に応じて最適なものを適宜選択することができる。 In this way, the amount of free carbon material present near the liquid surface after the centrifugation operation changes depending on the fixing strength between the inorganic pigment particles and the carbon material, and this changes at least one of the above-mentioned ΔL, Δa, and Δb. reflected in one. Therefore, at least one of ΔL, Δa, and Δb can be used as an indirect indicator of the fixing strength between the inorganic pigment particles and the carbon material. Which of ΔL, Δa, and Δb to use can be appropriately selected depending on the type (color) of the pigment.
無機顔料粒子として二酸化チタン等の白色顔料を用いる場合、無機白色顔料粒子とカーボン材料との固定強度についての間接的な指標として、上記ΔLを用いる。ΔLの値が20未満であると、二酸化チタン等の無機白色顔料粒子とカーボン材料との固定強度を十分に確保したものと評価することができる。すなわち、無機顔料粒子として二酸化チタン等の白色顔料を用いる場合、下記式で表されるΔLの値が20未満であることが好ましく、18以下がより好ましい。
ΔL=L1-L2
(L1は、前記複合材料と塩素化ポリオレフィン樹脂と水を含み、複合材料の顔料質量濃度を60%とした塗料組成物を作製し、その塗料組成物を分光測色計を用いて測定したL*a*b*表色系におけるL*値であり、L2は、前記塗料組成物を3000Gで10分間、遠心分離した後の液面近傍の組成物を分光測色計を用いて測定したL*a*b*表色系におけるL*値である。)
When using a white pigment such as titanium dioxide as the inorganic pigment particles, the above ΔL is used as an indirect index of the fixing strength between the inorganic white pigment particles and the carbon material. When the value of ΔL is less than 20, it can be evaluated that the fixing strength between the inorganic white pigment particles such as titanium dioxide and the carbon material is sufficiently secured. That is, when using a white pigment such as titanium dioxide as the inorganic pigment particles, the value of ΔL expressed by the following formula is preferably less than 20, more preferably 18 or less.
ΔL=L 1 -L 2
(L 1 was obtained by preparing a paint composition containing the composite material, chlorinated polyolefin resin, and water and setting the pigment mass concentration of the composite material to 60%, and measuring the paint composition using a spectrophotometer. L * a * b * is the L * value in the color system, and L 2 is the composition near the liquid surface after centrifuging the paint composition at 3000 G for 10 minutes using a spectrophotometer. (This is the L * value in the L * a * b * color system.)
本発明の複合材料において、無機顔料粒子とカーボン材料の混合比率は適宜設定することができ、例えば、カーボン材料の含有量の下限値は無機顔料粒子に対して、0.01質量%であるとカーボン材料の添加効果が得られるため好ましく、0.05質量%がより好ましく、0.1質量%が更に好ましい。一方、カーボン材料の含有量の上限値は目的に応じて適宜設定することができ、無機顔料粒子に対して20質量%が好ましく、10質量%がより好ましく、5質量%が更に好ましい。無機顔料粒子に対するカーボン材料の含有量は、熱重量分析によって求めることができる。 In the composite material of the present invention, the mixing ratio of the inorganic pigment particles and the carbon material can be set as appropriate. For example, the lower limit of the content of the carbon material is 0.01% by mass with respect to the inorganic pigment particles. It is preferable because the effect of adding the carbon material can be obtained, more preferably 0.05% by mass, and even more preferably 0.1% by mass. On the other hand, the upper limit of the content of the carbon material can be appropriately set depending on the purpose, and is preferably 20% by mass, more preferably 10% by mass, and even more preferably 5% by mass based on the inorganic pigment particles. The content of carbon material in inorganic pigment particles can be determined by thermogravimetric analysis.
二酸化チタン等の無機白色顔料粒子を用いる場合、黒色のカーボン材料の固定量が多いと複合材料が黒みを帯びてくるが、カーボン材料の含有量を無機白色顔料粒子に対して0.02質量%以上0.5質量%以下にすると白色の状態を維持することができるため好ましい。こうすることで、複合材料を含む塗膜において、良好な白色度と導電性とを実現することができる。 When using inorganic white pigment particles such as titanium dioxide, if the fixed amount of black carbon material is large, the composite material becomes darkish, but the content of carbon material is 0.02% by mass based on the inorganic white pigment particles. If the content is 0.5% by mass or less, the white state can be maintained, which is preferable. By doing so, good whiteness and conductivity can be achieved in the coating film containing the composite material.
また、本発明の複合材料においては、両末端にシラノール基を有するポリウレタンの質量(M1)とカーボン材料の質量(M2)との質量比(M1/M2)が、0.2以上であることが好ましく、0.5以上がより好ましい。こうすることで、無機顔料粒子とカーボン材料とをより強固に固定することができる。 Furthermore, in the composite material of the present invention, the mass ratio (M 1 /M 2 ) of the mass ( M 1 ) of the polyurethane having silanol groups at both ends to the mass (M 2 ) of the carbon material is 0.2 or more. It is preferable that it is, and 0.5 or more is more preferable. By doing so, the inorganic pigment particles and the carbon material can be more firmly fixed.
一方で、両末端にシラノール基を有するポリウレタンの量が大きければ大きいほど(M1/M2の値が大きいほど)、無機顔料粒子とカーボン材料との固定強度が大きくなるわけではなく、ある程度で固定強度は頭打ちになる。また、両末端にシラノール基を有するポリウレタンの量を必要最小限に留めることで、複合材料の導電性等に与える影響を最小限にすることができる。このことを考慮すれば、M1/M2の値の上限値は30程度であり、15以下が好ましく、5以下がより好ましく、3以下が一層好ましい。複合材料における両末端にシラノール基を有するポリウレタンとカーボン材料との質量比は、熱重量分析によって求めることができる。 On the other hand, the greater the amount of polyurethane having silanol groups at both ends (the greater the value of M 1 /M 2 ), the greater the fixing strength between the inorganic pigment particles and the carbon material; Fixed strength has reached a plateau. Further, by keeping the amount of polyurethane having silanol groups at both ends to the minimum necessary, the influence on the conductivity of the composite material can be minimized. Taking this into consideration, the upper limit of the value of M 1 /M 2 is about 30, preferably 15 or less, more preferably 5 or less, and even more preferably 3 or less. The mass ratio of the polyurethane having silanol groups at both ends and the carbon material in the composite material can be determined by thermogravimetric analysis.
本発明の複合材料は、例えば、少なくとも無機顔料粒子とカーボン材料と両末端にシラノール基を有するポリウレタンとを水性分散媒中で混合することによって、製造することができる。 The composite material of the present invention can be produced, for example, by mixing at least inorganic pigment particles, a carbon material, and a polyurethane having silanol groups at both ends in an aqueous dispersion medium.
前記の無機顔料粒子やカーボン材料及び両末端にシラノール基を有するポリウレタンとしては、上述のものを用いることができる。カーボン材料としては、粉体の形態のものに限らず、粉体を各種溶媒(水、ギ酸、メタノール、エタノール、1-プロパノール、2-プロパノール等)に分散させた形態のもの(分散液)を用いることもできる。 As the inorganic pigment particles, carbon material, and polyurethane having silanol groups at both ends, those described above can be used. Carbon materials are not limited to those in powder form, but also those in the form of dispersion of powder in various solvents (water, formic acid, methanol, ethanol, 1-propanol, 2-propanol, etc.) (dispersions). It can also be used.
前記の水性分散媒とは、水を主成分とするもの、すなわち、水の含有量が50質量%以上のものである。水性分散媒中の水の含有量は、好ましくは80質量%以上、より好ましくは90質量%以上、更に好ましくは100質量%である。水以外の成分としては、ギ酸や、水に溶解する各種の有機溶媒(メタノール、エタノール、イソプロパノール、ブタノール、アセトン、メチルエチルケトン、テトラヒドロフラン等)が挙げられる。 The above-mentioned aqueous dispersion medium is one whose main component is water, that is, the water content is 50% by mass or more. The content of water in the aqueous dispersion medium is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass. Components other than water include formic acid and various organic solvents that dissolve in water (methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, tetrahydrofuran, etc.).
上記の原料の混合は、どのような順序で行ってもよい。すなわち、無機顔料粒子と水性分散媒とを予め混合しておき、ここに両末端にシラノール基を有するポリウレタンを添加後、カーボン材料を添加してもよいし、カーボン材料と水性分散媒とを予め混合しておき、ここに両末端にシラノール基を有するポリウレタンを添加後、無機顔料粒子を添加してもよい。あるいは、すべての原料を一度に水性分散媒に添加し、混合してもよい。原料の混合比率は適宜設定することができ、上記の範囲で混合するのが好ましい。必要に応じて、分散剤、乳化剤、pH調整剤、増粘剤、消泡剤、表面調整剤、沈降防止剤等の添加剤を含ませることができる。 The above raw materials may be mixed in any order. That is, the inorganic pigment particles and the aqueous dispersion medium may be mixed in advance, and after adding the polyurethane having silanol groups at both ends, the carbon material may be added, or the carbon material and the aqueous dispersion medium may be mixed in advance. After mixing, the polyurethane having silanol groups at both ends may be added thereto, and then the inorganic pigment particles may be added. Alternatively, all ingredients may be added to the aqueous dispersion medium at once and mixed. The mixing ratio of the raw materials can be set as appropriate, and it is preferable to mix them within the above range. Additives such as a dispersant, an emulsifier, a pH adjuster, a thickener, an antifoaming agent, a surface conditioner, and an antisettling agent can be included as necessary.
特に、無機顔料粒子と水性分散媒との分散液に、両末端にシラノール基を有するポリウレタンを添加し、最後にカーボン材料を添加することが好ましい。また、カーボン材料は粉体の形態で添加するのではなく、予め溶媒に分散させた分散液の形態で添加することがより好ましい。こうすることで、無機顔料粒子とカーボン材料をより均一に固定させることができる。 In particular, it is preferable to add polyurethane having silanol groups at both ends to a dispersion of inorganic pigment particles and an aqueous dispersion medium, and finally add a carbon material. Moreover, it is more preferable to add the carbon material not in the form of powder but in the form of a dispersion liquid in which it is previously dispersed in a solvent. By doing so, the inorganic pigment particles and the carbon material can be more uniformly fixed.
上記原料の混合には、スターラー、ミキサー、ホモジナイザー、撹拌機等の公知の混合機を用いることができる。 For mixing the above raw materials, a known mixer such as a stirrer, mixer, homogenizer, or stirrer can be used.
二酸化チタン等の無機白色顔料粒子を用いる場合、カーボン材料の混合比率は、無機白色顔料粒子に対して0.02質量%以上0.5質量%以下とすることが好ましい。こうすることで、複合材料を含む塗膜において、良好な白色度と導電性とを実現することができる。また、両末端にシラノール基を有するポリウレタンの質量(M1)とカーボン材料の質量(M2)との質量比(M1/M2)が、0.2以上であることが好ましく、0.5以上がより好ましい。更に、M1/M2の値の上限値は30程度であり、15以下が好ましく、5以下がより好ましく、3以下が一層好ましい。こうすることで、無機白色顔料粒子とカーボン材料との固定強度を十分に確保しつつ、両末端にシラノール基を有するポリウレタンが複合材料の導電性に与える影響を最小限にすることができる。 When using inorganic white pigment particles such as titanium dioxide, the mixing ratio of the carbon material is preferably 0.02% by mass or more and 0.5% by mass or less based on the inorganic white pigment particles. By doing so, good whiteness and conductivity can be achieved in the coating film containing the composite material. Further, it is preferable that the mass ratio (M 1 /M 2 ) of the mass of the polyurethane having silanol groups at both ends ( M 1 ) to the mass of the carbon material (M 2 ) is 0.2 or more, and 0.2 or more. More preferably 5 or more. Further, the upper limit of the value of M 1 /M 2 is about 30, preferably 15 or less, more preferably 5 or less, and even more preferably 3 or less. By doing so, the influence of the polyurethane having silanol groups at both ends on the conductivity of the composite material can be minimized while ensuring sufficient fixing strength between the inorganic white pigment particles and the carbon material.
以上のようにして上記原料を混合して、本発明の複合材料を含む分散液を得る。この混合後に必要に応じて加熱したり、pH調整したりしてもよく、更に、必要に応じて、前記分散液を蒸発乾固したり、前記分散液を固液分離してもよく、その固形分を乾燥して粉体を得てもよい。固液分離には公知のろ過方法を用いることができ、例えば、通常、工業的に用いられるロータリープレス、フィルタープレス等の加圧ろ過によるろ過装置や、ヌッチェ、ムーアフィルター等の真空ろ過装置等を用いることができる。その際に、必要に応じて純水等で洗浄を行ってもよい。 The above raw materials are mixed in the manner described above to obtain a dispersion containing the composite material of the present invention. After this mixing, heating or pH adjustment may be performed as necessary.Furthermore, as necessary, the dispersion may be evaporated to dryness or the dispersion may be separated into solid and liquid. A powder may be obtained by drying the solid content. A known filtration method can be used for solid-liquid separation, for example, a filtration device using pressure filtration such as a rotary press or a filter press, which is usually used industrially, or a vacuum filtration device such as a Nutsche or Moore filter. Can be used. At that time, washing may be performed with pure water or the like, if necessary.
また、上記分散液又は上記分散液を固液分離によって得た固形分を、30℃以上180℃以下の温度、好ましくは30℃以上160℃以下で加熱する工程を含んでいてもよい。この加熱工程により、両末端にシラノール基を有するポリウレタンによる無機顔料粒子とカーボン材料との固定強度を更に大きくすることができる。上記加熱工程の温度は、60℃以上100℃以下であることがより好ましい。こうすることで、無機顔料粒子とカーボン材料との固定強度をより一層大きくすることができる。 Further, the method may include a step of heating the dispersion liquid or the solid content obtained from the dispersion liquid by solid-liquid separation at a temperature of 30°C or higher and 180°C or lower, preferably 30°C or higher and 160°C or lower. This heating step can further increase the fixing strength between the inorganic pigment particles and the carbon material by the polyurethane having silanol groups at both ends. The temperature in the heating step is more preferably 60°C or more and 100°C or less. By doing so, the fixing strength between the inorganic pigment particles and the carbon material can be further increased.
上記加熱工程は、分散液を上記固液分離によって得た固形分に対して実施することがより好ましい。こうすることで、無機顔料粒子とカーボン材料をより均一に固定させることができる。 It is more preferable that the heating step is performed on the solid content obtained from the solid-liquid separation of the dispersion. By doing so, the inorganic pigment particles and the carbon material can be more uniformly fixed.
また、上記温度での加熱時間は任意に設定できるが、0.5~5時間程度が好ましい。上記加熱工程においては、乾燥機、オーブン、電気炉等の加熱機器を用いることができる。 Further, the heating time at the above temperature can be set arbitrarily, but it is preferably about 0.5 to 5 hours. In the heating step, heating equipment such as a dryer, an oven, an electric furnace, etc. can be used.
上記の方法で製造した本発明の複合材料は、公知の粉砕機や分級機等を用いて、適宜粒度調整を行ってもよい。 The composite material of the present invention produced by the above method may be appropriately adjusted in particle size using a known pulverizer, classifier, or the like.
本発明の複合材料は、それが有する顔料特性を利用して顔料材料として用いることができる。また、それが有する導電性を利用して導電性材料として用いることができる。更に、本発明の複合材料は、それが有する熱伝導性を利用して熱伝導材料として用いることができる。それらの材料に用いるには、その用途に用いられる添加剤等を適宜混合することができる。 The composite material of the present invention can be used as a pigment material by utilizing its pigment properties. Furthermore, it can be used as a conductive material by utilizing its conductivity. Furthermore, the composite material of the present invention can be used as a thermally conductive material by utilizing its thermal conductivity. In order to use these materials, additives used for the purpose can be mixed as appropriate.
本発明の複合材料は、溶媒と混合して分散体、懸濁液とすることができる。また、塗料用の樹脂等と混合することで、塗料組成物とすることができる。また、複合材料、前記の導電性材料は、塗料用の樹脂等と混合して、導電性塗料組成物とすることができる。導電性塗料組成物としては、例えば静電塗装法に用いるプライマー塗料や、クリーンルーム等に用いる帯電防止塗料等が挙げられる。 The composite material of the present invention can be mixed with a solvent to form a dispersion or suspension. Furthermore, by mixing it with a paint resin or the like, it can be made into a paint composition. Further, the composite material and the above-mentioned conductive material can be mixed with a paint resin or the like to form a conductive paint composition. Examples of the conductive paint composition include primer paints used in electrostatic coating methods and antistatic paints used in clean rooms and the like.
分散体、懸濁液に用いられる溶媒としては、水溶媒や、アルコール(メタノール、ブタノール、エチレングリコール等)、エステル(酢酸エチル等)、エーテル、ケトン(アセトン、メチルエチルケトン等)、芳香族(トルエン、キシレン、ミネラルスピリット)、脂肪族炭化水素等の非水溶媒、又はこれらの混合溶媒が挙げられる。分散体、懸濁液には、必要に応じて、分散剤、乳化剤、不凍剤、pH調整剤、増粘剤、消泡剤等の添加剤を含ませることができる。 Solvents used for dispersions and suspensions include aqueous solvents, alcohols (methanol, butanol, ethylene glycol, etc.), esters (ethyl acetate, etc.), ethers, ketones (acetone, methyl ethyl ketone, etc.), aromatics (toluene, (xylene, mineral spirit), non-aqueous solvents such as aliphatic hydrocarbons, or mixed solvents thereof. The dispersion or suspension may contain additives such as a dispersant, an emulsifier, an antifreeze agent, a pH adjuster, a thickener, and an antifoaming agent, if necessary.
塗料組成物に用いられる樹脂としては、塗料用途で一般に用いられるものであれば特に限定されず、例えば、フェノール樹脂、アルキド樹脂、アクリルアルキド樹脂、アクリル樹脂、アクリルエマルション樹脂、ポリエステル樹脂、ポリエステルウレタン樹脂、ポリエーテル樹脂、ポリオレフィン樹脂、ポリウレタン樹脂、アクリルウレタン樹脂、エポキシ樹脂、変性エポキシ樹脂、シリコン樹脂、アクリルシリコン樹脂、フッ素樹脂、エチレン酢酸ビニル共重合体、アクリル-スチレン共重合体、アミノ樹脂、メタクリル樹脂、ポリカーボネート樹脂、ポリ塩化ビニル樹脂等の各種塗料用樹脂を用いることができる。 The resin used in the coating composition is not particularly limited as long as it is commonly used in coating applications, and examples include phenol resins, alkyd resins, acrylic alkyd resins, acrylic resins, acrylic emulsion resins, polyester resins, and polyester urethane resins. , polyether resin, polyolefin resin, polyurethane resin, acrylic urethane resin, epoxy resin, modified epoxy resin, silicone resin, acrylic silicone resin, fluororesin, ethylene vinyl acetate copolymer, acrylic-styrene copolymer, amino resin, methacrylic Various coating resins such as resin, polycarbonate resin, and polyvinyl chloride resin can be used.
導電性塗料組成物のうち、特に導電性プライマー塗料(プラスチック基材等を静電塗装するにあたり、該基材に導電性を付与する塗料)の用途に用いる場合、非極性基材に対する密着性の観点から、ポリオレフィン樹脂の一種である塩素化ポリオレフィン樹脂を使用することが好ましい。上記ポリオレフィン樹脂としては特に限定されず、例えば、1種又は2種以上のエチレン、プロピレン、ブテン等のオレフィン類の重合体、更にこれらのオレフィン類と酢酸ビニル、ブタジエン、アクリル酸エステル、メタクリル酸エステル等とのラジカル共重合体等を挙げることができる。更に、上記塩素化ポリオレフィンとしては、マレイン酸、無水マレイン酸等で変性したものを使用してもよい。塩素化ポリオレフィン樹脂の具体例としては、塩素化ポリエチレン、塩素化ポリプロピレン、塩素化エチレン-プロピレン共重合体、塩素化エチレン-酢酸ビニル共重合体等が好ましい。また、塩素化ポリオレフィンに重合性モノマーをグラフト重合させたものも使用できる。 Among conductive paint compositions, especially when used as a conductive primer paint (a paint that imparts conductivity to a plastic base material, etc. when electrostatically painting the base material), adhesion to a non-polar base material is particularly important. From this point of view, it is preferable to use a chlorinated polyolefin resin, which is a type of polyolefin resin. The above-mentioned polyolefin resin is not particularly limited, and includes, for example, polymers of one or more olefins such as ethylene, propylene, butene, and these olefins together with vinyl acetate, butadiene, acrylic ester, and methacrylic ester. Examples include radical copolymers with the like. Furthermore, as the above-mentioned chlorinated polyolefin, one modified with maleic acid, maleic anhydride, etc. may be used. Preferred examples of the chlorinated polyolefin resin include chlorinated polyethylene, chlorinated polypropylene, chlorinated ethylene-propylene copolymer, and chlorinated ethylene-vinyl acetate copolymer. Furthermore, a chlorinated polyolefin graft-polymerized with a polymerizable monomer can also be used.
塗料組成物は、必要に応じて、各種添加剤、溶媒等を含むことができる。添加剤としては各種の一般に用いられる分散剤、乳化剤、不凍剤、pH調整剤、増粘剤、消泡剤等が挙げられる。溶媒としては、水溶媒や、アルコール(メタノール、ブタノール、エチレングリコール等)、エステル(酢酸エチル等)、エーテル、ケトン(アセトン、メチルエチルケトン等)、芳香族(トルエン、キシレン、ミネラルスピリット)、脂肪族炭化水素等の非水溶媒、又はこれらの混合溶媒が挙げられる。 The coating composition can contain various additives, solvents, etc. as necessary. Examples of additives include various commonly used dispersants, emulsifiers, antifreeze agents, pH adjusters, thickeners, antifoaming agents, and the like. Examples of solvents include aqueous solvents, alcohols (methanol, butanol, ethylene glycol, etc.), esters (ethyl acetate, etc.), ethers, ketones (acetone, methyl ethyl ketone, etc.), aromatics (toluene, xylene, mineral spirits), carbonized aliphatics. Examples include non-aqueous solvents such as hydrogen, and mixed solvents thereof.
また、塗料組成物では、複合材料自体が着色力や隠蔽力を有するため、顔料等の着色剤を別途添加する必要はないが、着色力や隠蔽力の補填のため、各種の着色剤を含ませることができる。着色剤としては、例えば上述の無機顔料粒子等を用いることができる。 In addition, in paint compositions, since the composite material itself has coloring power and hiding power, there is no need to separately add colorants such as pigments. can be set. As the colorant, for example, the above-mentioned inorganic pigment particles can be used.
複合材料と、溶剤、必要に応じて上記添加剤、着色材、溶媒等とを混合機で混合し、必要に応じて脱泡して、溶剤分散体を調製することができる。また、複合材料と、樹脂、必要に応じて上記添加剤、着色材、溶媒等とを混合機で混合し、必要に応じて脱泡して、塗料組成物を調製することができる。混合機としては、例えば、通常工業的に用いられる2軸ミキサー、3本ロール、サンドミル等が挙げられ、ラボスケールであれば、ホモジナイザーやペイントシェーカー等を用いることができる。その際に、必要に応じて、ガラス、アルミナ、ジルコニア、珪酸ジルコニウム等を成分とする粉砕メディアを用いてもよい。 A solvent dispersion can be prepared by mixing the composite material, a solvent, and, if necessary, the above-mentioned additives, colorants, solvents, etc., in a mixer, and defoaming if necessary. Further, a coating composition can be prepared by mixing the composite material, a resin, and, if necessary, the above-mentioned additives, colorants, solvents, etc., in a mixer, and defoaming if necessary. Examples of the mixer include a twin-screw mixer, a three-roll mixer, a sand mill, etc. which are usually used industrially, and a homogenizer, a paint shaker, etc. can be used in the case of a laboratory scale. At that time, grinding media containing glass, alumina, zirconia, zirconium silicate, etc. may be used as necessary.
上述したように、本発明の複合材料では無機顔料粒子とカーボン材料とが強固に固定されている。従って、複合材料に外力(例えば、塗料作成時の剪断力)がかかる状況下においても、無機顔料粒子とカーボン材料とが分離することなく、複合化された状態を高度に維持することができる。その結果、溶剤分散体や塗料組成物では、長期保管時の「色分かれ」現象を効果的に抑制することができる。 As described above, in the composite material of the present invention, the inorganic pigment particles and the carbon material are firmly fixed. Therefore, even under conditions where external force (for example, shearing force during paint preparation) is applied to the composite material, the inorganic pigment particles and the carbon material do not separate and can maintain a highly composite state. As a result, in solvent dispersions and coating compositions, the phenomenon of "color separation" during long-term storage can be effectively suppressed.
前記の溶剤分散体や塗料組成物を基材に塗布して硬化させると塗膜を形成することができる。また、複合材料が導電性を有すると、導電性塗膜を得ることができる。また、複合材料が熱伝導性を有すると、熱伝導性塗膜を得ることができ、複合材料の特性を持った塗膜を作製することができる。 A coating film can be formed by applying the above-mentioned solvent dispersion or coating composition to a substrate and curing it. Moreover, when the composite material has electrical conductivity, an electrically conductive coating film can be obtained. Further, when the composite material has thermal conductivity, a thermally conductive coating film can be obtained, and a coating film having the characteristics of the composite material can be produced.
前記の溶剤分散体や塗料組成物を塗布する方法としては、スピンコート、スプレー塗装、ローラーコート、ディップコート、フローコート、ナイフコート、静電塗装、バーコート、ダイコート、ハケ塗り、液滴を滴下する方法等の一般的な方法を制限なく用いることができる。溶剤分散体や塗料組成物の塗布に用いる器具は、スプレーガン、ローラー、刷毛、バーコーター、ドクターブレード等の公知の器具から適宜選択できる。塗布後に乾燥させて硬化させると、塗膜を得ることができる。また、乾燥後に焼付を行ってもよい。焼付条件は適宜設定が可能であるが、例えば乾燥炉雰囲気中において、40℃以上150℃以下の温度範囲で1~120分間程度の焼付時間とすることができる。この設定条件とすることで、コイルコーティングラインの乾燥炉にて十分な焼付が可能となる。 Methods for applying the above-mentioned solvent dispersion and coating composition include spin coating, spray coating, roller coating, dip coating, flow coating, knife coating, electrostatic coating, bar coating, die coating, brush coating, and dropping droplets. General methods such as methods can be used without limitation. The equipment used for applying the solvent dispersion or coating composition can be appropriately selected from known equipment such as a spray gun, roller, brush, bar coater, and doctor blade. A coating film can be obtained by drying and curing after application. Furthermore, baking may be performed after drying. The baking conditions can be set as appropriate, and for example, the baking time can be set in a drying oven atmosphere at a temperature range of 40° C. or more and 150° C. or less for about 1 to 120 minutes. With these setting conditions, sufficient baking is possible in the drying oven of the coil coating line.
また、溶剤分散体や塗料組成物を塗布する基材としては、セラミックス製品、ガラス製品、金属製品、プラスチック製品、紙製品等が挙げられる。 Furthermore, examples of the substrate to which the solvent dispersion or coating composition is applied include ceramic products, glass products, metal products, plastic products, paper products, and the like.
前記の塗膜は、複合材料の有する顔料特性を保持することができる。また、複合材料の有する導電性特性を保持することができる。例えば、二酸化チタン等の無機白色顔料粒子を用いた複合材料と、塗料樹脂として塩素化ポリオレフィン樹脂を含む塗料組成物を用いて作製した塗膜において、Lab表色系における塗膜のL値を75以上とすることができ、好ましくは80以上とすることができる。 The coating film described above can retain the pigment properties of the composite material. Further, the conductive properties of the composite material can be maintained. For example, in a paint film made using a composite material using inorganic white pigment particles such as titanium dioxide and a paint composition containing a chlorinated polyolefin resin as a paint resin, the L value of the paint film in the Lab color system is 75. It can be more than 80, preferably 80 or more.
上記の塗膜のL値、a値、b値を測定する場合、例えば、顔料質量濃度(PWC)が60%の塗料組成物を調製し、これを4ミルのフィルムアプリケーターを用いて、乾燥塗膜の膜厚が約13μmとなるように白黒チャート紙に塗布し、塗膜を形成する。白黒チャート紙の黒地上に形成された塗膜について、測色計(カラーコンピューター SM-5:スガ試験機社製)を用いてL値、a値、b値を測定する。 When measuring the L value, a value, and b value of the above-mentioned coating film, for example, prepare a paint composition with a pigment mass concentration (PWC) of 60%, and apply the dry coating using a 4 mil film applicator. A coating film is formed by applying it to black and white chart paper so that the film thickness is about 13 μm. The L value, a value, and b value of the coating film formed on the black surface of black and white chart paper are measured using a colorimeter (Color Computer SM-5: manufactured by Suga Test Instruments Co., Ltd.).
また、前記の塗膜は、十分な導電性を発現することができる。例えば、シート抵抗(単位:Ω/□)としての表面抵抗率を1×109未満とすることができ、好ましくは1×108未満とすることができる。具体的に、二酸化チタン等の無機白色顔料粒子を用いた複合材料と、塗料樹脂として塩素化ポリオレフィン樹脂を含む塗料組成物を用いて作成した導電性塗膜において、シート抵抗(単位:Ω/□)としての表面抵抗率を1×109未満とすることができ、好ましくは1×108未満とすることができ、より好ましくは1×107未満とすることができる。 Further, the coating film described above can exhibit sufficient electrical conductivity. For example, the surface resistivity as a sheet resistance (unit: Ω/□) can be less than 1×10 9 , preferably less than 1×10 8 . Specifically, sheet resistance (unit: Ω/□ ) can be less than 1×10 9 , preferably less than 1×10 8 , more preferably less than 1×10 7 .
塗膜の表面抵抗率を測定する場合、例えば、顔料質量濃度(PWC)が60%の塗料組成物を調製し、これを4ミルのフィルムアプリケーターを用いて、乾燥塗膜の膜厚が約13μmとなるように白黒チャート紙に塗布し、塗膜を形成する。白黒チャート紙上に形成された塗膜について、表面抵抗計(Hiresta(登録商標)-UP MCP-HT450:三菱化学社製)を用いて、印加電圧は10Vの条件下で表面抵抗率を測定する。 When measuring the surface resistivity of a paint film, for example, a paint composition with a pigment mass concentration (PWC) of 60% is prepared, and a dry paint film thickness of approximately 13 μm is applied using a 4 mil film applicator. Coat it on black and white chart paper to form a coating film. The surface resistivity of the coating film formed on the black and white chart paper is measured using a surface resistivity meter (Hiresta (registered trademark)-UP MCP-HT450, manufactured by Mitsubishi Chemical Corporation) under the condition of an applied voltage of 10V.
以下に本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。 Examples of the present invention are shown below, but the present invention is not limited to these Examples.
<複合材料の作製>
(実施例1)
無機白色顔料粒子として二酸化チタン顔料(CR-95:石原産業社製)20gと純水150mlとをビーカーに入れて、室温で撹拌して混合した。この混合液に、二酸化チタン顔料に対して0.04質量%の水性シラノール化ウレタンポリマーを添加して、更に混合した。具体的には、有効成分として水性シラノール化ウレタンポリマーを40質量%含有する水性シリル化ウレタン系樹脂組成物(アクアリンカー(登録商標)SU500:コニシ社製)を純水で100倍希釈したものを準備し、この希釈液2.0gを上記混合液に添加し、室温で10分間撹拌して混合した。更にこの混合液に二酸化チタン顔料に対して0.04質量%のカーボンナノチューブ(表3、4中、CNTと表示する。)を添加して、更に混合した。具体的には、0.2質量%のカーボンナノチューブの水分散体(TUBALLTM COAT_E H2O DBD:OCSiAl社製)を4.0g加えて、室温で10分間撹拌して混合した。
上記混合液をブフナー漏斗で吸引ろ過して固形分を得た。この固形分を、実施例1の試料とした。
<Preparation of composite material>
(Example 1)
20 g of titanium dioxide pigment (CR-95, manufactured by Ishihara Sangyo Co., Ltd.) as inorganic white pigment particles and 150 ml of pure water were placed in a beaker and mixed by stirring at room temperature. To this liquid mixture, 0.04% by mass of an aqueous silanated urethane polymer based on the titanium dioxide pigment was added and further mixed. Specifically, an aqueous silylated urethane resin composition (Aqualincar (registered trademark) SU500, manufactured by Konishi Corporation) containing 40% by mass of an aqueous silanated urethane polymer as an active ingredient was diluted 100 times with pure water. 2.0 g of this diluted solution was added to the above mixed solution and mixed by stirring at room temperature for 10 minutes. Further, 0.04% by mass of carbon nanotubes (indicated as CNT in Tables 3 and 4) based on the titanium dioxide pigment was added to this liquid mixture, and the mixture was further mixed. Specifically, 4.0 g of a 0.2% by mass aqueous dispersion of carbon nanotubes (TUBALL TM COAT_E H 2 O DBD: manufactured by OCSiAl) was added and mixed by stirring at room temperature for 10 minutes.
The mixture was suction filtered using a Buchner funnel to obtain solid content. This solid content was used as the sample of Example 1.
(実施例2)
実施例1において、ろ別して得た固形分を、乾燥機(Inert Oven DN411I:ヤマト科学社製)を用いて150℃で3時間乾燥して、実施例2の試料を得た。
(Example 2)
The solid content obtained by filtration in Example 1 was dried at 150° C. for 3 hours using a dryer (Inert Oven DN411I: manufactured by Yamato Scientific Co., Ltd.) to obtain a sample of Example 2.
(実施例3)
実施例2において、水性シラノール化ウレタンポリマーの添加量を、二酸化チタン顔料に対して0.01質量%に変更したこと以外は実施例2と同様にして、実施例3の試料を得た。
(Example 3)
A sample of Example 3 was obtained in the same manner as in Example 2, except that the amount of the aqueous silanated urethane polymer added was changed to 0.01% by mass based on the titanium dioxide pigment.
(実施例4)
実施例2において、水性シラノール化ウレタンポリマーの添加量を、二酸化チタン顔料に対して0.5質量%に変更したこと以外は実施例2と同様にして、実施例4の試料を得た。
(Example 4)
A sample of Example 4 was obtained in the same manner as in Example 2, except that the amount of the aqueous silanated urethane polymer added was changed to 0.5% by mass based on the titanium dioxide pigment.
(実施例5)
実施例2において、水性シラノール化ウレタンポリマーの添加量を、二酸化チタン顔料に対して0.1質量%に変更するとともに、カーボンナノチューブの添加量を、二酸化チタン顔料に対して0.1質量%に変更したこと以外は実施例2と同様にして、実施例5の試料を得た。
(Example 5)
In Example 2, the amount of the aqueous silanated urethane polymer added was changed to 0.1% by mass relative to the titanium dioxide pigment, and the amount of carbon nanotubes added was changed to 0.1% by mass relative to the titanium dioxide pigment. A sample of Example 5 was obtained in the same manner as Example 2 except for the following changes.
(比較例1)
実施例2において、水性シラノール化ウレタンポリマーに代えて、市販のシランカップリング剤である3-アミノプロピルトリメトキシシラン(KBM-903:信越シリコーン社製)を用いたこと以外は実施例2と同様にして、比較例1の試料を得た。このシランカップリング剤は、分子の片方の末端のみに加水分解性のアルコキシシリル基を有するものである。
(Comparative example 1)
Example 2 was the same as Example 2 except that 3-aminopropyltrimethoxysilane (KBM-903: manufactured by Shin-Etsu Silicone Co., Ltd.), a commercially available silane coupling agent, was used instead of the aqueous silanated urethane polymer. A sample of Comparative Example 1 was obtained. This silane coupling agent has a hydrolyzable alkoxysilyl group only at one end of the molecule.
(比較例2)
実施例2において、水性シラノール化ウレタンポリマーに代えて、市販のシランカップリング剤である1,6-ビス(トリメトキシシリル)ヘキサン(KBM-3066:信越シリコーン社製)を用いたこと以外は実施例2と同様にして、比較例2の試料を得た。このシランカップリング剤は、分子の両末端に加水分解性のアルコキシシリル基を有し、且つ、アルコキシシリル基の間にポリウレタンとは異なる基本骨格(ヘキサン)を有するものである。
(Comparative example 2)
In Example 2, except that 1,6-bis(trimethoxysilyl)hexane (KBM-3066: manufactured by Shin-Etsu Silicone Co., Ltd.), a commercially available silane coupling agent, was used instead of the aqueous silanated urethane polymer. A sample of Comparative Example 2 was obtained in the same manner as Example 2. This silane coupling agent has hydrolyzable alkoxysilyl groups at both ends of the molecule, and has a basic skeleton (hexane) different from polyurethane between the alkoxysilyl groups.
(比較例3)
実施例2において、水性シラノール化ウレタンポリマーに代えて、市販のシランカップリング剤であるアミノシラン(KBP-90:信越シリコーン社製)を用いたこと以外は実施例2と同様にして、比較例3の試料を得た。このシランカップリング剤は、分子内に複数のシラノール基を有するが、シラノール基の間にポリウレタンウレタン骨格を有しないものである。
(Comparative example 3)
Comparative Example 3 was carried out in the same manner as in Example 2, except that a commercially available silane coupling agent, aminosilane (KBP-90, manufactured by Shin-Etsu Silicone Co., Ltd.) was used in place of the aqueous silanated urethane polymer. samples were obtained. This silane coupling agent has a plurality of silanol groups in its molecule, but does not have a polyurethane urethane skeleton between the silanol groups.
<塗料組成物の作製>
上記実施例1~5及び比較例1~3の試料を用いて、顔料質量濃度(PWC)60%にて塗料組成物を作製した。具体的には、下記表1に記載の組成にて原料を準備し、これらを70mlのマヨネーズ瓶に入れ、更にガラスビーズ25gを加えて、撹拌機(ペイントシェーカー:Red Devil社製)を用いて20分間混合した。ガラスビーズをろ別後、脱泡機(あわとり練太郎(登録商標)AR-250:THINKY社製)を用いて、2000rpmで1分間撹拌して脱泡し、実施例1~5及び比較例1~3の試料を含む塗料組成物を得た。
<Preparation of coating composition>
Using the samples of Examples 1 to 5 and Comparative Examples 1 to 3 above, coating compositions were prepared at a pigment mass concentration (PWC) of 60%. Specifically, raw materials were prepared with the composition shown in Table 1 below, and they were placed in a 70 ml mayonnaise bottle, 25 g of glass beads were added, and the mixture was mixed using a stirrer (paint shaker: manufactured by Red Devil). Mixed for 20 minutes. After filtering the glass beads, they were degassed by stirring at 2000 rpm for 1 minute using a defoaming machine (Awatori Rentaro (registered trademark) AR-250: manufactured by THINKY), and Examples 1 to 5 and Comparative Examples A coating composition containing samples 1 to 3 was obtained.
また、表2に記載の組成にて原料を準備し、上記と同様の方法にて比較例4の塗料組成物を得た。比較例4の塗料組成物は、実施例1の塗料組成物と同量の二酸化チタン顔料及びカーボンナノチューブを混合物の形態で含むものである。 Further, raw materials were prepared with the compositions shown in Table 2, and a coating composition of Comparative Example 4 was obtained in the same manner as above. The coating composition of Comparative Example 4 contains the same amount of titanium dioxide pigment and carbon nanotubes as the coating composition of Example 1 in the form of a mixture.
<塗料組成物の色分かれの評価>
塗料化直後の各実施例及び比較例の塗料組成物について、液面付近から4ml採取し、サンプル1とした。また、塗料化直後の各実施例及び比較例の塗料組成物を遠沈管(50PA:日立工機社製)に入れ、遠心分離機(CR21GII:日立工機社製)を用いて、25℃の温度条件下、3000Gで10分間遠心分離した。遠心分離後の塗料組成物の液面付近から4ml採取し、サンプル2とした。
<Evaluation of color separation of paint composition>
4 ml of each of the coating compositions of Examples and Comparative Examples immediately after being made into coatings was taken from near the liquid surface and designated as Sample 1. In addition, the coating compositions of the Examples and Comparative Examples immediately after being made into coatings were put into a centrifuge tube (50PA: manufactured by Hitachi Koki Co., Ltd.), and heated to 25°C using a centrifuge (CR21GII: manufactured by Hitachi Koki Co., Ltd.). Centrifugation was performed at 3000G for 10 minutes under temperature conditions. After centrifugation, 4 ml of the paint composition was taken from near the liquid surface and designated as Sample 2.
各実施例及び比較例のサンプル1、サンプル2の各々をポリスチレン製のディスポセル(#1937:Kartell社製、光路長10mm、光路幅10mm)に入れ、分光測色計(X-Rite eXact:エックスライト社製)を用いて、シングルL*a*b*モードにてL*値を測定した。サンプル1のL*値をL1、サンプル2のL*値をL2として、L1とL2との差(L1-L2)の値(ΔL)を算出した。その結果を表3に示す。 Each of Sample 1 and Sample 2 of each Example and Comparative Example was placed in a polystyrene disposable cell (#1937: manufactured by Kartell, optical path length 10 mm, optical path width 10 mm), and a spectrophotometer (X-Rite eXact: The L * value was measured in the single L * a * b * mode using the L*A*B* (manufactured by Wright Co., Ltd.). The L * value of Sample 1 was set as L 1 and the L * value of Sample 2 was set as L 2 , and the value (ΔL) of the difference (L 1 −L 2 ) between L 1 and L 2 was calculated. The results are shown in Table 3.
表3から明らかなように、カーボンナノチューブと二酸化チタン顔料とを混合しただけの塗料組成物(比較例4)では、ΔLの値が20以上となっている。比較例4の塗料組成物では、上記遠心分離後の塗料組成物の目視観察においても、液面付近にカーボンナノチューブの浮遊物が確認でき、液面付近が黒ずんで見える。このことが影響して、塗料組成物のΔLの値が大きくなっていると考えられる。 As is clear from Table 3, the value of ΔL is 20 or more in the coating composition (Comparative Example 4) in which only carbon nanotubes and titanium dioxide pigments are mixed. In the coating composition of Comparative Example 4, even in visual observation of the coating composition after centrifugation, suspended matter of carbon nanotubes was observed near the liquid surface, and the vicinity of the liquid surface appeared darkened. This is considered to be the reason why the value of ΔL of the coating composition becomes large.
また、各種のシランカップリング剤を用いてカーボンナノチューブと二酸化チタン顔料との固定を試みたもの(比較例1~3)においても、比較例4とほぼ同等のΔLの値となっており、目視観察においても同様の傾向が見られた。この結果から、比較例1~3の試料では、そもそも二酸化チタン顔料とカーボンナノチューブとが固定されていないか、あるいは一度は固定されたとしても、塗料化の際の剪断力でカーボンナノチューブと二酸化チタン顔料とが容易に分離してしまうために、「色分かれ」現象が生じているものと考えらえる。すなわち、比較例1~3では、カーボンナノチューブと二酸化チタン顔料との固定強度が不十分である。 In addition, in the cases in which carbon nanotubes and titanium dioxide pigments were tried to be fixed using various silane coupling agents (Comparative Examples 1 to 3), the ΔL value was almost the same as that in Comparative Example 4, and the visual A similar trend was observed in observations. From this result, in the samples of Comparative Examples 1 to 3, the titanium dioxide pigment and carbon nanotubes are not fixed in the first place, or even if they are fixed once, the carbon nanotubes and titanium dioxide are bonded together due to the shearing force during the coating process. It is thought that the "color separation" phenomenon occurs because the pigments are easily separated. That is, in Comparative Examples 1 to 3, the fixing strength between the carbon nanotubes and the titanium dioxide pigment was insufficient.
一方で、実施例1~5の塗料組成物は、ΔLの値が20未満と比較的低い値となっており、「色分かれ」現象が抑制されている。このことから、実施例1~5の試料(複合材料)では、カーボンナノチューブと二酸化チタン顔料とが水性シラノール化ウレタンポリマーによって強固に固定されていることが分かる。 On the other hand, the coating compositions of Examples 1 to 5 have relatively low ΔL values of less than 20, and the "color separation" phenomenon is suppressed. This shows that in the samples (composite materials) of Examples 1 to 5, the carbon nanotubes and the titanium dioxide pigment were firmly fixed by the aqueous silanated urethane polymer.
また、複合材料の製造における加熱工程の有無に着目して、実施例1と実施例2とを比較すると、加熱工程がある場合(実施例2)のほうがΔLはより低い値となっており、加熱によって二酸化チタン顔料とカーボンナノチューブとの固定強度を大きくすることができる。 In addition, when comparing Example 1 and Example 2 with a focus on the presence or absence of a heating process in the production of the composite material, ΔL is a lower value in the case where there is a heating process (Example 2), The fixing strength between the titanium dioxide pigment and the carbon nanotubes can be increased by heating.
更に、固定成分(水性シラノール化ウレタンポリマー)とカーボンナノチューブとの質量比に着目して、実施例2、実施例3及び実施例4を比較すると、質量比が最も小さい場合(実施例3:質量比0.25)であっても、ΔLの値は十分に低い値(20未満)であり、二酸化チタン顔料とカーボンナノチューブとの固定強度を十分に確保することができる。 Furthermore, when comparing Examples 2, 3, and 4 focusing on the mass ratio of the fixed component (aqueous silanated urethane polymer) to the carbon nanotubes, it is found that when the mass ratio is the smallest (Example 3: mass Even if the ratio is 0.25), the value of ΔL is a sufficiently low value (less than 20), and sufficient fixing strength between the titanium dioxide pigment and the carbon nanotubes can be ensured.
<塗膜の物性評価>
「色分かれ」現象が十分に抑制された実施例1~5の塗料組成物について、下記の方法にて塗膜を作成し、その表面抵抗率と白色度とを測定した。
<Evaluation of physical properties of paint film>
For the coating compositions of Examples 1 to 5 in which the "color separation" phenomenon was sufficiently suppressed, coating films were prepared by the following method, and the surface resistivity and whiteness of the coatings were measured.
(塗膜の作製)
実施例1~5の塗料組成物について、4ミルのフィルムアプリケーター(AP100:太佑機材社製)を用いて、白黒チャート紙(Form 5C Opacify Chart:LENETA社製)に塗布した。これを、乾燥機(SPHH-202:espec社製)を用いて80℃で5分間乾燥して、乾燥塗膜の膜厚が約13μmの塗膜を作製した。
(Preparation of coating film)
The coating compositions of Examples 1 to 5 were applied to black and white chart paper (Form 5C Opacify Chart, manufactured by LENETA) using a 4 mil film applicator (AP100, manufactured by Taiyu Kizai Co., Ltd.). This was dried at 80° C. for 5 minutes using a dryer (SPHH-202: manufactured by Espec) to produce a coating film with a dry coating thickness of about 13 μm.
(塗膜の表面抵抗率の測定)
上記の塗膜について、表面抵抗計(Hiresta(登録商標)-UP MCP-HT450:三菱化学社製)を用いて表面抵抗率(Ω/□)を測定した。測定時の電極にはJボックスUタイプを用いた。また、印加電圧は10Vとした。
(Measurement of surface resistivity of coating film)
The surface resistivity (Ω/□) of the above coating film was measured using a surface resistivity meter (Hiresta (registered trademark)-UP MCP-HT450: manufactured by Mitsubishi Chemical Corporation). A J-box U type was used as the electrode during measurement. Further, the applied voltage was 10V.
(塗膜の白色度の測定)
上記の塗膜について、測色計(カラーコンピューター SM-5:スガ試験機社製)を用いて、Lab表色系におけるL値(黒地上でのL値)を測定した。
(Measurement of whiteness of paint film)
Regarding the above coating film, the L value (L value on black ground) in the Lab color system was measured using a colorimeter (Color Computer SM-5: manufactured by Suga Test Instruments Co., Ltd.).
表4から明らかなように、実施例1~5の何れにおいても塗膜のL値が75以上であり、白色塗膜に一般に求められる白色度を十分達成していることが分かる。 As is clear from Table 4, in all of Examples 1 to 5, the L value of the coating film was 75 or more, indicating that the whiteness generally required for a white coating film was sufficiently achieved.
実施例1~5の何れにおいても、塗膜の表面抵抗率が1×109Ω/□未満であり、導電性塗膜に一般に求められる導電性を達成していることが分かる。 It can be seen that in any of Examples 1 to 5, the surface resistivity of the coating film was less than 1×10 9 Ω/□, achieving the conductivity generally required for a conductive coating film.
また、二酸化チタン顔料に対するカーボンナノチューブの含有量に着目して、実施例2と実施例5とを比較すると、含有量が大きい場合(実施例5)のほうが塗膜の表面抵抗率が小さく、高い導電性を実現することができる。 In addition, when comparing Example 2 and Example 5 with a focus on the content of carbon nanotubes relative to the titanium dioxide pigment, the surface resistivity of the coating film is smaller and higher when the content is larger (Example 5). Conductivity can be achieved.
更に、固定成分とカーボンナノチューブとの質量比に着目して、実施例2、実施例3及び実施例4を比較すると、質量比が小さいほど、塗膜の表面抵抗率が小さく、高い導電性を実現することができる。これは、固定成分の使用量を、二酸化チタン顔料とカーボンナノチューブとの固定に必要な必要最小限の量に留めることで、固定成分が塗膜の導電性に与える影響を最小化できるためであると考えられる。 Furthermore, when comparing Examples 2, 3, and 4 with a focus on the mass ratio of the fixed component to the carbon nanotubes, the smaller the mass ratio, the lower the surface resistivity of the coating film, and the higher the conductivity. It can be realized. This is because by keeping the amount of fixing component used to the minimum amount necessary to fix the titanium dioxide pigment and carbon nanotubes, the effect of the fixing component on the conductivity of the coating film can be minimized. it is conceivable that.
本発明の複合材料によれば、溶媒分散体や塗料組成物に配合した際の「色分かれ」現象が抑制でき、安定した塗膜特性(顔料特性、導電性、熱伝導性等)を得ることができる。従って、本発明の複合材料は、例えば静電塗装法に用いるプライマー塗料や、クリーンルーム等に用いる帯電防止塗料等の各種の導電性塗料組成物に有用である。 According to the composite material of the present invention, it is possible to suppress the "color separation" phenomenon when blended into a solvent dispersion or a coating composition, and to obtain stable coating film properties (pigment properties, electrical conductivity, thermal conductivity, etc.). Can be done. Therefore, the composite material of the present invention is useful for various conductive paint compositions, such as primer paints used in electrostatic coating methods and antistatic paints used in clean rooms and the like.
Claims (10)
形分を30℃以上180℃以下の温度で加熱する工程を含む、無機白色顔料粒子とカーボンナノチューブとが、両末端にシラノール基を有するポリウレタンで固定された複合材料の製造方法。 Inorganic white pigment particles and carbon , comprising a step of solid-liquid separation of the mixed liquid obtained in the mixing step according to claim 8 , and a step of heating the obtained solid content at a temperature of 30 ° C. or higher and 180 ° C. or lower. A method for producing a composite material in which nanotubes are fixed with polyurethane having silanol groups at both ends .
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JP2013221041A (en) | 2012-04-13 | 2013-10-28 | Kansai Paint Co Ltd | Water-based coating composition and method for forming multilayer coating film |
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