JP3884513B2 - Manufacturing method of color filter - Google Patents

Description

表１に示されるように、引張弾性率が５〜３００ｋＮ／ｍｍ² の範囲にある転写基材シートＡ〜Ｅを使用して作製したカラーフィルタ（試料１〜５）は、いずれも見当印の最大ずれ幅Ｚが１０μｍ以下と小さく、高精度の着色パターンを備えたカラーフィルタであることが確認された。
【００８７】
これに対して、引張弾性率が５ｋＮ／ｍｍ² 未満である転写基材シートＦを使用して作製したカラーフィルタ（試料６）は、第３の工程での転写基材シートの伸びの影響による見当印の最大ずれ幅Ｚが大きく、カラーフィルタとして実用に供し得ないものであった。また、引張弾性率が３００ｋＮ／ｍｍ² を超える転写基材シートＧを使用して作製したカラーフィルタ（試料７）は、転写基材シート自体が剛直であるために長尺の帯状シートとしての扱いが困難であり、転写のための位置合わせが非常に困難であった。
【００８８】
尚、赤色着色剤（イルカジンレッドＢＰＴ）の代わりに緑色着色剤（銅フタロシアニン）を添加して調製した緑色着色パターン用の感光性樹脂組成物を使用して、上述の第１の工程から第３の工程による赤色の着色パターン形成と同様に、緑色の着色パターンを同一のガラス基板上に形成し、この着色パターンについて、上述のように見当印の最大ずれ幅Ｚを測定したところ、同様の結果が得られた。
【００８９】
また、赤色着色剤（イルカジンレッドＢＰＴ）の代わりに青色着色剤（フタロシアニンブルー）を添加して調製した青色着色パターン用の感光性樹脂組成物を使用して、上述の第１の工程から第３の工程による赤色の着色パターン形成と同様に、青の着色パターンを同一のガラス基板上に形成し、この着色パターンについて、上述のように見当印の最大ずれ幅Ｚを測定したところ、同様の結果が得られた。
【００９０】
【発明の効果】
以上詳述したように、本発明によれば第１の工程で、転写基材シートと剥離フィルムの間に着色剤を含有した感光性樹脂層を形成し、第２の工程で、所定のフォトマスクを介して剥離フィルム側から感光性樹脂層を露光し、その後、剥離フィルムを剥離して感光性樹脂層の露光部を剥離フィルムとともに転写基材シートから除去し感光性樹脂層の未露光部を感光性樹脂パターンとして転写基材シート上に残し、次に、第３の工程で、カラーフィルタ用の透明基板を感光性樹脂パターン上に位置合わせして圧着し、透明基板側から感光性樹脂パターンを露光し、転写基材シートを剥離して感光性樹脂パターンを透明基板上に転写して着色パターンが形成され、この一連の操作において引張弾性率が５〜３００ｋＮ／ｍｍ² の範囲にある転写基材シートを使用するので、張力による転写基材シートの伸びが極めて少ないものとなり、透明基板上への感光性樹脂パターンの位置合わせを高い精度で行うことができ、したがって、透明基板上へ高い精度で着色パターンを形成することができ、色ずれや色抜け等のない高精細なカラーフィルタの製造が可能である。また、上記の第１の工程から第３の工程のいずれも、カラーフィルタ用の透明基板へのスピンコート等による塗布工程がないので材料ロスが極めて少なく、かつ、湿式現像工程や洗浄工程は不要で廃液処理の必要がなく、第１の工程から第３の工程を必要な色数分繰り返して、所望の色数の着色パターンを透明基板上に形成することによってカラーフィルタを製造するので、材料の使用効率が高く、工程が簡便なものとなり、したがって、製造コストの低減が可能となる。
【図面の簡単な説明】
【図１】本発明によるカラーフィルタの製造方法を説明するための工程図である。
【図２】本発明によるカラーフィルタの製造方法を説明するための工程図である。
【図３】本発明によるカラーフィルタの製造方法を説明するための工程図である。
【符号の説明】
１…カラーフィルタ
２…透明基板
３Ｒ，３Ｇ，３Ｂ…着色パターン
１１Ｒ，１１Ｇ，１１Ｂ…複合体
１２…転写基材シート
１３…剥離フィルム
１４（１４Ｒ，１４Ｇ，１４Ｂ）…感光性樹脂層
１５（１５Ｒ，１５Ｇ，１５Ｂ）…感光性樹脂パターン
２１Ｒ，２１Ｇ，２１Ｂ…フォトマスク[0001]
[Technical field to which the invention belongs]
The present invention relates to a method for manufacturing a color filter, and more particularly to a method for manufacturing a color filter used for a liquid crystal display or the like.
[0002]
[Prior art]
In a liquid crystal display (LCD), color filters are used in both the active matrix method and the simple matrix method in order to meet the recent demand for colorization. For example, in an active matrix type liquid crystal display using thin film transistors (TFTs), a color filter has coloring patterns of three primary colors of red (R), green (G), and blue (B), and each of R, G, and B By turning on and off the electrodes corresponding to the pixels, the liquid crystal operates as a shutter, and light is transmitted through the R, G, and B pixels to perform color display. Color mixing is visually performed on the retina according to the principle of additive color mixing in which liquid crystal shutters corresponding to pixels of two or more colors are opened and mixed to show different colors.
[0003]
As one type of manufacturing method of the above color filter, a colored light-sensitive material method has been conventionally used. In this colored photosensitive material method, a photosensitive composition in which a dye, an inorganic pigment, an organic pigment or the like is dispersed as a colorant in a transparent photosensitive resin is applied onto a transparent substrate by a spin coating method or the like to form a photosensitive resin layer. Then, the photosensitive resin layer is exposed through a predetermined photomask, and wet developing using a developer that dissolves the unexposed portion of the photosensitive resin layer to form a colored pattern is performed by R, G, A color pattern of each color is formed by performing B three times.
[0004]
[Problems to be solved by the invention]
However, in the conventional colored light-sensitive material method, material loss is unavoidable in the coating process by the spin coating method of the photosensitive resin composition on the transparent substrate, and the wet development process and the cleaning process for each colored pattern formation Therefore, waste liquid treatment is necessary, and it is difficult to improve the efficiency of material use and simplify the process, which hinders the reduction of manufacturing costs.
[0005]
In order to solve such a problem in the color sensitive material method, a manufacturing method that eliminates the need for a wet development step has been developed (Japanese Patent Laid-Open No. 2-151805). In this color filter manufacturing method, a radiation-sensitive support sheet B is coated with a photosensitive resin layer containing a colorant and dried, and then a radiation-transmissive support sheet A is laminated, and then the photosensitive resin layer is radiation-cured. The support sheet B is heated and peeled from the support sheet A, and the support sheet A holds the photosensitive resin layer of the uncured pattern portion, and then the uncured pattern portion of the photosensitive resin layer together with the support sheet A is a color filter. Pressure-bonding or thermo-compression bonding to a transparent substrate for use, radiation-curing an uncured pattern portion after the support sheet A is peeled off, and such operations on the same transparent substrate with respect to the photosensitive resin layer containing the colorant of each hue It repeats sequentially.
[0006]
However, the above color filter manufacturing method has an excellent advantage that the wet development process can be omitted, while the photosensitive resin layer pattern on the support sheet A is accurately positioned with respect to the transparent substrate for the color filter. In practice, it is difficult to transfer the images while aligning them, and it is extremely difficult to produce a good product free of color shift or color loss at a high yield. That is, the support sheet A made of a radiation transmissive resin film is stretched by tension at the time of exposure before release development, at the time of pressure bonding between the transparent substrate after the release development and the support sheet A, and at the time of subsequent exposure. This is because the pattern formed on the support sheet by the peeling development causes a significant shift in dimensions as compared to the arrangement when formed as a latent image by pattern exposure.
[0007]
The present invention has been made in view of the circumstances as described above, and is capable of producing a high-definition color filter, is excellent in material use efficiency, and does not include a wet development process and a cleaning process. An object is to provide a simple method for producing a color filter.
[0008]
[Means for Solving the Problems]
In order to achieve such an object, the present invention has a release film and a tensile modulus of 5 to 300 kN / mm.² A first step of forming a photosensitive resin layer containing a colorant between the transfer substrate sheet in the range of the above, and exposing the photosensitive resin layer from the release film side through a predetermined photomask Then, the exposed portion of the photosensitive resin layer is removed from the transfer base sheet by peeling off the release film, leaving the unexposed portion of the photosensitive resin layer on the transfer base sheet. A second step of forming a resin pattern, and a transparent substrate for a color filter is aligned and pressure-bonded to the photosensitive resin pattern formed on the transfer base sheet, and the photosensitive property is measured from the transparent substrate side. A third step of exposing the resin pattern and then transferring the photosensitive resin pattern onto the transparent substrate to form a colored pattern by peeling off the transfer base sheet, and a required number of colors. repeat It was thus configured as to form a desired number of colors colored pattern on the transparent substrate.
[0009]
Moreover, the manufacturing method of the color filter of this invention set it as the structure which uses the said transfer base material sheet as a bonded body of a metal steel strip or a metal steel strip and a resin film.
[0010]
  Moreover, the manufacturing method of the color filter of this invention was set as the structure which uses the said metal steel strip as a stainless steel strip.
  The color filter manufacturing method of the present invention is such that the thickness of the photosensitive resin layer formed in the first step is equal to or greater than the thickness of the photosensitive resin layer in the previous operation every time the required number of colors is repeated, and The thickness difference is 10% or less..
[0011]
In this invention, the transfer substrate sheet has a tensile modulus of 5 to 300 kN / mm.² Therefore, the photosensitive resin layer is exposed from the release film side through a predetermined photomask, the release film is peeled off, and the exposed portion of the photosensitive resin layer is removed together with the release film from the transfer substrate sheet. The unexposed portion of the photosensitive resin layer is left as a photosensitive resin pattern on the transfer substrate sheet, and then the color filter transparent substrate is aligned with the photosensitive resin pattern and pressed through a series of operations. The transfer base sheet has very little elongation, and a colored pattern can be formed on the transparent substrate with high accuracy.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[0013]
The present invention has been made by paying attention to the fact that the elongation of the transfer base sheet due to the tension in each operation of the color pattern transfer by peeling development and pressure bonding affects the color pattern accuracy of the color filter. That is, the present invention has a tensile elastic modulus of 5 to 300 kN / mm as a transfer substrate sheet.² Using the transfer base sheet in the range, the color pattern forming operation consisting of the first step to the third step is repeated for the required number of colors, thereby forming a desired number of color patterns on the transparent substrate. A color filter with extremely high accuracy is manufactured.
[0014]
1 to 3 are process diagrams for explaining an embodiment of a method for producing a color filter of the present invention. Here, a color filter having a coloring pattern of three primary colors of red (R), green (G), and blue (B) will be described as an example.
(1) Red colored pattern formation
First step
First, as a first step, as shown in FIG. 1A, a photosensitive resin layer 14R containing a red colorant is provided between the transfer base sheet 12 and the release film 13 to form the composite 11R. Form. The photosensitive resin layer 14R is formed on the transfer base sheet 12 by a known application means such as a direct gravure coating method, a gravure reverse coating method, a reverse roll coating method, a slide die coating method, or a slit die coating method. It can be formed by applying and drying the composition, and overlaying and pressing the release film 13 on the coating film. Alternatively, the photosensitive resin composition may be applied on the release film 13 and dried, and the transfer base sheet 12 may be stacked and pressure-bonded on the coating film. Note that the pressure bonding at the time of forming the composite 11R may be a heat pressure bonding. In this case, the heating temperature can be appropriately set according to the thermal physical properties of the photosensitive resin layer 14R.
[0015]
Here, the transfer substrate sheet used in the present invention will be described. In the present invention, the tensile elastic modulus is 5 to 300 kN / mm as the transfer base sheet 12 having flexibility and less deformation due to tension or pressure.² It is necessary to use materials in the range. Tensile modulus is 300 kN / mm² If it exceeds 1, the flexibility as a base material becomes low, and it becomes difficult to handle it as a belt-like base material, which is not preferable. Also, the tensile modulus is 5 kN / mm² If it is less than this, deformation due to tension or pressure becomes large, and it becomes difficult to perform alignment between the photosensitive resin pattern 15R and the transparent substrate 2 in a third step described later with high accuracy. In addition, let the tensile elasticity modulus in this invention be a numerical value measured using the test method prescribed | regulated to JISK7127. Further, the above test method is defined as a test method for plastic films and sheets, but in the present invention, the test object is applied to metal materials.
[0016]
Examples of the material used for the transfer base sheet 12 include stainless steel bands such as SUS430, SUS301, SUS304, SUS420J2 and SUS631, copper steel bands, metal steel bands such as aluminum steel bands, beryllium steel bands, copper foils, aluminum Examples thereof include metal foils such as foils. Among them, a stainless steel strip, preferably a SUS430 stainless steel strip, can be preferably used in that the thermal expansion coefficient is close to the thermal expansion coefficient of the color filter glass substrate. The thickness of the transfer base sheet 12 made of such a metal steel strip or metal foil is preferably about 6 to 2000 μm.
[0017]
Furthermore, as a material used for the transfer base sheet 12, a bonded body in which the above-described metal steel strip or metal foil is bonded to a resin film can also be used. When a metal steel strip is compared with a resin film, the resistance to tension per unit thickness is often superior to that of a metal steel strip, while the price per unit thickness is often less expensive for a resin film. In addition, many resin films have superior surface smoothness compared to metal steel strips, and transfer for transferring the color filter pixel pattern red (R), green (G), and blue (B) coloring patterns. It can be preferably used as the base sheet 12. Therefore, a transfer base sheet that balances resistance to tension per unit thickness, surface smoothness, and low material cost by appropriately bonding a resin film to a metal steel strip to form a transfer base sheet 12. 12 can be obtained. Specific examples of the resin film in this case include polyethylene film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, polypropylene film, polystyrene film, polymethacrylic acid film, polyvinyl chloride film, polyvinyl alcohol film. , Polyvinyl butyral film, nylon film, polyether ether ketone film, polysulfone film, polyether sulfone film, polytetrafluoroethylene-perfluoroalkyl vinyl ether film, polyvinyl fluoride film, tetrafluoroethylene-ethylene film, tetrafluoroethylene- Hexafluoropropylene film, polychlorotrifluoroethylene film, polyvinylidene Fluoride film, Polyethylene terephthalate film, Polyethylene naphthalate film, Polyester film, Cellulose triacetate film, Polycarbonate film, Polyurethane film, Polyimide film, Polyetherimide film, Films containing these resin materials and fillers, These resin materials A biaxially stretched film obtained by uniaxially stretching or biaxially stretching a film using the above, a biaxially stretched film in which the stretching ratio in the width direction is increased from the flow direction using these resin materials, and the flow direction from the width direction using these resin materials A biaxially stretched film with an increased stretch ratio, a film obtained by laminating the same or different kinds of these films, and the same or different kinds of resins selected from the raw resin used in these films. It can be mentioned composite films created by Rukoto.
[0018]
As for the thickness of the transfer base material sheet 12 which consists of such a bonding body, about 6-2000 micrometers is preferable, and the thickness of the resin film which comprises a bonding body has preferable about 2-200 micrometers.
[0019]
The transfer substrate sheet 12 as described above is selected in consideration of the characteristics of the release film 13 and the photosensitive resin layer 14 (including the photosensitive resin layer 14R and the photosensitive resin layers 14G and 14B described later). Can do. That is, the transfer substrate sheet 12 is used such that the adhesion force of the transfer substrate sheet 12 to the photosensitive resin layer 14 is stronger than the adhesion force of the release film 13 and the photosensitive resin layer 14. In addition, in order to improve the adhesive force with the photosensitive resin layer 14, you may form the primer layer which is mentioned later on the transfer base material sheet 12. FIG.
[0020]
The photosensitive resin composition for forming the photosensitive resin layer 14R in the first step is appropriately selected from known various photosensitive resin compositions containing a red colorant such as a dye, an inorganic pigment, and an organic pigment. You can select and use. As said photosensitive resin composition, what mix | blended the binder, the polymerization initiator, the coloring agent, etc. can be used so that it may mention later. The thickness of the formed photosensitive resin layer 14R can be set in the range of about 0.5 to 5.0 μm, preferably about 1.0 to 3.0 μm. And in this embodiment which forms a colored pattern on a transparent substrate in order of a red colored pattern, a green colored pattern, and a blue colored pattern, the thickness A1 of the photosensitive resin layer 14R and the photosensitive resin layer 14G described later It is necessary to set the thickness A2 and the thickness A3 of the photosensitive resin layer 14B so as to satisfy the relationship of A1 ≦ A2 ≦ A3. This is because it is necessary to transfer and form a colored pattern so as to fit in the valleys of other colored patterns already formed on the transparent substrate in forming a green colored pattern and a blue colored pattern described later. is there. When A1 and A2 or A2 and A3 are not equal, the difference is preferably small in consideration of the surface smoothness required for the color filter. For example, (A2-A1) is 10% or less of A1. , (A3-A2) is preferably set to be 10% or less of A2.
[0021]
Further, the release film 13 has flexibility as will be described later, and does not undergo significant deformation due to tension or pressure. Further, light for performing exposure at a desired exposure amount is transmitted through the photosensitive resin layer 14R. It is necessary to use materials to do. As described above, the release film 13 can be appropriately selected from the relationship with the transfer base sheet 12 in consideration of the characteristics of the photosensitive resin layer 14 (14R, 14G, 14B).
[0022]
The transfer base sheet 12 and the release film 13 described above may be a single wafer type or a long body. By making the transfer substrate sheet 12 and the release film 13 into a long body, the composite body 11R can be wound and stored in a roll shape, and a necessary amount can be sent out as needed to be used for manufacturing a color filter.
Second step
Next, the photosensitive resin layer 14R of the composite 11R is exposed through the photomask 21R for red coloring pattern (FIG. 1B). In this invention, it is essential to perform this exposure from the peeling film 13 side. Thereby, in the exposed portion of the photosensitive resin layer 14R, the curing proceeds preferentially from the release film 13 side, and the adhesive force to the release film 13 is greatly increased. The photosensitive resin layer 14R and the transfer base sheet 12 are adhered to each other with the force remaining.
[0023]
The exposure amount of the photosensitive resin layer 14R from the release film 13 side can be appropriately set within a range in which the photocuring reaction of the photosensitive resin layer 14R does not proceed to the transfer substrate sheet 12 side. The range of 2 to 60% of the minimum exposure amount required for the photocuring reaction of the conductive resin layer 14R to completely proceed. In this exposure, if the exposure amount is insufficient, the adhesive force between the transfer base sheet 12 and the unexposed portion of the photosensitive resin layer 14R is increased by the exposure of the release film 13 and the photosensitive resin layer 14R. It becomes insufficient, and the following peeling development cannot be performed satisfactorily. On the other hand, if the exposure amount is too close to the above minimum exposure amount, the adhesive force between the transfer base sheet 12 and the exposed portion of the photosensitive resin layer 14R becomes too large, and the exposure of the release film 13 and the photosensitive resin layer 14R. The difference becomes insufficient with respect to the adhesive strength with the part, and the following peeling development cannot be performed satisfactorily. By exposing the photosensitive resin layer 14R from the release film 13 side with the exposure amount as described above, the irradiation light arrival amount gradually decreases from the release film 13 side in the thickness direction in the exposed portion of the photosensitive resin layer 14R, The transfer substrate sheet 12 side of the photosensitive resin layer 14R is in an unexposed (uncured) state.
[0024]
Next, the exposed portion of the photosensitive resin layer 14R is removed together with the release film 13 from the transfer substrate sheet 12 by peeling the release film 13, and at least a part of the unexposed portion of the photosensitive resin layer 14R is removed from the photosensitive resin. Stripping development is performed so as to leave the pattern 15R on the transfer substrate sheet 12 (FIG. 1C). Since the exposure of the photosensitive resin layer 14R is performed under the exposure amount as described above, in this peeling development, the film breakability between the exposed portion and the unexposed portion of the photosensitive resin layer 14R is good, and the photosensitive The resin pattern 15R has a good pattern shape.
[0025]
Note that whether the entire unexposed portion of the photosensitive resin layer 14R remains on the transfer base sheet 12 as the photosensitive resin pattern 15R or whether a part in the thickness direction remains as the photosensitive resin pattern 15R. Is determined by the relationship between the adhesive force between the photosensitive resin layer 14R and the cohesive force of the photosensitive resin layer 14R. For this reason, according to the thickness required for the photosensitive resin pattern 15R, it is necessary to appropriately set the material of the release film 13, the constituent material of the photosensitive resin layer 14R, the layer thickness of the photosensitive resin layer 14R, and the like.
[0026]
Here, the photocuring reaction progress rate of the above-mentioned photosensitive resin layer 14 can be prescribed | regulated by a gel fraction. That is, a sample A on which a photosensitive resin layer having a certain area is formed is prepared, and the weight a of the photosensitive resin layer in the sample A is measured. Next, sample A is heated and refluxed with tetrahydrofuran according to a conventional method to extract and remove soluble components, insoluble components are separated and dried, and the weight b of sample B obtained is measured. Next, the weight c of the sample C irradiated with the ultraviolet ray having an arbitrary exposure amount is measured, and the dry weight d of the solvent-insoluble component D after extraction with tetrahydrofuran is measured in the same manner as the sample A. Next, the photosensitive resin composition content e contained in the sample C is calculated by the following formula (1).
[0027]
e = d−c × b ÷ a Equation (1)
Furthermore, the photosensitive resin composition content with respect to the total weight of the sample C, that is, the gel fraction f (%) is calculated by the following formula (2).
[0028]
f = (d−c × b ÷ a) ÷ c × 100 Formula (2)
Each of the gel fractions f was measured while changing the exposure amount of the ultraviolet rays for the sample C, and the value of the gel fraction f when the gel fraction f did not change even when the exposure amount was increased was determined as the final photosensitive resin composition. The product content g or the final gel fraction g is used, and the minimum exposure amount giving g is the photocuring reaction complete exposure amount. Moreover, the gel fraction f of each sample from which exposure amount differs is calculated, and the photocuring reaction progress rate h with respect to each exposure amount is calculated from following formula (3).
[0029]
h = f ÷ g × 100 Formula (3)
Third step
After the color filter transparent substrate 2 is aligned with the photosensitive resin pattern 15R formed on the transfer base sheet 12 in the second step described above, it is pressure-bonded (FIG. 1D).
[0030]
The alignment between the transparent substrate 2 and the photosensitive resin pattern 15R can be performed, for example, as follows. That is, in the exposure in the above-described second step, a photomask 21R provided with light shielding portions for forming register marks at the four corners and the peripheral portion is used, and on the transfer base sheet 12 simultaneously with the formation of the photosensitive resin pattern 15R. A registration mark for alignment is formed on the. On the other hand, a register mark having the same dimensional accuracy as the register mark on the transfer base sheet 12 is also provided in advance on the transparent substrate 2 for the color filter under the temperature condition when performing this alignment. Then, the transparent substrate 2 and the transfer base sheet 12 can be aligned using the above registration marks while applying the minimum tension necessary for preventing the transfer base sheet 12 from wrinkling. In the present invention, the tensile elastic modulus is 5 to 300 kN / mm.² Since the transfer base sheet in the range is used, the extension of the transfer base sheet 12 due to the tension applied in the above positioning operation is extremely small. Therefore, the photosensitive resin pattern 15R, which is a pattern latent image formed by exposure using the photomask 21R in the second step, can be brought into close contact with the transparent substrate 2 with extremely high accuracy.
[0031]
For example, when a black matrix is formed on the transparent substrate 2 in advance, the registration mark provided on the transparent substrate 2 can be formed simultaneously with the formation of the black matrix.
[0032]
Moreover, in order to improve the adhesiveness between the photosensitive resin pattern 15R and the transparent substrate 2, thermocompression bonding may be performed after the alignment of both.
[0033]
Next, the photosensitive resin pattern 15R is exposed (FIG. 1D). In the present invention, it is essential to perform this exposure from the transparent substrate 2 side. As a result, the photosensitive resin pattern 15R is preferentially cured on the transparent substrate 2 side, and the adhesive force to the transparent substrate 2 is greatly increased, while the original adhesive force remains on the transfer base sheet 12 side. In this state, the photosensitive resin pattern 15R and the transfer base sheet 12 are bonded. Therefore, by peeling the transfer base sheet 12, the photosensitive resin pattern 15R is transferred onto the transparent substrate 2 to form a red colored pattern 3R (FIG. 1E). Thereafter, the colored pattern 3R on the transparent substrate 2 is exposed or heated to complete the curing reaction, whereby the formation of the red colored pattern on the transparent substrate 2 is completed.
[0034]
The exposure of the photosensitive resin pattern 15R from the transparent substrate 2 side as described above can be performed with an exposure amount in a range in which the photocuring reaction of the photosensitive resin pattern 15R does not proceed to the transfer base sheet 12 side. The exposure can be performed at an exposure amount in the range of 2 to 60% of the minimum exposure amount necessary for the photocuring reaction of the photosensitive resin pattern 15R to proceed completely. In this exposure, if the exposure amount is insufficient, an increase in adhesive force due to exposure between the transparent substrate 2 and the photosensitive resin pattern 15R becomes insufficient, and a colored pattern cannot be formed on the transparent substrate 2 satisfactorily. On the other hand, if the exposure amount is too close to the minimum exposure amount, the adhesive force between the transfer base sheet 12 and the photosensitive resin pattern 15R becomes too large, resulting in an adhesive force between the transparent substrate 2 and the photosensitive resin pattern 15R. On the other hand, the difference becomes insufficient, and the colored pattern formation on the transparent substrate 2 cannot be performed well. By exposing the photosensitive resin pattern 15R from the transparent substrate 2 side with the exposure amount as described above, the amount of irradiated light reaching the photosensitive resin pattern 15R gradually decreases from the transparent substrate 2 side in the thickness direction. The sheet 12 side is in an unexposed (uncured) state. Here, the photocuring reaction progress rate of the photosensitive resin pattern 15R can be defined by the above-described gel fraction.
[0035]
The transfer substrate sheet 12 may be peeled off while the transfer substrate sheet 12 is heated.
(2) Green colored pattern formation
First step
Similarly to the above-described red coloring pattern formation, a photosensitive resin layer 14G containing a green colorant is provided between the transfer substrate sheet 12 and the release film 13 to form a composite 11G (FIG. 2A). ).
[0036]
In addition, the transfer base material sheet 12 and the peeling film 13 to be used can be the same as that of the above-mentioned red coloring pattern formation.
Second step
Next, the photosensitive resin layer 14G of the composite 11G is exposed from the release film 13 side through the green colored pattern photomask 21G (FIG. 2B). Thereby, in the exposed portion of the photosensitive resin layer 14G, the curing proceeds preferentially from the release film 13 side, and the adhesive force to the release film 13 is greatly increased. The photosensitive resin layer 14G and the transfer base sheet 12 are adhered to each other while maintaining the force. This exposure can also be performed with an exposure amount in a range in which the photocuring reaction of the photosensitive resin layer 14G does not proceed to the transfer base sheet 12 side. For example, the photocuring reaction of the photosensitive resin layer 14G completely proceeds. Can be performed at an exposure amount in the range of 2 to 60% of the minimum exposure amount required for the above.
[0037]
Next, the exposed portion of the photosensitive resin layer 14G is removed together with the release film 13 from the transfer substrate sheet 12 by peeling the release film 13, and at least a part of the unexposed portion of the photosensitive resin layer 14G is removed from the photosensitive resin. The pattern 15G is left on the transfer substrate sheet 12 (FIG. 2C).
[0038]
Note that whether the entire unexposed portion of the photosensitive resin layer 14G remains on the transfer substrate sheet 12 as the photosensitive resin pattern 15G or whether a part of the unexposed portion remains as the photosensitive resin pattern 15G and the photosensitive film pattern 15G. It is determined by the relationship between the adhesive strength with the resin layer 14G and the cohesive strength of the photosensitive resin layer 14G. For this reason, according to the thickness required for the photosensitive resin pattern 15G, it is necessary to appropriately set the material of the release film 13, the constituent material of the photosensitive resin layer 14G, the layer thickness of the photosensitive resin layer 14G, and the like.
Third step
The transparent substrate 2 for the color filter on which the red colored pattern 3R has already been formed is aligned and pressure-bonded to the photosensitive resin pattern 15G formed on the transfer base sheet 12 in the second step described above ( FIG. 2 (D)). The alignment between the transparent substrate 2 and the photosensitive resin pattern 15G can be performed in the same manner as the above-described red coloring pattern formation. In addition, in order to improve the adhesiveness of the photosensitive resin pattern 15G and the transparent substrate 2, you may heat-press both.
[0039]
Next, the photosensitive resin pattern 15G is exposed from the transparent substrate 2 side (FIG. 2D). Thereby, the photosensitive resin pattern 15G is preferentially cured on the transparent substrate 2 side, and the adhesive force to the transparent substrate 2 is greatly increased, while the original adhesive force is maintained on the transfer base sheet 12 side. In this state, the photosensitive resin pattern 15G and the transfer base sheet 12 are bonded. Therefore, by peeling the transfer base sheet 12, the photosensitive resin pattern 15G is transferred onto the transparent substrate 2 to form a green colored pattern 3G (FIG. 2 (E)). Thereafter, the colored pattern 3G on the transparent substrate 2 is exposed or heated to complete the curing reaction, whereby the formation of the green colored pattern on the transparent substrate 2 is completed.
[0040]
The exposure of the photosensitive resin pattern 15G from the transparent substrate 2 side as described above can be performed with an exposure amount in a range in which the photocuring reaction of the photosensitive resin pattern 15G does not proceed to the transfer base sheet 12 side. The exposure can be performed at an exposure amount in the range of 2 to 60% of the minimum exposure amount required for the photocuring reaction of the photosensitive resin pattern 15G to proceed completely.
[0041]
Even in the above-described green coloring pattern formation, the tensile elastic modulus is 5 to 300 kN / mm.² Since the transfer substrate sheet in the range is used, the elongation of the transfer substrate sheet 12 due to tension can be made extremely small. For this reason, the photosensitive resin pattern 15G, which is a pattern latent image formed by exposure using the photomask 21G in the second step, can be brought into close contact with the transparent substrate 2 with extremely high accuracy. The green colored pattern 3G can be formed without causing transfer defects such as color loss.
(3) Blue colored pattern formation
First step
Similar to the above-described red coloring pattern formation, a photosensitive resin layer 14B containing a blue colorant is provided between the transfer substrate sheet 12 and the release film 13 to form a composite 11B (FIG. 3A). ).
[0042]
In addition, the transfer base material sheet 12 and the peeling film 13 to be used can be the same as that of the above-mentioned red coloring pattern formation.
Second step
Next, the photosensitive resin layer 14B of the composite 11B is exposed from the release film 13 side through the photomask 21B for a blue coloring pattern (FIG. 3B). Thereby, in the exposed portion of the photosensitive resin layer 14B, the curing progresses preferentially from the release film 13 side, and the adhesive force to the release film 13 is greatly increased. The photosensitive resin layer 14B and the transfer base sheet 12 are adhered to each other with the force remaining. This exposure can also be performed with an exposure amount in such a range that the photocuring reaction of the photosensitive resin layer 14B does not proceed to the transfer base sheet 12 side. For example, the photocuring reaction of the photosensitive resin layer 14B proceeds completely. Can be performed at an exposure amount in the range of 2 to 60% of the minimum exposure amount required for the above.
[0043]
Next, the exposed portion of the photosensitive resin layer 14B is removed from the transfer base sheet 12 together with the release film 13 by peeling the release film 13, and at least a part of the unexposed portion of the photosensitive resin layer 14B is removed from the photosensitive resin. The pattern 15B is left on the transfer base sheet 12 (FIG. 3C).
[0044]
Note that whether the entire unexposed portion of the photosensitive resin layer 14B remains on the transfer base sheet 12 as the photosensitive resin pattern 15B or whether a part of the unexposed portion remains as the photosensitive resin pattern 15B and the photosensitive film pattern 15B. It is determined by the relationship between the adhesive strength with the resin layer 14B and the cohesive strength of the photosensitive resin layer 14B. For this reason, according to the thickness required for the photosensitive resin pattern 15B, it is necessary to appropriately set the material of the release film 13, the constituent material of the photosensitive resin layer 14B, the layer thickness of the photosensitive resin layer 14B, and the like.
Third step
Position the transparent substrate 2 for the color filter in which the red colored pattern 3R and the green colored pattern 3G are already formed on the photosensitive resin pattern 15B formed on the transfer base sheet 12 in the second step described above. Combined and crimped (FIG. 3D). The alignment between the transparent substrate 2 and the photosensitive resin pattern 15B can be performed in the same manner as the red colored pattern formation described above. In addition, in order to improve the adhesiveness of the photosensitive resin pattern 15B and the transparent substrate 2, you may heat-press both.
[0045]
Next, the photosensitive resin pattern 15B is exposed from the transparent substrate 2 side (FIG. 3D). As a result, the photosensitive resin pattern 15B is preferentially cured on the transparent substrate 2 side, and the adhesive strength to the transparent substrate 2 is greatly increased, while the original adhesive strength is maintained on the transfer base sheet 12 side. In this state, the photosensitive resin pattern 15B and the transfer base sheet 12 are bonded. Therefore, by peeling the transfer base sheet 12, the photosensitive resin pattern 15B is transferred onto the transparent substrate 2 to form a blue colored pattern 3B (FIG. 3E). Thereafter, the colored pattern 3B on the transparent substrate 2 is exposed or heated to complete the curing reaction, whereby the formation of the blue colored pattern on the transparent substrate 2 is completed.
[0046]
The exposure of the photosensitive resin pattern 15B from the transparent substrate 2 side as described above can be performed with an exposure amount in a range in which the photocuring reaction of the photosensitive resin pattern 15B does not proceed to the transfer base sheet 12 side. The exposure can be performed at an exposure amount in the range of 2 to 60% of the minimum exposure amount necessary for the photocuring reaction of the photosensitive resin pattern 15B to proceed completely.
[0047]
Even in the above-described blue coloring pattern formation, the tensile elastic modulus is 5 to 300 kN / mm.² Since the transfer substrate sheet in the range is used, the elongation of the transfer substrate sheet 12 due to tension can be made extremely small. Therefore, the photosensitive resin pattern 15B, which is a pattern latent image formed by exposure using the photomask 21B in the second step, can be brought into close contact with the transparent substrate 2 with extremely high accuracy. The blue colored pattern 3B can be formed without causing transfer defects such as color loss.
[0048]
As described in (1) to (3) above, the red coloring pattern 3R is obtained by repeating the first to third steps for three colors of red (R), green (G), and blue (B). The color filter 1 provided with the green coloring pattern 3G and the blue coloring pattern 3B on the transparent substrate 2 can be manufactured.
[0049]
In the present invention, as described above, the tensile elastic modulus is 5 to 300 kN / mm in forming each colored pattern.² Since the transfer substrate sheet in the range is used, elongation of the transfer substrate sheet 12 due to tension can be made extremely small, and a colored pattern can be formed with high accuracy without causing color misregistration or color loss. be able to.
[0050]
Further, in the present invention, in any of the first to third steps, there is no material loss in the coating process such as spin coating, and the wet development process and the cleaning process are unnecessary, and the use efficiency of the material is improved. High and simple process.
[0051]
The exposure in the second and third steps of the present invention can be performed using a known exposure means such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, or a laser.
[0052]
Further, in the above-described color filter manufacturing method, each time a colored pattern of each color is formed on the transparent substrate 2, exposure or heating is performed to complete the curing reaction, but red (R), green (G), blue After all the colored patterns of (B) are formed, the curing reaction may be completed by exposure or heating.
[0053]
In the above-described color filter manufacturing method, the photomasks 21R, 21G, and 21B for the colored patterns for each color are used. However, a photomask for a common colored pattern may be used.
[0054]
Furthermore, it is a matter of course that a black matrix can be formed in advance on the transparent substrate 2 for the color filter, and a colored pattern of each color can be formed on the non-formed portion of the black matrix.
[0055]
Next, materials other than the transfer substrate sheet used in the present invention will be described in detail.
Primer layer
First, the tensile elastic modulus used in the present invention is 5 to 300 kN / mm.² The primer layer that can be formed on the transfer substrate sheet 12 in the range of is described.
[0056]
When the adhesive force between the photosensitive resin layer 14 (14R, 14G, 14B) before pattern exposure and the transfer base sheet 12 is insufficient, or between the photosensitive resin layer 14 after pattern exposure and the transfer base sheet 12 In the case where the adhesive strength is too high, a primer layer may be provided in advance on the transfer base sheet 12 in order to adjust the adhesive strength between the two to an appropriate value. In addition, by providing such a primer layer, the primer layer material can be used even when the surface of the transfer base sheet 12 does not have the surface smoothness necessary for forming the photosensitive resin layer 14. It is also possible to give the transfer substrate sheet 12 the required surface smoothness by coating precisely so as to be smooth.
[0057]
Here, when the exposed portion of the photosensitive resin layer 14 is removed together with the release film 13 from the transfer substrate sheet 12 in the second step, the exposure is performed in order to peel off and remove the primer layer in contact with the photosensitive resin layer 14 together. It is necessary to cut the primer layer along the boundary between the part and the unexposed part. Therefore, it is necessary to select a material with a low cohesive strength in the layer that can be easily cut as the material of the primer layer. However, when such a primer layer is formed, the photosensitive resin pattern 15 (15R, 15G, 15B) formed on the transfer base sheet 12 by peeling development is used as a transparent substrate for color filters in the third step. When transferring to 2, the cohesive force inside the primer layer is low, so that the primer layer adheres to the surface of the colored pattern transferred and formed on the transparent substrate 2 by peeling off the transfer substrate sheet 12 Occurs. Therefore, in order to prevent such an inconvenience, when the exposed portion of the photosensitive resin layer 14 is removed from the transfer base sheet 12 by being cured and bonded to the release film 13, the primer layer is entirely attached to the transfer base sheet 12. It is desirable to keep it.
[0058]
When the primer layer having such performance is provided, the adhesive force between the transfer substrate sheet 12 and the primer layer is the adhesive force between the photosensitive resin layer 14 before and after exposure and the primer layer, and the photosensitive resin layer 14 before and after exposure. It is required that the adhesive strength with the release film 13, the cohesive force of the photosensitive resin layer 14 before and after exposure, and the cohesive force of the primer layer before and after exposure are high.
[0059]
Examples of materials that can be used for such a primer layer include ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene vinyl copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin, polymethacrylate. Acid resin, ethylene methacrylate resin, polyvinyl chloride resin, chlorinated vinyl chloride resin, polyvinyl alcohol, cellulose acetate propionate, cellulose acetate butyrate, nylon 6, nylon 66, nylon 12, polyethylene terephthalate, polybutylene terephthalate, polycarbonate , Polyvinyl acetal, polyether ether ketone, polyether sulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin, phenoxy resin Polyimide resin, polyamideimide resin, polyamic acid resin, polyetherimide resin, phenol resin, urea resin, polyvinyl formal, polyvinylpyrrolidone, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, carboxymethylethylcellulose, ethyl Examples thereof include hydroxyethyl cellulose, bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, and melamine resin.
[0060]
As will be described later, when a photocurable low molecular weight material such as acrylate monomers is blended in the binder of the photosensitive resin layer 14 (14R, 14G, 14B), the acrylate monomer or the like does not diffuse into the primer layer. It is preferable to use such a material. This is because when the acrylate monomer or the like gradually diffuses into the primer layer, the primer material softening temperature, tackiness, cohesive force, adhesion with the photosensitive resin layer 14 (14R, 14G, 14B), or transfer group This is because the possibility of the adhesive force with the material sheet 12 gradually changing along with this increases. Therefore, it is preferable to select a material that does not easily diffuse a photocurable low molecular weight substance such as acrylate monomers. Examples of such materials are water-soluble such as polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, polyvinyl formal, polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl ethyl cellulose, ethyl hydroxyethyl cellulose, etc. Resins can be mentioned. It is also possible to use a mixture of a plurality of these water-soluble resins.
[0061]
Moreover, it is good also as a primer layer which bridge | crosslinked said resin with crosslinking agents, such as an isocyanate type crosslinking agent and a chelate type crosslinking agent. The crosslinking agent can be appropriately selected according to the reactive functional group of the resin to be crosslinked, and can be arbitrarily selected from known ones. As an example of a cross-linking agent, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, an adduct obtained by adding the above diisocyanate to trimethylolpropane , Biurets of the above diisocyanates, trimers of the above diisocyanates, crosslinking agents having epoxy groups, aziridine groups and oxazoline groups, chelating agents having metal atoms such as aluminum, zinc, titanium and zirconium, etc. .
[0062]
When the primer layer is crosslinked as described above, a known catalyst can be added depending on the crosslinking agent to be blended. For example, when isocyanate is used as a crosslinking agent, di-n-butyltin dilaurate, di-n-octyltin dilaurate, tetramethylbutanediamine, N, N, N ′, N′-tetramethyl-1,3 -Butanediamine, 1,4-diaza-bicyclo [2,2,2] octane and the like can be used.
[0063]
In order to form the primer layer on the transfer substrate sheet 12, the surface of the transfer substrate sheet 12 (resin film surface in the case of a bonded body in which a resin film is bonded to a metal steel strip) is as described above. A resin added with necessary additives such as a crosslinking agent and a crosslinking reaction accelerating catalyst as necessary is dissolved in an appropriate organic solvent or water, dissolved in a mixed solvent of an organic solvent and water, or organic The dispersion dispersed in a solvent or water can be applied and dried by means such as a gravure direct coating method, a gravure reverse coating method, a reverse roll coating method, a slide die coating method, or a slit die coating method. Further, when the slide die coating method is used, the primer layer and the photosensitive resin layer 14 can be simultaneously applied and dried.
[0064]
The thickness of the primer layer to be formed can be set in the range of 0.05 to 5 μm, preferably 0.1 to 2 μm. When the thickness of the primer layer is less than 0.05 μm, the coating film strength required for the primer layer cannot be obtained. Moreover, when exceeding 5 micrometers, the problem that it becomes difficult to improve the uniformity of the surface of a coating film will arise.
[0065]
Even when the primer layer is provided on the transfer substrate sheet 12, the release film 13 is heated after the photosensitive resin layer 14 is applied and formed on the transfer substrate sheet 12 provided with the primer layer in the first step. Alternatively, thermocompression bonding can be performed, or after the photosensitive resin layer 14 is applied and applied to the release film 13, the transfer substrate sheet 12 provided with the primer layer can be crimped or thermocompression bonded.
Release sheet
Next, the release sheet 13 used in the present invention will be described. The release sheet 13 has flexibility and does not undergo significant deformation due to tension or pressure. Further, the photosensitive resin layer 14 (14R, 14G, 14B) is exposed to light for exposure with a desired exposure amount. It is necessary to use a permeable material.
[0066]
Specific examples of the release film 13 include polyethylene film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, polypropylene film, polystyrene film, polymethacrylic acid film, polyvinyl chloride film, polyvinyl alcohol film, Polyvinyl butyral film, nylon film, polyether ether ketone film, polysulfone film, polyether sulfone film, polytetrafluoroethylene-perfluoroalkyl vinyl ether film, polyvinyl fluoride film, tetrafluoroethylene-ethylene film, tetrafluoroethylene-hexa Fluoropropylene film, Polychlorotrifluoroethylene film, Polyvinylidene full Ride film, Polyethylene terephthalate film, Polyethylene naphthalate film, Polyester film, Cellulose triacetate film, Polycarbonate film, Polyurethane film, Polyimide film, Polyetherimide film, These resin materials are blended with filler, These resin materials A biaxially stretched film obtained by uniaxially stretching or biaxially stretching the used film, a biaxially stretched film in which the stretching ratio in the width direction is increased from the flow direction using these resin materials, and the flow direction from the width direction using these resin materials. A biaxially stretched film with an increased stretch ratio, a laminate of the same or different types of these films, and the same or different types of resins selected from the raw resin used in these films are coextruded. It can be mentioned composite films created by. Among these films, it is particularly preferable to use a biaxially stretched polyester film.
Photosensitive resin composition
Next, the photosensitive resin composition for forming the photosensitive resin layer 14 (14R, 14G, 14B) in this invention is demonstrated. As the photosensitive resin composition used in the present invention, those containing a curable binder, a non-curable binder, a polymerization initiator, a colorant and the like can be used.
[0067]
(i) curable binder
Specific examples of the curable binder include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acryloyl phosphate, tetrahydrofurfuryl acrylate, Cyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate -Neopentyl glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalate ester neopentyl glycol diacrylate, tripropylene glycol diacrylate, trimethylol propane triacrylate Pentaerythritol triacrylate, dipentaerythritol hexaacrylate, phenol-ethylene oxide modified acrylate, phenol-propylene oxide modified acrylate, N-vinyl-2-pyrrolidone, bisphenol A-ethylene oxide modified diacrylate, penta Erythritol diacrylate monostearate, tetraethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane propylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified triacrylate, trimethylolpropane ethylene oxide modified triacrylate, pentaerythritol pentaacrylate, penta Erythritol hexaacrylate, pentae Acrylate monomers such as sitolitol tetraacrylate, those obtained by substituting acrylate groups of these chemical structures with methacrylate groups, urethane acrylate oligomers in which an acrylate group is bonded to an oligomer having a polyurethane structure, acrylates to oligomers having a polyester structure Polyester acrylate oligomers with bonded groups, epoxy acrylate oligomers with acrylate groups bonded to oligomers with epoxy groups, urethane methacrylate oligomers with methacrylate groups bonded to oligomers with polyurethane structures, and methacrylate groups to oligomers with polyester structures Bonding methacrylate groups to bonded polyester methacrylate oligomers and oligomers with epoxy groups Epoxy methacrylate oligomer, polyurethane acrylate having acrylate group, polyester acrylate having acrylate group, epoxy acrylate resin having acrylate group, polyurethane methacrylate having methacrylate group, polyester methacrylate having methacrylate group, epoxy methacrylate resin having methacrylate group, etc. Can be mentioned. These are examples of curable binders that can be used and are not limited to these.
[0068]
(ii) Non-curable binder
Specific examples of the non-curable binder include ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene vinyl copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin, polymethacrylic acid resin, ethylene. Methacrylic acid resin, polyvinyl chloride resin, chlorinated vinyl chloride, polyvinyl alcohol, cellulose acetate propionate, cellulose acetate butyrate, nylon 6, nylon 66, nylon 12, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl acetal, poly Ether ether ketone, polyether sulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin, phenoxy resin, polyimide resin, poly Midoimido resin, polyamic acid resin, polyether imide resin, phenol resin, and urea resin.
[0069]
Preferably, polymethyl methacrylate resin, polyethyl methacrylate resin, polymethyl methacrylate resin and polyethyl methacrylate resin are used from the viewpoint of compatibility with the curable binder material used together and yellowing against heat. Polymers, phenoxy resins, polycarbonate resins, polystyrene resins, cellulose acetate propionate, cellulose acetate butyrate, ethyl hydroxyethyl cellulose, cellulose triacetate, and the like can be used.
[0070]
Particularly preferably, polymethyl methacrylate resin, polyethyl methacrylate resin, copolymer of polymethyl methacrylate resin and polyethyl methacrylate resin, phenoxy resin, epoxy resin, and modified products thereof can be used. .
[0071]
(iii) Photopolymerization initiator
Examples of the photopolymerization initiator include benzophenone, Michler ketone, N, N′tetramethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-ethylanthraquinone. , Aromatic ketones such as phenanthrene, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, benzoin such as methyl benzoin and ethyl benzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2 -(O-methoxyphenyl) -4,5 Diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-trichloromethyl-5 -Styryl-1,3,4-oxadiazol, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazol, 2-trichloromethyl-5- (p-methoxystyryl) Halomethylthiazole compounds such as -1,3,4-oxadiazol, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4-bis (trichloromethyl) -6 -(1-p-dimethylaminophenyl-1,3butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-S-tri Azine, 2- (naphth-1-yl) -4,6-bistrichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine Halomethyl-S-triazine compounds such as 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1,2-diphenylethane- 1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1 (4-morpholinophenyl) -butanone-1, -Hydroxy-cyclohexyl-phenyl-ketone, Irgacure 369 (Ciba Geigy), Irgacure 651 (Ciba Geigy), Irgacure 907 ( Bagaigi Co., Ltd.), and the like.
[0072]
In order to increase the photocuring reaction rate, it is also possible to use a mixture of these photopolymerization initiators.
[0073]
The addition amount of the photopolymerization initiator is desirably in the range of 0.1 to 10.0% by weight with respect to the total solid content of the photosensitive resin composition. When the addition amount of the photopolymerization initiator is less than 0.1% by weight, it is very difficult to develop the effect as a photopolymerization initiator regardless of the type of the photopolymerization initiator. On the other hand, if it exceeds 10.0% by weight, the reaction rate of photopolymerization becomes very fast, while the degree of photopolymerization initiator causing yellowing of the photosensitive resin layer increases, resulting in light resistance as a color filter. This causes a problem of lowering.
[0074]
(iv) Color pigment
A known pigment or dye can be used as a colorant to be contained in the photosensitive resin composition. When a pigment is used, it is desirable that the average particle size of the particles is 0.4 μm or less. When the average particle size exceeds 0.4 μm, the visible light transmittance of the formed colored pattern becomes extremely low, which impedes practicality as a color filter.
[0075]
Examples of preferred dyes and pigments that can be used as colorants include Victoria Pure Blue BO (C.I. 42595), Auramin (C.I. 41000), Fat Black HB (C.I. 26150), Monolite -Yellow GT (CI Pigment Yellow 12), Permanent Yellow GR (CI Pigment Yellow 17), Permanent Yellow HR (CI Pigment Yellow 83), Permanent Carmine FBB (C Pigment Red 146), Hoster Palm Red ESB (C.I. Pigment Violet 19), Permanent Ruby FBH (C.I. Pigment Red 11), Fastel Pink B. Subra (C.I. Pigment. Red 81), Monastral Fast Blue (CI Pi Mento Blue 15), Monolite First Black B (CI Pigment Black 1), Dolphin Red BPT, Copper Phthalocyanine (Green), Phthalocyanine Blue (Blue), Carbon, etc. .
[0076]
Furthermore, as a preferable pigment for forming a color filter, C.I. I. Pigment red 97, C.I. I. Pigment red 122, 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 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, 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, C.I. I. Pigment yellow 83, C.I. I. And CI Pigment Biolet 23.
[0077]
Further, a system in which a reactive dye described in JP-A-5-119213 is reacted with a binder polymer, and a fluorine-containing phthalocyanine compound described in JP-A-6-107663 is a system excellent in characteristics such as depolarization. Can be used as
[0078]
In addition, when making a photosensitive resin composition contain a coloring agent, in order to improve the dispersibility of a coloring agent, a well-known dispersing agent can be mix | blended suitably.
[0079]
The content ratio of the colorant to the photosensitive resin composition is preferably in the range of 5 to 30% by weight. In addition, a sensitizer, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, a stabilizer, and the like are used as necessary in the photosensitive resin composition.
Transparent substrate for color filter
The transparent substrate 2 for color filter that can be used in the above-described method for producing a color filter of the present invention is not particularly limited. For example, soda lime glass, alkali-free glass substrate, borosilicate glass substrate, quartz glass substrate, silicon substrate, etc. Can be used.
[0080]
Moreover, in order to improve the adhesiveness of the photosensitive resin pattern (colored pattern), the surface treatment can be performed on the transparent substrate surface for the color filter. For the surface treatment for such a purpose, various conventionally known methods can be used. An example thereof is a silane coupling agent. Examples of the silane coupling agent used include vinyltrichlorosilane, vinyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimethoxysilane, and γ-chloropropylmethyldisilane. Ethoxysilane, γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-mercaptopropyltri Methoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxyp Pills methyldimethoxysilane, mention may be made of vinyl tris (beta-methoxyethoxy) silane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, an N- phenyl--γ- aminopropyltrimethoxysilane.
[0081]
【Example】
Next, an Example is shown and this invention is demonstrated further in detail.
[0082]
A photosensitive resin composition for a red coloring pattern having the following composition was prepared.
Photosensitive resin composition for red coloring pattern
・ Polymethyl methacrylate
(Weight average molecular weight 40,000) 15 parts by weight
・ Trimethylolpropane triacrylate: 40 parts by weight
・ Urethane acrylate (M-1600, manufactured by Toagosei Co., Ltd.)
(Viscosity 8000-12000 cps / 50 ° C.) 25 parts by weight
・ Photopolymerization initiator (Irgacure 369 manufactured by Ciba-Geigy) 2 parts by weight
・ Dolphin Red BPT: 20 parts by weight
・ Methyl ethyl ketone: 150 parts by weight
・ Toluene: 150 parts by weight
Moreover, the following seven types of long transfer substrate sheets (A to G) were prepared as transfer substrate sheets. The tensile elastic modulus of each transfer base sheet (A to G) was measured according to JIS K7127 and is shown in Table 1 below.
Transfer base sheet
Transfer substrate sheet A: SUS430 steel strip
(Thickness 100 μm, tensile modulus 200 kN / mm² )
Transfer substrate sheet B: Aluminum steel strip
(Thickness 100 μm, tensile modulus 68 kN / mm² )
Transfer base sheet C: Copper steel strip
(Thickness 100 μm, tensile elastic modulus 117 kN / mm² )
Transfer substrate sheet D: Beryllium steel strip
(Thickness 100 μm, tensile modulus 120 kN / mm² )
Transfer base sheet E: SUS430 steel strip and biaxially stretched polyethylene terephthal
Bonded body with rate (PET) film (thickness 105μm)
(SUS430 / PET = 50 μm / 50 μm)
Transfer substrate sheet F: biaxially stretched polyethylene terephthalate film
(Thickness 100 μm, tensile modulus 2.9 kN / mm² )
Transfer substrate sheet G: Titanium alloy steel strip
(Thickness 200 μm, tensile modulus 320 kN / mm² )
Next, on the transfer substrate sheets (A to G), the above-described red photosensitive resin composition is applied by a gravure reverse coating method and dried to form a photosensitive resin layer (thickness 2.0 μm). A 12 μm-thick release film (biaxially stretched polyethylene terephthalate film) was layered on this photosensitive resin layer, and pressure-bonded with two rolls having a diameter of 100 mm to produce a red composite. (End of the first step)
Next, from the release film side of the red composite, the red photosensitive resin layer was exposed through a photomask (300 mm long × 400 mm wide) having rectangular openings of 270 μm × 80 μm in a predetermined pattern. As the photomask, a mask in which light shielding portions for forming register marks were provided at the four corners and the peripheral part with the same dimensional accuracy as the alignment register included in the following glass substrate was used. In addition, an ultra high pressure mercury lamp was used for this exposure, and the exposure amount was 5% of the minimum exposure amount of 20000 mJ necessary for completely curing the red photosensitive resin layer.
[0083]
Next, the release film is peeled off while holding the composite horizontally, the exposed portion of the photosensitive resin layer is removed together with the release film, and the peel development is performed in which the unexposed portion of the photosensitive resin layer is left on the transfer substrate sheet. The photosensitive resin pattern and the alignment register mark were formed on the transfer substrate sheet. (End of second step)
Next, a glass substrate for color filter (made of borosilicate glass, thickness 1 mm, length 300 mm × width 400 mm) having a matrix-like black matrix (opening 250 μm × 60 μm) formed by chromium vapor deposition and pattern etching and an alignment register. ) Was prepared. The registration mark provided on the glass substrate is the same as the light shielding part for the registration mark of the photomask described above, and has the same dimensional accuracy as the photomask under the temperature conditions at the time of exposure in the second step. . Then, alignment is performed using the alignment registration mark of the glass substrate and the alignment registration mark of the transfer base sheet, and the transfer base sheet is applied while applying a tension (30 N) so that the transfer base sheet is not wrinkled. The photosensitive resin pattern on the material sheet and the glass substrate were overlapped and pressure-bonded (linear pressure 0.1 kgf / cm) with two rolls having a diameter of 100 mm.
[0084]
Next, exposure was performed by irradiating ultraviolet rays using an ultrahigh pressure mercury lamp from the glass substrate side. The exposure amount in this exposure was set to 5% of the minimum exposure amount of 20000 mJ necessary for completely curing the red photosensitive resin pattern.
[0085]
After that, the transfer substrate sheet is peeled off, the red photosensitive resin pattern is transferred onto the glass substrate, and the photocuring reaction is completed by performing exposure by irradiating ultraviolet rays using an ultrahigh pressure mercury lamp from the photosensitive resin pattern side. Color filters (samples 1 to 7) having a red coloring pattern. The exposure amount in this exposure was set to an exposure amount necessary for the solvent resistance of the red colored pattern to tetrahydrofuran to no longer change. (End of step 3)
Regarding the above color filters (samples 1 to 7), the positional deviation width between the register marks formed by chromium vapor deposition on the glass substrate and the register marks transferred and formed together with the red colored pattern at the four corners and the peripheral portion is measured with a microscope. The measurement was shown in Table 1 below, where Z was the largest width value.
[0086]
[Table 1]

As shown in Table 1, the tensile modulus is 5 to 300 kN / mm² The color filters (samples 1 to 5) produced using the transfer base sheets A to E in the range of 1 to 5 were all provided with a highly accurate coloring pattern with a maximum registration mark width Z as small as 10 μm or less. The color filter was confirmed.
[0087]
In contrast, the tensile modulus is 5 kN / mm² The color filter (sample 6) produced using the transfer base sheet F that is less than the maximum has a large shift width Z of the register mark due to the influence of the extension of the transfer base sheet in the third step. It could not be put to practical use. Also, the tensile elastic modulus is 300 kN / mm² The color filter (sample 7) produced using a transfer substrate sheet G exceeding 1 mm is difficult to handle as a long belt-like sheet because the transfer substrate sheet itself is rigid. Matching was very difficult.
[0088]
The photosensitive resin composition for a green color pattern prepared by adding a green colorant (copper phthalocyanine) instead of the red colorant (Irukadin Red BPT) is used for the first step from the first step. Similarly to the formation of the red coloring pattern by the step 3, a green coloring pattern is formed on the same glass substrate, and the maximum deviation width Z of the register mark is measured for the coloring pattern as described above. Results were obtained.
[0089]
Further, using the photosensitive resin composition for a blue coloring pattern prepared by adding a blue coloring agent (phthalocyanine blue) instead of the red coloring agent (Irukadin Red BPT), Similarly to the formation of the red coloring pattern in the step 3, a blue coloring pattern is formed on the same glass substrate, and the maximum deviation width Z of the register mark is measured for the coloring pattern as described above. Results were obtained.
[0090]
【The invention's effect】
As described above in detail, according to the present invention, in the first step, a photosensitive resin layer containing a colorant is formed between the transfer base sheet and the release film, and in the second step, a predetermined photo is formed. The photosensitive resin layer is exposed from the release film side through the mask, and then the release film is peeled off, and the exposed portion of the photosensitive resin layer is removed from the transfer substrate sheet together with the release film, and the unexposed portion of the photosensitive resin layer is removed. Is left on the transfer substrate sheet as a photosensitive resin pattern, and then, in the third step, the transparent substrate for the color filter is aligned and pressure-bonded on the photosensitive resin pattern, and the photosensitive resin is applied from the transparent substrate side. The pattern is exposed, the transfer substrate sheet is peeled off, and the photosensitive resin pattern is transferred onto a transparent substrate to form a colored pattern. In this series of operations, the tensile elastic modulus is 5 to 300 kN / mm.² Since the transfer base sheet in the range is used, the extension of the transfer base sheet due to tension becomes extremely small, and the alignment of the photosensitive resin pattern on the transparent substrate can be performed with high accuracy. A colored pattern can be formed on a transparent substrate with high accuracy, and a high-definition color filter free from color shift or color omission can be produced. In addition, in any of the first to third steps described above, there is no application process such as spin coating on a transparent substrate for a color filter, so there is very little material loss, and no wet development process or cleaning process is required. No waste liquid treatment is required, and the color filter is manufactured by repeating the first to third steps for the required number of colors and forming a colored pattern of the desired number of colors on the transparent substrate. The use efficiency is high and the process is simple, so that the manufacturing cost can be reduced.
[Brief description of the drawings]
FIG. 1 is a process diagram for explaining a method of manufacturing a color filter according to the present invention.
FIG. 2 is a process diagram for explaining a method of manufacturing a color filter according to the present invention.
FIG. 3 is a process diagram for explaining a color filter manufacturing method according to the present invention;
[Explanation of symbols]
1 ... Color filter
2 ... Transparent substrate
3R, 3G, 3B ... coloring pattern
11R, 11G, 11B ... complex
12 ... Transfer base sheet
13 ... Release film
14 (14R, 14G, 14B) ... photosensitive resin layer
15 (15R, 15G, 15B) ... photosensitive resin pattern
21R, 21G, 21B ... Photomask

Claims (5)

A first step of forming a photosensitive resin layer containing a colorant between the release film and a transfer substrate sheet having a tensile elastic modulus in the range of 5 to 300 kN / mm ² ;
Exposing the photosensitive resin layer from the release film side through a predetermined photomask, and then removing the exposed portion of the photosensitive resin layer from the transfer substrate sheet by peeling the release film, A second step of forming a photosensitive resin pattern leaving an unexposed portion of the photosensitive resin layer on the transfer substrate sheet;
A transparent substrate for color filter is aligned and pressure-bonded to the photosensitive resin pattern formed on the transfer base sheet, and the photosensitive resin pattern is exposed from the transparent substrate side, and then the transfer group A third step of peeling the material sheet to transfer the photosensitive resin pattern onto the transparent substrate to form a colored pattern;
Is repeated for the required number of colors to form a colored pattern with a desired number of colors on the transparent substrate.   The method for producing a color filter according to claim 1, wherein the transfer base sheet is a metal steel strip.   The method for producing a color filter according to claim 1, wherein the transfer base sheet is a bonded body of a metal steel strip and a resin film.   The method for manufacturing a color filter according to claim 2 or 3, wherein the metal steel strip is a stainless steel strip. The thickness of the photosensitive resin layer formed in the first step is set to be equal to or greater than the thickness of the photosensitive resin layer in the previous operation every time the required number of colors are repeated, and the thickness difference is set to 10% or less. The method for producing a color filter according to any one of claims 1 to 4, wherein:

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