JP3893553B2 - Photosensitive transfer material - Google Patents

Description

【００８４】
次に、上記熱可塑性樹脂層上に、下記組成からなる塗布液Ｂ１を塗布、乾燥させ、乾燥膜厚が１．６μｍ厚の中間層を設けた。

【００８５】
前記の熱可塑性樹脂層および中間層を形成した仮支持体を４枚用意し、これらの仮支持体上に、表１の組成からなる、赤色（Ｒｅｄ層用）、青色（Ｂｌｕｅ層用）、緑色（Ｇｒｅｅｎ層用）及び黒色（Ｂｌａｃｋ層用）の４色の感光性樹脂層用塗布液を、それぞれ異なる仮支持体上に塗布し、乾燥させ、乾燥膜厚が２μｍの感光性樹脂層を形成した。
【００８６】
【表１】

【００８７】
さらに、上記４枚の感光性転写材料のそれぞれの感光性樹脂層上に、ポリプロピレン（厚さ１２μｍ）のカバーフィルムを圧着貼付して設け、赤色、青色、緑色および黒色の４枚の単色感光性転写材料を作製した。
【００８８】
これらの感光性転写材料を用いて、以下の方法によりカラーフイルターを作成した。
まず、赤色感光性転写材料のカバーフィルムを剥離し、感光性樹脂層面を透明ガラス基板（厚さ１．１ｍｍ）上に、ラミネーター（装置名：ＶＰ−II，大成ラミネータ（株）製）を用いて、０．８ｋｇ／ｃｍ² 、１３０℃の加圧加熱条件下で貼り合わせた。その後、仮支持体を熱可塑性樹脂層から剥離し、仮支持体を除去した。
【００８９】
次に、所定のフォトマスクを介して露光し、その後、１％トリエタノールアミン水溶液を用いて熱可塑性樹脂層および中間層を溶解除去した。この際、感光性樹脂層は、実質現像されていなかった。
次いで、１％炭酸ナトリウム水溶液を用いて感光性樹脂層を現像し、不要部を除去し、ガラス基板上に赤色の画素パターンを形成した。
【００９０】
さらに、この赤色画素パターンが形成されたガラス基板上に、緑色感光性転写材料を上記と同様にして貼り合わせ、剥離、露光、現像を行ない、緑色の画素パターンを形成した。
【００９１】
赤色および緑色の画素パターンを形成したガラス基板上に、同様な工程を繰り返して、さらに青色、黒色の画素パターンを形成し、カラーフィルターＡを作製した。
【００９２】
（実施例２）
実施例１で用いたベンジルメタクリレート（ＢｚＭＡ）／メタクリル酸（ＭＡＡ）／メタクリル酸メチル（ＭＭＡ）共重合体に代えて、共重合比がＢｚＭＡ／ＭＡＡ／ＭＭＡ＝３６／２２／４２で、ガラス転移点Ｔｇ＝９０℃のＢｚＭＡ／ＭＡＡ／ＭＭＡ共重合体を用いた以外、実施例１と同様にして４色の感光性転写材料を作製し、さらにこれらを用いて実施例１同様にカラーフィルターＢを作製した。
【００９３】
（実施例３）
実施例１で用いたベンジルメタクリレート（ＢｚＭＡ）／メタクリル酸（ＭＡＡ）／メタクリル酸メチル（ＭＭＡ）共重合体に代えて、共重合比がＢｚＭＡ／ＭＡＡ／ＭＭＡ＝２１／２１／５８で、ガラス転移点Ｔｇ＝１００℃のＢｚＭＡ／ＭＡＡ／ＭＭＡ共重合体を用いた以外、実施例１と同様にして４色の感光性転写材料を作製し、さらにこれらを用いて実施例１同様にカラーフィルターＣを作製した。
【００９４】
（実施例４）
実施例１で用いたベンジルメタクリレート（ＢｚＭＡ）／メタクリル酸（ＭＡＡ）／メタクリル酸メチル（ＭＭＡ）共重合体に代えて、共重合比がＢｚＭＡ／ＭＡＡ／ＭＭＡ＝１０／１９／７１で、ガラス転移点Ｔｇ＝１１０℃のＢｚＭＡ／ＭＡＡ／ＭＭＡ共重合体を用いた以外、実施例１と同様にして４色の感光性転写材料を作製し、さらにこれらを用いて実施例１同様にカラーフィルターＤを作製した。
【００９５】
（実施例５）
実施例１で用いたベンジルメタクリレート（ＢｚＭＡ）／メタクリル酸（ＭＡＡ）／メタクリル酸メチル（ＭＭＡ）共重合体に代えて、共重合比がＢｚＭＡ／ＭＡＡ／ＭＭＡ＝５０／１９／３１で、酸価８０、ガラス転移点Ｔｇ＝８０℃のＢｚＭＡ／ＭＡＡ／ＭＭＡ共重合体を用いた以外、実施例１と同様にして４色の感光性転写材料を作製し、さらにこれらを用いて実施例１同様にカラーフィルターＥを作製した。
【００９６】
（実施例６）
実施例１で用いたベンジルメタクリレート（ＢｚＭＡ）／メタクリル酸（ＭＡＡ）／メタクリル酸メチル（ＭＭＡ）共重合体に代えて、共重合比がＢｚＭＡ／ＭＡＡ／ＭＭＡ＝３２／１７／５１で、酸価８０、ガラス転移点Ｔｇ＝９０℃のＢｚＭＡ／ＭＡＡ／ＭＭＡ共重合体を用いた以外、実施例１と同様にして４色の感光性転写材料を作製し、さらにこれらを用いて実施例１同様にカラーフィルターＦを作製した。
【００９７】
（実施例７）
実施例１で用いたベンジルメタクリレート（ＢｚＭＡ）／メタクリル酸（ＭＡＡ）／メタクリル酸メチル（ＭＭＡ）共重合体に代えて、共重合比がＢｚＭＡ／ＭＡＡ／ＭＭＡ＝１８／１６／６６で、酸価８０、ガラス転移点Ｔｇ＝１００℃のＢｚＭＡ／ＭＡＡ／ＭＭＡ共重合体を用いた以外、実施例１と同様にして４色の感光性転写材料を作製し、さらにこれらを用いて実施例１同様にカラーフィルターＧを作製した。
【００９８】
（実施例８）
実施例１で用いたベンジルメタクリレート（ＢｚＭＡ）／メタクリル酸（ＭＡＡ）／メタクリル酸メチル（ＭＭＡ）共重合体に代えて、共重合比がＢｚＭＡ／ＭＡＡ／ＭＭＡ＝１／１４／８６で、酸価８０、ガラス転移点Ｔｇ＝１１５℃のＢｚＭＡ／ＭＡＡ／ＭＭＡ共重合体を用いた以外、実施例１と同様にして４色の感光性転写材料を作製し、さらにこれらを用いて実施例１同様にカラーフィルターＨを作製した。
【００９９】
（比較例１）
実施例１で用いたベンジルメタクリレート（ＢｚＭＡ）／メタクリル酸（ＭＡＡ）／メタクリル酸メチル（ＭＭＡ）共重合体に代えて、共重合比がＢｚＭＡ／ＭＡＡ／ＭＭＡ＝７３／２７／０で、酸価１００、ガラス転移点Ｔｇ＝７２℃のＢｚＭＡ／ＭＡＡ共重合体を用いた以外、実施例１と同様にして４色の感光性転写材料を作製し、さらにこれらを用いて実施例１同様にカラーフィルターＩを作製した。
【０１００】
（比較例２）
実施例１で用いたベンジルメタクリレート（ＢｚＭＡ）／メタクリル酸（ＭＡＡ）／メタクリル酸メチル（ＭＭＡ）共重合体に代えて、共重合比がＢｚＭＡ／ＭＡＡ／ＭＭＡ＝７３／２２／５で、酸価８０、ガラス転移点Ｔｇ＝７０℃のＢｚＭＡ／ＭＡＡ／ＭＭＡ共重合体を用いた以外、実施例１と同様にして４色の感光性転写材料を作製し、さらにこれらを用いて実施例１同様にカラーフィルターＪを作製した。
【０１０１】
（比較例３）
実施例１で用いたベンジルメタクリレート（ＢｚＭＡ）／メタクリル酸（ＭＡＡ）／メタクリル酸メチル（ＭＭＡ）共重合体に代えて、共重合比がＢｚＭＡ／ＭＡＡ／ＭＭＡ＝０／２３／７７で、酸価１３３、ガラス転移点Ｔｇ＝１２５℃のＭＡＡ／ＭＭＡ共重合体を用いた以外、実施例１と同様にして４色の感光性転写材料を作製し、さらにこれらを用いて実施例１同様にカラーフィルターＫを作製した。
【０１０２】
（比較例４）
実施例１で用いたベンジルメタクリレート（ＢｚＭＡ）／メタクリル酸（ＭＡＡ）／メタクリル酸メチル（ＭＭＡ）共重合体に代えて、共重合比がＢｚＭＡ／ＭＡＡ／ＭＭＡ＝０／２７／７３で、酸価１５７、ガラス転移点Ｔｇ＝１２９のＭＡＡ／ＭＭＡ共重合体を用いた以外、実施例１と同様にして４色の感光性転写材料を作製し、さらにこれらを用いて実施例１同様にカラーフィルターＬを作製した。
【０１０３】
（比較例５）
実施例１で用いたベンジルメタクリレート（ＢｚＭＡ）／メタクリル酸（ＭＡＡ）／メタクリル酸メチル（ＭＭＡ）共重合体に代えて、共重合比がＢｚＭＡ／ＭＡＡ／ＭＭＡ＝１０／９／８１で、酸価４７、ガラス転移点Ｔｇ＝１０２のＢｚＭＡ／ＭＡＡ／ＭＡＡ共重合体を用いた以外、実施例１と同様にして４色の感光性転写材料を作製し、さらにこれらを用いて実施例１同様にカラーフィルターＭを作製した。
【０１０４】
（比較例６）
実施例１で用いたベンジルメタクリレート（ＢｚＭＡ）／メタクリル酸（ＭＡＡ）／メタクリル酸メチル（ＭＭＡ）共重合体に代えて、共重合比がＢｚＭＡ／ＭＡＡ／ＭＭＡ＝９／２３／６８で、酸価１２４、ガラス転移点Ｔｇ＝１１４のＢｚＭＡ／ＭＡＡ／ＭＡＡ共重合体を用いた以外、実施例１と同様にして４色の感光性転写材料を作製し、さらにこれらを用いて実施例１同様にカラーフィルターＮを作製した。
【０１０５】
＜表面性の評価＞
上記のようにして得られた、画素パターンのあるカラーフィルターＡ〜Ｎのフィルター表面の凹凸度を、触針式膜厚計（Ｐ−１，Ｔｅｎｃｏｒ社製）を用いて測定した。得られた凹凸の膜厚差（凹凸の幅）を表面性評価の指針とし、下記に示す基準に従い評価を行った。
上記測定結果および評価結果を下記の表２に示す。
○： 膜厚差が０．０５μｍ以下であり、表面性に優る。
△： 膜厚差が０．１μｍ以下であり、実使用上問題ない。
×： 膜厚差が０．５μｍ以上あり、表面性に劣る。使用不可。
【０１０６】
【表２】

【０１０７】
表２より、感光性樹脂層に特定の樹脂を用いた実施例１〜８より得られた本発明の感光性転写材料Ａ〜Ｈは、カラーフィルター表面の凹凸の幅が０．１μｍ以下であり、しわ状の跡等のない均一な表面性を有していた。また、上記工程において、仮支持体は、熱可塑性樹脂層に対して優れた剥離性能を有しており、さらに、得られたカラーフィルターは、着色層とガラス基板との密着性に優れ、画素の欠落もなかった。
一方、比較例１〜４のように、Ｔｇ値が本発明に規定する範囲にない樹脂を感光性樹脂層中に用いた場合、比較例１〜２で得られたカラーフィルターＩ〜Ｊのフィルター表面の凹凸は０．５μｍ以上あり、目視でもしわ状の跡が認められ、また、比較例３〜４で得られたカラーフィルターＫ〜Ｌでは、その表面性には優れていたものの、樹脂のＴｇ値が高く、これに伴い酸価も高くなる結果、感光性転写材料を作製する段階で感光性樹脂層の樹脂膜の硬度が高くなりカバーフィルムが圧着形成できないうえ、さらに重合硬化後においても硬化部がアルカリ溶液に容易に溶解してしまい、所望のレジスト性が得られず、鮮鋭な画素パターンの形成ができなかった。
また、比較例５〜６のように、酸価が本発明に規定する範囲にない樹脂を感光性樹脂層中に用いた場合、やはり形成されたフィルターの表面性には優れていたものの、比較例５では感光性樹脂層の樹脂膜がアルカリ溶液に不溶となってしまい所望の画素パターンを形成することができず、一方、比較例６では重合硬化後においても硬化部がアルカリ溶液に容易に溶解してしまい、鮮鋭な画素パターンの形成ができなかった。
従って、カラーフィルターＩ〜Ｎでは、高精細な画像等の表示に用いる材料としては好ましくないと言える。
【０１０８】
【発明の効果】
本発明の感光性転写材料は、顔料等の含有量の少ない感光性樹脂層が転写不良を防止するクッション層上に設けられた転写材料であり、長期保存時においても、上記感光性樹脂層に経時的に発生する折れや重なり等の「しわ」（いわゆる、感光性樹脂層のレチキュレーション）を生じることなく、安定に維持することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a film-like photosensitive transfer material for transferring a photosensitive resin layer (colored layer) provided on a temporary support onto a substrate which is a transfer target and forming a colored layer on the substrate. Specifically, the present invention relates to a photosensitive transfer material in which a cushion layer (thermoplastic resin layer) for preventing transfer failure caused by unevenness on the surface of a substrate is provided on a temporary support.
[0002]
[Prior art]
Image forming material for forming a colored layer on a substrate by transferring a photosensitive resin layer (hereinafter sometimes referred to as “colored layer”) provided on a temporary support onto a substrate as a transfer target Is described in, for example, Japanese Patent Publication No. 56-40824, and is already known. This image forming material is used for the production of printed wiring, intaglio letterpress printing plates, name plates, multicolor trial printing samples, offset printing plates, screen printing stencils and the like.
The image forming material is formed by laminating a separation layer and a photopolymerizable layer on a temporary support, and the photopolymerizable layer surface of the image forming material is closely attached to a substrate which is a transfer target, and only the temporary support is attached. After peeling, an image can be formed on the substrate by exposing through a separating layer and further developing. In this case, the separation layer plays a role of blocking oxygen and works favorably for exposure in the air. However, since the film thickness is as thin as about 0.5 to 5 μm, it is particularly troublesome in terms of resolving power. It's not something to do.
[0003]
However, when a certain degree of unevenness exists on the substrate, which is the transfer target, when a thin photopolymerizable layer is transferred from the substrate, bubbles are formed between the photopolymerizable layer near the unevenness and the substrate. As a result, sufficient adhesion is not performed and transfer failure occurs. Therefore, when a dense multicolor filter is formed or a high-definition image is formed, the transfer is incomplete, which has been a problem in improving the quality of the product.
[0004]
In recent years, research and development for solving the above problems have been widely performed. For example, in JP-A-2-213849, an intermediate layer made of a polyvinyl alcohol derivative or the like is provided between a temporary support and a photosensitive resin layer. A transfer material is disclosed. However, this transfer material is intended to improve the peelability from the temporary support and the dissolution characteristics, and no consideration is given to the transfer performance when the substrate has irregularities.
[0005]
Japanese Patent Laid-Open No. 63-309946 discloses a transfer failure caused by a decrease in adhesiveness of a transfer layer due to minute dust, dust or the like present on the surface of a substrate or transfer layer as a transfer target, or both. In order to prevent this, the use of a compressible temporary support is described. This method has a sufficient improvement effect when transferring a non-adhesive photosensitive resin layer at room temperature onto a substrate having only minute irregularities as described above. When transferring onto a substrate having unevenness equivalent to the film thickness of the resin layer, the result is that bubbles are trapped, and in particular, a multicolor filter is formed using a plurality of photosensitive resin layers. In some cases, sufficient effects could not be obtained.
[0006]
Furthermore, in JP-A-5-80503, etc., a cushion layer mainly composed of a thermoplastic resin is provided between the temporary support and the photosensitive resin layer, so that the unevenness on the substrate can be reduced during adhesion during transfer. There has been proposed a technique for effectively eliminating bubbles that are easily trapped between the skirts and uneven portions and improving transferability. With this technology, sufficient adhesion can be ensured even in areas where transfer defects are likely to occur, and high-quality products can be stably manufactured.
[0007]
However, in recent years, especially in the field of liquid crystal displays and the like, technological advances and developments are remarkable, and there is a situation where a transmissive liquid crystal display, which has been the mainstream so far, is being shifted to a reflective liquid crystal display. The color filter used for the display is also actively developed for the reflective type.
[0008]
However, since the color filters used in conventional transmissive displays have a high color density for each color to be used for reflective displays, the transmissive ones cannot be used as they are. , G, R), a reflective color filter with a reduced amount of colorant added has been developed.
As described above, in order to reduce the color density and use it for the reflection type, the content of the pigment used as the colorant in the colored layer is reduced, but the resin component is increased accordingly, and the transfer material This resulted in a decrease in the film strength of the colored resin layer, that is, the photosensitive resin layer provided on the temporary support.
Due to this decrease in film strength, the photosensitive resin layer is reticulated at the stage where unused transfer materials are stored ("wrinkles" such as creases and overlaps that occur over time in the photosensitive resin layer, which is a colored layer). As a result, there arises a problem that the transferred image is also hindered.
[0009]
[Problems to be solved by the invention]
The object of the present invention is to provide reticulation of the photosensitive resin layer (photosensitive resin) even when the photosensitive resin layer having a low content of pigment or the like has a layer structure provided on a cushion layer that prevents transfer failure. Photosensitive transfer material that can be stably held for a long time without causing wrinkles such as creases or overlaps that occur over time in a layer, and can form a sharp and high-quality image Is to provide.
[0010]
[Means for Solving the Problems]
  In view of the above-described conventional problems, the present inventors focused on each component constituting the photosensitive resin layer (colored layer) provided on the temporary support of the photosensitive transfer material, and as a result of earnest studies, It has been found that the film strength of the photosensitive resin layer can be improved by incorporating a specific resin in the photosensitive resin layer, and the present invention has been completed.
  That is, the object is to provide the following photosensitive transfer material [A] to[B]Is achieved.
  In a photosensitive transfer material in which at least a thermoplastic resin layer and a photosensitive resin layer are laminated in this order on a temporary support, the photosensitive resin layer has an acid value of 50 to 120 and a glass transition point Tg of 75 to 123. It is a layer that contains a resin at ℃The resin contained in the photosensitive resin layer is a copolymer composed of benzyl methacrylate, methacrylic acid, and methyl methacrylate.A photosensitive transfer material [A].
[0012]
  The above photosensitive transfer material [A〕ofPhotosensitive transfer material comprising a photosensitive resin layer containing a colorant[B].
[0014]
DETAILED DESCRIPTION OF THE INVENTION
In the photosensitive transfer material of the present invention, at least a thermoplastic resin layer and a photosensitive resin layer are laminated in this order on a temporary support, and on the photosensitive resin layer, which is the outermost layer, contamination from the outside and It is a photosensitive transfer material that may be provided with a thin cover film for the purpose of protecting it from damage or the like.
[0015]
The photosensitive transfer material of the present invention is, for example, a film-like photosensitive material used as a material for forming a colored layer on a substrate serving as a filter support in the production of a color filter, on a temporary support. The photosensitive transfer material has a photosensitive resin layer colored in a desired hue, and a colored layer can be formed by transferring the photosensitive resin layer onto the substrate.
Therefore, in the case of forming a color filter, a plurality of photosensitive transfer materials colored in three primary colors (B, G, R) and black (BL) are used.
Hereinafter, each constituent layer of the photosensitive transfer material and constituent components, a support and the like included in the constituent layers will be described.
[0016]
First, the photosensitive resin layer that exhibits the effects of the present invention will be described in detail.
The photosensitive resin layer according to the present invention includes at least a resin as a binder, a polymerizable monomer, a polymerization initiator, and the like, and is a thermoplastic resin layer that is softened or tacky at least at a temperature of 150 ° C. or less. It is preferable that
[0017]
In the photosensitive resin layer according to the present invention, as a resin as the binder, when irradiated with light, it undergoes a polymerization reaction and cures, becomes insoluble in an alkaline solution, while unexposed portions that are not exposed are readily soluble in an alkaline solution. It is necessary to be a resin having high resistability, and among them, a resin having an acid value of 50 to 120 and a glass transition point Tg of 75 to 123 ° C. is used.
Among the resins in the above range, it is more preferable to use a resin having an acid value of 80 to 100 and a glass transition point Tg of 80 to 115, and the acid value and glass transition point Tg of the above numerical range. Any lower limit value or any of the acid value and Tg value adopted in the examples described later is set as the lower limit, and any of the upper limit value of the above numerical range or the acid value and Tg value adopted in the examples described later is used. A numerical range with any value as an upper limit is also preferable.
[0018]
When a resin not in the above range is used, a photosensitive transfer material having the effect of the present invention or sufficient resistability cannot be obtained.
When the acid value is less than 50, it becomes insoluble in an alkaline solution even in an unexposed portion, and the resist property necessary for image formation cannot be obtained. It is not preferable because it dissolves in an alkaline solution. In addition, when the glass transition point Tg is less than 75 ° C., the effect of the present invention cannot be achieved. When the glass transition point Tg exceeds 123 ° C., the acid value increases accordingly, and as described above, the glass transition point Tg becomes easily soluble in an alkaline solution and formed. Further, since the hardness of the photosensitive resin layer becomes too high and the cover film cannot be formed by pressure bonding, it is not preferable.
Further, as the resin, those that can be developed with an alkaline aqueous solution and those that can be developed with an organic solvent are known, but those that can be developed with an alkaline aqueous solution are preferable from the viewpoint of preventing pollution and ensuring occupational safety. .
[0019]
  Among the above resins, the resin used for the photosensitive resin layer according to the present invention is benzyl methacrylate.When, Methacrylic acidWhen,Methyl methacrylateConsisting ofUse copolymerThe
  By using the above-mentioned resin within the range specified in the present invention, it is possible to obtain high hardness and sufficient hardness to keep the layer stable.
[0020]
Among the above copolymers, the copolymerization ratio of each monomer with respect to the total weight is in the range of 0 to 60 parts by weight of benzyl methacrylate, 10 to 30 parts by weight of methacrylic acid, and 5 to 95 parts by weight of methyl methacrylate. It is more preferable to use a copolymer, and it is most preferable to use a copolymer in the range of 0 to 40 parts by weight of benzyl methacrylate, 10 to 30 parts by weight of methacrylic acid, and 20 to 95 parts by weight of methyl methacrylate. . Furthermore, the copolymerization ratio of each of the above monomers is either the lower limit value of each numerical range of each of the above monomers or the copolymerization ratio of each monomer employed in the examples described later. The upper limit of any of the numerical ranges of the respective monomers described above or the upper limit of any of the copolymerization ratios of the monomers employed in the examples described below is the upper limit. Is also preferable.
[0021]
A copolymer in which the copolymerization ratio of each monomer with respect to the total weight of the copolymer is not within the above range cannot satisfy the acid value and glass transition point Tg specified in the present invention, and as a result, sufficient This is not preferable because a sufficient resistability cannot be obtained or the effect of the present invention cannot be sufficiently achieved.
[0022]
As content of resin which consists of the said specific copolymer contained in the photosensitive resin layer which concerns on this invention, it is preferable to contain 20 to 60% of the total solid of the photosensitive resin layer, and it contains 30 to 50% More preferably. If it is less than 20%, the effect of the present invention cannot be achieved, and if it exceeds 60%, the content of the polymerizable monomer is relatively reduced, and the degree of curing by photopolymerization is unfavorable.
[0023]
The photosensitive resin layer of the photosensitive transfer material of the present invention may contain a colorant such as an organic pigment, an inorganic pigment, or a dye.
Examples of the colorant include yellow pigments, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 86, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 125, C.I. I. Pigment yellow 137, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 185, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 148, C.I. I. Pigment yellow 153, C.I. I. Pigment Yellow, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 166, C.I. I. Pigment Yellow 168, Monolite Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), etc.
[0024]
As an orange pigment, C.I. I. Pigment orange 36, C.I. I. Pigment orange 43, C.I. I. Pigment orange 51, C.I. I. Pigment orange 55, C.I. I. Pigment orange 59, C.I. I. Pigment Orange 61 etc.
[0025]
As a red pigment, C.I. I. Pigment red 9, C.I. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 217, C.I. I. Pigment red 220, C.I. I. Pigment red 223, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 227, C.I. I. Pigment red 228, C.I. I. Pigment red 240, C.I. I. Pigment Red 48: 1, Permanent Carmine FBB (C.I. Pigment Red 146), Permanent Ruby FFB (C.I. Pigment Red 11), Fastel Pink B Supra (C.I. Pigment Red 81), etc. The
[0026]
As a violet pigment, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 30, C.I. I. Pigment violet 37, C.I. I. Pigment violet 40, C.I. I. Pigment Violet 50 etc.
[0027]
As a blue pigment, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment Blue 64, Victoria Pure Blue BO (C.I. 42595), etc.
[0028]
As a green pigment, C.I. I. Pigment green 7, C.I. I. Pigment Green 36 etc.
[0029]
Further, as a brown pigment, C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment Brown 26 etc.
[0030]
Further, as black pigments, Monolite First Black B (CI Pigment Black 1), C.I. I. Pigment Black 7, Fat Black HB (C.I. 26150), etc.
[0031]
In addition, carbon black, auramine (C.I. 41000), and the like can be given.
[0032]
When the colorant as described above is used, the particle size of the pigment or dye is preferably 1 μm or less, more preferably 0.5 μm or less, and most preferably 0.1 μm or less. Since the photosensitive resin layer is a thin layer, when the particle size of the pigment or the like is not in the above range, it cannot be uniformly dispersed in the resin layer, and a high-quality color filter can be manufactured. Since it becomes difficult, it is not preferable.
[0033]
The photosensitive resin layer of the photosensitive transfer material of the present invention contains the colorant such as the pigment or the dye in a range of 30% or less of the total solid content of the photosensitive resin layer. In particular, when the content of the colorant is 30% or less, the effect of the present invention works effectively.
[0034]
The photosensitive resin layer in the present invention may form a colorless and transparent photosensitive resin layer without using a colorant such as a pigment. Using this transparent photosensitive resin layer, for example, the above-mentioned transparent photosensitive resin layer is transferred onto an image pattern already formed through processes such as transfer, exposure, and development on a substrate to cover the entire surface. A columnar space material can be formed on the overcoat layer and each pixel.
When these materials do not contain pigments or the like, a significant decrease in film strength is caused, and it is considered that reticulation such as “wrinkles” is more likely to occur in the resin layer. In such a case, the photosensitive transfer material of the present invention is useful.
[0035]
Examples of the polymerizable monomer used in the photosensitive resin layer include (meth) acrylic acid esters, urethane (meth) acrylates, (meth) acrylic acid amides, allyl compounds, and vinyl esters described in JP-A-60-258539. Among them, (meth) acrylic acid esters can be preferably used.
[0036]
The polymerizable monomer is preferably used in the range of 10 to 60% by weight of the total solid content of the photosensitive resin layer, and more preferably in the range of 20 to 50 parts by weight.
[0037]
The polymerization initiator used for the photosensitive resin layer preferably contains at least one component having a molecular extinction coefficient of at least about 50 in the range of about 300 to 500 nm. For example, aromatic ketones, lophine dimers, benzoin, benzoin ethers, polyhalogens, and two types thereof described in JP-A-2-48664, JP-A-1-152449, and JP-A-2-153353. Combinations of the above are mentioned. Among them, a combination of 4,4′-bis (diethylamino) benzophenone and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 4- [pN, N-di (ethoxycarbonylmethyl) -2 , 6-di (trichloromethyl) -s-triazine] is preferred.
[0038]
The polymerization initiator is preferably used in the range of 0.1 to 20% by weight, and more preferably in the range of 0.5 to 10 parts by weight, based on the amount of the polymerizable monomer used.
[0039]
The film thickness of the photosensitive resin layer is preferably in the range of 0.5 to 10 μm, and more preferably in the range of 1 to 6 μm. If the film thickness of the photosensitive resin layer is less than 0.5 μm, pinholes are likely to occur during coating, and this is not preferable for suitability for production. If it exceeds 10 μm, it takes a long time to dissolve and remove unexposed areas during development. .
[0040]
Next, the thermoplastic resin layer provided in the first layer on the temporary support will be described in detail.
As the thermoplastic resin used for the construction of the thermoplastic resin layer, alkali development after transfer is possible, or depending on the transfer conditions at the time of transfer, the above-mentioned resin protrudes to the surroundings (substrate to be transferred) (permanent support) From the viewpoint of enabling the removal treatment in a case where it is contaminated, the resin needs to be soluble in an alkaline aqueous solution. Furthermore, since this thermoplastic resin layer plays a role as a cushioning material for preventing transfer defects caused by unevenness existing on the substrate when transferring to the substrate, which is a transfer target, It is necessary to have a property that can be deformed in accordance with the unevenness on the substrate when in close contact.
[0041]
Accordingly, the resin constituting the thermoplastic resin layer preferably has a substantial softening point of 80 ° C. or lower.
Examples of alkali-soluble thermoplastic resins having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, vinyltoluene and (meta ) Saponified product with acrylic ester copolymer, poly (meth) acrylic ester, saponified product such as (meth) acrylic ester copolymer of butyl (meth) acrylate and vinyl acetate, etc. Although at least one kind is preferred, the softening point described in “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All Japan Plastics Molding Industry Association, published by the Industrial Research Council, issued on October 25, 1968) is approximately Among organic polymers having a temperature of 80 ° C. or lower, those soluble in an alkaline aqueous solution can also be used.
[0042]
Further, even if the organic polymer substance has a softening point of 80 ° C. or higher, by adding various plasticizers compatible with the organic polymer substance to the organic polymer substance, the substantial softening point can be reduced to 80. It can also be used at a temperature lower than ℃.
Examples of the plasticizer include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl diphenyl phosphate, and the like.
[0043]
Further, when the above organic polymer substance is used, various polymers, supercooling substances, and adhesives are used within the range where the substantial softening point does not exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support described later. An improving agent, a surfactant, a release agent, or the like can be added.
[0044]
The film thickness of the thermoplastic resin layer is preferably in the range of 6 to 100 μm, more preferably in the range of 6 to 50 μm. If the thickness of the thermoplastic resin layer is less than 6 μm, it is impossible to completely absorb unevenness on the substrate having a thickness of 1 μm or more, and if it exceeds 100 μm, the developability and production suitability are deteriorated.
[0045]
As the alkaline aqueous solution used for dissolving the photosensitive resin layer and the thermoplastic resin layer at the time of development after exposure and removal of unnecessary resin parts, a dilute aqueous solution of an alkaline substance is preferable, and a water-miscible organic material is also used. What added the solvent a little can also be used conveniently.
Examples of the alkaline substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonate such as sodium bicarbonate and potassium bicarbonate. Salts, alkali metal silicates such as sodium silicate and potassium silicate, alkali metal metasilicates such as sodium metasilicate and potassium metasilicate, triethanolamine, diethanolamine, monoethanolamine, morpholine, tetramethylammonium hydroxide, etc. And tetraalkylammonium hydroxides, trisodium phosphate and the like.
[0046]
The alkaline aqueous solution preferably has an alkaline substance concentration in the range of 0.01 to 30% by weight, and more preferably has a pH in the range of 8 to 14.
[0047]
Examples of water-miscible organic solvents include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, benzyl alcohol, and acetone. , Methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, and N-methylpyrrolidone.
The addition amount of the organic solvent having water miscibility is preferably in the range of 0.1 to 30% by weight.
[0048]
Various known surfactants can be added to the alkaline aqueous solution. The surfactant is preferably used in the range of 0.01 to 10% by weight.
[0049]
The alkaline developer used for development may be used as a developing bath in a container, or may be used by spraying.
At the time of development, when the uncured portion of the photosensitive resin layer is dissolved and removed, a method such as rubbing the surface of the layer with a rotating brush or a wet sponge can be combined in order to increase the solubility. The development temperature is usually preferably from about room temperature to 40 ° C. In addition, a step of washing with water can be added after the development processing.
[0050]
An intermediate layer can be provided between the photosensitive resin layer and the thermoplastic resin. Since an organic solvent is used for the photosensitive resin layer and the thermoplastic resin, it is possible to prevent the two layers from being mixed with each other by providing this intermediate layer.
The intermediate layer may be any material that can be dispersed or dissolved in water or an aqueous alkali solution, and preferably has a low oxygen permeability.
As the intermediate layer, a known one can be used. For example, a polyvinyl ether / maleic anhydride polymer described in JP-A No. 46-2121 and JP-B No. 56-40824, a water-soluble salt of carboxyalkyl cellulose, Water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches and the like Water-soluble salts of the group consisting of similar substances, styrene / maleic acid copolymers, maleate resins, and combinations of two or more of these.
Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.
[0051]
In this case, the polyvinyl alcohol preferably has a saponification rate of 80% or more, and the polyvinyl pyrrolidone is preferably contained in the range of 1 to 75% by weight of the total solid content of the intermediate layer. More preferably, it is contained in the range of 10% by weight, but most preferably in the range of 10-50% by weight. If it is less than 1% by weight, sufficient adhesion to the photosensitive resin layer cannot be obtained, and if it exceeds 75% by weight, the oxygen barrier ability is lowered, which is not preferable.
[0052]
The intermediate layer is preferably a thin layer, and the film thickness is preferably in the range of about 0.1 to 5 μm, more preferably in the range of 0.5 to 2 μm. If it is less than about 0.1 μm, the oxygen permeability is too high, and if it exceeds about 5 μm, it takes a long time to develop or remove the intermediate layer, which is not preferable.
[0053]
The temporary support on which the above layers are coated preferably has adhesiveness and peelability that do not hinder the separation from the thermoplastic resin layer, and is chemically and thermally stable. A flexible one is preferred.
Specifically, a thin film sheet such as Teflon, polyethylene terephthalate, polycarbonate, polyethylene, or polypropylene, or a laminate thereof is preferable.
[0054]
In order to ensure good releasability without destroying the photosensitive resin layer between the temporary support and the thermoplastic resin layer, surface treatment such as glow discharge is not performed, and gelatin It is preferable not to provide a coating layer.
Further, the thickness of the temporary support is suitably 5 to 300 μm, and preferably 20 to 150 μm.
[0055]
A cover film is preferably provided on the photosensitive resin layer in order to protect it from dirt and damage during storage.
The cover film can be made of either the same or similar material as the temporary support or a different material, but needs to be easily separable from the photosensitive resin layer. As a material used for the cover film, for example, silicone paper, polyolefin or polytetrafluoroethylene sheet is preferable, and among them, polyethylene or polypropylene film is more preferable.
[0056]
About 5-100 micrometers is preferable and, as for the thickness of a cover film, 10-30 micrometers is more preferable.
[0057]
In the photosensitive transfer material of the present invention, a thermoplastic resin layer coating solution is first applied on the temporary support and dried to provide a thermoplastic resin layer. A thermoplastic resin layer is formed on the thermoplastic resin layer. An intermediate layer solution using a solvent that does not dissolve is applied and dried to provide an intermediate layer. On the intermediate layer, a photosensitive resin layer coating solution is applied and dried using a solvent that does not dissolve the intermediate layer. It can form by providing a photosensitive resin layer and providing a cover film as needed on the photosensitive resin layer.
Alternatively, a photosensitive resin layer is provided on the cover film, while a thermoplastic resin layer and an intermediate layer are provided on the temporary support in the same manner as described above, and the intermediate layer and the photosensitive resin layer are respectively provided in this order. Alternatively, the photosensitive resin layer and the intermediate layer are provided in this order on the cover film, while the thermoplastic resin layer is provided on the temporary support, and each of the intermediate layers is formed in the same manner as described above. It can manufacture by bonding together so that a photosensitive resin layer may contact | connect.
[0058]
An antistatic effect can be imparted to the temporary support of the photosensitive transfer material of the present invention.
In the process of peeling the temporary support after the photosensitive transfer material formed as described above is closely attached to the substrate as the transfer target, the temporary support or the base is charged, and surrounding dust or the like is removed. For the purpose of preventing this charging, it is attracted and attached on the resin layer after peeling, and an unexposed part is formed in the subsequent exposure process, and that part may cause pinholes. By using a temporary support with conductivity, or by providing a conductive layer on at least one surface of the temporary support, the surface electrical resistance is 10¹³It is preferable to lower it to Ω or less.
[0059]
In order to provide the temporary support with conductivity, a conductive substance may be contained in the temporary support. For example, a method of kneading metal acid value fine particles and an antistatic agent in advance is preferable.
As the metal acid value, at least one crystal selected from acid value zinc, acid value titanium, acid value tin, acid value aluminum, acid value indium, acid value silicon, acid value magnesium, acid value barium and acid value molybdenum Metal acid value and / or fine particles of the complex acid value.
Examples of the antistatic agent include alkyl phosphate anionic surfactants such as Electro Stripper A (manufactured by Kao Corporation) and Elenon No19 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Amorgen K (Daiichi Kogyo Seiyaku Co., Ltd.) Betaine amphoteric surfactants such as Nitsan Nonion L (manufactured by NOF Corporation), non-ionic surfactants such as Emulgen 106, 120, 147, 420, 220, 905, Polyoxyethylene alkyl ether nonionic surfactants such as 910 (manufactured by Kao Corporation) and Nissan Nonion E (manufactured by Nippon Oil & Fats Co., Ltd.) are useful.
In addition, polyoxyethylene alkylphenol ethers, polyhydric alcohol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, and the like can be used as nonionic surfactants.
[0060]
When the conductive layer is provided on the temporary support, the conductive layer can be appropriately selected from known ones. As a conductive substance used for the conductive layer, ZnO, TiO₂, SnO₂, Al₂O_Three, In₂O_Three, SiO₂, MgO, BaO, MoO_ThreeAnd at least one crystalline metal acid value selected from the above and / or fine particles of the complex acid value.
The method of containing these and providing a conductive layer is preferable in that it has a stable conductive effect that is not affected by the humidity environment.
[0061]
The crystalline metal acid product and the composite acid product fine particles have a volume resistance of 10⁷It is preferably Ω · cm or less.^FiveMore preferably, it is Ω · cm or less. The particle diameter is preferably in the range of 0.01 to 0.7 μm, and more preferably in the range of 0.02 to 0.5 μm.
[0062]
A method for producing fine particles of the crystalline metal acid value and the complex acid value is described in detail in JP-A-56-143430.
That is, firstly, metal acid value fine particles are produced by firing and heat-treated in the presence of different atoms to improve conductivity, and secondly, the conductivity is improved when producing metal acid value fine particles by firing. And a third method for introducing oxygen defects by reducing the oxygen concentration in the atmosphere when producing metal fine particles by firing. Specific examples containing different atoms include Zn, Al, In, etc., TiO, etc.₂Nb, Ta, etc., SnO₂In contrast, the presence of Sb, Nb, halogen elements and the like can be mentioned.
[0063]
The addition amount of the different atoms is preferably in the range of 0.01 to 30 mol%, more preferably in the range of 0.1 to 10 mol%.
The amount of conductive particles used is 0.05 to 20 g / m.²Is preferably 0.1 to 10 g / m²Is more preferable.
[0064]
In the conductive layer provided on the temporary support of the photosensitive transfer material of the present invention, a cellulose ester such as gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, or cellulose acetate propionate is used as a binder. Homopolymers or copolymers containing vinylidene chloride, vinyl chloride, styrene, acrylonitrile, vinyl acetate, alkyl acrylates having 1 to 4 carbon atoms, vinyl pyrrolidone, etc .; soluble polyesters, polycarbonates, soluble polyamides and the like can be used.
[0065]
When conductive particles are dispersed in these binders, a dispersion liquid such as a titanium-based dispersant or a silane-based dispersant may be added. Moreover, a binder crosslinking agent etc. can also be added as needed.
[0066]
Examples of the titanium-based dispersant include titanate-based coupling agents and preneact (manufactured by Ajinomoto Co., Inc.) described in US Pat. Nos. 4,069,192 and 4,080,353. Can do.
Examples of the silane dispersant include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and the like. What is marketed as a "silane coupling agent" (made by Shin-Etsu Chemical Co., Ltd.) can be used conveniently.
Examples of the binder crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, an aziridine crosslinking agent, and an epoxy crosslinking agent.
[0067]
The conductive layer in the photosensitive transfer material of the present invention is formed on a temporary support obtained by applying a coating solution for conductive layer, in which conductive fine particles are dispersed in a binder, or applying a subbing treatment. It can be provided by adhering conductive fine particles.
[0068]
In the photosensitive transfer material of the present invention, when the conductive layer is provided on the surface opposite to the surface in close contact with the photosensitive resin layer of the temporary support, in order to ensure sufficient scratch resistance against the action applied from the outside, It is preferable to further provide a hydrophobic polymer layer on the conductive layer as a protective layer.
In this case, the hydrophobic polymer layer may be applied in a state dissolved in an organic solvent or in an aqueous latex state, and the coating amount is 0.05 to 1 g / m in terms of dry weight.²The degree is preferred.
Examples of the hydrophobic polymer include cellulose esters such as nitrocellulose and cellulose acetate; vinyl polymers including vinyl chloride, vinylidene chloride, vinyl acrylate and the like; polymers such as organic solvent-soluble polyamide and polyester.
In order to impart slipperiness to this hydrophobic polymer layer, for example, a slipping agent such as an organic carboxylic acid amide described in JP-A No. 55-79435 can be used. Moreover, a mat agent etc. can also be used as needed.
Even if such a hydrophobic polymer layer is provided, the effect of the conductive layer of the present invention is not substantially affected.
[0069]
An undercoat layer can also be provided between the temporary support and the conductive layer.
In this case, the chlorination described in JP-A-51-135526, US Pat. Nos. 3,143,421, 3,586,508, 2,698,235, 3,567,452 and the like. Vinylidene copolymers, diolefin copolymers such as butadiene described in JP-A-51-114120, US Pat. No. 3,615,556, etc., glycidyl acrylate or glycidyl described in JP-A-51-58469, etc. A methacrylate-containing copolymer, a polyamide / epichlorohydrin resin described in JP-A-48-24923, a maleic anhydride-containing copolymer described in JP-A-50-39536, and the like can be used.
[0070]
In the present invention, JP-A-56-82504, JP-A-56-143443, JP-A-57-104931, JP-A-57-118242, JP-A-58-62647, JP-A-60- A conductive layer described in No. 258541 can also be used as necessary.
[0071]
As another aspect, conductivity can be imparted to the temporary support by the following method.
When extruding a film for a temporary support, a conductive material is contained in a plastic raw material that is the same as or different from that of the temporary support, and when the film is extruded and co-extruded at the same time, adhesion, scratch resistance In this case, it is not necessary to provide the hydrophobic polymer layer or the undercoat layer.
This method is the most preferable embodiment as the conductivity-imparting provisional support in the photosensitive transfer material of the present invention.
[0072]
When a conductive layer solution is formed on a temporary support by forming a conductive layer, it can be applied by a known method such as roller coating, air knife coating, gravure coating, bar coating, curtain coating or the like. In order to obtain a sufficient antistatic effect, the surface electrical resistance value of the conductive layer or the temporary support provided with conductivity is set to 10¹³Ω or less is preferable, 10¹²More preferably, it is Ω or less.
[0073]
In addition, in order to prevent the photosensitive resin layer from firmly adhering to the temporary support, a slip agent composition containing known fine particles, a release agent composition containing a silicone compound, and the like are applied to the temporary support surface. You can also.
[0074]
In the case where a conductive layer is provided on the surface of the temporary support that does not adhere to the thermoplastic resin layer, for the purpose of improving the adhesion between the thermoplastic resin layer and the temporary support, Surface treatment such as discharge treatment, corona treatment, ultraviolet irradiation treatment, undercoating treatment such as phenolic substance, polyvinylidene chloride resin, styrene butadiene rubber, gelatin or a combination of these treatments can be applied.
[0075]
Next, an image forming method using the photosensitive transfer material of the present invention will be described.
First, the cover film of the photosensitive transfer material is removed, and the photosensitive resin layer is bonded onto a substrate that is a transfer target under pressure and heating. For bonding, a conventionally known laminator, vacuum laminator, or the like can be used, and an auto cut laminator can also be used in order to increase productivity.
Thereafter, the temporary support is peeled off, and the photosensitive resin layer is exposed through a predetermined mask, thermoplastic resin layer, and intermediate layer, and then developed. Development can be performed by a known method, using a solvent or an aqueous developer, in particular, an alkaline aqueous solution or the like, immersing the substrate after exposure or spraying with a spray or the like, and further rubbing with a brush or the like, Alternatively, it is performed by processing while irradiating ultrasonic waves.
By using a photosensitive transfer material having a plurality of photosensitive resin layers colored in different colors, a multicolor image can be formed by repeating this process a plurality of times.
[0076]
In addition, the transfer is performed on the final support after repeating the transfer process two or more times using a substrate for temporary transfer in the process before transferring to the permanent support, that is, the intermediate transfer substrate. The image may be formed through a plurality of transfers such as transfer. When a substrate having a high smoothness is used as the intermediate transfer substrate, the transferred photosensitive resin layer is in close contact with the substrate, so that the formed pixel pattern has an intermediate transfer substrate. The surface of the contact surface has excellent smoothness equivalent to the surface of the intermediate transfer member, and if this image pattern is further transferred onto a permanent support, a pixel pattern with extremely high surface smoothness can be obtained. . In particular, it is useful in the production of color filters and the like that are demanding of surface smoothness.
[0077]
Furthermore, a layer serving as a protective layer for the final pixel pattern may be provided in advance on the intermediate transfer substrate. That is, a protective layer is provided on a plate-like intermediate transfer substrate having high smoothness, and the photosensitive resin layer of the photosensitive transfer material of the present invention is transferred onto the protective layer, exposed, developed, and thereafter Furthermore, a desired protective layer can be formed on the pixel pattern by transferring onto the final support and peeling off the intermediate transfer substrate at the interface with the protective layer.
[0078]
As a material used for the protective layer, it is necessary to have good adhesion when it is brought into close contact with the photosensitive resin layer of the photosensitive transfer material of the present invention and to be resistant to an alkaline solution such as a developer. .
Specifically, materials having the necessary performance as a protective layer such as impact resistance, chemical resistance, solvent resistance, etc. from the adhesive layer materials described in JP-A-3-282404 may be appropriately selected and used. Alternatively, an alkali-soluble compound described in Japanese Patent Application No. 4-60668 can be preferably used. In the latter case, a protective layer film is formed on the intermediate transfer substrate by a method such as printing, coating, or transfer, and a pixel pattern is formed on this layer by the above method. At this time, the pixel pattern is sufficiently in close contact with the protective layer, sometimes embedded in the protective layer, and by transferring this pixel pattern to the final support, an image of the pixel pattern having a protective layer having excellent smoothness Can be obtained.
[0079]
Examples of the intermediate transfer substrate include surface-polished aluminum plates and stainless steel plates.
These thicknesses are preferably about 0.1 to 10 mm, particularly preferably about 0.1 to 1 mm. When a protective layer is provided on this plate-like substrate, the thickness of the protective layer is preferably about 10 μm or less, more preferably about 5 μm or less, and most preferably about 3 μm or less. When the thickness exceeds about 10 μm, it is not preferable because pixels may move and the image may be disturbed when the protective layer on which the image is formed is transferred to the final support.
[0080]
The main use of the photosensitive transfer material of the present invention is useful not only for the production of printed wiring boards, but also for the production of multicolor images, particularly color filters for liquid crystal displays and the like, and the production of protective layers for color filters.
A known copper-clad laminate is used as a substrate for the production of a printed wiring board, and a known glass plate as a substrate, a soda glass plate with an acid value silicon film formed on the surface, or the like is used for the production of a color filter. .
[0081]
【Example】
Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In the following examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
[0082]
Example 1
On a polyethylene terephthalate film temporary support having a thickness of 100 μm, a coating liquid H1 having the following composition was applied and dried to provide a thermoplastic resin layer having a dry film thickness of 20 μm.
[0083]

[0084]
Next, a coating liquid B1 having the following composition was applied on the thermoplastic resin layer and dried to provide an intermediate layer having a dry film thickness of 1.6 μm.

[0085]
Four temporary supports on which the thermoplastic resin layer and the intermediate layer are formed are prepared. On these temporary supports, the red (for the Red layer) and the blue (for the Blue layer) having the composition shown in Table 1 are prepared. A coating solution for photosensitive resin layers of four colors, green (for green layer) and black (for black layer), is applied to different temporary supports and dried to form a photosensitive resin layer having a dry film thickness of 2 μm. Formed.
[0086]
[Table 1]

[0087]
Furthermore, a cover film of polypropylene (thickness 12 μm) is provided on each photosensitive resin layer of the four photosensitive transfer materials by pressure bonding, and four single-color photosensitive colors of red, blue, green and black are provided. A transfer material was prepared.
[0088]
Using these photosensitive transfer materials, a color filter was prepared by the following method.
First, the red photosensitive transfer material cover film is peeled off, and the photosensitive resin layer surface is placed on a transparent glass substrate (thickness 1.1 mm) using a laminator (device name: VP-II, manufactured by Taisei Laminator Co., Ltd.). 0.8kg / cm²And bonding under pressure and heating conditions of 130 ° C. Thereafter, the temporary support was peeled from the thermoplastic resin layer, and the temporary support was removed.
[0089]
Next, it exposed through the predetermined | prescribed photomask, Then, the thermoplastic resin layer and the intermediate | middle layer were melt | dissolved and removed using 1% triethanolamine aqueous solution. At this time, the photosensitive resin layer was not substantially developed.
Next, the photosensitive resin layer was developed using a 1% aqueous sodium carbonate solution, unnecessary portions were removed, and a red pixel pattern was formed on the glass substrate.
[0090]
Further, on the glass substrate on which the red pixel pattern was formed, a green photosensitive transfer material was bonded in the same manner as described above, and peeling, exposure, and development were performed to form a green pixel pattern.
[0091]
The same process was repeated on the glass substrate on which the red and green pixel patterns were formed, and further blue and black pixel patterns were formed to produce a color filter A.
[0092]
(Example 2)
Instead of the benzyl methacrylate (BzMA) / methacrylic acid (MAA) / methyl methacrylate (MMA) copolymer used in Example 1, the copolymerization ratio was BzMA / MAA / MMA = 36/22/42, and the glass transition. A four-color photosensitive transfer material was prepared in the same manner as in Example 1 except that a BzMA / MAA / MMA copolymer having a point Tg of 90 ° C. was used. Was made.
[0093]
(Example 3)
Instead of the benzyl methacrylate (BzMA) / methacrylic acid (MAA) / methyl methacrylate (MMA) copolymer used in Example 1, the copolymerization ratio was BzMA / MAA / MMA = 21/21/58, and the glass transition A four-color photosensitive transfer material was prepared in the same manner as in Example 1 except that a BzMA / MAA / MMA copolymer having a point Tg = 100 ° C. was used. Was made.
[0094]
(Example 4)
Instead of the benzyl methacrylate (BzMA) / methacrylic acid (MAA) / methyl methacrylate (MMA) copolymer used in Example 1, the copolymerization ratio was BzMA / MAA / MMA = 10/19/71, and the glass transition. A four-color photosensitive transfer material was prepared in the same manner as in Example 1 except that a BzMA / MAA / MMA copolymer having a point Tg of 110 ° C. was used. Was made.
[0095]
(Example 5)
Instead of the benzyl methacrylate (BzMA) / methacrylic acid (MAA) / methyl methacrylate (MMA) copolymer used in Example 1, the copolymerization ratio was BzMA / MAA / MMA = 50/19/31, 80. A four-color photosensitive transfer material was prepared in the same manner as in Example 1 except that a BzMA / MAA / MMA copolymer having a glass transition point Tg = 80 ° C. was used. A color filter E was prepared.
[0096]
(Example 6)
Instead of the benzyl methacrylate (BzMA) / methacrylic acid (MAA) / methyl methacrylate (MMA) copolymer used in Example 1, the copolymerization ratio was BzMA / MAA / MMA = 32/17/51, and the acid value was 80. A four-color photosensitive transfer material was prepared in the same manner as in Example 1 except that a BzMA / MAA / MMA copolymer having a glass transition point Tg of 90 ° C. was used. A color filter F was prepared.
[0097]
(Example 7)
Instead of the benzyl methacrylate (BzMA) / methacrylic acid (MAA) / methyl methacrylate (MMA) copolymer used in Example 1, the copolymerization ratio was BzMA / MAA / MMA = 18/16/66, and the acid value was 80. A four-color photosensitive transfer material was prepared in the same manner as in Example 1 except that a BzMA / MAA / MMA copolymer having a glass transition point Tg = 100 ° C. was used. A color filter G was prepared.
[0098]
(Example 8)
Instead of the benzyl methacrylate (BzMA) / methacrylic acid (MAA) / methyl methacrylate (MMA) copolymer used in Example 1, the copolymerization ratio was BzMA / MAA / MMA = 1/14/86, and the acid value 80. A four-color photosensitive transfer material was prepared in the same manner as in Example 1 except that a BzMA / MAA / MMA copolymer having a glass transition point Tg = 115 ° C. was used. A color filter H was prepared.
[0099]
(Comparative Example 1)
Instead of the benzyl methacrylate (BzMA) / methacrylic acid (MAA) / methyl methacrylate (MMA) copolymer used in Example 1, the copolymerization ratio was BzMA / MAA / MMA = 73/27/0, and the acid value was 100, a four-color photosensitive transfer material was prepared in the same manner as in Example 1 except that a BzMA / MAA copolymer having a glass transition point Tg = 72 ° C. was used. Filter I was produced.
[0100]
(Comparative Example 2)
Instead of the benzyl methacrylate (BzMA) / methacrylic acid (MAA) / methyl methacrylate (MMA) copolymer used in Example 1, the copolymerization ratio was BzMA / MAA / MMA = 73/22/5, and the acid value was 80. A four-color photosensitive transfer material was prepared in the same manner as in Example 1 except that a BzMA / MAA / MMA copolymer having a glass transition point Tg = 70 ° C. was used. A color filter J was prepared.
[0101]
(Comparative Example 3)
Instead of the benzyl methacrylate (BzMA) / methacrylic acid (MAA) / methyl methacrylate (MMA) copolymer used in Example 1, the copolymerization ratio was BzMA / MAA / MMA = 0/23/77, and the acid value was 133, a four-color photosensitive transfer material was prepared in the same manner as in Example 1 except that a MAA / MMA copolymer having a glass transition point Tg of 125 ° C. was used. Filter K was produced.
[0102]
(Comparative Example 4)
Instead of the benzyl methacrylate (BzMA) / methacrylic acid (MAA) / methyl methacrylate (MMA) copolymer used in Example 1, the copolymerization ratio was BzMA / MAA / MMA = 0/27/73, and the acid value was 157, a four-color photosensitive transfer material was prepared in the same manner as in Example 1 except that a MAA / MMA copolymer having a glass transition point Tg of 129 was used. L was produced.
[0103]
(Comparative Example 5)
Instead of the benzyl methacrylate (BzMA) / methacrylic acid (MAA) / methyl methacrylate (MMA) copolymer used in Example 1, the copolymerization ratio was BzMA / MAA / MMA = 10/9/81, and the acid value 47. A four-color photosensitive transfer material was prepared in the same manner as in Example 1 except that a BzMA / MAA / MAA copolymer having a glass transition point Tg = 102 was used. A color filter M was produced.
[0104]
(Comparative Example 6)
Instead of the benzyl methacrylate (BzMA) / methacrylic acid (MAA) / methyl methacrylate (MMA) copolymer used in Example 1, the copolymerization ratio was BzMA / MAA / MMA = 9/23/68, 124. A four-color photosensitive transfer material was prepared in the same manner as in Example 1 except that a BzMA / MAA / MAA copolymer having a glass transition point Tg = 114 was used, and these were used as in Example 1. A color filter N was produced.
[0105]
<Surface property evaluation>
The degree of unevenness of the filter surfaces of the color filters A to N having a pixel pattern obtained as described above was measured using a stylus type film thickness meter (P-1, manufactured by Tencor). Evaluation was performed according to the following criteria, using the obtained unevenness thickness difference (irregularity width) as a guideline for surface property evaluation.
The measurement results and evaluation results are shown in Table 2 below.
○: The film thickness difference is 0.05 μm or less, which is superior in surface properties.
(Triangle | delta): A film thickness difference is 0.1 micrometer or less, and there is no problem in actual use.
X: The film thickness difference is 0.5 μm or more and the surface property is inferior. Usage prohibited.
[0106]
[Table 2]

[0107]
From Table 2, the photosensitive transfer materials A to H of the present invention obtained from Examples 1 to 8 in which a specific resin is used for the photosensitive resin layer have an uneven width of 0.1 μm or less on the color filter surface. It had a uniform surface property without wrinkle marks. Further, in the above process, the temporary support has excellent peeling performance with respect to the thermoplastic resin layer, and the obtained color filter has excellent adhesion between the colored layer and the glass substrate. There was no omission.
On the other hand, when the resin whose Tg value is not in the range prescribed in the present invention is used in the photosensitive resin layer as in Comparative Examples 1 to 4, the filters of the color filters I to J obtained in Comparative Examples 1 and 2 The surface irregularities are 0.5 μm or more, and wrinkle-like marks are visually observed. In the color filters K to L obtained in Comparative Examples 3 to 4, the surface properties are excellent, As a result of the high Tg value and the accompanying increase in the acid value, the hardness of the resin film of the photosensitive resin layer becomes high at the stage of producing the photosensitive transfer material, and the cover film cannot be formed by pressure bonding. The cured portion was easily dissolved in the alkaline solution, the desired resist properties could not be obtained, and a sharp pixel pattern could not be formed.
In addition, as in Comparative Examples 5 to 6, when a resin having an acid value not in the range specified in the present invention was used in the photosensitive resin layer, the surface properties of the formed filter were also excellent, In Example 5, the resin film of the photosensitive resin layer becomes insoluble in the alkaline solution and a desired pixel pattern cannot be formed. On the other hand, in Comparative Example 6, the cured portion easily becomes alkaline solution even after polymerization and curing. It was dissolved and a sharp pixel pattern could not be formed.
Therefore, it can be said that the color filters I to N are not preferable as materials used for displaying a high-definition image or the like.
[0108]
【The invention's effect】
The photosensitive transfer material of the present invention is a transfer material in which a photosensitive resin layer having a low content of pigment or the like is provided on a cushion layer that prevents transfer failure. It can be stably maintained without causing “wrinkles” (so-called reticulation of the photosensitive resin layer) such as folds and overlaps that occur over time.

Claims (2)

In a photosensitive transfer material in which at least a thermoplastic resin layer and a photosensitive resin layer are laminated in this order on a temporary support, the photosensitive resin layer has an acid value of 50 to 120 and a glass transition point Tg of 75 to 123. ℃ is a layer comprising a resin, a photosensitive said resin contained in the photosensitive resin layer and a benzyl methacrylate, and methacrylic acid, characterized in that it is a copolymer composed of methyl methacrylate Transfer material. The photosensitive transfer material according to claim 1 , wherein a colorant is contained in the photosensitive resin layer.