JP2009235296A - Low polarity prepolymer and photosensitive resin composition containing it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce a polymer having excellent solvent resistance by using a prepolymer having excellent solvent resistance, to provide a printing plate and a printing master plate improved in printing precision and printing durability by using the above polymer, to provide a method for producing a liquid crystal alignment film with high precision, to provide a method for producing a black matrix with high precision, to provide a method for producing a colored layer for a color filter with high precision, and to provide a method for producing a bank with high precision. <P>SOLUTION: The prepolymer for producing a printing plate or printing master plate consists of a repeating unit with a solubility parameter of <20 J<SP>1/2</SP>/cm<SP>3/2</SP>. A photosensitive resin composition for producing a printing plate or printing master plate contains a polymer (a) formed of the prepolymer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a novel polymer excellent in solvent resistance, a prepolymer excellent in solvent resistance and particularly suitable for producing a printing plate or printing original plate, and particularly for the production of a printing plate or printing original plate produced therefrom. The present invention relates to a suitable polymer, a photosensitive resin composition containing the polymer, and a printing original plate or printing plate.
In particular, prepolymers that have excellent durability against various solvents contained in inks for flexographic printing, etc., and contribute to greatly improving printing accuracy and printing durability, and polymers produced therefrom, The present invention relates to a photosensitive resin composition and a printing original plate or printing plate.
The present invention also relates to a method for producing a liquid crystal alignment film, a black matrix, a colored layer for a color filter, and a bank using the printing plate of the present invention having excellent solvent resistance.

In recent years, resin printing plates are often used in the printing field. In particular, a flexographic printing plate is used, and in flexographic printing whose specific gravity is increasing among various printing methods, a resin printing plate is exclusively used.
Various organic solvents are used for printing ink depending on the application. However, when the printing plate is made of resin, the durability to the organic solvent is often insufficient, the printing accuracy is insufficient, or the printing plate itself Problems such as lack of durability occur. Therefore, excellent solvent resistance against various solvents is desired for resin-made printing plates and printing original plates.

[Production method of liquid crystal alignment film]
In order to use a liquid crystal material as a device, it is generally necessary to align (orient) liquid crystals in a certain arrangement. Change. And utilizing the change of the optical property accompanying this is utilized in the field of various electronics.
The alignment control of the liquid crystal is generally performed by forming an alignment film on the substrate surface in contact with the liquid crystal. The alignment film includes a vertical alignment film that aligns the liquid crystal perpendicularly to the substrate or in a direction slightly inclined from the vertical direction, and a horizontal alignment that aligns the liquid crystal horizontally or slightly inclined from the horizontal direction. They are roughly classified into membranes and are used properly depending on the display method. Among these, the horizontal alignment film used in the twisted nematic (TN) mode and the super twisted nematic (STN) mode that has been widely used in the past is particularly important from an industrial point of view. As the horizontal alignment film, a polyimide film subjected to rubbing treatment is excellent in terms of alignment uniformity and reliability, and is widely used.
As a method of printing a liquid crystal alignment film, a glass substrate is often used as a substrate. Therefore, a method using a hard plate such as a metal printing plate such as a gravure printing method is not suitable, and a rubber plate having elasticity. In general, a relief printing method using a photosensitive resin plate (flexographic printing method) is appropriate and is generally used.

Actually, these offset printing methods are described in Patent Documents 1 and 2, for example. Moreover, in patent document 3, the description regarding the manufacturing method of the resin letterpress with a comparatively big dimension is seen corresponding to the market demand accompanying the enlargement of a liquid crystal display device.
A generally used plate for letterpress printing or offset printing is produced by the following method. That is, a plate is produced by a method in which a negative film is placed on the surface of a photosensitive resin applied to a substrate and light such as ultraviolet rays is irradiated from the negative film side. By this method, the photosensitive resin is cured at a location where the light beam has passed through the negative film, while the photosensitive resin is uncured at a location where the light beam is blocked by the negative film. Therefore, after irradiating with a light beam, development is performed, and the uncured photosensitive resin is washed away to obtain a resin relief plate in which the portion of the cured photosensitive resin becomes a convex portion.
In recent years, a thin light-absorbing layer called a black layer has been provided on the surface of the photosensitive resin, and this is irradiated with laser light to form a mask image directly on the photosensitive resin plate, and then light is irradiated through the mask to cause a crosslinking reaction. A so-called flexo CTP (Computer to Plate) technology has been developed in which the non-crosslinked portion of the light non-irradiated portion is washed away with a developing solution, and its adoption is progressing from the effect of improving the efficiency of printing plate making.

[Black matrix manufacturing method]
As a black matrix of a color filter for liquid crystal display, a resin black matrix made of a light shielding material, a resin and a solvent is used. A resin black matrix is formed by dispersing a composition composed of a resin and a light shielding material in an appropriate solvent to prepare a paint, applying the paint to a liquid crystal substrate, and patterning.

Patent Document 4 discloses a resin black matrix in which a pigment such as blue or purple is added as a complementary color pigment in addition to a light shielding material and a resin.
Patent Document 5 discloses a black organic pigment and / or an organic pigment composed of a mixed organic pigment obtained by mixing at least two kinds of organic pigments selected from red, blue, green, purple, yellow, cyanine, and magenta, and making them pseudo black. There has been proposed a resin black matrix comprising a system, at least one light shielding material selected from carbon black, chromium oxide, iron oxide, titanium black, and aniline black and a photosensitive resin.
Patent Document 6 discloses a black pigment characterized in that it is a photopolymerizable compound, a photopolymerization initiator, an alkali-soluble resin, carbon black coated with a resin, and a mixture of at least two kinds of metal oxides. Including black matrix forming materials have been proposed.
Furthermore, Patent Document 7 describes a resin black matrix made of titanium oxynitride and a resin.
Further, Patent Document 8 discloses a resin black matrix made of titan oxynitride particles whose surface is coated with an insulating film and a resin.
Furthermore, Patent Document 9 describes a resin black matrix made of polyimide resin or acrylic resin as a resin and carbon black and titanium oxynitride as a light shielding material.

[Method for producing colored layer for color filter]
In recent years, there has been an increasing demand for higher resolution, lighter weight, lower costs, etc. of input / output elements such as color filter imaging devices and color image display devices, and various elemental technologies that are indispensable for these devices. Development is progressing. In particular, the fundamental change of the image display apparatus is progressing, and a liquid crystal display that is light in weight and takes up little space instead of the conventional mainstream CTR has been rapidly spread.
Although the liquid crystal display is becoming very easy to use, it cannot be said that the price of a large-area display is still low enough, and attempts are being made to reduce the cost by various methods. Examples of such a method include an improvement from an active matrix type liquid crystal having TFTs to individual pixels to a ferroelectric liquid crystal having a switching characteristic of the liquid crystal itself, and an improvement of a simple matrix type STN liquid crystal. There is.
One of the major components of the cost of liquid crystal displays is a color filter that is indispensable for displaying color images. In general, the color filter divides the entire screen into a large number of fine pixels, and further divides one pixel into three parts, which are respectively red (R), green (G), and blue ( A fine optical filter element (about 100 μm or less) that transmits B) is formed. A method to improve color reproducibility by covering each fine filter element with an opaque grid-like mask (black matrix) to prevent blacks from becoming mixed with the adjacent colors is doing. As described above, since the structure of the color filter is quite complicated and fine, it has been accompanied with a big problem to manufacture the color filter with high accuracy and low cost.
Conventionally, as a method for producing a color filter, a process of providing a mordant layer made of a hydrophilic polymer material such as gelatin, casein, mulled or polyvinyl alcohol on a substrate and dyeing the mordant layer with a dye to form a colored layer. A so-called dyeing method in which red, green and blue are repeated is known. In this method, there are many usable dyes, and it is relatively easy to cope with the spectral characteristics required as a filter. However, in the dyeing process of the mordant layer, the mordant layer is immersed in a dye bath in which the dye is dissolved. The wet process is difficult to control. In addition, this method has complicated steps such as providing an anti-dyeing intermediate layer for each color, and using a photolithography process for each color for the mordanting layer and patterning for anti-dyeing, resulting in a long tact time and a high yield. It has the disadvantage of being bad. Further, since the heat resistance and light resistance of the dye used for the dyeing are low, there is a problem in durability of the color filter.

On the other hand, according to the methods disclosed in Patent Documents 10 to 13 and the like, in a so-called pigment dispersion method in which a colored resin film in which a colorant such as a pigment is mixed with a photosensitive resin is used for a color filter layer, the colored resin is used from the beginning. Since a coloring material such as a pigment is included, the step of dyeing after the formation of the color filter layer is unnecessary, and therefore the formation of an intermediate layer for anti-dyeing is also unnecessary, so that the process is simplified by the dyeing method.
The printing method is intended to form fine pixels by a high-precision printing technique such as flat plate offset printing or screen printing. For example, Patent Document 14 has a light shielding film in which a large number of openings are formed at a position where a pixel portion is provided, and a plurality of colored layers having the same number as a plurality of different colors of the pixel portion, The colored layer is formed of a visible light transparent material and has a colored portion colored in the same color at a portion corresponding to the opening of the light shielding film, and each colored layer is colored with a different color of the colored layer. Each of the colored portions is stacked so as not to overlap each other, and each of the colored portions forms a pixel portion in which a plurality of different colors are arranged through the opening of the light shielding film. Has been proposed.
Furthermore, in Patent Document 15, a colored paste prepared by adding a heat-resistant pigment to a polyimide precursor is applied to an opening of a black matrix formed in advance, and after forming a pattern, the polyimide precursor is heated. A method for curing and forming colored layers of red (R), green (R), and blue (B) colors has been proposed.

[About manufacturing methods for banks, etc.]
2. Description of the Related Art An organic EL display device is promising as a display device that replaces a liquid crystal display device in accordance with high image quality and low power consumption of a mobile phone or a portable information terminal. An organic EL element which is a display element used in this organic EL display device has a structure in which a lower electrode (also referred to as a pixel electrode), an organic EL layer, and an upper electrode are sequentially laminated on a substrate made of glass or the like. And emits light by passing a current between the upper electrode and the lower electrode. The organic EL layer may have, for example, a structure having only a light emitting layer, or may have a structure in which one or both of the light emitting layer, the hole transport layer and the electron transport layer are combined.
As a method for forming a light emitting layer or a hole transport layer on a substrate included in an organic EL element, when a low molecular weight material is used, a vacuum deposition method is known, and a high molecular weight material is used. In this case, methods such as a spin coating method, a dip method, a roll coating method, a doctor blade method, and various printing methods are known.
In recent years, an organic EL layer can be efficiently formed for each organic EL element portion (hereinafter abbreviated as “pixel forming portion”) that forms a pixel, and the arrangement (coating) of each organic material that should emit RGB colors. The inkjet method has been attracting attention because it has the advantage of being easily separated (Patent Document 16). Here, when this ink jet method is used, the liquid substance containing the organic material, which is ink ejected from the nozzles of the ink jet head, flows out from the pixel forming portion targeted for landing to the adjacent pixel forming portion. Sometimes. Such outflow occurs because a certain gap (interval) is formed between the inkjet head and the substrate in order to form droplets. That is, when ink is ejected from the nozzles of the inkjet head, the direction (angle) of ink ejection changes due to dirt or the like adhering to the tip of the nozzle, or the flight curve of ink due to the influence of air flow or the like. As a result, the position where the ink droplets land via the gap may deviate from the desired target position.

Further, when an organic EL element is manufactured, the position of the substrate is often mechanically controlled by placing the element on a movable XY table and driving the XY table. Therefore, outflow may occur due to a mechanical alignment error. Generally, the landing position accuracy determined by the ejection accuracy of the inkjet head and the alignment accuracy of the table is a value of about ± 15 to 30 μm. Due to the deviation of the landing position, it becomes difficult to form the organic EL layer with high accuracy at a desired position if the ink jet method is used without adopting a configuration that does not particularly cause the outflow.
Therefore, when an organic EL element is produced, it is water and oil repellency (hereinafter abbreviated as “liquid repellency”).
A method has been proposed in which each pixel formation portion is surrounded by a bank having (Patent Document 17). In this method, a plurality of pixel electrodes are formed by performing predetermined patterning on electrodes formed on a transparent substrate, and then a bank functioning as a partition is formed between adjacent pixel electrodes formed. In this method, an organic EL layer (for example, a charge injection / transport layer and / or a light emitting layer) is formed in a liquid phase in a region surrounded by the bank, and an upper electrode is formed thereon.
Here, the thickness of the bank is generally about 1 to 3 μm, and usually an organic resin material such as polyimide resin, polymethacrylate, novolac resin, etc. is used as the bank material. Photosensitivity is often imparted for ease. Further, the surface of the bank needs to have a small surface free energy relative to the ink in order to impart liquid repellency. In order to impart liquid repellency to the bank surface in this way, for example, a method in which an organic resin, which is a bank material, contains a functional group containing fluorine or an additive containing silicon in advance, or carbon tetrafluoride after patterning is used. A method of performing plasma treatment on the bank surface by using a fluorine-based gas is employed.

Further, the surface of the pixel electrode is imparted with hydrophilic / lipophilic property (hereinafter abbreviated as “lyophilic”), which is a property contrary to the liquid repellency imparted to the bank surface. As a material for the pixel electrode, ITO (Indium Tin Oxide) which becomes a transparent electrode is often used. For example, a UV / O ₃ treatment or an oxygen plasma treatment which is a known cleaning treatment method for the surface of the pixel electrode is used. To remove organic (hydrocarbon) impurities, and as a result, the lyophilicity of the pixel electrode surface can be enhanced. In the case of an organic EL element, the treatment can be expected to increase the ionization potential (work function) on the ITO surface and improve the hole injection efficiency.
As described above, liquid repellency is imparted to the bank surface and lyophilicity is imparted to the pixel electrode surface, so that even if a part of the ink lands on a part of the bank surface, Since the ink thus drawn is drawn into the surface of the pixel electrode having lyophilic properties and is uniformly patterned on the surface of the pixel electrode, the deviation of the landing position can be allowed (compensated) to some extent. According to such a method, as long as the ink does not land on the surface of the adjacent pixel electrode, the adjacent pixel formation portion is not contaminated with other types of ink, and thus color mixing of ink in the pixel formation portion is suppressed. The

JP 2001-91918 A JP-A-6-186551 Japanese Patent No. 3221661 Japanese Patent No. 2861391 Japanese Patent No. 2552391 JP 2000-147240 A JP 2000-143985 A JP 2001-83315 A JP-A-2005-75965 JP-A-55-134807 JP 60-129707 A JP-A-60-237441 JP 61-105505 A Japanese Patent Laid-Open No. 9-80223 JP-A-2005-75965 Japanese Patent Laid-Open No. 10-12377 Japanese Patent Laid-Open No. 11-87062

  In the prior art, regarding the printing plate and the printing original plate, the relationship between the structure of the constituent polymer and the solvent resistance has not been studied, and the improvement of the solvent resistance has not been achieved. Furthermore, in the prior art, the compatibility between the solvent resistance of the printing plate and the laser engraving property has not been achieved.

[Method for producing liquid crystal alignment film]

Since the general technique as disclosed in Patent Documents 14 to 16 is a method using photolithography for forming a pattern through exposure and development processes, there is a problem in the efficiency of printing plate making. Further, in this method, unevenness in the thickness of the plate due to cupping that the thickness of the central portion of the photocured pattern becomes thin occurs due to curing shrinkage in the exposure process and extraction into an uncured component developer in the development process. In addition, there is a problem of plate warpage in which the outer periphery of the plate is warped. Furthermore, when a printing plate with low thickness accuracy is used, the film thickness of the pattern obtained by printing becomes non-uniform, and the performance of the liquid crystal alignment film obtained and the liquid crystal display device using the same becomes non-uniform. It was.
The flexo CTP technology also has a limited efficiency improvement effect, such as the development process remaining, and there is a need to develop a technology that forms a relief image directly on the printing original plate using a laser and does not require development. It was. As the method, a method of engraving a printing original plate directly with a laser can be mentioned. Producing letterpress printing plates and stamps by this method has already been performed, and the materials used therefor have also been known. However, conventional printing plates using laser engraving do not have sufficient resistance depending on the type of printing liquid such as alignment film liquid used, and the printing liquid contains the patterned cured resin layer of the printing plate as printing continues. It has been pointed out that it swells by absorbing the components.

[Black matrix manufacturing method]
In Patent Documents 17 to 22, a black matrix is formed by patterning a coating film obtained by coating a black matrix coating composition using a method such as photolithography. That is, when the resin is a non-photosensitive resin, a photoresist film is formed thereon, and when the resin is a photosensitive resin, the resin is left as it is or an oxygen blocking film is formed. Later, exposure, development, and cleaning were performed to obtain a desired pattern, so that a great problem was left in terms of production efficiency.
On the other hand, an attempt has been made to directly form a black matrix coating composition by a printing method. According to this method, a black matrix can be formed with high efficiency. However, the substrate to be printed forming the black matrix is often a material that is easily damaged, such as glass, and a hard printing plate made of metal or the like is basically unusable. In that respect, a flexographic printing plate characterized by being a flexible plate is suitable, but conventional flexographic printing plate materials do not have sufficient resistance to the solvent used in the coating composition for black matrix. However, there is a problem that the ink swells while printing is continued and an accurate black matrix cannot be formed.

[Method for producing colored layer for color filter]
The patterning of the colored layer disclosed in Patent Documents 23 to 26 and the like still requires the use of a photolithography process for each of the three colors. However, there were drawbacks such as wasteful use of materials.
Various methods for forming a color filter by a simpler method instead of such a complicated method have been proposed. For example, the electrodeposition method using electrodeposition coating is one of them, but in the electrodeposition method, a transparent electrode is required only for electrodeposition of the coloring material, and the shape of the filter pixel is also required because the electrode is used. There were still problems for cost reduction and high definition due to restrictions.
According to the method disclosed in Patent Document 27, when manufacturing red (R), green (G), and blue (B) color filters,
(1) A step of applying a first colored layer made of a visible light transparent material on a light-shielding film of a transparent substrate. (2) A region other than a region that becomes a pixel of a first color (for example, R) of the colored layer. Step of curing to form a coloring prevention region (3) Supplying a coloring agent of the first color (R) by printing to a region to be a pixel of the first color (R) and coloring the colored portion Step of forming (4) Step of curing the colored first colored layer In the same manner, it is necessary to form the second and third colored layers. The number of steps is large, and improvement is required in terms of efficiency. Met.
Also in the method disclosed in Patent Document 28, pattern formation is performed by photolithography, and exposure, development, and washing are performed after applying a photosensitive resin to obtain a desired pattern. There was a big problem.
On the other hand, attempts have been made to directly form a color filter by a printing method. According to this method, a color filter can be formed with high efficiency. However, the substrate to be printed on which the color filter is formed is often a material that is easily damaged, such as glass, and a hard printing plate made of metal is basically unusable. In that respect, a flexographic printing plate characterized by being a flexible plate is suitable, but a conventional flexographic printing plate material does not have sufficient resistance to the solvent used in the ink for forming the color filter. There has been a problem that it swells as printing continues and an accurate pattern cannot be formed, and a solution to this problem has been strongly desired.
[About manufacturing methods for banks, etc.]
In the conventional method using a bank as disclosed in Patent Document 39, a method of patterning a bank uses a photoresist process. Therefore, after applying a photosensitive resin, exposure, development, and cleaning are performed. It is necessary to perform desired patterning, and it has been desired to develop a method for manufacturing a bank efficiently.

The present invention produces a polymer having excellent solvent resistance by using a prepolymer having excellent solvent resistance, and further provides a printing plate and printing original plate having improved printing accuracy and printing durability. For the purpose.
The present invention also provides a method for producing a liquid crystal alignment film with high accuracy, a method for producing a black matrix with high accuracy, and a method for producing a colored layer for a color filter with high accuracy. It is another object of the present invention to provide a method for manufacturing a bank with high accuracy.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have excellent durability against various types of solvents in which prepolymers having a specific structure and polymers produced from the prepolymers are used in inks and the like. Furthermore, the present inventors have found that printing plates and printing original plates produced from photosensitive resin compositions containing these polymers have significantly improved printing accuracy and printing durability, and have completed the present invention.
In addition, the present inventors can produce a liquid crystal alignment film with high accuracy, can produce a black matrix with high accuracy, and produce a colored layer for a color filter with high accuracy by using the printing plate having excellent solvent resistance. It was found that the bank can be manufactured with high accuracy, and the present invention has been completed.

（式中、Ｒ_ｐは、各々独立して、請求項１記載のプレポリマーから両末端活性水素基を除いた残基を表し、Ｒ_ｑは、ジイソシアナート化合物からイソシアナート基を除いた残基を表し、Ｒ_ｒは、イソシアナトアルキルアクリレート及び／又はイソシアナトアルキルメタクリレートのアルキル部分を表し、Ｒ_Ｓ、Ｒ_Ｔは、各々独立して、メチル基又は水素原子を表し、Ｌは、１以上の整数を表す。）
［６］ 請求項１記載のプレポリマーと、該プレポリマーの末端活性水素基の当量未満のイソシアナート基当量のポリイソシアナート化合物と、イソシアネートアルキルアクリレート及び／又はイソシアネートアルキルメタクリレートと、を反応させることを含む、請求項１〜５のいずれか一項に記載のポリマーの製造方法。
［７］ 溶解度パラメーターが２０Ｊ^１／２／ｃｍ^３／２未満の繰り返し単位からなる印刷版又は印刷原版製造用プレポリマー。
［８］ 数平均分子量が３００〜５０，０００である、請求項７に記載の印刷版又は印刷原版製造用プレポリマー。
［９］ 請求項７又は８に記載のプレポリマーと、該プレポリマーの末端水酸基の当量を超えるイソシアナート基当量のポリイソシアナート化合物と、が共有結合により重合して得られる印刷版又は印刷版製造用ポリマーであって、
該重合しているポリイソシアナート化合物の残存するイソシアナート基と、ヒドロキシアルキルアクリレート及び／又はヒドロキシアルキルメタクリレートと、がウレタン結合により結合している上記ポリマー。
［１０］ 前記ポリイソシアナート化合物がジイソシアナート化合物である、請求項９に記載のポリマー。
［１１］ 前記ポリイソシアナート化合物が芳香族ジイソシアナートである、請求項９又は１０に記載のポリマー。
［１２］ 下記式（２）で表される請求項９〜１１のいずれか一項に記載のポリマー。

（式中、Ｒ_ｐは、各々独立して、請求項１記載のプレポリマーから両末端活性水素基を除いた残基を表し、Ｒ_ｑは、ジイソシアナート化合物からイソシアナート基を除いた残基を表し、Ｒ_ｕは、ヒドロキシアルキルアクリレート及び／又はヒドロキシアルキルメタクリレートのアルキル部分を表し、Ｒ_Ｓ、Ｒ_Ｔは、各々独立して、メチル基又は水素原子を表し、ｍは、１以上の任意の整数を表す。）
［１３］ 請求項７又は８に記載のプレポリマーと、該プレポリマーの末端活性水素基の当量を超えるイソシアナート基当量のポリイソシアナート化合物と、ヒドロキシアルキルアクリレート及び／又はヒドロキシアルキルメタクリレートと、を反応させることを含む、請求項９〜１２のいずれか一項に記載のポリマーの製造方法。
［１４］ 請求項７又は８に記載のプレポリマーから製造されるポリマー（ａ）を含む印刷版又は印刷原版製造用感光性樹脂組成物。
［１５］ 前記ポリマー（ａ）が、前記プレポリマーの末端活性水素基と他の化合物との間で形成された共有結合を有するポリマーであって、重合性不飽和基を含むポリマーである、請求項１４に記載の感光性樹脂組成物。
［１６］ 前記共有結合がウレタン結合である、請求項１５に記載の感光性樹脂組成物。
［１７］ 前記重合性不飽和基が二重結合である、請求項１５又は１６に記載の感光性樹脂組成物。
［１８］ 前記ポリマー（ａ）が、請求項１〜５及び９〜１２のいずれか一項に記載のポリマーである、請求項１４〜１７のいずれか一項に記載の感光性樹脂組成物。
［１９］ 前記ポリマー（ａ）の数平均分子量が１，０００〜１００，０００である、請求項１４〜１８のいずれか一項に記載の感光性樹脂組成物。
［２０］ 重合性不飽和基を有し、数平均分子量が５，０００未満である有機化合物（ｂ）をさらに含む、請求項１４〜１９のいずれか一項に記載の感光性樹脂組成物。
［２１］ 無機系微粒子（ｃ）をさらに含む、請求項１４〜２０のいずれか一項に記載の感光性樹脂組成物。
［２２］ 光重合開始剤（ｄ）をさらに含む、請求項１４〜２１のいずれか一項に記載の感光性樹脂組成物。
［２３］ ポリマー（ａ）が、請求項７又は８に記載のプレポリマーと、芳香族ジイソシアナートとから製造された付加重合物を含有する、請求項１４〜２２のいずれか一項に記載の感光性樹脂組成物。
［２４］ レーザー彫刻用印刷原版製造用である、請求項１４〜２３のいずれか一項に記載の感光性樹脂組成物。
［２５］ 請求項７又は８のいずれかに記載のプレポリマーから製造されるポリマー（ａ）を含む印刷版又は印刷原版。
［２６］ 請求項１４〜２４のいずれか一項に記載の感光性樹脂組成物を用いて製造される印刷版又は印刷原版。
［２７］ 請求項１４〜２４のいずれか一項に記載の感光性樹脂組成物をシート状又は円筒状に成形する工程と、
該成形した感光性樹脂組成物を光又は電子線の照射により架橋硬化せしめる工程と、
を含む方法によって製造される印刷版又は印刷原版。
［２８］ レーザー彫刻用である、請求項２５〜２７のいずれか一項に記載の印刷版又は印刷原版。
［２９］ フレキソ印刷版又はフレキソ印刷原版である、請求項２５〜２８のいずれか一項に記載の印刷版又は印刷原版。
［３０］ 印刷版上の液晶配向膜液を被印刷基板上に転写し、転写された前記液晶配向膜液中の溶剤を乾燥除去し、該被印刷基板上に該液晶配向膜液を固定化することを含む液晶配向膜を製造する方法であって、
前記印刷版が、請求項２５〜２９のいずれか一項に記載の印刷版である、上記方法。
［３１］ 印刷版上のブラックマトリックス用被膜組成物を被印刷基板上に転写し、転写された該ブラックマトリックス用被膜組成物中の溶剤を乾燥除去して、又は転写された該ブラックマトリックス用被膜組成物に光を照射して硬化させて、該被印刷基板上に該ブラックマトリックス用被膜組成物を固定化することを含むブラックマトリックスを製造する方法であって、
該印刷版が、請求項２５〜２９のいずれか一項に記載の印刷版である、上記方法。
［３２］ 印刷版上の着色層用インクを被印刷基板上に転写し、転写された前記着色層用インク中の溶剤を乾燥除去して、又は転写された前記着色層用インクに光を照射して硬化させて、該被印刷基板上に該着色層用インクを固定化することを含むカラーフィルター用着色層を製造する方法であって、
該印刷版が、請求項２５〜２９のいずれか一項に記載の印刷版である、上記方法。
［３３］ 印刷版上のバンク形成用組成物を被印刷基板上に転写し、転写された該バンク形成用組成物中の溶剤を乾燥除去して、又は転写された前記バンク形成用組成物に光を照射して硬化させて、該被印刷基板上に該バンク形成用組成物を固定化することを含むバンクを製造する方法であって、
該印刷版が、請求項２５〜２９のいずれか一項に記載の印刷版である、上記方法。 That is, the present invention relates to a prepolymer having the following specific structures [1] to [33], a polymer produced from the prepolymer, a printing plate produced from a photosensitive resin composition containing the polymer, and The present invention relates to a method for producing a printing original plate and a liquid crystal alignment film.
[1] Prepolymer having a solubility parameter of a repeating unit of less than 20 J ^1/2 / cm ^3/2 and having active hydrogen groups at both ends, and an isocyanate group having an equivalent amount of terminal active hydrogen groups of the prepolymer An equivalent polyisocyanate compound and a polymer obtained by polymerization by covalent bond,
The above polymer in which the terminal active hydrogen group remaining in the polymerized prepolymer is bonded to the isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate by a covalent bond.
[2] The polymer according to claim 1, wherein the number average molecular weight of the prepolymer is 300 to 50,000.
[3] The polymer according to claim 1 or 2, wherein the polyisocyanate compound is a diisocyanate compound.
[4] The polymer according to any one of claims 1 to 3, wherein the polyisocyanate compound is an aromatic diisocyanate.
[5] The polymer according to any one of claims 1 to 4, which is represented by the following formula (1).

(Wherein R _p each independently represents a residue obtained by removing the active hydrogen groups at both ends from the prepolymer according to claim 1, and R _q represents a residue obtained by removing the isocyanate group from the diisocyanate compound. R _r represents an alkyl moiety of isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate, R _S and R _T each independently represents a methyl group or a hydrogen atom, and L represents 1 or more Represents an integer.)
[6] reacting the prepolymer according to claim 1, a polyisocyanate compound having an isocyanate group equivalent less than the equivalent of the terminal active hydrogen group of the prepolymer, and an isocyanate alkyl acrylate and / or an isocyanate alkyl methacrylate. The manufacturing method of the polymer as described in any one of Claims 1-5 containing these.
[7] A prepolymer for producing a printing plate or printing plate precursor comprising a repeating unit having a solubility parameter of less than 20 J ^1/2 / cm ^3/2 .
[8] The prepolymer for producing a printing plate or printing original plate according to claim 7, wherein the number average molecular weight is 300 to 50,000.
[9] A printing plate or printing plate obtained by polymerizing the prepolymer according to claim 7 or 8 and a polyisocyanate compound having an isocyanate group equivalent equivalent to the terminal hydroxyl group equivalent of the prepolymer by a covalent bond A production polymer comprising:
The above polymer in which the remaining isocyanate group of the polymerized polyisocyanate compound and hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate are bonded by a urethane bond.
[10] The polymer according to claim 9, wherein the polyisocyanate compound is a diisocyanate compound.
[11] The polymer according to claim 9 or 10, wherein the polyisocyanate compound is an aromatic diisocyanate.
[12] The polymer according to any one of claims 9 to 11 represented by the following formula (2).

(Wherein R _p each independently represents a residue obtained by removing the active hydrogen groups at both ends from the prepolymer according to claim 1, and R _q represents a residue obtained by removing the isocyanate group from the diisocyanate compound. R _u represents an alkyl moiety of hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate, R _S and R _T each independently represents a methyl group or a hydrogen atom, and m is one or more arbitrary Represents an integer.)
[13] The prepolymer according to claim 7 or 8, a polyisocyanate compound having an isocyanate group equivalent equivalent to the terminal active hydrogen group equivalent of the prepolymer, and a hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate. The manufacturing method of the polymer as described in any one of Claims 9-12 including making it react.
[14] A photosensitive resin composition for producing a printing plate or printing original plate comprising the polymer (a) produced from the prepolymer according to claim 7 or 8.
[15] The polymer (a) is a polymer having a covalent bond formed between a terminal active hydrogen group of the prepolymer and another compound, and a polymer containing a polymerizable unsaturated group. Item 15. A photosensitive resin composition according to Item 14.
[16] The photosensitive resin composition according to claim 15, wherein the covalent bond is a urethane bond.
[17] The photosensitive resin composition according to claim 15 or 16, wherein the polymerizable unsaturated group is a double bond.
[18] The photosensitive resin composition according to any one of claims 14 to 17, wherein the polymer (a) is the polymer according to any one of claims 1 to 5 and 9 to 12.
[19] The photosensitive resin composition according to any one of claims 14 to 18, wherein the polymer (a) has a number average molecular weight of 1,000 to 100,000.
[20] The photosensitive resin composition according to any one of claims 14 to 19, further comprising an organic compound (b) having a polymerizable unsaturated group and having a number average molecular weight of less than 5,000.
[21] The photosensitive resin composition according to any one of claims 14 to 20, further comprising inorganic fine particles (c).
[22] The photosensitive resin composition according to any one of claims 14 to 21, further comprising a photopolymerization initiator (d).
[23] The polymer (a) according to any one of claims 14 to 22, comprising an addition polymer produced from the prepolymer according to claim 7 or 8 and an aromatic diisocyanate. Photosensitive resin composition.
[24] The photosensitive resin composition according to any one of claims 14 to 23, which is used for producing a printing original plate for laser engraving.
[25] A printing plate or printing original plate containing the polymer (a) produced from the prepolymer according to any one of claims 7 and 8.
[26] A printing plate or printing original plate produced using the photosensitive resin composition according to any one of claims 14 to 24.
[27] A step of molding the photosensitive resin composition according to any one of claims 14 to 24 into a sheet shape or a cylindrical shape;
A step of crosslinking and curing the molded photosensitive resin composition by irradiation with light or an electron beam;
A printing plate or printing original plate produced by a method comprising:
[28] The printing plate or printing original plate according to any one of claims 25 to 27, which is for laser engraving.
[29] The printing plate or printing original plate according to any one of claims 25 to 28, which is a flexographic printing plate or a flexographic printing original plate.
[30] The liquid crystal alignment film liquid on the printing plate is transferred onto the substrate to be printed, the solvent in the transferred liquid crystal alignment film liquid is removed by drying, and the liquid crystal alignment film liquid is fixed on the substrate to be printed. A method for producing a liquid crystal alignment film comprising:
30. The method of claim 25, wherein the printing plate is a printing plate according to any one of claims 25-29.
[31] The black matrix coating composition on the printing plate is transferred onto a substrate to be printed, and the solvent in the transferred black matrix coating composition is removed by drying or transferred. A method for producing a black matrix, comprising: curing a composition by irradiating light to fix the black matrix coating composition on the substrate to be printed,
30. The method as described above, wherein the printing plate is the printing plate according to any one of claims 25 to 29.
[32] The colored layer ink on the printing plate is transferred onto the substrate to be printed, the solvent in the transferred colored layer ink is dried and removed, or the transferred colored layer ink is irradiated with light. A method for producing a colored layer for a color filter comprising fixing the colored layer ink on the substrate to be printed,
30. The method as described above, wherein the printing plate is the printing plate according to any one of claims 25 to 29.
[33] The bank-forming composition on the printing plate is transferred onto a substrate to be printed, and the solvent in the transferred bank-forming composition is removed by drying or transferred to the bank-forming composition. A method for producing a bank, comprising curing by irradiation with light, and immobilizing the bank-forming composition on the substrate to be printed,
30. The method as described above, wherein the printing plate is the printing plate according to any one of claims 25 to 29.

According to the present invention, a prepolymer or a polymer excellent in solvent resistance can be provided. By using this prepolymer or polymer, it is possible to provide a printing plate or printing original plate that has excellent durability with respect to various solvents contained in the ink and has greatly improved printing accuracy and printing durability. It becomes possible.
Further, according to the present invention, it is possible to provide an excellent printing plate or printing original plate that gives a high-quality printed matter even in printing with water-based ink.
Furthermore, according to the manufacturing method of the present invention, it is possible to efficiently manufacture a liquid crystal alignment film having a uniform film thickness, to provide a liquid crystal display device including the liquid crystal alignment film, to manufacture a black matrix with high accuracy, It is possible to manufacture a colored layer for a color filter with high accuracy and to manufacture a bank with high accuracy.

  Hereinafter, the best mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. However, the present embodiment is not limited to the following embodiment, and various modifications can be made within the scope of the gist.

The prepolymer of this embodiment will be described.
In the prepolymer of the present embodiment, it is essential that the solubility parameter of the repeating unit is less than 20 J ^1/2 / cm ^{3/2 and} that there are active hydrogen groups at both ends. It is used for manufacturing.
In order to develop excellent solvent resistance with respect to various solvents, it is necessary that the solubility parameter of the repeating unit of the prepolymer is less than 20 J ^1/2 / cm ^3/2 . Preferably, it is less than 20 J ^1/2 / cm ^3/2 and 10 J ^1/2 / cm ^3/2 or more. If it is less than 10 J ^1/2 / cm ^3/2 , industrial production of the prepolymer becomes difficult.
In the present invention, the solubility parameter of the repeating unit of the prepolymer is a value calculated by Fedor's estimation method (Hideki Kobayashi, “SP Value Basics / Applications and Calculation Methods” (Information Mechanism), p. 66) (δ [J ^1/2 / cm ^3/2 ], that is, for each functional group constituting the repeating unit of the prepolymer, the sum of the cohesive energy density (ΣE _coh [J / mol]) and the sum of the molar molecular volume (ΣV [Cm ³ / mol]) is obtained, and δ = (ΣE _coh / ΣV) ^1/2 is obtained.
The prepolymer of the present invention is not limited in its structure as long as the solubility parameter of the repeating unit is less than 20 J ^1/2 / cm ^3/2 . For example, polyolefin polyether etc. are mentioned. Moreover, any of aliphatic, aromatic, linear, and branched may be sufficient. From the viewpoint of ease of industrial production, polyolefin is preferred. In the present invention, it is an essential requirement that the solubility parameter of the repeating unit of the prepolymer is less than 20 J ^1/2 / cm ^3/2 , but 19.5 J ^1/2 / cm ³ or less from the viewpoint of solvent resistance. It is more preferable that it is 19.0 J ^1/2 / cm ³ or less.
It is essential for the prepolymer of the present invention to have both terminal active hydrogen groups. The active hydrogen group is not limited, and examples thereof include a hydroxyl group, a carboxyl group, an amino group, and a thiol group. From the viewpoint of reactivity with isocyanate, a hydroxyl group, a carboxyl group, and an amino group are preferable, and a hydroxyl group or a hydroxyl group is most preferable. It is a carboxyl group.

The prepolymer preferably has a number average molecular weight of 300 to 50,000. The number average molecular weight is preferably 300 or more from the viewpoint of solvent resistance. When the number average molecular weight is 50,000 or less, industrial production of the prepolymer can be favorably performed.
Next, the polymer (a) of the present embodiment produced from the prepolymer will be described.
The polymer (a) of the present embodiment is not particularly limited as long as it is produced from the prepolymer, but it involves the formation of a covalent bond between the terminal active hydrogen group of the prepolymer and another compound. It is preferably a polymer to be produced and a polymer containing a polymerizable unsaturated group. The type of the covalent bond and the polymerizable unsaturated group is not particularly limited, but the covalent bond is preferably a urethane bond, and the polymerizable unsaturated group is a double bond that can participate in radical polymerization or addition polymerization. preferable. In producing the printing plate or printing original plate, since the polymer (a) can be linked to various molecules, the polymer (a) preferably has a polymerizable unsaturated group.

  The polymer (a) preferably has a number average molecular weight of 1,000 to 100,000. The number average molecular weight is preferably 1,000 or more from the viewpoint of solvent resistance. The number average molecular weight is preferably 100,000 or less from the viewpoint of ease of production.

  As the polymer (a), a prepolymer, a polymer produced by reacting a polyisocyanate compound and an isocyanato (meth) alkyl acrylate, or a prepolymer, a polyisocyanate compound and a hydroxy (meth) alkyl acrylate are reacted. Preferably, the polymer is a polymer having a polymerizable unsaturated group such as a (meth) acryl group.

A preferred first example of the polymer (a) is a prepolymer having a solubility parameter of a repeating unit of less than 20 J ^1/2 cm ^3/2 and having active hydrogen groups at both ends, and the terminal hydroxyl groups of the prepolymer. Less than equivalent isocyanate group equivalent polyisocyanate compound is polymerized, and the remaining terminal active hydrogen group of the polymerized prepolymer is combined with isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate. The polymer which has been mentioned.

  The polymer (a) of the first example comprises a terminal active hydrogen group of the prepolymer, an isocyanate group equivalent polyisocyanate compound less than an equivalent amount of the terminal active hydrogen group of the prepolymer, an isocyanate alkyl acrylate, and It is produced by reacting with / or isocyanatoalkyl methacrylate.

  The polyisocyanate compound in the present embodiment is not limited as long as it is a compound having two or more isocyanate groups in one molecule. For example, when a diisocyanate compound is illustrated, as an aromatic diisocyanate, , Diphenylmethane diisocyanate, tolylene diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, etc .; aliphatic or cycloaliphatic diisocyanate As hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate And the like. Examples of triisocyanate compounds include triphenylmethane triisocyanate and tri (isocyanatophenyl) triphosphate. Examples of polyfunctional polyisocyanate compounds include polymeric (diphenylmethane diisocyanate). From the viewpoint of solvent resistance of the printing plate or printing original plate, a diisocyanate compound is preferable, an aromatic diisocyanate is more preferable, and tolylene diisocyanate is more preferable.

  The isocyanate group equivalent less than the equivalent of the terminal active hydrogen group of the prepolymer means that the equivalent (mol) of the isocyanate group of the polyisocyanate compound is less than the equivalent (mol) of the terminal active hydrogen group of the prepolymer. means. The isocyanate group equivalent is not limited as long as it is less than the equivalent of the terminal active hydrogen group of the prepolymer, but it is preferably 50 to 95% equivalent of the equivalent of the terminal active hydrogen group of the prepolymer, and preferably 60 to 90 It is more preferable that it is% equivalent.

  As the isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate, for example, a compound in which the alkyl portion in the acrylate compound is an alkylene group having 2 to 10 carbon atoms is preferable, and an alkylene group having 2 or 3 carbon atoms is preferable. Compounds are more preferred. Specific examples of isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate include isocyanatoethyl (meth) acrylate and isocyanatopropyl (meth) acrylate.

  Among such polymers (a), a polymer represented by the following formula (1) is preferable because it exhibits extremely excellent solvent resistance.

（式中、Ｒ_ｐは、各々独立して、前記プレポリマーから両末端活性水素基を除いた残基を表し、Ｒ_ｑは、ジイソシアナート化合物からイソシアナート基を除いた残基を表し、Ｒ_ｒは、イソシアナトアルキルアクリレート及び／又はイソシアナトアルキルメタクリレートのアルキル部分を表し、Ｒ_Ｓ、Ｒ_Ｔは、各々独立して、メチル基又は水素原子を表し、Ｌは、１以上の整数を表す。）

(Wherein, R _p each independently represents a residue obtained by removing the active hydrogen groups at both ends from the prepolymer, R _q represents a residue obtained by removing the isocyanate group from the diisocyanate compound, R _r represents an alkyl moiety of isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate, R _S and R _T each independently represent a methyl group or a hydrogen atom, and L represents an integer of 1 or more. .)

A preferred second example of the polymer (a) is a prepolymer having a repeating unit solubility parameter of less than 20 J ^1/2 / cm ^3/2 and having active hydrogen groups at both ends, and the terminal activity of the prepolymer. A polyisocyanate compound having an equivalent amount of hydrogen group is polymerized, and the remaining isocyanate group of the polymerized polyisocyanate compound and hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate are bonded by a urethane bond. Polymer.

  The polymer (a) of the second example comprises a terminal active hydrogen group of the prepolymer, an isocyanate group equivalent polyisocyanate compound that exceeds the equivalent of the terminal active hydrogen group of the prepolymer, a hydroxyalkyl acrylate, and / or Alternatively, it is produced by reacting with hydroxyalkyl methacrylate.

  The polyisocyanate compound in the present embodiment is not limited as long as it is a compound having two or more isocyanate groups in one molecule. For example, when a diisocyanate compound is illustrated, as an aromatic diisocyanate, , Diphenylmethane diisocyanate, tolylene diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, etc .; aliphatic or cycloaliphatic diisocyanate As hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate And the like. Examples of triisocyanate compounds include triphenylmethane triisocyanate and tri (isocyanatophenyl) triphosphate. Examples of polyfunctional polyisocyanate compounds include polymeric (diphenylmethane diisocyanate). From the viewpoint of solvent resistance of the printing plate or printing original plate, a diisocyanate compound is preferable, an aromatic diisocyanate is more preferable, and tolylene diisocyanate is more preferable.

  The isocyanate group equivalent exceeding the equivalent of the terminal active hydrogen group of the prepolymer means that the equivalent (mol) of the isocyanate group of the polyisocyanate compound exceeds the equivalent (mol) of the terminal active hydrogen group of the prepolymer. To do. The isocyanate group equivalent is not limited as long as it exceeds the equivalent of the terminal active hydrogen group of the prepolymer, but it is preferably 105 to 150% equivalent of the equivalent of the terminal active hydrogen group of the prepolymer. More preferably, it is 140% equivalent.

  As the hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate, for example, a compound in which the alkyl moiety in the acrylate compound is an alkylene group having 2 to 10 carbon atoms is preferable, and a compound having an alkylene group having 2 or 3 carbon atoms is preferable. More preferred. Specific examples of hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.

  Among such polymers (a), a polymer represented by the following formula (2) is preferable because it exhibits extremely excellent solvent resistance.

（式中、Ｒ_ｐは、各々独立して、前記プレポリマーから両末端活性水素基を除いた残基を表し、Ｒ_ｑは、ジイソシアナート化合物からイソシアナート基を除いた残基を表し、Ｒ_ｕは、ヒドロキシアルキルアクリレート及び／又はヒドロキシアルキルメタクリレートのアルキル部分を表し、Ｒ_Ｓ、Ｒ_Ｔは、各々独立して、メチル基又は水素原子を表し、ｍは、１以上の任意の整数を表す。）

(Wherein, R _p independently represents a residue obtained by removing the active hydrogen groups at both ends from the prepolymer, R _q represents a residue obtained by removing the isocyanate group from the diisocyanate compound, R _u represents an alkyl moiety of hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate, R _S and R _T each independently represents a methyl group or a hydrogen atom, and m represents an arbitrary integer of 1 or more. .)

In the above formulas (1) and (2), R _q is, for example, diphenylmethane diisocyanate, tolylene diisocyanate, tetramethylxylylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, tolidine diisocyanate. Aromatic diisocyanates such as p-phenylene diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate Examples include residues obtained by removing isocyanate groups from aliphatic or cycloaliphatic diisocyanates such as natates, among which residues obtained by removing isocyanate groups from aromatic diisocyanates are preferred. Most preferably, it is a residue obtained by removing the isocyanate group from tolylene diisocyanate.

In the formula (1) and the formula (2), R _{r and} R _u are preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 5 carbon atoms, still more preferably, It is an ethylene group or a propylene group, more preferably an ethylene group.

The method for producing the polymer (a) is not particularly limited. For example, the polymer (a) can be produced by the following method. The prepolymer, a polyisocyanate compound having an isocyanate group equivalent less than the equivalent of the terminal hydroxyl group of the prepolymer (having a hydroxyl group as a terminal active hydrogen group), and the urethanization catalyst at 50 to 90 ° C. for 1 to 5 hours After making it react, a polymer (a) can be manufactured by adding an isocyanatoalkyl (meth) acrylate and a urethanization catalyst, and making it react at 50-90 degreeC for 1 to 5 hours.
Further, the prepolymer, a polyisocyanate compound having an isocyanate group equivalent equivalent to the equivalent of the terminal hydroxyl group of the prepolymer (having a hydroxyl group as a terminal active hydrogen group), and a urethanization catalyst are mixed at 50 to 90 ° C. After making it react for -5 hours, a hydroxyalkyl (meth) acrylate and a urethanization catalyst are added, and a polymer (a) can be manufactured by making it react at 50-90 degreeC for 1 to 5 hours.

Next, the photosensitive resin composition of this Embodiment is demonstrated.
The photosensitive resin composition of the present embodiment is indispensable to contain the polymer (a) produced from the prepolymer in order to develop excellent solvent resistance with respect to various solvents. Or it is used for manufacture of a printing original plate.
In the photosensitive resin composition of the present embodiment, the polymer (a) is not particularly limited as long as it is the polymer produced from the prepolymer, but it is between the terminal hydroxyl group of the polyprepolymer and another compound. It is preferable that it is a polymer manufactured with the formation of a covalent bond, and a polymer containing a polymerizable unsaturated group. Although there is no restriction | limiting in particular in the kind of a covalent bond and a polymerizable unsaturated group, As a covalent bond, a urethane bond is preferable and a double bond is preferable as a polymerizable unsaturated group. In the photosensitive resin composition of the present embodiment, the polymer (a) produced with urethane bond formation includes a prepolymer (having a hydroxyl group as a terminal active hydrogen group), an aromatic diisocyanate, It is preferable that it is a polymer containing the urethanized prepolymer manufactured from this. Moreover, when manufacturing a printing plate or a printing original plate using the photosensitive resin composition, since the polymer (a) can be linked to various molecules, the polymer (a) may have a polymerizable unsaturated group. preferable.

Specifically, the polymer (a) includes the prepolymer (having a hydroxyl group as a terminal active hydrogen group), a diisocyanate compound having an isocyanate group equivalent less than the equivalent of the terminal hydroxyl group of the prepolymer, and an isocyanate alkyl. Polymer produced by reacting acrylate and / or isocyanatoalkyl methacrylate, or isocyanate group equivalent above the prepolymer (having a hydroxyl group as a terminal active hydrogen group) and the equivalent of the terminal hydroxyl group of the prepolymer The diisocyanate compound is preferably a polymer produced by reacting a hydroxyalkyl acrylate and / or a hydroxyalkyl methacrylate.
The polymer (a) preferably has a polymerizable unsaturated group. Having a polymerizable unsaturated group is convenient for linking with various molecules in the production of a printing original plate or the like.
Furthermore, as the polymer (a), the polymer represented by the formula (1) or the formula (2) is preferable because it is extremely excellent in solvent resistance.

The photosensitive resin composition of the present embodiment preferably further contains an organic compound (b) having a polymerizable unsaturated group and a number average molecular weight of less than 5,000.
The polymerizable unsaturated group in the present embodiment means an unsaturated group involved in radical polymerization or addition polymerization reaction. As the polymerizable unsaturated group involved in the radical polymerization reaction, for example, an acryl group or a methacryl group is preferable, and as the polymerizable unsaturated group involved in the addition polymerization reaction, for example, an epoxy group, an oxetane group or a vinyl ether group is preferable. .

Specific examples of the organic compound (b) include olefins such as ethylene, propylene, styrene, and divinylbenzene; (meth) acrylic acid and derivatives thereof; haloolefins; unsaturated nitriles such as acrylonitrile; (meth) acrylamide And allyl compounds such as allyl alcohol and allyl isocyanate; unsaturated dicarboxylic acids such as maleic anhydride, maleic acid and fumaric acid and derivatives thereof; vinyl acetates; N-vinylpyrrolidone; N-vinylcarbazole and the like. It is done.
As the organic compound (b), one or more organic compounds can be used in combination depending on the purpose.

As the organic compound (b), for example, (meth) acrylic acid or a derivative thereof is preferable. Examples of (meth) acrylic acid derivatives include esters with the following compounds having an alcoholic hydroxyl group. Examples of the compound include compounds having an alicyclic skeleton such as cycloalkyl alcohol, bicycloalkyl alcohol, cycloalkenyl alcohol, and bicycloalkenyl alcohol; compounds having an aromatic skeleton such as benzyl alcohol, phenol, and fluorenyl alcohol; Examples include alkyl alcohols, halogenated alkyl alcohols, alkoxyalkyl alcohols, phenoxyalkyl alcohols, hydroxyalkyl alcohols, aminoalkyl alcohols, tetrahydrofurfuryl alcohol, and allyl alcohol. Examples of (meth) acrylic acid derivatives include esters with glycidol, alkylene glycol, polyoxyalkylene glycol, (alkyl / allyloxy) polyalkylene glycol, and polyhydric alcohols such as trimethylolpropane. In addition, in the case where the derivative of (meth) acrylic acid is an ester with a compound having an aromatic skeleton, an organic compound such as an ester with a heteroaromatic compound containing nitrogen, sulfur or the like as a hetero atom Also mentioned.
Specific examples of the organic compound (b) include phenoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, diethylene glycol butyl ether (meth) acrylate, ethylene glycol phenyl ether (meth) acrylate, trimethylolpropane (meth) acrylate, lauryl ( And (meth) acrylate.

  As the organic compound (b), a compound having an epoxy group that undergoes a ring-opening addition polymerization reaction is preferable. Examples of the compound having an epoxy group that undergoes a ring-opening addition reaction include compounds obtained by reacting polyols such as various diols and triols with epichlorohydrin, and epoxy compounds obtained by reacting peracid with an ethylene bond in the molecule. It is done.

Specifically, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, glycerin diglycidyl ether,
Addition of ethylene oxide or propylene oxide to glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S propylene oxide diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A Diglycidyl ether, polytetramethylene glycol diglycidyl ether, poly (propylene glycol adipate) diol diglycidyl ether, poly (ethylene glycol adipate) diol diglycidyl ether, poly (caprolactone) diol diglycidyl ether, 3,4- Epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxyl 1-methyl-3,4-epoxycyclohexylmethyl-1′-methyl-3 ′, 4′-epoxycyclohexylcarboxylate, bis [1-methyl-3,4-epoxycyclohexyl] ester adipate, vinylcyclohexenedi Examples include epoxides, polyepoxy compounds obtained by reacting peracetic acid with polydienes such as polybutadiene and polyisoprene, and epoxidized soybean oil.

  When the photosensitive resin composition in the present embodiment is a printing original plate or printing plate, in addition to excellent solvent resistance to various solvents, laser engraving is an important characteristic in a method of directly forming a relief image with a laser. It also has the characteristic of being excellent in properties. In order to further improve the laser engraving property, the resin composition preferably further contains inorganic fine particles (c). The material and form of the inorganic fine particles (c) are not limited, but those having fine pores or fine voids in the particles are more preferable. The inorganic fine particles (c) have a function of effectively absorbing and removing the liquid gas generated when the printing original plate is decomposed by the laser, so that the inorganic fine particles (c) are contained in the photosensitive resin composition. In addition to improving the accuracy of the relief image by laser engraving, the cleaning operation after laser engraving becomes extremely simple.

Although the size of the inorganic fine particles (c) is not limited, the average particle size is preferably 0.01 to 100 μm, more preferably 0.1 to 20 μm, and still more preferably 1 to 10 μm. Although there is no restriction | limiting in the average pore diameter of inorganic type microparticles | fine-particles (c), it is 1-1000 nm, More preferably, it is 2-200 nm, More preferably, it is 2-50 nm. Although there is no restriction | limiting in the pore volume of inorganic type microparticles | fine-particles (c), 0.01-10 ml / g is preferable, More preferably, it is 0.1-5 ml / g. Although it does not restrict | limit to the specific surface area of inorganic type microparticles | fine-particles (c), 1-1,500m < ² > / g is preferable, More preferably, it is 10-800m < ² > / g.

  The shape of the inorganic fine particles (c) is not limited, but spherical, flat, needle-shaped, amorphous, or particles having protrusions on the surface can be used. In addition, particles in which the inside of the particles are hollow, spherical granules having a uniform pore diameter such as silica sponge, and the like can also be used. As the inorganic fine particles, both porous inorganic fine particles and nonporous inorganic fine particles can be used. For example, porous silica, mesoporous silica, silica-zirconia porous gel, mesoporous molecular sieve, porous alumina, porous Glass, alumina, silica, zirconium oxide, barium titanate, strontium titanate, titanium oxide, silicon nitride, boron nitride, silicon carbide, chromium oxide, vanadium oxide, tin oxide, bismuth oxide, germanium oxide, aluminum borate, nickel oxide Molybdenum oxide, tungsten oxide, iron oxide, cerium oxide, or the like can be used. Moreover, what has a space | gap of several nm-100 nm between layers like a layered clay compound can also be used as inorganic type fine particles.

  The photosensitive resin composition in the present embodiment preferably further contains a photopolymerization initiator. The photopolymerization initiator may be appropriately selected from known ones. For example, radical polymerization, cationic polymerization, and anion illustrated in “Polymer Data Handbook-Fundamentals” edited by the Society of Polymer Science (1986, published by Baifukan) A polymerization initiator such as polymerization can be used.

  Crosslinking of the photosensitive resin composition by photopolymerization using a photopolymerization initiator is useful as a method for producing a printing original plate or printing plate with high productivity while maintaining storage stability.

  Known polymerization initiators that can be used as the photopolymerization initiator include benzoin alkyl ethers such as benzoin and benzoin ethyl ether; 2-hydroxy-2-methylpropiophenone, 4′-isopropyl-2-hydroxy- Acetophenones such as 2-methylpropiophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone; 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2- Photo radical polymerization initiators such as morpholino-propan-1-one, methyl phenylglyoxylate, benzophenone, benzyl, diacetyl, diphenyl sulfide, eosin, thionine, anthraquinones; aromatic diazonium salts that generate acid by absorbing light And the like can be exemplified by absorbing light generates a base anionic photopolymerization initiator; aromatic iodonium salts, cationic photopolymerization initiators such as aromatic sulfonium salts.

  The composition of the photosensitive resin composition is not limited, but from the viewpoint of solvent resistance of the printing original plate or printing plate, a polymerizable unsaturated group is added to 100 parts by mass of the polymer (a) produced from the prepolymer. The organic compound (b) is preferably 5 to 200 parts by mass, and the inorganic fine particles (c) are preferably 1 to 100 parts by mass. Further, from the viewpoint of solvent resistance of the printing plate, 10 to 180 parts by mass of the organic compound (b) having a polymerizable unsaturated group is 10 to 180 parts by mass with respect to 100 parts by mass of the polymer (a) produced from the prepolymer. The system fine particles (c) are more preferably 1 to 80 parts by mass. Furthermore, it is preferable to contain 1-100 parts by mass of a photopolymerization initiator from the viewpoint of the efficiency of printing plate production, and from the viewpoint of solvent resistance of the printing plate, 1-80 parts by mass of a photopolymerization initiator is more preferably included. preferable.

  A polymerization inhibitor, an ultraviolet absorber, a dye, a lubricant, a surfactant, a plasticizer, a fragrance and the like can be added to the photosensitive resin composition according to the purpose and purpose. The total addition amount is preferably in the range of 10 parts by mass or less with respect to 100 parts by mass of the photosensitive resin composition.

Next, a printing plate and a printing original plate according to the present embodiment will be described.
The printing original plate and the printing plate of the present embodiment are not limited as long as they contain the polymer (a) produced from the prepolymer, but may be produced from the photosensitive resin composition. preferable. The printing original plate and the printing plate are obtained, for example, by curing a resin composition containing the polymer (a) produced from the prepolymer. Preferably, the printing original plate and the printing plate include the resin composition. A cured resin layer obtained by curing the resin composition layer is included. The printing original plate and the printing plate are produced by a method including forming the photosensitive resin composition into a sheet or cylinder, and crosslinking and curing the formed photosensitive resin composition by irradiation with light or an electron beam. More preferably.

There is no restriction | limiting in the method of shape | molding the photosensitive resin composition of this Embodiment in a sheet form or cylindrical shape, The shaping | molding method of the existing resin can be used. For example, a method of extruding a resin from a nozzle or a die with a machine such as a pump or an extruder and adjusting the thickness with a blade (casting method); a method of adjusting the thickness by calendaring with a roll can be exemplified. It is also possible to perform molding while heating within a range that does not deteriorate the performance of the resin. Moreover, you may perform a rolling process, a grinding process, etc. as needed. Usually, the resin composition is formed on an underlay called a back film made of a material such as PET (polyethylene terephthalate) or nickel, but it can also be formed directly on a cylinder of a printing press. In that case, a seamless seamless sleeve can be formed. In addition, a sleeve molding / engraving device (a laser light source for laser engraving in a device in which a liquid photosensitive resin composition is applied onto a cylindrical support and irradiated with light to crosslink and cure the liquid photosensitive resin composition) The printing original plate can also be formed using the one incorporating the above. When such an apparatus is used, a printing plate can be formed by laser engraving immediately after forming the sleeve, so that a conventional rubber sleeve that requires a period of several weeks for the forming process is hardly considered. Time machining can be realized.
The printing plate in the present embodiment is preferably a printing plate obtained by laser engraving a printing pattern on the surface of the printing original plate.
There is no limitation on the form of the printing plate of this embodiment, and it can be used as any printing plate such as a flexographic plate, a resin relief plate, or a blanket used for offset, dry offset, reversal offset or gravure offset. Preferably used.

In the present embodiment, the printing plate or printing original plate produced from the prepolymer exhibits excellent solvent resistance against a solvent having a solubility parameter of 20 J ^1/2 / cm ^3/2 or more. For example, the following solvents can be exemplified (the solubility parameter [J ^1/2 / cm ^3/2 ] is shown in parentheses). γ-butyrolactone (22.1), N-methyl-2-pyrrolidone (22.5), N, N-dimethylformamide (23.5), dimethyl sulfoxide (26.2), methyl benzoate (20.6) In particular, it exhibits excellent solvent resistance.

[Production method of liquid crystal alignment film]
The liquid crystal alignment film liquid used in the present embodiment is not particularly limited, and liquid crystal alignment film materials, solvents, and other additives that are added as necessary can be used.

The organic polymer used as the liquid crystal alignment film material is not particularly limited, and examples thereof include generally used polyimide resins.
More specifically, for example, an imidized polymer of polyamic acid (described in Japanese Patent Publication No. 5-60565 or Japanese Patent No. 2893671) or polyamic acid (described in Japanese Patent No. 2600368), polyamic acid and / or imidization. A mixture of polymers (described in JP-A No. 10-183120) or a partially imidized polymer (described in JP-A No. 05-216044) is required. Further, Japanese Patent No. 3206401 requires an epoxy group-containing compound having a specific structure. 1 or more types of polymers chosen from the group which consists of the liquid crystal aligning agent used as a component, the polymer which has a polyamic acid structure, and / or the polymer which has an imide structure, and the epoxy compound containing a nitrogen atom Liquid crystal alignment film material, or polyamic acid and monofunctional tertiary amination disclosed in JP-A-5-203953 Such goods and the composition dissolved in solvent.

  The solvent is not particularly limited as long as it dissolves the organic polymer. Specifically, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ -Butyrolactone, N-methylcaprolactam, dimethyl sulfoxide, hexamethylphosphoamide and the like are preferable from the viewpoint of solubility. In order to improve wettability, a carbitol-based or cellosolve-based solvent can be added as necessary.

  The solid content concentration of the liquid crystal alignment film liquid in the present embodiment varies depending on the coating method and the liquid viscosity, but is preferably in the range of 0.1 to 10% by mass. When the solid content concentration is 0.1% by mass or more, the film thickness of the liquid crystal alignment film can be controlled within the following range, and a good liquid crystal alignment film can be obtained. Moreover, when the solid content concentration is 10% by mass or less, the film thickness of the liquid crystal alignment film can be controlled within the following range, and a good liquid crystal alignment film can be obtained. Furthermore, from the viewpoint of coating characteristics due to the viscosity of the liquid crystal alignment film liquid, the solid content concentration is preferably 10% by mass or less.

  The film thickness of the liquid crystal alignment film in the present embodiment is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm after the solvent component in the liquid crystal alignment film liquid is removed by drying. . When the film thickness is 0.001 μm or more, uniform orientation can be achieved. Moreover, it is preferable from a viewpoint of coloring of the liquid crystal aligning film which is a coating film, and the drive voltage of an element that a film thickness is 0.5 micrometer or less.

The solvent resistance to the solvent contained in the liquid crystal alignment film liquid of the printing plate and printing original plate in this embodiment is evaluated by a solvent immersion swelling test, and the mass change rate of the printing original plate before and after immersion in the solvent is 10. It is preferably at most mass%, more preferably at most 5 mass%.
The solvent immersion swelling test in the present embodiment is performed by immersing a test sample in a solvent at room temperature for 24 hours. If the mass change rate of the printing original plate before and after the immersion is 10% by mass or less, the dimensional change of the printing plate is small, and not only the printing of a fine pattern and the uniform application of the liquid crystal alignment film is possible. Dimensional stability can be secured, the durability of the printing plate can be improved, and it can withstand repeated printing processes.

  When a printing pattern is formed on the printing original plate surface by laser engraving, the depth of the formed pattern is preferably 1 μm or more and 1,000 μm or less. More preferably, they are 5 micrometers or more and 700 micrometers or less, More preferably, they are 20 micrometers or more and 500 micrometers or less. If the depth of the printing pattern is 1 μm or more, the liquid crystal alignment film liquid transferred from the printing plate can be held on the substrate to be printed. If the printing pattern is 1,000 μm or less, the printing pattern may be deformed during the printing process. It is preferable because it is not destroyed.

The method for producing a liquid crystal alignment film according to the present embodiment transfers a liquid crystal alignment film liquid on a printing plate onto a substrate to be printed, and removes the solvent in the transferred liquid crystal alignment film liquid by drying. A method for producing a liquid crystal alignment film comprising fixing a liquid crystal alignment film liquid on
A photosensitive resin composition containing a polymer (a) comprising a repeating unit represented by the formula (1) and / or the formula (2) and having both terminal groups being hydroxyl groups is cured. In the above method, the liquid crystal alignment film liquid is transferred onto the substrate to be printed using the obtained printing plate.

  When the flexographic printing method is used in the manufacturing method of the present embodiment, the method for transferring the liquid crystal alignment film liquid on the flexographic printing plate onto the substrate to be printed is not particularly limited, but the convexity of the flexographic printing plate with unevenness is not limited. The liquid crystal alignment film liquid is supplied to the surface of the part with an ink supply roll or the like, and then the flexographic printing plate is brought into contact with the substrate to be printed, and the liquid crystal alignment film liquid on the convex surface is transferred to the substrate to be printed The method etc. are mentioned.

In the manufacturing method of the present embodiment, the method of fixing the liquid crystal alignment film liquid on the substrate to be printed is obtained by drying and removing the solvent in the liquid crystal alignment film liquid transferred by the above-described method. This is a method of fixing the alignment film liquid.
As a method for drying and removing the solvent in the liquid crystal alignment film liquid and fixing the liquid crystal alignment film liquid, for example, the solvent is vaporized and dried by heat treatment in the presence of an inert gas such as nitrogen gas. The method of doing is mentioned.

[Black matrix manufacturing method]
The black matrix in the present embodiment is a film formed on a substrate such as glass by transferring and fixing the black matrix coating composition, and means a black film that prevents color mixture.

  The coating composition for black matrix in the present embodiment is not particularly limited, and a material composed of a light shielding material, a resin, a solvent, and other various additives added as necessary can be used.

  As the light-shielding material used as the black matrix coating composition in the present embodiment, metal chromium, chromium oxide, iron oxide, titanium black, molybdenum, tantalum, aluminum or oxides thereof, titanium oxynitride, carbon black, A black pigment such as aniline black is used, and a resin in which the light shielding material is dispersed is used as a coating composition for a black matrix. Among them, a resin in which metallic chromium, carbon, or a black pigment is dispersed is preferable in terms of light shielding properties, film forming properties, and the like.

The resin used as the black matrix coating composition of the present embodiment is not particularly limited and can be either photosensitive or non-photosensitive, and commonly used acrylic resins, acrylic epoxy resins, and siloxanes. Polyimide resins such as polymer resins, polyimide resins, silicon acid-containing polyimide resins, polyimide siloxane resins, and polymaleimide resins are preferably used.
The polyimide resin is formed, for example, by heating and ring-closing imidization of a polyamic acid as a precursor. The polyamic acid usually contains a structural unit represented by the following formula (9) as a main component.

ここで、式（９）のＸは１又は２の整数である。Ｒａ及びＲｂは、各々独立に、少なくとも２個の炭素原子を有する有機基を示す。耐熱性の観点から、Ｒａ及びＲｂは、各々独立に、環状炭化水素、芳香族環又は芳香族複素環を含有し、かつ、炭素数６から３０の基が好ましい。Ｒａ及びＲｂとしては、特に制限されるものではないが、例えば、フェニル基、ビフェニル基、ターフェニル基、ナフタレン基、ペリレン基、ジフェニルエーテル基、ジフェニルスルホン基、ジフェニルプロパン基、ベンゾフェノン基、ビフェニルトリフルオロプロパン基、ジフェニルメタン基、シクロヘキシルメタン基などから誘導された基などが挙げられる。

Here, X in Formula (9) is an integer of 1 or 2. Ra and Rb each independently represents an organic group having at least two carbon atoms. From the viewpoint of heat resistance, each of Ra and Rb independently contains a cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring, and is preferably a group having 6 to 30 carbon atoms. Ra and Rb are not particularly limited. For example, phenyl group, biphenyl group, terphenyl group, naphthalene group, perylene group, diphenyl ether group, diphenylsulfone group, diphenylpropane group, benzophenone group, biphenyltrifluoro And groups derived from a propane group, a diphenylmethane group, a cyclohexylmethane group, and the like.

  The solvent is not particularly limited as long as it dissolves the resin. Specifically, for example, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. Solvents such as solvents, lactone polar solvents such as β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, dimethyl sulfoxide, hexamethylphosphoramide, etc. To preferred. Among them, γ-butyrolactone is preferable from the viewpoint of solubility of the polyimide precursor.

  A small amount of a complementary color pigment may be added to the black matrix coating composition of the present embodiment to such an extent that the degree of shading is not lowered. Examples of the complementary color pigment include one or more of a blue pigment, a purple pigment, a green pigment, a yellow pigment, and an orange pigment. The proportion of the complementary color pigment in the light shielding material is preferably 10% by mass or less. If it is more than this, the light shielding performance of the black matrix is lowered, which is not preferable.

The solvent resistance to the solvent contained in the black matrix coating composition of the printing plate and printing original plate according to the present embodiment was evaluated by a solvent immersion swelling test, and the mass change rate of the printing original plate before and after immersion in the solvent. Is preferably 10% by mass or less, and more preferably 5% by mass or less.
The solvent immersion swelling test in the present embodiment is performed by immersing a test sample in a solvent at room temperature for 24 hours. If the mass change rate of the printing original plate before and after dipping is 10% by mass or less, the dimensional change of the printing plate is small, and not only fine pattern printing and uniform application of black matrix are possible, but also the printing plate dimensions. Stability can be secured, the durability of the printing plate can be improved, and it can withstand repeated printing processes.

  In the present embodiment, when a pattern is formed on the surface of the printing original plate by laser engraving, the depth of the formed pattern varies depending on the printing method, but is preferably 1 μm or more and 1000 μm or less. More preferably, they are 5 micrometers or more and 700 micrometers or less, More preferably, they are 20 micrometers or more and 500 micrometers or less. If it is 1 micrometer or more, the coating composition for black matrices transferred from a printing plate can be hold | maintained, and if it is 1000 micrometers or less, a pattern will not deform | transform or destroy during a printing process.

  The thickness of the black matrix that can be printed on the substrate to be printed in the printing method according to the present embodiment is within the range that can be used as the black matrix after the solvent component in the black matrix coating composition is removed by drying. Although it does not restrict | limit in particular, Preferably it is 0.5-2.0 micrometers, More preferably, it is 0.7-1.5 micrometers.

The black matrix production method of the present embodiment includes transferring the black matrix coating composition on the printing plate onto a substrate to be printed, and drying and removing the solvent in the transferred black matrix coating composition, or A method for producing a black matrix, comprising immobilizing a black matrix coating composition on a substrate to be printed by irradiating and curing the transferred black matrix coating composition,
A photosensitive resin composition containing a polymer (a) comprising a repeating unit represented by the formula (1) and / or the formula (2) and having both terminal groups being hydroxyl groups is cured. In the above method, the black matrix coating composition is transferred onto a substrate to be printed using the resulting printing plate.

  When the flexographic printing method is used in the production method of the present embodiment, the method for transferring the black matrix coating composition on the flexographic printing plate onto the substrate to be printed is not particularly limited, but the flexographic printing plate having unevenness is used. The black matrix coating composition is supplied to the surface of the convex portion with an ink supply roll or the like, and then the flexographic printing plate is brought into contact with the substrate to be printed to print the black matrix coating composition on the convex portion surface. Examples of the method include transferring to a substrate.

In the manufacturing method of the present embodiment, the first aspect of the method for immobilizing the black matrix coating composition on the substrate to be printed is that the solvent in the black matrix coating composition transferred by the above method is removed by drying. Thus, the black matrix coating composition is fixed on the substrate to be printed.
As a method for fixing the black matrix coating composition by drying and removing the solvent in the black matrix coating composition, for example, the solvent is removed by heat treatment in the presence of an inert gas such as nitrogen gas. The method of evaporating and drying is mentioned.

In the manufacturing method of the present embodiment, the second aspect of the method for fixing the black matrix coating composition on the substrate to be printed is that the black matrix coating composition transferred by the above method is irradiated with light. In this method, the black matrix coating composition is fixed on a substrate to be printed by curing.
Examples of a method for fixing the black matrix coating composition by irradiating it with light include curing a photopolymerizable monomer such as a (meth) acrylic acid derivative blended in the black matrix coating composition with light. The method etc. are mentioned.

[Method for producing colored layer for color filter]
The color layer ink of the color filter of the present embodiment is not particularly limited, and an ink composed of a pigment, a resin, a solvent, and other various additives added as necessary can be used.
There is no particular limitation on the pigment used in the color layer ink of the color filter of the present embodiment, but a pigment excellent in light resistance, heat resistance and chemical resistance is desirable. Specific examples of typical pigments are indicated by color index (CI) numbers. Examples of yellow pigments include Pigment Yellow 12, 13, 14, 17, 20, 24, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153. 154, 166, 173 and the like. Examples of the orange pigment include Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and the like. Examples of the red pigment include Pigment Red 9, 97, 122, 123, 144, 149, 166, 168, 177, 190, 192, 215, 216, 224 and the like. Examples of purple pigments include pigment violet 19, 23, 29, 32, 33, 36, 37, 38, and the like. Examples of blue pigments include Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 22, 60, 64, and the like. In addition, you may use the pigment to which surface treatments, such as a rosin process, an acidic group process, a basic group process, are given as needed. Moreover, in order to improve the adhesive force with a black matrix, you may use what coated the pigment surface with resin as needed.

There is no restriction | limiting in particular in resin used for the ink for colored layers of the color filter of this Embodiment, An acrylic resin, polyvinyl alcohol, polyamide, a polyimide, etc. can be used. It is preferable to use a pigment-dispersed resin film as the pixel from the viewpoint of simplicity of the manufacturing process, heat resistance, light resistance, and the like. From the viewpoint of ease of pattern formation, it is preferable to use a photosensitive acrylic resin in which a pigment is dispersed. From the viewpoint of heat resistance and chemical resistance, it is preferable to use a pigment-dispersed polyimide resin.
The polyimide resin is formed, for example, by heating and ring-closing imidization of a polyamic acid as a precursor. The polyamic acid usually contains a structural unit represented by the following formula (9) as a main component.

ここで、式（９）のＸは１又は２の整数である。Ｒａ及びＲｂは、各々独立に、少なくとも２個の炭素原子を有する有機基を示す。耐熱性の観点から、Ｒａ及びＲｂは、各々独立に、環状炭化水素、芳香族環又は芳香族複素環を含有し、かつ、炭素数６から３０の基が好ましい。Ｒａ及びＲｂとしては、特に制限されるものではないが、例えば、フェニル基、ビフェニル基、ターフェニル基、ナフタレン基、ペリレン基、ジフェニルエーテル基、ジフェニルスルホン基、ジフェニルプロパン基、ベンゾフェノン基、ビフェニルトリフルオロプロパン基、ジフェニルメタン基、シクロヘキシルメタン基などから誘導された基などが挙げられる。

Here, X in Formula (9) is an integer of 1 or 2. Ra and Rb each independently represents an organic group having at least two carbon atoms. From the viewpoint of heat resistance, each of Ra and Rb independently contains a cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring, and is preferably a group having 6 to 30 carbon atoms. Ra and Rb are not particularly limited. For example, phenyl group, biphenyl group, terphenyl group, naphthalene group, perylene group, diphenyl ether group, diphenylsulfone group, diphenylpropane group, benzophenone group, biphenyltrifluoro And groups derived from a propane group, a diphenylmethane group, a cyclohexylmethane group, and the like.

  The solvent is not particularly limited as long as it dissolves the resin. Specifically, for example, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. Solvents such as solvents, lactone polar solvents such as β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, dimethyl sulfoxide, hexamethylphosphoramide, etc. To preferred. Among them, γ-butyrolactone is preferable from the viewpoint of solubility of the polyimide precursor.

  The thickness of the colored layer for a color filter that can be printed on the substrate to be printed in the printing method according to the present embodiment is not particularly limited as long as it can be used as a colored layer, but is preferably 0.1 to 10 μm. More preferably, it is 0.2-7 micrometers.

The solvent resistance to the solvent contained in the color layer ink of the printing plate and printing original plate in this embodiment is evaluated by a solvent immersion swelling test, and the mass change rate before and after immersion in the solvent is 10% by mass or less. It is preferable that it is 5 mass% or less.
The solvent immersion swelling test in the present embodiment is performed by immersing a test sample in a solvent at room temperature for 24 hours. If the mass change rate of the printing original plate before and after immersion is 10% by mass or less, the dimensional change of the printing plate is small, and not only fine pattern printing and uniform coating of a thin film are possible, but also the dimensional stability of the printing plate. Can be ensured, the durability of the printing plate is improved, and it can withstand repeated printing processes.

  In the present embodiment, when a pattern is formed on the surface of the printing original plate by laser engraving, the depth of the formed pattern varies depending on the printing method, but is preferably 1 μm or more and 1000 μm or less. More preferably, they are 5 micrometers or more and 700 micrometers or less, More preferably, they are 20 micrometers or more and 500 micrometers or less. If it is 1 μm or more, the colored layer ink transferred from the printing plate can be retained, and if it is 1000 μm or less, the pattern is not deformed or destroyed during the printing process.

The method for producing a colored layer for a color filter according to the present embodiment includes transferring a colored layer ink on a printing plate onto a substrate to be printed, and drying or removing the solvent in the transferred colored layer ink. A method for producing a colored layer for a color filter, comprising: curing the colored layer ink by irradiating light to fix the colored layer ink on a substrate to be printed,
A photosensitive resin composition containing a polymer (a) comprising a repeating unit represented by the formula (1) and / or the formula (2) and having both terminal groups being hydroxyl groups is cured. It is the said method which transfers the ink for colored layers on a to-be-printed substrate using the printing plate obtained.

  When the flexographic printing method is used in the production method of the present embodiment, the method for transferring the colored layer ink on the flexographic printing plate onto the substrate to be printed is not particularly limited, but the convexity of the flexographic printing plate with unevenness is not limited. A method in which the ink is supplied to the surface of the portion with an ink supply roll or the like, then the flexographic printing plate is brought into contact with the substrate to be printed, and the ink on the surface of the convex portion is transferred to the substrate to be printed. It is done.

In the manufacturing method of the present embodiment, the first aspect of the method for fixing the colored layer ink on the substrate to be printed is that the solvent in the ink transferred by the method is removed by drying, and the substrate to be printed is This is a method of fixing the colored layer ink on the top.
Examples of the method for fixing the ink by drying and removing the solvent in the ink include a method in which the solvent is vaporized and dried by heat treatment in the presence of an inert gas such as nitrogen gas. Can be mentioned.

In the manufacturing method of the present embodiment, the second aspect of the method for fixing the color layer ink on the substrate to be printed is that the ink transferred by the method is cured by irradiating light to be printed. In this method, the colored layer ink is fixed on the substrate.
Examples of the method of fixing the ink by irradiating with light include a method of curing a photopolymerizable monomer such as a (meth) acrylic acid derivative blended in the ink with light.
[About manufacturing methods for banks, etc.]
The resin used in the composition for forming a bank in the present embodiment is not particularly limited. For example, a novolak resin, a polyamic acid, a polyimide resin, polymethacrylate, polyhexafluoropropylene, polytetrafluoroethylene , Polytrifluoride ethylene, polyvinylidene fluoride, polyethylene, polybutadiene, polystyrene, fluorinated polystyrene, ethyl polyacrylate, perfluorooctylethyl methacrylate, polyvinyl alcohol, polychloroprene, polyvinyl chloride, methyl polyacrylate, polyvinylidene chloride , 6 nylon, 6-6 nylon, 7-7 nylon, polyethylene terephthalate, polyhexamethylene adipamide and other organic materials, silolite, silophobic (manufactured by Fuji Silysia Chemical Ltd.) And, these organic materials, inorganic materials a positive resist can be used such as those dispersed in a negative resist.

  The solvent for the bank forming composition is not particularly limited as long as it dissolves the resin used in the bank forming composition. Specifically, for example, N, N-dimethylformamide, N, N- Amide solvents such as dimethylacetamide and N-methylpyrrolidone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, lactone solvents such as ε-caprolactone, alkoxy such as butyl cellosolve Alkyl alcohol solvents, dimethyl sulfoxide, hexamethylphosphoramide and the like are preferable from the viewpoint of solubility. Among them, γ-butyrolactone is preferable from the viewpoint of solubility. Moreover, 1 type may be used as a solvent for bank formation, and 2 or more types may be mixed and used for it.

  When the bank forming composition is cured by irradiation with light, a photopolymerizable monomer may be contained in the composition. Examples of the photopolymerizable monomer include urethane acrylate and epoxy acrylate.

  The polyimide resin is formed, for example, by heating and ring-closing imidization of a polyamic acid as a precursor. The polyamic acid usually contains a structural unit represented by the following formula (9) as a main component.

ここで、式（９）のＸは１又は２の整数である。Ｒａ及びＲｂは、各々独立に、少なくとも２個の炭素原子を有する有機基を示す。耐熱性の観点から、Ｒａ及びＲｂは、各々独立に、環状炭化水素、芳香族環又は芳香族複素環を含有し、かつ、炭素数６から３０の基が好ましい。Ｒａ及びＲｂとしては、特に制限されるものではないが、例えば、フェニル基、ビフェニル基、ターフェニル基、ナフタレン基、ペリレン基、ジフェニルエーテル基、ジフェニルスルホン基、ジフェニルプロパン基、ベンゾフェノン基、ビフェニルトリフルオロプロパン基、ジフェニルメタン基、シクロヘキシルメタン基などから誘導された基などが挙げられる。

Here, X in Formula (9) is an integer of 1 or 2. Ra and Rb each independently represents an organic group having at least two carbon atoms. From the viewpoint of heat resistance, each of Ra and Rb independently contains a cyclic hydrocarbon, an aromatic ring or an aromatic heterocyclic ring, and is preferably a group having 6 to 30 carbon atoms. Ra and Rb are not particularly limited. For example, phenyl group, biphenyl group, terphenyl group, naphthalene group, perylene group, diphenyl ether group, diphenylsulfone group, diphenylpropane group, benzophenone group, biphenyltrifluoro And groups derived from a propane group, a diphenylmethane group, a cyclohexylmethane group, and the like.

  The solvent in the case of using a polyamic acid as a bank forming composition is not particularly limited as long as it dissolves the polyamic acid. Specifically, for example, N, N-dimethylformamide, N, N- Amide solvents such as dimethylacetamide and N-methylpyrrolidone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, lactone solvents such as ε-caprolactone, alkoxy such as butyl cellosolve Alkyl alcohol solvents, dimethyl sulfoxide, hexamethylphosphoramide and the like are preferable from the viewpoint of solubility. Among them, γ-butyrolactone is preferable from the viewpoint of solubility. Moreover, 1 type may be used as a solvent of a polyamic acid, or 2 or more types may be mixed and used for it.

  The film thickness of the bank is not particularly limited, but specifically, the film thickness is preferably in the range of 0.1 μm to 10 μm. The film thickness of the bank is preferably 10 μm or less from the viewpoint of productivity. Moreover, it is preferable from a viewpoint of comprehensive performance that the film thickness of a bank shall be 0.1 micrometer or more. The film thickness of the bank is more preferably in the range of 0.2 μm to 8 μm from the viewpoint of overall performance.

The solvent resistance against the solvent contained in the composition for forming a bank of a printing plate in the present embodiment can be evaluated by a solvent immersion swelling test. The mass change rate of the printing original plate before and after immersion in the solvent is preferably 10% by mass or less, and more preferably 5% by mass or less.
The solvent immersion swelling test is performed by immersing a test sample in a solvent at room temperature for 24 hours. If the mass change rate of the printing original plate before and after the immersion is 10% by mass or less, the dimensional change of the printing plate is small, and fine pattern printing and uniform bank application are possible. Further, if the mass change rate is 10% by mass or less, the dimensional stability of the printing plate can be secured and the durability of the printing plate can be improved, so that it can withstand repeated printing processes.

  In order to describe the present embodiment in more detail, examples and comparative examples are shown below, but these examples specifically illustrate the description of the present embodiment and the effects obtained thereby. Thus, the present embodiment is not limited at all. Various characteristics in the following examples and comparative examples were measured according to the following methods.

<Measurement method>
1. Mass change rate of printing original plate The printing original plate was cut into 1 cm × 2 cm, immersed in each solvent at room temperature for 24 hr, and the mass change rate was determined using the following calculation formula (iii).
Mass change rate (%) = {(mass after immersion−mass before immersion) / mass before immersion} × 100
(Iii)

2. Laser engraving of the printing original plate Laser engraving of the printing original plate was performed using a carbon dioxide laser engraving machine (output: 12 watts, trademark Laser Pro Venus, manufactured by GCC). The engraving was performed by creating a pattern including a line drawing with a convex line having a width of 200 μm. The engraving depth (relief depth) was 400 μm. The presence or absence of viscous liquid residue generated by laser engraving and the sharpness of the line drawing were visually determined.

[Synthesis Example 1]
As a prepolymer, poly (oxyoctane-1,8-diyl) (poly (oxyoctane-1,8-diyl)) was synthesized by a known method. Table 1 shows the solubility parameter of the repeating unit (according to Fedor's estimation method) and the number average molecular weight (Mn).
In a 300 ml separable flask equipped with a stirrer, 34.1 g of this prepolymer, 1.61 g of tolylene diisocyanate, 0.04 g of 2,6-di-tert-butyl-4-methylphenol, 0.01 g of adipic acid, Then, 0.001 g of di-n-butyltin dilaurate was added, and the mixture was stirred at 80 ° C. for 3 hours in a dry air atmosphere. Thereafter, 1.44 g of 2-methacryloyloxyethyl isocyanate and 0.001 g of di-n-butyltin dilaurate were added, and the mixture was stirred at 80 ° C. for 2 hours in a dry air atmosphere. At this stage, it was confirmed by infrared spectroscopic analysis that a terminal hydroxyl group of the polycarbonate diol was linked by a urethane bond and a polymer having a double bond was obtained.
Thereafter, 12.54 g of lauryl methacrylate, 3.59 g of diethylene glycol butyl ether methacrylate, 0.07 g of trimethylolpropane trimethacrylate, 2.90 g of silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.), silicone oil KF-410 (Shin-Etsu Chemical Co., Ltd.) ) 0.63 g, 2,2-dimethoxy-2-phenylacetophenone 0.38 g, benzophenone 0.63 g, 2,6-di-tert-butyl-4-methylphenol 0.38 g, triphenyl phosphate 1.13 g, And Sanol LS-785 (Sankyo Co., Ltd.) 0.63g was added and it degassed by depressurizing to 13 kPa, stirring at 80 degreeC, and the solid photosensitive resin composition was obtained at room temperature.
[Synthesis Example 2]
As a prepolymer, a hydrogenated polybutadiene resin (GI-200, manufactured by Nippon Soda Co., Ltd.) was used to obtain a resin composition as shown below. Table 1 shows the solubility parameter of the repeating unit (according to Fedor's estimation method) and the number average molecular weight (Mn).
In a 300 ml separable flask equipped with a stirrer, 29.2 g of this prepolymer, 1.61 g of tolylene diisocyanate, 0.04 g of 2,6-di-tert-butyl-4-methylphenol, 0.01 g of adipic acid, Then, 0.001 g of di-n-butyltin dilaurate was added, and the mixture was stirred at 80 ° C. for 3 hours in a dry air atmosphere. Thereafter, 1.44 g of 2-methacryloyloxyethyl isocyanate and 0.001 g of di-n-butyltin dilaurate were added, and the mixture was stirred at 80 ° C. for 2 hours in a dry air atmosphere. At this stage, it was confirmed by infrared spectroscopic analysis that a terminal hydroxyl group of the polycarbonate diol was linked by a urethane bond and a polymer having a double bond was obtained.
Thereafter, 12.54 g of lauryl methacrylate, 3.59 g of diethylene glycol butyl ether methacrylate, 0.07 g of trimethylolpropane trimethacrylate, 2.90 g of silica gel C-1504 (Fuji Silysia Chemical Co., Ltd.), silicone oil KF-410 (Shin-Etsu Chemical Co., Ltd.) ) 0.63 g, 2,2-dimethoxy-2-phenylacetophenone 0.38 g, benzophenone 0.63 g, 2,6-di-tert-butyl-4-methylphenol 0.38 g, triphenyl phosphate 1.13 g, And Sanol LS-785 (Sankyo Co., Ltd.) 0.63g was added and it degassed by depressurizing to 13 kPa, stirring at 80 degreeC, and the solid photosensitive resin composition was obtained at room temperature.
[Synthesis Example 3]
A photosensitive resin composition was synthesized in the same manner as in Synthesis Example 2 except that hexamethylene diisocyanate was used instead of tolylene diisocyanate.
[Comparative Synthesis Example 1]
Instead of poly (oxyoctane-1,8-diyl), poly (oxypropane-1,3-diyloxyglutaryl) synthesized by a known method (poly (oxypropane-1,3-dioxyglutaryl)) (Mn: 2376) ) A photosensitive resin composition was obtained in the same manner as in Synthesis Example 1 except that 33.0 g was used.

[Examples 1 to 3, Comparative Example 1]
Using each of the photosensitive resin compositions obtained in Synthesis Examples 1 to 5 and Comparative Synthesis Example 1, printing original plates were produced by the following method. In addition, Examples 1-3 were implemented using the photosensitive resin composition of the synthesis examples 1-3, and Comparative Example 1 was implemented using the photosensitive resin composition of the comparative synthesis example 1, respectively.
After thinly applying diethylene glycol to a 12 × 11 × 0.3 cm glass plate, a PET film was placed thereon and rubbed closely with a spatula. A square frame with a side of 10 cm made of a sponge frame fixed by double-sided sealing on the film and an aluminum spacer with a thickness of 3 mm were placed at the four corners outside the frame. The prepared jig was placed on a hot plate at about 90 ° C.
After pouring each resin composition into the frame of the jig, a glass plate coated with diethylene glycol and placed with a PET film was covered so that the PET film surface was in contact with the resin composition. Thereafter, the upper and lower glass plates were clamped and fixed.
About this jig, after exposing 500 mJ / cm ² (illuminance 33.7 mW / cm ² , time 14.8 seconds) using a high-pressure mercury lamp (HC-98, Sen Engineering Co., Ltd.), the jig surface was reversed, Further, exposure was performed at 500 mJ / cm ² . This was performed again on both sides, and a total of 2000 mJ / cm ^{2 was} exposed to prepare a printing original plate.

  Table 1 shows the results of measuring the laser engraving property and the rate of mass change with respect to each solvent for the printing original plates of each Example and Comparative Example.

Printing plate of example, printing a solubility parameter of ^{20 J} 1/2 ^{/ cm 3/2} or more mass change ratio with respect to the solvent, the solubility parameter of the repeating units of the Comparative Example is ^{20 J} 1/2 ^{/ cm 3/2} or more It was lower than the original plate and was excellent in solvent resistance against the solvent.
In addition, when producing an original printing plate, when aromatic diisocyanate is used as the polyisocyanate compound, better performance in terms of solvent resistance and laser engraving than when aliphatic diisocyanate is used. A printing original plate having was obtained.
[Examples 4 to 5]
(Printing evaluation of liquid crystal alignment film)
Printing masters were prepared in the same manner as in Examples 1 and 2 using the photosensitive resin compositions obtained in Synthesis Examples 1 and 2, respectively. Table 2 shows the laser engraving properties of the printing original plate. Printing evaluation of the alignment liquid for liquid crystal was carried out using a printing plate in which 50% halftone dots (relief depth 20 μm) were drawn on the printing original plate by laser engraving. For printing, a flexo printability tester (IGT-F1 manufactured by IG Testing Systems Co., Ltd.) was used, and the printing plate was pasted on the plate cylinder using a double-sided tape. As a substrate to be printed, an ITO film (anode) having a thickness of 0.1 μm is formed on the surface of a glass substrate having a thickness of 1.0 mm by a vacuum deposition method, and then UV-ozone cleaning is performed to remove deposits such as organic matter. After the removal, a 3% by mass solution of polyamic acid varnish (solvent: N-methyl-2-pyrrolidone / butyl cellosolve = 90/10) was applied to the surface of the equipment on the ITO film side and baked at 220 ° C. for 1 hour. A polyimide film was used. The results are shown in Table 2.
(Measurement of mass change rate)
A test sample prepared from the printing original plate was immersed in a mixed solvent of N-methyl-2-pyrrolidone / butylcellosolve = 90/10 (mass ratio) used in the liquid crystal alignment film solution at 20 ° C. for 24 hours, and then the surface The droplet adhering to the surface was wiped off, and the mass change rate was determined by the mass change rate measurement method by measuring the amount of mass increase. The results are shown in Table 2.
[Comparative Example 2]
(Printing evaluation of liquid crystal alignment film)
A printing original plate was prepared in the same manner as in Comparative Example 1 using the photosensitive resin composition obtained in Comparative Synthesis Example 1. Table 2 shows the laser engraving properties of the printing original plate. Printing, drying, and baking were performed in the same manner as in Examples 4 to 5 using a printing plate in which 50% halftone dots (relief depth 20 μm) were drawn on the printing original plate by laser engraving. The results are shown in Table 2.

(Measurement of mass change rate)
A test sample prepared from the printing original plate was immersed in the N-methyl-2-pyrrolidone / butyl cellosolve = 90/10 mixed solvent used in the liquid crystal alignment film solution at 20 ° C. for 24 hours, and then adhered to the surface. The mass change rate was calculated | required by the said mass change rate measuring method by wiping a drop and measuring the amount of mass increase. The results are shown in Table 2.

［ブラックマトリックスの製造方法について］
〔実施例６〜７〕
（ポリアミック酸溶液の作製）
γ−ブチロラクトン（３８２５ｇ）溶剤中で、ピロメリット酸二無水物（１４９．６ｇ）、ベンゾフェノンテトラカルボン酸二無水物（２２５．５ｇ）、３，３’−ジアミノジフェニルエーテル（２１０．２ｇ）、ビス−３−（アミノプロピル）テトラメチルシロキサン（１７．４ｇ）を６０℃、３時間反応させた後、無水マレイン酸（２．２５ｇ）を添加し、更に６０℃、１時間反応させることによって、前駆体であるポリアミック酸溶液（ポリマー濃度１５質量％）を得た。
（顔料分散液の作製）
酸化シリコンで表面被覆したチタンブラック粒子１１．２ｇ、前記ポリマー濃度１５質量％のポリアミック酸溶液１８．７ｇ、Ｎ−メチル−２−ピロリドン５７．２ｇ、及び３−メチル−３−メトキシブチルアセテート１２．９ｇをガラスビーズ１００ｇとともに、ホモジナイザーを用いて、７０００ｒｐｍで３０分間処理後、ガラスビーズを濾過により除去し、顔料濃度１４質量％の顔料分散液を得た。このときのチタンブラック／ポリイミド樹脂の質量比率は８０／２０であった。
なお、チタンブラック樹脂表面への絶縁被膜の形成方法は下記のとおりである。まず、チタンブラックを水中に分散させた後、ダイノミル解砕機でチタンブラックを十分解砕した。該分散液に、シリコンテトタエトキシドのエチルアルコール溶液を滴下しながらチタンブラック表面に絶縁被膜である酸化シリコンの被膜を形成した。その後、生成物を濾過して乾燥後、粉砕することによって絶縁被膜の形成されたチタンブラックを得た。
顔料分散液２７．５ｇに、前記のポリマー濃度１５質量％のポリアミック酸溶液３．７ｇ、γ−ブチロラクトン１ｇ、Ｎ−メチル−２−ピロリドン６ｇ、３−メチル−３−メトキシブチルアセテート１．８ｇを添加混合し、黒色ペーストを作製した。
（ブラックマトリックスの印刷評価）
合成例１〜２で得られた感光性樹脂組成物を用いて実施例１〜２とそれぞれ同様にして印刷原版を作成した。当該印刷原版のレーザー彫刻性を表３に示す。当該印刷原版にレーザー彫刻によりパターンを描画した印刷版を用い、前記黒色ペーストの印刷評価を実施した。印刷にはフレキソ用印刷適性テスター（アイジーティ・テスティングシステムズ社製ＩＧＴ−Ｆ１）を用い、版胴上に前記印刷版を、両面テープを用いて貼り付けた。被印刷体としては、厚さ１．０ｍｍの無アルカリガラス基板を用いた。焼成後のブラックマトリックスの膜厚が、１μｍとなるように前記黒色ペーストを印刷した後、１４５℃でプリベークを行い、ポリイミド前駆体薄膜を形成した。次いで該ポリイミド前駆体薄膜を２９０℃に加熱して熱硬化を行いポリイミドに転換してブラックマトリックスとした。結果を表３に示す。
（質量変化率の測定）
前記印刷原版から作製した試験サンプルを、Ｎ−メチル−２−ピロリドン／γ−ブチロラクトン／３−メチル−３−メトキシブチルアセテート＝１／１／１（質量比）混合溶剤中に、２０℃、２４時間浸漬後、表面に付着した液滴をふき取り、質量増加量を測定することにより、前記質量変化率測定法により質量変化率を求めた。結果を表３に示す。

[Black matrix manufacturing method]
[Examples 6 to 7]
(Preparation of polyamic acid solution)
In a solvent of γ-butyrolactone (3825 g), pyromellitic dianhydride (149.6 g), benzophenonetetracarboxylic dianhydride (225.5 g), 3,3′-diaminodiphenyl ether (210.2 g), bis- After reacting 3- (aminopropyl) tetramethylsiloxane (17.4 g) at 60 ° C. for 3 hours, maleic anhydride (2.25 g) was added, and the mixture was further reacted at 60 ° C. for 1 hour. A polyamic acid solution (polymer concentration: 15% by mass) was obtained.
(Preparation of pigment dispersion)
12.1 g of titanium black particles surface-coated with silicon oxide, 18.7 g of a polyamic acid solution having a polymer concentration of 15% by mass, 57.2 g of N-methyl-2-pyrrolidone, and 12.3 methyl-3-methoxybutyl acetate. 9 g was treated with 100 g of glass beads together with a homogenizer at 7000 rpm for 30 minutes, and then the glass beads were removed by filtration to obtain a pigment dispersion having a pigment concentration of 14% by mass. At this time, the mass ratio of titanium black / polyimide resin was 80/20.
In addition, the formation method of the insulating film on the titanium black resin surface is as follows. First, after disperse | distributing titanium black in water, the titanium black was fully disintegrated with the dynomill disintegrator. A silicon oxide film, which is an insulating film, was formed on the titanium black surface while dropping an ethyl alcohol solution of silicon tetota ethoxide into the dispersion. Thereafter, the product was filtered, dried, and pulverized to obtain titanium black on which an insulating film was formed.
To 27.5 g of the pigment dispersion, 3.7 g of the polyamic acid solution having a polymer concentration of 15% by mass, 1 g of γ-butyrolactone, 6 g of N-methyl-2-pyrrolidone, and 1.8 g of 3-methyl-3-methoxybutyl acetate are added. Addition and mixing were performed to prepare a black paste.
(Black matrix printing evaluation)
Printing masters were prepared in the same manner as in Examples 1 and 2 using the photosensitive resin compositions obtained in Synthesis Examples 1 and 2, respectively. Table 3 shows the laser engraving properties of the printing original plate. Printing evaluation of the black paste was carried out using a printing plate on which a pattern was drawn by laser engraving on the printing original plate. For printing, a flexo printability tester (IGT-F1 manufactured by IG Testing Systems Co., Ltd.) was used, and the printing plate was pasted on the plate cylinder using a double-sided tape. As the substrate to be printed, an alkali-free glass substrate having a thickness of 1.0 mm was used. The black paste was printed so that the film thickness of the black matrix after firing was 1 μm, and then prebaked at 145 ° C. to form a polyimide precursor thin film. Next, the polyimide precursor thin film was heated to 290 ° C. to be thermoset and converted to polyimide to obtain a black matrix. The results are shown in Table 3.
(Measurement of mass change rate)
A test sample prepared from the printing original plate was mixed with N-methyl-2-pyrrolidone / γ-butyrolactone / 3-methyl-3-methoxybutyl acetate = 1/1/1 (mass ratio) mixed solvent at 20 ° C., 24 ° C. After immersion for a period of time, the droplets adhering to the surface were wiped off, and the amount of mass increase was measured to determine the mass change rate by the mass change rate measurement method. The results are shown in Table 3.

[Comparative Example 3]
(Black matrix printing evaluation)
A printing original plate was prepared in the same manner as in Comparative Example 1 using the photosensitive resin composition obtained in Comparative Synthesis Example 1. Table 3 shows the laser engraving properties of the printing original plate. Printing, drying, and baking were performed in the same manner as in Examples 6 to 7, using a printing plate on which a pattern was drawn by laser engraving on the printing original plate. The results are shown in Table 3.
(Measurement of mass change rate)
A test sample prepared from the printing original plate was mixed with N-methyl-2-pyrrolidone / γ-butyrolactone / 3-methyl-3-methoxybutyl acetate = 1/1/1 (mass ratio) mixed solvent at 20 ° C., 24 ° C. After immersion for a period of time, the droplets adhering to the surface were wiped off, and the amount of mass increase was measured to determine the mass change rate by the mass change rate measurement method. The results are shown in Table 3.

[Method for producing colored layer for color filter]
[Examples 8 to 9]
(Pixel preparation)
In a mixed solvent of γ-butyrolactone and N-methyl-2-pyrrolidone, pyromellitic dianhydride (0.49 molar equivalent), 4,4′-diaminodiphenyl ether (0.95 molar equivalent), and bis-3 -(Aminopropyl) tetramethylsiloxane (0.05 molar equivalent) was reacted to obtain a polyamic acid solution (polymer concentration 20% by mass). 200 g of this polyamic acid solution was taken out, and 186 g of γ-butyrolactone and 64 g of butyl cellosolve were added thereto to obtain a polyamic acid for a pixel having a polymer concentration of 10% by mass.
Pigment Red 177 (anthraquinone red) 4 g, γ-butyrolactone 40 g, and butyl cellosolve 6 g were dispersed together with glass beads 100 g using a homogenizer at 7000 rpm for 30 minutes, the glass beads were removed by filtration, and a pigment concentration of 8% by mass was dispersed. A liquid was obtained. To 30 g of the pigment dispersion, 30 g of the pixel polyamic acid solution having a polymer concentration of 10% by mass was added and mixed to obtain a red paste.
(Pixel print evaluation)
Printing masters were prepared in the same manner as in Examples 1 and 2 using the photosensitive resin compositions obtained in Synthesis Examples 1 and 2, respectively. Table 4 shows the laser engraving properties of the printing original plate. Printing evaluation of the red paste was performed using a printing plate on which a pattern was drawn by laser engraving on the printing original plate. For printing, a flexo printability tester (IGT-F1 manufactured by IG Testing Systems Co., Ltd.) was used, and the printing plate was pasted on the plate cylinder using a double-sided tape. As the substrate to be printed, an alkali-free glass substrate having a thickness of 1.0 mm was used. The red paste was printed so that the thickness of the colored layer after firing was 1 μm, prebaked at 145 ° C., and then heated to 290 ° C. to perform thermosetting. The results are shown in Table 4.
(Measurement of mass change rate)
The test sample prepared from the printing original plate was immersed in a mixed solvent of N-methyl-2-pyrrolidone / γ-butyrolactone / butyl cellosolve = 1/1/1 (mass ratio) at 20 ° C. for 24 hours, and then adhered to the surface. The droplets were wiped off, and the mass increase rate was measured to determine the mass change rate by the mass change rate measurement method. The results are shown in Table 4.
[Comparative Example 4]
(Pixel print evaluation)
A printing original plate was prepared in the same manner as in Comparative Example 1 using the photosensitive resin composition obtained in Comparative Synthesis Example 1. Table 4 shows the laser engraving properties of the printing original plate. Printing, drying, and baking were performed in the same manner as in Examples 8 to 9, using a printing plate on which a pattern was drawn by laser engraving on the printing original plate. The results are shown in Table 4.
(Measurement of mass change rate)
A test sample prepared from a printing original plate was immersed in a mixed solvent of N-methyl-2-pyrrolidone / γ-butyrolactone / butyl cellosolve = 1/1/1 (mass ratio) at 20 ° C. for 24 hours, and then a liquid adhered to the surface The mass change rate was calculated | required with the said mass change rate measuring method by wiping a drop and measuring the amount of mass increase. The results are shown in Table 4.

[About manufacturing methods for banks, etc.]
[Examples 10 to 11]
(Preparation of polyamic acid composition for bank formation)
In a mixed solvent of γ-butyrolactone and N-methyl-2-pyrrolidone, pyromellitic dianhydride (0.49 molar equivalent), 4,4′-diaminodiphenyl ether (0.95 molar equivalent), bis-3- (Aminopropyl) tetramethylsiloxane (0.05 molar equivalent) was reacted to obtain a polyamic acid solution (polymer concentration 20% by mass). 200 g of this polyamic acid solution was taken out, and 186 g of γ-butyrolactone and 64 g of butyl cellosolve were added thereto to obtain a polyamic acid composition for bank formation having a polymer concentration of 10% by mass.
(Bank printing evaluation)
Printing masters were prepared in the same manner as in Examples 1 and 2 using the photosensitive resin compositions obtained in Synthesis Examples 1 and 2, respectively. Table 5 shows the laser engraving properties of the printing original plate. Printing evaluation of the polyamic acid for bank formation was performed using a printing plate in which a pattern was drawn on the printing original plate by laser engraving. For printing, a flexo printability tester (IGT-F1 manufactured by IG Testing Systems Co., Ltd.) was used, and the printing plate was pasted on the plate cylinder using a double-sided tape. As the substrate to be printed, an ITO film (anode) having a thickness of 0.1 μm is formed on the surface of a non-alkali glass substrate having a thickness of 1.0 mm by a vacuum deposition method, and then UV-ozone cleaning is performed to attach an organic substance or the like What removed the kimono was used. The bank-forming polyamic acid composition was printed on the surface of the substrate on the ITO film side, prebaked at 145 ° C., and then heated to 290 ° C. for thermosetting to produce a bank. The results are shown in Table 5.
(Measurement of mass change rate)
The test sample prepared from the printing original plate was immersed in a mixed solvent of N-methyl-2-pyrrolidone / γ-butyrolactone / butyl cellosolve = 1/1/1 (mass ratio) at 20 ° C. for 24 hours, and then adhered to the surface. The mass change rate was determined by wiping the droplets and measuring the amount of mass increase. The results are shown in Table 5.

[Comparative Example 5]
(Bank printing evaluation)
A printing original plate was prepared in the same manner as in Comparative Example 1 using the photosensitive resin composition obtained in Comparative Synthesis Example 1. Table 5 shows the laser engraving properties of the printing original plate. Printing, drying, and baking were performed in the same manner as in Examples 10 to 11 using a printing plate on which a pattern was drawn by laser engraving on the printing original plate. The results are shown in Table 5.
(Measurement of mass change rate)
The test sample prepared from the printing original plate was immersed in a mixed solvent of N-methyl-2-pyrrolidone / γ-butyrolactone / butyl cellosolve = 1/1/1 (mass ratio) at 20 ° C. for 24 hours, and then adhered to the surface. The mass change rate was determined by wiping the droplets and measuring the amount of mass increase. The results are shown in Table 5.

Since the prepolymer of the present invention and the polymer produced therefrom are excellent in solvent resistance, they can be used in various applications such as clothing and electronic parts that may be exposed to a solvent. For printing that may contain the ink, for example, relief printing such as flexographic printing and letterpress printing; lithographic printing such as offset printing; intaglio printing such as gravure printing; various printing such as stencil printing such as screen printing It is possible to manufacture printing plates and printing original plates.
In particular, the prepolymer of the present invention, the polymer produced therefrom, and the photosensitive resin composition containing this polymer are suitable for producing a printing original plate for laser engraving which forms a printing plate by forming an image by laser engraving.
By the method for producing a liquid crystal alignment film of the present invention, it is possible to efficiently produce a liquid crystal alignment film having a uniform film thickness. A liquid crystal display device including the liquid crystal alignment film can be provided.
The black matrix can be produced with high accuracy by the black matrix production method of the present invention. Further, it is possible to provide a color filter for liquid crystal display including the black matrix.
With the method for producing a colored layer for a color filter of the present invention, it is possible to produce a colored layer for a color filter with high accuracy. In addition, it is possible to provide a color filter including the colored layer.
The bank manufacturing method of the present invention can provide a method for manufacturing a bank with high accuracy.

Claims (33)

A polymer having a repeating unit solubility parameter of less than 20 J ^1/2 / cm ^3/2 and having an active hydrogen group at both ends and an isocyanate group equivalent of less than the equivalent of the terminal active hydrogen group of the prepolymer; An isocyanate compound and a polymer obtained by polymerizing by a covalent bond,
The above polymer in which the terminal active hydrogen group remaining in the polymerized prepolymer is bonded to the isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate by a covalent bond.   The polymer of Claim 1 whose number average molecular weights of the said prepolymer are 300-50,000.   The polymer according to claim 1 or 2, wherein the polyisocyanate compound is a diisocyanate compound.   The polymer according to any one of claims 1 to 3, wherein the polyisocyanate compound is an aromatic diisocyanate. The polymer as described in any one of Claims 1-4 represented by following formula (1).

(Wherein R _p each independently represents a residue obtained by removing the active hydrogen groups at both ends from the prepolymer according to claim 1, and R _q represents a residue obtained by removing the isocyanate group from the diisocyanate compound. R _r represents an alkyl moiety of isocyanatoalkyl acrylate and / or isocyanatoalkyl methacrylate, R _S and R _T each independently represents a methyl group or a hydrogen atom, and L represents 1 or more Represents an integer.)   Reacting an isocyanate alkyl acrylate and / or an isocyanate alkyl methacrylate with a polyisocyanate compound having an isocyanate group equivalent of less than the equivalent of the terminal active hydrogen group of the prepolymer, and the isocyanate polymer. The manufacturing method of the polymer as described in any one of Claims 1-5. A prepolymer for producing a printing plate or printing original plate comprising a repeating unit having a solubility parameter of less than 20 J ^1/2 / cm ^3/2 .   The prepolymer for producing a printing plate or printing plate precursor according to claim 7, wherein the number average molecular weight is 300 to 50,000. A printing plate or a printing plate production polymer obtained by polymerizing the prepolymer according to claim 7 or 8 and a polyisocyanate compound having an isocyanate group equivalent equivalent to the terminal hydroxyl group equivalent of the prepolymer by a covalent bond Because
The above polymer in which the remaining isocyanate group of the polymerized polyisocyanate compound and hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate are bonded by a urethane bond.   The polymer according to claim 9, wherein the polyisocyanate compound is a diisocyanate compound.   The polymer according to claim 9 or 10, wherein the polyisocyanate compound is an aromatic diisocyanate. The polymer as described in any one of Claims 9-11 represented by following formula (2).

(Wherein R _p each independently represents a residue obtained by removing the active hydrogen groups at both ends from the prepolymer according to claim 1, and R _q represents a residue obtained by removing the isocyanate group from the diisocyanate compound. R _u represents an alkyl moiety of hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate, R _S and R _T each independently represents a methyl group or a hydrogen atom, and m is one or more arbitrary Represents an integer.)   A reaction between the prepolymer according to claim 7 or 8, a polyisocyanate compound having an isocyanate group equivalent equivalent to the equivalent of the terminal active hydrogen group of the prepolymer, and a hydroxyalkyl acrylate and / or hydroxyalkyl methacrylate. The manufacturing method of the polymer as described in any one of Claims 9-12 containing this.   A photosensitive resin composition for producing a printing plate or printing original plate comprising the polymer (a) produced from the prepolymer according to claim 7 or 8.   The polymer (a) is a polymer having a covalent bond formed between a terminal active hydrogen group of the prepolymer and another compound, and a polymer containing a polymerizable unsaturated group. The photosensitive resin composition as described.   The photosensitive resin composition of Claim 15 whose said covalent bond is a urethane bond.   The photosensitive resin composition according to claim 15 or 16, wherein the polymerizable unsaturated group is a double bond.   The photosensitive resin composition as described in any one of Claims 14-17 whose said polymer (a) is a polymer as described in any one of Claims 1-5 and 9-12.   The photosensitive resin composition as described in any one of Claims 14-18 whose number average molecular weights of the said polymer (a) are 1,000-100,000.   The photosensitive resin composition according to any one of claims 14 to 19, further comprising an organic compound (b) having a polymerizable unsaturated group and having a number average molecular weight of less than 5,000.   The photosensitive resin composition according to any one of claims 14 to 20, further comprising inorganic fine particles (c).   The photosensitive resin composition according to any one of claims 14 to 21, further comprising a photopolymerization initiator (d).   The photosensitivity according to any one of claims 14 to 22, wherein the polymer (a) contains an addition polymer produced from the prepolymer according to claim 7 or 8 and an aromatic diisocyanate. Resin composition.   The photosensitive resin composition according to any one of claims 14 to 23, which is used for producing a printing original plate for laser engraving.   A printing plate or printing original plate comprising the polymer (a) produced from the prepolymer according to claim 7 or 8.   The printing plate or printing original plate manufactured using the photosensitive resin composition as described in any one of Claims 14-24. A step of molding the photosensitive resin composition according to any one of claims 14 to 24 into a sheet shape or a cylindrical shape,
A step of crosslinking and curing the molded photosensitive resin composition by irradiation with light or an electron beam;
A printing plate or printing original plate produced by a method comprising:   The printing plate or printing original plate according to any one of claims 25 to 27, which is used for laser engraving.   The printing plate or printing original plate as described in any one of Claims 25-28 which is a flexographic printing plate or a flexographic printing original plate. Transferring the liquid crystal alignment film liquid on the printing plate onto the printing substrate, drying and removing the solvent in the transferred liquid crystal alignment film liquid, and immobilizing the liquid crystal alignment film liquid on the printing substrate. A method for producing a liquid crystal alignment film comprising:
30. The method of claim 25, wherein the printing plate is a printing plate according to any one of claims 25-29. The black matrix coating composition on the printing plate is transferred onto the substrate to be printed, the solvent in the transferred black matrix coating composition is removed by drying, or the transferred black matrix coating composition is transferred to the black matrix coating composition. A method for producing a black matrix comprising curing by irradiation with light and immobilizing the coating composition for black matrix on the substrate to be printed,
30. The method as described above, wherein the printing plate is the printing plate according to any one of claims 25 to 29. The colored layer ink on the printing plate is transferred onto the substrate to be printed, and the solvent in the transferred colored layer ink is removed by drying, or the transferred colored layer ink is irradiated with light and cured. A method for producing a colored layer for a color filter, comprising immobilizing the colored layer ink on the substrate to be printed,
30. The method as described above, wherein the printing plate is the printing plate according to any one of claims 25 to 29. The bank-forming composition on the printing plate is transferred onto the substrate to be printed, the solvent in the transferred bank-forming composition is removed by drying, or the transferred bank-forming composition is irradiated with light. And a method of producing a bank comprising fixing the bank-forming composition on the substrate to be printed,
30. The method as described above, wherein the printing plate is the printing plate according to any one of claims 25 to 29.