JP2015048432A - Color material, color material dispersion liquid, and resin composition - Google Patents
Color material, color material dispersion liquid, and resin composition Download PDFInfo
- Publication number
- JP2015048432A JP2015048432A JP2013182103A JP2013182103A JP2015048432A JP 2015048432 A JP2015048432 A JP 2015048432A JP 2013182103 A JP2013182103 A JP 2013182103A JP 2013182103 A JP2013182103 A JP 2013182103A JP 2015048432 A JP2015048432 A JP 2015048432A
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- general formula
- color material
- colorant
- solvent
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- 239000000463 material Substances 0.000 title claims abstract description 137
- 239000006185 dispersion Substances 0.000 title claims abstract description 77
- 239000011342 resin composition Substances 0.000 title claims description 45
- 239000007788 liquid Substances 0.000 title abstract description 7
- 150000001768 cations Chemical class 0.000 claims abstract description 35
- 150000001450 anions Chemical class 0.000 claims abstract description 33
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims description 65
- 239000003086 colorant Substances 0.000 claims description 59
- 239000011230 binding agent Substances 0.000 claims description 36
- 239000002270 dispersing agent Substances 0.000 claims description 34
- 238000004040 coloring Methods 0.000 claims description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 125000001424 substituent group Chemical group 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 abstract description 15
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 abstract description 6
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 abstract description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 abstract description 2
- NGYMZFJVHHKJQR-UHFFFAOYSA-N 4-bromo-n,n-diethylaniline Chemical compound CCN(CC)C1=CC=C(Br)C=C1 NGYMZFJVHHKJQR-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 37
- -1 salt compound Chemical class 0.000 description 35
- 230000015572 biosynthetic process Effects 0.000 description 30
- 238000003786 synthesis reaction Methods 0.000 description 30
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- 239000011347 resin Substances 0.000 description 27
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- 230000000052 comparative effect Effects 0.000 description 21
- 125000003118 aryl group Chemical group 0.000 description 17
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- 125000003710 aryl alkyl group Chemical group 0.000 description 15
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
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- 125000000217 alkyl group Chemical group 0.000 description 11
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
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- 229910052757 nitrogen Inorganic materials 0.000 description 9
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 6
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- 125000002947 alkylene group Chemical group 0.000 description 6
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- 239000000049 pigment Substances 0.000 description 6
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- 150000002500 ions Chemical class 0.000 description 5
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- 238000002360 preparation method Methods 0.000 description 5
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 238000002356 laser light scattering Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920000083 poly(allylamine) Polymers 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002873 Polyethylenimine Chemical class 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 238000007792 addition Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 125000002091 cationic group Chemical group 0.000 description 2
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- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000003566 oxetanyl group Chemical group 0.000 description 2
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
本発明は、色材、当該色材を含有する色材分散液、及び当該色材を含有する樹脂組成物に関する。 The present invention relates to a color material, a color material dispersion containing the color material, and a resin composition containing the color material.
近赤外線吸収色素は、例えば、赤外線吸収フィルター、熱線吸収フィルター、バンドパスフィルター、不可視印刷用インク、赤外線吸収塗料、フラッシュトナー、電子写真感光体、増感剤、光ディスク等の光記録材料、光センサーや、赤外線レーザーを用いた製板等の用途に用いられている。このような近赤外線吸収色素として、ポリメチン系色素、フタロシアニン系色素、アミニウム系色素、ジイモニウム系色素等が知られており、近赤外線の吸収に優れている点から、アミニウム系色素やジイモニウム系色素が広く用いられている。
アミニウム系色素やジイモニウム系色素は、一般に、フタロシアニン系色素よりも可視光線の吸収が小さいため着色しにくいというメリットがある一方、アミニウム系色素及びジイモニウム系色素は、一般に、耐熱性や耐光性が低いという問題があった。
Near-infrared absorbing pigments include, for example, infrared absorbing filters, heat ray absorbing filters, bandpass filters, invisible printing inks, infrared absorbing paints, flash toners, electrophotographic photoreceptors, sensitizers, optical recording materials such as optical disks, optical sensors, etc. It is also used for applications such as plate making using an infrared laser. As such near-infrared absorbing dyes, polymethine dyes, phthalocyanine dyes, aminium dyes, diimonium dyes, and the like are known. From the viewpoint of excellent near-infrared absorption, aminium dyes and diimonium dyes are used. Widely used.
Aminium dyes and diimonium dyes generally have a merit that they are hard to be colored because they absorb less visible light than phthalocyanine dyes, while aminium dyes and diimonium dyes generally have low heat resistance and light resistance. There was a problem.
アミニウム系色素やジイモニウム系色素の各種耐性を向上するために様々な方法が試みられている。 Various methods have been tried to improve various resistances of aminium dyes and diimonium dyes.
特許文献1には、特定のジイモニウムカチオンと、1価の特定のアニオンからなるジイモニウム塩化合物が開示されている。特許文献1によれば、上記特定のジイモニウム塩化合物は耐熱性及び耐湿熱安定性に優れているとされている。しかしながら、特許文献1のジイモニウム塩化合物は、耐熱性、耐光性共に不十分であった。 Patent Document 1 discloses a diimonium salt compound comprising a specific diimonium cation and a specific monovalent anion. According to Patent Document 1, the specific diimonium salt compound is said to be excellent in heat resistance and moist heat resistance. However, the diimonium salt compound of Patent Document 1 is insufficient in both heat resistance and light resistance.
特許文献2には、特定のジイモニウムカチオンと、2種類の1価のアニオンを組み合わせた特定のジイモニウム塩化合物が開示されている。特許文献2によれば、上記特定のジイモニウム塩化合物は耐熱性及び耐湿熱安定性に優れているとされている。しかしながら、特許文献2のジイモニウム塩化合物は、耐熱性、耐光性共に不十分であった。 Patent Document 2 discloses a specific diimonium salt compound in which a specific diimonium cation and two types of monovalent anions are combined. According to Patent Document 2, it is said that the specific diimonium salt compound is excellent in heat resistance and moist heat resistance. However, the diimonium salt compound of Patent Document 2 is insufficient in both heat resistance and light resistance.
本発明は、上記実情に鑑みてなされたものであり、耐熱性及び耐光性に優れた色材、耐熱性及び耐光性に優れた塗膜を形成可能な色材分散液、及び、樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above circumstances, a colorant excellent in heat resistance and light resistance, a colorant dispersion capable of forming a coating film excellent in heat resistance and light resistance, and a resin composition The purpose is to provide.
本発明に係る色材は、下記一般式(I)で表される化合物であることを特徴とする。 The coloring material according to the present invention is a compound represented by the following general formula (I).
本発明に係る色材分散液は、前記一般式(I)で表わされる色材と、分散剤と、23℃における前記色材の溶解度が0.1(mg/10g溶媒)以下の溶媒とを含有することを特徴とする。 The colorant dispersion according to the present invention comprises a colorant represented by the general formula (I), a dispersant, and a solvent having a solubility of the colorant at 23 ° C. of 0.1 (mg / 10 g solvent) or less. It is characterized by containing.
また、本発明に係る樹脂組成物は、前記一般式(I)で表される色材と、バインダー成分とを含有することを特徴とする。 The resin composition according to the present invention is characterized by containing the colorant represented by the general formula (I) and a binder component.
本発明に係る色材、色材分散液、及び樹脂組成物においては、前記Xa−が、モリブデン原子及びタングステン原子より選択される1種以上を含む、a価のヘテロポリ酸アニオンであることが、耐熱性及び耐光性に優れる点から好ましい。 In the color material, the color material dispersion, and the resin composition according to the present invention, the X a- is an a-valent heteropolyacid anion containing at least one selected from a molybdenum atom and a tungsten atom. From the viewpoint of excellent heat resistance and light resistance.
本発明によれば、耐熱性及び耐光性に優れた色材、耐熱性及び耐光性に優れた塗膜を形成可能な色材分散液、及び、樹脂組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the color material excellent in heat resistance and light resistance, the color material dispersion liquid which can form the coating film excellent in heat resistance and light resistance, and a resin composition can be provided.
以下、本発明の色材、色材分散液、及び樹脂組成物について順に詳細に説明する。
なお、本発明において「色材」とは、可視光線(波長400nm〜700nmの光)及び近赤外線(波長700nm〜1100nmの光)のうちの少なくとも一部を吸収する化合物をいい、近赤外線のみを吸収する化合物も含まれる。
また、本発明において(メタ)アクリルとは、アクリル又はメタアクリルの各々を表し、(メタ)アクリレートとは、アクリレート又はメタクリレートの各々を表す。
Hereinafter, the coloring material, the coloring material dispersion, and the resin composition of the present invention will be described in detail in order.
In the present invention, the “coloring material” refers to a compound that absorbs at least a part of visible light (light having a wavelength of 400 nm to 700 nm) and near infrared light (light having a wavelength of 700 nm to 1100 nm). Absorbing compounds are also included.
In the present invention, (meth) acryl represents each of acryl or methacryl, and (meth) acrylate represents each of acrylate or methacrylate.
[色材]
本発明に係る色材は、下記一般式(I)で表される化合物であることを特徴とする。
[Color material]
The coloring material according to the present invention is a compound represented by the following general formula (I).
本発明に係る色材は、耐熱性及び耐光性に優れている。その理由は、未解明ではあるが、以下のように推定される。
本発明の色材は、アミニウムカチオン及びジイモニウムカチオンの対イオンとして2価以上のヘテロポリ酸アニオンを用いる。ヘテロポリ酸はそれ自体が耐熱性及び耐光性に優れている。また、多価のヘテロポリ酸アニオンを用いることにより、カチオンとアニオンが1対1でイオン結合しているのではなく、1個のヘテロポリ酸アニオンに2個以上の色素カチオンがイオン結合している。そのため、ヘテロポリ酸アニオンを中心として複数のカチオンが1つの分子を構成する。その結果、1個のアミニウムカチオン乃至ジイモニウムカチオンが1分子を構成する従来のアミニウム色素やジイモニウム色素よりも見かけの分子量が増大し、熱運動を低下させて耐熱性が向上するものと推定される。
また、ヘテロポリ酸は酸性度が高くアニオン安定性に優れるため、対となるアミニウムカチオンやジイモニウムカチオンの安定性が向上する。そのため、カチオンの発色性が安定するとともに、耐光性が向上するものと推定される。
これらのことから、本発明の色材は、耐熱性及び耐光性に優れ、赤外線吸収性にも優れている。
The color material according to the present invention is excellent in heat resistance and light resistance. The reason is unclear, but is estimated as follows.
The coloring material of the present invention uses a divalent or higher heteropoly acid anion as a counter ion of an aminium cation and a diimonium cation. The heteropolyacid itself is excellent in heat resistance and light resistance. Further, by using a polyvalent heteropoly acid anion, the cation and the anion are not ion-bonded one-on-one, but two or more dye cations are ion-bonded to one heteropoly acid anion. Therefore, a plurality of cations centering on the heteropolyacid anion constitute one molecule. As a result, it is presumed that the apparent molecular weight is increased as compared with the conventional aminium dye or diimonium dye in which one aminium cation or diimonium cation constitutes one molecule, and the heat resistance is lowered to improve the heat resistance. .
In addition, since the heteropolyacid has high acidity and excellent anion stability, the stability of a pair of aminium cation and diimonium cation is improved. Therefore, it is presumed that the cation coloring property is stabilized and the light resistance is improved.
For these reasons, the coloring material of the present invention is excellent in heat resistance and light resistance, and is excellent in infrared absorption.
R1〜R8における炭化水素基は、脂肪族炭化水素基だけでなく、脂肪族炭化水素基が置換されていても良い芳香族炭化水素基、芳香族炭化水素が置換されている脂肪族炭化水素基も含まれる。脂肪族炭化水素基は直鎖、分岐、環状のいずれであっても良い。脂肪族炭化水素基は飽和脂肪族炭化水素基であっても不飽和脂肪族炭化水素基であっても良い。
R1〜R8における炭化水素基としては、例えば、炭素原子数が1〜10の脂肪族炭化水素基、炭素原子数が6〜10の芳香族炭化水素基が置換した脂肪族炭化水素基、炭素原子数が6〜30の芳香族炭化水素基等が好適なものとして用いられる。
The hydrocarbon group in R 1 to R 8 is not only an aliphatic hydrocarbon group, but also an aromatic hydrocarbon group in which the aliphatic hydrocarbon group may be substituted, or an aliphatic hydrocarbon in which the aromatic hydrocarbon is substituted. A hydrogen group is also included. The aliphatic hydrocarbon group may be linear, branched or cyclic. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.
Examples of the hydrocarbon group for R 1 to R 8 include an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aliphatic hydrocarbon group substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms, An aromatic hydrocarbon group having 6 to 30 carbon atoms is preferably used.
炭素原子数1〜8のアルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基等が挙げられ、直鎖であっても分岐を有していてもよく、また炭素原子数が3以上の場合は環状であっても良い。環状のアルキル基の具体例としては、例えば、シクロヘキシル基、シクロペンチルメチル基、シクロペンチルエチル基、シクロペンチルブチル基、シクロヘキシルメチル基、シクロヘキシルエチル基等が挙げられる。
炭素原子数が6〜10の芳香族炭化水素基が置換した脂肪族炭化水素基の具体例としては、例えば、ベンジル基、フェネチル基、フェニルプロピル基等が挙げられる。
炭素原子数が6〜30の芳香族炭化水素基としては、例えば、ベンゼン環の他、ナフタレン環、テトラリン環、インデン環、フルオレン環、アントラセン環、フェナントレン環等の縮合多環芳香族炭化水素;ビフェニル、ターフェニル、ジフェニルメタン、トリフェニルメタン、スチルベン等の鎖状多環式炭化水素が挙げられる。
Specific examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group, which may be linear or branched. In addition, when the number of carbon atoms is 3 or more, it may be cyclic. Specific examples of the cyclic alkyl group include a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclopentylbutyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.
Specific examples of the aliphatic hydrocarbon group substituted by an aromatic hydrocarbon group having 6 to 10 carbon atoms include a benzyl group, a phenethyl group, and a phenylpropyl group.
Examples of the aromatic hydrocarbon group having 6 to 30 carbon atoms include condensed polycyclic aromatic hydrocarbons such as naphthalene ring, tetralin ring, indene ring, fluorene ring, anthracene ring and phenanthrene ring in addition to benzene ring; Examples thereof include chain polycyclic hydrocarbons such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene.
炭化水素基が有していてもよい置換基としては、水酸基、スルホン酸基、ニトロ基、アミノ基、シアノ基、アルコキシ基、ハロゲン原子等が挙げられる。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、塩素原子又は臭素原子であることが好ましい。
Examples of the substituent that the hydrocarbon group may have include a hydroxyl group, a sulfonic acid group, a nitro group, an amino group, a cyano group, an alkoxy group, and a halogen atom.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a bromine atom is preferable.
R1とR2、R3とR4、R5とR6、及びR7とR8は、それぞれ独立に、互いに結合して窒素原子を含む脂環族複素環を形成してもよい。脂肪族複素環としては、例えば、ピペリジン、モルホリン、インドリン等が挙げられ、置換基として、水酸基、スルホン酸基、ニトロ基、アミノ基、シアノ基、アルコキシ基、ハロゲン原子を有していてもよい。 R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , and R 7 and R 8 may be independently bonded to each other to form an alicyclic heterocycle containing a nitrogen atom. Examples of the aliphatic heterocyclic ring include piperidine, morpholine, indoline and the like, and the substituent may have a hydroxyl group, a sulfonic acid group, a nitro group, an amino group, a cyano group, an alkoxy group, or a halogen atom. .
R1〜R8としては、耐熱性及び耐光性の点から、中でも、炭素原子数が1〜10の脂肪族炭化水素基、炭素原子数が6〜10の芳香族炭化水素基が置換した脂肪族炭化水素基が好ましい。
R1〜R8として好ましい置換基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、シクロヘキシルメチル基、シアノプロピル基、トリフルオロメチル基、トリフルオロエチル基、ヘキサフルオロエチル基、トリクロロメチル基等が挙げられる。
As R 1 to R 8 , from the viewpoint of heat resistance and light resistance, an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aliphatic hydrocarbon group having 6 to 10 carbon atoms are substituted. A group hydrocarbon group is preferred.
Specific examples of preferable substituents as R 1 to R 8 include methyl group, ethyl group, propyl group, butyl group, pentyl group, cyclohexylmethyl group, cyanopropyl group, trifluoromethyl group, trifluoroethyl group, hexafluoro group. An ethyl group, a trichloromethyl group, etc. are mentioned.
本発明の色材において、カチオン(A)は、一般式(II)で表されるカチオン、及び一般式(III)で表されるカチオンのうち、1種単独で又は2種以上を組み合わせて用いることができる。本発明においては、耐熱性及び耐光性の点から、中でも、一般式(III)で表されるカチオンを含むことが好ましい。 In the color material of the present invention, the cation (A) is used alone or in combination of two or more of the cation represented by the general formula (II) and the cation represented by the general formula (III). be able to. In the present invention, from the viewpoint of heat resistance and light resistance, it is preferable to include a cation represented by the general formula (III).
本発明の色材においては、アミニウムカチオン及びジイモニウムカチオンの対アニオン(Xa−)として2価以上のヘテロポリ酸アニオンが用いられる。対アニオンとしてこのようなヘテロポリ酸アニオンを用いることにより、アミニウム色素やジイモニウム色素よりも見かけの分子量が増大して耐熱性が向上するとともに、酸化による退色が抑制されることにより耐光性も向上する。 In the color material of the present invention, a divalent or higher valent heteropolyacid anion is used as a counter anion (X a− ) of an aminium cation and a diimonium cation. By using such a heteropolyacid anion as a counter anion, the apparent molecular weight is increased as compared with an aminium dye or a diimonium dye, the heat resistance is improved, and the light resistance is also improved by suppressing fading due to oxidation.
本発明で用いられるヘテロポリ酸アニオンは、2価以上のヘテロポリ酸アニオンイオンであって、式(LlMmOn)a−(aは2以上の数を表す)で表される。当該イオン式中、Lはヘテロ原子、Mはポリ原子、Oは酸素原子、l、m及びnはそれぞれの原子の組成比を表す。ポリ原子Mとしては、例えば、Mo、W、V、Ti、Nb、Al、Ta等が挙げられる。ヘテロ原子Lとしては、特に限定されないが、例えば、Si、P、As、S、Fe、Co等が挙げられる。また、一部にNa+やH+等の対カチオンが含まれていてもよい。
本発明においてアニオン(Xa−)は、耐熱性及び耐光性の点から、中でも、モリブデン原子及びタングステン原子より選択される1種以上を含む、a価のヘテロポリ酸アニオンであることが好ましい。
The heteropolyacid anion used in the present invention is a divalent or higher valent heteropolyacid anion ion represented by the formula (L 1 M m O n ) a- (a represents a number of 2 or more). In the ionic formula, L represents a hetero atom, M represents a poly atom, O represents an oxygen atom, and l, m, and n represent the composition ratio of each atom. Examples of the poly atom M include Mo, W, V, Ti, Nb, Al, Ta, and the like. The hetero atom L is not particularly limited, and examples thereof include Si, P, As, S, Fe, and Co. Moreover, a counter cation such as Na + or H + may be partially included.
In the present invention, the anion (X a− ) is preferably an a-valent heteropolyacid anion containing at least one selected from a molybdenum atom and a tungsten atom from the viewpoint of heat resistance and light resistance.
モリブデン原子及びタングステン原子のうち1種以上を含む2価以上のヘテロポリ酸アニオンの具体例としては、例えば、ケギン型リンタングステン酸イオンα−[PW12O40]3−、ドーソン型リンタングステン酸イオンα−[P2W18O62]6−、β−[P2W18O62]6−、ケギン型ケイタングステン酸イオンα−[SiW12O40]4−、β−[SiW12O40]4−、γ−[SiW12O40]4−、さらにその他の例として[P2W17O61]10−、[P2W15O56]12−、[H2P2W12O48]12−、[NaP5W30O110]14−、α−[SiW9O34]10−、γ−[SiW10O36]8−、α−[SiW11O39]8−、β−[SiW11O39]8−、α−[PMo12O40]3−、α−[PW11MoO40]3−、α−[PW9Mo3O40]3−、α−[PW3Mo9O40]3−、α−[SiMo12O40]4−、α−[P2Mo18O62]6−等が挙げられる。
モリブデン原子及びタングステン原子のうち1種以上を含む2価以上のヘテロポリ酸アニオンとしては、耐熱性及び耐光性の点、及び原料入手の容易さの点から、P(リン原子)を含むヘテロポリ酸であることがより好ましい。
モリブデン原子及びタングステン原子のうち1種以上を含む2価以上のヘテロポリ酸アニオンは、1種単独で、又は2種以上を組み合わせて用いることができる。
Specific examples of a divalent or higher valent heteropolyacid anion containing one or more of a molybdenum atom and a tungsten atom include, for example, Keggin-type phosphotungstate ion α- [PW 12 O 40 ] 3− , Dawson-type phosphotungstate ion α- [P 2 W 18 O 62 ] 6− , β- [P 2 W 18 O 62 ] 6− , Keggin-type silicotungstate ion α- [SiW 12 O 40 ] 4− , β- [SiW 12 O 40 ] 4- , γ- [SiW 12 O 40 ] 4− , and as other examples, [P 2 W 17 O 61 ] 10− , [P 2 W 15 O 56 ] 12− , [H 2 P 2 W 12 O 48] 12-, [NaP 5 W 30 O 110] 14-, α- [SiW 9 O 34] 10-, γ- [SiW 10 O 36] 8-, α- [SiW 11 O 39 8-, β- [SiW 11 O 39 ] 8-, α- [PMo 12 O 40] 3-, α- [PW 11 MoO 40] 3-, α- [PW 9 Mo 3 O 40] 3-, α -[PW 3 Mo 9 O 40 ] 3− , α- [SiMo 12 O 40 ] 4− , α- [P 2 Mo 18 O 62 ] 6− and the like.
The divalent or higher valent heteropolyacid anion containing one or more of molybdenum atom and tungsten atom is a heteropolyacid containing P (phosphorus atom) from the viewpoint of heat resistance and light resistance and easy availability of raw materials. More preferably.
The divalent or higher valent heteropolyacid anion containing one or more of molybdenum atoms and tungsten atoms can be used singly or in combination of two or more.
ヘテロポリ酸がモリブデンとタングステンを共に含む場合、モリブデンとタングステンとのモル比は、特に限定されない。 When the heteropolyacid contains both molybdenum and tungsten, the molar ratio of molybdenum to tungsten is not particularly limited.
前記一般式(I)において、aはヘテロポリ酸アニオンの価数を表し、異なる価数のヘテロポリ酸アニオンを組み合わせて用いた場合にはその平均値を表す。また、カチオン(A)の価数は、前記一般式(II)で表されるカチオンの価数(1価)及び前記一般式(III)で表されるカチオン(2価)の平均値である。
b及びcは、それぞれ1以上の数を表し、カチオン(A)の価数が、a×c/bを満たすとき、一般式(I)で表される色材は正塩となる。
In the said general formula (I), a represents the valence of a heteropolyacid anion, and when a heteropolyacid anion of a different valence is used in combination, the average value is represented. The valence of the cation (A) is the average value of the cation (monovalent) represented by the general formula (II) and the cation (divalent) represented by the general formula (III). .
b and c each represent a number of 1 or more, and when the valence of the cation (A) satisfies a × c / b, the color material represented by the general formula (I) is a normal salt.
<一般式(I)で表される色材の製造方法>
一般式(I)で表される色材は、例えば、上記一般式(II)で表されるカチオン及び上記一般式(III)で表されるカチオンより選択される1種以上のカチオンと、a価のヘテロポリ酸アニオンとを溶媒中で混合し、必要に応じて加熱することにより得ることができる。
<The manufacturing method of the color material represented by general formula (I)>
The colorant represented by the general formula (I) includes, for example, one or more cations selected from the cation represented by the general formula (II) and the cation represented by the general formula (III), and a It can be obtained by mixing a valent heteropolyacid anion in a solvent and heating as necessary.
アミニウムカチオン及びジイモニウムカチオンは、例えば、特許第4942320号公報、国際公開第2008/010501号パンフレット等に記載の方法を参考に合成することができる。また、市販品を用いてもよい。 The aminium cation and the diimonium cation can be synthesized with reference to, for example, the methods described in Japanese Patent No. 4942320, International Publication No. 2008/010501, etc. Moreover, you may use a commercial item.
[色材分散液]
本発明に係る色材分散液は、下記一般式(I)で表わされる色材と、分散剤と、23℃における前記色材の溶解度が0.1(mg/10g溶媒)以下の溶媒とを含有することを特徴とする。
[Colorant dispersion]
The color material dispersion according to the present invention comprises a color material represented by the following general formula (I), a dispersant, and a solvent having a solubility of the color material at 23 ° C. of 0.1 (mg / 10 g solvent) or less. It is characterized by containing.
本発明の色材分散液は、一般式(I)で表される色材と分散剤を組み合わせて、当該色材が実質的に溶解しない溶媒又は難溶性の溶媒中に分散させて用いることにより、染料と同様の高透過率を達成しながら、耐熱性及び耐光性に優れた塗膜を形成可能な色材分散液が得られる。 The color material dispersion of the present invention is used by combining the color material represented by the general formula (I) and a dispersant and dispersing the color material in a solvent in which the color material is not substantially dissolved or a hardly soluble solvent. A colorant dispersion capable of forming a coating film excellent in heat resistance and light resistance while achieving the same high transmittance as that of the dye can be obtained.
本発明に係る色材分散液は、少なくとも色材と、分散剤と、溶媒とを含有するものであり、必要に応じて他の成分を含有してもよいものである。
以下、このような本発明の色材分散液の各成分について順に詳細に説明するが、一般式(I)で表される色材については、前述のとおりであるためここでの説明は省略する。
The color material dispersion according to the present invention contains at least a color material, a dispersant, and a solvent, and may contain other components as necessary.
Hereinafter, each component of the color material dispersion liquid of the present invention will be described in detail in order. However, the color material represented by the general formula (I) is as described above, and the description thereof is omitted here. .
(分散剤)
本発明に係る色材分散液において、前記一般式(I)で表される色材は溶媒中に分散させて用いられる。本発明においては色材を良好に分散させるために、分散剤が用いられる。分散剤としては、従来、顔料分散剤として用いられているものの中から適宜選択して用いることができる。分散剤としては、例えば、カチオン系、アニオン系、ノニオン系、両性、シリコーン系、フッ素系等の界面活性剤を使用できる。界面活性剤の中でも、均一に、微細に分散し得る点から、高分子界面活性剤(高分子分散剤)が好ましい。
(Dispersant)
In the color material dispersion according to the present invention, the color material represented by the general formula (I) is used by being dispersed in a solvent. In the present invention, a dispersant is used in order to favorably disperse the color material. The dispersant can be appropriately selected from those conventionally used as pigment dispersants. Examples of the dispersant that can be used include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be uniformly and finely dispersed.
高分子分散剤としては、例えば、ポリアクリル酸エステル等の不飽和カルボン酸エステルの(共)重合体類;ポリアクリル酸等の不飽和カルボン酸の(共)重合体の(部分)アミン塩、(部分)アンモニウム塩や(部分)アルキルアミン塩類;水酸基含有ポリアクリル酸エステル等の水酸基含有不飽和カルボン酸エステルの(共)重合体やそれらの変性物;ポリウレタン類;不飽和ポリアミド類;ポリシロキサン類;長鎖ポリアミノアミドリン酸塩類;ポリエチレンイミン誘導体(ポリ(低級アルキレンイミン)と遊離カルボキシル基含有ポリエステルとの反応により得られるアミドやそれらの塩基);ポリアリルアミン誘導体(ポリアリルアミンと、遊離のカルボキシル基を有するポリエステル、ポリアミド又はエステルとアミドの共縮合物(ポリエステルアミド)の3種の化合物の中から選ばれる1種以上の化合物とを反応させて得られる反応生成物)等が挙げられる。 Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salts and (partial) alkylamine salts; (co) polymers of hydroxyl group-containing unsaturated carboxylic acid esters such as hydroxyl group-containing polyacrylates and their modified products; polyurethanes; unsaturated polyamides; polysiloxanes Long chain polyaminoamide phosphates; polyethylenimine derivatives (amides and their bases obtained by reaction of poly (lower alkylene imines) with free carboxyl group-containing polyesters); polyallylamine derivatives (polyallylamine and free carboxyls) Polyester, polyamide or ester-amide co-condensation with groups The reaction product obtained by reacting one or more compound selected from among the three compounds of (polyester amide)), and the like.
高分子分散剤としては、中でも、上記一般式(I)で表される色材を好適に分散でき、分散安定性が良好である点から、主鎖又は側鎖に窒素原子を含む高分子分散剤が好ましい。主鎖又は側鎖に窒素原子を含む高分子分散剤を用いた場合には、一般式(I)で表される色材を良好に分散させるのみならず、一般式(I)で表される色材を、イオン対の状態で、安定して存在させる作用をも有するものと推定される。その結果、耐熱性及び耐光性に優れている。 Among the polymer dispersants, among them, the colorant represented by the above general formula (I) can be suitably dispersed, and the polymer dispersion containing a nitrogen atom in the main chain or side chain from the viewpoint of good dispersion stability Agents are preferred. When a polymer dispersant containing a nitrogen atom in the main chain or side chain is used, not only the colorant represented by the general formula (I) is well dispersed but also represented by the general formula (I). It is presumed that the coloring material also has an effect of stably existing in the state of ion pairs. As a result, it is excellent in heat resistance and light resistance.
主鎖又は側鎖に窒素原子を含む高分子分散剤としては、例えば、ポリアクリル酸等の不飽和カルボン酸の(共)重合体の(部分)アミン塩、(部分)アンモニウム塩や(部分)アルキルアミン塩類;ポリウレタン類;不飽和ポリアミド類;ポリエチレンイミン誘導体;ポリアリルアミン誘導体等が挙げられる。
主鎖又は側鎖に窒素原子を含む高分子分散剤の具体例としては、例えば、国際公開第2012/144521号パンフレットに記載のもの等が挙げられる。
Examples of the polymer dispersant containing a nitrogen atom in the main chain or side chain include (partial) amine salts, (partial) ammonium salts and (partial) of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid. Examples include alkylamine salts; polyurethanes; unsaturated polyamides; polyethyleneimine derivatives; polyallylamine derivatives.
Specific examples of the polymer dispersant containing a nitrogen atom in the main chain or side chain include those described in International Publication No. 2012/144521 pamphlet.
主鎖又は側鎖に窒素原子を含む高分子分散剤の市販品として、例えば以下のものが挙げられる。
ポリアクリル酸等の不飽和カルボン酸の(共)重合体の(部分)アミン塩、(部分)アンモニウム塩や(部分)アルキルアミン塩類としては、例えばDisperbyk2000、2001(以下全てビックケミー社製)等を用いることができる。
ポリウレタン類としては、例えばDisperbyk161等を用いることができる。
不飽和ポリアミド類としては、例えばDisperbyk101、130等を用いることができる。
ポリアリルアミン誘導体としては、例えば、アジスパーPB821、PB822、PB824、PB827(味の素ファインテクノ株式会社製)等を用いることができる。
ポリエチレンイミン誘導体としては、例えば、Solsperse33500(日本ルーブリゾール社製)等を用いることができる。
その他市販されている分散剤としては、Dysperbyk116、同140、同160、同162、同163、同164、同166、同167、同168、同170、同171、同174、同182、同2050、同6919(以上ビックケミー社製)、;EFKA4046、同4047、(以上EFKA CHEMICALS社製);Solsperse12000、同13250、同13940、同17000、同20000、同24000GR、同24000SC、同27000、同28000、同32000、同33500、同35200、同37500(以上、日本ルーブリゾール社製);アジスパーPB711、823、880(以上、味の素ファインテクノ製)等を挙げることができる。
Examples of commercially available polymer dispersants containing a nitrogen atom in the main chain or side chain include the following.
Examples of (partial) amine salts, (partial) ammonium salts, and (partial) alkylamine salts of (co) polymers of unsaturated carboxylic acids such as polyacrylic acid include Disperbyk 2000, 2001 (all manufactured by BYK Chemie). Can be used.
As the polyurethane, for example, Disperbyk 161 can be used.
As unsaturated polyamides, for example, Disperbyk 101 and 130 can be used.
As the polyallylamine derivative, for example, Azisper PB821, PB822, PB824, PB827 (manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like can be used.
As the polyethyleneimine derivative, for example, Solsperse 33500 (manufactured by Nippon Lubrizol Co., Ltd.) can be used.
Other commercially available dispersants include Dysperbyk 116, 140, 160, 162, 163, 164, 166, 167, 168, 170, 171, 174, 182, and 2050. 6919 (manufactured by Big Chemie); EFKA 4046, 4047, (manufactured by EFKA CHEMICALS); Solsperse 12000, 13250, 13940, 17000, 20000, 24000GR, 24000SC, 27000, 28000, 32000, 33500, 35200, 37500 (above, manufactured by Nihon Lubrizol Corporation); Azisper PB711, 823, 880 (above, manufactured by Ajinomoto Fine Techno Co., Ltd.).
主鎖又は側鎖に窒素原子を含む高分子分散剤の中でも、色材の分散性及び分散安定性の点から、下記一般式(IV)で表される構成単位を有する重合体であることが好ましく、当該構成単位が有するアミノ基と、下記一般式(V)及び、下記一般式(VI)より選択される1種以上の有機酸化合物とが塩を形成した共重合体であることがより好ましい。 Among polymer dispersants containing a nitrogen atom in the main chain or side chain, it may be a polymer having a structural unit represented by the following general formula (IV) from the viewpoint of the dispersibility and dispersion stability of the coloring material. Preferably, the amino group of the structural unit is a copolymer in which a salt is formed with one or more organic acid compounds selected from the following general formula (V) and the following general formula (VI). preferable.
xは1〜18の整数、yは1〜5の整数、zは1〜18の整数を示す。)
x is an integer of 1 to 18, y is an integer of 1 to 5, and z is an integer of 1 to 18. )
Rbは、炭素原子数1〜18のアルキル基、炭素原子数2〜18のアルケニル基、アラルキル基、アリール基、−[CH(Rc)−CH(Rd)−O]s−Re、−[(CH2)t−O]u−Re、又は−O−Rb’で示される1価の基である。Rb’は、炭素原子数1〜18のアルキル基、炭素原子数2〜18のアルケニル基、アラルキル基、アリール基、−[CH(Rc)−CH(Rd)−O]s−Re、又は−[(CH2)t−O]u−Reで示される1価の基である。
Rc及びRdは、それぞれ独立に水素原子又はメチル基であり、Reは、水素原子、あるいは炭素原子数1〜18のアルキル基、炭素原子数2〜18のアルケニル基、アラルキル基、アリール基、−CHO、−CH2CHO、−CO−CH=CH2、−CO−C(CH3)=CH2又は−CH2COORfで示される1価の基であり、Rfは水素原子又は炭素原子数1〜5のアルキル基である。
Ra、Ra’、及びRbにおいて、アルキル基、アルケニル基、アラルキル基、アリール基はそれぞれ、置換基を有していてもよい。
sは1〜18の整数、tは1〜5の整数、uは1〜18の整数を示す。)
R b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R c ) —CH (R d ) —O] s —R e. , — [(CH 2 ) t —O] u —R e , or —O—R b ′ . R b ′ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R c ) —CH (R d ) —O] s —R. e or a monovalent group represented by — [(CH 2 ) t —O] u —R e .
R c and R d are each independently a hydrogen atom or a methyl group, and R e is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl Group, —CHO, —CH 2 CHO, —CO—CH═CH 2 , —CO—C (CH 3 ) ═CH 2 or —CH 2 COOR f , and R f is a hydrogen atom. Or it is a C1-C5 alkyl group.
In R a , R a ′ , and R b , each of the alkyl group, alkenyl group, aralkyl group, and aryl group may have a substituent.
s is an integer of 1 to 18, t is an integer of 1 to 5, and u is an integer of 1 to 18. )
上記一般式(IV)の2価の連結基Qとしては、例えば、炭素原子数1〜10のアルキレン基、アリーレン基、−CONH−基、−COO−基、炭素原子数1〜10のエーテル基(−R’−OR”−:R’及びR”は、各々独立にアルキレン基)及びこれらの組み合わせ等が挙げられる。中でも、得られた共重合体の耐熱性の点から、Qは、−COO−基であることが好ましい。 Examples of the divalent linking group Q in the general formula (IV) include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH— group, a —COO— group, and an ether group having 1 to 10 carbon atoms. (—R′—OR ″ —: R ′ and R ″ are each independently an alkylene group) and combinations thereof. Especially, it is preferable that Q is a -COO- group from the heat resistant point of the obtained copolymer.
上記一般式(IV)の2価の有機基R10は、炭素原子数1〜8のアルキレン基、−[CH(R14)−CH(R15)−O]x−CH(R14)−CH(R15)−又は−[(CH2)y−O]z−(CH2)y−である。上記炭素原子数1〜8のアルキレン基は、直鎖状、分岐状のいずれであってもよく、例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基、各種ブチレン基、各種ペンチレン基、各種へキシレン基、各種オクチレン基などである。
R14及びR15は、それぞれ独立に水素原子又はメチル基である。
上記R10としては、分散性の点から、炭素原子数1〜8のアルキレン基が好ましく、中でも、R10がメチレン基、エチレン基、プロピレン基、ブチレン基であることが更に好ましく、メチレン基及びエチレン基がより好ましい。
The divalent organic group R 10 in the general formula (IV) is an alkylene group having 1 to 8 carbon atoms, — [CH (R 14 ) —CH (R 15 ) —O] x —CH (R 14 ) —. CH (R 15 ) — or — [(CH 2 ) y —O] z — (CH 2 ) y —. The alkylene group having 1 to 8 carbon atoms may be linear or branched, and includes, for example, a methylene group, an ethylene group, a trimethylene group, a propylene group, various butylene groups, various pentylene groups, various types. Xylene group, various octylene groups and the like.
R 14 and R 15 are each independently a hydrogen atom or a methyl group.
R 10 is preferably an alkylene group having 1 to 8 carbon atoms from the viewpoint of dispersibility. Among them, R 10 is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. An ethylene group is more preferable.
上記一般式(IV)のR11、R12が互いに結合して形成する環状構造としては、例えば5〜7員環の含窒素複素環単環又はこれらが2個縮合してなる縮合環が挙げられる。該含窒素複素環は芳香性を有さないものが好ましく、飽和環であればより好ましい。 Examples of the cyclic structure formed by combining R 11 and R 12 in the general formula (IV) with each other include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. It is done. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring.
上記一般式(IV)で表される繰り返し単位としては、(メタ)アクリロイルオキシプロピルジメチルアミン、(メタ)アクリロイルオキシエチルジメチルアミン、(メタ)アクリロイルオキシプロピルジエチルアミン、(メタ)アクリロイルオキシエチルジエチルアミン等から誘導される繰り返し単位が挙げられるが、これらに限定されない。 Examples of the repeating unit represented by the general formula (IV) include (meth) acryloyloxypropyldimethylamine, (meth) acryloyloxyethyldimethylamine, (meth) acryloyloxypropyldiethylamine, (meth) acryloyloxyethyldiethylamine, and the like. Examples include, but are not limited to, derived repeating units.
一般式(V)においてRa及び/又はRa’が、−O−Ra”の場合、酸性リン酸エステルとなる。また、一般式(VI)においてRbが、−O−Rb’の場合、酸性硫酸エステルとなる。 In the general formula (V), when R a and / or R a ′ is —O—R a ″ , it is an acidic phosphate ester. In the general formula (VI), R b is —O—R b ′. In this case, it becomes an acidic sulfate ester.
上記一般式(V)で表される有機酸化合物としては、Ra及びRa’が、それぞれ独立に、水素原子、水酸基、メチル基、エチル基、置換基を有していても良いアリール基又はアラルキル基、ビニル基、アリル基、−[CH(Rc)−CH(Rd)−O]s−Re、又は−[(CH2)t−O]u−Re、あるいは、−O−Ra’’で示される1価の基であり、Ra及びRa’のいずれかは炭素原子を含み、且つ、Ra’’が、メチル基、エチル基、置換基を有していても良いアリール基又はアラルキル基、ビニル基、アリル基、−[CH(Rc)−CH(Rd)−O]s−Re、又は−[(CH2)t−O]u−Reであり、Rc及びRdが、それぞれ独立に水素原子又はメチル基であり、Reが−CO−CH=CH2又は−CO−C(CH3)=CH2であるものが色材の分散性を向上し、且つ、耐熱性に優れる点から好ましい。 As the organic acid compound represented by the general formula (V), R a and R a ′ are each independently a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, or an aryl group which may have a substituent. Or an aralkyl group, a vinyl group, an allyl group, — [CH (R c ) —CH (R d ) —O] s —R e , or — [(CH 2 ) t —O] u —R e , or — A monovalent group represented by O—R a ″ , one of R a and R a ′ contains a carbon atom, and R a ″ has a methyl group, an ethyl group, and a substituent; Aryl group or aralkyl group, vinyl group, allyl group, — [CH (R c ) —CH (R d ) —O] s —R e , or — [(CH 2 ) t —O] u — is R e, R c and R d are each independently a hydrogen atom or a methyl group, R e is -CO-CH = CH Or -CO-C (CH 3) = ones is CH 2 can improve the dispersibility of the colorant, and, from the viewpoint of excellent heat resistance.
また、一般式(VI)で表される有機酸化合物としては、Rbが、メチル基、エチル基、置換基を有していても良いアリール基又はアラルキル基、ビニル基、アリル基、−[CH(Rc)−CH(Rd)−O]s−Re、又は−[(CH2)t−O]u−Re、あるいは、−O−Rb’で示される1価の基であり、Rb’が、メチル基、エチル基、置換基を有していても良いアリール基又はアラルキル基、ビニル基、アリル基、−[CH(Rc)−CH(Rd)−O]s−Re、又は−[(CH2)t−O]u−Reであり、Rc及びRdが、それぞれ独立に水素原子又はメチル基であり、Reが−CO−CH=CH2又は−CO−C(CH3)=CH2であるものが色材の分散性を向上し、耐熱性に優れる点から好ましい。 Moreover, as an organic acid compound represented by general formula (VI), Rb is a methyl group, an ethyl group, the aryl group or aralkyl group which may have a substituent, a vinyl group, an allyl group,-[ CH (R c) -CH (R d) -O] s -R e, or - [(CH 2) t -O ] u -R e, or a monovalent group represented by -O-R b ' And R b ′ is a methyl group, an ethyl group, an aryl group or an aralkyl group which may have a substituent, a vinyl group, an allyl group, — [CH (R c ) —CH (R d ) —O S —R e or — [(CH 2 ) t —O] u —R e , R c and R d are each independently a hydrogen atom or a methyl group, and R e is —CO—CH═. Since CH 2 or —CO—C (CH 3 ) ═CH 2 improves the dispersibility of the color material and is excellent in heat resistance. preferable.
中でも、上記一般式(V)及び一般式(VI)で表される有機酸化合物は、Ra、Ra’及び/又はRa’’、並びに/或いは、Rb及び/又はRb’として、芳香環を有することが色材の分散性を向上し、耐熱性に優れる点から好ましい。Ra、Ra’及びRa’’の少なくとも1つ、或いは、Rb又はRb’が、置換基を有していても良いアリール基又はアラルキル基、より具体的には、ベンジル基、フェニル基、トリル基、ナフチル基、ビフェニル基であることが、色材分散性の点から好ましい。前記一般式(V)においては、Ra及びRa’の一方が芳香環を有する場合には、Ra及びRa’の他方は、水素原子や水酸基であるものも好適に用いられる。 Of these, organic acid compound represented by the above general formula (V) and the general formula (VI), R a, R a 'and / or R a'', and / or as R b and / or R b' An aromatic ring is preferable from the viewpoint of improving the dispersibility of the coloring material and excellent heat resistance. At least one of R a , R a ′ and R a ″ , or R b or R b ′ , an aryl group or aralkyl group which may have a substituent, more specifically, a benzyl group, A phenyl group, a tolyl group, a naphthyl group, and a biphenyl group are preferable from the viewpoint of dispersibility of the coloring material. In the general formula (V), when one of R a and R a ′ has an aromatic ring, the other of R a and R a ′ is preferably a hydrogen atom or a hydroxyl group.
また、耐熱性や耐薬品性、特に耐アルカリ性の点からは、上記一般式(V)及び一般式(VI)で表される有機酸化合物としては、リン(P)や硫黄(S)に炭素原子が直接結合した化合物であることが好ましく、Ra及びRa’が、それぞれ独立に水素原子、水酸基、炭素原子数1〜18のアルキル基、炭素原子数2〜18のアルケニル基、アラルキル基、アリール基、−[CH(Rc)−CH(Rd)−O]s−Re、−[(CH2)t−O]u−Reで示される1価の基であり、Ra及びRa’のいずれかは炭素原子を含むことが好ましい。また、Rbが、炭素原子数1〜18のアルキル基、炭素原子数2〜18のアルケニル基、アラルキル基、アリール基、−[CH(Rc)−CH(Rd)−O]s−Re、−[(CH2)t−O]u−Reで示される1価の基であることが好ましい。 In addition, from the viewpoint of heat resistance and chemical resistance, particularly alkali resistance, the organic acid compounds represented by the general formula (V) and the general formula (VI) include phosphorus (P), sulfur (S), and carbon. It is preferably a compound in which atoms are directly bonded, and R a and R a ′ are each independently a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aralkyl group. , An aryl group,-[CH (R c ) -CH (R d ) -O] s -R e ,-[(CH 2 ) t -O] u -R e , a monovalent group represented by R one of a and R a 'preferably contains carbon atoms. R b is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aralkyl group, an aryl group, — [CH (R c ) —CH (R d ) —O] s —. A monovalent group represented by R e , — [(CH 2 ) t —O] u —R e is preferable.
また、上記一般式(V)及び一般式(VI)で表される有機酸化合物は、Ra、Ra’及び/又はRa’’、並びに/或いは、Rb及び/又はRb’としては、重合性基を有するものが好ましい。重合性基としては、例えば、ラジカル重合性基や、オキシラン環、オキセタン環等の環状エーテル含有基を含むカチオン重合性基等が挙げられる。中でも、ラジカル重合性基が好ましく、エチレン性不飽和結合含有基が好ましい。エチレン性不飽和結合含有基としては、例えば、ビニル基、アリル基あるいは−[CH(Rc)−CH(Rd)−O]s−Re、又は−[(CH2)t−O]u−Reであり、且つ、Reが−CO−CH=CH2又は−CO−C(CH3)=CH2であるものが好ましく、特に、Ra、Ra’及び/又はRa’’、並びに/或いは、Rb及び/又はRb’が、ビニル基、アリル基、2−メタクリロイルオキシエチル基、2−アクリロイルオキシエチル基であるものが好ましい。 The organic acid compound represented by the above general formula (V) and the general formula (VI), R a, R a 'and / or R a'', and / or as R b and / or R b' Preferably have a polymerizable group. Examples of the polymerizable group include a radical polymerizable group and a cationic polymerizable group including a cyclic ether-containing group such as an oxirane ring and an oxetane ring. Among these, a radical polymerizable group is preferable, and an ethylenically unsaturated bond-containing group is preferable. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, an allyl group, — [CH (R c ) —CH (R d ) —O] s —R e , or — [(CH 2 ) t —O]. It is preferable that u −R e and R e be —CO—CH═CH 2 or —CO—C (CH 3 ) ═CH 2 , particularly R a , R a ′ and / or R a. '' And / or R b and / or R b ′ are preferably a vinyl group, an allyl group, a 2-methacryloyloxyethyl group, or a 2-acryloyloxyethyl group.
本発明において分散剤は、更に、溶剤親和性を有する構成単位を含むことが好ましい。中でも、溶剤親和性を良好にし、分散性を向上する点から、非塩基性モノマーから誘導される繰り返し単位の中から、溶剤親和性を有するように溶剤に応じて適宜選択して用いられることが好ましい。ここで非塩基性モノマーとは、25℃の水に0.1Nの濃度(飽和濃度が0.1N未満の時は、飽和濃度)で溶解した時、7.1より低いpHを有する溶液を与える重合性モノマーをいう。溶剤親和性を有するブロック部としては、例えば、ポリアクリル酸エステル等の不飽和カルボン酸エステルの重合体、ポリアクリル酸等の不飽和カルボン酸の重合体等が挙げられる。中でも、下記一般式(V)で表される、繰り返し単位を有する重合体であることが、色材の分散性及び分散安定性を向上させながら、耐熱性も向上する点から好ましい。 In the present invention, the dispersant preferably further includes a structural unit having solvent affinity. Among them, from the viewpoint of improving solvent affinity and improving dispersibility, it may be used by appropriately selecting from repeating units derived from non-basic monomers according to the solvent so as to have solvent affinity. preferable. Here, the non-basic monomer gives a solution having a pH lower than 7.1 when dissolved in water at 25 ° C. at a concentration of 0.1 N (saturation concentration when the saturation concentration is less than 0.1 N). A polymerizable monomer. As a block part which has solvent affinity, the polymer of unsaturated carboxylic acid esters, such as polyacrylic acid ester, unsaturated carboxylic acid polymers, such as polyacrylic acid, etc. are mentioned, for example. Among these, a polymer having a repeating unit represented by the following general formula (V) is preferable from the viewpoint of improving heat resistance while improving dispersibility and dispersion stability of the coloring material.
このような一般式(II)で表される構成単位を有するブロック部と一般式(V)で表される構成単位を有するブロック部とを有するブロック共重合体、及び一般式(II)で表される構成単位を有するグラフト共重合体の具体例としては、特開2013−76764号公報等に記載のブロック共重合体、及びグラフト共重合体を好適なものとして挙げることができる。 A block copolymer having a block part having a structural unit represented by the general formula (II) and a block part having a structural unit represented by the general formula (V), and represented by the general formula (II) As specific examples of the graft copolymer having the structural unit, a block copolymer and a graft copolymer described in JP2013-76764A and the like can be preferably exemplified.
本発明において分散剤は、1種単独で又は2種以上組み合わせて用いることができる。分散剤の含有量は、用いる色材の種類等に応じて適宜選定される。本発明の色材分散液において、分散剤は、色材100質量部に対して、通常、5〜200質量部の範囲であり、10〜100質量部であることが好ましく、20〜80質量部であることがより好ましい。含有量が上記範囲内にあれば、色材を均一に分散させることができる。また、後述する樹脂組成物において、相対的にバインダー成分の配合比率が低下することがなく、十分な硬度を持った着色層が形成できる。 In this invention, a dispersing agent can be used individually by 1 type or in combination of 2 or more types. Content of a dispersing agent is suitably selected according to the kind etc. of coloring material to be used. In the colorant dispersion of the present invention, the dispersant is usually in the range of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, with respect to 100 parts by weight of the colorant. It is more preferable that If the content is within the above range, the color material can be uniformly dispersed. Moreover, in the resin composition described later, a colored layer having sufficient hardness can be formed without relatively reducing the blending ratio of the binder component.
(溶媒)
本発明に用いられる溶媒は、前記一般式(I)で表される色材を実質的に溶解しない溶媒又は難溶性の溶媒であり、23℃における前記色材の溶解度が、0.1(mg/10g溶媒)以下の溶媒である。このような溶媒を用いることにより、本発明に係る色材分散液は前記色材を溶媒中で粒子(凝集体)として分散させて用いることができる。本発明に用いられる前記一般式(I)で表される色材は、その凝集状態を保持したまま溶媒中に分散させて用いることにより、耐熱性及び耐光性に優れる。中でも、23℃における前記色材の溶解度が、0.01(mg/10g溶媒)以下である溶媒が好ましく、更に、前記色材を実質的に溶解しない溶媒がより好ましい。
(solvent)
The solvent used in the present invention is a solvent that does not substantially dissolve the color material represented by the general formula (I) or a hardly soluble solvent, and the solubility of the color material at 23 ° C. is 0.1 (mg). / 10 g solvent) The following solvents. By using such a solvent, the color material dispersion according to the present invention can be used by dispersing the color material as particles (aggregates) in a solvent. The color material represented by the general formula (I) used in the present invention is excellent in heat resistance and light resistance by being dispersed in a solvent while maintaining its aggregation state. Among them, a solvent having a solubility of the coloring material at 23 ° C. of 0.01 (mg / 10 g solvent) or less is preferable, and a solvent that does not substantially dissolve the coloring material is more preferable.
なお、本発明において、一般式(I)で表される色材を23℃における前記色材の溶解度が、0.1(mg/10g溶媒)以下の溶媒は、以下の評価方法により簡易的に判定することができる。
20mLサンプル管瓶に評価する溶媒を10g投入し、更に前記色材0.1gを投入し、ふたをして20秒間よく振った後、23℃のウォーターバス内で10分間静置する。この上澄み液5gをろ過し不溶物を除く。得られたろ液を更に1000倍に希釈した溶液の吸光スペクトルを紫外可視近赤外分光光度計(例えば、島津製作所社製 UV−3100PC)で1cmセルを用いて測定し、最大吸収波長における吸光度を求める。このとき、最大吸収波長における吸光度が2未満であれば当該溶媒は、一般式(I)で表される色材を23℃における前記色材の溶解度が、0.1(mg/10g溶媒)以下の溶媒(難溶性の溶媒)であると評価できる。
In the present invention, a solvent having a colorant represented by the general formula (I) having a solubility of the colorant at 23 ° C. of 0.1 (mg / 10 g solvent) or less can be simply determined by the following evaluation method. Can be determined.
Into a 20 mL sample tube, 10 g of the solvent to be evaluated is added, 0.1 g of the coloring material is further added, the lid is covered, shaken well for 20 seconds, and then allowed to stand in a 23 ° C. water bath for 10 minutes. 5 g of this supernatant liquid is filtered to remove insoluble matters. The absorbance spectrum of a solution obtained by further diluting the obtained filtrate 1000 times was measured with a UV-visible near-infrared spectrophotometer (for example, UV-3100PC manufactured by Shimadzu Corporation) using a 1 cm cell, and the absorbance at the maximum absorption wavelength was measured. Ask. At this time, if the absorbance at the maximum absorption wavelength is less than 2, the solvent has a colorant represented by the general formula (I) having a solubility of the colorant at 23 ° C. of 0.1 (mg / 10 g solvent) or less. It can be evaluated that it is a solvent (slightly soluble solvent).
また、上記の評価方法において、得られたろ液を希釈せずに、上記と同様に吸光スペクトルを測定し、最大吸収波長における吸光度を求める。このとき、最大吸収波長における吸光度が2未満であれば、当該溶媒は、一般式(I)で表される色材を実質的に溶解しない溶媒であると評価できる。 Further, in the above evaluation method, an absorbance spectrum is measured in the same manner as above without diluting the obtained filtrate, and the absorbance at the maximum absorption wavelength is obtained. At this time, if the absorbance at the maximum absorption wavelength is less than 2, the solvent can be evaluated as a solvent that does not substantially dissolve the coloring material represented by the general formula (I).
23℃における前記色材の溶解度が、0.1(mg/10g溶媒)以下の溶媒としては、一般式(I)で表される色材を実質的に溶解しない溶媒又は難溶性の溶媒であれば特に限定されず、色材分散液中の各成分とは反応せず、これらを溶解若しくは分散可能な溶媒から適宜選択して用いればよい。 The solvent having a solubility of the coloring material at 23 ° C. of 0.1 (mg / 10 g solvent) or less may be a solvent that does not substantially dissolve the coloring material represented by the general formula (I) or a hardly soluble solvent. There is no particular limitation, and it does not react with each component in the colorant dispersion, and may be appropriately selected from solvents that can be dissolved or dispersed.
本発明の色材分散液においては、中でも、エステル系溶媒を用いることが分散安定性の点から好ましい。
エステル系溶媒としては、例えば、酢酸エチル、酢酸ブチル、メトキシプロピオン酸メチル、エトキシプロピオン酸エチル、乳酸エチル、メトキシエチルアセテート、プロ、ピレングリコールモノメチルエーテルアセテート、3−メトキシ−3−メチル−1−ブチルアセテート、3−メトキシブチルアセテート、メトキシブチルアセテート、エトキシエチルアセテート、エチルセロソルブアセテート等が挙げられる。
In the colorant dispersion of the present invention, it is particularly preferable to use an ester solvent from the viewpoint of dispersion stability.
Examples of the ester solvents include ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methoxyethyl acetate, pro, pyrene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1-butyl. Examples include acetate, 3-methoxybutyl acetate, methoxybutyl acetate, ethoxyethyl acetate, and ethyl cellosolve acetate.
これらの溶媒は単独もしくは2種以上を組み合わせて使用してもよい。
本発明の色材分散液は、以上のような溶媒を、当該溶媒を含む色材分散液の全量に対して、通常は60〜85質量%の割合で用いて調製する。溶媒が少なすぎると、粘度が上昇し、分散性が低下しやすい。また、溶媒が多すぎると、色材濃度が低下し、用途によっては十分な近赤外線吸収効果が得られない恐れがある。
These solvents may be used alone or in combination of two or more.
The color material dispersion of the present invention is prepared by using the solvent as described above usually at a ratio of 60 to 85% by mass with respect to the total amount of the color material dispersion containing the solvent. When there are too few solvents, a viscosity will rise and a dispersibility will fall easily. Moreover, when there are too many solvents, color material density | concentration will fall and there exists a possibility that sufficient near-infrared absorption effect may not be acquired depending on a use.
(その他の成分)
本発明の色材分散液には、更に必要に応じて、顔料、染料、分散補助樹脂、その他の成分を配合してもよい。
顔料及び染料は、色調の制御を目的として必要に応じて配合される。顔料及び染料は従来公知のものを目的に応じて選択することができ、1種単独で又は2種以上組み合わせて用いることができる。顔料及び染料の配合量は、本発明の効果が損なわれない範囲であれば特に限定されず、後述する樹脂組成物で用いる場合と同様とすることができる。
分散補助樹脂としては、例えばアルカリ可溶性樹脂が挙げられる。アルカリ可溶性樹脂の立体障害によって色材粒子同士が接触しにくくなり、分散安定化することやその分散安定化効果によって分散剤を減らす効果がある場合がある。
また、その他の成分としては、例えば、濡れ性向上のための界面活性剤、密着性向上のためのシランカップリング剤、消泡剤、ハジキ防止剤、酸化防止剤、凝集防止剤、紫外線吸収剤などが挙げられる。
(Other ingredients)
If necessary, the colorant dispersion of the present invention may further contain pigments, dyes, dispersion auxiliary resins, and other components.
The pigment and the dye are blended as necessary for the purpose of controlling the color tone. Conventionally known pigments and dyes can be selected according to the purpose, and can be used singly or in combination of two or more. The blending amount of the pigment and the dye is not particularly limited as long as the effect of the present invention is not impaired, and can be the same as that used in the resin composition described later.
Examples of the dispersion auxiliary resin include alkali-soluble resins. The steric hindrance of the alkali-soluble resin makes it difficult for the colorant particles to come into contact with each other, and may have the effect of stabilizing the dispersion or reducing the dispersant due to the dispersion stabilizing effect.
Other components include, for example, surfactants for improving wettability, silane coupling agents for improving adhesion, antifoaming agents, repellency inhibitors, antioxidants, anti-aggregation agents, and UV absorbers. Etc.
<色材分散液の製造方法>
本発明の色材分散液は、前記分散剤を前記溶媒に混合、撹拌し、分散剤溶液を調製した後、当該分散剤溶液に、前記本発明に係る色材と必要に応じてその他の化合物を混合し、分散機を用いて分散させることによって調製することができる。また、本発明の色材分散液は、色材と分散剤を溶媒に混合し、公知の分散機を用いて分散させることによって調製してもよい。
<Method for producing colorant dispersion>
The colorant dispersion of the present invention is prepared by mixing and stirring the dispersant in the solvent to prepare a dispersant solution, and then adding the colorant according to the present invention and other compounds as necessary to the dispersant solution. Can be mixed and dispersed using a disperser. The color material dispersion of the present invention may be prepared by mixing a color material and a dispersant in a solvent and dispersing the mixture using a known disperser.
分散処理を行うための分散機としては、2本ロール、3本ロール等のロールミル、ボールミル、振動ボールミル等のボールミル、ペイントコンディショナー、連続ディスク型ビーズミル、連続アニュラー型ビーズミル等のビーズミルが挙げられる。ビーズミルの好ましい分散条件として、使用するビーズ径は0.03〜2.00mmが好ましく、より好ましくは0.10〜1.0mmである。 Examples of the dispersing machine for performing the dispersion treatment include roll mills such as two rolls and three rolls, ball mills such as a ball mill and a vibrating ball mill, bead mills such as a paint conditioner, a continuous disk type bead mill, and a continuous annular type bead mill. As a preferable dispersion condition of the bead mill, the bead diameter to be used is preferably 0.03 to 2.00 mm, and more preferably 0.10 to 1.0 mm.
具体的には、ビーズ径が比較的大きめな2mmジルコニアビーズで予備分散を行い、更にビーズ径が比較的小さめな0.1mmジルコニアビーズで本分散することが挙げられる。また、分散後、0.1〜0.5μmのメンブランフィルターで濾過することが好ましい。 Specifically, preliminary dispersion is performed with 2 mm zirconia beads having a relatively large bead diameter, and main dispersion is further performed with 0.1 mm zirconia beads having a relatively small bead diameter. Moreover, it is preferable to filter with a 0.1-0.5 micrometer membrane filter after dispersion | distribution.
本発明においては、公知の分散機を用いて分散させる分散時間は、適宜調整され特に限定されないが、前記一般式(I)で表される色材を微細化して高い近赤外線吸収性を実現する点から、5〜40時間に設定されることが好ましい。
このようにして、色材粒子の分散性に優れた色材分散液が得られる。
In the present invention, the dispersion time for dispersion using a known disperser is appropriately adjusted and is not particularly limited. However, the color material represented by the general formula (I) is refined to achieve high near infrared absorption. From the point of view, it is preferably set to 5 to 40 hours.
In this way, a color material dispersion excellent in dispersibility of the color material particles is obtained.
本発明に用いられる色材の色材分散液中の平均分散粒径としては、用途に応じて適宜設定すればよく特に限定されないが、耐熱性及び耐光性に優れる点から、10〜150nmの範囲内であることが好ましく、20〜125nmの範囲内であることがより好ましい。色材の平均分散粒径が上記範囲であることにより、本発明の色材分散液を塗工した面が、均一で優れた赤外線吸収性能を発揮する。
色材分散液中の色材の平均分散粒径は、少なくとも溶媒を含有する分散媒体中に分散している色材粒子の分散粒径であって、レーザー光散乱粒度分布計により測定されるものである。レーザー光散乱粒度分布計による粒径の測定としては、色材分散液に用いられている溶媒で、色材分散液をレーザー光散乱粒度分布計で測定可能な濃度に適宜希釈(例えば、1000倍など)し、レーザー光散乱粒度分布計(例えば、日機装社製なのトラック粒度分布測定装置UPA−EX150)を用いて動的光散乱法により23℃にて測定することができる。ここでの平均分散粒径は、体積平均粒径である。
The average dispersed particle size in the colorant dispersion of the colorant used in the present invention is not particularly limited as long as it is appropriately set depending on the application, but is in the range of 10 to 150 nm from the viewpoint of excellent heat resistance and light resistance. Is preferably within the range of 20 to 125 nm. When the average dispersed particle diameter of the color material is in the above range, the surface coated with the color material dispersion of the present invention exhibits uniform and excellent infrared absorption performance.
The average dispersed particle size of the color material in the color material dispersion is a dispersed particle size of the color material particles dispersed in a dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is. The particle size can be measured with a laser light scattering particle size distribution meter by appropriately diluting the color material dispersion liquid to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times). Etc.) and can be measured at 23 ° C. by a dynamic light scattering method using a laser light scattering particle size distribution meter (for example, a track particle size distribution measuring device UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average dispersed particle size here is a volume average particle size.
色材分散液は、後述する樹脂組成物を調製するための予備調製物として用いることができる。すなわち、色材分散液とは、後述の樹脂組成物を調製する前段階において、予備調製される(組成物中の色材分質量)/(組成物中の色材以外の固形分質量)比の高い色材分散液である。具体的には、(組成物中の色材分質量)/(組成物中の色材以外の固形分質量)比は通常1.0以上である。色材分散液と少なくともバインダー成分を混合することにより、分散性に優れた樹脂組成物を調製することができる。 The color material dispersion can be used as a preliminary preparation for preparing a resin composition described later. That is, the colorant dispersion is a preliminarily prepared (colorant content mass in the composition) / (solid content mass other than the colorant in the composition) ratio in the pre-stage of preparing the resin composition described later. Is a high colorant dispersion. Specifically, the ratio of (mass of coloring material in composition) / (mass of solid content other than coloring material in composition) is usually 1.0 or more. By mixing the color material dispersion and at least the binder component, a resin composition having excellent dispersibility can be prepared.
[樹脂組成物]
本発明に係る樹脂組成物は、下記一般式(I)で表わされる色材と、バインダー成分とを含有することを特徴とする。
[Resin composition]
The resin composition according to the present invention contains a colorant represented by the following general formula (I) and a binder component.
本発明の樹脂組成物は、前記本発明の色材と、バインダー成分とを組み合わせて用いることにより、耐熱性及び耐光性に優れた着色層を形成することができる。
本発明の樹脂組成物は、少なくとも前記本発明に係る色材、及びバインダー成分を含有するものであり、必要に応じて他の成分を有してもよいものである。
また、本発明の樹脂組成物は、前記色材分散液にバインダー成分を組み合わせて用いてもよい。この場合、本発明の樹脂組成物は、一般式(I)で表される色材と、バインダー成分と、分散剤と、23℃における前記色材の溶解度が0.1(mg/10g溶媒)以下の溶媒とを含有する。
以下、本発明の樹脂組成物の各成分について詳細に説明する。なお、前記本発明に係る色材分散液に含まれ得る成分については、上記色材分散液の箇所において説明したものと同様のものを用いることができるので、ここでの説明は省略する。
The resin composition of the present invention can form a colored layer excellent in heat resistance and light resistance by using the color material of the present invention in combination with a binder component.
The resin composition of the present invention contains at least the colorant according to the present invention and a binder component, and may have other components as necessary.
Moreover, you may use the resin composition of this invention combining a binder component with the said color material dispersion liquid. In this case, the resin composition of the present invention has a colorant represented by the general formula (I), a binder component, a dispersant, and a solubility of the colorant at 23 ° C. of 0.1 (mg / 10 g solvent). Contains the following solvents.
Hereinafter, each component of the resin composition of this invention is demonstrated in detail. The components that can be included in the color material dispersion according to the present invention can be the same as those described in the above-mentioned color material dispersion, and thus the description thereof is omitted here.
(バインダー成分)
本発明においてバインダー成分は少なくとも樹脂を含有する。当該樹脂としては、熱可塑性樹脂、熱硬化性樹脂、光硬化性樹脂のいずれであってもよい。
(Binder component)
In the present invention, the binder component contains at least a resin. The resin may be any of a thermoplastic resin, a thermosetting resin, and a photocurable resin.
熱可塑性樹脂としては、エポキシ樹脂;ポリメタクリル酸メチル、ポリアクリル酸アミド等のアクリル系樹脂;ポリスチレン系樹脂;ニトロセルロース、エチルセルロース等のセルロース系樹脂;ポリエステル系樹脂;熱可塑性ウレタン系樹脂;塩素化ポリエチレン、塩素化ポリプロピレン等の変性オレフィン系樹脂;酢酸ビニル樹脂、塩化ビニル−酢酸ビニル共重合体、ブチラール樹脂等のビニル系樹脂、ノルボルネン構造を有する非晶性ポリオレフィン等が好適なものとして挙げられる。中でも、ガラス転移温度が90〜180℃の範囲にあることが好ましく、特に120〜180℃の範囲であることが好ましい。 As thermoplastic resins, epoxy resins; acrylic resins such as polymethyl methacrylate and polyacrylic amide; polystyrene resins; cellulose resins such as nitrocellulose and ethyl cellulose; polyester resins; thermoplastic urethane resins; Preferred examples include modified olefin resins such as polyethylene and chlorinated polypropylene; vinyl resins such as vinyl acetate resins, vinyl chloride-vinyl acetate copolymers and butyral resins, and amorphous polyolefins having a norbornene structure. Among these, the glass transition temperature is preferably in the range of 90 to 180 ° C, particularly preferably in the range of 120 to 180 ° C.
本発明においては、成膜性や被塗工面に対する密着性を付与し、塗膜に充分な硬度を付与するために、熱硬化性樹脂又は光硬化性樹脂を含む硬化性バインダー成分を含有することが好ましい。硬化性バインダー成分としては、特に限定されず、従来公知の硬化性バインダー成分を適宜用いることができる。
硬化性バインダー成分としては、例えば、可視光線、紫外線、電子線等により重合硬化させることができる光硬化性樹脂を含む光硬化性バインダー成分や、加熱により重合硬化させることができる熱硬化性樹脂を含む熱硬化性バインダー成分を含むものを用いることができる。
In the present invention, a curable binder component containing a thermosetting resin or a photocurable resin is included in order to impart film formability and adhesion to the surface to be coated, and to impart sufficient hardness to the coating film. Is preferred. It does not specifically limit as a curable binder component, A conventionally well-known curable binder component can be used suitably.
Examples of the curable binder component include a photocurable binder component containing a photocurable resin that can be polymerized and cured by visible light, ultraviolet light, electron beam, and the like, and a thermosetting resin that can be polymerized and cured by heating. What contains the thermosetting binder component to contain can be used.
熱硬化性バインダーとしては、1分子中に熱硬化性官能基を2個以上有する化合物と硬化剤の組み合わせが通常用いられ、更に、熱硬化反応を促進できる触媒を添加しても良い。熱硬化性官能基としては、エポキシ基、オキセタニル基、イソシアネート基、エチレン性不飽和結合等が挙げられる。熱硬化性官能基としてはエポキシ基が好ましく用いられる。熱硬化性バインダー成分の具体例としては、例えば、国際公開第2012/144521号パンフレットに記載のものを挙げることができる。 As the thermosetting binder, a combination of a compound having two or more thermosetting functional groups in one molecule and a curing agent is usually used, and a catalyst capable of promoting a thermosetting reaction may be added. Examples of the thermosetting functional group include an epoxy group, an oxetanyl group, an isocyanate group, and an ethylenically unsaturated bond. An epoxy group is preferably used as the thermosetting functional group. Specific examples of the thermosetting binder component include those described in International Publication No. 2012/144521 pamphlet.
一方、着色層を形成する際にフォトリソグラフィー工程を用いる場合には、アルカリ現像性を有する感光性バインダー成分が好適に用いられる。
以下、感光性バインダー成分について説明するが、硬化性バインダー成分はこれらに限定されるものではない。
On the other hand, when using a photolithography process when forming a colored layer, the photosensitive binder component which has alkali developability is used suitably.
Hereinafter, although the photosensitive binder component is demonstrated, a curable binder component is not limited to these.
(1)感光性バインダー成分
感光性バインダー成分としては、ポジ型感光性バインダー成分とネガ型感光性バインダー成分が挙げられる。ポジ型感光性バインダー成分としては、例えば、アルカリ可溶性樹脂及び感光性付与成分としてo−キノンジアジド基含有化合物を含んだ系が挙げられ、アルカリ可溶性樹脂としては、例えば、ポリイミド前駆体等が挙げられる。
(1) Photosensitive binder component Examples of the photosensitive binder component include a positive photosensitive binder component and a negative photosensitive binder component. Examples of the positive photosensitive binder component include an alkali-soluble resin and a system containing an o-quinonediazide group-containing compound as a photosensitizing component, and examples of the alkali-soluble resin include a polyimide precursor.
ネガ型感光性バインダー成分としては、アルカリ可溶性樹脂と、多官能性モノマーと、光開始剤を少なくとも含有する系が好適に用いられる。アルカリ可溶性樹脂と、多官能性モノマーと、光開始剤の具体例としては、例えば、国際公開第2012/144521号パンフレットに記載のものを挙げることができる。 As the negative photosensitive binder component, a system containing at least an alkali-soluble resin, a polyfunctional monomer, and a photoinitiator is preferably used. Specific examples of the alkali-soluble resin, the polyfunctional monomer, and the photoinitiator include those described in International Publication No. 2012/144521 pamphlet.
(任意添加成分)
本発明の樹脂組成物には、本発明の目的が損なわれない範囲で、必要に応じ他の色材や各種添加剤を含むものであってもよい。
(Optional additive)
The resin composition of the present invention may contain other colorants and various additives as necessary within a range that does not impair the object of the present invention.
(他の色材)
他の色材は、色調の制御を目的として必要に応じて配合される。色材は従来公知のものを目的に応じて選択することができ、1種又は2種以上用いることができる。
(Other color materials)
Other color materials are blended as needed for the purpose of controlling the color tone. Conventionally known color materials can be selected according to the purpose, and one or more color materials can be used.
(添加剤)
添加剤としては、例えば重合停止剤、連鎖移動剤、レベリング剤、可塑剤、界面活性剤、消泡剤、シランカップリング剤、紫外線吸収剤、密着促進剤等などが挙げられる。
界面活性剤及び可塑剤の具体例としては、例えば、国際公開第2012/144521号パンフレットに記載のものが挙げられる。
(Additive)
Examples of the additive include a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a surfactant, an antifoaming agent, a silane coupling agent, an ultraviolet absorber, and an adhesion promoter.
Specific examples of the surfactant and the plasticizer include those described in International Publication No. 2012/144521 pamphlet.
(樹脂組成物における各成分の配合割合)
一般式(I)で表される色材及び必要に応じて配合される他の色材の合計の含有量は、樹脂組成物の固形分全量に対して、5〜65質量%、より好ましくは8〜55質量%の割合で配合することが好ましい。色材が少なすぎると、所望の赤外線吸収性を得ることが困難となる恐れがある。また色材等が多すぎると、樹脂組成物を基材へ塗布し硬化させた際の基材への密着性、硬化膜の表面荒れ、塗膜硬さ等の塗膜としての特性が不十分となるおそれがあり、また樹脂組成物中の色材の分散に使われる分散剤の量の比率も多くなるために耐溶剤性等の特性が不十分になる恐れがある。尚、本発明において固形分は、上述した溶媒以外のもの全てであり、溶媒中に溶解している多官能性モノマー等も含まれる。
また、分散剤を用いる場合、当該分散剤の含有量は、色材を均一に分散できる範囲で適宜調整すればよい。例えば、色材100質量部に対して10〜150質量部用いることが好ましく、色材100質量部に対して15〜45質量部の割合で配合するのがより好ましく、15〜40質量部の割合で配合するのが更により好ましい。また、分散剤の含有量は、樹脂組成物の固形分全量に対して、1〜60質量%の範囲内であることが好ましく、中でも5〜50質量%の範囲内であることが好ましい。分散剤の含有量が、樹脂組成物の固形分全量に対して、1質量%未満の場合には、色材を均一に分散することが困難になる恐れがあり、60質量%を超える場合には、硬化性、現像性の低下を招く恐れがある。
バインダー成分は、その合計の含有量が、樹脂組成物の固形分全量に対して24〜94質量%、40〜90質量%の割合で配合するのが好ましい。
また、溶媒を用いる場合、その含有量は、色材の分散性や、樹脂組成物の塗工性等の点から適宜調整すればよい。溶媒は、該溶媒を含む樹脂組成物の全量に対して、通常、65〜95質量%の範囲内であることが好ましく、中でも75〜88質量%の範囲内であることがより好ましい。
(Mixing ratio of each component in the resin composition)
The total content of the coloring material represented by the general formula (I) and other coloring materials blended as necessary is 5 to 65% by mass, more preferably based on the total solid content of the resin composition. It is preferable to mix | blend in the ratio of 8-55 mass%. When there are too few coloring materials, there exists a possibility that it may become difficult to obtain desired infrared absorptivity. Also, if there are too many coloring materials, the properties as a coating film such as adhesion to the substrate when the resin composition is applied to the substrate and cured, surface roughness of the cured film, coating film hardness, etc. are insufficient. In addition, since the ratio of the amount of the dispersant used for dispersing the coloring material in the resin composition increases, characteristics such as solvent resistance may be insufficient. In addition, in this invention, solid content is all things other than the solvent mentioned above, and the polyfunctional monomer etc. which are melt | dissolving in the solvent are also contained.
Moreover, when using a dispersing agent, what is necessary is just to adjust suitably content of the said dispersing agent in the range which can disperse | distribute a coloring material uniformly. For example, it is preferable to use 10 to 150 parts by mass with respect to 100 parts by mass of the color material, more preferably 15 to 45 parts by mass with respect to 100 parts by mass of the color material, and a ratio of 15 to 40 parts by mass. It is even more preferable to blend with. Moreover, it is preferable that content of a dispersing agent exists in the range of 1-60 mass% with respect to the solid content whole quantity of a resin composition, and it is preferable to exist in the range of 5-50 mass% especially. When the content of the dispersant is less than 1% by mass with respect to the total solid content of the resin composition, it may be difficult to uniformly disperse the color material, and when the content exceeds 60% by mass. May cause a decrease in curability and developability.
The total content of the binder component is preferably 24 to 94% by mass and 40 to 90% by mass with respect to the total solid content of the resin composition.
Moreover, what is necessary is just to adjust the content suitably, when using a solvent from points, such as the dispersibility of a coloring material and the coating property of a resin composition. The solvent is usually preferably in the range of 65 to 95% by mass, and more preferably in the range of 75 to 88% by mass, based on the total amount of the resin composition containing the solvent.
(樹脂組成物の製造)
樹脂組成物の製造方法は、特に限定されない。前記本発明に係る色材分散液を用いて樹脂組成物を調製する場合、例えば、(1)溶媒中に、前記本発明に係る色材分散液と、バインダー成分と、所望により用いられる各種添加成分とを同時に投入し、混合する方法、(2)溶媒中に、バインダー成分と、所望により用いられる各種添加成分とを添加し、混合したのち、これに前記本発明に係る色材分散液を加えて混合する方法などが挙げられる。
(Manufacture of resin composition)
The method for producing the resin composition is not particularly limited. When preparing a resin composition using the colorant dispersion according to the present invention, for example, (1) In the solvent, the colorant dispersion according to the present invention, a binder component, and various additions used as desired (2) A binder component and various additive components used as desired are added to a solvent and mixed, and then the colorant dispersion according to the present invention is added thereto. In addition, there is a method of mixing.
本発明に係る樹脂組成物は、例えば、不可視印刷用インク、赤外線吸収塗料として用いることができる。また、本発明に係る樹脂組成物を用いて形成された着色層は、例えば、赤外線吸収フィルター、熱線吸収フィルター、バンドパスフィルター等の各種フィルター用途に用いることができる。 The resin composition according to the present invention can be used, for example, as an invisible printing ink or an infrared absorbing paint. Moreover, the colored layer formed using the resin composition which concerns on this invention can be used for various filter uses, such as an infrared rays absorption filter, a heat ray absorption filter, a band pass filter, for example.
以下、本発明について実施例を示して具体的に説明する。これらの記載により本発明を制限するものではない。 Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention.
(合成例1:ジイモニウム化合物の合成)
1,4−フェニレンジアミン1.1g(10.2mmol)、4−ブロモ−N,N−ジエチルアニリン10g、ナトリウム−tert−ブトキシド4.56g、トリ−tert−ブチルホスフィン226mg、ビス(ジベンジリデンアセトン)パラジウム(0)172mg、トルエン110ml混合溶液を窒素気流下、100℃まで加熱し、5時間還流させた。薄層クロマトグラフィー(TLC)で反応終了を確認した後、室温まで冷却し、水200ml、トルエン100mlを添加した。トルエンで抽出、水、ブラインで洗浄後、硫酸マグネシウムで乾燥した。
減圧下、ロータリーエバポレーターで溶媒を留去し、得られた固体を酢酸エチル/ノルマルへキサン=1/2で洗浄し、茶褐色固体のジイモニウム化合物5.7gを得た。(収率80%)
(Synthesis Example 1: Synthesis of diimonium compound)
1.1 g (10.2 mmol) of 1,4-phenylenediamine, 10 g of 4-bromo-N, N-diethylaniline, 4.56 g of sodium-tert-butoxide, 226 mg of tri-tert-butylphosphine, bis (dibenzylideneacetone) A mixed solution of 172 mg of palladium (0) and 110 ml of toluene was heated to 100 ° C. under a nitrogen stream and refluxed for 5 hours. After confirming the completion of the reaction by thin layer chromatography (TLC), the reaction mixture was cooled to room temperature, and 200 ml of water and 100 ml of toluene were added. Extraction with toluene, washing with water and brine, followed by drying over magnesium sulfate.
Under reduced pressure, the solvent was distilled off with a rotary evaporator, and the obtained solid was washed with ethyl acetate / normal hexane = 1/2 to obtain 5.7 g of a brown solid diimonium compound. (Yield 80%)
(合成例2:ジイモニウム化合物の塩化物塩(比較色材A)の合成)
合成例1で得られたジイモニウム化合物5.7gを酢酸エチル/アセトン=2/1に溶解させ、第二塩化鉄3.0gを含む水46mlの水溶液を添加し、50℃で4時間攪拌した。
反応終了後室温まで冷却し、減圧下、ロータリーエバポレーターで溶媒を留去し得られた固体をアセトンで洗浄し、下記化学式(1)で表される比較色材A(緑色固体6.0g)を得た。(収率95%)
(Synthesis Example 2: Synthesis of chloride salt of diimonium compound (comparative colorant A))
5.7 g of the dimonium compound obtained in Synthesis Example 1 was dissolved in ethyl acetate / acetone = 2/1, an aqueous solution of 46 ml of water containing 3.0 g of ferric chloride was added, and the mixture was stirred at 50 ° C. for 4 hours.
After completion of the reaction, the reaction mixture was cooled to room temperature, the solvent was distilled off with a rotary evaporator under reduced pressure, and the resulting solid was washed with acetone to give a comparative colorant A (green solid 6.0 g) represented by the following chemical formula (1). Obtained. (Yield 95%)
(合成例3:色材Aの合成)
合成例2で得られた比較色材A2.0gを水に添加し、加熱しながら攪拌して溶解させた。そこへ、リンタングステン酸n水和物(n=25.6)5.48gを含む80mlの水溶液を滴下した。反応終了後、室温まで冷却し析出した固体をろ過、水で洗浄し、下記化学式(2)で表される色材A5.6g(収率86%)を得た。
(Synthesis Example 3: Synthesis of Color Material A)
2.0 g of the comparative color material A obtained in Synthesis Example 2 was added to water and dissolved by stirring while heating. Thereto, 80 ml of an aqueous solution containing 5.48 g of phosphotungstic acid n-hydrate (n = 25.6) was added dropwise. After completion of the reaction, the mixture was cooled to room temperature, and the precipitated solid was filtered and washed with water to obtain 5.6 g (yield 86%) of colorant A represented by the following chemical formula (2).
(合成例4:色材Bの合成)
合成例3において、リンタングステン酸n水和物の代わりに、リンタングステン酸n水和物とリンモリブデン酸n水和物(n=73.0)の混合物(70:30(モル比))を用いた以外は、合成例3と同様にして、下記化学式(3)で表される色材Bを得た(収率81%)。
(Synthesis Example 4: Synthesis of Color Material B)
In Synthesis Example 3, a mixture of phosphotungstic acid n hydrate and phosphomolybdic acid n hydrate (n = 73.0) (70:30 (molar ratio)) was used instead of phosphotungstic acid n hydrate. A coloring material B represented by the following chemical formula (3) was obtained in the same manner as in Synthesis Example 3 except that it was used (yield 81%).
(合成例5:色材Cの合成)
合成例4において、リンタングステン酸n水和物とリンモリブデン酸n水和物のモル比が50/50になるようにした以外は、合成例4と同様にして、下記化学式(4)で表される色材Cを得た(収率74%)。
(Synthesis Example 5: Synthesis of Color Material C)
In Synthesis Example 4, except that the molar ratio of phosphotungstic acid n-hydrate to phosphomolybdic acid n-hydrate was 50/50, the same as in Synthesis Example 4, represented by the following chemical formula (4) Colorant C was obtained (yield 74%).
(合成例6:色材Dの合成)
合成例3において、リンタングステン酸n水和物の代わりに、リンモリブデン酸n水和物を用いた以外は、合成例3と同様にして、下記化学式(5)で表される色材Dを得た(収率87%)。
(Synthesis Example 6: Synthesis of Color Material D)
In Synthesis Example 3, a coloring material D represented by the following chemical formula (5) was prepared in the same manner as in Synthesis Example 3 except that phosphomolybdic acid n hydrate was used instead of phosphotungstic acid n hydrate. Obtained (yield 87%).
(合成例7:バインダー樹脂Aの合成)
冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた反応器に、溶剤としてジエチレングリコールエチルメチルエーテル(略称EMDG)130質量部を仕込み、窒素雰囲気下で110℃に昇温した後、メタクリル酸メチル32質量部、メタクリル酸シクロヘキシル22質量部、メタクリル酸24質量部、開始剤としてα,α’−アゾビスイソブチロニトリル(略称AIBN)2質量部および連鎖移動剤としてn−ドデシルメルカプタン4.5質量部を含む混合物を、それぞれ1.5時間かけて連続的に滴下した。
その後、合成温度を保持して反応を続け、滴下終了から2時間後に重合禁止剤として、p−メトキシフェノール0.05質量部を添加した。
次に、空気を吹き込みながら、メタクリル酸グリシジル22質量部を添加して、110℃に昇温した後、トリエチルアミン0.2質量部を添加して110℃で15時間付加反応させ、バインダー樹脂A(固形分44質量%)を得た。
得られたバインダー樹脂Aの質量平均分子量Mwは8500、酸価は85mgKOH/gであった。なお、質量平均分子量Mwは、ポリスチレンを標準物質とし、THFを溶離液としてゲルパーミエーションクロマトグラフィー(GPC)にて算出し、酸価はJIS−K0070に従い測定した。
(Synthesis Example 7: Synthesis of Binder Resin A)
A reactor equipped with a condenser, addition funnel, nitrogen inlet, mechanical stirrer, and digital thermometer was charged with 130 parts by mass of diethylene glycol ethyl methyl ether (abbreviated as EMDG) as a solvent, and the temperature was raised to 110 ° C. in a nitrogen atmosphere. After that, 32 parts by mass of methyl methacrylate, 22 parts by mass of cyclohexyl methacrylate, 24 parts by mass of methacrylic acid, 2 parts by mass of α, α′-azobisisobutyronitrile (abbreviation AIBN) as an initiator and n as a chain transfer agent -The mixture containing 4.5 mass parts of dodecyl mercaptan was dripped continuously over 1.5 hours, respectively.
Thereafter, the reaction was continued while maintaining the synthesis temperature, and 0.05 parts by mass of p-methoxyphenol was added as a polymerization inhibitor 2 hours after the completion of the dropping.
Next, while blowing air, 22 parts by mass of glycidyl methacrylate was added, the temperature was raised to 110 ° C., 0.2 parts by mass of triethylamine was added, and an addition reaction was carried out at 110 ° C. for 15 hours. 44 mass% solid content) was obtained.
The obtained binder resin A had a mass average molecular weight Mw of 8,500 and an acid value of 85 mgKOH / g. The mass average molecular weight Mw was calculated by gel permeation chromatography (GPC) using polystyrene as a standard substance and THF as an eluent, and the acid value was measured according to JIS-K0070.
(製造例1:色材分散液Aの調製)
色材として、合成例3の色材Aを6.00質量部、3級アミノ基を含むブロック共重合体(商品名:BYK−LPN6919、ビックケミー社製)を3.73質量部(有効固形分0.60質量部)、フェニルフォスフィン酸を0.76質量部、合成例3のバインダー樹脂A4.60質量部(有効固形分39.14質量部)、PGMEA84.91質量部を混合し、ペイントシェーカー(浅田鉄工製)にて予備分散として2mmジルコニアビーズで1時間、さらに本分散として0.1mmジルコニアビーズで4時間分散し、色材分散液Aを得た。
(Production Example 1: Preparation of colorant dispersion A)
As a colorant, 6.03 parts by mass of the colorant A of Synthesis Example 3 and 3.73 parts by mass (effective solid content) of a block copolymer containing a tertiary amino group (trade name: BYK-LPN6919, manufactured by BYK Chemie). 0.60 parts by mass), 0.76 parts by mass of phenylphosphinic acid, 4.60 parts by mass of binder resin A in Synthesis Example 3 (39.14 parts by mass of effective solid content), 84.91 parts by mass of PGMEA, and paint With a shaker (manufactured by Asada Tekko), dispersion was performed with 2 mm zirconia beads for 1 hour as a preliminary dispersion, and further with 0.1 mm zirconia beads as a main dispersion for 4 hours to obtain a colorant dispersion A.
(製造例2:色材分散液Bの調製)
色材を合成例4の色材Bに代えた以外は製造例1と同様にして色材分散液Bを得た。
(Production Example 2: Preparation of colorant dispersion B)
A color material dispersion B was obtained in the same manner as in Production Example 1 except that the color material was replaced with the color material B of Synthesis Example 4.
(製造例3:色材分散液Cの調製)
色材を合成例5の色材Cに代えた以外は製造例1と同様にして色材分散液Cを得た。
(Production Example 3: Preparation of colorant dispersion C)
A color material dispersion C was obtained in the same manner as in Production Example 1 except that the color material was replaced with the color material C of Synthesis Example 5.
(製造例4:色材分散液Dの調製)
色材を合成例6の色材Dに代えた以外は製造例1と同様にして色材分散液Dを得た。
(Production Example 4: Preparation of colorant dispersion D)
A color material dispersion D was obtained in the same manner as in Production Example 1 except that the color material was replaced with the color material D of Synthesis Example 6.
(実施例1)
製造例1で得られた色材分散液A25.68質量部、下記バインダー組成物A35.34質量部、PGMEA38.54質量部、界面活性剤R08MH(DIC製)0.04質量部、シランカップリング剤KBM503(信越シリコーン製)0.4質量部を添加混合し、加圧濾過を行って、実施例1の着色樹脂組成物Aを得た。
(Example 1)
25.68 parts by mass of the colorant dispersion A obtained in Production Example 1, 35.34 parts by mass of the following binder composition A, 38.54 parts by mass of PGMEA, 0.04 parts by mass of a surfactant R08MH (manufactured by DIC), silane coupling Agent KBM503 (manufactured by Shin-Etsu Silicone) (0.4 parts by mass) was added and mixed, and pressure filtration was performed to obtain colored resin composition A of Example 1.
<バインダー組成物A(固形分40質量%)>
・アルカリ可溶性樹脂(合成例3のバインダー樹脂A、固形分44質量%):18.18質量部
・5〜6官能アクリレートモノマー(商品名:アロニックスM403、東亞合成製):8.00質量部
・光重合開始剤:2−メチル−1[4−(メチルチオ)フェニル]−2−モリフォリノプロパン−1−オン(商品名:イルガキュア907、BASF製)):3.00質量部
・光増感剤:2,4ジエチルチオキサントン(商品名:カヤキュアーDETX−S、日本化薬製):1.00質量部
・溶剤:プロピレングリコールモノメチルエーテルアセテート(PGMEA):19.82質量部
<Binder composition A (solid content 40% by mass)>
Alkali-soluble resin (Binder resin A of Synthesis Example 3, solid content 44% by mass): 18.18 parts by mass5 to 6-functional acrylate monomer (trade name: Aronix M403, manufactured by Toagosei Co., Ltd.): 8.00 parts by mass Photopolymerization initiator: 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by BASF): 3.00 parts by mass / photosensitization Agent: 2,4 Diethylthioxanthone (trade name: Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.): 1.00 parts by mass; Solvent: propylene glycol monomethyl ether acetate (PGMEA): 19.82 parts by mass
(実施例2)
色材分散液を製造例2の色材分散液Bに代えた以外は実施例1と同様にして着色樹脂組成物Bを得た。
(Example 2)
A colored resin composition B was obtained in the same manner as in Example 1 except that the color material dispersion was replaced with the color material dispersion B of Production Example 2.
(実施例3)
色材分散液を製造例3の色材分散液Cに代えた以外は実施例1と同様にして着色樹脂組成物Cを得た。
Example 3
A colored resin composition C was obtained in the same manner as in Example 1 except that the color material dispersion was changed to the color material dispersion C of Production Example 3.
(実施例4)
色材分散液を製造例4の色材分散液Dに代えた以外は実施例1と同様にして着色樹脂組成物を得た。
Example 4
A colored resin composition was obtained in the same manner as in Example 1 except that the color material dispersion was replaced with the color material dispersion D of Production Example 4.
(比較例1)
メタノールにポリヒドロキシエチルメタクリレート樹脂(PHEMA樹脂(Mw=20000))を溶解させた10%溶液99.5質量部に合成例2で得られた比較色材A0.5質量部を加え30分間攪拌し色材溶解液Eを得た。
次いで、実施例1において、色材分散液Aの代わりに、上記色材溶解液Eを用いた以外は、実施例1と同様にして、比較例1の着色樹脂組成物Eを得た。
(Comparative Example 1)
To 99.5 parts by mass of a 10% solution obtained by dissolving polyhydroxyethyl methacrylate resin (PHEMA resin (Mw = 20000)) in methanol, 0.5 part by mass of the comparative colorant A obtained in Synthesis Example 2 was added and stirred for 30 minutes. Colorant solution E was obtained.
Next, in Example 1, a colored resin composition E of Comparative Example 1 was obtained in the same manner as Example 1 except that the color material solution E was used instead of the color material dispersion A.
(比較例2)
PGMEAにポリメチルメタアクリレート樹脂(PMMA樹脂(Mw=3000))を溶解させた10%溶液99.5質量部にCIR−1085F(日本カーリット社製、ジイモニウム色素(ジイモニウムカチオンとビストリフルオロメチルスルホニルイミドアニオンとの塩)、以下、比較色材Bとする。)0.5質量部を加え30分間攪拌し色材溶解液Fを得た。
次いで、実施例1において、色材分散液Aの代わりに、上記色材溶解液Fを用いた以外は、実施例1と同様にして、比較例2の着色樹脂組成物Fを得た。
(Comparative Example 2)
CIR-1085F (manufactured by Nippon Carlit Co., Ltd., diimonium dye (diimonium cation and bistrifluoromethylsulfonylimide anion) was dissolved in 99.5 parts by mass of a 10% solution of polymethyl methacrylate resin (PMMA resin (Mw = 3000)) dissolved in PGMEA. ), Hereinafter referred to as comparative color material B.) 0.5 parts by mass was added and stirred for 30 minutes to obtain a color material solution F.
Next, in Example 1, a colored resin composition F of Comparative Example 2 was obtained in the same manner as Example 1 except that the color material solution F was used instead of the color material dispersion A.
(評価)
<耐熱性評価>
色材A〜D及び比較色材A、Bをそれぞれ、TG−DTA(SHIMADZU社製 DTG−60A)で10℃/分で昇温し、600℃まで加熱した。耐熱性評価として、重量が5%減少したときの温度を測定し、これを5%重量減少温度とした。結果を表1に示す。5%重量減少温度が高いほど、耐熱性に優れていると評価される。
(Evaluation)
<Heat resistance evaluation>
Color materials A to D and comparative color materials A and B were heated at 10 ° C./min with TG-DTA (DTG-60A manufactured by SHIMADZU) and heated to 600 ° C., respectively. As the heat resistance evaluation, the temperature when the weight was reduced by 5% was measured, and this was defined as the 5% weight reduction temperature. The results are shown in Table 1. It is evaluated that the higher the 5% weight loss temperature, the better the heat resistance.
<光学性能評価、耐熱性評価>
各実施例及び比較例で得られた着色樹脂組成物を、それぞれ厚み0.7mmのガラス基板(日本電気硝子製、「OA−10G」)上に、スピンコーターを用いて塗布した。その後、80℃のホットプレート上で3分間加熱乾燥を行った。次いで、超高圧水銀灯を用いて40mJ/cm2の紫外線を照射することによって硬化膜とした。上記塗膜を有する着色基板をクリーンオーブンで150℃で30分間ポストベーク処理し、得られた着色膜の吸光度をSHIMADZU製「UV−3100」を用いて、ポストベーク前後における塗膜の吸光度を測定した。波長550nm及び波長900nmにおける吸光度を表2に示す。
なお、ポストベーク前後における吸光度変化率を下記式により算出した。
変化率 = ポストベーク後の吸光度 / ポストベーク前の吸光度
変化率が1に近いほど、耐熱性に優れていると評価される。
<Optical performance evaluation, heat resistance evaluation>
The colored resin compositions obtained in each Example and Comparative Example were each coated on a glass substrate having a thickness of 0.7 mm (manufactured by Nippon Electric Glass, “OA-10G”) using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. Subsequently, it was set as the cured film by irradiating 40 mJ / cm < 2 > of ultraviolet-rays using an ultrahigh pressure mercury lamp. The colored substrate having the above-mentioned coating film is post-baked at 150 ° C. for 30 minutes in a clean oven, and the absorbance of the obtained colored film is measured with “UV-3100” manufactured by SHIMADZU before and after the post-baking. did. Table 2 shows the absorbance at a wavelength of 550 nm and a wavelength of 900 nm.
The absorbance change rate before and after post-baking was calculated by the following formula.
Rate of change = absorbance after post-bake / absorbance before post-bake The closer the rate of change to 1, the better the heat resistance.
<耐光性評価>
各実施例及び比較例で得られた着色樹脂組成物を、厚み0.7mmのガラス基板(日本電気硝子製、「OA−10G」)上に、スピンコーターを用いて塗布した。その後、80℃のホットプレート上で3分間加熱乾燥を行った。次いで、超高圧水銀灯を用いて40mJ/cm2の紫外線を照射することによって硬化膜を得た。当該塗膜を有する着色基板をそれぞれ大気圧下でキセノンランプ(アトラス社製Ci4000ウェザメータ、内側フィルター:石英、外側フィルター:ソーダライム&赤外線吸収コーティング(CIRA))を用い、420nmの波長で、照度を1.2W/m2として、12時間(50kJ/m2相当)照射した。キセノンランプによる光照射前後の塗膜の吸光度をSHIMADZU製「UV−3100」を用いて測定した。結果を表3に示す。
なお、光照射前後における吸光度変化率を下記式により算出した。
変化率 = 光照射後の吸光度 / 光照射前の吸光度
変化率が1に近いほど、耐光性に優れていると評価される。
<Light resistance evaluation>
The colored resin compositions obtained in each Example and Comparative Example were applied on a glass substrate having a thickness of 0.7 mm (manufactured by Nippon Electric Glass, “OA-10G”) using a spin coater. Then, it heat-dried for 3 minutes on an 80 degreeC hotplate. Subsequently, the cured film was obtained by irradiating 40 mJ / cm < 2 > of ultraviolet-rays using an ultrahigh pressure mercury lamp. Each of the colored substrates having the coating film is subjected to a illuminance at a wavelength of 420 nm using a xenon lamp (Atlas Co., Ltd., Ci4000 Weathermeter, inner filter: quartz, outer filter: soda lime & infrared absorption coating (CIRA)) at atmospheric pressure. Irradiation was performed at 1.2 W / m 2 for 12 hours (equivalent to 50 kJ / m 2 ). The absorbance of the coating film before and after light irradiation with a xenon lamp was measured using “UV-3100” manufactured by SHIMADZU. The results are shown in Table 3.
The absorbance change rate before and after the light irradiation was calculated by the following formula.
Rate of change = Absorbance after light irradiation / Absorbance before light irradiation The closer the rate of change to 1, the better the light resistance.
[結果のまとめ]
表1の結果から、ジイモニウムの塩化物である比較色材Aは、耐熱性が悪かった。このような比較色材Aを用いた比較例1の着色樹脂組成物Fを用いて形成された塗膜は、表2及び表3に示される通り、ポストベークや光照射によって、波長550nmの光の吸光度が上昇し、波長900nmの光の吸光度が低下した。このように比較例1の塗膜は、熱乃至光により赤外線吸収効果が低減され、着色することが明らかとなった。
表1に示される通り、比較色材Bは、色材A〜Dと比較しても耐熱性は良好であった。しかしながら当該比較色材Bを用いた比較例2の塗膜は、表2の通り実施例1〜4と比較して耐熱性が悪かった。これは、比較色材Bが溶剤に溶解していたためであると推定される。また、比較例2の塗膜は、表3の通り耐光性が悪かった。
ヘテロポリ酸アニオンを有する色材A〜Dは、当該色材自体の耐熱性に優れていた。また、当該色材A〜Dを用いた実施例1〜4の塗膜は、耐熱性及び耐光性に優れていることが明らかとなった。
[Summary of results]
From the results of Table 1, the comparative colorant A, which is a diimonium chloride, had poor heat resistance. As shown in Tables 2 and 3, the coating film formed using the colored resin composition F of Comparative Example 1 using the comparative color material A is light having a wavelength of 550 nm by post-baking or light irradiation. Increased, and the absorbance of light having a wavelength of 900 nm decreased. As described above, it was revealed that the coating film of Comparative Example 1 was colored by reducing the infrared absorption effect by heat or light.
As shown in Table 1, the comparative color material B had good heat resistance even when compared with the color materials A to D. However, the coating film of Comparative Example 2 using the comparative color material B had poor heat resistance as compared with Examples 1 to 4 as shown in Table 2. This is presumably because the comparative color material B was dissolved in the solvent. Further, the coating film of Comparative Example 2 had poor light resistance as shown in Table 3.
Color materials A to D having a heteropolyacid anion were excellent in heat resistance of the color material itself. Moreover, it became clear that the coating film of Examples 1-4 using the said color materials AD is excellent in heat resistance and light resistance.
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