TW202204501A - Resin composition, wiring board and method for producing conductive pattern - Google Patents
Resin composition, wiring board and method for producing conductive pattern Download PDFInfo
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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
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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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- 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
- G03F7/20—Exposure; Apparatus therefor
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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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
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- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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Abstract
Description
本發明係關於樹脂組成物、配線基板及導電性圖案之製造方法。The present invention relates to a method for producing a resin composition, a wiring board, and a conductive pattern.
近年來,於電視與行動電話、汽車導航、電子看板等各式各樣的顯示器正在發展大型化、高精細化。由於伴隨著大型化,電子配線的配線長度變長,從維持功耗的觀點來看,對配線的導電性提升,亦即對低電阻化的要求正在提高。對於高精細化,由於若將電子配線微細化則配線截面積會變小,因此為了使配線電阻相同而變得必須要提高導電性。In recent years, various types of displays such as televisions, mobile phones, car navigation, and electronic signboards have been developing in large-scale and high-definition displays. With the increase in size, the wiring length of the electronic wiring has increased, and from the viewpoint of maintaining power consumption, the electrical conductivity of the wiring has been improved, that is, the demand for lower resistance is increasing. In the case of high definition, since the cross-sectional area of the wiring becomes smaller when the electronic wiring is made finer, it becomes necessary to improve the electrical conductivity in order to make the wiring resistance the same.
作為形成使用在電子配線的導電性圖案之方法,一般是使用含有導電性粒子與黏結劑樹脂之樹脂組成物,在基板上形成圖案後,藉由加熱使導電性粒子接觸,而得到導電性圖案之方法(專利文獻1)。作為在基板上形成圖案之方法,可舉出例如:網版印刷法、噴墨法或光刻法。其中,據信網版印刷法與噴墨法不適合形成微細圖案,對於形成微細圖案來說,光刻法是適合的。As a method of forming a conductive pattern used in electronic wiring, a resin composition containing conductive particles and a binder resin is generally used, and after patterning on a substrate, the conductive particles are brought into contact with each other by heating to obtain a conductive pattern. method (Patent Document 1). As a method of forming a pattern on a board|substrate, a screen printing method, an inkjet method, or a photolithography method is mentioned, for example. Among them, it is believed that the screen printing method and the ink jet method are not suitable for forming fine patterns, and photolithography is suitable for forming fine patterns.
在此情形,已知一種技術,藉由使用粒徑足夠小的導電性微粒來減低粒子的表面能,促進導電性粒子彼此的熔接而提升電子配線的導電性。作為使用了粒徑足夠小的導電性微粒之樹脂組成物,可舉出使用了經表面被覆的銀微粒(專利文獻2)之樹脂組成物。藉由使用經表面被覆的銀微粒,能適當地控制銀微粒的表面能。In this case, there is known a technique for improving the conductivity of electronic wiring by using conductive fine particles with a sufficiently small particle size to reduce the surface energy of the particles and promote the fusion of the conductive particles. As a resin composition using electroconductive fine particles having a sufficiently small particle size, a resin composition using surface-coated silver fine particles (Patent Document 2) can be mentioned. By using the surface-coated silver fine particles, the surface energy of the silver fine particles can be appropriately controlled.
另一方面,對於使用在彩色濾光片等的著色圖案也同樣正在尋求高精細化。著色圖案係使用含有顏料與黏結劑樹脂之含著色顏料的樹脂組成物,並以與導電性圖案相同的方法形成。 [先前技術文獻] [專利文獻]On the other hand, the coloring patterns used in color filters and the like are similarly sought to be refined. The colored pattern is formed by the same method as the conductive pattern using a colored pigment-containing resin composition containing a pigment and a binder resin. [Prior Art Literature] [Patent Literature]
專利文獻1 日本特開2000-199954號公報 專利文獻2 日本特開2013-196997號公報Patent Document 1 Japanese Patent Laid-Open No. 2000-199954 Patent Document 2 Japanese Patent Application Laid-Open No. 2013-196997
[發明欲解決之課題][The problem to be solved by the invention]
然而,在使用經表面被覆的銀微粒之樹脂組成物中,存在下述課題:若為了提升導電性而藉由高溫加熱等來促進銀微粒表面的熔接,則與基材的密著性會降低。另一方面,為了賦予密著性,有添加具有胺基的密著改良劑之方法,但會有使銀微粒在樹脂組成物中的分散性變差且讓導電性降低的問題。因此,兼顧密著性與導電性提升是有困難的。However, in the resin composition using the surface-coated silver fine particles, there is a problem in that if the surface of the silver fine particles is heated by high temperature to promote the fusion of the surface of the silver fine particles in order to improve the conductivity, the adhesiveness to the base material is reduced. . On the other hand, in order to impart adhesion, there is a method of adding an adhesion improver having an amine group, but there is a problem in that the dispersibility of the silver fine particles in the resin composition is deteriorated and the electrical conductivity is lowered. Therefore, it is difficult to achieve both adhesion and conductivity improvement.
另外,即便在含著色顏料的樹脂組成物中,亦有在添加了具有胺基的密著改良劑的情形,顏料的分散性會變差且使保存穩定性降低的課題。Moreover, even in the resin composition containing a coloring pigment, when the adhesion improver which has an amine group is added, the dispersibility of a pigment deteriorates, and there exists a subject that the storage stability falls.
本發明係鑒於相關的先前技術的缺點而創立的,其目的在於得到分散性與密著性優良的圖案,特別是提供一種樹脂組成物,其在含有導電性粒子的樹脂組成物中,即便是為了提升導電性而促進銀微粒表面的熔接,也能維持與基材的密著性。藉由使用此種樹脂組成物,可得到兼具良好的分散性(亦即,在含有導電性粒子的樹脂組成物中之良好的導電性)與密著性之圖案。 [用以解決課題之手段]The present invention was conceived in view of the shortcomings of the related prior art, and its object is to obtain a pattern excellent in dispersibility and adhesion, and in particular, to provide a resin composition which, in a resin composition containing conductive particles, is In order to improve electrical conductivity, the fusion of the surfaces of the silver fine particles is promoted, and the adhesion to the base material can also be maintained. By using such a resin composition, a pattern having both good dispersibility (that is, good conductivity in a resin composition containing conductive particles) and adhesiveness can be obtained. [means to solve the problem]
本發明人等戮力研究的結果,發現使具有提高基材密著性的結構及藉由熱產生胺基的官能基之化合物(B)含有在樹脂組成物中,對於解決上述課題是極為有效的。As a result of intensive research by the inventors of the present invention, it has been found that containing the compound (B) having a structure that improves adhesion to substrates and a functional group that generates an amine group by heat in a resin composition is extremely effective for solving the above-mentioned problems of.
亦即,本發明為一種樹脂組成物,其包含:微粒、具有以通式(1)所表示的結構及藉由熱產生胺基之官能基的化合物(B)、以及黏結劑樹脂(C),該微粒係有機顏料(F)或具有包含碳的被覆層之無機粒子(G)。That is, the present invention is a resin composition comprising: fine particles, a compound (B) having a structure represented by the general formula (1) and a functional group that generates an amine group by heat, and a binder resin (C) , the fine particles are organic pigments (F) or inorganic particles (G) having a coating layer containing carbon.
(通式(1)中,X係表示Si、Ti或Zr原子。R1 ~R3 各自獨立地表示羥基、甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基或碳數1~6的烴基。R1 ~R3 各自可以相同也可以相異,但其中至少一個為羥基、甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基或異丁氧基。) [發明之效果](In the general formula (1), X represents a Si, Ti or Zr atom. R 1 to R 3 each independently represent a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, Isobutoxy or hydrocarbon group having 1 to 6 carbon atoms. R 1 to R 3 may be the same or different, but at least one of them is hydroxyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy.) [Effect of Invention]
依據本發明之樹脂組成物,即使是在微細的圖案,也能得到兼具優良的分散性(也就是在包含導電性粒子的樹脂組成物中之優良的導電性)與密著性之圖案。According to the resin composition of the present invention, even in a fine pattern, a pattern having both excellent dispersibility (that is, excellent conductivity in the resin composition containing conductive particles) and adhesion can be obtained.
[用以實施發明的形態][Form for carrying out the invention]
本發明之樹脂組成物的特徵為:包含微粒、具有以通式(1)所表示之結構及藉由熱產生胺基的官能基之化合物(B)、以及黏結劑樹脂(C),其中該微粒為有機顏料(F)或具有包含碳的被覆層之無機粒子(G)。The resin composition of the present invention is characterized by comprising fine particles, a compound (B) having a structure represented by the general formula (1) and a functional group that generates an amine group by heat, and a binder resin (C), wherein the The fine particles are organic pigments (F) or inorganic particles (G) having a coating layer containing carbon.
[有機顏料(F)] 本發明之樹脂組成物較佳包含有機顏料(F)作為微粒。[Organic Pigment (F)] The resin composition of the present invention preferably contains the organic pigment (F) as fine particles.
作為有機顏料,有著色有機顏料,例如可列舉:二酮吡咯并吡咯系顏料;偶氮、雙偶氮、多偶氮等的偶氮系顏料;銅酞青、鹵化銅酞青、無金屬酞青等的酞青系顏料;胺蒽醌、二胺基二蒽醌、蔥嘧啶、黃士酮、蒽嵌蒽醌(anthanthrone)、陰丹士林、皮蒽酮、紫蒽酮等的蒽醌系顏料;喹吖酮系顏料;二㗁系顏料;培林酮(perinone)系顏料;苝系顏料;硫靛藍系顏料;異吲哚啉系顏料;異吲哚啉酮系顏料;喹啉黃系顏料;士林(threne)系顏料;金屬錯合物系顏料等。Examples of organic pigments include colored organic pigments, and examples thereof include diketopyrrolopyrrole-based pigments; azo-based pigments such as azo, disazo, and polyazo; copper phthalocyanine, copper halide phthalocyanine, and metal-free phthalocyanine. Phthalocyanine pigments such as blue; anthraquinones such as amine anthraquinone, diamine dianthraquinone, allion pyrimidine, flavonoids, anthraquinone (anthanthrone), indanthrene, picanthrone, violanthrone, etc. pigment; quinacridone pigment; two 㗁 Pigments; Perinone pigments; Perylene pigments; Sulfindigo pigments; Isoindolinone pigments; Isoindolinone pigments; Quinoline yellow pigments; Threne pigments; Metal complex pigments, etc.
作為有機顏料,可舉出例如黑色有機顏料、混色有機顏料等。作為黑色有機顏料,可舉出例如:碳黑、苝黑、苯胺黑、苯并呋喃酮系顏料等。作為混色有機顏料,可舉出將2種以上具有紅、藍、綠、紫、黃色、洋紅、靛青等色彩的顏料加以混色並擬黑色化而成的顏料。也可含有2種以上的這些有機顏料。這些顏料之中,從進一步提升著色膜的遮光性,調整著色膜的導電性之觀點來看,較佳為碳黑。As an organic pigment, a black organic pigment, a color mixing organic pigment, etc. are mentioned, for example. Examples of black organic pigments include carbon black, perylene black, aniline black, benzofuranone-based pigments, and the like. Examples of color-mixing organic pigments include those obtained by mixing two or more pigments having colors such as red, blue, green, violet, yellow, magenta, and indigo, and making them pseudo-black. Two or more of these organic pigments may be contained. Among these pigments, carbon black is preferable from the viewpoint of further improving the light-shielding properties of the colored film and adjusting the electrical conductivity of the colored film.
又,本發明中,為了使其效果更顯著,有機顏料(F)的表面較佳經過酸性處理。藉由表面經過酸性處理,在使分散穩定性提升的同時,藉由與化合物(B)的交互作用,而能提升基材密著性。作為將碳黑的表面進行酸性處理之方法,已知有:藉由O3 將表面氧化之方法(日本特開平11-181326號公報)、表面的濕式氧化處理之方法(日本特許第4464081號公報)、及以包含磺酸基等的非聚合物基之有機基所致的表面改質之方法(國際公開第2006/044676號)等。Moreover, in this invention, in order to make the effect more remarkable, it is preferable that the surface of an organic pigment (F) is acid-processed. When the surface is acid-treated, the dispersion stability can be improved, and the adhesion to the substrate can be improved by the interaction with the compound (B). As a method of acid-treating the surface of carbon black, a method of oxidizing the surface by O 3 (Japanese Patent Laid-Open No. 11-181326) and a method of wet oxidation of the surface (Japanese Patent No. 4464081) are known. Gazette), a method of surface modification by an organic group including a sulfonic acid group and other non-polymeric groups (International Publication No. 2006/044676), and the like.
本發明之樹脂組成物中,相對於固體含量100質量%,有機顏料(F)的含量比率較佳為10~70質量%。藉由含量比率在10質量%以上,能以薄膜來形成具有著色力的被膜。含量比率較佳為20質量%以上。另一方面,藉由含量比率在70質量%以下,在能夠提升有機顏料(F)的分散穩定性的同時,還能確保與基材的密著性。含量比率較佳為60質量%以下。在此,總固體含量係指在樹脂組成物所含有的成分內,排除溶劑的全部成分。In the resin composition of the present invention, the content ratio of the organic pigment (F) is preferably 10 to 70 mass % with respect to 100 mass % of the solid content. When the content ratio is 10% by mass or more, a film having coloring power can be formed as a thin film. The content ratio is preferably 20% by mass or more. On the other hand, when the content ratio is 70 mass % or less, the dispersion stability of the organic pigment (F) can be improved, and the adhesion to the substrate can be secured. The content ratio is preferably 60% by mass or less. Here, the total solid content means all the components excluding the solvent among the components contained in the resin composition.
[具有包含碳的被覆層之無機粒子(G)] 本發明之樹脂組成物較佳含有具有包含碳的被覆層之無機粒子(G)(以下簡稱為「無機粒子(G)」。)。無機粒子(G)係例如以碳化合物等來被覆表面而成的粒子。作為碳化合物的例子,可舉出:芳香族烴、脂肪族烴、或它們的氧化物、氮化物、硫化物、磷化物等。其中,從能抑制在低溫下的無機粒子(G)彼此熔接之觀點來看,較佳為芳香族烴、脂肪族烴或它們的氧化物。藉由含有無機粒子(G),而能對本發明之樹脂組成物的硬化物賦予導電性、遮光性等各種功能。另外,由於利用包含碳的被覆層被覆無機粒子(G)的表面,所以可抑制低溫下的無機粒子(G)彼此的熔接,並可抑制因粒子粗大化所造成的解析度降低、殘渣的產生。更進一步,藉由與後述的藉由熱產生胺基之官能基反應,而能提升密著性。[Inorganic particles (G) having a coating layer containing carbon] The resin composition of the present invention preferably contains inorganic particles (G) having a coating layer containing carbon (hereinafter simply referred to as "inorganic particles (G)"). The inorganic particles (G) are particles in which the surface is covered with, for example, a carbon compound or the like. Examples of carbon compounds include aromatic hydrocarbons, aliphatic hydrocarbons, or their oxides, nitrides, sulfides, phosphides, and the like. Among them, aromatic hydrocarbons, aliphatic hydrocarbons, or oxides thereof are preferred from the viewpoint of suppressing fusion of inorganic particles (G) at low temperatures. By containing the inorganic particles (G), various functions such as conductivity and light-shielding properties can be imparted to the cured product of the resin composition of the present invention. In addition, since the surfaces of the inorganic particles (G) are covered with a coating layer containing carbon, fusion of the inorganic particles (G) at low temperatures can be suppressed, and resolution reduction and generation of residues due to particle coarsening can be suppressed. . Furthermore, adhesiveness can be improved by reacting with the functional group which generate|occur|produces an amine group by heat mentioned later.
作為無機粒子(G),可舉出導電性粒子(A)。作為導電性粒子,可舉出例如:金(Au)、銀(Ag)、銅(Cu)、鎳(Ni)、錫(Sn)、鉍(Bi)、鉛(Pb)、鋅(Zn)、鈀(Pd)、鉑(Pt)、鋁(Al)、鎢(W)或鉬(Mo)等的金屬微粒。其中較佳為含有選自包含金、銀、銅、鎳、錫、鉍、鉛、鋅、鈀、鉑及鋁之群組中的至少一個元素之金屬微粒;從提升導電性的觀點來看,更佳為銀的微粒。As inorganic particle (G), electroconductive particle (A) is mentioned. Examples of the conductive particles include gold (Au), silver (Ag), copper (Cu), nickel (Ni), tin (Sn), bismuth (Bi), lead (Pb), zinc (Zn), Metal fine particles such as palladium (Pd), platinum (Pt), aluminum (Al), tungsten (W), or molybdenum (Mo). Among them, metal fine particles containing at least one element selected from the group consisting of gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum and aluminum are preferred; from the viewpoint of enhancing conductivity, More preferably, they are fine particles of silver.
作為以包含碳的被覆層來被覆無機粒子的表面之方法,可舉出例如:藉由熱電漿法來使反應性氣體與無機粒子接觸之方法(日本特開2007-138287號公報)。無機粒子(G)的表面較佳為完全被被覆,但只要是達成本發明之目的,有一部分被覆不完全的粒子存在是被容許的。As a method of covering the surfaces of the inorganic particles with a coating layer containing carbon, for example, a method of bringing a reactive gas into contact with the inorganic particles by a thermoplasma method (Japanese Patent Laid-Open No. 2007-138287 ). It is preferable that the surface of the inorganic particle (G) is completely covered, but as long as the object of the present invention is achieved, it is acceptable that some particles are not completely covered.
被覆層的平均厚度較佳為0.1~10nm。若在此範圍,則藉由抑制無機微細粒子彼此的熔接,能使微細圖案加工性提升,且可藉由在300℃以下的溫度進行熱處理而進一步提升期望的功能。The average thickness of the coating layer is preferably 0.1 to 10 nm. Within this range, fine pattern workability can be improved by suppressing fusion of inorganic fine particles, and desired functions can be further improved by heat treatment at a temperature of 300° C. or lower.
被覆層的平均厚度係測定無機粒子(G)藉由熱天平測定的質量減少,假設該數值全部是因碳的燃燒所產生,將碳的密度設為2.0,而能由粒徑來算出被覆層的平均厚度。在粒徑(Dp)已知的導電性粒子以平均厚度A(μm)被覆碳,將經碳被覆的導電性粒子的個數設為n。將在熱天平測定中最初秤取的質量設為W1 (g)、將完全燃燒碳後的質量設為W2 (g)、將無機粒子的密度設為ρ時,若已知Dp與W2 ,則能由以下的式子來算出n。 W2 =π/6×Dp3 ρ×n 並且,能由以下的式子來算出被覆層的平均厚度A。 W1 -W2 ={4/3×π(Dp/2+A)3 -π/6×Dp3 }×2.0×n 無機粒子(G)之導電性粒子(A)依據形成包含碳的被覆層之材料的種類,表面會帶有酸性或鹼性。使導電性粒子(A)以1質量%的濃度懸浮在水中的懸浮液的pH較佳為4.0~10.0。此pH係如下測定。在2.7g的純水中添加0.3g的導電性粒子(A),調製濃度1質量%的懸浮液,然後攪拌5分鐘,靜置15分鐘。採取所得到的懸浮液之上部澄清液,用pH計測定。在pH為4.0以上時,由於碳被覆層與後述的分散劑堅固地交互作用,所以即便是少許的分散劑含量也能穩定地分散。在pH為10.0以下時,在能抑制導電性粒子(A)與黏結劑樹脂(C)的反應的同時,將樹脂組成物的pH保持在適當範圍,能讓保存穩定性良好。為了控制導電性粒子(A)的懸浮液之pH,例如在藉由熱電漿法製作導電性粒子(A)的情形,能藉由變更反應性氣體的種類、導入比例來達成。The average thickness of the coating layer is measured by the mass reduction of the inorganic particles (G) measured by a thermobalance. Assuming that this value is all caused by the combustion of carbon, the coating layer can be calculated from the particle size by setting the carbon density to 2.0. average thickness. Carbon is coated on the electroconductive particle whose particle diameter (Dp) is known by the average thickness A (micrometer), and let the number of objects of the electroconductive particle coated with carbon be n. When the mass first weighed in the thermobalance measurement is W 1 (g), the mass after complete combustion of carbon is W 2 (g), and the density of inorganic particles is ρ, if Dp and W are known 2 , n can be calculated from the following formula. W 2 =π/6×Dp 3 ρ×n Further, the average thickness A of the coating layer can be calculated from the following equation. W 1 -W 2 ={4/3×π(Dp/2+A) 3 -π/6×Dp 3 }×2.0×n The conductive particles (A) of the inorganic particles (G) form a coating containing carbon The type of material of the layer, the surface will be acidic or alkaline. The pH of the suspension in which the electroconductive particle (A) is suspended in water at a concentration of 1% by mass is preferably 4.0 to 10.0. This pH is determined as follows. After adding 0.3 g of conductive particles (A) to 2.7 g of pure water to prepare a suspension having a concentration of 1 mass %, the mixture was stirred for 5 minutes and left to stand for 15 minutes. The upper clear liquid of the obtained suspension was collected and measured with a pH meter. When the pH is 4.0 or more, since the carbon coating layer strongly interacts with the dispersant described later, even a small amount of the dispersant can be stably dispersed. When the pH is 10.0 or less, the reaction between the conductive particles (A) and the binder resin (C) can be suppressed, and the pH of the resin composition can be maintained in an appropriate range, thereby achieving good storage stability. In order to control the pH of the suspension of electroconductive particle (A), for example, when producing electroconductive particle (A) by the thermoplasma method, it can be achieved by changing the kind of reactive gas, and an introduction ratio.
微粒的平均一次粒徑較佳為1~700nm。特別是導電性粒子(A)的平均一次粒徑較佳為1~700nm。藉由平均一次粒徑在1nm以上,能使粒子比表面積變小,即使是少許的分散劑量也能穩定地分散。又,藉由平均一次粒徑為700nm以下,能形成微細的圖案。此處,微粒的平均一次粒徑係使用掃描式電子顯微鏡以隨機選出的100個一次粒子之粒徑的平均值算出。各個一次粒子的粒徑係測定一次粒子的長徑與短徑,自其平均值算出。The average primary particle diameter of the fine particles is preferably 1 to 700 nm. In particular, it is preferable that the average primary particle diameter of electroconductive particle (A) is 1-700 nm. When the average primary particle size is 1 nm or more, the specific surface area of the particles can be reduced, and even a small amount of dispersing amount can be stably dispersed. Moreover, when the average primary particle diameter is 700 nm or less, a fine pattern can be formed. Here, the average primary particle diameter of the fine particles is calculated as an average value of particle diameters of 100 randomly selected primary particles using a scanning electron microscope. The particle diameter of each primary particle is calculated by measuring the major axis and minor axis of the primary particle from the average value.
本發明之樹脂組成物中,相對於固體含量100質量%,無機粒子(G)的含量比率較佳為65~95質量%。藉由含量比率在65質量%以上,殘留的有機成分不會妨礙無機粒子(G)彼此的接觸,在無機粒子(G)為導電性粒子(A)的情形導電性更為提升。含量比率較佳為75質量%以上。另一方面,藉由含量比率在95質量%以下,殘留的有機成分能使樹脂組成物中的無機粒子(G)的分散性穩定化,而形成微細的圖案,能減低基板上的殘渣。含量比率較佳為85質量%以下。此處,總固體含量係指樹脂組成物所含有的成分內,排除溶劑的全部成分。In the resin composition of the present invention, the content ratio of the inorganic particles (G) is preferably 65 to 95% by mass relative to 100% by mass of the solid content. When the content ratio is 65 mass % or more, the remaining organic components do not hinder the contact of the inorganic particles (G), and the conductivity is further improved when the inorganic particles (G) are the conductive particles (A). The content ratio is preferably 75% by mass or more. On the other hand, when the content ratio is 95 mass % or less, the residual organic components can stabilize the dispersibility of the inorganic particles (G) in the resin composition, form fine patterns, and reduce residues on the substrate. The content ratio is preferably 85% by mass or less. Here, the total solid content means all the components excluding the solvent among the components contained in the resin composition.
總固體含量中無機粒子(G)所佔的比率能藉由對樹脂組成物的全部成分進行定量分析來算出。其中,後述的各成分的比例也能以相同方法來算出。The ratio of the inorganic particles (G) in the total solid content can be calculated by quantitatively analyzing all the components of the resin composition. However, the ratio of each component mentioned later can also be calculated by the same method.
樹脂組成物的全部成分之分析方法如下。 (i) 以有機溶媒將樹脂組成物稀釋,進行1 H-NMR測定、GC測定及GC/MS測定,調查其大概內容物。 (ii) 以有機溶媒萃取樹脂組成物後進行離心分離,分離成可溶成分與不溶成分。 (iii) 對上述不溶成分,以高極性有機溶媒萃取後進行離心分離,進一步分離成可溶成分與不溶成分。 (iv) 對上述(ii)及(iii)所得到的可溶成分之混合液進行IR測定、1 H-NMR測定及GC/MS測定。進一步對上述混合液作GPC分離。對所得到的分離物進行IR測定及1 H-NMR測定。又,對該分離物視需要進行GC測定、GC/MS測定、熱裂解GC/MS測定及MALDI/MS測定。 (v) 對上述(iii)所得到的不溶成分進行IR測定或TOF-SIMS測定。於確認到有機物存在之情形,進行熱裂解GC/MS或TPD/MS測定。 (vi) 藉由將上述(i)、(iv)及(v)的測定結果進行綜合判斷,可求出樹脂組成物所含有的各成分之含有率。其中,作為在上述(iii)所使用的高極性有機溶媒,較佳為氯仿或甲醇等。The analysis method of all the components of the resin composition is as follows. (i) The resin composition was diluted with an organic solvent, 1 H-NMR measurement, GC measurement, and GC/MS measurement were performed to investigate the approximate contents. (ii) The resin composition is extracted with an organic solvent and then centrifuged to separate the soluble component and the insoluble component. (iii) The above-mentioned insoluble components are extracted with a highly polar organic solvent, and then centrifuged, and further separated into soluble components and insoluble components. (iv) IR measurement, 1 H-NMR measurement, and GC/MS measurement were performed on the mixed solution of the soluble components obtained in the above (ii) and (iii). The above mixture was further separated by GPC. The obtained isolate was subjected to IR measurement and 1 H-NMR measurement. In addition, GC measurement, GC/MS measurement, pyrolysis GC/MS measurement, and MALDI/MS measurement are carried out on the isolate as necessary. (v) IR measurement or TOF-SIMS measurement is performed on the insoluble component obtained in the above (iii). When the presence of organic matter is confirmed, thermal cracking GC/MS or TPD/MS measurement is performed. (vi) The content rate of each component contained in the resin composition can be obtained by comprehensively judging the measurement results of the above (i), (iv) and (v). Among them, as the highly polar organic solvent used in the above (iii), chloroform, methanol, or the like is preferable.
[具有以通式(1)所表示之結構及藉由熱產生胺基的官能基之化合物(B)] 本發明之樹脂組成物係包含具有以下述通式(1)所表示之結構及藉由熱產生胺基的官能基之化合物(B)(以下簡稱為「化合物(B)」。)。[Compound (B) having a structure represented by the general formula (1) and a functional group that generates an amine group by heat] The resin composition of the present invention contains a compound (B) having a structure represented by the following general formula (1) and a functional group that generates an amine group by heat (hereinafter abbreviated as "compound (B)").
通式(1)中,X表示Si、Ti或Zr原子。R1 ~R3 各自獨立地表示羥基、甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基或碳數1~6的烴基。R1 ~R3 各自可以相同也可以相異,但其中至少一個為羥基、甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基或異丁氧基。In the general formula (1), X represents a Si, Ti or Zr atom. R 1 to R 3 each independently represent a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, or a hydrocarbon group having 1 to 6 carbon atoms. Each of R 1 to R 3 may be the same or different, but at least one of them is hydroxy, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy.
作為碳數1~6的烴基,可舉出脂肪族烴基。脂肪族烴基可以是直鏈的也可以是分支的,也可以是一部分或全體為環狀的。碳數1~6的烴基可舉出例如:甲基、乙基、丙基、異丙基、丁基、異丁基、戊基、環戊基、己基或環己基等。這些之中,從立體阻礙小、不妨礙與基板的密著之觀點來看,較佳為甲基、乙基或丙基。Examples of the hydrocarbon group having 1 to 6 carbon atoms include aliphatic hydrocarbon groups. The aliphatic hydrocarbon group may be linear or branched, and may be partially or entirely cyclic. As a C1-C6 hydrocarbon group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, etc. are mentioned, for example. Among these, a methyl group, an ethyl group, or a propyl group is preferable from the viewpoint that the steric hindrance is small and the adhesion with the substrate is not hindered.
化合物(B)係在形成圖案後,藉由在例如100~300℃的溫度範圍加熱5~120分鐘,而生成胺基。所生成的胺基與有機顏料(F)或無機粒子(G)的表面相互作用,藉以通式(1)所表示之結構與基材相互作用,提升圖案與基材的密著性。密著性係依據JIS K5600-5-6(1999年),以百格測試(cross-cut test)評價。此外,R1 ~R3 之中,羥基、甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基藉由加熱而脫離並生成矽醇基,矽醇基彼此聚縮合,生成具有以通式(2)所表示的結構及胺基之化合物(E)。The compound (B) generates an amine group by heating in a temperature range of, for example, 100 to 300° C. for 5 to 120 minutes after patterning. The generated amine group interacts with the surface of the organic pigment (F) or the inorganic particle (G), whereby the structure represented by the general formula (1) interacts with the substrate to improve the adhesion between the pattern and the substrate. Adhesion was evaluated by a cross-cut test in accordance with JIS K5600-5-6 (1999). In addition, among R 1 to R 3 , hydroxyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy are removed by heating to form silanol groups, silanols The groups are polycondensed with each other to generate a compound (E) having a structure represented by the general formula (2) and an amine group.
(通式(2)中,Y表示Si、Ti或Zr原子。R4 ~R6 各自獨立地表示羥基、甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、碳數1~6的烴基或架橋氧。R4 ~R6 各自可以相同也可以相異,但其中至少一個為架橋氧。) 另一方面,由於在加熱前的樹脂組成物中,化合物(B)中不存在胺基,故化合物(B)不會與有機顏料(F)或無機粒子(G)的表面反應,而能穩定地存在。因此,於樹脂組成物的保存中,防止因黏度變化、有機顏料(F)或無機粒子(G)的分散性惡化所造成的功能抑制,在樹脂組成物的塗布膜中不會導致因顯影殘渣而造成基板的穿透率降低。另外,能提升圖案加工性。此處,目的為產生胺基之加熱,亦能同時進行與目的為賦予樹脂組成物圖案功能之加熱。(In the general formula (2), Y represents a Si, Ti or Zr atom. R 4 to R 6 each independently represent a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isopropoxy group, and an isopropyl group. Butoxy group, hydrocarbon group having 1 to 6 carbon atoms, or bridging oxygen. R 4 to R 6 may be the same or different, but at least one of them is bridging oxygen.) On the other hand, since in the resin composition before heating, , there is no amine group in the compound (B), so the compound (B) does not react with the surface of the organic pigment (F) or the inorganic particle (G), and can exist stably. Therefore, during the storage of the resin composition, function inhibition due to viscosity change and deterioration of the dispersibility of the organic pigment (F) or inorganic particles (G) is prevented, and development residues do not occur in the coating film of the resin composition. As a result, the penetration rate of the substrate is reduced. In addition, pattern workability can be improved. Here, the heating for the purpose of generating the amine group and the heating for the purpose of imparting a pattern function to the resin composition can be simultaneously performed.
作為通式(1)的中心元素X,從反應性的觀點來看較佳為Si。而作為通式(1)的R1 ~R3 ,從與基材的密著性之觀點來看,較佳為甲氧基或乙氧基,更佳為甲氧基。The central element X of the general formula (1) is preferably Si from the viewpoint of reactivity. On the other hand, as R 1 to R 3 in the general formula (1), a methoxy group or an ethoxy group is preferable, and a methoxy group is more preferable from the viewpoint of the adhesiveness with the base material.
作為藉由熱產生胺基之官能基,可舉出醯胺基、亞胺基、脲基及異氰酸酯基。藉由使用這些官能基之中的至少一種,能提高樹脂組成物及塗布膜的穩定性,進一步提升與加熱後的基材之密著性。從提高樹脂組成物的有機顏料(F)與無機粒子(G)之分散穩定性而進一步提升導電性、抑制殘渣的觀點來看,特別以脲基為較佳的。As a functional group which generates an amine group by heat, an amide group, an imine group, a urea group, and an isocyanate group can be mentioned. By using at least one of these functional groups, the stability of the resin composition and the coating film can be improved, and the adhesion to the heated substrate can be further improved. From the viewpoints of improving the dispersion stability of the organic pigment (F) and the inorganic particles (G) in the resin composition, further improving the conductivity, and suppressing residues, the urea group is particularly preferred.
化合物(B)具體來說可舉出:3-三甲氧矽基-N-(1,3-二甲基亞丁基)丙胺、3-三乙氧矽基-N-(1,3-二甲基亞丁基)丙胺、3-三丙氧矽基-N-(1,3-二甲基亞丁基)丙胺、3-三甲氧矽基-N-(苯亞甲基)丙胺、3-三乙氧矽基-N-(苯亞甲基)丙胺、3-三丙氧矽基-N-(苯亞甲基)丙胺、3-脲丙基三乙氧基矽烷、3-脲丙基三甲氧基矽烷、3-異氰酸酯基丙基三乙氧基矽烷及3-異氰酸酯基丙基三甲氧基矽烷。其中,作為具有脲基的化合物,更佳為3-脲丙基三乙氧基矽烷、3-脲丙基三甲氧基矽烷。特佳可舉出3-脲丙基三甲氧基矽烷。Specific examples of the compound (B) include: 3-trimethoxysilyl-N-(1,3-dimethylbutylene)propylamine, 3-triethoxysilyl-N-(1,3-dimethylene) butylene)propylamine, 3-tripropoxysilyl-N-(1,3-dimethylbutylene)propylamine, 3-trimethoxysilyl-N-(benzylidene)propylamine, 3-triethyl Oxysilyl-N-(benzylidene)propylamine, 3-tripropoxysilyl-N-(benzylidene)propylamine, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxy Silane, 3-Isocyanatopropyltriethoxysilane and 3-Isocyanatopropyltrimethoxysilane. Among them, as the compound having a urea group, 3-ureidopropyltriethoxysilane and 3-ureidopropyltrimethoxysilane are more preferable. Particularly preferred is 3-ureidopropyltrimethoxysilane.
本發明之樹脂組成物中,化合物(B)的含量相對於100質量份的微粒,較佳為0.1~10質量份。特別是相對於100質量份的導電性粒子(A),較佳為0.1~2.5質量份。於含量在0.1質量份以上時,能進一步提升密著性。化合物(B)的含量更佳為0.5質量份以上。另一方面,於含量在2.5質量份以下時,能進一步提升導電性。化合物(B)的含量更佳為1.0質量份以下。In the resin composition of the present invention, the content of the compound (B) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of fine particles. In particular, it is preferable that it is 0.1-2.5 mass parts with respect to 100 mass parts of electroconductive particles (A). When the content is 0.1 part by mass or more, the adhesiveness can be further improved. The content of the compound (B) is more preferably 0.5 part by mass or more. On the other hand, when the content is 2.5 parts by mass or less, the conductivity can be further improved. The content of the compound (B) is more preferably 1.0 part by mass or less.
本發明之樹脂組成物中,化合物(B)的含量係相對於100質量份的有機顏料(F),較佳為0.5~10質量份。於含量在0.5質量份以上時,能進一步提升密著性。化合物(B)的含量更佳為1.0質量份以上。另一方面,於含量在10質量份以下時,能進一步提升保存穩定性。化合物(B)的含量更佳為7.0質量份以下。In the resin composition of the present invention, the content of the compound (B) is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the organic pigment (F). When the content is 0.5 parts by mass or more, the adhesiveness can be further improved. The content of the compound (B) is more preferably 1.0 part by mass or more. On the other hand, when the content is 10 parts by mass or less, the storage stability can be further improved. The content of the compound (B) is more preferably 7.0 parts by mass or less.
[黏結劑樹脂(C)] 本發明之樹脂組成物含有黏結劑樹脂(C)。黏結劑樹脂(C)係配合樹脂組成物的黏度等來適當選擇,不受特別限制。作為黏結劑樹脂(C),較佳為使用例如:乙基纖維素、硝化纖維素等的纖維素系樹脂、聚乙烯醇縮丁醛等的縮醛系樹脂、將甲基丙烯酸丁酯、甲基丙烯酸甲酯等加以聚合所得到之丙烯酸系樹脂等,而從組成設計的容易性之觀點來看,特佳為丙烯酸系樹脂。此處丙烯酸系樹脂係指在樹脂成分中至少共聚合有(甲基)丙烯酸系單體之樹脂。此處作為(甲基)丙烯酸系單體可舉出例如:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸三級丁氧羰酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸甲基金剛烷基酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸四氫哌喃酯、(甲基)丙烯酸二環戊基酯、(甲基)丙烯酸二環戊烯基酯、(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸異莰酯或(甲基)丙烯酸苯酯。[Binder resin (C)] The resin composition of the present invention contains a binder resin (C). The binder resin (C) is appropriately selected according to the viscosity of the resin composition and the like, and is not particularly limited. As the binder resin (C), it is preferable to use, for example, cellulose-based resins such as ethyl cellulose and nitrocellulose, acetal-based resins such as polyvinyl butyral, butyl methacrylate, methyl methacrylate, and the like. Acrylic resins obtained by polymerizing methyl methacrylate and the like are particularly preferred from the viewpoint of ease of composition design. Here, the acrylic resin refers to a resin in which at least a (meth)acrylic monomer is copolymerized in the resin component. Here, as a (meth)acrylic-type monomer, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, Tertiary butyl (meth)acrylate, tertiary butoxycarbonyl (meth)acrylate, benzyl (meth)acrylate, methyladamantyl (meth)acrylate, cyclohexyl (meth)acrylate ester, tetrahydropyranyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylate 2-hydroxyethyl acrylate, isobornyl (meth)acrylate or phenyl (meth)acrylate.
作為(甲基)丙烯酸系單體以外的共聚成分,能使用具有碳-碳雙鍵的化合物。作為此種化合物,可舉出例如:苯乙烯、對甲基苯乙烯、鄰甲基苯乙烯、間甲基苯乙烯、α-甲基苯乙烯或對羥基苯乙烯等的芳香族乙烯基化合物、(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺或N-乙烯基吡咯啶酮等的醯胺系不飽和化合物、(甲基)丙烯腈、丙烯醇、乙酸乙烯酯、環己基乙烯基醚、正丙基乙烯基醚、異丙基乙烯基醚、正丁基乙烯基醚、異丁基乙烯基醚、2-羥乙基乙烯基醚或4-羥丁基乙烯基醚。As a copolymerization component other than a (meth)acrylic-type monomer, the compound which has a carbon-carbon double bond can be used. Examples of such compounds include aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α-methylstyrene, and p-hydroxystyrene, (meth)acrylamide, N-methylol (meth)acrylamide, N-vinylpyrrolidone and other amide-based unsaturated compounds, (meth)acrylonitrile, allyl alcohol, vinyl acetate , cyclohexyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-hydroxyethyl vinyl ether, or 4-hydroxybutyl vinyl ether base ether.
黏結劑樹脂(C)較佳具有酸解離性基。酸解離性基係在加熱下藉由酸的作用而熱氧化分解並脫離之有機基。於具有此種酸解離性基時,例如在酸性氣體環境下,藉由以100~300℃加熱,酸解離性基會輕易地熱氧化分解並脫離,本發明之樹脂組成物的硬化物會收縮,使該硬化物中的微粒比率上升,而能進一步提升功能。而其結果,例如在微粒為無機粒子(G)的情形,會變得容易得到比電阻10~1,000μΩ・cm之期望的導電性。在此情形,若並用後述的光酸產生劑及/或熱酸產生劑,該效果會變得更為明顯。The binder resin (C) preferably has an acid dissociable group. The acid dissociable group is an organic group that is thermally oxidatively decomposed and released by the action of an acid under heating. When there is such an acid dissociable group, for example, in an acidic gas environment, by heating at 100-300° C., the acid dissociable group is easily thermally oxidized and decomposed and detached, and the cured product of the resin composition of the present invention will shrink. By increasing the particle ratio in the cured product, the function can be further improved. As a result, for example, when the fine particles are inorganic particles (G), it becomes easy to obtain desired electrical conductivity with a specific resistance of 10 to 1,000 μΩ·cm. In this case, when the photoacid generator and/or the thermal acid generator mentioned later are used together, this effect becomes more remarkable.
酸解離性基較佳為碳數4~15的有機基。於酸解離性基的碳數在4以上時,脫離後,由於在低溫氣化,所以不會在前述硬化物中產生大氣泡,妨礙微粒彼此的接觸,故進一步提升了功能。酸解離性基的碳數較佳為6以上。另一方面,於酸解離性基的碳數為15以下時,脫離後,解離性基不會殘存在前述硬化物中妨礙微粒彼此的接觸,所以更進一步提升功能。又,在前述硬化物中即使產生氣泡也容易藉由加熱使其消失。The acid dissociable group is preferably an organic group having 4 to 15 carbon atoms. When the number of carbon atoms of the acid dissociable group is 4 or more, since it is vaporized at a low temperature after detachment, large bubbles are not generated in the hardened product, and the contact of the fine particles is not prevented, so the function is further improved. The carbon number of the acid dissociable group is preferably 6 or more. On the other hand, when the number of carbon atoms of the acid dissociable group is 15 or less, the dissociable group does not remain in the hardened product after dissociation and prevents the contact between the fine particles, so that the function is further improved. Moreover, even if bubbles generate|occur|produce in the said hardened material, it is easy to make it disappear by heating.
作為酸解離性基,可舉出例如:三級丁基、三級丁氧羰基、苯甲基、甲基金剛烷基或四氫哌喃基。As an acid dissociable group, a tertiary butyl group, a tertiary butoxycarbonyl group, a benzyl group, a methyladamantyl group, or a tetrahydropyranyl group is mentioned, for example.
黏結劑樹脂(C)較佳為共聚合20~80莫耳%的具有酸解離性基之化合物而成的樹脂。特別在黏結劑樹脂(C)為丙烯酸系樹脂之情形,於丙烯酸系樹脂中較佳包含20~80莫耳%的具有酸解離性基之(甲基)丙烯酸酯作為單體成分。The binder resin (C) is preferably a resin obtained by copolymerizing 20 to 80 mol % of a compound having an acid dissociable group. In particular, when the binder resin (C) is an acrylic resin, the acrylic resin preferably contains 20 to 80 mol % of (meth)acrylate having an acid dissociable group as a monomer component.
將本發明之樹脂組成物使用作為感光性樹脂組成物,由於能形成微細的配線圖案所以是較佳的。為了作為感光性樹脂組成物,較佳進一步具有後述的感光劑(D),黏結劑樹脂(C)較佳具有鹼溶性基。作為鹼溶性基,可舉出:羧基、醇性羥基、酚性羥基、磺酸基、磷酸基、酸酐基等,特別從反應性與通用性的觀點來看,較佳為羧基。It is preferable to use the resin composition of the present invention as a photosensitive resin composition because a fine wiring pattern can be formed. As a photosensitive resin composition, it is preferable to further have a photosensitizer (D) mentioned later, and it is preferable that a binder resin (C) has an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group, an acid anhydride group, and the like, and a carboxyl group is particularly preferred from the viewpoint of reactivity and versatility.
於黏結劑樹脂(C)為具有鹼溶性基之丙烯酸系樹脂時,組成設計的容易性為更佳的。於黏結劑樹脂(C)為具有鹼溶性基之丙烯酸系樹脂的情形,賦予鹼溶性的共聚合成分之含有羧基的化合物,可舉出例如:(甲基)丙烯酸、伊康酸、巴豆酸、馬來酸或富馬酸或它們的酸酐。When the binder resin (C) is an acrylic resin having an alkali-soluble group, the ease of composition design is better. In the case where the binder resin (C) is an acrylic resin having an alkali-soluble group, the carboxyl group-containing compound that imparts the alkali-soluble copolymerization component includes, for example, (meth)acrylic acid, itonic acid, crotonic acid, Maleic or fumaric acid or their anhydrides.
黏結劑樹脂(C)的羧酸當量較佳為50~1,000g/mol。黏結劑樹脂(C)的羧酸當量能藉由測定酸價來算出。又,黏結劑樹脂(C)的雙鍵當量,為了能以高水準兼顧硬度與抗裂性,較佳為150~10,000g/mol。黏結劑樹脂(C)的雙鍵當量能藉由測定碘價來算出。The carboxylic acid equivalent of the binder resin (C) is preferably 50 to 1,000 g/mol. The carboxylic acid equivalent of the binder resin (C) can be calculated by measuring the acid value. In addition, the double bond equivalent of the binder resin (C) is preferably 150 to 10,000 g/mol in order to achieve both hardness and crack resistance at a high level. The double bond equivalent of the binder resin (C) can be calculated by measuring the iodine value.
黏結劑樹脂(C)的重量平均分子量(Mw),藉由凝膠滲透層析(GPC)測定以聚苯乙烯換算,較佳為1,000~100,000。藉由使重量平均分子量(Mw)在上述範圍,可得到優良的塗布特性,形成圖案時對顯影液的溶解性也會變好。The weight average molecular weight (Mw) of the binder resin (C) is preferably 1,000 to 100,000 in terms of polystyrene measured by gel permeation chromatography (GPC). By making the weight average molecular weight (Mw) in the above-mentioned range, excellent coating properties can be obtained, and the solubility in a developing solution at the time of pattern formation can also be improved.
在將本發明之樹脂組成物使用作為感光性樹脂組成物的情形,為了增加感光性樹脂組成物的藉由曝光所致的硬化反應之速度,較佳為黏結劑樹脂(C)成為於側鏈或分子末端具有碳-碳雙鍵的(甲基)丙烯酸系共聚物。作為具有碳-碳雙鍵的官能基,可舉出例如:乙烯基、烯丙基或(甲基)丙烯酸基。為了使此種官能基加成至(甲基)丙烯酸系共聚物上,有下述方法:使具有環氧丙基或異氰酸酯基和碳-碳雙鍵之化合物或者(甲基)丙烯醯氯或烯丙氯,與(甲基)丙烯酸系共聚物中的巰基、胺基、羥基或羧基進行加成反應。When the resin composition of the present invention is used as the photosensitive resin composition, in order to increase the speed of the curing reaction by the exposure of the photosensitive resin composition, it is preferable that the binder resin (C) becomes a side chain Or a (meth)acrylic copolymer having a carbon-carbon double bond at the molecular end. As a functional group which has a carbon-carbon double bond, a vinyl group, an allyl group, or a (meth)acrylic group is mentioned, for example. In order to add such a functional group to the (meth)acrylic copolymer, there is a method as follows: a compound having a glycidyl group or an isocyanate group and a carbon-carbon double bond or a (meth)acryloyl chloride or Allyl chloride undergoes an addition reaction with a mercapto group, an amine group, a hydroxyl group or a carboxyl group in the (meth)acrylic copolymer.
作為具有環氧丙基和碳-碳雙鍵之化合物,可舉出例如:(甲基)丙烯酸環氧丙酯、烯丙基環氧丙基醚或丙烯酸環氧丙基乙酯、巴豆醯基環氧丙基醚、巴豆酸環氧丙酯或異巴豆酸環氧丙酯。作為具有異氰酸酯基和碳-碳雙鍵之化合物,可舉出例如:(甲基)丙烯醯基異氰酸酯或(甲基)丙烯醯氧乙基異氰酸酯。Examples of compounds having glycidyl and carbon-carbon double bonds include glycidyl (meth)acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl Glycidyl ether, glycidyl crotonate or glycidyl isocrotonate. As a compound which has an isocyanate group and a carbon-carbon double bond, (meth)acryloyl isocyanate and (meth)acryloyloxyethyl isocyanate are mentioned, for example.
本發明之樹脂組成物中,黏結劑樹脂(C)的含量,在將固體含量設為100質量%之情形,較佳係在1~30質量%之範圍內。於設為1質量%以上時,能調整成適合塗布的樹脂組成物之黏度,於設為30質量%以下時,能進一步提升功能。In the resin composition of the present invention, the content of the binder resin (C) is preferably in the range of 1 to 30 mass % when the solid content is set to 100 mass %. When it is 1 mass % or more, the viscosity of the resin composition suitable for coating can be adjusted, and when it is 30 mass % or less, the function can be further improved.
[感光劑(D)] 本發明之樹脂組成物在使用作為感光性樹脂組成物之情形,從形成微細的圖案之觀點來看,較佳為含有感光劑(D)。於含有感光劑(D)時,能對樹脂組成物賦予正型或負型的感光性。[Sensitizer (D)] When the resin composition of the present invention is used as a photosensitive resin composition, it is preferable to contain a photosensitizer (D) from the viewpoint of forming a fine pattern. When the photosensitizer (D) is contained, positive or negative photosensitivity can be imparted to the resin composition.
作為感光劑(D),較佳為使用光聚合起始劑、光酸產生劑、光鹼產生劑。作為光聚合起始劑,可舉出例如:苯乙酮系化合物、二苯基酮系化合物、苯偶姻醚系化合物、α-胺烷基苯基酮系化合物、9-氧硫 系化合物、有機過氧化物、咪唑系化合物、二茂鈦系化合物、三系化合物、醯基膦氧化物化合物、醌化合物或肟酯系化合物,其中較佳為即使是少量添加也有高敏感度之肟酯系化合物,更佳為具有咔唑骨架的肟酯系化合物。As a photosensitizer (D), it is preferable to use a photopolymerization initiator, a photoacid generator, and a photobase generator. Examples of photopolymerization initiators include acetophenone-based compounds, benzophenone-based compounds, benzoin ether-based compounds, α-aminoalkyl phenyl ketone-based compounds, and 9-oxysulfur series compounds, organic peroxides, imidazole series compounds, titanocene series compounds, three system compounds, acylphosphine oxide compounds, quinone compounds, or oxime ester-based compounds, among them, oxime-ester-based compounds having high sensitivity even when added in small amounts are preferred, and oxime-ester-based compounds having a carbazole skeleton are more preferred.
作為沒有咔唑骨架的肟酯系化合物之具體例,可舉出:1,2-丙二酮-3-環戊烷,1-[4-(苯硫基)-2-(O-苯甲醯肟)]、1,2-辛二酮,1-[4-(苯硫基)-2-(O-苯甲醯肟)]等,作為具有咔唑骨架的肟酯系化合物之具體例,可舉出:3-環戊基乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯肟)、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯肟)等。Specific examples of the oxime ester-based compound without a carbazole skeleton include 1,2-propanedione-3-cyclopentane, 1-[4-(phenylthio)-2-(O-benzyl) As specific examples of oxime ester compounds having a carbazole skeleton , for example: 3-cyclopentyl ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O- Acetoxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetoxime), etc. .
本發明之樹脂組成物中,光聚合起始劑(D)的含量,係相對於100質量份的黏結劑樹脂(C),較佳在1~50質量份之範圍。In the resin composition of the present invention, the content of the photopolymerization initiator (D) is preferably in the range of 1 to 50 parts by mass relative to 100 parts by mass of the binder resin (C).
作為光酸產生劑,可舉出:醌二疊氮(quinonediazide)化合物、鋶鹽、鏻鹽、重氮鹽、錪鹽等,其中更佳為醌二疊氮化合物。醌二疊氮化合物為具有5-萘醌二疊氮磺醯基(5-naphthoquinone diazide sulfonyl group)者、具有4-萘醌二疊氮磺醯基者,其中任一種都能較佳地使用。該醌二疊氮磺酸酯可舉出為:醌二疊氮的磺酸以酯鍵結至多羥化合物上而成者、醌二疊氮的磺酸以磺醯胺鍵結至多胺化合物上而成者、醌二疊氮的磺酸以酯及/或磺醯胺鍵結至多羥多胺化合物上而成者等。本發明之樹脂組成物中,光酸產生劑的含量,相對於100質量份的黏結劑樹脂(C),較佳在1~50質量份之範圍。As a photoacid generator, a quinonediazide compound, a pernium salt, a phosphonium salt, a diazonium salt, an iodonium salt, etc. are mentioned, Among them, a quinonediazide compound is more preferable. The quinonediazide compound has a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group, and any of them can be preferably used. Examples of the quinonediazide sulfonic acid ester include those in which the sulfonic acid of quinonediazide is ester-bonded to the polyhydroxy compound, and the sulfonic acid of quinonediazide is bonded to the polyamine compound with sulfonamides. A quinonediazide sulfonic acid is bound to a polyhydroxy polyamine compound with an ester and/or a sulfonamide, and the like. In the resin composition of the present invention, the content of the photoacid generator is preferably in the range of 1 to 50 parts by mass relative to 100 parts by mass of the binder resin (C).
作為光鹼產生劑,可舉出醯胺化合物、銨鹽等。As a photobase generator, an amide compound, an ammonium salt, etc. are mentioned.
作為醯胺化合物,可舉出例如:2-硝基苯基甲基-4-甲基丙烯醯氧基哌啶-1-羧酸酯(2-nitrophenylmethyl-4-methacryloxy piperidine-1-carboxylate)、胺基甲酸9-蒽基甲基-N,N-二甲酯(9-anthrylmethyl-N,N-dimethyl carbamate)、1-(蒽醌-2-基)乙基咪唑羧酸酯(1- (anthraquinone-2-yl) ethyl imidazole carboxylate)、(E)-1-[3-(2-羥苯基)-2-丙烯醯基]哌啶等。Examples of the amide compound include 2-nitrophenylmethyl-4-methacryloxy piperidine-1-carboxylate, 2-nitrophenylmethyl-4-methacryloxy piperidine-1-carboxylate, 9-anthrylmethyl-N,N-dimethyl carbamate, 1-(anthrylmethyl-N,N-dimethyl carbamate), 1-(anthraquinone-2-yl)ethylimidazole carboxylate (1-( anthraquinone-2-yl) ethyl imidazole carboxylate), (E)-1-[3-(2-hydroxyphenyl)-2-propenyl] piperidine, etc.
作為銨鹽,可舉出例如:2-(3-苯甲醯苯基)丙酸1,2-二異丙基-3-[(雙(二甲胺基)亞甲基]胍鎓、肆(3-氟苯基)硼酸(Z)-{[雙(二甲胺基)甲烯基]胺基}-N-環己基胺基)甲銨、正丁基三苯基硼酸1,2-二環己基-4,4,5,5-四甲基雙胍鎓等。Examples of the ammonium salt include 1,2-diisopropyl-3-[(bis(dimethylamino)methylene]guanidinium 2-(3-benzylphenyl)propanoate, (3-Fluorophenyl)boronic acid (Z)-{[bis(dimethylamino)methenyl]amino}-N-cyclohexylamino)methylammonium, n-butyltriphenylboronic acid 1,2- Dicyclohexyl-4,4,5,5-tetramethylbiguanidinium, etc.
本發明之樹脂組成物中,光鹼產生劑的含量相對於100質量份的黏結劑樹脂(C),較佳在1~50質量份之範圍。In the resin composition of the present invention, the content of the photobase generator is preferably in the range of 1 to 50 parts by mass relative to 100 parts by mass of the binder resin (C).
[分散劑] 本發明之樹脂組成物也可含有分散劑。於含有分散劑時,能使微粒穩定地存在於樹脂組成物中。[Dispersant] The resin composition of the present invention may contain a dispersant. When a dispersant is contained, fine particles can be stably present in the resin composition.
作為分散劑,較佳為胺系分散劑。作為市售之胺系的分散劑,可舉出例如:DISPERBYK(註冊商標)142、145、161、167、180、2001、2008、2022、2150、6919或21116(以上均為BYK-Chemie Japan製)。As the dispersant, an amine-based dispersant is preferred. Examples of commercially available amine-based dispersants include DISPERBYK (registered trademark) 142, 145, 161, 167, 180, 2001, 2008, 2022, 2150, 6919, or 21116 (all of the above are manufactured by BYK-Chemie Japan). ).
為了進一步提升分散性,分散劑較佳具有丙烯酸系嵌段共聚物結構。作為具有丙烯酸系嵌段共聚物結構的市售胺系分散劑,可舉出例如:DISPERBYK(註冊商標)2001、2008、2022、2150、6919或21116。In order to further improve the dispersibility, the dispersant preferably has an acrylic block copolymer structure. As a commercially available amine-type dispersing agent which has an acrylic block copolymer structure, DISPERBYK (registered trademark) 2001, 2008, 2022, 2150, 6919, or 21116 is mentioned, for example.
本發明之樹脂組成物中,分散劑的含量係相對於樹脂組成物中微粒與後述的其它粒子之合計100質量份,較佳為1~10質量份。藉由使分散劑的含量在此範圍,於樹脂組成物中微粒良好地分散,且能微細的圖案加工,在微粒係導電性粒子(A)之情形,導電性粒子(A)於樹脂組成物中進行接觸及熔接,能得到更高功能。In the resin composition of the present invention, the content of the dispersant is 100 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass in total of the fine particles and other particles described later in the resin composition. By setting the content of the dispersing agent within this range, fine particles are well dispersed in the resin composition, and fine pattern processing is possible. In the case of the fine particle-based conductive particles (A), the conductive particles (A) are incorporated Contact and welding are performed in the middle, and higher functions can be obtained.
[丙烯酸單體] 本發明之樹脂組成物從調整感光性能、提升圖案加工性之觀點來看,於微粒為導電性粒子(A)之情形,也可在不妨礙導電性粒子彼此的接觸及熔接之範圍內含有丙烯酸單體。[Acrylic monomer] From the viewpoint of adjusting photosensitivity and improving pattern workability, the resin composition of the present invention may contain acrylic acid in the range where the fine particles are the conductive particles (A) within a range that does not hinder the contact and fusion of the conductive particles. monomer.
作為丙烯酸單體可舉出例如:三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇五(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯或二新戊四醇五(甲基)丙烯酸酯或是它們的烷基改性產物、烷基醚改性產物或烷基酯改性產物。Examples of the acrylic monomer include trimethylolpropane tri(meth)acrylate, neotaerythritol tri(meth)acrylate, neotaerythritol penta(meth)acrylate, neotaerythritol Tetra(meth)acrylate, dipivalerythritol hexa(meth)acrylate or dipeptaerythritol penta(meth)acrylate or their alkyl-modified products, alkyl ether-modified products or Alkyl ester modified products.
樹脂組成物中的丙烯酸單體的含量相對於100質量份的黏結劑樹脂(C),較佳在10~200質量份之範圍。The content of the acrylic monomer in the resin composition is preferably in the range of 10 to 200 parts by mass relative to 100 parts by mass of the binder resin (C).
[溶劑] 本發明之樹脂組成物也可含有溶劑。作為溶劑,可舉出例如:丙二醇單甲醚、丙二醇單丁醚、二丙酮醇、丙二醇單乙醚乙酸酯、乙醯乙酸乙酯、環戊酮、環己酮、γ-丁內酯、乙二醇單丁醚乙酸酯、二乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯、二乙二醇二甲醚、二乙二醇二乙醚、二乙二醇甲乙醚、二丙二醇甲醚乙酸酯、二丙二醇二甲基醚、丙二醇二乙酸酯、1,3-丁二醇二乙酸酯、環己醇乙酸酯、二甲亞碸、甲乙酮、乙酸異丁酯、乙酸丁酯、乙酸丙酯、乙酸異丙酯或乙醯丙酮。[solvent] The resin composition of the present invention may contain a solvent. Examples of the solvent include propylene glycol monomethyl ether, propylene glycol monobutyl ether, diacetone alcohol, propylene glycol monoethyl ether acetate, ethyl acetate, cyclopentanone, cyclohexanone, γ-butyrolactone, ethyl acetate Glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether Diethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol dimethyl ether, propylene glycol diacetate, 1,3-butanediol diacetate, cyclohexanol acetate, dimethylsulfoxide, methyl ethyl ketone, acetic acid Isobutyl, butyl acetate, propyl acetate, isopropyl acetate or acetone.
[聚合抑制劑] 本發明之樹脂組成物也可含有聚合抑制劑。於適量包含聚合抑制劑時,顯影後的解析度會提升。作為聚合抑制劑沒有特別限定,能使用眾所皆知者,可舉出例如:二-三級丁基羥基甲苯、丁基羥基茴香醚、氫醌、4-甲氧苯酚、1,4-苯醌、三級丁基兒茶酚。又,作為市售的聚合抑制劑,可舉出:「IRGANOX 1010」、「IRGANOX 245」、(以上、BASF製)等。[polymerization inhibitor] The resin composition of the present invention may also contain a polymerization inhibitor. When a proper amount of polymerization inhibitor is included, the resolution after development will be improved. The polymerization inhibitor is not particularly limited, and well-known ones can be used, for example, di-tertiary butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzene Quinone, tertiary butylcatechol. Moreover, as a commercially available polymerization inhibitor, "IRGANOX 1010", "IRGANOX 245", (above, BASF make) etc. are mentioned.
[紫外線吸收劑] 本發明之樹脂組成物也可含有紫外線吸收劑。於含有紫外線吸收劑時,所得到的硬化物的耐光性會提升,於必須要圖案加工的用途,顯影後的解析度會提升。作為紫外線吸收劑沒有特別限定,能使用眾所皆知者,而從透明性、非著色性方面來看,較佳為使用苯并三唑系化合物、二苯基酮系化合物、三系化合物。[Ultraviolet Absorber] The resin composition of the present invention may contain an ultraviolet absorber. When an ultraviolet absorber is contained, the light resistance of the obtained hardened|cured material will improve, and the resolution after image development will improve for the application which requires pattern processing. The ultraviolet absorber is not particularly limited, and well-known ones can be used, but from the viewpoints of transparency and non-coloring properties, benzotriazole-based compounds, benzophenone-based compounds, and triphenyl ketone-based compounds are preferably used. series compounds.
[其它粒子] 本發明之樹脂組成物為了提升分散性、控制導電性,也可包含有機顏料(F)、無機粒子(G)以外的其它粒子。作為其它粒子,可舉出例如沒有表面被覆之導電性粒子或金屬氧化物微粒或無機顏料。[other particles] The resin composition of the present invention may contain particles other than the organic pigment (F) and the inorganic particles (G) in order to improve dispersibility and control conductivity. Examples of other particles include electroconductive particles without surface coating, metal oxide fine particles, or inorganic pigments.
這些其它粒子的粒徑較佳為1~100nm。若粒徑在1nm以上,則能減少使用用於分散穩定化之分散劑,在微粒為導電性粒子(A)之情形能更進一步提升導電性。另一方面,藉由粒徑在100nm以下,圖案的解析度會提升,能形成微細的圖案。The particle diameter of these other particles is preferably 1 to 100 nm. When the particle diameter is 1 nm or more, the use of a dispersant for dispersion stabilization can be reduced, and when the fine particles are the conductive particles (A), the conductivity can be further improved. On the other hand, when the particle size is 100 nm or less, the resolution of the pattern is improved, and a fine pattern can be formed.
[熱酸產生劑及光酸產生劑] 本發明之樹脂組成物也可含有熱酸產生劑。在黏結劑樹脂(C)為具有酸解離性基的黏結劑樹脂之情形,由產生的酸促進酸解離性基的分解,而能降低在空氣下的熱處理溫度。又,含有光酸產生劑也沒關係。光酸產生劑如先前已經提過的一樣。[Thermal acid generator and photoacid generator] The resin composition of the present invention may contain a thermal acid generator. In the case where the binder resin (C) is a binder resin having an acid-dissociable group, the generated acid promotes the decomposition of the acid-dissociable group, so that the heat treatment temperature in air can be lowered. In addition, it does not matter if a photoacid generator is contained. The photoacid generator is as previously mentioned.
作為藉由熱產生酸的化合物之熱酸產生劑,可舉出例如:SI-150L、SI-160L、SI-180L或SI-200(以上均為三新化學工業(股)製)、4-羥苯基二甲基鋶、苯甲基-4-羥苯基甲基鋶、2-甲基苯甲基-4-羥苯基甲基鋶、2-甲基苯甲基-4-乙醯苯基甲基鋶或2-甲基苯甲基-4-苯甲醯氧基苯基甲基鋶或它們的甲磺酸鹽、三氟甲磺酸鹽、樟腦磺酸鹽或對甲苯磺酸鹽。其中,較佳為使用4-羥苯基二甲基鋶、苯甲基-4-羥苯基甲基鋶、2-甲基苯甲基-4-羥苯基甲基鋶、2-甲基苯甲基-4-乙醯苯基甲基鋶或2-甲基苯甲基-4-苯甲醯氧基苯基甲基鋶或它們的甲磺酸鹽、三氟甲磺酸鹽、樟腦磺酸鹽或對甲苯磺酸鹽。As a thermal acid generator of a compound that generates an acid by heat, for example, SI-150L, SI-160L, SI-180L, or SI-200 (all of the above are manufactured by Sanshin Chemical Industry Co., Ltd.), 4- Hydroxyphenyldimethyl strontium, benzyl-4-hydroxyphenylmethyl strontium, 2-methylbenzyl-4-hydroxyphenylmethyl strontium, 2-methylbenzyl-4-acetonitrile Phenylmethylsulfuric acid or 2-methylbenzyl-4-benzyloxyphenylmethylsulfuric acid or their mesylate, triflate, camphorsulfonate or p-toluenesulfonic acid Salt. Among them, it is preferable to use 4-hydroxyphenyl dimethyl strontium, benzyl-4-hydroxyphenylmethyl strontium, 2-methylbenzyl-4-hydroxyphenylmethyl strontium, 2-methyl sulfite Benzyl-4-acetonitrile or 2-methylbenzyl-4-benzyloxyphenylmethyl succinate or their mesylate, triflate, camphor Sulfonate or p-toluenesulfonate.
本發明之樹脂組成物中,熱酸產生劑的含量,為了促進包含酸解離性基的黏結劑樹脂(C)中之酸解離性基的分解,且不妨礙無機粒子(G)彼此的接觸,得到更高的功能,相對於100質量份的黏結劑樹脂(C),較佳在1~50質量份之範圍。In the resin composition of the present invention, the content of the thermal acid generator is in order to promote the decomposition of the acid dissociable group in the binder resin (C) containing the acid dissociable group, and not prevent the contact of the inorganic particles (G) with each other, To obtain a higher function, the range of 1 to 50 parts by mass is preferable with respect to 100 parts by mass of the binder resin (C).
[增感劑] 本發明之樹脂組成物在含有光酸產生劑之情形,樹脂組成物也可進一步含有增感劑。增感劑較佳為經由熱處理而氣化者,或是即便於殘存在本發明之樹脂組成物的硬化物中之情形,也會因照射光而褪色者,從在圖案加工時的高解析度之觀點來看,更佳為因照射光而褪色者。[sensitizer] When the resin composition of the present invention contains a photoacid generator, the resin composition may further contain a sensitizer. It is preferable that the sensitizer is vaporized by heat treatment, or even if it remains in the cured product of the resin composition of the present invention, it is discolored by irradiation of light, from high resolution during pattern processing. From the viewpoint of light, it is more preferable to be discolored by light.
作為經由熱處理而氣化或是因照射光而褪色之增感劑,可舉出例如:3,3’-羰基雙(二乙胺基香豆素)等的香豆素、9,10-蒽醌等的蒽醌、二苯基酮、4,4’-二甲氧基二苯基酮、苯乙酮、4-甲氧基苯乙酮或苯甲醛等的芳香族酮或聯苯、1,4-二甲基萘、9-茀酮、茀、菲、聯伸三苯、芘、蒽、9-苯基蒽、9-甲氧基蒽、9,10-二苯基蒽、9,10-雙(4-甲氧基苯基)蒽、9,10-雙(三苯基矽基)蒽、9,10-二甲氧基蒽、9,10-二乙氧基蒽、9,10-二丙氧基蒽(DPA;川崎化成(股)製)、9,10-二丁氧基蒽(DBA;川崎化成(股)製)、9,10-二戊氧基蒽、2-三級丁基-9,10-二丁氧基蒽或9,10-雙(三甲矽基乙炔基)蒽等的稠合芳香族。Examples of sensitizers that are vaporized by heat treatment or discolored by light irradiation include coumarins such as 3,3'-carbonylbis(diethylaminocoumarin), and 9,10-anthracene. Anthraquinone such as quinone, diphenyl ketone, 4,4'-dimethoxydiphenyl ketone, acetophenone, 4-methoxyacetophenone, or aromatic ketone such as benzaldehyde, or biphenyl, 1 ,4-dimethylnaphthalene, 9-phenanthrene, fentanyl, phenanthrene, triphenylene, pyrene, anthracene, 9-phenylanthracene, 9-methoxyanthracene, 9,10-diphenylanthracene, 9,10 -Bis(4-methoxyphenyl)anthracene, 9,10-bis(triphenylsilyl)anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10 -Dipropoxyanthracene (DPA; manufactured by Kawasaki Chemical Co., Ltd.), 9,10-dibutoxyanthracene (DBA; manufactured by Kawasaki Chemical Co., Ltd.), 9,10-dipentoxyanthracene, 2-tris Condensed aromatics such as butyl-9,10-dibutoxyanthracene or 9,10-bis(trimethylsilylethynyl)anthracene.
作為經由熱處理氣化之增感劑,較佳為經由熱處理而昇華、蒸發或是熱分解產生的熱分解物昇華或蒸發者。作為增感劑的氣化溫度,於乾燥溫度不會氣化,在熱硬化時分解及氣化,在微粒為導電性粒子(A)之情形為了使導電性粒子彼此接觸及熔接,較佳為150~300℃。The sensitizer vaporized by heat treatment is preferably one that is sublimated or evaporated by heat treatment, or one that sublimates or evaporates a thermal decomposition product generated by thermal decomposition. As the vaporization temperature of the sensitizer, it does not vaporize at the drying temperature, but is decomposed and vaporized at the time of thermal hardening, and when the fine particles are the conductive particles (A), in order to make the conductive particles contact and weld each other, it is preferably 150~300℃.
本發明之樹脂組成物中,增感劑的含量,為了讓使光酸產生劑感光的增感效果變得充分,不妨礙微粒彼此的接觸,得到更高的功能,相對於100質量份的黏結劑樹脂(C),較佳為0.001~20質量份,更佳為0.005~15質量份。In the resin composition of the present invention, the content of the sensitizer is such that the sensitization effect of the photoacid generator to be sensitized is sufficient, the contact between the fine particles is not hindered, and a higher function is obtained, relative to 100 parts by mass of the binding agent. The agent resin (C) is preferably 0.001 to 20 parts by mass, more preferably 0.005 to 15 parts by mass.
[在可見光有吸收的顏料及/或染料] 本發明之樹脂組成物,於微粒為導電性粒子(A)之情形,在不妨礙導電性粒子彼此的接觸及熔接的範圍,也可含有在可見光有吸收的顏料及/或染料。藉由樹脂組成物含有在可見光有吸收的無機顏料及/或染料,能抑制加熱後的圖案之可見光反射。還較佳為:前述無機粒子(G)為無機顏料。[Pigments and/or dyes that absorb visible light] When the fine particles are the conductive particles (A), the resin composition of the present invention may contain pigments and/or dyes that absorb visible light within a range that does not prevent contact and fusion of the conductive particles. When the resin composition contains an inorganic pigment and/or dye that absorbs visible light, the visible light reflection of the pattern after heating can be suppressed. It is also preferable that the inorganic particles (G) are inorganic pigments.
作為在可見光有吸收的顏料,可舉出例如:內醯胺系顏料、苝系顏料、酞菁系顏料、異吲哚啉系顏料、二胺蒽醌系顏料、二㗁系顏料、陰丹士林系顏料、碳黑或無機顏料。Examples of pigments that absorb visible light include lactamide-based pigments, perylene-based pigments, phthalocyanine-based pigments, isoindoline-based pigments, diamineanthraquinone-based pigments, and diamine-based pigments. pigments, indanthrene pigments, carbon black or inorganic pigments.
作為藍色的顏料,可舉出例如:C.I.顏料藍(以下稱為「PB」)15、PB15:1、PB15:2、PB15:3、PB15:4、PB15:5、PB15:6、PB16或PB60。作為紫色的顏料,可舉出例如:C.I.顏料紫(以下稱為「PV」)19、PV23或PV37。作為紅色的顏料,可舉出例如:C.I.顏料紅(以下稱為「PR」)149、PR166、PR177、PR179、PR209或PR254。作為綠色的顏料,可舉出例如:C.I.顏料綠(以下稱為「PG」)7、PG36或PG58。作為黃色的顏料,可舉出例如:C.I.顏料黃(以下稱為「PY」)150、PY138、PY139或PY185。作為黑色的顏料,可舉出例如:HCF、MCF、LFF、RCF、SAF、ISAF、HAF、XCF、FEF、GPF或SRF等的爐黑、FT或MT等的熱碳黑、槽黑或乙炔黑等的碳黑或內醯胺系顏料(例如:「Irgaphor」(註冊商標)Black S0100CF;BASF公司製)。其中,於耐熱性、耐光性及可見光的吸收性上優良之碳黑係較佳的,從分散性的觀點來看,更佳為爐黑或內醯胺系顏料。Examples of blue pigments include CI Pigment Blue (hereinafter referred to as "PB") 15, PB15:1, PB15:2, PB15:3, PB15:4, PB15:5, PB15:6, PB16 or PB60. Examples of purple pigments include C.I. Pigment Violet (hereinafter referred to as "PV") 19, PV23, or PV37. Examples of red pigments include C.I. Pigment Red (hereinafter referred to as "PR") 149, PR166, PR177, PR179, PR209, or PR254. Examples of green pigments include C.I. Pigment Green (hereinafter referred to as "PG") 7, PG36, or PG58. Examples of yellow pigments include C.I. Pigment Yellow (hereinafter referred to as "PY") 150, PY138, PY139, or PY185. Examples of black pigments include furnace blacks such as HCF, MCF, LFF, RCF, SAF, ISAF, HAF, XCF, FEF, GPF, and SRF, thermal blacks such as FT and MT, channel blacks, and acetylene blacks. etc. carbon black or lactamide-based pigments (for example: "Irgaphor" (registered trademark) Black S0100CF; manufactured by BASF Corporation). Among them, carbon black-based pigments excellent in heat resistance, light resistance, and visible light absorption are preferred, and from the viewpoint of dispersibility, furnace black or lactamide-based pigments are more preferred.
本發明之樹脂組成物中,在可見光有吸收的顏料的含量相對於組成物中的總固體含量,較佳為0.1~10質量%。In the resin composition of the present invention, the content of the pigment absorbing visible light is preferably 0.1 to 10% by mass relative to the total solid content in the composition.
作為在可見光有吸收的染料,可舉出例如:二茂鐵系染料、茀酮系染料、苝系染料、三苯甲烷系染料、香豆素系染料、二苯胺系染料、喹吖酮系染料、喹啉黃系染料、酞菁系染料或 系染料,於耐熱性、耐光性及可見光的吸收性上優良的黑色染料為較佳的,較佳為VALIFAST(註冊商標) Black 1888、VALIFAST(註冊商標) Black 3830、NUBIAN(註冊商標) Black PA-2802或OIL Black 860。Examples of dyes that absorb visible light include ferrocene-based dyes, perylene-based dyes, perylene-based dyes, triphenylmethane-based dyes, coumarin-based dyes, diphenylamine-based dyes, and quinacridone-based dyes , quinoline yellow dyes, phthalocyanine dyes or It is a type of dye, preferably a black dye excellent in heat resistance, light resistance and visible light absorption, preferably VALIFAST (registered trademark) Black 1888, VALIFAST (registered trademark) Black 3830, NUBIAN (registered trademark) Black PA -2802 or OIL Black 860.
本發明之樹脂組成物中,在可見光有吸收的染料的含量,相對於組成物中的總固體含量,較佳為0.1~10質量%。In the resin composition of the present invention, the content of the dye absorbing visible light is preferably 0.1 to 10% by mass relative to the total solid content in the composition.
[密著改良劑] 本發明之樹脂組成物除了化合物(B)以外也可進一步含有密著改良劑。作為密著改良劑,可舉出例如:3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-甲基丙醯氧基丙基三甲氧基矽烷、3-甲基丙醯氧基丙基三乙氧基矽烷、3-丙醯氧基丙基三甲氧基矽烷或3-丙醯氧基丙基三乙氧基矽烷等的矽烷偶合劑。[Adhesion Improver] The resin composition of the present invention may further contain an adhesion improver in addition to the compound (B). Examples of the adhesion improver include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxy ring Hexyl) Ethyltrimethoxysilane, 3-Methylpropionyloxypropyltrimethoxysilane, 3-Methylpropionyloxypropyltriethoxysilane, 3-Propionyloxypropyltrimethoxysilane Silane coupling agent such as alkoxysilane or 3-propionyloxypropyltriethoxysilane.
[界面活性劑] 本發明之樹脂組成物也可進一步視需要含有界面活性劑。[surfactant] The resin composition of the present invention may further contain a surfactant if necessary.
作為界面活性劑,可舉出例如:月桂基硫酸銨或聚氧乙烯烷基醚硫酸三乙醇胺等的陰離子界面活性劑、硬脂胺乙酸酯或氯化月桂基三甲基銨等的陽離子界面活性劑、月桂基二甲基氧化胺或月桂基羧甲基羥乙基咪唑鎓甜菜鹼等的兩性界面活性劑、聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚或去水山梨醇單硬脂酸酯等的非離子界面活性劑、氟系界面活性劑或聚矽氧系界面活性劑。Examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, and cationic interfaces such as stearylamine acetate and lauryltrimethylammonium chloride. Active agents, amphoteric surfactants such as lauryl dimethyl amine oxide or lauryl carboxymethyl hydroxyethyl imidazolium betaine, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or sorbitan mono Nonionic surfactants such as stearate, fluorine-based surfactants, or polysiloxane-based surfactants.
本發明之樹脂組成物中,界面活性劑的含量,為了使塗布性及塗膜表面的均勻性變好,相對於組成物全體,較佳為0.001~10質量%。於界面活性劑的含量在0.001質量%以上時,塗布性及塗膜表面的均勻性會提升。界面活性劑的含量更佳為0.01質量%以上。另一方面,於界面活性劑的含量在10質量%以下時,能抑制塌凹或凹陷等的塗膜缺陷、以及粒子的凝集。In the resin composition of the present invention, the content of the surfactant is preferably 0.001 to 10% by mass relative to the entire composition in order to improve the coatability and uniformity of the coating film surface. When the content of the surfactant is 0.001 mass % or more, the coatability and the uniformity of the coating film surface are improved. The content of the surfactant is more preferably 0.01 mass % or more. On the other hand, when the content of the surfactant is 10 mass % or less, coating film defects such as sags and dents, and aggregation of particles can be suppressed.
本發明之配線基板較佳具備由包含導電性粒子(A)的本發明之樹脂組成物的硬化物構成之導電性圖案。本發明之配線基板的基材較佳為透明基板。作為透明基板,可舉出玻璃基板、樹脂薄膜。由形成圖案時顯影液容易浸透、抑制殘渣的觀點來看,作為透明基板較佳為玻璃基板。作為玻璃基板,可舉出:於表面包含SiO2 層或SiO2 層之玻璃基板、無鹼玻璃基板等。作為樹脂薄膜,可舉出:由選自包含聚醯亞胺、聚醯亞胺矽氧烷、聚醚碸、聚苯并㗁唑、芳香聚醯胺、聚碸及環氧樹脂之群組中的至少一種材料構成之薄膜等。於樹脂薄膜的表面也可包含SiO2 層。藉由把這些材料使用作為基材,可得到與由本發明之樹脂組成物的硬化物構成的導電性圖案的密著性高之配線基板。It is preferable that the wiring board of this invention is equipped with the electroconductive pattern which consists of the hardened|cured material of the resin composition of this invention containing electroconductive particle (A). The base material of the wiring board of the present invention is preferably a transparent substrate. As a transparent substrate, a glass substrate and a resin film are mentioned. A glass substrate is preferable as a transparent substrate from the viewpoint of easy penetration of the developer during pattern formation and suppression of residues. As a glass substrate, the glass substrate containing a SiO2 layer or a SiO2 layer on the surface, an alkali-free glass substrate, etc. are mentioned. Examples of the resin film include those selected from the group consisting of polyimide, polyimide siloxane, polyether, polybenzoxazole, aromatic polyamide, polysiloxane, and epoxy resins. A film composed of at least one material, etc. A SiO 2 layer may also be included on the surface of the resin film. By using these materials as a base material, it is possible to obtain a wiring board having high adhesion to the conductive pattern formed of the cured product of the resin composition of the present invention.
又,本發明之配線基板除了由本發明之樹脂組成物的硬化物構成之導電性圖案以外,也可具有包含有機成分的薄膜。從保護導電性圖案的觀點來看,包含有機成分的薄膜較佳形成在導電性圖案的上部。於具有包含有機成分的薄膜時,能防止因外力等所造成的刮痕,能得到可靠度高的配線基板。Moreover, the wiring board of this invention may have a thin film containing an organic component other than the electroconductive pattern which consists of the hardened|cured material of the resin composition of this invention. From the viewpoint of protecting the conductive pattern, the thin film containing the organic component is preferably formed on the upper portion of the conductive pattern. When there is a thin film containing an organic component, scratches due to external force or the like can be prevented, and a highly reliable wiring board can be obtained.
又,本發明之配線基板能合適地使用作為觸控面板用構件。於使用作為觸控面板用構件之情形,能使用在將配置成網格狀的觸控感測器配線與觸控感測器配線連接起來的配線。另外,同時形成觸控感測器配線與引繞配線也是較佳的。本發明之配線基板的基材也可使用作為蓋玻璃,本發明之配線基板上也可透過OCA貼合覆蓋材料。Moreover, the wiring board of this invention can be used suitably as a member for touch panels. When using it as a member for a touch panel, the wiring which connects the touch sensor wiring and the touch sensor wiring arrange|positioned in a grid shape can be used. In addition, it is also preferable to form the touch sensor wiring and the routing wiring at the same time. The substrate of the wiring board of the present invention can also be used as a cover glass, and the wiring board of the present invention can also be pasted with a cover material through OCA.
本發明之配線基板,前述導電性圖案的寬度較佳為1~6μm。於導電性圖案的寬度在1μm以上時,不容易受到因異物等造成的缺陷影響,能形成期望的形狀之導電性圖案。另一方面,藉由導電性圖案的寬度在6μm以下,配線變得難以目視辨認出來。導電性圖案的寬度更佳為4μm以下。In the wiring board of the present invention, the width of the conductive pattern is preferably 1 to 6 μm. When the width of the conductive pattern is 1 μm or more, it is less likely to be affected by defects due to foreign matter and the like, and a conductive pattern of a desired shape can be formed. On the other hand, when the width of the conductive pattern is 6 μm or less, it becomes difficult to visually recognize the wiring. The width of the conductive pattern is more preferably 4 μm or less.
本發明之配線基板較佳進一步具有黑色層。於具有黑色層時,能降低配線圖案的反射並抑制外部光反射,同時能抑制配線可見性並大幅提升可見度。作為黑色層的形成方法,可舉出方法如:形成配線圖案後把黑色正型感光性組成物塗布到整個面上,經由透過配線圖案從基材面進行曝光,留下配線圖案上部使其可溶於顯影液,再藉由顯影去除。The wiring board of the present invention preferably further has a black layer. When the black layer is provided, the reflection of the wiring pattern can be reduced, the reflection of external light can be suppressed, and the visibility of the wiring can be suppressed and the visibility can be greatly improved. As a method of forming the black layer, for example, after forming a wiring pattern, applying a black positive photosensitive composition to the entire surface, exposing through the wiring pattern from the substrate surface, leaving the upper part of the wiring pattern so that it can be exposed Dissolved in the developer, and then removed by development.
[樹脂組成物之製造方法] 本發明之樹脂組成物,能在將微粒、化合物(B)、以及黏結劑樹脂(C)混合後,使用球磨機、砂磨機、三滾筒研磨機、溫和分散機(mild disperser)、無介質分散機等的分散機製造出來。在想將微粒均勻分散之情形,也可藉由以下方法製造:使用分散劑,預先調製將微粒分散於有機溶劑中而成的分散液,將此分散液與包含單體、聚合物、密著改良劑、界面活性劑及聚合抑制劑等之溶液混合。特別是具有包含碳的被覆層之無機粒子(G)的分散液,為了防止表面被覆層受到損傷,較佳使用溫和分散機或無介質分散機來分散,更佳為使用無介質分散機來分散。具有包含碳的被覆層之無機粒子(G)的分散液,係如下製造:使用溫和分散機Nano Getter(註冊商標)(Ashizawa Finetech (股))或高壓濕式無介質微粒化裝置Nanomizer(Nanomizer(股))等的分散機,將具有包含碳的被覆層之無機粒子(G)分散於有機溶劑中。[Manufacturing method of resin composition] The resin composition of the present invention can be dispersed using a ball mill, a sand mill, a three-roller mill, a mild disperser, or a medium-free after mixing the fine particles, the compound (B), and the binder resin (C). Machine and other dispersing machines are produced. When it is desired to disperse the fine particles uniformly, it can also be produced by the following method: using a dispersing agent, a dispersion liquid prepared by dispersing fine particles in an organic solvent is prepared in advance, and this dispersion liquid is mixed with monomers, polymers, adhesives, etc. The solution of modifier, surfactant and polymerization inhibitor is mixed. In particular, in order to prevent the surface coating layer from being damaged, the dispersion liquid of the inorganic particles (G) having a carbon-containing coating layer is preferably dispersed using a mild disperser or a medium-less disperser, more preferably a medium-less disperser. . The dispersion liquid of inorganic particles (G) having a coating layer containing carbon was produced by using a mild disperser Nano Getter (registered trademark) (Ashizawa Finetech Co., Ltd.) or a high-pressure wet medium-less micronizing device Nanomizer (Nanomizer ( The inorganic particles (G) having a carbon-containing coating layer are dispersed in an organic solvent using a dispersing machine such as a carbon-containing coating layer.
[導電性及著色圖案之製造方法] 本發明之導電性圖案之製造方法具備:將本發明之樹脂組成物以成為期望的圖案形狀之方式塗布在基板上而得到塗布膜之塗布步驟、將上述塗布膜乾燥來得到乾燥膜之乾燥步驟、將上述乾燥膜加熱來得到導電膜之加熱步驟。[Manufacturing method of conductivity and colored pattern] The method for producing a conductive pattern of the present invention includes a coating step of applying the resin composition of the present invention on a substrate so as to have a desired pattern shape to obtain a coating film, and a drying step of drying the coating film to obtain a dry film and the heating step of heating the above-mentioned dry film to obtain a conductive film.
本發明之導電性圖案之製造方法包含將本發明之樹脂組成物以成為期望的圖案形狀之方式塗布在基板上而得到塗布膜之塗布步驟。The manufacturing method of the electroconductive pattern of this invention includes the coating process of apply|coating the resin composition of this invention on a board|substrate so that it may become a desired pattern shape, and obtains a coating film.
作為在塗布步驟所使用之基材,可舉出例如:矽晶圓、陶瓷基板或有機系基板。作為陶瓷基板,可舉出例如:鈉玻璃、將SiO2 濺鍍於表面上而成的鈉玻璃、無鹼玻璃、硼矽玻璃或石英玻璃等的玻璃基板、氧化鋁基板、氮化鋁基板或碳化矽基板。作為有機系基板,可舉出例如:環氧基板、聚醚醯亞胺樹脂基板、聚醚酮樹脂基板、聚碸系樹脂基板、聚醯亞胺薄膜或聚酯薄膜。As a base material used in a coating process, a silicon wafer, a ceramic substrate, or an organic type board|substrate is mentioned, for example. Examples of ceramic substrates include soda glass, soda glass obtained by sputtering SiO 2 on the surface, alkali-free glass, glass substrates such as borosilicate glass or quartz glass, alumina substrates, aluminum nitride substrates, or Silicon carbide substrate. As an organic-type board|substrate, an epoxy board|substrate, a polyetherimide resin board|substrate, a polyetherketone resin board|substrate, a polyamide-type resin board|substrate, a polyimide film, or a polyester film is mentioned, for example.
作為將本發明之樹脂組成物塗布在基材面上之方法,可舉出例如:使用旋塗機、刮棒塗布機、刮刀塗布機、輥式塗布機、模頭塗布機、壓延塗布機或彎月面塗布機(meniscus coater)塗布、網版印刷、噴塗或浸塗。As a method of coating the resin composition of the present invention on the surface of a substrate, for example, the use of a spin coater, a bar coater, a knife coater, a roll coater, a die coater, a calender coater, or a Meniscus coater coating, screen printing, spray coating or dip coating.
本發明之導電性圖案之製造方法包含將塗布膜乾燥來得到乾燥膜之乾燥步驟。The manufacturing method of the electroconductive pattern of this invention includes the drying process of drying a coating film to obtain a dry film.
作為乾燥步驟中的乾燥方法,可舉出例如:藉由加熱板、熱風乾燥機(烘箱)、減壓乾燥、真空乾燥或紅外線照射來乾燥。As a drying method in a drying process, drying by a hot plate, a hot air dryer (oven), reduced-pressure drying, vacuum drying, or infrared irradiation is mentioned, for example.
乾燥的溫度及時間,依照樹脂組成物的組成、乾燥的塗布膜之膜厚來適當決定即可,較佳在50~150℃的溫度範圍加熱10秒鐘~30分鐘。The drying temperature and time may be appropriately determined according to the composition of the resin composition and the film thickness of the dried coating film, and it is preferable to heat in a temperature range of 50 to 150° C. for 10 seconds to 30 minutes.
其中,把在加熱板或熱風乾燥機(烘箱)的加熱,與減壓乾燥並用,由於能一邊抑制塗布膜所包含的樹脂之熱硬化,一邊將溶劑乾燥去除,所以是較佳的。作為減壓乾燥的到達壓力較佳為5~200Pa,更佳為10~100Pa。Among them, heating on a hot plate or a hot air dryer (oven) combined with drying under reduced pressure is preferable because it can dry and remove the solvent while suppressing thermal hardening of the resin contained in the coating film. It is preferable that it is 5-200Pa as a reaching pressure of drying under reduced pressure, and it is more preferable that it is 10-100Pa.
本發明之導電性圖案之製造方法包含加熱乾燥膜來得到導電膜之加熱步驟。The manufacturing method of the electroconductive pattern of this invention includes the heating process of heating and drying a film to obtain a conductive film.
在經由加熱樹脂組成物的乾燥膜得到導電性的同時,使化合物(B)變成具有胺基,由於與具有包含碳的被覆層之無機粒子(G)的被覆層交互作用,所以與基材的密著性提升。By heating the dried film of the resin composition to obtain conductivity, the compound (B) is made to have an amine group, and the compound (B) interacts with the coating layer of the inorganic particles (G) having a coating layer containing carbon, so that the compound (B) interacts with the coating layer of the inorganic particles (G) of the coating layer containing carbon. Adhesion is improved.
作為在加熱步驟的加熱方法,可舉出與乾燥步驟相同的方法。加熱的氣體環境、溫度及時間依照樹脂組成物的組成、加熱之塗布膜的膜厚來適當決定即可,於空氣中較佳在100~300℃之溫度範圍加熱5~120分鐘。更佳為在150~270℃,再更佳為在160~260℃之溫度範圍,加熱30~120分鐘。As a heating method in a heating step, the same method as a drying step is mentioned. The heating gas environment, temperature and time can be appropriately determined according to the composition of the resin composition and the film thickness of the heated coating film. More preferably, it is heated for 30 to 120 minutes at a temperature of 150 to 270°C, and still more preferably in a temperature range of 160 to 260°C.
又,還較佳為:在前述的乾燥步驟與加熱步驟之間,具備將前述乾燥膜曝光來得到曝光膜之曝光步驟、與將前述曝光膜顯影來形成圖案之顯影步驟,並以光刻法來形成導電性圖案。在此情形,由於在曝光步驟化合物(B)不具有胺基,不會與無機粒子(G)反應,所以在接下去的顯影步驟中能形成顯影液溶解性佳、沒有顯影殘渣之優良圖案。形成圖案後,於加熱步驟出現胺基,能提升與基材的密著性。Furthermore, it is also preferable that between the drying step and the heating step, an exposure step of exposing the dried film to obtain an exposed film and a development step of developing the exposed film to form a pattern are provided, and a photolithography method is used. to form a conductive pattern. In this case, since the compound (B) has no amine group and does not react with the inorganic particles (G) in the exposure step, an excellent pattern with good developer solubility and no development residue can be formed in the subsequent development step. After the pattern is formed, amine groups appear in the heating step, which can improve the adhesion to the substrate.
作為在曝光步驟使用之光源,較佳為例如汞燈的j線、i線、h線或g線。As the light source used in the exposure step, for example, a j-line, i-line, h-line or g-line of a mercury lamp is preferable.
作為在顯影步驟使用於鹼性顯影液中之鹼性物質,可舉出例如:氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、矽酸鈉、偏矽酸鈉或氨水等的無機鹼類、乙胺或正丙胺等的一級胺類、二乙胺或二正丙胺等的二級胺類、三乙胺或甲基二乙基胺等的三級胺類、氫氧化四甲銨(TMAH)等的氫氧化四烷基銨類、膽鹼等的四級銨鹽、三乙醇胺、二乙醇胺、單乙醇胺、二甲胺乙醇或二乙胺乙醇等的醇胺類或吡咯、哌啶、1,8-二吖雙環[5.4.0]-7-十一烯、1,5-二吖雙環[4.3.0]-5-壬烯或啉等的環狀胺類等的有機鹼類,也可對它們適當添加乙醇、γー丁內酯、二甲基甲醯胺或N-甲基-2-吡咯啶酮等的水溶性有機溶劑。Examples of the alkaline substance used in the alkaline developer in the developing step include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, or ammonia water. , primary amines such as ethylamine or n-propylamine, secondary amines such as diethylamine or di-n-propylamine, tertiary amines such as triethylamine or methyldiethylamine, tetramethylammonium hydroxide (TMAH ) tetraalkylammonium hydroxides, quaternary ammonium salts such as choline, alcoholamines such as triethanolamine, diethanolamine, monoethanolamine, dimethylamine ethanol or diethylamine ethanol, or pyrrole, piperidine, 1 ,8-Diazabicyclo[5.4.0]-7-undecene, 1,5-Diazabicyclo[4.3.0]-5-nonene or Organic bases such as cyclic amines such as linoline, and water-soluble organic solvents such as ethanol, γーbutyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be appropriately added to these .
又,為了得到更優良的導電性圖案,還較佳為對這些鹼性顯影液進一步添加0.01~1質量%的非離子系界面活性劑等的界面活性劑。Moreover, in order to obtain a more excellent electroconductive pattern, it is also preferable to further add 0.01-1 mass % of surfactants, such as a nonionic surfactant, to these alkaline developing solutions.
若在基板上以網格狀形成導電性圖案,則能使用作為觸控面板、液晶或有機EL等的顯示面板或可穿戴式產品等所具備的透明導電配線。 [實施例]When a conductive pattern is formed in a grid shape on a substrate, it can be used as a transparent conductive wiring included in a touch panel, a display panel such as a liquid crystal or an organic EL, a wearable product, or the like. [Example]
以下舉出實施例來進一步具體說明本發明,但本發明並非限定於這些實施例。關於在合成例及實施例所使用的化合物之中,使用簡稱者係如下所示。 AIBN:2,2’-偶氮雙(異丁腈) TMAH:氫氧化四甲銨。Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Among the compounds used in Synthesis Examples and Examples, the abbreviations used are as follows. AIBN: 2,2'-azobis(isobutyronitrile) TMAH: Tetramethylammonium hydroxide.
首先,說明實施例及比較例所使用的材料。First, materials used in Examples and Comparative Examples will be described.
[有機顏料(F)] (F-1)表面經磺酸基改質之碳黑(Cabot製TPK1227)。[Organic Pigment (F)] (F-1) Carbon black whose surface was modified with a sulfonic acid group (TPK1227 manufactured by Cabot).
(F-2)沒有進行特殊表面處理之碳黑(三菱化學製MA-100) [具有包含碳的被覆層之無機粒子(G)] (A-1)該被覆層的平均厚度為3nm,且一次粒徑為50nm之銀粒子(Nisshin Engineering股份公司製)。濃度1質量%之水的懸浮液的pH為8.0。(F-2) Carbon black without special surface treatment (MA-100 manufactured by Mitsubishi Chemical) [Inorganic particles (G) having a coating layer containing carbon] (A-1) Silver particles (manufactured by Nisshin Engineering Co., Ltd.) having an average thickness of the coating layer of 3 nm and a primary particle diameter of 50 nm. The pH of the suspension in water having a concentration of 1% by mass was 8.0.
(A-2)該被覆層的平均厚度為3nm,且一次粒徑為40nm之銀粒子(Nisshin Engineering股份公司製)。濃度1質量%之水的懸浮液的pH為4.5。(A-2) Silver particles (manufactured by Nisshin Engineering Co., Ltd.) having an average thickness of the coating layer of 3 nm and a primary particle diameter of 40 nm. The pH of the suspension in water with a concentration of 1% by mass was 4.5.
(A-3)一次粒徑為200nm的銀粒子(產品名稱:DJA03N;東洋化學工業股份公司製)。濃度1質量%之水的懸浮液的pH為5.0。沒有包含碳的被覆層。(A-3) Silver particles with a primary particle diameter of 200 nm (product name: DJA03N; manufactured by Toyo Chemical Industry Co., Ltd.). The pH of the suspension in water with a concentration of 1% by mass was 5.0. There is no coating layer containing carbon.
[具有以通式(1)所表示的結構及藉由熱產生胺基的官能基之化合物(B)] (B-1)KBM-585:3-脲丙基三甲氧基矽烷(信越化學股份公司製) (B-2)KBE-585:3-脲丙基三乙氧基矽烷(信越化學股份公司製) (B-3)KBE-9007:3-異氰酸酯基丙基三乙氧基矽烷(信越化學股份公司製) (B’-4)KBE-903:3-胺丙基三乙氧基矽烷(信越化學股份公司製)。[Compound (B) having a structure represented by the general formula (1) and a functional group that generates an amine group by heat] (B-1) KBM-585: 3-Ureapropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) (B-2) KBE-585: 3-Ureapropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) (B-3) KBE-9007: 3-Isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) (B'-4) KBE-903: 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.).
[黏結劑樹脂(C)] (C-1) 在500ml的燒瓶中加入2.0g的AIBN、50g的PGMEA。然後加入38.7g的甲基丙烯酸、79.3g的甲基丙烯酸苯甲酯、22.0g的甲基丙烯酸三環[5.2.1.0(2,6)]癸-8-酯,於室溫一邊攪拌,一邊藉由鼓泡對燒瓶內充分進行氮氣取代後,在70℃加熱攪拌5小時。接下來,對所得到的溶液加入21.3g的甲基丙烯酸環氧丙酯、1g的二甲基苯甲胺、0.2g的對甲氧苯酚、100g的PGMEA,在90℃加熱攪拌4小時,對所得到的丙烯酸聚合物溶液加入PGMEA,以使固體含量濃度成為40wt%,得到黏結劑樹脂(C-1)的溶液。以藉由GPC法測定之聚苯乙烯換算出的重量平均分子量Mw為18,000。[Binder resin (C)] (C-1) In a 500 ml flask, 2.0 g of AIBN and 50 g of PGMEA were added. Then, 38.7 g of methacrylic acid, 79.3 g of benzyl methacrylate, and 22.0 g of tricyclo[5.2.1.0(2,6)]dec-8-ester methacrylate were added and stirred at room temperature while stirring. After fully substituting nitrogen in the flask by bubbling, it was heated and stirred at 70° C. for 5 hours. Next, 21.3 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours. The obtained acrylic polymer solution was added to PGMEA so that the solid content concentration was 40 wt % to obtain a solution of binder resin (C-1). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 18,000.
(C-2) 在500ml的燒瓶中加入1.5g的AIBN、50g的PGMEA。然後加入38.7g的甲基丙烯酸、46.9g的苯乙烯、22.0g的甲基丙烯酸三環[5.2.1.0(2,6)]癸-8-酯,於室溫一邊攪拌,一邊藉由鼓泡對燒瓶內充分進行氮氣取代後,在70℃加熱攪拌5小時。接下來,對所得到的溶液加入21.3g的甲基丙烯酸環氧丙酯、1g的二甲基苯甲胺、0.2g的對甲氧苯酚、100g的PGMEA,在90℃加熱攪拌4小時,對所得到的丙烯酸聚合物溶液加入PGMEA,以使固體含量濃度成為40wt%,得到黏結劑樹脂(C-2)的溶液。以藉由GPC法測定之聚苯乙烯換算出的重量平均分子量Mw為14,000。(C-2) In a 500 ml flask, 1.5 g of AIBN and 50 g of PGMEA were added. Then, 38.7 g of methacrylic acid, 46.9 g of styrene, and 22.0 g of tricyclo[5.2.1.0(2,6)]dec-8-ester methacrylate were added and stirred at room temperature while bubbling After fully substituting nitrogen in the flask, it was heated and stirred at 70° C. for 5 hours. Next, 21.3 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol, and 100 g of PGMEA were added to the obtained solution, followed by heating and stirring at 90° C. for 4 hours. The obtained acrylic polymer solution was added to PGMEA so that the solid content concentration became 40 wt % to obtain a solution of the binder resin (C-2). The weight average molecular weight Mw in terms of polystyrene measured by the GPC method was 14,000.
[分散劑] DISPERBYK(註冊商標)21116(BYK-Chemie Japan股份公司製)。[Dispersant] DISPERBYK (registered trademark) 21116 (manufactured by BYK-Chemie Japan Co., Ltd.).
[溶劑] PGMEA:丙二醇單甲基醚乙酸酯(三協化學(股)製) DPM:二丙二醇單甲基醚(東邦化學工業(股)製)。[solvent] PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Sankyo Chemical Co., Ltd.) DPM: Dipropylene glycol monomethyl ether (manufactured by Toho Chemical Industry Co., Ltd.).
[光聚合起始劑] NCI-831E(註冊商標)(肟酯系化合物;ADEKA(股)製)。[Photopolymerization initiator] NCI-831E (registered trademark) (oxime ester compound; manufactured by ADEKA Corporation).
[丙烯酸單體] LIGHT ACRYLATE(註冊商標)PE-3A(共榮社化學(股)製)。[Acrylic monomer] LIGHT ACRYLATE (registered trademark) PE-3A (Kyoeisha Chemical Co., Ltd.).
二新戊四醇六丙烯酸酯(日本化藥(股)製DPHA)。Dipivalerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.).
[正型光阻] (P-1) 乾燥氮氣氣流下,將29.3g(0.08莫耳)的2,2-雙(3-胺基-4-羥基苯基)六氟丙烷(BAHF;Central Glass(股)製)、1.24g(0.005莫耳)的1,3-雙(3-胺丙基)四甲基二矽氧烷、3.27g(0.03莫耳)的作為封端劑之3-胺基苯酚溶解於150g的N-甲基-2-吡咯啶酮(NMP)。將31.0g(0.1莫耳)的3,3’,4,4’-二苯醚四甲酸二酐(ODPA;MANAC(股)製)與50g的NMP一起加入其中,於20℃攪拌1小時,接下來於50℃攪拌4小時。然後,添加15g的二甲苯,一邊將水與二甲苯一起共沸,一邊於150℃攪拌5小時。攪拌結束後,將溶液投入3L的水,蒐集白色沉澱物。以過濾收集此沉澱物,以水清洗3次後,以80℃的真空乾燥機乾燥24小時,得到聚醯亞胺樹脂。[Positive photoresist] (P-1) Under a stream of dry nitrogen, 29.3 g (0.08 mol) of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF; manufactured by Central Glass Co., Ltd.), 1.24 g (0.005 mol) ear) 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 3.27g (0.03mol) of 3-aminophenol as a capping agent were dissolved in 150g of N-methyl- 2-pyrrolidone (NMP). 31.0 g (0.1 mol) of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (ODPA; manufactured by MANAC Co., Ltd.) was added together with 50 g of NMP, and the mixture was stirred at 20° C. for 1 hour. Next, stirring was carried out at 50°C for 4 hours. Then, 15 g of xylene was added, and the mixture was stirred at 150° C. for 5 hours while azeotroping water and xylene. After the stirring, the solution was put into 3 L of water, and the white precipitate was collected. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain a polyimide resin.
又,另外在乾燥氮氣氣流下,將15.3g的TrisP-HAP(本州化學工業(股)製)與40.3g的5-萘醌二疊氮磺醯氯溶解於450g的1,4-二㗁烷中,作成室溫。對其中,以使系統內不達到35℃以上之方式滴加與50g的1,4-二㗁烷混合的15.2g三乙胺,但不要使其達到。滴加後,於30℃攪拌2小時。將三乙胺鹽過濾,使濾液投入水中。將其後析出的沉澱物用真空乾燥機乾燥,得到醌二疊氮化合物。In addition, under a stream of dry nitrogen, 15.3 g of TrisP-HAP (manufactured by Honshu Chemical Industry Co., Ltd.) and 40.3 g of 5-naphthoquinonediazidesulfonyl chloride were dissolved in 450 g of 1,4-dioxane. , set to room temperature. To this, 15.2 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the inside of the system did not reach 35°C or higher, but did not reach it. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was put into water. The precipitate deposited after that was dried with a vacuum dryer to obtain a quinonediazide compound.
將所得到之11.0g的聚醯亞胺樹脂、4.0g的醌二疊氮化合物、63.75g的乳酸乙酯及21.25g的PGMEA加入100ml的PP瓶中,並攪拌。接下來,以0.2μm的濾器進行過濾,得到正型光阻(P-1)。The obtained 11.0 g of polyimide resin, 4.0 g of quinonediazide compound, 63.75 g of ethyl lactate, and 21.25 g of PGMEA were put into a 100-ml PP bottle and stirred. Next, filtering was performed with a 0.2 μm filter to obtain a positive photoresist (P-1).
[基板] (S-1)表面上濺鍍有SiO2 之玻璃基板(TU060;TOKEN公司製) (S-2)無鹼玻璃基板(OA-10G;日本電氣硝子股份公司製) (S-3)聚醯亞胺薄膜(Neopulim;三菱瓦斯化學股份公司製)。[Substrate] (S-1) Glass substrate (TU060; manufactured by TOKEN Co., Ltd.) sputtered with SiO 2 on the surface (S-2) Alkali-free glass substrate (OA-10G; manufactured by Nippon Electric Glass Co., Ltd.) (S-3 ) polyimide film (Neopulim; manufactured by Mitsubishi Gas Chemical Co., Ltd.).
實施例1~14、比較例1~3 <導電性評價> 對於樹脂組成物1,使用旋塗機(MIKASA(股)製「1H-360S(商品名)」),以300rpm 10秒、500rpm 1秒之條件旋塗至(S-1)基板上,並使用加熱板(大日本SCREEN製造(股)製「SCW-636(商品名)」)將基板在100℃預烤5分鐘,得到膜厚1μm的預烤膜。然後,使用烘箱(「IHPS-222」;ESPEC(股)製)並在230℃實施30分鐘(空氣中)後烘烤,藉此得到由樹脂組成物1構成之固膜(solid film)。使用旋塗機(MIKASA(股)製「1H-360S(商品名)」)將正型光阻(P-1)以300rpm 10秒、1000rpm 5秒之條件旋塗在所得到的固膜上,並使用加熱板(大日本SCREEN製造(股)製「SCW-636(商品名)」)對基板以100℃預烤2分鐘,得到膜厚1μm的預烤膜。使用平行光光刻機(佳能(股)製「PLA-501F(商品名)」)以超高壓汞燈作為光源,透過期望的遮罩對預烤膜曝光。然後,使用自動顯影裝置(Takizawa Sangyo(股)製「AD-1200(商品名)」),以2.38wt%TMAH水溶液噴淋顯影(shower development)60秒鐘,接下來以水清洗30秒鐘,進行圖案加工。經由使所得到的基板浸漬至濃度55%的硝酸鐵(III)水溶液中,進行蝕刻,經由曝光、顯影,藉此將光阻剝離。然後,使用烘箱(「IHPS-222」;ESPEC(股)製),在230℃施予後烘烤30分鐘(空氣中),得到體積電阻率評價圖案。Examples 1 to 14, Comparative Examples 1 to 3 <Evaluation of Conductivity> The resin composition 1 was spin-coated on the substrate (S-1) under the conditions of 300 rpm for 10 seconds and 500 rpm for 1 second using a spin coater (“1H-360S (trade name)” manufactured by MIKASA Co., Ltd.). A hot plate (“SCW-636 (trade name)” manufactured by Dainippon SCREEN Co., Ltd.) prebaked the substrate at 100° C. for 5 minutes to obtain a prebaked film with a film thickness of 1 μm. Then, by performing post-baking at 230° C. for 30 minutes (in air) using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), a solid film composed of the resin composition 1 was obtained. Using a spin coater (“1H-360S (trade name)” manufactured by MIKASA Co., Ltd.), a positive photoresist (P-1) was spin-coated on the obtained solid film at 300 rpm for 10 seconds and 1000 rpm for 5 seconds. The substrate was prebaked at 100° C. for 2 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon SCREEN Co., Ltd.) to obtain a prebaked film with a thickness of 1 μm. The prebaked film was exposed to light through a desired mask using a parallel lithography machine (“PLA-501F (trade name)” manufactured by Canon Inc.) using an ultra-high pressure mercury lamp as a light source. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), a 2.38 wt% TMAH aqueous solution was used for shower development (shower development) for 60 seconds, followed by washing with water for 30 seconds. Perform pattern processing. The photoresist was peeled off by immersing the obtained board|substrate in the iron (III) nitrate aqueous solution with a density|concentration of 55%, etching, exposing, and developing. Then, using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), it was baked at 230° C. for 30 minutes (in air) after application, and a volume resistivity evaluation pattern was obtained.
對於樹脂組成物2~17,使用旋塗機(MIKASA(股)製「1H-360S(商品名)」),以300rpm 10秒、500rpm 1秒之條件旋塗在(S-1)~(S-3)各基板上,並使用加熱板(大日本SCREEN製造(股)製「SCW-636(商品名)」)對基板以100℃預烤5分鐘,得到膜厚1μm的預烤膜。使用平行光光刻機(佳能(股)製「PLA-501F(商品名)」)以超高壓汞燈作為光源,透過期望的遮罩對預烤膜曝光。然後,使用自動顯影裝置(Takizawa Sangyo (股)製「AD-1200(商品名)」),以0.07wt%TMAH水溶液噴淋顯影60秒鐘,接下來以水清洗30秒鐘,進行圖案加工。然後,使用烘箱(「IHPS-222」;ESPEC(股)製),以230℃施予後烘烤30分鐘(空氣中),得到體積電阻率評價圖案。Resin compositions 2 to 17 were spin-coated on (S-1) to (S -3) On each substrate, the substrate was prebaked at 100° C. for 5 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon SCREEN Co., Ltd.) to obtain a prebaked film with a film thickness of 1 μm. The prebaked film was exposed to light through a desired mask using a parallel lithography machine (“PLA-501F (trade name)” manufactured by Canon Inc.) using an ultra-high pressure mercury lamp as a light source. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), it was subjected to shower development with a 0.07 wt % TMAH aqueous solution for 60 seconds, followed by washing with water for 30 seconds to perform patterning. Then, using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), it was applied at 230° C. for 30 minutes (in air) and post-baking was performed to obtain a volume resistivity evaluation pattern.
對所得到的體積電阻率評價圖案測定以表面抵抗測定機(Loresta(註冊商標)-FP;三菱油化股份公司製)測定之表面電阻值ρs(Ω/□),及以表面粗糙度形狀測量儀(SURFCOM(註冊商標)1400D;東京精密股份公司製)測定之膜厚t(cm),經由將兩個數值相乘來算出體積電阻率(μΩ・cm)。For the obtained volume resistivity evaluation pattern, the surface resistance value ρs (Ω/□) measured with a surface resistance measuring machine (Loresta (registered trademark)-FP; manufactured by Mitsubishi Oil & Chemical Co., Ltd.) and the surface roughness shape were measured. The volume resistivity (μΩ・cm) was calculated by multiplying the film thickness t (cm) measured with a meter (SURFCOM (registered trademark) 1400D; manufactured by Tokyo Seiki Co., Ltd.).
<密著性評價> 對於樹脂組成物1,使用旋塗機(MIKASA(股)製「1H-360S(商品名)」),以300rpm 10秒、500rpm 1秒之條件旋塗至(S-1)上,並使用加熱板(大日本SCREEN製造(股)製「SCW-636(商品名)」)對基板以100℃預烤5分鐘,得到膜厚1μm的預烤膜。然後,使用烘箱(「IHPS-222」;ESPEC(股)製),以230℃施予後烘烤30分鐘(空氣中),得到由樹脂組成物1構成之固膜。<Adhesion evaluation> Resin composition 1 was spin-coated on (S-1) at 300 rpm for 10 seconds and 500 rpm for 1 second using a spin coater (“1H-360S (trade name)” manufactured by MIKASA Co., Ltd.), and heated A board ("SCW-636 (trade name)" manufactured by Dainippon SCREEN Co., Ltd.) was prebaked on the substrate at 100° C. for 5 minutes to obtain a prebaked film with a film thickness of 1 μm. Then, using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), it was applied and baked at 230° C. for 30 minutes (in air) to obtain a solid film composed of the resin composition 1.
另外,使用旋塗機(MIKASA(股)製「1H-360S(商品名)」),以300rpm 10秒、500rpm 1秒之條件,將樹脂組成物2~17旋塗至(S-1)~(S-3)各基板上,再使用加熱板(大日本SCREEN製造(股)製「SCW-636(商品名)」)對基板以100℃預烤5分鐘,得到膜厚1μm的預烤膜。使用平行光光刻機(佳能(股)製「PLA-501F(商品名)」)以超高壓汞燈作為光源,不透過遮罩對預烤膜曝光。然後,使用自動顯影裝置(Takizawa Sangyo(股)製「AD-1200(商品名)」),以0.07wt%TMAH水溶液噴淋顯影60秒鐘,接下來以水清洗30秒鐘。然後,使用烘箱(「IHPS-222」;ESPEC(股)製),以230℃施予後烘烤30分鐘(空氣中),得到由樹脂組成物2~17的各樹脂組成物構成之固膜。In addition, using a spin coater (“1H-360S (trade name)” manufactured by MIKASA Co., Ltd.), under the conditions of 300 rpm for 10 seconds and 500 rpm for 1 second, the resin compositions 2 to 17 were spin-coated to (S-1) to (S-1). (S-3) On each substrate, a hot plate (“SCW-636 (trade name)” manufactured by Dainippon SCREEN Co., Ltd.) was used to pre-bake the substrate at 100° C. for 5 minutes to obtain a pre-baked film with a film thickness of 1 μm . Using a parallel lithography machine (“PLA-501F (trade name)” manufactured by Canon Co., Ltd.) with an ultra-high pressure mercury lamp as a light source, the pre-baked film was exposed without passing through a mask. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), it was subjected to shower development with a 0.07 wt % TMAH aqueous solution for 60 seconds, followed by washing with water for 30 seconds. Then, using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), it was applied at 230° C. for 30 minutes (in air) and post-baked, to obtain a solid film composed of each of resin compositions 2 to 17.
對所得到的固膜評價與基材的密著性。具體來說係依據JIS K5600-5-6(1999年),進行依照5B~0B之6階段評價(數字越大,密著性越高)的百格測試。其中,若密著性在2B以下,由於可能引起因硬化物的剝離而造成觸控面板的故障等,所以密著性較佳為3B以上,更佳為4B以上。The obtained solid film was evaluated for adhesion to the substrate. Specifically, according to JIS K5600-5-6 (1999), a 100-grid test was performed according to 6-stage evaluation of 5B to 0B (the larger the number, the higher the adhesion). Among them, when the adhesiveness is 2B or less, since there is a possibility of causing a failure of the touch panel due to peeling of the cured product, etc., the adhesiveness is preferably 3B or more, and more preferably 4B or more.
<圖案化性評價> 使用旋塗機(MIKASA(股)製「1H-360S(商品名)」),以300rpm 10秒、500rpm 1秒之條件,將樹脂組成物2~17旋塗至(S-1)~(S-3)各基板上,並使用加熱板(大日本SCREEN製造(股)製「SCW-636(商品名)」)對基板以100℃預烤5分鐘,得到膜厚1μm的預烤膜。使用平行光光刻機(佳能(股)製「PLA-501F(商品名)」)以超高壓汞燈作為光源,透過期望的遮罩對預烤膜曝光。然後,使用自動顯影裝置(Takizawa Sangyo(股)製「AD-1200(商品名)」),以0.07wt%TMAH水溶液噴淋顯影60秒鐘,接下來以水清洗30秒鐘,進行圖案加工。曝光、顯影後,測定在以1比1的寬度形成5μm的線寬線距圖案之曝光量下顯影後的最小圖案尺寸,來作為解析度。曝光量係以I線照度計測定。<Patternability evaluation> Using a spin coater (“1H-360S (trade name)” manufactured by MIKASA Co., Ltd.), the resin compositions 2 to 17 were spin-coated to (S-1) to (S -3) On each substrate, the substrate was prebaked at 100° C. for 5 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon SCREEN Co., Ltd.) to obtain a prebaked film with a film thickness of 1 μm. The prebaked film was exposed to light through a desired mask using a parallel lithography machine (“PLA-501F (trade name)” manufactured by Canon Inc.) using an ultra-high pressure mercury lamp as a light source. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), it was subjected to shower development with a 0.07 wt % TMAH aqueous solution for 60 seconds, followed by washing with water for 30 seconds to perform patterning. After exposure and development, the minimum pattern size after development was measured at the exposure amount to form a 5 μm line width and line spacing pattern with a width of 1:1 as the resolution. The exposure amount was measured with an I-line illuminometer.
<基板上殘渣評價> 對上述以樹脂組成物2~17形成體積電阻率評價圖案之基板的未曝光部分,藉由透射率評價來評價基板上的殘渣。具體來說係對未曝光部分,用分光光度計(U-3410;日立製作所股份公司製)測定形成膜前後在400nm之透射率。然後,將形成膜前的透射率設為T0 、形成膜後的透射率設為T,算出以式(T0 -T)/T0 ×100所表示之透射率變化。於透射率變化為1.0%以下之情形,判定殘渣抑制的效果是充分的。<Evaluation of Residues on Substrates> The residues on the substrates were evaluated by transmittance evaluation on the unexposed portions of the substrates in which the volume resistivity evaluation patterns were formed with the resin compositions 2 to 17. Specifically, the transmittance at 400 nm before and after film formation was measured with a spectrophotometer (U-3410; manufactured by Hitachi, Ltd.) about the unexposed portion. Then, the transmittance before film formation was set to T 0 and the transmittance after film formation was set to T, and the transmittance change represented by the formula (T 0 -T)/T 0 ×100 was calculated. When the transmittance change was 1.0% or less, it was judged that the effect of suppressing residues was sufficient.
(實施例1) 對80.00g的具有包含碳的被覆層之導電性粒子(A-1)、2.00g的DISPERBYK21116、100.00g的PGMEA、100.00g的DPM以均質機施予1200rpm、30分鐘的混合處理,再進一步使用高壓濕式無介質微粒化裝置Nanomizer(Nanomizer(股))分散,得到銀粒子分散體。對282.00g的此銀微粒分散體,混合0.50g的具有以通式(1)所表示的結構及藉由熱產生胺基的官能基之化合物(B-1)、43.75g的固體含量濃度40質量%的黏結劑樹脂(C-1),對混合物添加73.75g的PGMEA、100.00g的DPM並攪拌,藉此得到樹脂組成物1。(Example 1) 80.00 g of conductive particles (A-1) having a carbon-containing coating layer, 2.00 g of DISPERBYK21116, 100.00 g of PGMEA, and 100.00 g of DPM were mixed with a homogenizer at 1200 rpm for 30 minutes, and then used. It disperse|distributed by the high pressure wet medium-less micronizing apparatus Nanomizer (Nanomizer (stock)), and obtained the silver particle dispersion. To 282.00 g of this silver fine particle dispersion, 0.50 g of a compound (B-1) having a structure represented by the general formula (1) and a functional group that generates an amine group by heat, 43.75 g of a solid content concentration of 40 were mixed. Resin composition 1 was obtained by adding 73.75 g of PGMEA and 100.00 g of DPM to the mixture with respect to the binder resin (C-1) of % by mass, and stirring the mixture.
將導電性及密著性評價的結果示於表1。Table 1 shows the results of evaluation of electrical conductivity and adhesion.
(實施例2) 首先,對80.00g的具有包含碳的被覆層之導電性粒子(A-1)、2.00g的DISPERBYK21116、100.00g的PGMEA、100.00g的DPM,以均質機施予1200rpm、30分鐘的混合處理,再進一步使用高壓濕式無介質微粒化裝置Nanomizer(Nanomizer(股))分散,得到銀粒子分散體。對282.00g的此銀微粒分散體,混合0.50g的具有以通式(1)所表示的結構及藉由熱產生胺基的官能基之化合物(B-1)、25.00g的固體含量濃度40質量%的黏結劑樹脂(C-1)、1.50g的(D)感光劑之NCI-831E、6.00g的PE-3A,對此混合物添加85.00g的PGMEA、100.00g的DPM並攪拌,藉此得到樹脂組成物2。(Example 2) First, 80.00 g of conductive particles (A-1) having a coating layer containing carbon, 2.00 g of DISPERBYK21116, 100.00 g of PGMEA, and 100.00 g of DPM were mixed with a homogenizer at 1200 rpm for 30 minutes. Furthermore, it disperse|distributed using a high pressure wet medium-less micronizing apparatus Nanomizer (Nanomizer (stock)), and obtained the silver particle dispersion. To 282.00 g of this silver fine particle dispersion, 0.50 g of a compound (B-1) having a structure represented by the general formula (1) and a functional group that generates an amine group by heat, 25.00 g of a solid content concentration of 40 Mass % of binder resin (C-1), 1.50 g of (D) NCI-831E of the sensitizer, and 6.00 g of PE-3A, 85.00 g of PGMEA and 100.00 g of DPM were added to this mixture and stirred, thereby Resin composition 2 was obtained.
將圖案化性、導電性、基板上殘渣及密著性評價的結果示於表1。Table 1 shows the results of evaluation of patternability, electrical conductivity, residues on the substrate, and adhesion.
(實施例3~14及比較例1~3) 以與實施例2相同的方法,得到表1~2記載的組成之感光性樹脂組成物3~17,對各感光性樹脂組成物,於表1~2記載的基板上進行與實施例2相同的評價。將評價結果示於表1~2。(Examples 3 to 14 and Comparative Examples 1 to 3) In the same manner as in Example 2, photosensitive resin compositions 3 to 17 having the compositions described in Tables 1 to 2 were obtained, and the photosensitive resin compositions were subjected to the same procedures as in Example 2 on the substrates described in Tables 1 to 2 for each photosensitive resin composition. evaluation of. The evaluation results are shown in Tables 1 and 2.
(實施例15~19、比較例4~5) (著色樹脂組成物1) 將300g的表面經磺酸基改質之碳黑(Cabot製TPK1227)、150g的丙烯酸聚合物(C-1)之丙二醇單甲基醚乙酸酯(PGMEA)40重量%溶液、37.5g的作為高分子分散劑之具有三級胺基與四級銨鹽的「DISPERBYK」(註冊商標)LPN-21116以及1012.5g的PGMEA加入槽中,以均質機攪拌20分鐘,得到預先分散液。對具備填充有75體積%的0.05mmφ氧化鋯珠之離心分離器的壽工業(股)製分散機Ultra Apex Mill,供給所得到的預先分散液,以旋轉速度8m/s進行分散3小時,得到固體含量濃度25重量%、著色材料/樹脂(重量比)=80/20之著色材料分散液Bk-1。(Examples 15 to 19, Comparative Examples 4 to 5) (Colored resin composition 1) 300 g of carbon black (TPK1227 manufactured by Cabot), 150 g of propylene glycol monomethyl ether acetate (PGMEA) 40% by weight solution of acrylic polymer (C-1), 37.5 g of "DISPERBYK" (registered trademark) LPN-21116 having a tertiary amine group and a quaternary ammonium salt as a polymer dispersant, and 1012.5 g of PGMEA were added to the tank and stirred with a homogenizer for 20 minutes to obtain a preliminary dispersion. The obtained preliminary dispersion liquid was supplied to a dispersing machine Ultra Apex Mill manufactured by Shougyo Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of 0.05 mmφ zirconia beads, and the dispersion was carried out at a rotational speed of 8 m/s for 3 hours to obtain Coloring material dispersion liquid Bk-1 with a solid content concentration of 25% by weight, coloring material/resin (weight ratio)=80/20.
對碳黑分散液Bk-1(822.6g),添加將丙烯酸聚合物(C-1)之丙二醇單甲基醚乙酸酯40重量%溶液(344.5g)、作為密著改良劑之信越化學(股)製KBM-585(7.5g)、聚矽氧系界面活性劑之丙二醇單甲基醚乙酸酯10重量%溶液(4.0g)溶解於丙二醇單甲基醚乙酸酯(218.5g)而成之溶液,得到著色樹脂組成物1。To the carbon black dispersion liquid Bk-1 (822.6 g), a 40% by weight solution (344.5 g) of propylene glycol monomethyl ether acetate of the acrylic polymer (C-1) and Shin-Etsu Chemical ( KBM-585 (7.5g) manufactured by Co., Ltd., a 10% by weight solution (4.0g) of propylene glycol monomethyl ether acetate of polysiloxane-based surfactant was dissolved in propylene glycol monomethyl ether acetate (218.5g) The resulting solution was obtained to obtain a colored resin composition 1.
(著色樹脂組成物2) 將300g的表面經磺酸基改質之碳黑(Cabot製TPK1227)、150g的丙烯酸聚合物(C-1)之丙二醇單甲基醚乙酸酯(PGMEA)40重量%溶液、37.5g的作為高分子分散劑之具有三級胺基與四級銨鹽的「DISPERBYK」(註冊商標)LPN-21116及1012.5g的PGMEA加入槽中,以均質機攪拌20分鐘,得到預先分散液。對具備填充有75體積%的0.05mmφ氧化鋯珠之離心分離器的壽工業(股)製分散機Ultra Apex Mill,供給所得到的預先分散液,以旋轉速度8m/s進行分散3小時,得到固體含量濃度25重量%、著色材料/樹脂(重量比)=80/20之著色材料分散液Bk-1。(Colored resin composition 2) 300 g of carbon black (TPK1227 manufactured by Cabot), 150 g of propylene glycol monomethyl ether acetate (PGMEA) 40% by weight solution of acrylic polymer (C-1), 37.5 g of "DISPERBYK" (registered trademark) LPN-21116 and 1012.5 g of PGMEA having a tertiary amine group and a quaternary ammonium salt of the polymer dispersant were added to the tank and stirred with a homogenizer for 20 minutes to obtain a preliminary dispersion. The obtained pre-dispersion liquid was supplied to a dispersing machine Ultra Apex Mill manufactured by Shou Kogyo Co., Ltd. equipped with a centrifugal separator filled with 75% by volume of 0.05 mmφ zirconia beads, and the dispersion was carried out at a rotational speed of 8 m/s for 3 hours to obtain Coloring material dispersion liquid Bk-1 with a solid content concentration of 25% by weight, coloring material/resin (weight ratio)=80/20.
對碳黑分散液Bk-1(822.6g),添加將丙烯酸聚合物(C-1)之丙二醇單甲基醚乙酸酯40重量%溶液(117.3g)、作為多官能單體之二新戊四醇六丙烯酸酯(日本化藥(股)製DPHA)的丙二醇單甲基醚乙酸酯50重量%溶液(92.7g)、作為光聚合起始劑之ADEKA(股)「ADEKA ARKLS」NCI-831(11.6g)、作為密著改良劑之信越化學(股)製KBM-585(7.5g)、聚矽氧系界面活性劑之丙二醇單甲基醚乙酸酯10重量%溶液(4.0g)溶解於丙二醇單甲基醚乙酸酯(218.5g)而成之溶液,得到著色樹脂組成物2。To the carbon black dispersion liquid Bk-1 (822.6 g), a 40% by weight solution (117.3 g) of propylene glycol monomethyl ether acetate of the acrylic polymer (C-1) and dipivale as a polyfunctional monomer were added A 50% by weight solution (92.7 g) of tetraol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), ADEKA Co., Ltd. "ADEKA ARKLS" NCI- as a photopolymerization initiator 831 (11.6g), KBM-585 (7.5g) manufactured by Shin-Etsu Chemical Co., Ltd. as an adhesion improver, 10% by weight solution of propylene glycol monomethyl ether acetate as a polysiloxane-based surfactant (4.0g) Colored resin composition 2 was obtained by dissolving a solution in propylene glycol monomethyl ether acetate (218.5 g).
(著色樹脂組成物3~7) 以與著色樹脂組成物2相同之方法,得到表3記載的組成之著色樹脂組成物3~7。(Colored resin compositions 3 to 7) By the same method as the colored resin composition 2, colored resin compositions 3 to 7 having the compositions described in Table 3 were obtained.
<保存穩定性評價> 對上述的著色樹脂組成物1~7,用黏度計(東機產業製RE105L)溫度設定在25.0±0.2℃,以轉速50rpm,測定著色樹脂組成物調製完當下的黏度及將著色樹脂組成物於室溫(30℃)放置1週後的黏度,算出其黏度變化率。黏度變化率為15%以上者判定為保存穩定性不良。<Storage stability evaluation> For the above-mentioned colored resin compositions 1 to 7, use a viscometer (RE105L manufactured by Toki Sangyo Co., Ltd.) to set the temperature at 25.0 ± 0.2°C, and at a rotational speed of 50 rpm, measure the viscosity of the colored resin composition when the coloring resin composition is prepared and put the colored resin composition in. The viscosity after standing at room temperature (30°C) for 1 week was calculated, and the viscosity change rate was calculated. When the viscosity change rate was 15% or more, the storage stability was judged to be poor.
<密著性評價> 使用旋塗機(MIKASA(股)製「1H-DS(商品名)」)將著色樹脂組成物1旋塗至(S-2)上,並使用加熱板(大日本SCREEN製造(股)製「SCW-636(商品名)」)對基板以100℃預烤10分鐘,得到預烤膜。然後,使用烘箱(「IHPS-222」;ESPEC(股)製),以230℃施予後烘烤30分鐘(空氣中),得到厚度1.5μm的由著色樹脂組成物1構成之固膜。<Adhesion evaluation> Colored resin composition 1 was spin-coated on (S-2) using a spin coater ("1H-DS (trade name)" manufactured by MIKASA Co., Ltd.), and a hot plate ("1H-DS (trade name)" manufactured by Dainippon SCREEN Co., Ltd.) was used. SCW-636 (trade name)") prebaked the substrate at 100°C for 10 minutes to obtain a prebaked film. Then, using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), it was applied and baked at 230° C. for 30 minutes (in air) to obtain a solid film of colored resin composition 1 having a thickness of 1.5 μm.
另外,使用旋塗機(MIKASA(股)製「1H-DS(商品名)」)將著色樹脂組成物2~7旋塗至(S-2)上,再使用加熱板(大日本SCREEN製造(股)製「SCW-636(商品名)」)對基板以100℃預烤10分鐘,得到預烤膜。使用光刻機(Union Optical(股)製)以超高壓汞燈作為光源,不透過遮罩對預烤膜曝光。然後,使用自動顯影裝置(Takizawa Sangyo(股)製「AD-1200(商品名)」),以0.045質量%KOH水溶液噴淋顯影60秒鐘,接下來以水清洗30秒鐘。然後,使用烘箱(「IHPS-222」;ESPEC(股)製),以230℃施予後烘烤30分鐘(空氣中),得到由著色樹脂組成物2~7的各樹脂組成物構成之厚度1.5μm的固膜。In addition, the coloring resin compositions 2 to 7 were spin-coated on (S-2) using a spin coater (“1H-DS (trade name)” manufactured by MIKASA Co., Ltd.), and then a hot plate (manufactured by Dainippon SCREEN) was used. Co., Ltd. "SCW-636 (trade name)") prebaked the substrate at 100° C. for 10 minutes to obtain a prebaked film. Using a photolithography machine (manufactured by Union Optical Co., Ltd.) with an ultra-high pressure mercury lamp as a light source, the pre-baked film was exposed without passing through the mask. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), it was subjected to shower development with a 0.045 mass % KOH aqueous solution for 60 seconds, followed by washing with water for 30 seconds. Then, using an oven (“IHPS-222”; manufactured by ESPEC Co., Ltd.), it was applied at 230° C. for 30 minutes (in air), and then baked for 30 minutes (in the air) to obtain coloring resin compositions 2 to 7 each having a thickness of 1.5 μm solid film.
對所得到的固膜評價與基材的密著性。具體來說係依據JIS K5600-5-6(1999年),進行依照5B~0B之6階段評價(數字越大,密著性越高)的百格測試。其中,若密著性在2B以下,由於可能引起因硬化物的剝離而造成觸控面板的故障等,所以密著性較佳為3B以上,更佳為4B以上。The obtained solid film was evaluated for adhesion to the substrate. Specifically, according to JIS K5600-5-6 (1999), a 100-grid test was performed according to 6-stage evaluation of 5B to 0B (the larger the number, the higher the adhesion). Among them, when the adhesiveness is 2B or less, since there is a possibility of causing a failure of the touch panel due to peeling of the cured product, etc., the adhesiveness is preferably 3B or more, and more preferably 4B or more.
<圖案化性評價> 使用旋塗機(MIKASA(股)製「1H-DS(商品名)」)將著色樹脂組成物2~7旋塗至(S-2)上,並使用加熱板(大日本SCREEN製造(股)製「SCW-636(商品名)」)對基板以100℃預烤10分鐘,得到預烤膜。使用光刻機(Union Optical(股)製)以超高壓汞燈作為光源,透過期望的遮罩對預烤膜曝光。然後,使用自動顯影裝置(Takizawa Sangyo(股)製「AD-1200(商品名)」),以0.045質量%KOH水溶液噴淋顯影60秒鐘,接下來以水清洗30秒鐘,進行圖案加工。曝光、顯影後,測定在以1比1的寬度形成5μm的線寬線距圖案之曝光量下顯影後的最小圖案尺寸,來作為解析度。曝光量係以I線照度計測定。<Patternability evaluation> Colored resin compositions 2 to 7 were spin-coated on (S-2) using a spin coater (“1H-DS (trade name)” manufactured by MIKASA Co., Ltd.), and a hot plate (manufactured by Dainippon SCREEN Co., Ltd.) was used. "SCW-636 (trade name)") was prebaked on the substrate at 100° C. for 10 minutes to obtain a prebaked film. The prebaked film was exposed through a desired mask using a photolithography machine (manufactured by Union Optical Co., Ltd.) with an ultra-high pressure mercury lamp as a light source. Then, using an automatic developing device (“AD-1200 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), spray development was performed for 60 seconds with a 0.045 mass % KOH aqueous solution, followed by washing with water for 30 seconds to perform patterning. After exposure and development, the minimum pattern size after development was measured at the exposure amount to form a 5 μm line width and line spacing pattern with a width of 1:1 as the resolution. The exposure amount was measured with an I-line illuminometer.
將各評價的結果示於表3。The results of each evaluation are shown in Table 3.
[表1]
[表2]
[表3]
本發明之樹脂組成物能適用於形成被使用在觸控面板、顯示器、影像感測器、有機電激發光照明或太陽電池等之導電性圖案及著色圖案。The resin composition of the present invention can be suitable for forming conductive patterns and coloring patterns used in touch panels, displays, image sensors, organic electroluminescent lighting, solar cells, and the like.
無。without.
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