JP5281241B2 - Base material with transparent colored film and coating liquid for forming transparent colored film - Google Patents
Base material with transparent colored film and coating liquid for forming transparent colored film Download PDFInfo
- Publication number
- JP5281241B2 JP5281241B2 JP2006354822A JP2006354822A JP5281241B2 JP 5281241 B2 JP5281241 B2 JP 5281241B2 JP 2006354822 A JP2006354822 A JP 2006354822A JP 2006354822 A JP2006354822 A JP 2006354822A JP 5281241 B2 JP5281241 B2 JP 5281241B2
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- Japan
- Prior art keywords
- colored film
- transparent colored
- colorant
- film
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011248 coating agent Substances 0.000 title claims description 91
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- 239000011347 resin Substances 0.000 claims abstract description 93
- 239000003086 colorant Substances 0.000 claims abstract description 80
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
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- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical class CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- WDUXKFKVDQRWJN-UHFFFAOYSA-N triethoxysilylmethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)COC(=O)C=C WDUXKFKVDQRWJN-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Landscapes
- Optical Filters (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、基材との密着性、耐擦傷性、膜硬度等に優れるとともに、膜表面の平滑性、耐光性、コントラスト、表示性能等に優れた透明性着色膜付基材および該透明性着色膜を形成するために好適に用いることのできる安定性に優れた透明性着色膜形成用塗布液に関する。 The present invention is excellent in adhesion to a substrate, scratch resistance, film hardness, etc., and also has a transparent colored film substrate having excellent film surface smoothness, light resistance, contrast, display performance, and the like, and the transparency The present invention relates to a coating solution for forming a transparent colored film having excellent stability, which can be suitably used for forming a colored film.
ガラス、プラスチックシート、プラスチックレンズ、各種表示装置等の基材表面の反射を防止するために、その表面に反射防止膜を形成することが知られている。たとえば、コート法、蒸着法、ＣＶＤ法等によって、フッ素樹脂、フッ化マグネシウムのような低屈折率の物質の被膜をガラスやプラスチックの基材表面に形成したり、シリカ微粒子等の低屈折率微粒子を含む塗布液を基材表面に塗布して、反射防止被膜を形成する方法が知られている（たとえば、特開平７-１３３１０５号公報など参照）。さらに、基材に帯電防止性能、電磁波遮蔽性能を付与するために金属微粒子、導電性の酸化物微粒子を含む導電性被膜を形成することも行われている。 In order to prevent reflection on the surface of a substrate such as glass, plastic sheet, plastic lens, and various display devices, it is known to form an antireflection film on the surface. For example, a coating of a low refractive index material such as fluororesin or magnesium fluoride is formed on the surface of a glass or plastic substrate by a coating method, a vapor deposition method, a CVD method or the like, or a low refractive index fine particle such as a silica fine particle. There has been known a method of forming an antireflection coating by applying a coating solution containing a liquid to a substrate surface (for example, see JP-A-7-133105). Further, in order to impart antistatic performance and electromagnetic wave shielding performance to the base material, a conductive film containing metal fine particles and conductive oxide fine particles is also formed.
このような、反射防止膜、導電性被膜を設ける場合においても耐擦傷性を向上させるために基材と反射防止膜および／または導電性被膜とに間にハードコート膜を形成することも行われている。 Even when such an antireflection film or conductive film is provided, a hard coat film may be formed between the substrate and the antireflection film and / or the conductive film in order to improve the scratch resistance. ing.
また、表示装置の外表面にフィルターを設けてコントラストを向上させる際に、ガラス膜が用いられるが、所望のフィルター特性を持たせるために金属アルコキシドからなるガラス膜に平均粒子径が３〜３００ｎｍの色素を含有させることが開示されている。（特開平０５−１７８６２３号公報）
また、特開２００５−１８１９５２号公報には、液晶表示装置を高コントラストで表示品位の高いものとするために、偏光板に設けうる保護フィルムに染料あるいは顔料を適当量添加した着色フィルムを用いることが開示されている。
Further, when a filter is provided on the outer surface of the display device to improve the contrast, a glass film is used. In order to give a desired filter characteristic, the glass film made of metal alkoxide has an average particle diameter of 3 to 300 nm. The inclusion of a dye is disclosed. (Japanese Patent Laid-Open No. 05-178623)
Japanese Patent Application Laid-Open No. 2005-181952 uses a colored film in which an appropriate amount of a dye or a pigment is added to a protective film that can be provided on a polarizing plate in order to make a liquid crystal display device with high contrast and high display quality. Is disclosed.
しかしながら、従来の着色膜は、色素（染料）あるいは顔料、金属微粒子等の着色剤によってはマトリックス成分（バインダー成分と言うことがある）との親和性がなく、分散性が不充分であるために透明性、ヘーズが必ずしも充分でなく、コントラストも満足のいくものでなく、加えて基材あるいは前記した同時に設けることのある他の被膜との密着性、耐擦傷性、膜の強度等が必ずしも充分とはいえなかった。また、耐光性が不充分で着色が経時的に褪色する問題があった。
本発明は、基材との密着性、耐擦傷性、硬度等に優れるとともに透明性を有し、膜表面の平滑性、耐光性、コントラストに優れた透明性着色膜付基材および該透明性着色膜を形成するための透明性着色膜形成用塗布液を提供することを目的としている。 The present invention is excellent in adhesion to a substrate, scratch resistance, hardness and the like, and has transparency, and has a transparent colored film substrate having smoothness, light resistance, and contrast on the film surface, and the transparency It aims at providing the coating liquid for transparent colored film formation for forming a colored film.
本発明者等は、上記課題を解決すべく鋭意検討した結果、着色剤粒子を無機酸化物または樹脂で被覆することにより、基材との密着性、耐擦傷性、膜硬度等に優れ、且つ、透明
性を有するとともに耐光性およびコントラストに優れた着色膜を形成できることを見出して本発明を完成するに至った。
[1]基材と、基材上の片面または両面に形成された透明性着色膜とからなり、
該透明性着色膜が、マトリックス成分と、着色剤として無機酸化物または樹脂で被覆された顔料粒子および／または金属微粒子とを含んでなり、着色膜中の該着色剤の含有量が０．１〜５０重量％の範囲にあることを特徴とする透明性着色膜付基材。
[2]前記着色剤が下記式(1)で表される有機珪素化合物で表面処理されている[1]の透明性
着色膜付基材。
Ｒn-ＳiＸ4-n （１）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、シラノール基、ハロゲン、水素、ｎ：０〜３の整数）
[3]前記着色剤が下記式(2)で表される有機珪素化合物で表面処理されている[1]または[2]の透明性着色膜付基材。
Ｘ-Ｒ-Ｓi(ＯＲ)3 （２）
（式中、Ｒは、置換または非置換の炭化水素基から選ばれる炭素数１〜１０の有機基を表す。Xはγ-グリシドキシ基、または（メタ）アクリロイル基を示す。）
[4]前記透明性着色膜が着色剤としてさらに染料を含んでなる[1]〜[3]の透明性着色膜付
基材。
[5]前記透明性着色膜は、
少なくとも波長５６０〜６２０ｎｍの光透過率（I）が４０〜９８％にあるか、あるい
は波長４５０〜５００ｎｍの光透過率（II）が４０〜９８％の範囲にある[1]〜[4]の透明性着色膜付基材。
[6]さらに前記透明性着色膜の他の被膜が設けられてなる[1]〜[5]の透明性着色膜付基材
。
[7]マトリックス形成成分と、着色剤として無機酸化物または樹脂で被覆された顔料粒子
および／または金属微粒子とを含んでなり、マトリックス形成成分と着色剤との合計の濃度が固形分として０．５〜６０重量％の範囲にあり、該着色剤を透明性着色膜中に固形分として０．１〜５０重量％となるように含有している透明性着色膜形成用塗布液。
[8]前記着色剤が下記式(1)で表される有機珪素化合物で表面処理されている[7]の透明性
着色膜形成用塗布液。
Ｒn-ＳiＸ4-n （１）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、シラノール基、ハロゲン、水素、ｎ：０〜３の整数）
[9]前記着色剤がさらに下記式(2)で表される有機珪素化合物で表面処理されている[7]ま
たは[8]の透明性着色膜形成用塗布液。
Ｘ-Ｒ-Ｓi(ＯＲ)3 （２）
（式中、Ｒは、置換または非置換の炭化水素基から選ばれる炭素数１〜１０の有機基を表す。X-はγ-グリシドキシ基、（メタ）アクリロイル基を示す。）
[10]着色剤としてさらに染料を含んでなる[7]〜[9]の透明性着色膜形成用塗布液。
As a result of intensive studies to solve the above-mentioned problems, the present inventors are excellent in adhesion to the substrate, scratch resistance, film hardness, etc. by coating the colorant particles with an inorganic oxide or resin, and The present invention has been completed by finding that a colored film having transparency and excellent light resistance and contrast can be formed.
[1] consisting of a base material and a transparent colored film formed on one or both sides of the base material,
The transparent colored film comprises a matrix component and pigment particles and / or metal fine particles coated with an inorganic oxide or resin as a colorant, and the content of the colorant in the colored film is 0.1. A substrate with a transparent colored film, characterized by being in the range of ˜50% by weight.
[2] The transparent colored film-coated substrate according to [1], wherein the colorant is surface-treated with an organosilicon compound represented by the following formula (1).
R n -SiX 4-n (1 )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
[3] The substrate with a transparent colored film according to [1] or [2], wherein the colorant is surface-treated with an organosilicon compound represented by the following formula (2).
X-R-Si (OR) 3 (2)
(In the formula, R represents an organic group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group. X represents a γ-glycidoxy group or a (meth) acryloyl group.)
[4] The substrate with a transparent colored film according to [1] to [3], wherein the transparent colored film further contains a dye as a colorant.
[5] The transparent colored film is
The light transmittance (I) at least at a wavelength of 560 to 620 nm is 40 to 98%, or the light transmittance (II) at a wavelength of 450 to 500 nm is in the range of 40 to 98%. A substrate with a transparent colored film.
[6] The transparent colored film-coated substrate according to [1] to [5], which is further provided with another coating of the transparent colored film.
[7] A matrix-forming component and pigment particles and / or metal fine particles coated with an inorganic oxide or a resin as a colorant, and the total concentration of the matrix-forming component and the colorant is 0. A coating solution for forming a transparent colored film which is in the range of 5 to 60% by weight and contains the colorant in the transparent colored film so that the solid content is 0.1 to 50% by weight.
[8] The coating solution for forming a transparent colored film according to [7], wherein the colorant is surface-treated with an organosilicon compound represented by the following formula (1).
R n -SiX 4-n (1 )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
[9] The coating solution for forming a transparent colored film according to [7] or [8], wherein the colorant is further surface-treated with an organosilicon compound represented by the following formula (2):
X-R-Si (OR) 3 (2)
(In the formula, R represents an organic group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group. X- represents a γ-glycidoxy group or a (meth) acryloyl group.)
[10] The coating solution for forming a transparent colored film according to [7] to [9], further comprising a dye as a colorant.
本発明によれば、透明性着色膜に着色剤としてＲＧＢの発光スペクトルの重なり合いやすい波長域５６０〜６２０ｎｍや波長域４５０〜５００ｎｍに吸収のある無機酸化物または樹脂で被覆された顔料粒子および／または金属微粒子、必要に応じてさらに特定の有機珪素化合物で表面処理された顔料粒子および／または金属微粒子が含まれているので透明性着色膜中に着色剤が均一に分散しており、特定波長領域での光透過率が低く、その他の波長領域の光透過率が高く、基材との密着性、耐擦傷性、硬度等に優れるとともに透明性を有し、膜表面の平滑性、耐光性、コントラストに優れた透明性着色膜付基材および該透
明性着色膜を形成するための透明性着色膜形成用塗布液を提供することができる。
According to the present invention, pigment particles coated with an inorganic oxide or a resin that absorbs in the wavelength range of 560 to 620 nm or the wavelength range of 450 to 500 nm, where the emission spectrum of RGB tends to overlap as a colorant on the transparent colored film, and / or Because it contains fine metal particles, and if necessary, pigment particles and / or fine metal particles that have been surface-treated with a specific organosilicon compound, the colorant is uniformly dispersed in the transparent colored film. With low light transmittance, high light transmittance in other wavelength regions, excellent adhesion to the substrate, scratch resistance, hardness, etc. and transparency, film surface smoothness, light resistance, A substrate with a transparent colored film having excellent contrast and a coating liquid for forming a transparent colored film for forming the transparent colored film can be provided.
また、透明性着色膜付基材は透過鮮明度が高く、コントラストに優れているので表示装置等に好適に用いることができる。 In addition, since the transparent colored film-coated substrate has high transmission definition and excellent contrast, it can be suitably used for a display device or the like.
以下、本発明に係る透明性着色膜付基材について説明する。
透明性着色膜付基材
本発明に係る透明性着色膜付基材は、基材と、基材上の片面または両面に形成された透明性着色膜とからなる。
Hereinafter, the transparent colored film-coated substrate according to the present invention will be described.
The base material with a transparent colored film The base material with a transparent colored film according to the present invention comprises a base material and a transparent colored film formed on one or both surfaces of the base material.
基材
本発明に用いる基材としては、公知のものを特に制限なく使用することが可能であり、ガラス、ポリカーボネート、アクリル樹脂、ＰＥＴ、ＴＡＣ、シクロポレオレフィンン、ノルボルネン等のプラスチックシート、プラスチックフィルム等、プラスチックパネル等があげられる。中でも樹脂系基材は好適に用いることができる。
透明性着色膜
透明性着色膜は、マトリックス成分と、着色剤として無機酸化物または樹脂で被覆された顔料粒子および／または金属微粒子とを含んでいる。
(i)マトリックス成分
マトリックス成分としては、従来公知のマトリックス成分を用いることができるが、樹脂マトリックスが好適である。
Substrate As the substrate used in the present invention, known materials can be used without particular limitation, and glass, polycarbonate, acrylic resin, PET, TAC, cyclopoleolefin, norbornene and other plastic sheets, plastic films Etc., and plastic panels. Among these, a resin-based substrate can be preferably used.
Transparent colored film The transparent colored film contains a matrix component and pigment particles and / or metal fine particles coated with an inorganic oxide or resin as a colorant.
(i) Matrix component As the matrix component, a conventionally known matrix component can be used, and a resin matrix is preferable.
このような樹脂マトリックスとして、塗料用樹脂として公知の熱硬化性樹脂、熱可塑性樹脂、紫外線硬化等のいずれも採用することができる。具体的には、従来から用いられているポリエステル樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリフェニレンオキサイド樹脂、アクリル樹脂、塩化ビニル樹脂、フッ素樹脂、酢酸ビニル樹脂、シリコーンゴムなどの熱可塑性樹脂、ウレタン樹脂、メラミン樹脂、ブチラール樹脂、シリコーン樹脂、フェノール樹脂、エポキシ樹脂、不飽和ポリエステル樹脂等が挙げられる。さらにはこれら樹脂の２種以上の共重合体や変性体であってもよい。 As such a resin matrix, any of known thermosetting resins, thermoplastic resins, ultraviolet curing and the like as coating resins can be employed. Specifically, conventionally used polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, silicone rubber and other thermoplastic resins, urethane resins, melamines Resins, butyral resins, silicone resins, phenol resins, epoxy resins, unsaturated polyester resins and the like can be mentioned. Further, it may be a copolymer or modified body of two or more of these resins.
これらの樹脂は、エマルジョン樹脂、水溶性樹脂、親水性樹脂であってもよい。さらに、熱硬化性樹脂の場合、紫外線硬化型のものであっても、電子線硬化型のものであってもよく、熱硬化性樹脂の場合、硬化触媒が含まれていてもよい。
(ii)着色剤
本発明に用いる着色剤としては従来公知の顔料、金属微粒子を無機酸化物または樹脂で被覆したものが用いられる
顔料としては、チタン白、ベンガラ、黄鉛、コバルトブルー等の無機顔料、アゾ系黄色顔料（ベンジジンイエロー、カーミンＦＢ等）、赤色顔料、縮合顔料（ペリレン、ペリノン、ジオキサジン、チオインジゴ、イソインドリノン、キノフタロン、キナクロボン、キナクリドン等）、フタロシアニン系顔料（フタロシアニンブルー等）等が挙げられる。
These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further, in the case of a thermosetting resin, it may be an ultraviolet curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst may be included.
(ii) Colorant As the colorant used in the present invention, a conventionally known pigment, or a metal fine particle coated with an inorganic oxide or resin is used. Examples of the pigment include inorganic materials such as titanium white, bengara, yellow lead, and cobalt blue. Pigments, azo yellow pigments (benzidine yellow, carmine FB, etc.), red pigments, condensation pigments (perylene, perinone, dioxazine, thioindigo, isoindolinone, quinophthalone, quinacrobone, quinacridone, etc.), phthalocyanine pigments (phthalocyanine blue, etc.), etc. Is mentioned.
このような顔料は、平均粒子径が５〜５００ｎｍ、さらには１０〜２００ｎｍの範囲にあることが好ましい。
顔料の平均粒子径が小さいものは得ることが困難であり、得られたとしても塗布液に用いた場合に安定性が不充分となり、得られる透明性着色膜の基材との密着性、耐擦傷性、硬度および透明性が不充分となることがある。顔料の平均粒子径が大きすぎると膜の表面に凹凸が生じて光の散乱が生じ、また内部でも光の散乱が生じ、透明性（透過鮮明度ということがある）が低下する場合がある。なお、顔料は粒子径が５００ｎｍを越える場合、粉砕等により粒子径を前記範囲に調整してもよい。
Such pigments preferably have an average particle size in the range of 5 to 500 nm, more preferably 10 to 200 nm.
It is difficult to obtain a pigment having a small average particle diameter, and even if it is obtained, the stability becomes insufficient when used in a coating solution, and the resulting transparent colored film has good adhesion and resistance to the substrate. Abrasion, hardness and transparency may be insufficient. If the average particle diameter of the pigment is too large, irregularities are generated on the surface of the film and light is scattered, and light is also scattered inside, and transparency (sometimes referred to as transmission sharpness) may be lowered. When the particle diameter of the pigment exceeds 500 nm, the particle diameter may be adjusted to the above range by pulverization or the like.
金属微粒子としては、可視光領域に特性吸収のある粒子が好適に用いられ、具体的にはＡｇ，Ａｕ、Ｐｄ、Ｐｔ、Ｒｕ、Ｃｕ、Ｎｄ等の金属微粒子およびこれらを含む合金微粒子が挙げられる。 As the metal fine particles, particles having characteristic absorption in the visible light region are preferably used. Specific examples include metal fine particles such as Ag, Au, Pd, Pt, Ru, Cu, and Nd, and alloy fine particles containing these. .
また、金属微粒子は、平均粒子径が１〜２００ｎｍ、さらには２〜１００ｎｍの範囲にあることが好ましい。金属微粒子も、平均粒子径が前記下限よりも小さいものは得ることが困難であり、得られたとしても塗布液に用いた場合に安定性が不充分となり、得られる透明性着色膜の基材との密着性、耐擦傷性、硬度および透明性が不充分となることがある。金属微粒子の平均粒子径が大きすぎても、膜の表面および内部で光の散乱が生じ、透過線明度が低下する場合がある。 The metal fine particles preferably have an average particle diameter in the range of 1 to 200 nm, more preferably 2 to 100 nm. It is difficult to obtain metal fine particles having an average particle size smaller than the lower limit, and even if it is obtained, the stability of the substrate is insufficient when used in a coating solution, and the resulting transparent colored film substrate is obtained. Adhesion, scratch resistance, hardness and transparency may be insufficient. Even if the average particle diameter of the metal fine particles is too large, light scattering may occur on the surface and inside of the film, and the transmission line brightness may decrease.
このような顔料および金属微粒子は無機酸化物または樹脂で被覆されている。
無機酸化物としては、ＳiＯ2、ＴiＯ2、ＺrＯ２、ＳnＯ2、ＣeＯ2、ＺnＯ2、Ｆe2Ｏ5およびこれらの混合物あるいは複合酸化物が挙げられる。
Such pigments and metal fine particles are coated with an inorganic oxide or resin.
As the inorganic oxide, SiO 2, TiO 2, ZrO 2, SnO 2, CeO 2, ZnO 2, Fe 2 O 5 , and mixtures or composite oxides thereof.
また、樹脂としては、ポリエステル樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリフェニレンオキサイド樹脂、アクリル樹脂、塩化ビニル樹脂、フッ素樹脂、酢酸ビニル樹脂、シリコーンゴムなどの熱可塑性樹脂、ウレタン樹脂、メラミン樹脂、ブチラール樹脂、シリコーン樹脂、フェノール樹脂、エポキシ樹脂、不飽和ポリエステル樹脂等が挙げられる。 Also, as the resin, polyester resin, polycarbonate resin, polyamide resin, polyphenylene oxide resin, acrylic resin, vinyl chloride resin, fluororesin, vinyl acetate resin, silicone rubber and other thermoplastic resins, urethane resin, melamine resin, butyral resin, Silicone resin, phenol resin, epoxy resin, unsaturated polyester resin and the like can be mentioned.
顔料および金属微粒子を被覆する無機酸化物または樹脂の量は、顔料および金属微粒子に対し固形分として１〜１００重量％、さらには５〜５０重量％の範囲にあることが好ましい。 The amount of the inorganic oxide or resin covering the pigment and the metal fine particles is preferably in the range of 1 to 100% by weight, more preferably 5 to 50% by weight as a solid content with respect to the pigment and the metal fine particles.
被覆する無機酸化物または樹脂の量が少ないと、安定性向上効果が不充分で、塗布液に用いた場合、分散性、安定性が低く凝集を引き起こす場合があり、その結果、得られる透明性着色膜の基材との密着性、耐擦傷性、硬度および透明性が不充分となることがある。 When the amount of the inorganic oxide or resin to be coated is small, the effect of improving the stability is insufficient, and when used in the coating liquid, the dispersibility and stability are low, which may cause agglomeration. The adhesion of the colored film to the substrate, scratch resistance, hardness and transparency may be insufficient.
被覆する無機酸化物または樹脂の量が多すぎても、さらに分散性、安定性が向上することもなく、このため得られる透明性着色膜の基材との密着性、耐擦傷性、硬度および透明性がさらに向上することもない。 Even if the amount of the inorganic oxide or resin to be coated is too large, the dispersibility and stability are not further improved, and thus the adhesion of the transparent colored film obtained to the base material, scratch resistance, hardness and Transparency is not further improved.
顔料もしくは金属微粒子を無機酸化物で被覆する方法としては、顔料、金属微粒子表面を前記無機酸化物で被覆できれば特に制限はなく、従来公知の方法を採用することができる。 The method for coating the pigment or the metal fine particle with the inorganic oxide is not particularly limited as long as the surface of the pigment or the metal fine particle can be coated with the inorganic oxide, and a conventionally known method can be adopted.
例えば、顔料を無機酸化物で被覆する場合は、顔料粒子分散液に前記無機酸化物の前駆体になる金属塩水溶液あるいは混合金属塩水溶液を所定量添加し、加水分解して析出させ、必要に応じて熟成、洗浄、乾燥、焼成等することによって被覆することができる。 For example, when a pigment is coated with an inorganic oxide, a predetermined amount of a metal salt aqueous solution or a mixed metal salt aqueous solution to be used as a precursor of the inorganic oxide is added to the pigment particle dispersion, followed by hydrolysis and precipitation. Accordingly, it can be coated by aging, washing, drying, firing, and the like.
また、顔料をシリカで被覆する場合は上記方法以外に、顔料粒子分散液にケイ酸アルカリを脱アルカリして得た珪酸液を添加し、必要に応じて熟成、洗浄、乾燥、焼成等することによって被覆することができる。 In addition, when the pigment is coated with silica, in addition to the above method, a silica solution obtained by dealkalizing alkali silicate is added to the pigment particle dispersion, and aging, washing, drying, firing, etc. are performed as necessary. Can be coated.
また、金属微粒子を無機酸化物で被覆する場合は、金属アルコキシドを酸やアルカリで加水分解させ酸化物化させたのち熟成、洗浄、乾燥、焼成等することによって被覆することができる。 Further, when the metal fine particles are coated with an inorganic oxide, the metal alkoxide can be coated with an acid, an alkali, and the like after oxidization and then aging, washing, drying, firing, and the like.
また、顔料もしくは金属微粒子を樹脂で被覆する方法としては、顔料、金属微粒子表面を前記樹脂で被覆できれば特に制限はなく、従来公知の方法を採用することができる。
例えば、顔料もしくは金属微粒子のアルコール分散液に所定量の樹脂（エマルジョン）を混合し、通常４０〜６０℃で過熱攪拌することによって被覆することができる。
The method for coating the pigment or metal fine particle with the resin is not particularly limited as long as the surface of the pigment or metal fine particle can be coated with the resin, and a conventionally known method can be employed.
For example, a predetermined amount of resin (emulsion) is mixed with an alcohol dispersion of pigments or fine metal particles, and coating is usually performed by heating and stirring at 40 to 60 ° C.
具体例としては、金微粒子の２-プロパノール分散液に1,6-ヘキサンジオールジアクリ
レート混合し、加熱攪拌することによって被覆することができる。
さらに、本発明に用いる着色剤は前記無機酸化物または樹脂で被覆した顔料が下記式(1)で表される有機珪素化合物で表面処理されていることが好ましい。
Ｒn-ＳiＸ4-n （１）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、シラノール基、ハロゲン、水素、ｎ：０〜３の整数）
具体的には、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシシラン、テトラブトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ジフェニルジエトキシシラン、イソブチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（βメトキシエトキシ）シラン、3,3,3−トリフルオロプロピルトリメトキシシラン、メチル-3,3,3−トリフルオロプロピルジメトキシシラン、β−（3,4-エポキシシクロヘキシル）エチルトリメトキシシラン、γ-グリシドキシメチルトリメトキシシラン、γ-グリシドキシメチルトリエキシシラン、γ-グリシドキシエチルトリメトキシシラン、γ-グリシドキシエチルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ−（β−グリシドキシエトキシ）プロピルトリメトキシシラン、γ-（メタ）アクリロオキシメチルトリメトキシシラン、γ-（メタ）アクリロオキシメチルトリエキシシラン、γ-（メタ）アクリロオキシエチルトリメトキシシラン、γ-（メタ）アクリロオキシエチルトリエトキシシラン、γ-（メタ）アクリロオキシプロピルトリメトキシシラン、γ-（メタ）アクリロオキシプロピルトリメトキシシラン、γ-（メタ）アクリロオキシプロピルトリエトキシシラン、γ-（メタ）アクリロオキシプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ-アミノプロピルメチルジメトキシシラン、Ｎ−β（アミノエチル）γ-アミノプロピルトリメトキシシラン、Ｎ-フェニル-γ-アミノプロピルトリメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、トリメチルシラノール、メチルトリクロロシラン等およびこれらの混合物が挙げられる。（有機珪素化合物処理すると、加水分解残基が存在し、分散性の向上に寄与する）
式(1)で表される有機珪素化合物の内、４官能の有機珪素化合物（ｎ＝０）を用いる場
合、４官能の有機珪素化合物と無機酸化物または樹脂で被覆した顔料粒子との重量比（有機珪素化合物をＳiＯ2に換算した重量／被覆粒子の重量）は顔料粒子の平均粒子径や被覆層の種類によっても異なるが、１〜１００重量％、さらには５〜５０重量％の範囲にあることが好ましい。重量比が小さい場合は、塗布液の分散性、安定性が不充分となることがあり、得られる透明性着色膜の基材との密着性、耐擦傷性、硬度および透明性が不充分となることがある。重量比が大きくしても、さらに分散性、安定性が向上することもなく、このため得られる透明性着色膜の基材との密着性、耐擦傷性、硬度および透明性がさらに向上することもない。
As a specific example, coating can be performed by mixing 1,6-hexanediol diacrylate in a 2-propanol dispersion of gold fine particles and stirring with heating.
Furthermore, the colorant used in the present invention is preferably such that the pigment coated with the inorganic oxide or resin is surface-treated with an organosilicon compound represented by the following formula (1).
R n -SiX 4-n (1 )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
Specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3, 3,3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltrioxy Silane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxy Silane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) acryloxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltri Excisilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acryloxyethyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acrylooxy Propyltrimethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane , Γ- (meth) acrylooxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ- Examples include aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, methyltrichlorosilane, and the like, and mixtures thereof. (When treated with an organosilicon compound, hydrolyzed residues are present, contributing to improved dispersibility)
When using a tetrafunctional organosilicon compound (n = 0) among the organosilicon compounds represented by the formula (1), the weight ratio between the tetrafunctional organosilicon compound and pigment particles coated with an inorganic oxide or resin (Weight of organosilicon compound converted to SiO 2 / weight of coating particle) varies depending on the average particle diameter of pigment particles and the type of coating layer, but is in the range of 1 to 100% by weight, more preferably 5 to 50% by weight. Preferably there is. When the weight ratio is small, the dispersibility and stability of the coating solution may be insufficient, and the adhesion of the resulting transparent colored film to the substrate, scratch resistance, hardness and transparency may be insufficient. May be. Even if the weight ratio is increased, the dispersibility and stability are not further improved, and the adhesion, scratch resistance, hardness, and transparency of the obtained transparent colored film to the base material are further improved. Nor.
式(1)で表される有機珪素化合物のうち、４官能以外の有機珪素化合物（ｎ＝１、２、
３）を用いる場合、４官能以外の有機珪素化合物と無機酸化物または樹脂で被覆した顔料粒子との重量比（有機珪素化合物をＳiＯ2に換算した重量／被覆粒子の重量）は顔料粒子の平均粒子径や被覆層の種類によっても異なるが、５〜８０％、さらには１０〜５０％範
囲にあることが好ましい。
Of the organosilicon compounds represented by the formula (1), organosilicon compounds other than tetrafunctional (n = 1, 2,
When 3) is used, the weight ratio of the organosilicon compound other than tetrafunctional to pigment particles coated with an inorganic oxide or resin (weight of organosilicon compound converted to SiO 2 / weight of coated particles) is the average of the pigment particles Although it varies depending on the particle diameter and the kind of the coating layer, it is preferably in the range of 5 to 80%, more preferably 10 to 50%.
前記重量比が小さい場合は分散性、安定性が不充分となることがあり、このため得られる透明性着色膜の基材との密着性、耐擦傷性、硬度および透明性が不充分となることがある。前記重量比が大きすぎてもさらに分散性、安定性が向上することもなく、このため得られる透明性着色膜の基材との密着性、耐擦傷性、硬度および透明性がさらに向上することもない。 When the weight ratio is small, dispersibility and stability may be insufficient, and therefore, the adhesion of the transparent colored film obtained to the substrate, scratch resistance, hardness and transparency are insufficient. Sometimes. Even if the weight ratio is too large, dispersibility and stability are not further improved, and adhesion of the transparent colored film obtained to the substrate, scratch resistance, hardness and transparency are further improved. Nor.
なかでも、前記着色剤が下記式(2)で表される３官能の有機珪素化合物で表面処理され
ていることが好ましい。
Ｘ-Ｒ-Ｓi（ＯＲ）3 （２）
（式中、Ｒは、置換または非置換の炭化水素基から選ばれる炭素数１〜１０の有機基を表す。X-はγ-グリシドキシ基、（メタ）アクリロイル基）
具体的にはγ-グリシドキシメチルトリメトキシシラン、γ-グリシドキシメチルトリエキシシラン、γ-グリシドキシエチルトリメトキシシラン、γ-グリシドキシエチルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ−（β−グリシドキシエトキシ）プロピルトリメトキシシラン、γ-（メタ）アクリロオキシメチルトリメトキシシラン、γ-（メタ）アクリロオキシメチルトリエキシシラン、γ-（メタ）アクリロオキシエチルトリメトキシシラン、γ-（メタ）アクリロオキシエチルトリエトキシシラン、γ-（メタ）アクリロオキシプロピ
ルトリメトキシシラン、γ-（メタ）アクリロオキシプロピルトリメトキシシラン、γ-（メタ）アクリロオキシプロピルトリエトキシシラン、γ-（メタ）アクリロオキシプロピルトリエトキシシラン等が挙げられる。
In particular, the colorant is preferably surface-treated with a trifunctional organosilicon compound represented by the following formula (2).
X-R-Si (OR) 3 (2)
(In the formula, R represents an organic group having 1 to 10 carbon atoms selected from a substituted or unsubstituted hydrocarbon group. X- represents a γ-glycidoxy group and a (meth) acryloyl group).
Specifically, γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyl Trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ -(Meth) acryloxymethyltrimethoxysilane, γ- (meth) acryloxymethyltriethoxysilane, γ- (meth) acryloxyethyltrimethoxysilane, γ- (meth) acrylooxyethyltriethoxysilane , Γ- (meth) acrylooxypropyltrimethoxysilane, γ- (meth) acrylooxy Examples include cyclopropyltrimethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, and the like.
このような３官能の有機珪素化合物で表面処理されていると、マトリックス成分として、樹脂マトリックス、特に紫外線硬化樹脂マトリックスを使用した場合、着色剤とマトリックスとの結合が促進され、耐擦傷性や硬度が向上する。 When the surface treatment is performed with such a trifunctional organosilicon compound, when a resin matrix, particularly an ultraviolet curable resin matrix is used as a matrix component, the bonding between the colorant and the matrix is promoted, and the scratch resistance and hardness are increased. Will improve.
このような着色剤の透明性着色膜中の含有量は、着色剤の種類、着色膜の厚さ、必要に応じて設ける他の被膜の種類等によっても異なるが固形分として０．１〜５０重量％さらには０．５〜４０％の範囲にあることが好ましい。 The content of such a colorant in the transparent colored film varies depending on the type of the colorant, the thickness of the colored film, the type of other coating provided as necessary, etc. It is preferable that it is in the range of 0.5% to 40% by weight.
透明性着色膜中の着色剤の含有量が少ないと、着色剤の吸収ピークが明確でなく、充分なコントラストが得られない場合がある。また、着色剤の含有量が多すぎても、膜厚によっても異なるが光透過率が下がり透過鮮明度が不充分となる場合がある。 When the content of the colorant in the transparent color film is small, the absorption peak of the colorant is not clear and sufficient contrast may not be obtained. Moreover, even if there is too much content of a coloring agent, although it changes with film thickness, the light transmittance may fall and a permeation | transmission clarity may become inadequate.
なお、着色剤としては、顔料もしくは金属微粒子を直接、前記した有機珪素化合物で表面処理したものを用いることができるが、有機珪素化合物が、顔料もしくは金属微粒子と反応性が低いために充分な分散性、安定性等の表面処理効果が充分得られない。しかしながら、前記した無機酸化物または樹脂で被覆されていると有機珪素化合物の加水分解物と被覆した無機酸化物や樹脂の−ＯＨ基とが反応しやすく、充分な表面処理効果が得られ、即ち、分散性、安定性に優れた着色剤が得られ、このため得られる透明性着色膜は基材との密着性、耐擦傷性、硬度および透明性に優れ、さらに膜表面の平滑性に優れている。 As the colorant, a pigment or metal fine particles which are directly surface-treated with the above-mentioned organosilicon compound can be used. However, since the organosilicon compound has low reactivity with the pigment or metal fine particles, it is sufficiently dispersed. The surface treatment effects such as properties and stability cannot be obtained sufficiently. However, if it is coated with the inorganic oxide or resin, the hydrolyzate of the organosilicon compound and the —OH group of the coated inorganic oxide or resin are likely to react, and a sufficient surface treatment effect is obtained. A colorant having excellent dispersibility and stability can be obtained, and thus the transparent colored film obtained has excellent adhesion to the substrate, scratch resistance, hardness and transparency, and excellent smoothness of the film surface. ing.
なお、本発明では、前記無機酸化物または樹脂で被覆された顔料粒子および／または金属微粒子とともに必要に応じて所望の染料を用いることができる。
染料としてはシアン、マゼンタ、イエロー等の染料が挙げられる。
In the present invention, a desired dye can be used as needed together with the pigment particles and / or metal fine particles coated with the inorganic oxide or resin.
Examples of the dye include dyes such as cyan, magenta, and yellow.
シアン染料として、アントラキノン染料、アゾ染料、トリフェニルメタン染料等が挙げ
られる。このような染料は後述する光透過率が所定の範囲内となるように使用することができる。
Examples of cyan dyes include anthraquinone dyes, azo dyes, and triphenylmethane dyes. Such a dye can be used so that the light transmittance described later falls within a predetermined range.
本発明の透明性着色膜には、前記着色剤に加えて従来公知の金属酸化物微粒子を含んでいてもよい。
金属酸化物微粒子としては、着色膜を設ける目的であるコントラストの向上、表示性能の向上以外の目的によっても異なるが、例えば、反射防止性能を有する被膜には通常屈折率が１．４５以下、さらには１．４０以下の従来公知の微粒子が用いられ、具体的にはＳiＯ2、内部に空洞を有するＳiＯ2粒子あるいはこれらに導電性を有する金属酸化物を被覆した粒子等が挙げられる。
The transparent colored film of the present invention may contain conventionally known metal oxide fine particles in addition to the colorant.
The metal oxide fine particles vary depending on the purpose other than the improvement of contrast, which is the purpose of providing a colored film, and the improvement of display performance. For example, the coating having antireflection performance usually has a refractive index of 1.45 or less, Conventionally known fine particles having a particle size of 1.40 or less are used. Specific examples thereof include SiO 2 , SiO 2 particles having cavities therein, or particles coated with a conductive metal oxide.
ハードコート膜に用いる金属酸化物微粒子としては、ＺrＯ2、ＴiＯ2、Ｓb2Ｏ5、ＺnＯ2、Ａl2Ｏ3、ＳnＯ2、あるいはこれら粒子が鎖状に連結した鎖状粒子、あるいは前記した屈折率が１．４５以下のシリカ系微粒子等従来公知の微粒子が挙げられる。 Examples of the metal oxide fine particles used in the hard coat film include ZrO 2 , TiO 2 , Sb 2 O 5 , ZnO 2 , Al 2 O 3 , SnO 2 , chain particles in which these particles are connected in a chain, Conventionally known fine particles such as silica-based fine particles having a refractive index of 1.45 or less can be mentioned.
高屈折率膜に用いる金属酸化物微粒子としては、通常屈折率が１．６０以上、さらには１．８０以上の微粒子が用いられ、具体的にはＺrＯ2、ＴiＯ2、Ｓb2Ｏ5、ＺnＯ2、Ａl2
Ｏ3、ＳnＯ2、アンチモンドープ酸化錫、錫ドープ酸化インジウム、酸化錫ドープリン（
ＰＴＯ）等従来公知の微粒子が挙げられる。
The metal oxide fine particles used for the high refractive index film are usually fine particles having a refractive index of 1.60 or more, more preferably 1.80 or more. Specifically, ZrO 2 , TiO 2 , Sb 2 O 5 , ZnO. 2 , Al 2
O 3 , SnO 2 , antimony-doped tin oxide, tin-doped indium oxide, tin oxide-doped phosphorus (
Conventionally known fine particles such as PTO).
導電性膜に用いる金属酸化物微粒子としては、通常Ｓb２Ｏ５、ＳnＯ２、アンチモンドープ酸化錫、錫ドープ酸化インジウム、酸化錫ドープリン（ＰＴＯ）、あるいはこれら導電性材料で表面を被覆したシリカ系微粒子あるいは内部に空洞を有するシリカ系微粒子等従来公知の微粒子が挙げられる。 The metal oxide fine particles used for the conductive film are usually Sb 2 O 5 , SnO 2 , antimony-doped tin oxide, tin-doped indium oxide, tin oxide-doped phosphorus (PTO), or silica-based whose surface is coated with these conductive materials. Conventionally known fine particles such as fine particles or silica-based fine particles having cavities inside may be mentioned.
このような金属酸化物微粒子も前記した着色剤と同様に表面処理されていることが好ましい。また、金属酸化物微粒子の平均粒子径は１〜５００ｎｍ、さらには５〜２００ｎｍの範囲にあることが好ましい。平均粒子径が前記範囲の下限よりも小さいものは、得ることが困難であり、得られたとしても、安定性が低く凝集することがある。平均粒子径を大きくしても、膜の表面に凹凸が生じやすく、光の散乱、膜硬度の低下が生じる場合がある。 Such metal oxide fine particles are preferably surface-treated in the same manner as the colorant described above. The average particle size of the metal oxide fine particles is preferably in the range of 1 to 500 nm, more preferably 5 to 200 nm. Those having an average particle size smaller than the lower limit of the above range are difficult to obtain, and even if obtained, the stability may be low and agglomerate. Even if the average particle size is increased, irregularities are likely to occur on the surface of the film, which may cause light scattering and a decrease in film hardness.
透明性着色膜中の金属酸化物微粒子あるいは表面処理された金属酸化物微粒子の含有量は使用目的あるいは金属酸化物微粒子の種類によっても異なるが、固形分として１０〜９０重量％、さらには２０〜７０重量％の範囲にあることが好ましい。 The content of the metal oxide fine particles or the surface-treated metal oxide fine particles in the transparent colored film varies depending on the purpose of use or the type of the metal oxide fine particles, but is 10 to 90% by weight, more preferably 20 to 20% as a solid content. It is preferably in the range of 70% by weight.
本発明で形成される透明性着色膜の膜厚は２０〜１００００ｎｍ、さらには８０〜５０００ｎｍの範囲にあることが好ましい。透明性着色膜の膜厚が薄いと、着色剤を添加しても充分な着色が得られず、コントラストが向上しない場合がある。また、膜厚が厚すぎると光透過率が低くなりすぎて透過鮮明度が不充分となる場合がある。 The film thickness of the transparent colored film formed in the present invention is preferably in the range of 20 to 10,000 nm, more preferably 80 to 5000 nm. If the transparent colored film is thin, sufficient coloring may not be obtained even if a colorant is added, and the contrast may not be improved. On the other hand, if the film thickness is too thick, the light transmittance may be too low and the transmission definition may be insufficient.
本発明で形成される透明性着色膜は、少なくとも波長５６０〜６２０ｎｍの光透過率（I）が４０〜９８％にあるか、波長４５０〜５００ｎｍの光透過率（II）が４０〜９８％
にあることが好ましい。
The transparent colored film formed in the present invention has at least a light transmittance (I) of 40 to 98% at a wavelength of 560 to 620 nm, or a light transmittance (II) of 40 to 98% at a wavelength of 450 to 500 nm.
It is preferable that it exists in.
波長５６０〜６２０ｎｍの光透過率（I）が４０％未満の場合は透過鮮明度が不充分と
なることがある。また、波長５６０〜６２０ｎｍの光透過率（I）が９８％を超えると、
吸収ピークが小さく、ＲＧＢの発光スペクトルの重なり部分の光を充分キャンセルできず充分なコントラストが得られないことがある。なお、光透過率（I）のさらに好ましい範
囲は５０％〜８０％である。
When the light transmittance (I) at a wavelength of 560 to 620 nm is less than 40%, the transmission sharpness may be insufficient. When the light transmittance (I) at a wavelength of 560 to 620 nm exceeds 98%,
In some cases, the absorption peak is small, and the light in the overlapping portions of the RGB emission spectra cannot be canceled sufficiently, and sufficient contrast cannot be obtained. In addition, the more preferable range of the light transmittance (I) is 50% to 80%.
また、波長４５０〜５００ｎｍの光透過率（II）が４０％未満の場合は透過鮮明度が不充分となることがある。波長４５０〜５００ｎｍの光透過率（II）が９８％を超えると吸収ピークが小さく吸収ピークが小さく、ＲＧＢの発光スペクトルの重なり部分の光を充分キャンセルできず充分なコントラストが得られないことがある。なお光透過率（II）のさらに好ましい範囲は５０％〜８０％である。 Further, when the light transmittance (II) at a wavelength of 450 to 500 nm is less than 40%, the transmission sharpness may be insufficient. When the light transmittance (II) at a wavelength of 450 to 500 nm exceeds 98%, the absorption peak is small and the absorption peak is small, and the light at the overlapping portion of the RGB emission spectrum cannot be sufficiently canceled and sufficient contrast may not be obtained. . A more preferable range of the light transmittance (II) is 50% to 80%.
なお、本発明の光透過率は、日本分光（株）製 Ｕ−Ｖｅｓｔ５６０を使用して測定す
ることができる。
他の被膜
本発明の透明性着色膜付基材は、基材上の片面または両面に形成された透明性着色膜以外の他の被膜が設けられていてもよい。
In addition, the light transmittance of this invention can be measured using JASCO Corporation U-Vest560.
Other coatings The base material with a transparent colored film of the present invention may be provided with a coating other than the transparent colored film formed on one side or both sides of the base material.
例えば、（１）基材上に透明性着色膜を設け、該透明性着色膜上に低屈折率の反射防止膜を設けてもよく、（２）基材上にハードコート層を設け、該ハードコート層上に透明性着色膜を設けてもよく、（３）基材上にハードコート層を設け、該ハードコート層上に透明性着色膜を設け、該透明性着色膜上に低屈折率の反射防止膜を設けてもよい。 For example, (1) a transparent colored film may be provided on a substrate, and a low refractive index antireflection film may be provided on the transparent colored film. (2) a hard coat layer may be provided on the substrate, A transparent colored film may be provided on the hard coat layer. (3) A hard coat layer is provided on the substrate, a transparent colored film is provided on the hard coat layer, and the refractive index is low on the transparent colored film. An antireflective film with a rate may be provided.
なお、反射防止膜の下層に設ける透明性着色膜は、屈折率が反射防止膜の屈折率が低いことが重要であり、好ましくは屈折率差が０．０２以上、さらには０．０３以上あることが好ましい。 In addition, it is important that the transparent coloring film provided in the lower layer of the antireflection film has a low refractive index, and the refractive index difference is preferably 0.02 or more, more preferably 0.03 or more. It is preferable.
ハードコート層としては、従来公知のハードコート層を設けることができる。具体的には、前記マトリックス成分、好ましくはハードコート層に好適に用いることのできるＺr
Ｏ2、ＴiＯ2、Ｓb2Ｏ5、ＺnＯ2、Ａl2Ｏ3、ＳnＯ2、あるいはこれら粒子が鎖状に連結し
た鎖状粒子、あるいは前記した屈折率が１．４５以下のシリカ系微粒子等従来公知の金属酸化物微粒子とからなるハードコート層が好ましい。
A conventionally known hard coat layer can be provided as the hard coat layer. Specifically, Zr which can be suitably used for the matrix component, preferably a hard coat layer.
O 2 , TiO 2 , Sb 2 O 5 , ZnO 2 , Al 2 O 3 , SnO 2 , chain particles in which these particles are linked in a chain, or silica-based fine particles having a refractive index of 1.45 or less, etc. A hard coat layer composed of conventionally known metal oxide fine particles is preferred.
マトリックス成分としては、塗料用樹脂として公知の熱硬化性樹脂、熱可塑性樹脂等のいずれも採用することができ、たとえば、従来から用いられているポリエステル樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリフェニレンオキサイド樹脂、熱可塑性アクリル樹脂、塩化ビニル樹脂、フッ素樹脂、酢酸ビニル樹脂、シリコーンゴムなどの熱可塑性樹脂、ウレタン樹脂、メラミン樹脂、ケイ素樹脂、ブチラール樹脂、反応性シリコーン樹脂、フェノール樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、熱硬化性アクリル樹脂などの熱硬化性樹脂などが挙げられる。さらにはこれら樹脂の２種以上の共重合体や変性体であってもよい。 As the matrix component, any of known thermosetting resins, thermoplastic resins, and the like as coating resins can be employed. For example, conventionally used polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, Thermoplastic acrylic resin, vinyl chloride resin, fluororesin, vinyl acetate resin, silicone rubber and other thermoplastic resins, urethane resin, melamine resin, silicon resin, butyral resin, reactive silicone resin, phenol resin, epoxy resin, unsaturated polyester Examples thereof include thermosetting resins such as resins and thermosetting acrylic resins. Further, it may be a copolymer or modified body of two or more of these resins.
これらの樹脂は、エマルジョン樹脂、水溶性樹脂、親水性樹脂であってもよい。さらに、熱硬化性樹脂の場合、紫外線硬化型のものであっても、電子線硬化型のものであってもよく、熱硬化性樹脂の場合、硬化触媒が含まれていてもよい。 These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further, in the case of a thermosetting resin, it may be an ultraviolet curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst may be included.
ハードコート層の厚さは０.１〜２０μｍ、さらには０.２〜１０μｍの範囲にあることが好ましい。
反射防止膜としても従来公知の反射防止膜を設けることができ、具体的にはマトリックス成分、好ましくはマトリックス成分と前記した反射防止膜に好適に用いることのできる屈折率が１．４５以下、さらには１．４０以下の従来公知の微粒子が用いられ、具体的にはＳiＯ2、内部に空洞を有するＳiＯ2あるいはこれらに導電性を有する金属酸化物を被覆した微粒子等、あるいは従来公知の低屈折率成分とからなる反射防止膜が好ましい。
反射防止膜のマトリックス成分としては、前記ハードコート層用と同様のマトリックス成分を使用することができる。
The thickness of the hard coat layer is preferably in the range of 0.1 to 20 μm, more preferably 0.2 to 10 μm.
As the antireflection film, a conventionally known antireflection film can be provided. Specifically, the matrix component, preferably the refractive index that can be suitably used for the matrix component and the above-described antireflection film is 1.45 or less, and Is a conventionally known fine particle of 1.40 or less, specifically, SiO 2 , SiO 2 having a cavity inside, or a fine particle coated with a conductive metal oxide, or a conventionally known low refractive index An antireflection film composed of a rate component is preferred.
As the matrix component of the antireflection film, the same matrix component as that for the hard coat layer can be used.
また、マトリックス成分として加水分解性有機珪素化合物の重縮合物を用いることも可能である。
反射防止膜の厚さは通常５０〜３００ｎｍ、さらには８０〜２００ｎｍの範囲であり、屈折率は下層の屈折率によっても異なるが、通常１．３５〜１．４５の範囲である。
It is also possible to use a polycondensate of a hydrolyzable organosilicon compound as the matrix component.
The thickness of the antireflection film is usually in the range of 50 to 300 nm, further 80 to 200 nm, and the refractive index is usually in the range of 1.35 to 1.45, although it varies depending on the refractive index of the lower layer.
なお、本発明の透明性着色膜付基材は、上記他の被膜とともに設けた着色膜の反対側の基材上に透明性着色膜を設けてもよく、他の被膜を設けた反対側の基材上に透明性着色膜を設けてもよい。この場合、通常、ガラス基板や偏光板と張り合わせるため、粘着層中に着色剤を混合してもよい。
透明性着色膜形成用塗布液
つぎに、本発明に係る透明性着色膜形成用塗布液について説明する。
In addition, the base material with a transparent colored film of the present invention may be provided with a transparent colored film on the base material on the opposite side of the colored film provided with the other film, or on the opposite side provided with the other film. A transparent colored film may be provided on the substrate. In this case, in general, a colorant may be mixed in the adhesive layer in order to adhere to a glass substrate or a polarizing plate.
Next, the coating liquid for forming a transparent colored film according to the present invention will be described.
本発明に係る透明性着色膜形成用塗布液は、マトリックス形成成分と着色剤として無機酸化物または樹脂で被覆された顔料粒子および／または金属微粒子とを含んでなり、マトリックス形成成分と着色剤との合計の濃度が固形分として０．５〜６０重量％の範囲にあり、該着色剤を透明性着色膜中に固形分として０．１〜５０重量％となるように含有していることを特徴としている。
マトリックス形成成分
マトリックス形成成分としては前記したマトリックス性分となる樹脂が用いられる。
具体的には塗料用樹脂として公知の熱硬化性樹脂、熱可塑性樹脂、紫外線硬化樹脂等のいずれも採用することができ、たとえば、従来から用いられているポリエステル樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリフェニレンオキサイド樹脂、アクリル樹脂、塩化ビニル樹脂、フッ素樹脂、酢酸ビニル樹脂、シリコーンゴム性樹脂、ウレタン樹脂、メラミン樹脂、ブチラール樹脂、シリコーン樹脂、フェノール樹脂、エポキシ樹脂、不飽和ポリエステル樹脂などが挙げられる。さらにはこれら樹脂の２種以上の共重合体や変性体であってもよい。
The coating liquid for forming a transparent colored film according to the present invention comprises a matrix-forming component and pigment particles and / or metal fine particles coated with an inorganic oxide or resin as a colorant. The total concentration of the solid content is in the range of 0.5 to 60% by weight as a solid content, and the colorant is contained in the transparent colored film so as to be 0.1 to 50% by weight as the solid content. It is a feature.
Matrix-forming component As the matrix-forming component, the resin having the matrix property described above is used.
Specifically, any of known thermosetting resins, thermoplastic resins, ultraviolet curable resins, and the like can be employed as coating resins. For example, conventionally used polyester resins, polycarbonate resins, polyamide resins, polyphenylenes can be used. Examples include oxide resins, acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, silicone rubber resins, urethane resins, melamine resins, butyral resins, silicone resins, phenol resins, epoxy resins, and unsaturated polyester resins. Further, it may be a copolymer or modified body of two or more of these resins.
これらの樹脂は、エマルジョン樹脂、水溶性樹脂、親水性樹脂であってもよい。さらに、熱硬化性樹脂の場合、紫外線硬化型のものであっても、電子線硬化型のものであってもよく、熱硬化性樹脂の場合、硬化触媒が含まれていてもよい。 These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Further, in the case of a thermosetting resin, it may be an ultraviolet curable type or an electron beam curable type, and in the case of a thermosetting resin, a curing catalyst may be included.
このようなマトリックス形成成分の透明性着色膜形成用塗布液中の濃度は、固形分として０．１〜６０重量％、さらには０．５〜５０重量％の範囲にあることが好ましい。
マトリックス形成成分の透明性着色膜形成用塗布液中の濃度が固形分として０．１重量％未満の場合は、得られる透明性着色膜の膜厚が２０ｎｍ未満となることがあり、所定の光透過率が得られないことがあり、また所定の光透過率を得るために繰り返し塗布する必要が生じる。
マトリックス形成成分の透明性着色膜形成用塗布液中の濃度が固形分として６０重量％を超えると、塗布液の安定性が不充分となり得られる透明性着色膜にムラが発生したり、基材との密着性、耐擦傷性、硬度、透明性等が不充分となることがある。
The concentration of such a matrix-forming component in the coating solution for forming a transparent colored film is preferably in the range of 0.1 to 60% by weight, more preferably 0.5 to 50% by weight as the solid content.
When the concentration of the matrix-forming component in the coating liquid for forming the transparent colored film is less than 0.1% by weight as the solid content, the film thickness of the obtained transparent colored film may be less than 20 nm, and the predetermined light The transmittance may not be obtained, and it may be necessary to apply repeatedly to obtain a predetermined light transmittance.
If the concentration of the matrix-forming component in the coating liquid for forming the transparent colored film exceeds 60% by weight as the solid content, the stability of the coating liquid becomes insufficient and unevenness occurs in the resulting transparent colored film, or the substrate Adhesiveness, scratch resistance, hardness, transparency and the like may be insufficient.
着色剤
着色剤としては前記したと同様のものが用いられる。
透明性着色膜形成用塗料中の着色剤の濃度は、固形分として０．１〜６０重量％、さらには０．５〜５０重量％の範囲にあることが好ましい。着色剤の濃度が少ないと、所定の光透過率が得られないことがある。着色剤の濃度が高すぎても、塗布液の安定性が不充分となり得られる透明性着色膜にムラや凝集物が発生したり、基材との密着性、耐擦傷性、硬度、透明性等が不充分となることがある。着色剤は、透明性着色膜中に固形分として０．１〜５０重量％、さらには０．２〜４０重量％となるように含有されていることが好ましい。
The same colorant as described above is used as the colorant.
It is preferable that the density | concentration of the coloring agent in the coating material for transparent colored film formation exists in the range of 0.1 to 60 weight% as solid content, and also 0.5 to 50 weight%. If the concentration of the colorant is low, a predetermined light transmittance may not be obtained. Even if the concentration of the colorant is too high, the coating solution may be insufficiently stable, resulting in unevenness and agglomeration in the transparent colored film, adhesion to the substrate, scratch resistance, hardness, and transparency. Etc. may be insufficient. The colorant is preferably contained in the transparent colored film so that the solid content is 0.1 to 50% by weight, more preferably 0.2 to 40% by weight.
重合開始剤
本発明の透明性着色膜形成用塗布液には重合開始剤が含まれていてもよい。
重合開始剤としては前記マトリックス形成成分を重合、硬化させることができれば特に制限はなく、樹脂によって適宜選択し、従来公知の重合開始剤を用いることができる。
Polymerization initiator The coating liquid for forming a transparent colored film of the present invention may contain a polymerization initiator.
The polymerization initiator is not particularly limited as long as the matrix-forming component can be polymerized and cured, and can be appropriately selected depending on the resin, and conventionally known polymerization initiators can be used.
例えば、アシルホスフィンオキシド類、アセトフェノン類、プロピオフェノン類、ベンジル類、ベンゾイン類、ベンゾフェノン類、チオキサントン類等の重合開始剤の他、カチオン系光重合開始剤等が挙げられる。 For example, in addition to polymerization initiators such as acylphosphine oxides, acetophenones, propiophenones, benzyls, benzoins, benzophenones, and thioxanthones, cationic photopolymerization initiators and the like can be mentioned.
透明被膜形成用塗料中の重合開始剤の濃度はマトリックス形成成分の種類によっても異なるが、マトリックス形成成分および重合開始剤を固形分としたとき、マトリックス形成成分の０．１〜２０重量％、さらには０．５〜１０重量％の範囲にあることが好ましい。重合開始剤の含有量が少ないと、塗膜の硬化が不充分となることがあり、多すぎても、塗料の安定性が不充分となったり、得られる透明被膜の硬度が不充分となることがある。
分散媒
分散媒としてはマトリックス形成成分、必要に応じて用いる重合開始剤を溶解あるいは分散できるとともに着色剤を均一に分散することができれば特に制限はなく、従来公知の溶媒を用いることができる。
The concentration of the polymerization initiator in the coating for forming a transparent film varies depending on the type of the matrix-forming component, but when the matrix-forming component and the polymerization initiator are solids, 0.1 to 20% by weight of the matrix-forming component, Is preferably in the range of 0.5 to 10% by weight. If the content of the polymerization initiator is low, the coating film may be insufficiently cured. If it is too high, the coating stability may be insufficient, or the resulting transparent film may have insufficient hardness. Sometimes.
The dispersion medium is not particularly limited as long as it can dissolve or disperse the matrix-forming component and, if necessary, the polymerization initiator and uniformly disperse the colorant, and a conventionally known solvent can be used.
具体的には、水、メタノール、エタノール、プロパノール、2-プロパノール（ＩＰＡ）、ブタノール、ジアセトンアルコール、フルフリルアルコール、テトラヒドロフルフリルアルコール、エチレングリコール、ヘキシレングリコール、イソプロピルグリコールなどのアルコール類；酢酸メチルエステル、酢酸エチルエステル、酢酸ブチルなどのエステル類；ジエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルなどのエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセト酢酸エステルなどのケトン類、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、トルエン、シクロヘキサノン、イソホロン等が挙げられる。なかでもカルボニル基を有する溶媒は好適に用いることができる。 Specifically, alcohols such as water, methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, isopropyl glycol; acetic acid Esters such as methyl ester, ethyl acetate, butyl acetate; ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone Ketones such as acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, toluene, cyclohexanone, isophorone and the like. Among these, a solvent having a carbonyl group can be preferably used.
カルボニル基を有する溶媒が含まれていると、表面処理した顔料粒子および／または金属微粒子が均一に分散するとともに塗料の安定性がよく、均一性、基材との密着性、強度等に優れるとともに、凹凸を有する透明被膜を再現性よく形成することができる。 When a solvent having a carbonyl group is contained, the surface-treated pigment particles and / or metal fine particles are uniformly dispersed, and the stability of the paint is good, and the uniformity, adhesion to the substrate, strength, etc. are excellent. A transparent film having irregularities can be formed with good reproducibility.
これらは単独で使用してもよく、また２種以上混合して使用することもできるが、本発明では沸点の異なる２種以上の溶媒を混合して用いることが好ましい。
金属酸化物微粒子
本発明の透明性着色膜形成用塗料には、前記着色剤に加えて金属酸化物微粒子を含んでいてもよい。
These may be used singly or in combination of two or more. In the present invention, it is preferable to use a mixture of two or more solvents having different boiling points.
Metal oxide fine particles The coating material for forming a transparent colored film of the present invention may contain metal oxide fine particles in addition to the colorant.
金属酸化物微粒子としては、前記した金属酸化物微粒子あるいは表面処理された金属酸化物微粒子を用いることができる。
透明性着色膜形成用塗料中の金属酸化物微粒子あるいは表面処理された金属酸化物微粒子の含有量は固形分として０．１〜５０重量％、さらには０．２〜４０重量％の範囲にあることが好ましい。金属酸化物微粒子（表面処理されたものも含む）の濃度が少ないと、金属酸化物粒子の固有の特性、高屈折率機能、低屈折率機能、導電性機能、ハードコート機能などを充分発現できない場合があり、また多すぎると、着色剤を低減する必要が生じ
てしまい、充分な着色剤添加効果が得られない場合がある。
As the metal oxide fine particles, the above-described metal oxide fine particles or surface-treated metal oxide fine particles can be used.
The content of the metal oxide fine particles or the surface-treated metal oxide fine particles in the paint for forming a transparent colored film is in the range of 0.1 to 50% by weight, further 0.2 to 40% by weight as the solid content. It is preferable. If the concentration of metal oxide fine particles (including those that have been surface-treated) is low, the intrinsic properties, high refractive index function, low refractive index function, conductivity function, hard coat function, etc. of the metal oxide particles cannot be sufficiently exhibited. If the amount is too large, it may be necessary to reduce the colorant, and a sufficient colorant addition effect may not be obtained.
このような透明性着色膜形成用塗布液をディップ法、スプレー法、スピナー法、ロールコート法等の周知の方法で基材に塗布し、乾燥し、マトリックス形成成分が熱硬化性樹脂の場合は硬化させた後、熱可塑性樹脂の場合は、さらに必要に応じて基材の軟化点未満の温度で加熱処理することによって透明性着色膜を形成することができる。 When such a coating solution for forming a transparent colored film is applied to a substrate by a known method such as a dipping method, a spray method, a spinner method, or a roll coating method, and dried, and the matrix forming component is a thermosetting resin After being cured, in the case of a thermoplastic resin, a transparent colored film can be formed by further heat treatment at a temperature lower than the softening point of the substrate, if necessary.
透明性着色膜付基材が他の被膜を有する場合、他の被膜がハードコート層である場合には、基材上にハードコート層形成用塗料を塗布し、乾燥し、必要に応じて硬化し、ついで、前記透明性着色膜形成用塗布液を塗布し、乾燥し、硬化して透明性着色膜付基材を得ることができる。 When the substrate with a transparent colored film has another coating, if the other coating is a hard coat layer, apply a coating for forming a hard coat layer on the substrate, dry, and cure as necessary. Then, the transparent colored film-forming coating solution is applied, dried and cured to obtain a substrate with a transparent colored film.
また、他の被膜が反射防止膜である場合は、前記透明性着色膜形成用塗布液を塗布し、乾燥し、必要に応じて硬化した後、反射防止膜形成用塗料を塗布し、乾燥し、硬化して透明性着色膜付基材を得ることができる。 When the other coating is an antireflection film, the transparent colored film forming coating solution is applied, dried, cured as necessary, and then coated with an antireflection film forming coating and dried. It can be cured to obtain a substrate with a transparent colored film.
なお、透明性着色膜に粘着性を付与することも可能であり、この場合、基材上にあるいは他の被膜等を設けた反対側の基材上に透明性着色膜形成用塗布液をディップ法、スプレー法、スピナー法、ロールコート法等の周知の方法で基材に塗布し、他の基材に貼り付けた後、必要に応じて乾燥し、マトリックス形成成分が熱硬化性樹脂の場合は硬化させた後、熱可塑性樹脂の場合は、さらに必要に応じて基材の軟化点未満の温度で加熱処理することによって透明性着色膜を形成することができる。 It is also possible to impart adhesiveness to the transparent colored film. In this case, dip the coating liquid for forming the transparent colored film on the base material or on the opposite base material provided with other coatings. When the matrix forming component is a thermosetting resin, it is applied to a substrate by a well-known method such as the spray method, spray method, spinner method, roll coating method, etc., pasted on another substrate, and then dried as necessary. After being cured, in the case of a thermoplastic resin, a transparent colored film can be formed by further heat treatment at a temperature lower than the softening point of the substrate, if necessary.
[実施例]
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例により限定されるものではない。
［実施例１］
透明性着色膜形成用塗布液(1)の調製
顔料粒子としてキナクリドン系顔料分散液（御国色素社製：ハイミクロンＫバイオレット13718Ｓ、固形分濃度１０重量％、水分散媒）１００ｇにＳiＯ2濃度５重量％の珪酸液
５０ｇを添加し５０℃の浴槽中で１時間混合攪拌を行い固形分濃度８．３重量％の着色剤（ＣＨ-1）分散液を得た。得られた着色剤（ＣＨ-1）分散液２４．１ｇとアクリル系紫外線硬化樹脂（大日本インキ（株）製：ユニデックＶ５５００）２８ｇとＩＰＡ/ブチルセ
ロソルブ＝９／１混合溶液４７．９ｇとを混合攪拌し固形分濃度３０重量％（固形分中の着色剤（ＣＨ-1）含有量６．７重量％）の透明性着色膜形成用塗布液(1)を調製した。
透明性着色膜付基材(F-1)の製造
透明性着色膜形成用塗布液(1)をＴＡＣフィルム（厚さ：８０μｍ、屈折率：１.４９、基材透過率８８％）にバーコーター法で塗布し、８０℃で１分間乾燥した後、高圧水銀灯（８０Ｗ／ｃｍ）を２００ｍＪ／ｃｍ2で照射して硬化させ、透明性着色膜付基材(F-1)を調製した。このときの膜厚は５μｍであった。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.
[Example 1]
Preparation of coating liquid (1) for forming transparent colored film As a pigment particle, quinacridone pigment dispersion (manufactured by Mikuni Dye Co., Ltd .: Himicron K Violet 13718S, solid content concentration 10% by weight, water dispersion medium) 100 g of SiO 2 concentration 5 50% by weight of silicic acid solution was added and mixed and stirred in a 50 ° C. bath for 1 hour to obtain a colorant (CH-1) dispersion having a solid content of 8.3% by weight. 24.1 g of the obtained colorant (CH-1) dispersion, 28 g of an acrylic UV curable resin (Dainippon Ink Co., Ltd .: Unidec V5500), and 47.9 g of IPA / butyl cellosolve = 9/1 mixed solution were mixed. The mixture was stirred to prepare a coating solution (1) for forming a transparent colored film having a solid content concentration of 30% by weight (the colorant (CH-1) content in the solid content was 6.7% by weight).
Production of transparent colored film-coated substrate (F-1) The transparent colored film forming coating solution (1) was applied to a TAC film (thickness: 80 μm, refractive index: 1.49, substrate transmittance of 88%). After coating by a coater method and drying at 80 ° C. for 1 minute, a high pressure mercury lamp (80 W / cm) was irradiated and cured at 200 mJ / cm 2 to prepare a transparent colored film-coated substrate (F-1). The film thickness at this time was 5 μm.
得られた透明性着色膜付基材(F-1)について、コントラスト、光透過率、反射率、ヘー
ズ、表面抵抗、鉛筆硬度、耐擦傷性および密着性を下記の方法および評価基準で評価し、結果を表に示した。
About the obtained substrate with transparent colored film (F-1), the contrast, light transmittance, reflectance, haze, surface resistance, pencil hardness, scratch resistance and adhesion were evaluated by the following methods and evaluation criteria. The results are shown in the table.
光透過率は、分光光度計（日本分光製 U-vest560）を用い吸収ピーク波長における光
透過率を測定し、同じ波長における基材のみの光透過率との差を透明性着色膜(F-1)の光
透過率とした。反射率は、分光光度計（日本分光製 U-vest560）を用い可視光領域の最
小反射率を測定した。また、ヘーズはヘーズメーター（スガ試験機（株）製）により測定した。
The light transmittance is measured by measuring the light transmittance at the absorption peak wavelength using a spectrophotometer (Nippon Bunko U-vest560), and the difference from the light transmittance of only the base material at the same wavelength is measured with a transparent colored film (F- The light transmittance was 1). The reflectance was measured by using a spectrophotometer (U-vest560 manufactured by JASCO Corporation) to measure the minimum reflectance in the visible light region. The haze was measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.).
表面抵抗は、表面抵抗計（三菱化学（株）製：ハイレスタ）にて測定した。
コントラスト
透明性着色膜付基材(F-1)を液晶モニター（三菱電機製：Diamondcrysta RDTISILM）に
貼り、基材のみを貼ったときと比較した赤・緑・黄・黒の見え方以下の基準で評価した。非常に鮮やかに見える ：◎
鮮やかに見える ：○
やや鮮やかに見える ：△
基材のみの場合と殆ど変わらない：×
鉛筆硬度の測定
ＪＩＳ−Ｋ−５４００に準じて鉛筆硬度試験器により測定した。
The surface resistance was measured with a surface resistance meter (manufactured by Mitsubishi Chemical Corporation: Hiresta).
A substrate with contrast transparent colored film (F-1) is attached to a liquid crystal monitor (Mitsubishi Electric: Diamondcrysta RDTISILM), and the standard below the appearance of red, green, yellow and black compared to the case where only the substrate is attached. It was evaluated with. Looks very vivid: ◎
Visible ： ○
Somewhat vivid: △
Almost the same as the case of only the base material: ×
Measurement of pencil hardness It measured with the pencil hardness tester according to JIS-K-5400.
耐擦傷性の測定
＃００００スチールウールを用い、荷重５００ｇ／ｃｍ2で５０回摺動し、膜の表面を
目視観察し、以下の基準で評価した。
Measurement of scratch resistance Using # 0000 steel wool, sliding 50 times at a load of 500 g / cm 2 , visually observing the surface of the film, and evaluating according to the following criteria.
筋条の傷が認められない ：◎
筋条の傷が僅かに認められる ：○
筋条の傷が多数認められる ：△
膜の表面が全体的に削られている ：×
密着性
透明性着色膜付基材(F-1)の表面にナイフで縦横１ｍｍの間隔で１１本の平行な傷を付
けて１００個の升目を作り、これにセロハンテープ（登録商標）を接着し、ついで、セロハンテープを剥離したときに剥離せず残存している升目の数を、以下の基準で評価した。残存升目の数９５個以上 ：◎
残存升目の数９０〜９４個 ：○
残存升目の数８５〜８９個 ：△
残存升目の数８４個以下 ：×
［実施例２］
透明性着色膜形成用塗布液(2)の調製
実施例1と同様にして調製した着色剤（ＣＨ−１）分散液１００ｇにγ-アクリロキシプロピルトりメトキシシラン（信越化学製：ＫＢＭ-5103、１００％）０．４２ｇを加し、
５０℃の浴槽中で１時間混合攪拌を行い固形分濃度８．７重量％の着色剤（ＣＨ-２）分
散液を得た。
得られた着色剤（ＣＨ-２）分散液２２．９ｇとアクリル系紫外線硬化樹脂（大日本イン
キ（株）製：ユニデックＶ５５００）２８ｇとＩＰＡ/ブチルセロソルブ＝９／１混合溶
液を４９．１ｇとを混合攪拌し、固形分濃度３０重量％（固形分中の着色剤（ＣＨ−２）６．７重量％）の透明性着色膜形成用塗布液(2)を調製した。
透明性着色膜付基材(F-2)の製造
実施例１において、透明性着色膜形成用塗布液(2)を用いた以外は同様にして透明性着
色膜付基材(F-2)を調製した。このときの膜厚は５μｍであった。
得られた透明性着色膜付基材(F-2)について実施例1と同様の評価を行い、結果を表に示した。
［実施例３］
透明性着色膜形成用塗布液(3)の調製
顔料粒子としてフタロシアニン系顔料分散液（御国色素社製：ハイミクロンＫブルー5007Ａ、固形分濃度８重量％、水分散媒）１００ｇにアクリル樹脂（日本化薬製：1.6ヘキ
サンジオールジアクリレート）４ｇとＩＰＡ５０ｇとを添加し５０℃の浴槽中で１時間混合攪拌を行い固形分濃度７．８重量％の着色剤（ＣＨ-３）分散液を得た。得られた着色
剤（ＣＨ-３）を３８．５ｇとアクリル系紫外線硬化樹脂（大日本インキ（株）製：ユニ
デックＶ５５００）７ｇとＩＰＡ/ブチルセロソルブ＝９／１混合溶液５４．５ｇとを混
合攪拌し固形分１０重量％（固形分中の着色剤（ＣＨ−３）含有量３０重量％）の透明性着色膜形成塗布液(3)を調製した。
透明性着色膜付基材(F-3)の製造
実施例１において、透明性着色膜形成用塗布液(3)を用いた以外は同様にして透明性着
色膜付基材(F-3)を調製した。このときの膜厚は０．１μｍであった。
得られた透明性着色膜付基材(F-3)について実施例1と同様の評価を行い、結果を表に示した。
［実施例４］
透明性着色膜形成用塗布液(4)の調製
実施例２と同様にして調製した固形分濃度８．７重量％の着色剤（ＣＨ-２）分散液２
２．９ｇと５酸化アンチモン粒子分散液（触媒化成製：ＥＬＣＯＭ Ｖ-4521、固形分濃度３０重量％、ＩＰＡ分散媒、平均粒子径２０ｎｍ）３０ｇとアクリル系紫外線硬化樹脂（大日本インキ（株）製：ユニデックＶ５５００）１９ｇとＩＰＡ/ブチルセロソルブ＝９
／１混合溶液２８．１ｇとを混合攪拌し固形分濃度３０重量％（固形分中の着色剤（ＣＨ-２）６．７重量％、Ｓｂ2Ｏ5濃度３０重量％）の透明性着色膜形成塗布液(4)を調製した。
透明性着色膜付基材(F-4)の製造
実施例１において、透明性着色膜形成用塗布液(4)を用いた以外は同様にして透明性着
色膜付基材(F-4)を調製した。このときの膜厚は５μｍであった。
得られた透明性着色膜付基材(F-4)について実施例1と同様の評価を行い、結果を表に示した。
［実施例５］
透明性着色膜形成用塗布液(5)の調製
金微粒子分散液（触媒化成製：CG-001、固形分濃度１０重量％、水分散媒、平均粒子径２ｎｍ）１００ｇにＳiＯ2濃度５重量％の珪酸液５０ｇを添加し５０℃の浴槽中で１時間混合攪拌を行い固形分濃度８．３重量％の着色剤（ＣＨ-５）分散液を得た。得られた着色
剤（ＣＨ-５）分散液４８．２ｇとアクリル系紫外線硬化樹脂（大日本インキ（株）製：
ユニデックＶ５５００）２６ｇとＩＰＡ/ブチルセロソルブ＝９／１混合溶液２５．８ｇ
とを混合攪拌し固形分濃度３０重量％（固形分中の着色剤（ＣＨ-５）含有量１３．４重
量％）の透明性着色膜形成塗布液(5)を調製した。
透明性着色膜付基材(F-5)の製造
実施例１において、透明性着色膜形成用塗布液(5)を用いた以外は同様にして透明性着
色膜付基材(F-5)を調製した。このときの膜厚は５μｍであった。
得られた透明性着色膜付基材(F-4)について実施例1と同様の評価を行い、結果を表に示した。
［実施例６］
透明性着色膜形成用塗布液(6)の調製
金微粒子分散液（触媒化成製：CS-001、固形分濃度１０重量％、水分散媒、平均粒子径６ｎｍ）１００ｇにＳiＯ2濃度５重量％の珪酸液５０ｇを添加し５０℃の浴槽中で１時間混合攪拌を行い、ついでγ-グリシドキシプロピルトリメトキシシラン（信越化学製：ＫＢ
Ｍ-403、１００重量％）０．４２ｇ加え５０℃の浴槽中でさらに１時間撹拌して固形分濃度８．６重量％の着色剤（ＣＨ-６）分散液を得た。得られた着色剤（ＣＨ-６）分散液３４．９ｇとアクリル系紫外線硬化樹脂（大日本インキ（株）製：ユニデックＶ５５００）５ｇとＩＰＡ/ブチルセロソルブ＝９／１混合溶液６０．１ｇとを混合攪拌し固形分濃度１０重量％（固形分中の着色剤（ＣＨ−６）含有量３０重量％）の透明性着色膜形成用塗布液(6)を調製した。
透明性着色膜付基材(F-6)の製造
実施例１において、透明性着色膜形成用塗布液(6)を用いた以外は同様にして透明性着
色膜付基材(F-6)を調製した。このときの膜厚は０．１μｍであった。
得られた透明性着色膜付基材(F-6)について実施例1と同様の評価を行い、結果を表に示し
た。
［実施例７］
透明性着色膜付基材(F-7)の製造
実施例４と同様にして調製した透明性着色膜付基材(F-4)（着色膜の屈折率＝１．５３
）上に、反射防止膜形成塗布液（触媒化成製：ELCOM P-5013、中空シリカ粒子(平均粒子
径５０ｎｍ)と紫外線硬化型アクリル系樹脂でからなり、固形分濃度２．５重量％）バー
コーター法で塗布し、８０℃で１分間乾燥した後、高圧水銀灯（８０Ｗ／ｃｍ）を２００ｍＪ／ｃｍ2で照射して硬化させ、透明性着色膜付基材(F-7)を調製した。このときの反射防止膜の膜厚は０．１μｍ、屈折率は１．４０であった。
No streak injury is found: ◎
Slight flaws are observed: ○
Many streak wounds are found: △
The entire surface of the film is scraped: ×
Adhesive transparency Colored film-coated substrate (F-1) surface is made of 11 parallel scratches with a knife at intervals of 1 mm in length and width to make 100 squares, and cellophane tape (registered trademark) is adhered to it Then, the number of cells remaining without peeling when the cellophane tape was peeled was evaluated according to the following criteria. Number of remaining cells: 95 or more: ◎
Number of remaining squares 90-94: ○
Number of remaining squares: 85 to 89: Δ
Number of remaining squares: 84 or less: ×
[Example 2]
Preparation of coating liquid for forming transparent colored film (2) 100 g of a colorant (CH-1) dispersion prepared in the same manner as in Example 1 was added to γ-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical: KBM-5103). , 100%) 0.42 g,
The mixture was stirred for 1 hour in a 50 ° C. bath to obtain a colorant (CH-2) dispersion having a solid content of 8.7% by weight.
22.9 g of the obtained colorant (CH-2) dispersion, 28 g of an acrylic ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidec V5500), and 49.1 g of a mixed solution of IPA / butyl cellosolve = 9/1. After mixing and stirring, a coating solution (2) for forming a transparent colored film having a solid content concentration of 30% by weight (6.7% by weight of the colorant (CH-2) in the solid content) was prepared.
Production of transparent colored film-coated substrate (F-2) In Example 1, the transparent colored film-coated substrate (F-2) was used except that the transparent colored film-forming coating solution (2) was used. Was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (F-2) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 3]
Preparation of coating liquid for forming transparent colored film (3) As pigment particles, 100 g of phthalocyanine pigment dispersion (manufactured by Mikuni Dye Co., Ltd .: Himicron K Blue 5007A, solid concentration 8 wt%, water dispersion medium) and acrylic resin (Japan) Kagaku: 1.6 hexanediol diacrylate) 4 g and IPA 50 g were added and mixed and stirred in a 50 ° C. bath for 1 hour to obtain a colorant (CH-3) dispersion having a solid content concentration of 7.8 wt%. . 38.5 g of the obtained colorant (CH-3), 7 g of an acrylic ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidec V5500) and 54.5 g of a mixed solution of IPA / butyl cellosolve = 9/1 were mixed and stirred. A transparent colored film forming coating solution (3) having a solid content of 10% by weight (colorant (CH-3) content in the solid content of 30% by weight) was prepared.
Production of transparent colored film-coated substrate (F-3) In Example 1, the transparent colored film-coated substrate (F-3) was used except that the transparent colored film-forming coating solution (3) was used. Was prepared. The film thickness at this time was 0.1 μm.
The obtained transparent colored film-coated substrate (F-3) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 4]
Preparation of coating liquid (4) for forming transparent colored film Colorant (CH-2) dispersion 2 having a solid content concentration of 8.7% by weight prepared in the same manner as in Example 2.
2.9 g, antimony pentoxide particle dispersion (catalyst conversion: ELCOM V-4521, solid content concentration 30% by weight, IPA dispersion medium, average particle size 20 nm) and acrylic UV curable resin (Dainippon Ink Co., Ltd.) (Manufactured by: Unidec V5500) 19 g and IPA / butyl cellosolve = 9
/ 2 1 g of the mixed solution is mixed and stirred, and a transparent colored film having a solid content of 30% by weight (colorant (CH-2) 6.7% by weight, Sb 2 O 5 concentration 30% by weight in the solid) A forming coating solution (4) was prepared.
Production of transparent colored film-coated substrate (F-4) In Example 1, the transparent colored film-coated substrate (F-4) was used except that the transparent colored film-forming coating solution (4) was used. Was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (F-4) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 5]
Preparation of coating solution for forming transparent colored film (5) Gold fine particle dispersion (catalyst conversion: CG-001, solid content concentration 10% by weight, water dispersion medium, average particle size 2 nm) in 100 g of SiO 2 50 g of 5% by weight silicic acid solution was added and mixed and stirred in a 50 ° C. bath for 1 hour to obtain a colorant (CH-5) dispersion having a solid content of 8.3% by weight. 48.2 g of the obtained colorant (CH-5) dispersion and an acrylic UV curable resin (manufactured by Dainippon Ink Co., Ltd .:
UNIDEC V5500) 26g and IPA / butyl cellosolve = 9/1 mixed solution 25.8g
Were mixed and stirred to prepare a transparent colored film-forming coating solution (5) having a solid content concentration of 30% by weight (colorant (CH-5) content in solid content: 13.4% by weight).
Production of transparent colored film-coated substrate (F-5) In Example 1, the transparent colored film-coated substrate (F-5) was used except that the transparent colored film-forming coating solution (5) was used. Was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (F-4) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 6]
Preparation of coating liquid (6) for forming transparent colored film Gold fine particle dispersion (catalyst conversion: CS-001, solid content concentration: 10% by weight, water dispersion medium, average particle diameter: 6 nm) in 100 g of SiO 2 50 g of a 5% strength by weight silicic acid solution was added and mixed and stirred in a 50 ° C. bath for 1 hour, and then γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical: KB)
M-403 (100 wt%) 0.42 g was added, and the mixture was further stirred for 1 hour in a 50 ° C. bath to obtain a colorant (CH-6) dispersion having a solid content concentration of 8.6 wt%. 34.9 g of the resulting colorant (CH-6) dispersion, 5 g of an acrylic ultraviolet curable resin (Dainippon Ink Co., Ltd .: Unidec V5500), and 60.1 g of a mixed solution of IPA / butyl cellosolve = 9/1 were mixed. The mixture was stirred to prepare a coating solution (6) for forming a transparent colored film having a solid content concentration of 10% by weight (colorant (CH-6) content in the solid content of 30% by weight).
Production of transparent colored film-coated substrate (F-6) In Example 1, the transparent colored film-coated substrate (F-6) was used except that the transparent colored film-forming coating solution (6) was used. Was prepared. The film thickness at this time was 0.1 μm.
The obtained transparent colored film-coated substrate (F-6) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 7]
Production of transparent colored film-coated substrate (F-7) Transparent colored film-coated substrate (F-4) prepared in the same manner as in Example 4 (refractive index of colored film = 1.53)
) Above, anti-reflective coating solution (catalyst conversion: ELCOM P-5013, consisting of hollow silica particles (average particle size 50 nm) and UV curable acrylic resin, solid content concentration 2.5 wt%) After coating by a coater method and drying at 80 ° C. for 1 minute, a high pressure mercury lamp (80 W / cm) was irradiated and cured at 200 mJ / cm 2 to prepare a transparent colored film-coated substrate (F-7). At this time, the thickness of the antireflection film was 0.1 μm, and the refractive index was 1.40.
得られた透明性着色膜付基材(F-7)について実施例1と同様の評価を行い、結果を表に示した。
［実施例８］
透明性着色膜付基材(F-8)の製造
実施例４と同様にして調製した透明性着色膜付基材(F-4)（着色膜の屈折率＝１．５３
）上に、実施例６と同様にして調製した透明性着色膜形成用塗布液（6）をバーコーター
法で塗布し、８０℃で１分間乾燥した後、高圧水銀灯（８０Ｗ／ｃｍ）を２００ｍＪ／ｃｍ2で照射して硬化させ、透明性着色膜付基材(F-8)を調製した。このときの透明性着色膜の合計膜厚は５．１μｍであった。
得られた透明性着色膜付基材(F-8)について実施例1と同様の評価を行い、結果を表に示した。
［実施例９］
透明性着色膜形成用塗布液(9)の調製
顔料粒子としてキナクリドン系顔料分散液（御国色素社製：ハイミクロンＫバイオレット13718Ｓ、固形分濃度１０重量％、水分散媒）１００ｇにＳiＯ2濃度５重量％の珪酸液
６ｇを添加し５０℃の浴槽中で１時間混合攪拌を行い固形分濃度９．７ｇ重量％の着色剤（ＣＨ-９）分散液を得た。得られた着色剤（ＣＨ-９）分散液２０．６ｇとアクリル系紫外線硬化樹脂（大日本インキ（株）製：ユニデックＶ５５００）２８ｇとＩＰＡ/ブチル
セロソルブ＝９／１混合溶液５１．４ｇとを混合攪拌し固形分濃度３０重量％（固形分中の着色剤（ＣＨ-９）含有量６．７重量％）の透明性着色膜形成用塗布液(9)を調製した。 透明性着色膜付基材(F-9)の製造
実施例１において、透明性着色膜形成用塗布液(9)を用いた以外は同様にして透明性着
色膜付基材(F-9)を調製した。このときの膜厚は５μｍであった。
得られた透明性着色膜付基材(F-9)について実施例1と同様の評価を行い、結果を表に示した。
［比較例１］
透明性着色膜形成用塗布液(R1)の製造
五酸化アンチモン粒子分散液（触媒化成工業（株）製；ＥＬＣＯＭ ＰＣ−１４、平均
粒子径２０ｎｍ、Ｓb2Ｏ5濃度２０重量％、分散媒：エチルセロソルブ／エタノール重量
比＝９４／６）２００ｇに紫外線硬化樹脂（大日本インキ（株）製：ユニデックＶ５５００）１６０ｇとエチルセロソルブ６４０ｇとを混合して透明性着色膜形成用塗布液(R1)を調製した。
透明性着色膜付基材(RF-1)の製造
実施例１において、透明性着色膜形成用塗布液(RF-1)を用いた以外は同様にして透明性着色膜付基材(RF-1)を調製した。このときの膜厚は５μｍであった。
得られた透明性着色膜付基材(RF-1)について実施例1と同様の評価を行い、結果を表に示
した。
［比較例２］ （HC厚膜のブルー膜、着色剤添加過多）
透明性着色膜形成用塗布液(R2)の調製
実施例３と同様にして固形分濃度７．８重量％の着色剤（ＣＨ-３）分散液得た。得ら
れた着色剤（ＣＨ-３）を７６．９ｇとアクリル系紫外線硬化樹脂（大日本インキ（株）
製：ユニデックＶ５５００）２ｇとＩＰＡ/ブチルセロソルブ＝９／１混合溶液２１．１
ｇとを混合攪拌し固形分１０重量％（固形分中の着色剤（ＣＨ−３）含有量７５重量％）の透明性着色膜形成塗布液（R2）を調製した。
透明性着色膜付基材（RF-2）の製造
実施例１において、透明性着色膜形成用塗布液(R2)を用いた以外は同様にして透明性着色膜付基材(RF-2)を調製した。このときの膜厚は０．１μｍであった。
The obtained transparent colored film-coated substrate (F-7) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 8]
Production of transparent colored film-coated substrate (F-8) Transparent colored film-coated substrate (F-4) prepared in the same manner as in Example 4 (refractive index of colored film = 1.53)
) A transparent colored film forming coating solution (6) prepared in the same manner as in Example 6 was applied by the bar coater method and dried at 80 ° C. for 1 minute, and then a high pressure mercury lamp (80 W / cm) was applied at 200 mJ. / Cm 2 was irradiated and cured to prepare a transparent colored film-coated substrate (F-8). The total film thickness of the transparent colored film at this time was 5.1 μm.
The obtained transparent colored film-coated substrate (F-8) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Example 9]
Preparation of coating liquid for forming transparent colored film (9) As a pigment particle, quinacridone pigment dispersion (manufactured by Mikuni Dye Co., Ltd .: Himicron K Violet 13718S, solid content concentration 10% by weight, water dispersion medium) 100 g of SiO 2 concentration 5 6 g of a weight percent silicic acid solution was added and mixed and stirred in a 50 ° C. bath for 1 hour to obtain a colorant (CH-9) dispersion having a solid content concentration of 9.7 g weight percent. 20.6 g of the resulting colorant (CH-9) dispersion, 28 g of an acrylic UV curable resin (Dainippon Ink Co., Ltd .: Unidec V5500), and 51.4 g of IPA / butyl cellosolve = 9/1 mixed solution were mixed. The mixture was stirred to prepare a coating liquid (9) for forming a transparent colored film having a solid content concentration of 30% by weight (colorant (CH-9) content in the solid content: 6.7% by weight). Production of transparent colored film-coated substrate (F-9) In Example 1, the transparent colored film-coated substrate (F-9) was used except that the transparent colored film-forming coating solution (9) was used. Was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (F-9) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Comparative Example 1]
Manufacture of coating liquid (R1) for forming transparent colored film Antimony pentoxide particle dispersion (manufactured by Catalyst Kasei Kogyo Co., Ltd .; ELCOM PC-14, average particle diameter 20 nm, Sb 2 O 5 concentration 20% by weight, dispersion medium: Ethyl cellosolve / ethanol weight ratio = 94/6) 200 g of UV curable resin (Dainippon Ink Co., Ltd .: Unidec V5500) 160 g and ethyl cellosolve 640 g were mixed to prepare a transparent colored film forming coating solution (R1). Prepared.
Production of transparent colored film-coated substrate (RF-1) In Example 1, the transparent colored film-coated substrate (RF- 1) was used except that the transparent colored film-forming coating solution (RF-1) was used. 1) was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (RF-1) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Comparative Example 2] (HC thick film blue film, excessive colorant addition)
Preparation of Transparent Colored Film Forming Coating Liquid (R2) A colorant (CH-3) dispersion having a solid content concentration of 7.8% by weight was obtained in the same manner as in Example 3. 76.9 g of the obtained colorant (CH-3) and an acrylic UV curable resin (Dainippon Ink Co., Ltd.)
(Product: Unidec V5500) 2 g and IPA / butyl cellosolve = 9/1 mixed solution 21.1
g was mixed and stirred to prepare a transparent colored film-forming coating solution (R2) having a solid content of 10% by weight (a colorant (CH-3) content of 75% by weight in the solid content).
Production of substrate with transparent colored film (RF-2) Substrate with transparent colored film (RF-2) was produced in the same manner as in Example 1 except that the coating liquid for transparent colored film formation (R2) was used. Was prepared. The film thickness at this time was 0.1 μm.
得られた透明性着色膜付基材(RF-2)について実施例1と同様の評価を行い、結果を表に
示した。
［比較例３］
透明性着色膜形成用塗布液(R3)の調製
顔料粒子としてキナクリドン系顔料分散液（御国色素社製：ハイミクロンＫバイオレット13718Ｓ、固形分濃度１０重量％、水分散媒）２０ｇとアクリル系紫外線硬化樹脂（大
日本インキ（株）製：ユニデックＶ５５００）２８ｇとＩＰＡ/ブチルセロソルブ＝９／
１混合溶液５２ｇとを混合攪拌し固形分濃度３０重量％（固形分中の顔料粒子含有量６．７重量％）の透明性着色膜形成用塗布液(R3)を調製した。
透明性着色膜付基材(RF-3)の製造
実施例１において、透明性着色膜形成用塗布液(R3)を用いた以外は同様にして透明性着色膜付基材(RF-3)を調製した。このときの膜厚は５μｍであった。
得られた透明性着色膜付基材(RF-3)について実施例1と同様の評価を行い、結果を表に示
した。
［比較例４］（［実施例５］で（厚膜のAu、酸化物被覆無し）
透明性着色膜形成用塗布液(R4)の調製
金微粒子分散液（触媒化成製：CG-001、固形分濃度１０重量％、水分散媒、平均粒子径２ｎｍ）４０ｇとアクリル系紫外線硬化樹脂（大日本インキ（株）製：ユニデックＶ５５００）２６ｇとＩＰＡ/ブチルセロソルブ＝９／１混合溶液５４ｇとを混合攪拌し固形分
濃度３０重量％（固形分中の金微粒子含有量１３．３重量％）の透明性着色膜形成塗布液(RF-4)を調製した。
透明性着色膜付基材(RF-4)の製造
実施例１において、透明性着色膜形成用塗布液(RF-4)を用いた以外は同様にして透明性着色膜付基材(RF-4)を調製した。このときの膜厚は５μｍであった。
得られた透明性着色膜付基材(RF-4)について実施例1と同様の評価を行い、結果を表に示
した。
The obtained transparent colored film-coated substrate (RF-2) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Comparative Example 3]
Preparation of coating liquid (R3) for forming transparent colored film 20 g of quinacridone pigment dispersion (manufactured by Mikuni Dye Co., Ltd .: Himicron K Violet 13718S, solid content concentration 10% by weight, water dispersion medium) as pigment particles and acrylic UV curing 28 g of resin (Dainippon Ink Co., Ltd .: Unidec V5500) and IPA / butyl cellosolve = 9 /
1 g of the mixed solution 52 g was mixed and stirred to prepare a transparent colored film forming coating solution (R3) having a solid content concentration of 30% by weight (pigment particle content in the solid content 6.7% by weight).
Production of transparent colored film-coated substrate (RF-3) In Example 1, the transparent colored film-coated substrate (RF-3) was used in the same manner except that the transparent colored film-forming coating solution (R3) was used. Was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (RF-3) was evaluated in the same manner as in Example 1, and the results are shown in the table.
[Comparative Example 4] (in [Example 5] (thick Au, no oxide coating)
Preparation of coating liquid (R4) for forming transparent colored film Gold fine particle dispersion (catalyst conversion: CG-001, solid content concentration 10% by weight, water dispersion medium, average particle diameter 2 nm) and acrylic UV curable resin ( Dainippon Ink & Co., Ltd .: Unidec V5500) 26 g and IPA / butyl cellosolve = 9/1 mixed solution 54 g were mixed and stirred, and the solid content concentration was 30 wt% (the content of gold fine particles in the solid content was 13.3% wt). A transparent colored film forming coating solution (RF-4) was prepared.
Production of transparent colored film-coated substrate (RF-4) In Example 1, the transparent colored film-coated substrate (RF-) was used except that the transparent colored film-forming coating solution (RF-4) was used. 4) was prepared. The film thickness at this time was 5 μm.
The obtained transparent colored film-coated substrate (RF-4) was evaluated in the same manner as in Example 1, and the results are shown in the table.
Claims (8)
該透明性着色膜が、
マトリックス成分と、着色剤として、(i)シリカまたは樹脂で被覆された顔料粒子および／または(ii)シリカまたは樹脂で被覆された金属微粒子とを含んでなり
マトリックス成分が樹脂マトリックスであり、
着色剤が下記式(1)で表される有機珪素化合物で表面処理されてなり、
着色膜中の該着色剤の含有量が０．１〜５０重量％の範囲にあり、樹脂マトリックスの含有量が60.5〜93.3重量％の範囲にある（ただし合計量は100重量％を越えない）ことを特徴とする透明性着色膜付基材；
Ｒn-ＳiＸ4-n （１）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、シラノール基、ハロゲン、水素、ｎ：０〜３の整数） Consisting of a substrate and a transparent colored film formed on one or both sides of the substrate,
The transparent colored film is
Comprising a matrix component and, as a colorant, (i) pigment particles coated with silica or resin and / or (ii) metal fine particles coated with silica or resin, and the matrix component is a resin matrix,
The colorant is surface-treated with an organosilicon compound represented by the following formula (1),
The content of the colorant in the colored film is in the range of 0.1 to 50% by weight, and the content of the resin matrix is in the range of 60.5 to 93.3% by weight (however, the total amount does not exceed 100% by weight) A substrate with a transparent colored film,
R n -SiX 4-n (1 )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
Ｘ'-Ｒ'-Ｓi(ＯＲ'')3 （２）
（式中、Ｒ''は炭素数1〜４の非置換の炭化水素基を表す。Ｘ'-Ｒ'-はγ-グリシドキシメチル、γ-グリシドキシエチル、γ-グリシドキシプロピル、γ−（β−グリシドキシエトキシ）プロピル、γ-（メタ）アクリロオキシメチル、γ-（メタ）アクリロオキシエチル、γ-（メタ）アクリロオキシプロピルのいずれかを示す。） 2. The substrate with a transparent colored film according to claim 1, wherein the organosilicon compound represented by the formula (1) is an organosilicon compound represented by the following formula (2).
X'-R'-Si (OR '') 3 (2)
(In the formula , R ″ represents an unsubstituted hydrocarbon group having 1 to 4 carbon atoms. X′-R′- represents γ-glycidoxymethyl, γ-glycidoxyethyl, γ-glycidoxypropyl. , Γ- (β-glycidoxyethoxy) propyl, γ- (meth) acrylooxymethyl, γ- (meth) acrylooxyethyl, γ- (meth) acrylooxypropyl ).
少なくとも波長５６０〜６２０ｎｍの光透過率（I）が４０〜９８％にあるか、あるいは 波長４５０〜５００ｎｍの光透過率（II）が４０〜９８％の範囲にあることを特徴とする請求項１〜３のいずれかに記載の透明性着色膜付基材。 The transparent colored film is
The light transmittance (I) at least at a wavelength of 560 to 620 nm is 40 to 98%, or the light transmittance (II) at a wavelength of 450 to 500 nm is in the range of 40 to 98%. The base material with a transparent coloring film in any one of -3.
マトリックス形成成分が樹脂マトリックスであり、着色剤が下記式(1)で表される有機珪素化合物で表面処理されてなり、
マトリックス形成成分と着色剤との合計の濃度が固形分として０．５〜６０重量％の範囲にあり、
該着色剤を透明性着色膜中に固形分として０．１〜５０重量％、樹脂マトリックスの含有量を60.5〜93.3重量％の範囲となるように（ただし合計は100重量％を越えない）含有していることを特徴とする透明性着色膜形成用塗布液；
Ｒn-ＳiＸ4-n （１）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、シラノール基、ハロゲン、水素、ｎ：０〜３の整数） A matrix-forming component, and (i) pigment particles coated with silica or resin and / or (ii) fine metal particles coated with silica or resin as a colorant,
The matrix forming component is a resin matrix, and the colorant is surface-treated with an organosilicon compound represented by the following formula (1),
The total concentration of the matrix-forming component and the colorant is in the range of 0.5-60% by weight as solids,
The colorant is contained in the transparent colored film in a solid content of 0.1 to 50% by weight, and the resin matrix content is in the range of 60.5 to 93.3% by weight (the total does not exceed 100% by weight). A coating liquid for forming a transparent colored film, characterized in that:
R n -SiX 4-n (1 )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms or a silanol group) , Halogen, hydrogen, n: an integer of 0 to 3)
Ｘ'-Ｒ'-Ｓi(ＯＲ'')3 （２）
（式中、Ｒ''は炭素数1〜４の非置換の炭化水素基を表す。Ｘ'-Ｒ'-はγ-グリシドキシメチル、γ-グリシドキシエチル、γ-グリシドキシプロピル、γ−（β−グリシドキシエトキシ）プロピル、γ-（メタ）アクリロオキシメチル、γ-（メタ）アクリロオキシエチル、γ-（メタ）アクリロオキシプロピルのいずれかを示す。） The coating solution for forming a transparent colored film according to claim 6, wherein the organosilicon compound represented by the formula (1) is an organosilicon compound represented by the following formula (2).
X'-R'-Si (OR '') 3 (2)
(In the formula , R ″ represents an unsubstituted hydrocarbon group having 1 to 4 carbon atoms. X′-R′- represents γ-glycidoxymethyl, γ-glycidoxyethyl, γ-glycidoxypropyl. , Γ- (β-glycidoxyethoxy) propyl, γ- (meth) acrylooxymethyl, γ- (meth) acrylooxyethyl, γ- (meth) acrylooxypropyl).
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