TWI701297B - Black resin composition for light-shielding film, substrate with the light-shielding film formed by curing that composition, and color filter or touch panel with that substrate - Google Patents
Black resin composition for light-shielding film, substrate with the light-shielding film formed by curing that composition, and color filter or touch panel with that substrate Download PDFInfo
- Publication number
- TWI701297B TWI701297B TW105106683A TW105106683A TWI701297B TW I701297 B TWI701297 B TW I701297B TW 105106683 A TW105106683 A TW 105106683A TW 105106683 A TW105106683 A TW 105106683A TW I701297 B TWI701297 B TW I701297B
- Authority
- TW
- Taiwan
- Prior art keywords
- light
- shielding film
- black
- shielding
- component
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 85
- 239000000758 substrate Substances 0.000 title claims abstract description 83
- 239000000203 mixture Substances 0.000 title description 36
- 239000002245 particle Substances 0.000 claims abstract description 151
- 229920005989 resin Polymers 0.000 claims abstract description 71
- 239000011347 resin Substances 0.000 claims abstract description 71
- 239000006185 dispersion Substances 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000011163 secondary particle Substances 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 56
- 239000006229 carbon black Substances 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 17
- 238000000576 coating method Methods 0.000 claims description 17
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 16
- 238000000206 photolithography Methods 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002612 dispersion medium Substances 0.000 claims description 10
- 238000007639 printing Methods 0.000 claims description 9
- 238000007641 inkjet printing Methods 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
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- 239000000047 product Substances 0.000 description 19
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
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- 230000007423 decrease Effects 0.000 description 7
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- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 5
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- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
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- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
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- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G02F1/1333—Constructional arrangements; Manufacturing methods
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- G06F—ELECTRIC DIGITAL DATA PROCESSING
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- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
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Landscapes
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- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
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- Materials For Photolithography (AREA)
- Optical Elements Other Than Lenses (AREA)
- Liquid Crystal (AREA)
Abstract
Description
本發明有關遮光膜用黑色樹脂組成物、於玻璃等透明基板上具有使該組成物硬化而成的遮光膜的附遮光膜基板、以及以該附遮光膜基板為構成要素的LCD等顯示器用彩色濾光片及顯示裝置用觸控面板。詳言之，本發明有關適合於透明基板上形成微細的遮光膜的藉由光或熱硬化的黑色樹脂組成物、及於選擇性的位置上形成有使該黑色樹脂組成物硬化而得的遮光膜的附遮光膜基板。 The present invention relates to a black resin composition for a light-shielding film, a substrate with a light-shielding film having a light-shielding film formed by curing the composition on a transparent substrate such as glass, and a color for displays such as LCDs using the substrate with a light-shielding film as a constituent element Filters and touch panels for display devices. In detail, the present invention relates to a black resin composition cured by light or heat suitable for forming a fine light-shielding film on a transparent substrate, and a light-shielding formed by curing the black resin composition at a selective position Film with light-shielding film substrate.
於觸控面板外框設置有用以遮光背面的液晶面板周邊部的漏光的遮光膜(邊框)，且於液晶面板中彩色濾光片內設置有對TFT元件遮光的黑色矩陣。隨著最近行動終端的發展，使用於屋外或車載的觸控面板及液晶面 板等顯示裝置增加，設置於玻璃基板或塑膠膜基板上的遮光膜對於來自面板外部的入射光而產生的反射光，會影響液晶顯示裝置等在非開燈時的顯示，因此將遮光膜設成與來自周圍的著色膜等的反射光有同等的反射率、及控制色相(反射色度)都成為新的技術課題。 A light-shielding film (frame) is provided on the outer frame of the touch panel to shield the light leakage from the peripheral portion of the liquid crystal panel on the back side, and a black matrix for light-shielding the TFT element is provided in the color filter of the liquid crystal panel. With the recent development of mobile terminals, touch panels and LCD panels used outdoors or in vehicles Display devices such as panels have increased, and the light shielding film provided on the glass substrate or plastic film substrate will reflect light from incident light from outside the panel, which will affect the display of the liquid crystal display device when the light is not turned on. Therefore, the light shielding film is set To achieve the same reflectance as the reflected light from surrounding colored films, etc., and to control the hue (reflected chromaticity) have become new technical issues.
如此的遮光膜係將以硬化性樹脂與遮光材為主體的組成物印刷於透明基板上而形成(專利文獻1、2)。遮光材大多採用碳黑或黑色氧化鈦等吸收可見光的黑色顏料。為了利用該等黑色顏料提升遮光膜的遮光性(為降低遮光膜的光穿透性)，而增加遮光膜中的黑色顏料濃度時，相較於透明基板或硬化性樹脂，黑色顏料的折射率較高，且由與透明基板的形成有遮光膜的面相反的面側觀看時的反射率變高。亦即，在透明基板上形成的遮光膜與透明基板的界面的反射增加，且相較於在透明基板上的著色層與透明基板的界面的反射或在著色邊框與空氣的界面的反射變大的情況時，產生遮光膜上的反光或與彩色濾光片著色部的反射率的差異造成黑色矩陣邊界明顯的課題。因此，愈是欲設成高遮光時，就愈是難以兼具與遮光膜以外的著色層及著色邊緣有同等的反射率之類的需求特性。 Such a light-shielding film is formed by printing a composition mainly composed of a curable resin and a light-shielding material on a transparent substrate (Patent Documents 1 and 2). Most of the light-shielding materials use black pigments that absorb visible light such as carbon black or black titanium oxide. In order to use these black pigments to improve the light-shielding properties of the light-shielding film (to reduce the light penetration of the light-shielding film), when the concentration of black pigment in the light-shielding film is increased, the refractive index of the black pigment is compared with that of a transparent substrate or a curable resin It is high, and the reflectance when viewed from the side opposite to the surface on which the light-shielding film of the transparent substrate is formed becomes high. That is, the reflection at the interface between the light-shielding film formed on the transparent substrate and the transparent substrate increases, and the reflection at the interface between the colored layer on the transparent substrate and the transparent substrate or the reflection at the interface between the colored frame and the air becomes larger In this case, the reflection on the light-shielding film or the difference in reflectance from the colored part of the color filter causes a problem that the black matrix boundary is obvious. Therefore, the more high light-shielding is desired, the more difficult it is to have the required characteristics such as the same reflectance as the colored layer and colored edges other than the light-shielding film.
就降低不同種材料間的界面產生的反射的手段而言，已提案有例如於基板表面設置使外光反射降低的低折射率膜的方式(例如1/4波長圓偏光板)、使基板表面變粗的抗眩光方式等，以及研討形成具有基板與遮光膜的中間折射率的薄膜的手段等附加式的手段。具有中間折射 率的薄膜的膜厚係由相當於可見光波長的4分之1波長分的100至300μm的透明膜或該等多層膜所形成(非專利文獻1)。 As for the means to reduce the reflection at the interface between different kinds of materials, for example, a method of providing a low-refractive-index film to reduce the reflection of external light on the surface of the substrate (for example, a quarter-wave circular polarizing plate), and making the surface of the substrate The thickening anti-glare method, etc., as well as additional methods such as the method of forming a thin film with an intermediate refractive index between the substrate and the light-shielding film, are considered. With intermediate refraction The film thickness of the high-efficiency thin film is formed of a transparent film of 100 to 300 μm corresponding to a quarter of the wavelength of visible light, or such a multilayer film (Non-Patent Document 1).
液晶面板中的彩色濾光片上的黑色矩陣或觸控面板面框用遮光膜中，有只於必要的部位使遮光膜形成圖案的必要性，在研討如前述的附加式手段時，必須將以低反射化為目的的薄膜(低反射膜)事先形成於透明基板與遮光膜之間，亦即例如以光刻法分別進行低反射膜與遮光膜的圖案形成，而形成有低反射膜與遮光膜的二層構造。或者，考慮有形成透明薄膜後再形成遮光膜，將遮光膜以照相法進行圖案曝光/顯像，以此作為光罩使用而進行透明薄膜的圖案形成的方法。在此方法中，遮光膜用黑色樹脂組成物必需對於事先形成的透明薄膜不具侵蝕性。 In the black matrix on the color filter of the liquid crystal panel or the light-shielding film for the face frame of the touch panel, it is necessary to pattern the light-shielding film only in necessary parts. When studying the aforementioned additional methods, it is necessary to A thin film (low-reflection film) for the purpose of low reflection is formed in advance between the transparent substrate and the light-shielding film, that is, for example, the low-reflection film and the light-shielding film are patterned separately by photolithography to form a low-reflection film and Two-layer structure of shading film. Alternatively, a method of forming a light-shielding film after forming a transparent film, patterning the light-shielding film by photographic exposure and development, and using it as a mask for pattern formation of the transparent film is considered. In this method, the black resin composition for the light-shielding film must not be corrosive to the transparent thin film formed in advance.
以往的遮光膜用黑色樹脂組成物，係以硬化性樹脂成分與遮光材成分為主體，在降低折射率為更高的遮光材濃度的同時，並且在透明基板上形成之遮光膜具有符合期望的遮光度(OD值)4以上的膜厚，可降低所形成的遮光膜與透明基板的界面的反射率。然而，欲利用光刻法形成圖案遮光膜為超過1.5μm的膜厚時，於曝光/顯像後的熱燒製過程中，在曝光過的部分有相對於膜厚方向的交聯密度的差，故在塗膜表面與透明基板附近於熱硬化收縮產生差異，造成塗膜表面粗糙度增大、表面平滑性劣化、表面產生皺褶的課題。另一方面，專利文獻3中，揭示了藉由使遮光膜組成物中共存有具有指定的平均一次粒徑範 圍的氧化矽粒子，即使在超過1.5μm厚膜的情況，仍可形成圖案的邊緣形狀的銳度良好的圖案，且即使在後續的熱燒製步驟中，塗膜表面平滑且不會因熱硬化收縮導致表面粗糙度劣化的技術，然而為得其效果，對於遮光材必需添加一定量以上的氧化矽。又，在專利文獻4揭示了包含有丙烯酸樹脂微粒子與碳黑的樹脂組成物的技術，惟此時，也為了使厚膜的圖案形狀安定化，對於遮光材必需添加一定以上的丙烯酸粒子。 The conventional black resin composition for light-shielding film is mainly based on curable resin components and light-shielding material components, while reducing the refractive index to a higher light-shielding material concentration, and the light-shielding film formed on a transparent substrate has a desirable The film thickness of the light shielding degree (OD value) 4 or more can reduce the reflectance of the interface between the light shielding film formed and the transparent substrate. However, when the patterned light-shielding film to be formed by photolithography has a film thickness of more than 1.5μm, during the thermal firing process after exposure/development, there is a difference in crosslinking density relative to the thickness direction of the exposed part Therefore, there is a difference in thermal curing shrinkage between the surface of the coating film and the vicinity of the transparent substrate, causing problems such as increased surface roughness of the coating film, deterioration of surface smoothness, and surface wrinkles. On the other hand, Patent Document 3 discloses that by coexisting a light-shielding film composition with a specified average primary particle size range The surrounding silicon oxide particles can form a pattern with good sharpness of the edge shape of the pattern even in the case of a thick film of more than 1.5μm, and even in the subsequent thermal firing step, the surface of the coating film is smooth and will not be affected by heat. It is a technology that deteriorates the surface roughness due to hardening shrinkage. However, in order to achieve its effect, it is necessary to add a certain amount of silicon oxide to the shading material. In addition, Patent Document 4 discloses a technique of a resin composition containing acrylic resin fine particles and carbon black. However, in this case, in order to stabilize the pattern shape of the thick film, it is necessary to add a certain amount of acrylic particles to the light-shielding material.
近年來，已提案利用噴墨法於透明基板上印刷直接硬化性樹脂組成物的方法(專利文獻5)。由於噴墨印刷法是形成直接印刷圖案，基本上不需有如光刻法等用於圖案形成的曝光/顯像步驟，只要檢討已考量可靠性的硬化物組成即可。只進行熱硬化時，與併用光硬化的情況相比，厚膜時會產生皺褶的疑慮更少，但另一方面，為了確保硬化遮光膜的可靠性(透明電極或配線等的圖案蝕刻時的耐藥品性)，必需使熱硬化反應的硬化劑及/或硬化促進劑共存，具表面活性的氧化矽粒子等的共存則有使熱硬化性樹脂組成物的保存安定性降低的疑慮。 In recent years, a method of printing a directly curable resin composition on a transparent substrate by an inkjet method has been proposed (Patent Document 5). Since the inkjet printing method forms a direct printing pattern, there is basically no need for exposure/development steps for pattern formation such as photolithography. It is only necessary to review the composition of the hardened product that has been considered for reliability. When only thermal curing is performed, there is less concern about wrinkles in thick film than when using light curing together. On the other hand, to ensure the reliability of the cured light-shielding film (when etching transparent electrodes or wiring patterns, etc.) It is necessary to coexist the curing agent and/or the curing accelerator of the thermosetting reaction. The coexistence of surface-active silicon oxide particles and the like may reduce the storage stability of the thermosetting resin composition.
[專利文獻1]日本特開平4-177202號公報 [Patent Document 1] Japanese Patent Application Laid-Open No. 4-177202
[專利文獻2]日本特開平8-278629號公報 [Patent Document 2] Japanese Patent Application Laid-Open No. 8-278629
[專利文獻3]日本特開2008-304583號公報 [Patent Document 3] JP 2008-304583 A
[專利文獻4]日本特開2010-256589號公報 [Patent Document 4] JP 2010-256589 A
[專利文獻5]WO2011/155446號公報 [Patent Document 5] WO2011/155446 Publication
[非專利文獻1]光學薄膜使用者手冊，James D. Rancourt著，小倉繁太郎譯，pp.10 [Non-Patent Document 1] Optical Film User Manual, written by James D. Rancourt, translated by Shigetaro Ogura, pp.10
本發明為有鑑於該技術的諸多缺點所創作者，其目的在於提供遮光膜用黑色樹脂組成物及該遮光膜，該遮光膜用黑色樹脂組成物為遮光性高的黑色遮光膜，且可形成使反射光降低至與彩色濾光片的彩色(著色)部分相等程度的遮光膜。更進一步，該遮光膜形成用黑色樹脂組成物之黏度安定性優異，且所形成的圖案遮光膜的表面平滑性優異。 The present invention was created in view of the many shortcomings of this technology, and its object is to provide a black resin composition for a light-shielding film and the light-shielding film. The black resin composition for a light-shielding film is a black light-shielding film with high light-shielding properties and can be formed A light-shielding film that reduces reflected light to the same degree as the color (coloring) portion of the color filter. Furthermore, the black resin composition for forming a light-shielding film is excellent in viscosity stability, and the surface smoothness of the formed pattern light-shielding film is excellent.
本發明人等，為了解決上述以往技術的問題點進行深入研究，結果發現，藉由添加與遮光膜用黑色樹脂組成物中的黑色遮光性粒子以及經由光或熱而硬化的樹脂相比折射率較低的透明粒子，可達成本案目的。 The inventors of the present invention conducted intensive studies in order to solve the above-mentioned problems of the prior art. As a result, they found that the addition of black light-shielding particles in a black resin composition for light-shielding films and a resin hardened by light or heat have a refractive index Lower transparent particles can reach the cost of the project.
亦即，本發明的要旨如以下所述。 That is, the gist of the present invention is as follows.
(1)一種遮光膜用黑色樹脂組成物，係以下列者作為必須成分：(A)會因為光或熱而硬化的硬化性樹脂、及/或會因為光或熱而硬化的硬化性單體；(B)在分散媒中分散黑色遮光性粒子而成的含有黑色遮光性粒子的分散液；以及(C) 在分散媒中分散透明粒子而成的含有透明粒子的分散液，其中，(C)成分中的透明粒子的平均二次粒徑DC與(B)成分中的黑色遮光性粒子的平均二次粒徑DB的比DC/DB為0.2至1.0的範圍，(C)成分中的透明粒子的質量mC與(B)成分的黑色遮光性粒子的質量mB的質量比mC/mB為0.015至0.20的範圍，並且前述透明粒子的折射率為前述(A)成分的硬化物的折射率以下。 (1) A black resin composition for a light-shielding film, which contains the following as essential components: (A) a curable resin that is cured by light or heat, and/or a curable monomer that is cured by light or heat (B) a dispersion liquid containing black light-shielding particles formed by dispersing black light-shielding particles in a dispersion medium; and (C) a dispersion liquid containing transparent particles formed by dispersing transparent particles in a dispersion medium, wherein (C ) of the transparent particles having an average secondary particle diameter of component D C and (B) than the average secondary particle diameter D C D B component of the light-shielding black particles / D B is the range of 0.2 to 1.0, (C) The mass ratio of the mass m C of the transparent particles in the component and the mass m B of the black light-shielding particles of the component (B) m C /m B is in the range of 0.015 to 0.20, and the refractive index of the transparent particles is the aforementioned (A) The refractive index of the cured product of the component is below.
(2)本發明亦為(1)的遮光膜用黑色樹脂組成物中，前述(C)成分中的透明粒子的折射率為1.55以下。 (2) In the black resin composition for a light-shielding film of this invention also (1), the refractive index of the transparent particle in the said (C) component is 1.55 or less.
(3)本發明亦為(1)或(2)的遮光膜用黑色樹脂組成物中，前述(B)成分中的黑色遮光性粒子為碳黑，並且前述(C)成分中的透明粒子為經由分子內具有反應性(甲基)丙烯醯基的矽烷耦合劑表面處理後的氧化矽。 (3) In the black resin composition for a light-shielding film according to the present invention (1) or (2), the black light-shielding particles in the component (B) are carbon black, and the transparent particles in the component (C) are Silicon oxide surface treated with a silane coupling agent with reactive (meth)acrylic groups in the molecule.
(4)本發明亦為(1)至(3)中任一項的遮光膜用黑色樹脂組成物中，前述(C)成分中的前述分散媒為具有(甲基)丙烯醯基的硬化性單體，並且前述透明粒子為經由分子內具有(甲基)丙烯醯基的矽烷耦合劑表面處理後的氧化矽。 (4) The present invention is also the black resin composition for a light-shielding film of any one of (1) to (3), wherein the dispersion medium in the component (C) is curable having a (meth)acryloyl group It is a monomer and the aforementioned transparent particles are silicon oxide surface-treated with a silane coupling agent having a (meth)acryloyl group in the molecule.
(5)本發明亦為(1)至(4)中任一項的遮光膜用黑色樹脂組成物中，經由光或熱硬化而得的遮光膜的遮光率OD為2.8/μm以上。 (5) In the black resin composition for a light-shielding film of any one of (1) to (4) in the present invention, the light-shielding film obtained by curing with light or heat has a light-shielding ratio OD of 2.8/μm or more.
(6)本發明亦為(1)至(5)中任一項的遮光膜用黑色樹脂組成物中，前述遮光膜用黑色樹脂組成物係包含(D)溶劑，以 作為前述(B)成分及(C)成分中的分散媒及/或作為追加成分，尚且該(D)溶劑包含沸點180℃以上的溶劑為主成分，藉此該遮光膜用黑色樹脂組成物係使用作為噴墨印刷用的遮光膜用黑色樹脂組成物。 (6) The present invention is also the black resin composition for light-shielding films of any one of (1) to (5), wherein the black resin composition for light-shielding films contains (D) a solvent, As a dispersion medium and/or as an additional component in the aforementioned (B) component and (C) component, and the (D) solvent contains a solvent with a boiling point of 180°C or higher as the main component, the black resin composition system for light-shielding film The black resin composition for a light-shielding film for inkjet printing is used.
(7)本發明亦為(1)至(5)中任一項的遮光膜用黑色樹脂組成物中，前述遮光膜用黑色樹脂組成物係藉由含有作為前述(A)成分的光硬化性鹼性可溶性樹脂及/或(E)鹼性可溶性樹脂，而使用作為光刻法用的遮光膜用黑色樹脂組成物。 (7) The present invention is also the black resin composition for a light-shielding film of any one of (1) to (5), wherein the black resin composition for a light-shielding film is formed by containing the photocuring property as the component (A) The alkaline soluble resin and/or (E) the alkaline soluble resin is used as a black resin composition for a light-shielding film for photolithography.
(8)本發明亦為一種附遮光膜基板，係(1)至(7)中任一項所述之遮光膜用黑色樹脂組成物塗佈或印刷於透明基板上的單面，再使其硬化而得的附遮光膜基板，且硬化後的遮光膜的膜厚為1至3μm。 (8) The present invention is also a substrate with a light-shielding film. The black resin composition for a light-shielding film described in any one of (1) to (7) is coated or printed on one side of a transparent substrate, and then made The cured substrate with a light-shielding film has a thickness of 1 to 3 μm.
(9)本發明亦為一種彩色濾光片，係具有(8之附遮光膜基板。 (9) The present invention is also a color filter, which has a substrate with a light-shielding film (8).
(10)本發明亦為一種觸控面板，係具有(8)之附遮光膜基板。 (10) The present invention is also a touch panel, which has the substrate with light-shielding film of (8).
根據本發明的遮光膜用黑色樹脂組成物，藉由添加相對於黑色遮光性粒子為較少量的相對於黑色遮光性粒子在分散媒中的平均二次粒徑為一定程度的平均二次粒徑的透明粒子，相較於未添加透明粒子的情況下，可使遮光膜的反射率降低。在此，作為透明粒子者，使用折射率較黑色遮光性粒子小的粒子為有效，特別是使用氧化 矽等無機粒子時，藉由進行特定的表面處理，在有機溶劑中或藉由光或熱硬化的硬化性單體中以具有期望的平均二次粒徑的方式，分散透明粒子為有效。藉由使用如此的遮光膜用黑色樹脂組成物，可提供具有高遮光率且外觀性亦優異的遮光膜作為彩色濾光片或觸控面板用的遮光膜。 According to the black resin composition for a light-shielding film of the present invention, by adding a relatively small amount of the black light-shielding particles with respect to the average secondary particle size of the black light-shielding particles in the dispersion medium, the average secondary particles Compared with the case where transparent particles are not added, the reflectance of the light shielding film can be reduced. Here, as transparent particles, it is effective to use particles with a lower refractive index than black light-shielding particles, especially oxidized particles. In the case of inorganic particles such as silicon, it is effective to disperse the transparent particles in an organic solvent or a curable monomer cured by light or heat to have a desired average secondary particle size by performing a specific surface treatment. By using such a black resin composition for a light-shielding film, a light-shielding film having a high light-shielding rate and excellent appearance can be provided as a light-shielding film for a color filter or a touch panel.
以下詳細說明本發明。 The present invention will be described in detail below.
本發明的遮光膜用黑色樹脂組成物中，作為(A)成分的會因為光或熱而硬化的硬化性樹脂及/或會因為光或熱而硬化的硬化性單體，宜使用分子內至少具有1個以上會因為光或熱而產生硬化反應的官能基，亦即(甲基)丙烯醯基、乙烯基等乙烯性不飽和雙鍵、或環氧基、氧雜環丁烷基等環狀反應性基的樹脂或單體。 In the black resin composition for light-shielding films of the present invention, as the component (A), the curable resin that is cured by light or heat and/or the curable monomer that is cured by light or heat, preferably at least It has one or more functional groups that can cause a hardening reaction due to light or heat, that is, ethylenically unsaturated double bonds such as (meth)acrylic groups and vinyl groups, or rings such as epoxy groups and oxetanyl groups. Resins or monomers like reactive groups.
作為前述的會因為光或熱而硬化的硬化性樹脂者，較佳為從丙烯酸、甲基丙烯酸、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯等丙烯酸烷基酯或甲基丙烯酸烷基酯(以下，有時將此等統合記載為「(甲基)丙烯酸烷基酯」等)、環狀的丙烯酸環己酯或甲基丙烯酸環己酯、丙烯酸羥基乙酯或甲基丙烯酸羥基乙酯、苯乙烯等之中使用3至5種類左右的單體進行合成之分子量為5000至100000左右的聚合物(丙烯酸系樹脂)並且在側鏈及/或尾端具有1個以上之 前述會因為熱或光而產生硬化反應的官能基者。例如，作為丙烯酸系樹脂的一部分經不飽和雙鍵加成而成的樹脂者，就耐熱性、顯像性等觀點而言，較佳為使用使在上述的丙烯酸系樹脂中具有羧基的單體共聚合後的樹脂，與具有異氰酸酯基與至少1個以上的乙烯性不飽和雙鍵的異氰酸酯丙烯酸酯、甲基丙烯醯基異氰酸酯等化合物反應而得的酸價50至150的感光性共聚物。 As the aforementioned curable resin that hardens by light or heat, it is preferably selected from acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, Alkyl acrylate such as butyl methacrylate or alkyl methacrylate (hereinafter, sometimes collectively referred to as "(meth)acrylate" etc.), cyclic cyclohexyl acrylate or methyl methacrylate Cyclohexyl acrylate, hydroxyethyl acrylate or hydroxyethyl methacrylate, styrene, etc., are synthesized using about 3 to 5 types of monomers (acrylic resin) with a molecular weight of about 5000 to 100000 and Have more than 1 in the side chain and/or tail The aforementioned functional groups that produce hardening reactions due to heat or light. For example, as a resin in which a part of acrylic resin is added with unsaturated double bonds, it is preferable to use a monomer having a carboxyl group in the above-mentioned acrylic resin in terms of heat resistance, developability, etc. The copolymerized resin is a photosensitive copolymer having an acid value of 50 to 150, which is obtained by reacting a compound having an isocyanate group and at least one ethylenically unsaturated double bond such as isocyanate acrylate or methacrylic isocyanate.
更且，適合使用使雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚醛清漆型環氧樹脂、多元羧酸化合物的聚縮水甘油酯、多元醇化合物的聚縮水甘油醚、脂肪族或脂環式環氧樹脂、縮水甘油胺型環氧樹脂、三苯酚甲烷型環氧樹脂、二羥基苯型環氧樹脂等的環氧樹脂與(甲基)丙烯酸反應所得的(甲基)丙烯酸環氧酯等通常的可光聚合的樹脂，再者，藉由使(甲基)丙烯酸環氧酯與酸酐反應，則亦適合使用作為可利用光刻法形成顯像圖案的樹脂組成物。 Furthermore, it is suitable to use bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, polyglycidyl ester of polycarboxylic acid compound, polyglycidyl ether of polyhydric alcohol compound, aliphatic Or (meth)acrylic acid obtained by reacting epoxy resins such as alicyclic epoxy resin, glycidylamine epoxy resin, triphenolmethane epoxy resin, dihydroxybenzene epoxy resin, and (meth)acrylic acid Common photopolymerizable resins such as epoxy esters can also be suitably used as a resin composition capable of forming a development pattern by photolithography by reacting epoxy (meth)acrylate with acid anhydride.
又，具有乙烯性不飽和雙鍵的聚合性單體，可列舉例如：(甲基)丙烯酸-2-羥基乙酯、(甲基)丙烯酸-2-羥基丙酯、(甲基)丙烯酸-2-羥基己酯等具有羥基的(甲基)丙烯酸酯類、或乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、四甲二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基乙烷三(甲基)丙烯酸酯、新戊四醇二(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新 戊四醇四(甲基)丙烯酸酯、二新戊四醇四(甲基)丙烯酸酯、甘油(甲基)丙烯酸酯、山梨糖醇五(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、或二新戊四醇六(甲基)丙烯酸酯、山梨糖醇六(甲基)丙烯酸酯、磷腈(phosphazene)的聚(環氧烷)改質六(甲基)丙烯酸酯、己內酯改質二新戊四醇六(甲基)丙烯酸酯等(甲基)丙烯酸酯類。 In addition, the polymerizable monomer having an ethylenically unsaturated double bond includes, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid-2 -(Meth)acrylates having hydroxyl groups such as hydroxyhexyl ester, or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylic acid Ester, tetraethylene glycol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth) Acrylate, neopentyl erythritol di (meth) acrylate, neopentyl erythritol tri (meth) acrylate, new Pentaerythritol tetra(meth)acrylate, dineopentaerythritol tetra(meth)acrylate, glycerol (meth)acrylate, sorbitol penta(meth)acrylate, dineopentaerythritol penta(meth)acrylate Meth) acrylate, or dineopentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene poly(alkylene oxide) modified hexa(meth) Acrylate and caprolactone are used to modify (meth)acrylates such as dineopentaerythritol hexa(meth)acrylate.
分子內具有至少1個以上環氧基、氧雜環丁烷基等環狀反應性基的具體例，可列舉：雙酚A型環氧化合物、雙酚F型環氧化合物、雙酚茀型環氧化合物、苯酚酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物、多元醇的縮水甘油醚、多元羧酸的縮水甘油酯、含有(甲基)丙烯酸縮水甘油酯為單元的聚合物、以3,4-環氧基環己烷羧酸(3’,4’-環氧基環己基)甲酯為代表的脂環式環氧化合物、具有二環戊二烯骨架的多官能環氧化合物(例如DIC公司製HP7200系列)、2,2-雙(羥基甲基)-1-丁醇的1,2-環氧基-4-(2-環氧乙烷基)環己烷加成物(例如Daicel公司製「EHPE3150」)、環氧化聚丁二烯(例如日本曹達公司製「nisso-pb．jp-100」)、具有聚矽氧骨架的環氧化合物等。該等會因為光或熱而硬化的硬化性樹脂或單體可單獨使用或混合複數種，藉此可賦予可靠性等特性。 Specific examples of having at least one cyclic reactive group such as epoxy group and oxetanyl group in the molecule include: bisphenol A type epoxy compound, bisphenol F type epoxy compound, and bisphenol pyridine type Epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, glycidyl ethers of polyhydric alcohols, glycidyl esters of polycarboxylic acids, polymers containing glycidyl (meth)acrylate as units , Alicyclic epoxy compounds represented by 3,4-epoxycyclohexanecarboxylic acid (3',4'-epoxycyclohexyl) methyl ester, and a multifunctional ring with a dicyclopentadiene skeleton Oxygen compounds (such as HP7200 series manufactured by DIC), 1,2-epoxy-4-(2-oxiranyl) cyclohexane of 2,2-bis(hydroxymethyl)-1-butanol Finished products (for example, "EHPE3150" manufactured by Daicel), epoxidized polybutadiene (for example, "nisso-pb.jp-100" manufactured by Nippon Soda), epoxy compounds having a polysiloxane skeleton, and the like. These curable resins or monomers that harden by light or heat can be used alone or in a mixture of plural kinds, thereby imparting characteristics such as reliability.
更且，通常較佳係將該等樹脂或單體與會因為光或熱進行反應的化合物，例如具有羧基、胺基、羥基、巰基的化合物，以及會因為紫外線或熱產生自由基、陽離子、陰離子等的光聚合起始劑、熱聚合起始劑等共存 而使用。 Furthermore, it is generally preferable to use these resins or monomers with compounds that react with light or heat, such as compounds with carboxyl, amine, hydroxyl, and sulfhydryl groups, and generate free radicals, cations, and anions due to ultraviolet rays or heat. Coexistence of photopolymerization initiators, thermal polymerization initiators, etc. And use.
針對所列示的(A)成分，較佳係選擇其硬化物的折射率達指定的1.48至1.6的範圍者。例如，為丙烯酸樹脂系硬化物時，其折射率為1.48至1.55，藉由使化學構造中含有芳香族基，例如藉由與苯乙烯單體的共聚合，可調整折射率。環氧樹脂系時為1.50至1.60，使用雙酚系環氧樹脂或芳香族酸酐硬化劑時，折射率變高，當使用脂肪族環氧樹脂、脂環式環氧樹脂或脂環式酸酐硬化劑時，折射率變得較低。 Regarding the listed component (A), it is preferable to select a cured product whose refractive index reaches the specified range of 1.48 to 1.6. For example, in the case of an acrylic resin-based cured product, the refractive index is 1.48 to 1.55. The refractive index can be adjusted by including an aromatic group in the chemical structure, for example, by copolymerization with a styrene monomer. It is 1.50 to 1.60 for epoxy resin. When bisphenol epoxy resin or aromatic acid anhydride hardener is used, the refractive index becomes higher. When aliphatic epoxy resin, alicyclic epoxy resin or alicyclic acid anhydride is used for hardening The refractive index becomes lower when it is added.
(B)成分中的黑色遮光性粒子，從目標薄膜中的遮光率及遮光膜用組成物的保存安定性的觀點而言，係使用折射率超過1.6，吸收可見光的黑色顏料作為主體而使用。本發明所使用的黑色顏料，較佳為碳黑。碳黑可使用燈黑、乙炔黑、熱碳黑、槽黑、爐黑等之任一種。就調整其他黑色染料等的遮光性為目的，可將1種或複數種混合使用，惟黑色遮光性粒子在全遮光材中較佳為60質量%以上。例如，有機顏料系/染料系的遮光材使用過多時，遮光率降低。 (B) The black light-shielding particles in the component are mainly used as black pigments that have a refractive index exceeding 1.6 and absorb visible light from the viewpoint of the light-shielding rate in the target film and the storage stability of the light-shielding film composition. The black pigment used in the present invention is preferably carbon black. As the carbon black, any of lamp black, acetylene black, thermal carbon black, channel black, furnace black, etc. can be used. For the purpose of adjusting the light-shielding properties of other black dyes and the like, one type or a plurality of types may be mixed and used, but the black light-shielding particles are preferably 60% by mass or more in the total light-shielding material. For example, when an organic pigment-based/dye-based light-shielding material is used too much, the light-shielding rate decreases.
將該等遮光材與例如高分子分散劑或溶劑等分散媒一起在珠磨機中分散，形成含有黑色遮光性粒子的分散液，藉由與前述(A)成分及後述的(C)成分混合，調製出本案目標的遮光膜用黑色樹脂組成物。分散液中的黑色遮光性粒子的平均二次粒徑DB，較佳係調製成60nm至150nm，更佳為調製成80nm至120nm。於本發明中，所謂 「平均二次粒徑」是指以分散溶媒或相當的溶劑稀釋，以動態光散射法測定，並利用累積量法所求得的平均粒徑值。例如，碳黑為以PGMEA溶劑中0.1質量%粒子濃度所測定的值。平均二次粒徑DB未達60nm時，為了達成高遮光率而提高黑色遮光性粒子的濃度時，所需的高分子分散劑的添加量會增加，並且保存時容易發生黏度增加。平均二次粒徑DB超過150nm時，所形成的遮光膜的表面平滑性不佳，且由光刻法形成時的圖案邊緣的直線性受損。 These light-shielding materials are dispersed in a bead mill together with a dispersion medium such as a polymer dispersant or a solvent to form a dispersion liquid containing black light-shielding particles, by mixing with the aforementioned (A) component and the later-described (C) component , To prepare the black resin composition for the light-shielding film targeted by this project. The average secondary particle diameter D B of the black light shielding dispersion particles, the preferred system to prepare a 60nm 150nm, more preferably 80nm to prepare a 120nm. In the present invention, the "average secondary particle size" refers to the average particle size value obtained by diluting with a dispersion solvent or an equivalent solvent, measuring by dynamic light scattering method, and using cumulant method. For example, carbon black is a value measured with a particle concentration of 0.1% by mass in the PGMEA solvent. When the average secondary particle diameter D B is less than 60 nm, when the concentration of black light-shielding particles is increased in order to achieve a high light-shielding ratio, the amount of polymer dispersant required to be added increases, and the viscosity is likely to increase during storage. When the average secondary particle diameter D B exceeds 150nm, the surface smoothness of the formed light-shielding film is poor, and the linearity is impaired when the pattern edge is formed by photolithography.
順帶一提，觸控面板用遮光膜及彩色濾光片用黑色矩陣中的遮光度(OD=-log[穿透度])要求為OD4以上，另一方面，膜厚要求為3μm以下，較佳為2μm以下的薄膜化。其理由是，在觸控面板的情形中，為了防止在遮光膜上的金屬配線與觸控面板上導電膜的連接時之斷線之故，在彩色濾光片的情形中，為了確保於黑色矩陣上形成RGB畫素後的平坦性之故。以即使為如此薄的遮光膜仍得到高遮光度為目的，例如將碳黑設為在組成物中相對於全固形份為35質量%以上70質量%以下。 By the way, the shading degree (OD=-log[transmittance]) in the black matrix for the light-shielding film for touch panels and the black matrix for color filters is required to be OD4 or more. On the other hand, the film thickness is required to be 3μm or less. It is preferably thinner than 2 μm. The reason is that in the case of a touch panel, in order to prevent disconnection of the metal wiring on the light shielding film and the conductive film on the touch panel, in order to ensure that the color filter Because of the flatness after RGB pixels are formed on the matrix. For the purpose of obtaining a high light shielding degree even with such a thin light shielding film, for example, carbon black is set to be 35% by mass or more and 70% by mass or less with respect to the total solid content in the composition.
另一方面，將組成物的全固形份(硬化後殘存於基板上的總成分)中的黑色遮光性粒子的濃度調高時，有形成於透明基板上的遮光膜與透明基板之間的反射增加、遮光膜上的反光、或因與彩色濾光片著色部的反射率的差異使邊界變明顯的課題存在。亦即，不含後述的(C)成分，只有硬化樹脂成分(A)與遮光材成分(B)時，所硬化/形成的遮光膜中的遮光膜與透明基板之間的反射率，主要 取決於(A)成分與(B)成分中的黑色遮光性粒子的質量比，若質量比率為一定，即使將遮光膜的膜厚增厚，反射率也不會顯著降低。 On the other hand, when the concentration of black light-shielding particles in the total solid content (total components remaining on the substrate after curing) of the composition is increased, there is reflection between the light-shielding film formed on the transparent substrate and the transparent substrate There is a problem of increased, light reflection on the light-shielding film, or the difference in reflectance from the colored part of the color filter, which makes the boundary obvious. That is, when the component (C) described later is not included and only the cured resin component (A) and the light-shielding material component (B) are used, the reflectance between the light-shielding film and the transparent substrate in the light-shielding film that is cured/formed is mainly Depending on the mass ratio of the black light-shielding particles in the component (A) and the component (B), if the mass ratio is constant, even if the thickness of the light-shielding film is increased, the reflectance does not significantly decrease.
有鑑於如上述的事實，本發明人等發現藉由使具有折射率為(A)成分的硬化物的折射率以下的透明粒子共存於(A)成分的硬化物中，將組成物的全固形份中的黑色遮光性粒子的濃度設為相同的同時(維持遮光度的同時)，可降低反射率。亦即，本發明中以具有折射率為(A)成分的硬化物的折射率以下透明粒子作為必須成分〔以分散於分散媒的狀態作為(C)成分使用〕，透明粒子可列示公知的氧化矽等金屬氧化物等無機系透明微粒子；丙烯酸樹脂、苯乙烯-丙烯酸樹脂、聚矽氧樹脂、環氧樹脂或三聚氰胺樹脂等樹脂系透明微粒子。由於樹脂製的透明微粒子在本發明的組成物中有作為分散於有機溶劑的分散溶液供應之情形，故較佳係由不溶於有機溶劑的交聯樹脂所構成。 In view of the above facts, the inventors of the present invention found that by coexisting transparent particles having a refractive index equal to or lower than that of the cured product of component (A) in the cured product of component (A), the complete solidification of the composition When the concentration of the black light-shielding particles in the composition is the same (while maintaining the light-shielding degree), the reflectance can be reduced. That is, in the present invention, transparent particles having a refractive index equal to or lower than the refractive index of the cured product of component (A) are used as an essential component [used as component (C) in a state dispersed in a dispersion medium], and the transparent particles can be listed Inorganic transparent particles such as metal oxides such as silicon oxide; resin-based transparent particles such as acrylic resin, styrene-acrylic resin, silicone resin, epoxy resin, or melamine resin. Since resin-made transparent fine particles may be supplied as a dispersion solution dispersed in an organic solvent in the composition of the present invention, they are preferably composed of a crosslinked resin that is insoluble in an organic solvent.
作為(A)成分被含有、成為(B)成分中的黑色遮光性粒子或(C)成分中的透明粒子的基材的藉由光或熱使硬化樹脂及/或硬化性單體硬化而成的(A)成分的硬化物，其折射率取決於化學構造，較佳為1.48至1.6的範圍。因此，構成(C)成分的透明粒子的成分的折射率為(A)成分的硬化物的折射率以下，較佳為1.40至1.60的範圍，更佳為1.42至1.55。此外，於本發明中，所謂「(A)成分的硬化物的折射率」是指從本發明的遮光膜用黑色樹脂組成物中扣除(B)成分中的黑色遮光性粒子及(C)成分中的透明粒 子或在硬化過程中被去除的溶劑等之後，使遮光膜的塗膜形成成分硬化而成的硬化物的折射率，當為了藉由光或熱使(A)成分硬化而共存有硬化劑或聚合起始劑等時，則為包含有該等的硬化物的折射率。(C)成分中的透明粒子的折射率超過前述「(A)成分的硬化物的折射率」時，反射率的降低效果消失。作為公知的透明粒子使用的成分的折射率，氧化矽為1.44至1.50、丙烯酸樹脂系或環氧樹脂系為1.47至1.60、聚矽氧樹脂系為1.40至1.45。該等可單獨亦可2種類以上使用。此外，透明粒子的透明性以全光線穿透率計為10%以上，只要透明性的光波長依存性有助於遮光膜的無彩色化，亦可進行著色使用。 As a base material that contains the (A) component and becomes the black light-shielding particles in the (B) component or the transparent particles in the (C) component, it is made by curing a hardening resin and/or a curable monomer by light or heat The refractive index of the cured product of component (A) depends on the chemical structure, and is preferably in the range of 1.48 to 1.6. Therefore, the refractive index of the components constituting the transparent particles of the component (C) is equal to or less than the refractive index of the cured product of the component (A), preferably in the range of 1.40 to 1.60, more preferably 1.42 to 1.55. In addition, in the present invention, the "refractive index of the cured product of (A) component" means that the black light-shielding particles and (C) component in the (B) component are subtracted from the black resin composition for light-shielding films of the present invention Transparent particles The refractive index of the cured product formed by curing the coating film-forming component of the light-shielding film after the solvent or the solvent removed during the curing process, when the curing agent or the curing agent or In the case of a polymerization initiator, etc., it is the refractive index of the cured product containing these. When the refractive index of the transparent particles in the component (C) exceeds the aforementioned "refractive index of the cured product of the component (A)", the effect of reducing the reflectance disappears. The refractive index of the components used for the known transparent particles is 1.44 to 1.50 for silicon oxide, 1.47 to 1.60 for acrylic resin or epoxy resin, and 1.40 to 1.45 for silicone resin. These can be used individually or in 2 or more types. In addition, the transparency of the transparent particles is 10% or more in terms of total light transmittance, and as long as the light wavelength dependence of the transparency contributes to the achromatization of the light-shielding film, they can also be used for coloring.
更且，(C)成分中的透明粒子，其平均二次粒徑DC與(B)成分中的黑色遮光性粒子的平均二次粒徑DB的比DC/DB為0.2至1.0的範圍，並且在前述組成物中的(C)成分中的透明粒子的質量mC與(B)成分中的黑色遮光性粒子的質量mB的比mC/mB為0.015至0.20，較佳為0.03至0.10，更佳為0.03至0.09的範圍內使用。平均二次粒徑DC係以分散溶媒或相當的溶劑稀釋後，以動態光散射法測定，並利用累積量法求得的平均粒徑的值。例如，氧化矽粒子為在甲醇中1至10質量%粒子濃度的測定值。平均二次粒徑比DC/DB超過1.0時，所形成的遮光膜表面的平滑性不佳，且遮光率(OD/μm)降低，又，DC/DB低於0.2時，所形成的遮光膜的反射率降低效果減弱。組成物中的質量比mC/mB低於0.015時，所形成的遮光膜的反射率的降低效果 消失，且超過0.20時，遮光膜的遮光率(OD/μm)降低。此外，特別是因應增加遮光率(OD/μm)而大量使用(B)成分時，由於(A)的藉由光或熱硬化的成分的構成比率減少，容易發生基材的硬化物性未達到期望的程度，或以光刻法進行的圖案形成不夠充分的問題，因此本發明中，即使(C)成分中的透明粒子的添加量減少，仍可降低反射率，而非常有用。 More and transparent particles (C) component, the average secondary particle diameter D C and (B) than the average secondary particle diameter D C D B component of the light-shielding black particles / D B is from 0.2 to 1.0 range, transparent particles and component (C) in the composition of the mass m C and (B) mass m B of the component in the black shading particles than m C / m B is from 0.015 to 0.20, more It is preferably 0.03 to 0.10, and more preferably used in the range of 0.03 to 0.09. The average secondary particle diameter D C to the solvent-based or solvent-dispersed dilution equivalent to a dynamic light scattering method, using the determined value of the average particle diameter of cumulant method. For example, the silica particles are measured values of the particle concentration of 1 to 10% by mass in methanol. When the average secondary particle size ratio D C /D B exceeds 1.0, the smoothness of the formed light-shielding film surface is not good, and the light-shielding ratio (OD/μm) decreases. In addition, when D C /D B is less than 0.2, The formed light-shielding film has a reduced reflectivity reduction effect. When the mass ratio m C /m B in the composition is less than 0.015, the effect of reducing the reflectance of the formed light-shielding film disappears, and when it exceeds 0.20, the light-shielding ratio (OD/μm) of the light-shielding film decreases. In addition, especially when the component (B) is used in a large amount in order to increase the light-shielding ratio (OD/μm), the composition ratio of the component (A) that is cured by light or heat decreases, and the hardened physical properties of the substrate are likely to fail to meet expectations. Therefore, in the present invention, even if the addition amount of the transparent particles in the component (C) is reduced, the reflectance can be reduced, which is very useful.
以硬化本組成物而成的遮光膜所構成的附遮光膜基板中，所顯現的反射降低效果的機制，係推測如下述。亦即，遮光膜係將包含溶劑的遮光性樹脂組成物塗佈於透明基板上的單面，乾燥後使其硬化作成遮光膜。乾燥後的塗膜沒有不均勻且表面為平滑時，在塗膜內部屬於低黏性體的(A)成分成為基材，屬於彈性體的(B)成分中的黑色遮光性粒子成為分散於(A)成分的形態。於乾燥過程中，塗膜內隨著溶劑揮發，會往膜厚方向產生體積收縮，但因排除分散的粒子間的溶劑而縮短粒子間距離。於透明基板與所塗佈的組成物的界面亦相同。此時的硬化性樹脂及單體成分，相較於屬於彈性體的黑色遮光性粒子為屬於黏性高的黏性體，故在分散的粒子間變形/收縮，最終藉由硬化而固定化黑色遮光性粒子的位置。自如此的附遮光膜基板的透明基板側入射的光的一部分，係完全在透明基板界面與其附近的遮光膜內藉由黑色遮光性粒子〔碳黑的折射率約為2且充分高於(A)成分的硬化物的折射率〕進行反射及散射而從透明基板側射出。因此，增加組成物中的黑 色遮光性粒子濃度時，由該黑色遮光性粒子導致的反射/散乱會增加。另一方面，認為共存有透明粒子時，與黑色遮光性粒子具有相同彈性的透明粒子，係相較於(A)成分不會變形而是存在於黑色遮光性粒子間及透明基板與黑色遮光性粒子之間。因此，推定藉由較黑色遮光性粒子折射率為低的透明粒子產生的反射/散射變少，且入射於存在於透明基板界面的透明粒子的光會再被周邊的黑色遮光性粒子吸收，此吸收對具某種程度厚的膜厚者為有效。 The mechanism of the reflection reduction effect exhibited in a substrate with a light-shielding film composed of a light-shielding film formed by curing the composition is estimated as follows. That is, the light-shielding film is a light-shielding film by coating a light-shielding resin composition containing a solvent on one side of a transparent substrate, and after drying, it is hardened to form a light-shielding film. When the coating film after drying is not uneven and the surface is smooth, the low-viscosity component (A) inside the coating film becomes the base material, and the black light-shielding particles in the elastomer component (B) become dispersed in ( A) The form of the ingredients. During the drying process, as the solvent volatilizes in the coating film, the volume shrinks in the thickness direction of the film, but the distance between the particles is shortened due to the elimination of the solvent between the dispersed particles. The same applies to the interface between the transparent substrate and the applied composition. The curable resin and monomer components at this time are a viscous body with a higher viscosity than the black light-shielding particles which are elastomers. Therefore, they deform/shrink between the dispersed particles and finally fix the black by curing. The position of the light-shielding particles. A part of the light incident from the transparent substrate side of such a light-shielding film substrate is completely in the transparent substrate interface and the light-shielding film nearby by black light-shielding particles (the refractive index of carbon black is about 2 and sufficiently higher than (A ) The refractive index of the cured product of the component] reflects and scatters and exits from the transparent substrate side. Therefore, increase the black in the composition At the time of the concentration of the color light-shielding particles, the reflection/scattering caused by the black light-shielding particles will increase. On the other hand, when transparent particles coexist, transparent particles with the same elasticity as black light-shielding particles are not deformed compared to component (A) but exist between black light-shielding particles and between transparent substrate and black light-shielding particles. Between particles. Therefore, it is estimated that the reflection/scattering caused by the transparent particles with a lower refractive index than the black light-shielding particles is reduced, and the light incident on the transparent particles existing at the interface of the transparent substrate will be absorbed by the surrounding black light-shielding particles. Absorption is effective for those with a certain degree of thick film thickness.
為使上述的反射率降低的機制有效發揮，據信：在組成物中以及在塗佈於透明基板上而成的膜中，均必須以不會自主凝集之方式，使透明粒子與黑色遮光性粒子一起安定地分散。因此，作為有效使黑色遮光性粒子及透明粒子的分散安定性提升的手段，認為組成物的黏度安定性為其指標。本發明所使用的(C)成分中的透明粒子藉由進行粒子表面處理，有助於抑制其再凝集。 In order to make the above-mentioned reflectance reduction mechanism effective, it is believed that both the composition and the film coated on a transparent substrate must be made so that the transparent particles and black light-shielding properties are not automatically agglomerated. The particles are dispersed stably together. Therefore, as a means for effectively improving the dispersion stability of black light-shielding particles and transparent particles, the viscosity stability of the composition is considered as an index. The transparent particles in the component (C) used in the present invention contribute to the suppression of re-aggregation by performing particle surface treatment.
例如，作為本發明的(C)成分中的透明粒子使用的氧化矽，較佳係經分子內具有反應性(甲基)丙烯醯基的矽烷耦合劑表面處理過的氧化矽，經膠狀氧化矽表面處理的氧化矽係由日本特開昭57-131214號公報、日本特開2000-289172號公報等記載的周知手段所調製。該等經表面處理的氧化矽可以高分子分散劑共存且相對安定地分散於單烷基醚、單烷基醚乙酸酯等溶劑中，而適合作為分散液〔(C)成分〕供應於本遮光膜用黑色樹脂組成物。更且，即使在前述的具有乙烯性不飽和基的(甲基)丙烯酸酯等硬 化性單體中，仍同樣可相對容易進行經表面處理過的氧化矽的分散，不只溶劑，亦可以藉由光或熱硬化的硬化性單體中分散有透明粒子的形態作為(C)成分。又，在溶劑與硬化性單體的混合物中，亦可再分散於溶解硬化性樹脂的溶液中而使用。使用於該表面處理過的氧化矽的氧化矽粒子，係由一般的氣相反應或液相反應之類的製造法所製造，且不侷限於形狀(球狀、非球狀)，惟利用電子顯微鏡觀察時的其一次粒徑為20至40nm。採用該等氧化矽粒子經公知的方法表面處理，再將表面處理過的氧化矽在有機溶劑中利用珠磨機分散後的分散液在甲醇中稀釋至1至10wt%所成的樣本，經動態光散射法測定再利用累積量法求得的平均二次粒徑為30至100nm、較佳為30至60nm者，係相對容易製造，而可作為本發明的(C)成分中的透明粒子予以調配。 For example, the silica used as the transparent particles in the component (C) of the present invention is preferably silica that has been surface-treated with a silane coupling agent having a reactive (meth)acryloyl group in the molecule, and is colloidally oxidized. The silicon surface-treated silicon oxide is prepared by well-known methods described in Japanese Patent Laid-Open No. 57-131214 and 2000-289172. These surface-treated silicas can coexist with a polymer dispersant and be relatively stably dispersed in solvents such as monoalkyl ether, monoalkyl ether acetate, etc., and are suitable for supply as a dispersion [(C) component] in this Black resin composition for light-shielding film. Moreover, even in the aforementioned hard (meth)acrylates such as ethylenically unsaturated group In the chemical monomer, it is still relatively easy to disperse the surface-treated silicon oxide. Not only the solvent, but also the form of transparent particles dispersed in the curable monomer cured by light or heat as the (C) component . In addition, in a mixture of a solvent and a curable monomer, it may be redispersed in a solution in which the curable resin is dissolved and used. The silicon oxide particles used in the surface-treated silicon oxide are manufactured by a general gas-phase reaction or liquid-phase reaction and other manufacturing methods, and are not limited to shapes (spherical, non-spherical), but use electrons The primary particle size when observed under a microscope is 20 to 40 nm. The silica particles are surface-treated by a known method, and then the surface-treated silica particles are dispersed in an organic solvent by a bead mill and diluted to 1 to 10wt% in methanol. The average secondary particle diameter determined by the light scattering method and the cumulant method is 30 to 100 nm, preferably 30 to 60 nm, which is relatively easy to manufacture and can be used as the transparent particles in the component (C) of the present invention Deployment.
另一方面，為了有效發揮遮光性並確保分散安定性，黑色遮光性粒子的碳黑的平均二次粒徑DB，如前述為60nm至150nm，較佳為80至120nm。因此，表面處理氧化矽的平均二次粒徑為碳黑的平均二次粒徑以下是相較容易的方法。 On the other hand, in order to effectively exert the light-shielding properties and ensure dispersion stability, the average secondary particle diameter D B of the carbon black of the black light-shielding particles is 60 nm to 150 nm, preferably 80 to 120 nm as described above. Therefore, it is relatively easy for the average secondary particle size of surface-treated silica to be equal to or less than that of carbon black.
再者，(C)成分中的透明粒子較佳為丙烯酸樹脂粒子，丙烯酸樹脂粒子不侷限於製造法或形狀(球狀、非球狀、單核構造、內核-外殼構造等)，惟就凝集性少且分散性優異者而言，可利用日本Paint製交聯丙烯酸微粒子Fine sphere系列、日本特開2010-256589號公報記載的 丙烯酸微粒子等。 Furthermore, the transparent particles in the component (C) are preferably acrylic resin particles. The acrylic resin particles are not limited to the manufacturing method or shape (spherical, non-spherical, mono-core structure, core-shell structure, etc.), but aggregate For those with low performance and excellent dispersibility, the Fine sphere series of cross-linked acrylic particles manufactured by Japan Paint, as described in JP 2010-256589 A Acrylic particles, etc.
以溶解或分散本發明的必須成分為目的，可含有1種或複數種類的溶劑，且無特別限定。可列舉例如：甲醇、乙醇、正丙醇、異丙醇、乙二醇、丙二醇等醇類、α-或β-萜品醇等萜烯類等；丙酮、甲基乙基酮、環己酮、N-甲基-2-吡咯烷酮等酮類；甲苯、二甲苯、四甲苯等芳香族烴類；賽珞蘇、甲基賽珞蘇、乙基賽珞蘇、卡必醇、甲基卡必醇、乙基卡必醇、丁基卡必醇、丙二醇單甲基醚、丙二醇單乙基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、二乙二醇二甲基醚、二乙二醇乙基甲基醚、二乙二醇二乙基醚等二醇醚類；乙酸乙酯、乙酸丁酯、賽珞蘇乙酸酯、乙基賽珞蘇乙酸酯、丁基賽珞蘇乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯等乙酸酯類等，藉由使用該等數種類進行溶解、混合，可形成安定地分散有黑色遮光性粒子或透明粒子等的均勻組成物。 For the purpose of dissolving or dispersing the essential components of the present invention, one or more kinds of solvents may be contained, and they are not particularly limited. Examples include: methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol and other alcohols, α- or β-terpineol and other terpenes; acetone, methyl ethyl ketone, cyclohexanone , N-methyl-2-pyrrolidone and other ketones; toluene, xylene, tetramethylbenzene and other aromatic hydrocarbons; serosol, methyl serosol, ethyl serosol, carbitol, methyl carbitol Alcohol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, three Glycol ethers such as ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether; ethyl acetate, butyl acetate, Acetic acid esters such as loxo acetate, ethyl serosol acetate, butyl serosol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc., by using These several types are dissolved and mixed to form a uniform composition in which black light-shielding particles or transparent particles are stably dispersed.
又，於本發明的遮光膜用黑色樹脂組成物中，視需要可調配硬化促進劑、熱聚合抑制劑、抗氧化劑、可塑劑、調平劑、消泡劑、耦合劑、界面活性劑等添加劑。熱聚合抑制劑可列舉氫醌、氫醌單甲基醚、連苯三酚、第三丁基苯二酚、酚噻
將遮光膜用黑色樹脂組成物塗佈於透明基板上的方法，除了公知的溶液浸漬法、噴霧法以外，尚可採用使用噴墨機、捲筒式塗佈機、背緣塗佈機(land coater)、狹縫式塗佈機或旋床機的方法等之中任一種方法。為了得到良好的塗佈膜藉由調整溶劑至合適黏度，利用該等的方法，塗佈成期望的厚度之後，在加熱或減壓下去除溶劑(預烘)，藉此形成乾燥塗膜。接著藉由光及/或熱進行硬化而製作目的的附遮光膜基板。 In addition to the well-known solution dipping method and spray method, the black resin composition for the light-shielding film can be coated on the transparent substrate. In addition to the well-known solution immersion method and spray method, it is also possible to use inkjet machines, roll coaters, and back edge coaters. coater), slot coater or lathe machine method. In order to obtain a good coating film by adjusting the solvent to a suitable viscosity, using these methods, after coating to a desired thickness, the solvent is removed under heating or reduced pressure (pre-baking), thereby forming a dry coating film. Then, it is hardened by light and/or heat to produce a target substrate with a light-shielding film.
前述的使遮光膜用黑色樹脂組成物藉由光或熱所硬化而得的本發明中的遮光膜，其遮光率OD較佳為達2.8/μm以上，較佳為使用如具有如此特性的遮光膜用樹脂組成物。觸控面板用遮光膜以及彩色濾光片用黑色矩陣中的遮光度(OD=-log[穿透度])要求為OD4以上，另一方面，膜厚較佳為3μm以下，更佳為2μm以下的薄膜。其理由為，在觸控面板的情形中，為了防止在遮光膜上的金屬配線與觸控面板上導電膜的連接時之斷線之故，在彩色濾光片的情形中，為了確保於黑色矩陣上形成RGB畫素後的平坦性之故。以即使為如此薄的遮光膜也得到高遮光度為目的，例如將碳黑設成在組成物中相對於全固形份為35質量%以上，便可調製遮光度2.8/μm以上的遮光膜。另一方面，OD/μm為未達2.8的遮光膜時，在透明基板與遮光膜之間反射L*成為5.5以下，實質上不成問題。 The light-shielding film of the present invention obtained by curing the black resin composition for light-shielding film by light or heat preferably has a light-shielding ratio OD of 2.8/μm or more, and it is preferable to use a light-shielding film having such characteristics Resin composition for film. The light-shielding film for touch panels and the black matrix for color filters must have a light-shielding degree (OD=-log[transmittance]) of OD4 or more. On the other hand, the film thickness is preferably 3μm or less, more preferably 2μm The following film. The reason is that in the case of a touch panel, in order to prevent disconnection of the metal wiring on the light shielding film and the conductive film on the touch panel, in order to ensure that the color filter is black Because of the flatness after RGB pixels are formed on the matrix. For the purpose of obtaining high light-shielding even with such a thin light-shielding film, for example, by setting carbon black to be 35% by mass or more with respect to the total solid content in the composition, a light-shielding film with a light-shielding degree of 2.8/μm or more can be prepared. On the other hand, when the OD/μm is a light-shielding film of less than 2.8, the reflection L* between the transparent substrate and the light-shielding film becomes 5.5 or less, which is substantially no problem.
於透明基板上形成遮光膜圖案的方法係有 光刻法，其係將本發明的遮光膜用黑色樹脂組成物塗佈於透明基板上，透過光罩向已乾燥的塗膜照射紫外線，將未曝光部分利用顯像液去除，再進行加熱處理。又，係有網版印刷法、凹版印刷、凹版印刷法等使用轉印版進行印刷的方法等，甚至近年來，噴墨印刷法係以不需要遮罩或印刷版的數位印刷方法受到矚目。本發明的遮光膜用黑色樹脂組成物可適用於任一種遮光膜圖案形成方法，為了形成具有適合各種方法的黏度、表面張力的樹脂組成物，選定硬化性樹脂樹/硬化性單體(單體)、以及溶劑或界面活性劑脂組成物。又，依據遮光膜圖案的精度或解像度等來選定形成方法、印刷機等。特別是本發明的遮光膜用黑色樹脂組成物中黑色遮光性粒子或透明粒子係安定地分散，不會發生由於分散粒子的凝集造成的粗大粒子，且保存時的黏度安定性優異，故可特別適合使用在噴墨印刷法或光刻法。 The method of forming a light-shielding film pattern on a transparent substrate includes Photolithography is a method of coating the black resin composition for a light-shielding film of the present invention on a transparent substrate, irradiating ultraviolet rays to the dried coating film through a photomask, removing the unexposed parts with a developer solution, and then performing heat treatment . In addition, there are methods such as screen printing, gravure printing, and gravure printing using transfer plates. In recent years, inkjet printing methods have attracted attention as digital printing methods that do not require masks or printing plates. The black resin composition for a light-shielding film of the present invention can be applied to any method for forming a pattern of a light-shielding film. In order to form a resin composition having a viscosity and surface tension suitable for various methods, a curable resin tree/curable monomer (monomer) is selected. ), and solvent or surfactant lipid composition. In addition, the forming method, printer, etc. are selected based on the accuracy and resolution of the light-shielding film pattern. In particular, the black light-shielding particles or transparent particles in the black resin composition for light-shielding films of the present invention are stably dispersed, and no coarse particles caused by aggregation of the dispersed particles are generated, and the viscosity stability during storage is excellent, so it can be particularly Suitable for use in inkjet printing or photolithography.
例如，使用本發明的遮光膜用黑色樹脂組成物以噴墨印刷法形成遮光膜時，由於黑色遮光性粒子及透明粒子再凝集的情況少，因此間歇吐出時的噴墨噴嘴的閉塞少，且保存時的黏度安定，故有助於連續印刷時的圖案膜厚的安定性。噴墨裝置只要是可調整組成物的吐出液量者就無特別制限，惟在一般常用的壓電元件的噴墨頭，安定地形成液滴的墨水組成物的物性係依據頭的構成而有所不同，惟在頭內部的溫度下，黏度可為3mPa‧sec至150mPa‧sec，較佳可為4mPa‧sec至30mPa‧sec。黏度的值較此大時，無法吐出液滴，相反的，黏度的值較此小時， 則液滴的吐出量不安定。又，頭內部的溫度，依所使用的墨水組成物的安定性而有不同，較佳為在室溫20℃至45℃使用。其中，為了增加墨水組成物中的固形份以提高膜厚，一般採用可安定吐出黏度的35至40℃左右的溫度。 For example, when the black resin composition for a light-shielding film of the present invention is used to form a light-shielding film by the inkjet printing method, the black light-shielding particles and transparent particles are less likely to re-aggregate, so there is less clogging of inkjet nozzles during intermittent discharge, and The viscosity during storage is stable, so it contributes to the stability of the pattern film thickness during continuous printing. The inkjet device is not particularly limited as long as the discharge amount of the composition can be adjusted. However, in the inkjet head of the commonly used piezoelectric element, the physical properties of the ink composition that stably forms droplets depend on the structure of the head. The difference is that at the temperature inside the head, the viscosity can be 3mPa‧sec to 150mPa‧sec, preferably 4mPa‧sec to 30mPa‧sec. When the viscosity value is larger than this, the droplets cannot be discharged. On the contrary, the viscosity value is smaller than this. Then, the discharge amount of the droplet is unstable. In addition, the temperature inside the head varies depending on the stability of the ink composition used, and it is preferably used at room temperature from 20°C to 45°C. Among them, in order to increase the solid content in the ink composition to increase the film thickness, a temperature of about 35 to 40°C that can stabilize the discharge viscosity is generally used.
用以上述等噴墨印刷法的遮光膜用黑色樹脂組成物的特性，主要是依構成該遮光膜用黑色樹脂組成物的溶劑或界面活性劑來調整，再者為了抑制連續印刷時噴嘴部分中的該組成物的乾燥，溶劑以沸點180℃以上者為主體，並且在全溶劑成分中為60%以上、較佳為80%以上的範圍內，可使用單獨或複數種。沸點180℃以上的溶劑可使用：乙二醇單甲基醚乙酸酯等乙二醇單烷基醚乙酸酯類；二乙二醇單甲基醚、二乙二醇單乙基醚等二乙二醇單烷基醚類；二乙二醇單正丁基醚乙酸酯等二乙二醇單烷基醚乙酸酯類；丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯等丙二醇單烷基醚乙酸酯類；二乙二醇二甲基醚等其他醚類；γ-丁內酯等高沸點溶劑類等。 The characteristics of the black resin composition for light-shielding films used in the above-mentioned inkjet printing methods are mainly adjusted according to the solvent or surfactant constituting the black resin composition for the light-shielding film, and in order to prevent the nozzle part from being trapped during continuous printing. For the drying of the composition, the solvent mainly has a boiling point of 180°C or higher, and the total solvent component is 60% or more, preferably 80% or more, and can be used alone or in plural. Solvents with a boiling point above 180°C can be used: ethylene glycol monomethyl ether acetate and other ethylene glycol monoalkyl ether acetates; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and other two Ethylene glycol monoalkyl ethers; diethylene glycol mono-n-butyl ether acetate and other diethylene glycol monoalkyl ether acetates; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetic acid Propylene glycol monoalkyl ether acetates such as esters; other ethers such as diethylene glycol dimethyl ether; high boiling point solvents such as γ-butyrolactone, etc.
另一方面，光刻法中，本發明的遮光膜用黑色樹脂組成物因黑色遮光性粒子及透明粒子的再凝集造成的粗大粒子發生較少，故可使顯像後的圖案邊緣直線性為良好。該粗大粒子的發生抑制，亦適合於其他的圖案形成法，例如將裝載於印刷版上的印刷墨水轉印至透明基板上之情形，或用於降低印刷圖案的表面異物、銲疤等缺陷。 On the other hand, in the photolithography method, the black resin composition for a light-shielding film of the present invention generates less coarse particles due to the re-aggregation of black light-shielding particles and transparent particles, so that the linearity of the pattern edge after development can be good. The suppression of the generation of coarse particles is also suitable for other pattern forming methods, such as transferring printing ink loaded on a printing plate to a transparent substrate, or for reducing defects such as surface foreign matter and welding scars of the printed pattern.
光刻法所使用的本發明的遮光膜用黑色樹脂組成物中，(A)成分為光硬化性樹脂及/或光硬化性單 體，並進一步混合用以使其溶解於鹼性顯像液中的鹼性可溶性樹脂。鹼性可溶性樹脂可列舉例如：使用由丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯等丙烯酸烷基酯或甲基丙烯酸烷基酯，具有環狀的官能基的丙烯酸環己酯或甲基丙烯酸環己酯，具有羥基的丙烯酸羥基乙酯或甲基丙烯酸羥基乙酯，苯乙烯等單體中選出的2至5種類的單體，與丙烯酸、甲基丙烯酸等具有羧基的單體(單體)所合成的分子量5000至100000的共聚物，且不具光硬化性的官能基的(E)鹼性可溶性樹脂。 In the black resin composition for a light-shielding film of the present invention used in photolithography, the component (A) is a photocurable resin and/or a photocurable resin. And further mix the alkaline soluble resin to dissolve it in the alkaline developing solution. Examples of alkaline soluble resins include the use of alkyl acrylates or alkyl methacrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate. Ester, cyclohexyl acrylate or cyclohexyl methacrylate with cyclic functional group, hydroxyethyl acrylate or methacrylate with hydroxyl group, 2 to 5 types of monomers selected from monomers such as styrene It is a copolymer with a molecular weight of 5000 to 100,000 synthesized with monomers (monomers) having carboxyl groups such as acrylic acid and methacrylic acid, and (E) alkaline soluble resin without photocurable functional groups.
更且，鹼性可溶性樹脂的合適例，可列舉於分子內具有聚合性不飽和基與羧基等酸性基的含有聚合性不飽和基的鹼性可溶性樹脂，屬於(A)成分的一種的光硬化性樹脂本身為含有該聚合性不飽和基的鹼性可溶性樹脂時，亦適合使用。此時，可併用不具有前述光硬化性官能基的(E)鹼性可溶性樹脂而使用。含有聚合性不飽和基的鹼性可溶性樹脂，可使用例如使(甲基)丙烯酸與(甲基)丙烯酸酯化合物自由基共聚合而得的樹脂中羧基的一部分，與1分子中具有(甲基)丙烯酸縮水甘油酯等聚合性不飽和基與環氧基的化合物反應所得的含有聚合性不飽和基的鹼性可溶性樹脂；或者，使環氧樹脂與(甲基)丙烯酸反應而得的環氧基(甲基)丙烯酸酯樹脂再加成酸酐所得的含有聚合性不飽和基的鹼性可溶性樹脂為首之眾多的樹脂。 Furthermore, suitable examples of alkaline soluble resins include polymerizable unsaturated group-containing alkaline soluble resins having acidic groups such as polymerizable unsaturated groups and carboxyl groups in the molecule, and are a kind of photocuring of component (A) When the resin itself is an alkaline soluble resin containing the polymerizable unsaturated group, it is also suitable for use. In this case, the (E) alkaline soluble resin that does not have the aforementioned photocurable functional group can be used in combination. Alkaline soluble resins containing polymerizable unsaturated groups can be used, for example, by radically copolymerizing (meth)acrylic acid and (meth)acrylic acid ester compounds. ) Alkaline soluble resins containing polymerizable unsaturated groups obtained by reacting polymerizable unsaturated groups such as glycidyl acrylate with epoxy compounds; or epoxy resins obtained by reacting epoxy resins with (meth)acrylic acid Alkaline soluble resins containing polymerizable unsaturated groups obtained by adding acid anhydrides to base (meth)acrylate resins are among the many resins.
印刷於透明基板上的遮光膜的硬化方法以 及硬化性樹脂成分(A)，係依透明基板的耐熱性或所使用的環境、所要求的尺寸精度、符合的可靠性而選定。 The curing method of the shading film printed on the transparent substrate is based on The curable resin component (A) is selected according to the heat resistance of the transparent substrate, the environment in which it is used, the required dimensional accuracy, and the reliability.
以下，列舉實施例等進一步詳細說明本發明，但本發明並不限定於該等實施例。 Hereinafter, the present invention will be described in further detail with examples and the like, but the present invention is not limited to these examples.
以下實施例中各種評價除非另有說明則如下所述進行。 Unless otherwise specified, various evaluations in the following examples were performed as follows.
將1g的後述合成例中所得的樹脂溶液含浸於玻璃過濾器〔質量：W0(g)〕並加以秤量〔W1(g)〕，以160℃加熱2小時後的質量〔W2(g)〕依下式求出。 1g of the resin solution obtained in the synthesis example described later is impregnated in a glass filter [mass: W 0 (g)] and weighed [W 1 (g)], and the mass after heating at 160°C for 2 hours [W 2 (g) )] According to the following formula.
固形份濃度(質量%)=100×(W2-W0)/(W1-W0)〔酸價〕 Solid content concentration (mass%)=100×(W 2 -W 0 )/(W 1 -W 0 ) (acid value)
將樹脂溶液溶解於二
〔分子量〕 〔Molecular weight〕
使用凝膠滲透層析儀(GPC){TOSOH股份有限公司製HLC-8220GPC、溶劑：四氫呋喃、管柱：TSKgelSuperH-2000(2條)+TSKgelSuperH-3000(1條)+TSKgelSuperH-4000(1條)+TSKgelSuper-H5000(1條)〔TOSOH股份有限公司製〕、溫度：40℃、速度：0.6ml/min}進行測定，以標準聚苯乙烯〔TOSOH股份有限公司製PS-Oligomer Kit〕換算值求出重量平均分子量(Mw)的值。 Use gel permeation chromatography (GPC) {HLC-8220GPC manufactured by TOSOH Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) +TSKgelSuper-H5000 (1 piece) [manufactured by TOSOH Co., Ltd.], temperature: 40°C, speed: 0.6 ml/min}, measured by standard polystyrene [PS-Oligomer Kit manufactured by TOSOH Co., Ltd.] Get the value of the weight average molecular weight (Mw).
〔一次粒徑測定〕 [Primary particle size measurement]
以溶劑將含有粒子溶液稀釋至粒子濃度為0.1wt%左右，將所得的分散液滴下至附碳支持膜的金屬性篩網後作成的測定用樣本，利用穿透型電子顯微鏡(TEM；日本電子公司製、JEM-2000EX)觀測，以所得的粒徑作為一次粒徑。 Dilute the particle-containing solution with a solvent to a particle concentration of about 0.1% by weight, and drop the resulting dispersion onto a metal mesh with a carbon support film. The sample is used for measurement using a transmission electron microscope (TEM; JEOL Company made, JEM-2000EX) observed, and the obtained particle size was used as the primary particle size.
〔平均二次粒徑測定〕 [Measurement of average secondary particle size]
針對所得的含有黑色遮光性粒子的分散液或含有透明粒子的分散液，利用動態光散射法的粒度分佈計(大塚電子股份有限公司製、粒徑分析儀FPAR-1000)，分別測定根據累積量法求得的平均二次粒徑。含有黑色遮光性粒子的分散液，以丙二醇單甲基醚乙酸酯(PGMEA)使其分散後的粒子濃度成為0.1至0.5質量%的方式來稀釋，並作為測定用樣本。又，為使含有透明粒子的分散液達到可測定的散射強度，以甲醇稀釋粒子濃度至1至10w%後作為測定用樣本。 For the obtained dispersion liquid containing black light-shielding particles or the dispersion liquid containing transparent particles, use a particle size distribution meter (manufactured by Otsuka Electronics Co., Ltd., particle size analyzer FPAR-1000) of the dynamic light scattering method to measure the cumulative amount. The average secondary particle size obtained by the method. The dispersion liquid containing black light-shielding particles is diluted so that the particle concentration after dispersion of propylene glycol monomethyl ether acetate (PGMEA) becomes 0.1 to 0.5% by mass, and is used as a sample for measurement. In addition, in order to make the dispersion liquid containing transparent particles have a measurable scattering intensity, the particle concentration was diluted with methanol to 1 to 10w% and used as a measurement sample.
〔黏度測定〕 〔Determination of viscosity〕
使用E型黏度計(東機產業製、RE80L)以23℃測定遮光膜用黑色樹脂組成物的黏度。測定係在該組成物的調製後立即進行，然後移動至可密封的容器，在5℃冷藏保管1個月後以及在40℃加速熟化一星期後，以同樣的條件測定黏度，判定相較於初期黏度的黏度上升。 The viscosity of the black resin composition for light-shielding films was measured at 23°C using an E-type viscometer (manufactured by Toki Sangyo, RE80L). The measurement is carried out immediately after the preparation of the composition, and then moved to a sealable container. After 1 month of refrigerated storage at 5°C and accelerated aging at 40°C for 1 week, the viscosity is measured under the same conditions and judged as compared to The viscosity of the initial viscosity increases.
〔遮光度(OD值)測定〕 〔Measurement of opacity (OD value)〕
使用後烘後的附遮光膜玻璃基板，以大塚電子製OD計測定。 The glass substrate with a light-shielding film baked after use was measured with an OD meter manufactured by Otsuka Electronics.
〔膜厚測定〕 〔Measurement of film thickness〕
將後烘後的附遮光膜玻璃基板使用觸針式膜厚計〔Tencor股份有限公司製〕來測定。 The post-baked glass substrate with a light-shielding film was measured using a stylus-type film thickness meter [manufactured by Tencor Co., Ltd.].
〔折射率的測定〕 [Measurement of refractive index]
使用阿貝(abbe)折射率計測定。 It is measured using an abbe refractometer.
〔反射光學特性的測定〕 [Measurement of reflective optical properties]
使用後烘後的附遮光膜玻璃基板，自已形成遮光膜的面的相反側的面側使用Konica Minolta公司製的測色計CM2600d，以D65光源、10°視野進行測定。 After using the post-baked glass substrate with a light-shielding film, the surface side opposite to the surface where the light-shielding film was formed was measured using a colorimeter CM2600d manufactured by Konica Minolta Co., with a D65 light source and a 10° field of view.
又，反射率係利用由該反射光學特性的測定所得的L*的測定值，根據以下的計算式求得。 In addition, the reflectance is obtained by the following calculation formula using the measured value of L* obtained by the measurement of the reflection optical characteristic.
反射率(%)={(L*+16)/116}3×100 Reflectance (%)={(L*+16)/116} 3 ×100
〔噴墨吐出安定性試驗〕 [Inkjet discharge stability test]
將遮光膜用黑色樹脂組成物添加至Konica Minolta IJ製壓電元件驅動型噴墨頭(14pL/drop；KM512M)，在沖洗、噴墨頭吐出面的洗淨實施後，使用飛翔觀察相機連續30分鐘確認該組成物的吐出狀態，若未吐出液滴，即飛翔軌道沒有明顯非垂直等顯著的缺陷時評為○。接著，在間歇吐出試驗(噴墨頭吐出面洗淨後静置30分鐘，計算再吐出時的不吐出噴嘴的次數)中，全部512噴嘴中不吐出噴嘴的數未達10個時評為○，未達30個時為△、30個以上時為×。 The black resin composition for the light-shielding film was added to the piezo element driven inkjet head (14pL/drop; KM512M) manufactured by Konica Minolta IJ. After flushing and cleaning of the ejection surface of the inkjet head, the flying observation camera was used for 30 consecutive cycles. The ejection state of the composition was confirmed within minutes, and if the droplets were not ejected, that is, when the flight path did not have significant defects such as obvious non-verticality, it was rated as ○. Next, in the intermittent discharge test (the inkjet head was left to stand for 30 minutes after the discharge surface was cleaned, and the number of non-discharge nozzles when re-discharging was counted), the number of non-discharge nozzles out of all 512 nozzles was rated as ○. If there are less than 30, it is △, and if there are more than 30, it is ×.
〔顯像特性評價〕 〔Evaluation of imaging characteristics〕
使用旋轉塗佈機將遮光膜用黑色樹脂組成物，以後烘 後的膜厚成為1.2μm的方式，塗佈於125mm×125mm的玻璃基板上，以80℃預烘1分鐘。然後，調整曝光間距至80μm，於乾燥塗膜的上覆蓋線寬/線距=20μm/20μm的負型光罩，以I線照度30mW/cm2的超高壓水銀燈照射100mJ/cm2的紫外線，並進行感光部分的光硬化反應。其次，使該曝光結束的塗板在0.05%氫酸化鉀水溶液中以23℃進行1kgf/cm2壓淋浴顯像，觀察到圖案的時間設為顯像脫落時間(BT秒)，再進行20秒的顯像後，進行5kgf/cm2壓的噴霧水洗，去除塗膜的未曝光部，於玻璃基板上形成像素圖案，然後，使用熱風乾燥機以230℃熱後烘30分鐘。各實施例、及比較例中所得的遮光膜的評價項目與方法如下所述。圖案直線性以及塗膜表面的平滑性：對後烘後的20μm線以顯微鏡以及SEM觀察，當觀測到帶有鋸齒時評為×，沒有時評為○。又，由粗大粒子所得的線膜厚產生不均勻時，平滑性判定為×。 The black resin composition for the light-shielding film was coated on a glass substrate of 125 mm x 125 mm using a spin coater so that the film thickness after baking became 1.2 μm, and prebaked at 80° C. for 1 minute. Then, to adjust the exposure distance 80 m, the dried coating film covering the line / space negative photomask = 20μm / 20μm to I-line illumination intensity 30mW / cm 2 pressure mercury lamp ultraviolet irradiation 100mJ / cm 2, and And carry out the photohardening reaction of the photosensitive part. Next, the coated plate after the exposure was developed in a 0.05% potassium hydrochloride aqueous solution at 23°C at a pressure of 1 kgf/cm 2 for shower development. The time for observing the pattern was set as the development detachment time (BT seconds), and a further 20 seconds After the development, spray water washing at a pressure of 5 kgf/cm 2 was performed to remove the unexposed parts of the coating film, and the pixel pattern was formed on the glass substrate, and then heated at 230° C. for 30 minutes using a hot air dryer. The evaluation items and methods of the light-shielding film obtained in each Example and Comparative Example are as follows. Pattern linearity and smoothness of the coating film surface: The 20 μm line after post-baking was observed with a microscope and SEM. When sawtooth was observed, it was rated as x, and when there was no sawtooth, it was rated as ○. In addition, when unevenness of the line film thickness obtained from the coarse particles occurred, the smoothness was judged to be ×.
其次，顯示實施例所使用的樹脂的合成例，首先，顯示在下述的合成例、實施例中所使用的略號。BPFE：9,9-雙(4-羥基苯基)茀與氯甲基環氧乙烷的反應物。 Next, the synthesis examples of the resins used in the examples are shown. First, the symbol numbers used in the following synthesis examples and examples are shown. BPFE: 9,9-bis(4-hydroxyphenyl) sulfide and chloromethyl oxirane reactant.
BPDA：3,3’,4,4’-聯苯基四羧酸二酐 BPDA: 3,3’,4,4’-biphenyltetracarboxylic dianhydride
THPA：1,2,3,6-四氫化鄰苯二甲酸酐 THPA: 1,2,3,6-tetrahydrophthalic anhydride
TPP：三苯基膦 TPP: Triphenylphosphine
PGMEA：丙二醇單甲基醚乙酸酯 PGMEA: Propylene glycol monomethyl ether acetate
BDGAC：二乙二醇單丁基醚乙酸酯 BDGAC: Diethylene glycol monobutyl ether acetate
DPHA：二新戊四醇六丙烯酸酯與二新戊四醇五丙烯酸酯的混合物〔日本化藥股份有限公司製商品名DPHA〕 DPHA: a mixture of dineopentaerythritol hexaacrylate and dineopentaerythritol pentaacrylate [trade name DPHA manufactured by Nippon Kayaku Co., Ltd.]
HDDA：1,6-己二醇二丙烯酸酯 HDDA: 1,6-hexanediol diacrylate
TMPTA：三羥甲基丙烷三丙烯酸酯 TMPTA: Trimethylolpropane triacrylate
〔合成例1〕 [Synthesis Example 1]
於附有迴流冷卻器的500ml四頸燒瓶中，添加BPFE 78.63g(0.17mol)、丙烯酸24.50g(0.34mol)、TPP 0.45g、及PGMEA 114g，在100至105℃的加熱下攪拌12小時，得到反應生成物。 In a 500ml four-necked flask with a reflux cooler, 78.63g (0.17mol) of BPFE, 24.50g (0.34mol) of acrylic acid, 0.45g of TPP, and 114g of PGMEA were added, and stirred for 12 hours under heating at 100 to 105°C. The reaction product is obtained.
接著，於所得的反應生成物中添加BPDA 25.01g(0.085mol)及THPA 12.93g(0.085mol)，在120至125℃的加熱下攪拌6小時，得到含有聚合性不飽和基的鹼性可溶性樹脂溶液(A)-1。所得的樹脂溶液的固形份濃度為55.8wt%，酸價(經固形份換算)為103mgKOH/g，藉由GPC分析測得的Mw為2600。 Next, 25.01g (0.085mol) of BPDA and 12.93g (0.085mol) of THPA were added to the obtained reaction product, and the mixture was stirred under heating at 120 to 125°C for 6 hours to obtain a polymerizable unsaturated group-containing alkaline soluble resin Solution (A)-1. The solid content concentration of the obtained resin solution was 55.8 wt%, the acid value (converted by solid content) was 103 mgKOH/g, and the Mw measured by GPC analysis was 2600.
〔樹脂溶液的調製：A成分溶液〕 [Preparation of resin solution: A component solution]
調製含有以下(A)成分的樹脂溶液A1至A3。該樹脂溶液A1至A3分別經乾燥/硬化後的硬化物的折射率均為1.50至1.55。 Resin solutions A1 to A3 containing the following (A) components were prepared. The refractive index of the cured product after the resin solutions A1 to A3 are dried/cured respectively is 1.50 to 1.55.
(1)樹脂溶液A1(噴墨印刷用-1)：光硬化型樹脂組成物 (1) Resin solution A1 (for inkjet printing-1): light-curing resin composition
將BDGAC 86.9質量份、胺酯丙烯酸酯〔共榮社化學股份有限公司製商品名UA-306H〕10.0質量份、光起始劑OXE-02(BASF製)0.75質量份、BYK Japan股份有限公司製 商品名BYK(註冊商標)-333的10% BDGAC稀釋溶液1.23質量份、3-脲基丙基三乙氧基矽烷〔信越化學工業股份有限公司製商品名KBE-585〕1.14質量份予以混合，藉由1μm深層式過濾器進行加壓過濾，調製樹脂溶液A1。 86.9 parts by mass of BDGAC, 10.0 parts by mass of urethane acrylate (trade name UA-306H manufactured by Kyoeisha Chemical Co., Ltd.), 0.75 parts by mass of photoinitiator OXE-02 (manufactured by BASF), manufactured by BYK Japan Co., Ltd. 1.23 parts by mass of a 10% BDGAC diluted solution of the trade name BYK (registered trademark)-333 and 1.14 parts by mass of 3-ureidopropyltriethoxysilane (trade name KBE-585 manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed, Pressure filtration was performed with a 1 μm depth filter to prepare resin solution A1.
(2)樹脂溶液A2(噴墨印刷用-2)：熱硬化型樹脂組成物 (2) Resin solution A2 (for inkjet printing-2): thermosetting resin composition
將BDGAC 82.9質量份、由合成例1所得的含有聚合性不飽和基的鹼性可溶性樹脂溶液(A)-1 6.3質量份、苯酚酚醛清漆型環氧樹脂〔三菱化學股份有限公司製商品名JER154、環氧當量178、1分子中的平均官能基數3.0〕3.2質量份、DPHA 4.0質量份、BYK Japan股份有限公司製商品名BYK(註冊商標)-333的10% BDGAC稀釋溶液1.24質量份、3-脲基丙基三乙氧基矽烷〔信越化學工業股份有限公司製商品名KBE-585〕2.95質量份予以混合，調製樹脂溶液A2。 82.9 parts by mass of BDGAC, 6.3 parts by mass of the polymerizable unsaturated group-containing alkaline soluble resin solution (A) obtained in Synthesis Example 1, and phenol novolak type epoxy resin (trade name JER154 manufactured by Mitsubishi Chemical Corporation) , Epoxy equivalent 178, average number of functional groups per molecule 3.0] 3.2 parts by mass, DPHA 4.0 parts by mass, BYK Japan Co., Ltd. product name BYK (registered trademark)-333 10% BDGAC diluted solution 1.24 parts by mass, 3 -Ureapropyltriethoxysilane (trade name KBE-585 manufactured by Shin-Etsu Chemical Co., Ltd.) 2.95 parts by mass were mixed to prepare resin solution A2.
(3)樹脂溶液A3(光刻用)：光硬化型樹脂組成物 (3) Resin solution A3 (for photolithography): photocurable resin composition
將PGMEA 78.7質量份、由合成例1所得的含有聚合性不飽和基的鹼性可溶性樹脂溶液(A)-1 12.3質量份、DPHA 2.41質量份、光聚合起始劑OXE-02(BASF製)0.81質量份、BYK Japan股份有限公司製商品名BYK(註冊商標)-333的10%BDGAC稀釋溶液1.24質量份、3-脲基丙基三乙氧基矽烷〔信越化學工業股份有限公司製商品名KBE-585〕2.95質量份予以混合，調製樹脂溶液A3。 PGMEA 78.7 parts by mass, the polymerizable unsaturated group-containing alkaline soluble resin solution (A) obtained in Synthesis Example 1 12.3 parts by mass, 2.41 parts by mass of DPHA, and photopolymerization initiator OXE-02 (made by BASF) 0.81 parts by mass, 1.24 parts by mass of a 10% BDGAC diluted solution manufactured by BYK Japan Co., Ltd. product name BYK (registered trademark)-333, 3-ureidopropyltriethoxysilane (product name manufactured by Shin-Etsu Chemical Co., Ltd.) KBE-585] 2.95 parts by mass were mixed to prepare resin solution A3.
〔含有黑色遮光性粒子分散液的調製：B成分〕 [Preparation of dispersion liquid containing black light-shielding particles: component B]
(1)碳黑分散液B1(噴墨印刷用)：使在BDGAC中碳黑濃度成為25質量%、分散樹脂〔樹脂溶液(A)-1中的樹脂成分〕成為8質量%、高分子分散劑成為2質量%之方式，在珠磨機中進行分散，並作為碳黑分散液B1。所得的分散液中的碳黑平均二次粒徑為106nm。 (1) Carbon black dispersion B1 (for inkjet printing): Make the carbon black concentration in BDGAC 25% by mass, the dispersion resin [resin component in resin solution (A)-1] to 8% by mass, and polymer dispersion The agent is 2% by mass, dispersed in a bead mill, and used as a carbon black dispersion B1. The average secondary particle diameter of carbon black in the obtained dispersion liquid was 106 nm.
(2)碳黑分散液B2(光刻用)：使在PGMEA中碳黑濃度成為25質量%、分散樹脂〔樹脂溶液(A)-1中的樹脂成分〕成為8質量%、高分子分散劑成為2質量%之方式，在珠磨機中進行分散，並作為碳黑分散液B2。所得的分散液中的碳黑平均二次粒徑為98nm。 (2) Carbon black dispersion B2 (for photolithography): Make the concentration of carbon black in PGMEA 25% by mass, disperse resin [resin component in resin solution (A)-1] to 8% by mass, polymer dispersant It becomes 2% by mass, and it is dispersed in a bead mill and used as a carbon black dispersion B2. The average secondary particle size of carbon black in the obtained dispersion liquid was 98 nm.
〔含有透明粒子分散液的調製：C成分〕 [Preparation of dispersion liquid containing transparent particles: component C]
氧化矽的折射率採用1.45(文獻值)、氧化鋁的折射率採用1.74(文獻值)。所調製的分散液的特性表示於表1。 The refractive index of silicon oxide is 1.45 (document value), and the refractive index of alumina is 1.74 (document value). The characteristics of the prepared dispersion are shown in Table 1.
(1)氧化矽分散液C1：將日產化學工業股份有限公司製膠狀氧化矽以γ-甲基丙烯醯氧基丙基三甲氧基矽烷進行表面處理，使該表面處理過的氧化矽成為50質量%濃度的方式，與高分子分散劑5質量%一起在HDDA中利用珠磨機進行分散，並作為氧化矽分散液C1。 (1) Silica dispersion liquid C1: The colloidal silica manufactured by Nissan Chemical Industry Co., Ltd. is surface-treated with γ-methacryloxypropyltrimethoxysilane, so that the surface-treated silica becomes 50%. In the method of mass% concentration, it is dispersed in HDDA by a bead mill together with a polymer dispersant of 5 mass% and used as a silica dispersion liquid C1.
(2)氧化矽分散液C2：將日產化學工業股份有限公司製膠狀氧化矽以γ-甲基丙烯醯氧基丙基三甲氧基矽烷進行表面處理，使該表面處理過的氧化矽成為30質量%濃度的方式，與高分子分散劑3質量%一起在DPHA中利用珠磨機 進行分散，並作為氧化矽分散液C2。 (2) Silica dispersion liquid C2: The colloidal silica produced by Nissan Chemical Industry Co., Ltd. is surface-treated with γ-methacryloxypropyltrimethoxysilane, so that the surface-treated silica becomes 30 Mass% concentration method, together with 3 mass% polymer dispersant, use a bead mill in DPHA Disperse it as silica dispersion liquid C2.
(3)氧化矽分散液C3：將日產化學工業股份有限公司製膠狀氧化矽以γ-甲基丙烯醯氧基丙基三甲氧基矽烷進行表面處理後，使氧化矽的濃度成為30質量%的方式，與高分子分散劑3質量%一起在TMPTA中利用珠磨機進行分散，並作為氧化矽分散液C3。 (3) Silica dispersion liquid C3: After surface treatment of colloidal silica manufactured by Nissan Chemical Industry Co., Ltd. with γ-methacryloxypropyltrimethoxysilane, the concentration of silica becomes 30% by mass The method, together with the polymer dispersant 3% by mass, was dispersed in a bead mill in TMPTA and used as a silica dispersion liquid C3.
(4)氧化矽分散液C4：使粒狀氧化矽(日本Aerosil公司製Aerosil)成為濃度20質量%的方式，與高分子分散劑10質量%一起在PGMEA中利用珠磨機進行分散，並作為氧化矽分散液C4。 (4) Silica dispersion liquid C4: The granular silica (Aerosil manufactured by Japan Aerosil Co., Ltd.) has a concentration of 20% by mass, and is dispersed in a bead mill in PGMEA with a polymer dispersant of 10% by mass. Silica dispersion liquid C4.
(5)氧化鋁分散液C5：將日產化學工業股份有限公司製膠狀氧化鋁以γ-甲基丙烯醯氧基丙基三甲氧基矽烷進行表面處理，使表面處理過的膠狀氧化鋁的濃度成為30質量%的方式，與高分子分散劑3質量%一起在HDDA中利用珠磨機進行分散，並作為氧化鋁分散液C5。 (5) Alumina dispersion C5: The colloidal alumina produced by Nissan Chemical Industry Co., Ltd. is surface-treated with γ-methacryloxypropyltrimethoxysilane to make the surface-treated colloidal alumina When the concentration became 30% by mass, it was dispersed in HDDA with a bead mill in HDDA together with 3% by mass of the polymer dispersant, and was used as an alumina dispersion liquid C5.
〔遮光膜用黑色樹脂組成物及其遮光膜的調製以及評價〕 [Preparation and evaluation of black resin composition for light-shielding film and light-shielding film]
將14.5質量份的樹脂溶液A2、15質量份的碳黑分散液B1、0.5質量份的氧化矽分散液C1予以混合，(總共30質量份)，藉由1μm深層式過濾器進行加壓過濾，調製遮光膜用黑色樹脂組成物。所調製的該組成物的初期黏度(室溫)為10.3mPa‧sec。將該遮光膜用黑色樹脂組成物在無鹼玻璃上以旋轉塗佈改變旋轉數並塗佈，將該等以90℃乾燥 5分鐘，再以230℃後烘30分鐘以作為附遮光膜玻璃基板。 Mix 14.5 parts by mass of resin solution A2, 15 parts by mass of carbon black dispersion B1, and 0.5 parts by mass of silica dispersion C1, (30 parts by mass in total), and perform pressure filtration with a 1 μm depth filter, Prepare a black resin composition for a light-shielding film. The initial viscosity (room temperature) of the prepared composition was 10.3mPa‧sec. The black resin composition for a light-shielding film was applied to alkali-free glass by spin coating, changing the number of rotations, and dried at 90°C 5 minutes, then post-bake at 230°C for 30 minutes as a glass substrate with light-shielding film.
〔實施例2至3、比較例1至3〕 [Examples 2 to 3, Comparative Examples 1 to 3]
前述的樹脂溶液A2及碳黑分散液B1與含有透明粒子的分散液依照表2至3所示的質量份予以混合，調製遮光膜用黑色樹脂組成物，與實施例1同樣地進行黏度測定。再將該遮光膜用黑色樹脂組成物塗佈於無鹼玻璃上，以90℃乾燥5分鐘，再以230℃後烘30分鐘後，作成附遮光膜玻璃基板。結果表示於表2至3。 The aforementioned resin solution A2 and carbon black dispersion liquid B1 and the dispersion liquid containing transparent particles were mixed in parts by mass shown in Tables 2 to 3 to prepare a black resin composition for a light-shielding film, and the viscosity was measured in the same manner as in Example 1. Then, the black resin composition for the light-shielding film was coated on the alkali-free glass, dried at 90°C for 5 minutes, and then post-baked at 230°C for 30 minutes, to form a glass substrate with a light-shielding film. The results are shown in Tables 2 to 3.
相較於不含透明粒子的比較例1的附遮光膜玻璃基板，實施例1至3的附遮光膜玻璃基板中儘管為相同的碳黑濃度，該等可降低反射率。另一方面，含有氧化鋁粒子(折射率文獻值1.74)的比較例2的附遮光膜玻璃基板並未見反射率的降低。並且使用平均二次粒徑較碳黑粒子為大的氧化矽粒子的比較例3之中，雖然附遮光膜玻璃基板的反射率降低，但以SEM觀察時，其硬化膜表面觀察到由凝集粒子構成的硬化膜表面的突起物而為不佳，且膜厚也有不均勻。且於遮光膜用黑色樹脂組成物中，其40℃保管時的黏度相較初期值時有顯著的增黏，甚至於噴墨吐出試驗中發生噴嘴阻塞。 Compared with the glass substrate with a light-shielding film of Comparative Example 1 which does not contain transparent particles, the glass substrates with a light-shielding film of Examples 1 to 3 have the same carbon black concentration, which can reduce the reflectance. On the other hand, the glass substrate with a light-shielding film of Comparative Example 2 containing alumina particles (refractive index literature value 1.74) did not see a decrease in reflectance. Furthermore, in Comparative Example 3 using silica particles with a larger average secondary particle size than carbon black particles, although the reflectance of the glass substrate with a light-shielding film was reduced, when observed by SEM, aggregated particles were observed on the surface of the cured film. The protrusions on the surface of the formed cured film are not good, and the film thickness is also uneven. In addition, in the black resin composition for light-shielding film, the viscosity during storage at 40°C was significantly thicker than the initial value, and even nozzle clogging occurred in the inkjet discharge test.
〔實施例4〕 [Example 4]
將14.5質量份的樹脂溶液A1、15質量份的碳黑分散液B1、0.5質量份的氧化矽分散液C1予以混合(總共30質量份)，利用1μm深層式過濾器進行加壓過濾，調製遮光膜用黑色樹脂組成物。所調製的該組成物的初期黏度(室 溫)為10.0mPa‧sec。將該遮光膜用黑色樹脂組成物在無鹼玻璃上以旋轉塗佈改變旋轉數並塗佈，以90℃乾燥5分鐘，再以紫外線曝光1000mJ(365nm基準)、120℃後烘30分鐘後，作成附遮光膜玻璃基板。 14.5 parts by mass of resin solution A1, 15 parts by mass of carbon black dispersion B1, and 0.5 parts by mass of silica dispersion C1 were mixed (30 parts by mass in total), and pressure-filtered with a 1μm depth filter to prepare shading Black resin composition for film. The initial viscosity (chamber Temperature) is 10.0mPa‧sec. The black resin composition for a light-shielding film was applied to alkali-free glass by spin coating, and then dried at 90°C for 5 minutes, and then exposed to 1000mJ (365nm standard) with ultraviolet rays and baked at 120°C for 30 minutes. Make a glass substrate with a shading film.
〔實施例5至6、比較例4至6〕 [Examples 5 to 6, Comparative Examples 4 to 6]
將前述的樹脂溶液A1及碳黑分散液B1與含有透明粒子的分散液依照表2至3所示的質量份予以混合，調製遮光膜用黑色樹脂組成物，與實施例1同樣地進行黏度測定。再將該遮光膜用黑色樹脂組成物在無鹼玻璃上以旋轉塗佈改變旋轉數並塗佈，以90℃乾燥5分鐘，再以紫外線曝光1000mJ(365nm基準)、120℃後烘30分鐘後，作成附遮光膜玻璃基板。 The aforementioned resin solution A1 and carbon black dispersion liquid B1 and the dispersion liquid containing transparent particles were mixed according to the mass parts shown in Tables 2 to 3 to prepare a black resin composition for a light-shielding film, and the viscosity was measured in the same manner as in Example 1. . Then the black resin composition for the light-shielding film was applied on the alkali-free glass by spin coating to change the number of rotations, dried at 90°C for 5 minutes, and then exposed to 1000mJ (365nm standard) with ultraviolet rays, and then baked at 120°C for 30 minutes , Make a glass substrate with shading film.
相較於不含透明粒子的比較例4，實施例4至6中的附遮光膜玻璃基板中儘管為相同的碳黑濃度，該等可降低反射率。另一方面，含有氧化鋁粒子(折射率文獻值1.74)的比較例5的附遮光膜玻璃基板中未見反射率的降低。且使用平均二次粒徑較碳黑粒子為大的氧化矽粒子的比較例6中，雖然附遮光膜玻璃基板的反射率降低，但其硬化膜表面的平滑性並不佳。 Compared with Comparative Example 4 that does not contain transparent particles, the glass substrates with light-shielding film in Examples 4 to 6 have the same carbon black concentration, which can reduce reflectivity. On the other hand, the glass substrate with a light-shielding film of Comparative Example 5 containing alumina particles (refractive index document value 1.74) did not see a decrease in reflectance. Furthermore, in Comparative Example 6 using silicon oxide particles having an average secondary particle diameter larger than that of carbon black particles, although the reflectance of the glass substrate with a light-shielding film was reduced, the smoothness of the cured film surface was not good.
〔實施例7、比較例7至8〕 [Example 7, Comparative Examples 7 to 8]
將相對於總固形份濃度的碳黑濃度改為40質量%，調製與實施例1以及比較例3及比較例1同樣的遮光膜用黑色樹脂組成物，對其黏度與附遮光膜玻璃基板的光學特性進行評價。結果表示於表2至3。 The carbon black concentration relative to the total solid content concentration was changed to 40% by mass, and the same black resin composition for a light-shielding film as in Example 1, Comparative Example 3 and Comparative Example 1 was prepared, and its viscosity was compared with that of the glass substrate with a light-shielding film. The optical properties are evaluated. The results are shown in Tables 2 to 3.
相較於不含透明粒子的比較例8，在實施例7的附遮光膜玻璃基板中儘管為相同的碳黑濃度，其可降低反射率。另一方面，在使用平均二次粒徑較碳黑粒子為大的氧化矽粒子的比較例7中，雖然附遮光膜玻璃基板的反射率降低，但以SEM觀察時，其硬化膜表面觀察到由凝集粒子構成的部位的硬化膜表面的突起物而不佳，並觀察到膜厚有不均勻。且於遮光膜用黑色樹脂組成物中，其40℃保管時的黏度相較初期值有顯著的增黏，甚至於噴墨吐出試驗中發生噴嘴阻塞。 Compared with Comparative Example 8 which does not contain transparent particles, in the glass substrate with a light-shielding film of Example 7, although the carbon black concentration is the same, the reflectance can be reduced. On the other hand, in Comparative Example 7 using silicon oxide particles having an average secondary particle size larger than that of carbon black particles, although the reflectance of the glass substrate with a light-shielding film decreased, when observed by SEM, the surface of the cured film was observed The protrusions on the surface of the cured film at the site composed of aggregated particles were not good, and uneven film thickness was observed. And in the black resin composition for light-shielding film, the viscosity during storage at 40°C was significantly higher than the initial value, and even nozzle clogging occurred in the inkjet discharge test.
〔實施例8及比較例9至10〕 [Example 8 and Comparative Examples 9 to 10]
調製作為樹脂溶液A3及碳黑分散液B2的光刻用的遮光膜用黑色樹脂組成物，同樣進行黏度測定。將該遮光膜用黑色樹脂組成物在無鹼玻璃上以旋轉塗佈進行塗佈，以80℃乾燥5分鐘，通過石英遮罩進行紫外線曝光100mJ(365nm基準)，在0.05% KOH的水溶液中以23℃浸漬/浸透40秒，再以230℃後烘30分鐘，作成附遮光膜玻璃基板。結果表示於表4。 A black resin composition for a light-shielding film for photolithography as the resin solution A3 and the carbon black dispersion liquid B2 was prepared, and the viscosity was measured in the same manner. The black resin composition for the light-shielding film was coated on alkali-free glass by spin coating, dried at 80°C for 5 minutes, and exposed to 100mJ (365nm standard) with ultraviolet rays through a quartz mask, and then used in a 0.05% KOH aqueous solution Dip/soak at 23°C for 40 seconds, then post-bake at 230°C for 30 minutes to make a glass substrate with a light-shielding film. The results are shown in Table 4.
相較於不含透明粒子的比較例9，在實施例8的附遮光膜基板中儘管為相同的碳黑濃度，其反射率下降。另一方面，使用平均二次粒徑較碳黑粒子為大的氧化矽粒子的比較例10中，雖然附遮光膜基板的反射率降低，但以SEM觀察時，硬化膜表面觀察到由凝集粒子構成的硬化膜表面的突起物而不佳，並觀察到膜厚有不均勻。並且於20μm線的邊緣形狀觀察到在實施例8及比較例9沒有觀察到的 鋸齒狀。且遮光膜用黑色樹脂組成物中其40℃保管時的黏度相較初期值有增黏。 Compared with Comparative Example 9 which does not contain transparent particles, in the substrate with a light-shielding film of Example 8, even though the carbon black concentration is the same, the reflectance is lowered. On the other hand, in Comparative Example 10 using silica particles with an average secondary particle size larger than that of carbon black particles, although the reflectance of the substrate with a light-shielding film was reduced, when observed by SEM, aggregated particles were observed on the surface of the cured film. The protrusions on the surface of the formed cured film were not good, and uneven film thickness was observed. And the edge shape of the 20μm line was observed, which was not observed in Example 8 and Comparative Example 9. Jagged. In addition, the viscosity of the black resin composition for a light-shielding film when stored at 40°C is higher than the initial value.
〔實施例9至10〕 [Examples 9 to 10]
將樹脂溶液作為A2及碳黑分散液為B1，改變相對於總固形份濃度的氧化矽濃度(C1)，以調製遮光膜用黑色樹脂組成物，與實施例1同樣地評價附遮光膜玻璃基板的光學特性。結果表示於表5。可知該等均因氧化矽分散液的添加而降低反射率。 Using the resin solution as A2 and the carbon black dispersion as B1, the silica concentration (C1) relative to the total solid concentration was changed to prepare a black resin composition for a light-shielding film, and the glass substrate with light-shielding film was evaluated in the same manner as in Example 1. Optical properties. The results are shown in Table 5. It can be seen that all of these have decreased reflectance due to the addition of silica dispersion.
〔實施例11至12〕 [Examples 11 to 12]
將樹脂溶液作為A3及碳黑分散液為B2，改變相對於總固形份濃度的氧化矽濃度(C1)，以調製遮光膜用黑色樹脂組成物，與實施例8同樣地評價附遮光膜玻璃基板的光學特性。結果表示於表5。可知該等均因氧化矽分散液的添加而降低反射率。 Using the resin solution as A3 and the carbon black dispersion as B2, the silica concentration (C1) relative to the total solid concentration was changed to prepare a black resin composition for a light-shielding film, and the glass substrate with a light-shielding film was evaluated in the same manner as in Example 8. Optical properties. The results are shown in Table 5. It can be seen that all of these have decreased reflectance due to the addition of silica dispersion.
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