JP2007025427A - Ink discharged printed material and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a printed material with high quality and high reliability while preventing color mixing and a void in inexpensively producing a printed material in a simple process using an ink discharge system, and to provide a method for manufacturing the printed material. <P>SOLUTION: A compound having two moieties, one moiety showing compatibility with a resin binder in a resin composition used for forming a barrier wall and the other moiety showing ink-repelling property, and having 40,000 to 100,000 number average molecular weight is incorporated as an ink repelling agent into the resin composition. The obtained resin composition is used to form a barrier wall on a substrate. The barrier wall shows 24 to 30 mN/m critical surface tension. The ink repelling compound is concentrated on an interface between the barrier wall and the environment, with the moiety showing compatibility with the resin binder being oriented inside the barrier wall and the moiety showing ink repelling property being oriented outside the barrier wall. Thereby, it is found that the barrier wall shows appropriate ink repelling property. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a printed matter manufactured using an ink ejection device. As this printed matter, a color filter can be exemplified, and a colored layer of the color filter is formed using an ink discharge device. Moreover, an electroluminescent element can also be illustrated as said printed matter, and this organic light emitting layer is formed using an ink discharge apparatus. In addition, circuit boards, thin film transistors, microlenses, biochips and the like can be exemplified as printed matter.

For example, various studies have been made on a method for forming a colored layer of the color filter, and a photolithography method, an ink discharge method, and the like are known as typical methods. The pixel pattern formation of the color filter by the photolithography method forms the coating film of the photosensitive resin layer of each color on the entire substrate, and after exposing the pattern, removes the unnecessary part of the coating film, and the remaining pattern is replaced with each pixel. And In this method, a large amount of material is wasted because most of the coating film is developed and removed. Furthermore, since the exposure and development processes are performed for each pixel, the number of processes increases. This photolithography system is used not only for color filters but also for manufacturing various optical elements and electric elements such as electroluminescence elements.
And the said problem of the photolithographic system became remarkable with the enlargement of a board | substrate, and came to show a problem both in cost and an environmental aspect. As a method for overcoming this problem, a method of manufacturing an optical element by an ink discharge method has recently attracted attention. For example, when a color filter is manufactured by an ink ejection method, resin compositions of three colors R, G, and B are used as inks, and each color can be printed simultaneously in a single process. For this reason, ink materials such as pigments are hardly wasted, and at the same time, the formation process of the three-color pixels is shortened, so that a reduction in environmental burden and a significant cost reduction can be expected.

  As described above, since the ink ejection method can simplify the manufacturing process and reduce the cost, it is applied to the manufacture of optical elements such as color filters and electroluminescence elements. However, as a problem of the ink ejection method, there are problems of “color mixing” and “white spot”. Hereinafter, a case where a color filter is manufactured will be described as an example.

  “Mixed color” is a defect in which inks are mixed between adjacent pixels and colored inks of different colors are mixed. Color mixing occurs when the discharged ink overflows beyond the partition wall. In order to solve this problem, methods described in Patent Documents 1 to 5 have been proposed as a method of manufacturing a color filter substrate using an ink ejection method. In Patent Documents 1 to 5, a black resin layer containing an ink repellent agent such as a fluorine-containing compound is formed by a photolithography method or the like in order to prevent ink bleeding and color mixing in the ink ejection process of the ink. It is described to do.

“White spots” are defects that occur mainly because the applied ink cannot sufficiently and uniformly diffuse into the area surrounded by the partition walls. This causes display defects such as lowering of the screen. White spots occur when the ink repellent oozes from the side surface of the partition wall. The exudation of the ink repellent from the side surface of the partition wall is promoted by heating. Referring to FIG. 1, when the partition walls are formed by photolithography, the resin composition 20 to be the partition walls is applied to the substrate 10 (FIG. 1A), and then exposed and developed using a mask (FIG. 1 ( b) After (c)), the partition is heated (post-baked). At this time, as shown in FIG. 1D, the ink repellent oozes out from a part of the partition wall, and the ink 41 ejected from the ink ejection part 100 (head part) of the ink ejection device does not spread out and is white. (FIG. 1 (e)).
In addition, when a photosensitive resin composition containing an ink repellent agent is applied onto a substrate, and this is exposed and developed to form a partition, the ink repellent agent present in the partition opening is not sufficiently removed by the developer, Even when the ink repellent agent remains in the pixel, white spots occur (FIGS. 2A to 2E).

Hereinafter, a typical method for manufacturing an optical element using an ink discharge apparatus will be described in Patent Documents 1 to 5. Patent Documents 1 to 4 describe a method in which a fluorine-containing material is used as an ink repellent for the partition walls of a color filter manufactured by an ink ejection method. According to this method, color mixing by the ink ejection device can be prevented, but since the resin molecules of the ink repellent agent generally contain fluorine atoms, the polarity of the entire resin molecules is high, and other resins contained in the ink Compatibility with components and solvent components was low. For this reason, in the process of heating and baking after the exposure and development of the partition wall pattern, the ink repellent agent oozes out from the partition wall to the pixel, resulting in a problem of “white spots”. Furthermore, even when the partition walls are formed using this ink repellent agent, the ink repellent component is not concentrated on the partition wall surface and the ink repellent agent molecules are dispersed. ”May occur, and it cannot be said that the“ color mixing ”problem has been sufficiently solved.
Therefore, in order to prevent the ink repellent from adhering to the partition wall and oozing into the pixel, and at the same time to maintain sufficient ink repellency, one side of the ink repellent is a resin-compatible alkyl group and the other side is ink repellent. There has been proposed a method using a compound having a characteristic perfluoroalkyl group and imparting ink repellency only to one side of the molecular chain (Patent Document 5).

However, even if a compound having a structure in which a molecular chain having resin compatibility and a molecular chain having ink repellency are linked is used as an ink repellant, the ink repellant easily oozes out from the side wall of the partition. The problem of “missing” could not be solved.
JP-A-6-347637 JP-A-7-35915 Japanese Patent Laid-Open No. 7-35916 JP 7-35917 A JP-A-9-203803 (described in paragraphs 0030 to 0035)

  The present invention has been made in order to solve the above-mentioned problems, and when producing printed matter at low cost by a simple process using an ink ejection method, it prevents color mixing and white spots and has high quality and high reliability. It is to provide a printed material and a manufacturing method thereof.

By the way, the present inventors have found that a resin composition for forming a partition wall has a compound having two parts, a part exhibiting compatibility with a resin binder in the resin composition and a part having ink repellency (hereinafter referred to as “repellency”). Ink compound) was added as an ink repellent agent, and a pattern was formed on the substrate using this resin composition and heated to form partition walls. At this time, when the ink repellent compound was polymerized by a reprecipitation method and the number average molecular weight was adjusted to 40,000 to 100,000, the critical surface tension of the partition after heating was 24 to 30 mN / m.
In the partition wall thus prepared, the ink repellent compound is concentrated on the interface between the partition wall surface and the outside, and the portion of the ink repellent compound that exhibits compatibility with the resin binder is oriented inside the partition wall, The site | part which has ink repellency among compounds was orientated to the partition outer side.
Further, it was found that the ink repellent agent does not ooze out from the side wall of this partition wall.
And when ink was discharged with the ink discharge apparatus with respect to the board | substrate which has this partition, this partition showed favorable ink repellency, and color mixing and the white-out defect did not generate | occur | produce.

The present invention has been made based on such knowledge, and the invention according to claim 1 comprises a substrate,
A partition that divides the surface of the substrate into a number of regions;
An ink film ejected and formed using an ink ejection device on the multiple areas;
In the ink discharge printed matter having
The partition wall is made of an ink repellent material containing a resin binder and an ink repellent agent,
This ink repellent agent is a compound having a part exhibiting compatibility with the resin binder and a part having ink repellency,
The partition wall has a critical surface tension of 24 to 30 mN / m,
A number average molecular weight of the ink repellent agent is 40,000 to 100,000.

The invention according to claim 2 is the ink-discharge printed matter according to claim 1, wherein the site having ink repellency is a fluoroalkyl group.

According to a third aspect of the present invention, there is provided the ink ejected printed matter according to the first or second aspect, wherein the portion having ink repellency is a perfluoroalkyl group.

Invention of Claim 4 is an ink discharge printed matter in any one of Claims 1-3 in which the site | part which has compatibility with a resin binder contains the principal chain of an alkyl group, an alkylene group, and a polyvinyl alcohol group.

According to a fifth aspect of the present invention, there is provided the ink ejection printed matter according to any one of the first to fourth aspects, wherein the partition is a light shielding layer.

The invention according to claim 6 is the ink-discharged printed matter according to claim 5, wherein the partition is a light shielding layer including a black light shielding member.

The invention according to claim 7 is that the substrate is a transparent substrate, the ink film is a colored layer formed of an ink containing a colorant, and a color filter having a plurality of colored layers. It is an ink discharge printed matter in any one of Claims 1-6 characterized by the above-mentioned.

According to an eighth aspect of the present invention, the substrate is a transparent substrate, the ink film is an organic light emitting layer formed of an ink containing an organic light emitting material, and an organic electroluminescent device comprising a plurality of colors of organic light emitting layers. It is a sense element, The ink discharge printed matter according to any one of claims 1 to 6.

  According to the present invention, when the partition walls are formed, the ink repellent agent can be concentrated on the interface of the partition walls, and the ink repellency can be improved. At the same time, it was possible to prevent the ink repellent from exuding from the side surface of the partition wall. As a result, it is possible to produce an ink discharge printed matter that does not cause color mixing or white spots by a simple process with a high yield by the ink discharge method.

Hereinafter, preferred embodiments of the present invention will be described.
In addition, the printed matter according to the present invention can be suitably used as an optical component constituting a display screen of a display display. In this case, a large number of the regions correspond to pixels constituting the display screen. In addition, a black light shielding member can be mixed in the partition wall to have a function as a light shielding layer.
As the optical component, for example, a color filter constituting a display screen of a color liquid crystal display can be exemplified, and in this case, the ink film constitutes a colored layer for coloring transmitted light, and this colored layer is different for each region. A plurality of colors having colors.
Moreover, an organic electroluminescent element can also be illustrated as an optical component, and an ink film comprises an organic light emitting material layer in this case. In addition, the organic light emitting material layer of a plurality of colors having different colors for each region.
In addition, examples of the printed material according to the present invention include circuit boards, thin film transistors, microlenses, and biochips.

  The substrate of the present invention is used as a support substrate for printed matter. Specifically, a known transparent substrate material such as a glass substrate, a quartz substrate, a plastic substrate, a dry film, or the like can be used. Among them, the glass substrate is excellent in transparency, strength, heat resistance, and weather resistance.

The partition wall of the present invention has a function of dividing the surface of the substrate into a plurality of areas and preventing color mixing of the ink ejected into each of the many areas. In the present invention, by adjusting the critical surface tension of the partition wall to 24 to 30 mN / m, ink color mixing is prevented and at the same time, white spots are prevented. When the critical surface tension of the partition wall is less than 24 mN / m, the ink repellent agent oozes out from the partition wall, causing a white spot problem. When the partition surface exceeds 30 mN / m, the ink repellency is insufficient and the ink color mixing problem occurs. . As will be described later, as one of means for adjusting the critical surface tension of the partition wall, adjusting the number average molecular weight of the ink repellent agent can be mentioned.
Further, when the printed material is an optical component that constitutes the display screen of the display, the contrast of the display screen can be improved by providing light shielding to the partition walls. In any case, it is necessary to contain the resin composition constituting the partition, the resin binder and the ink repellent as essential components.
The resin binder fixes and fixes the partition wall to the substrate, and imparts ink resistance to the partition wall. As the binder resin, a resin containing an amino group, an amide base, a carboxyl group, or a hydroxyl group is preferable. Specifically, a cresol-novolak resin, a polyvinylphenol resin, an acrylic resin, a methacrylic resin, and the like can be given. These resin binders may be used alone or in combination of two or more.
The ink repellent agent imparts ink repellency to the partition walls. As the ink repellent agent, a polymer compound (ink repellent compound) having a portion exhibiting compatibility with a resin binder and a portion having ink repellency is used for the resin composition. For example, a block copolymer having a block showing compatibility with a resin binder and a block having ink repellency can be used as the ink repellent compound.
Such an ink repellent agent having both parts appears on the partition wall surface over time or by heating. And the site | part which shows compatibility with a resin binder is made into an inner side, the site | part which has ink repellency is made into the outer side, it stops on the partition surface, and the above-mentioned optimal critical surface tension is provided to the surface. The number average molecular weight of the ink repellent compound is adjusted to 40,000 to 10,000. As the number average molecular weight of the ink repellent, a value obtained by converting data measured by a GPC (gel permeation chromatography) method into a conversion value based on a calibration curve of a polystyrene standard sample is used.
When the number average molecular weight of the ink repellent agent is less than 40,000, the intermolecular interaction between the ink repellent agent and the resin binder becomes weak, and the critical surface tension of the partition wall increases. As a result, the ink repellent effect cannot be achieved and a problem of color mixing occurs. In addition, the ink repellent agent is eluted from the partition wall, causing a problem of white spots. On the other hand, if the number average molecular weight of the ink repellent agent exceeds 100,000, the intermolecular interaction between the ink repellent agent and the resin binder becomes strong, and the critical surface tension of the partition wall may be too low.
The site having water repellency can use a fluoroalkyl group, and more preferably a perfluoroalkyl group. As a site exhibiting compatibility with the resin binder, a known lipophilic polymer such as an alkyl group, an alkylene group, or polyvinyl alcohol can be used.
In addition, the fluorine-containing compound or silicon-containing compound described later can be used at the same time as the ink repellent agent. Specific examples of the fluorine-containing compound include vinylidene fluoride, vinyl fluoride, ethylene trifluoride and the like, and fluorinated resins such as copolymers thereof. These fluorine-containing compounds can be used alone or in combination of two or more. Examples of the silicon-containing compound include organic silicon in the main chain or side chain, and include silicon resins and silicone rubbers containing a siloxane component. These silicon-containing compounds can be used alone or in combination of two or more. Further, the fluorine-containing compound and the silicon-containing compound, or other ink repellent components may be used in combination.
The ink repellent agent in the present invention is preferably 0.01% by weight to 10% by weight with respect to the resin composition.
In addition, the black light shielding member imparts light shielding properties to the partition walls and improves the contrast of the display screen. As the black light shielding member, black pigment, black dye, carbon black, aniline black, graphite, iron black, titanium oxide, inorganic pigment, and organic pigment can be used. These black light shielding members may be used alone or in combination of two or more.
Moreover, the resin composition can be used by diluting with an appropriate solvent as required. Specific examples of the solvent include dichloromethane, dichloroethane, chloroform, acetone, cyclohexanone, ethyl acetate, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethylethoxyacetate, 2-butoxyethyl acetate, 2-methoxyethyl ether, 2-ethoxyethyl ether, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2′ethoxyethoxy) ethyl acetate, 2- (2-butoxyethoxy) ) Ethyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, tetrahydrofuran and the like can be used. The amount of the solvent used is desirably a coating that is uniform when printed or coated on a substrate, and can form a coating film without pinholes and uneven coating. As a content ratio of such a solvent, it is preferable to prepare such that the solvent amount is 50 to 97% by weight with respect to the total weight of the resin composition.

In addition, compatible additives such as leveling agents, chain transfer agents, stabilizers, sensitizing dyes, surfactants, coupling agents, and the like can be added to the resin composition as necessary.
Next, the partition wall can be formed using a resin composition by a printing method, a photolithography method, a transfer method, or the like. In the case where the partition walls are formed by photolithography, a photosensitive resin composition obtained by imparting photosensitivity to the resin composition is used. Moreover, when forming a partition by a printing method, resin compositions, such as a thermosetting resin composition, can be used.

<Partition formation by printing method>
First, the case where the partition is formed by a printing method will be described. A resin composition (hereinafter referred to as a printing material) is printed on the substrate using a printing apparatus. The printing material contains a resin binder and an ink repellent as essential components, and further contains a crosslinking agent and a solvent. Further, a black shielding member and the additive may be added. The critical surface tension of the printing material is preferably 30 to 40 mN / m. If it is less than 30 mN / m, the printed resin composition is easily affected by the unevenness of the substrate surface, and if it exceeds 40 mN / m, the printability deteriorates. Subsequently, the printing material is heated in a range of 100 ° C. to 250 ° C. and 3 minutes to 60 minutes.

  In order to optimize the critical surface tension of the partition walls, the printing material preferably has a critical surface tension in the range of 24 to 30 mN / m after being heated under specific heating conditions. If it exceeds 30 mN / m, the ink repellency is insufficient and a problem of white spots occurs when ink is ejected later by an ink ejection device. On the other hand, if it is less than 24 mN / m, the ink repellent agent is excessively concentrated on the surface of the printing material (partition wall), so that the ink repellent agent oozes out from the side surface of the printing material (partition wall) and causes a problem of white spots. The specific heating condition is a case where a hot plate, a hot air furnace, a far-infrared furnace or the like is set at a temperature of about 180 ° C. and heated for about 10 minutes.

<Partition wall formation by photolithography>
A case where the partition walls are formed by photolithography will be described. A resin composition (hereinafter referred to as a photosensitive resin composition) is applied onto the substrate using a spin coater, a slit coater, or the like. The photosensitive resin composition is roughly classified into a positive type and a negative type, and in the case of a negative type photosensitive resin composition, it includes a resin binder, a monomer, a photopolymerization initiator, and the ink repellent. In the case of a positive photosensitive resin composition, the positive photosensitive resin and the ink repellent agent are included. These photosensitive resin compositions may further contain a crosslinking agent, a black shielding member, a pigment, and the additives as necessary. The critical surface tension of the photosensitive resin composition is preferably 30 to 40 mN / m. When it is less than 30 mN / m, the applied resin composition is affected by the unevenness of the substrate surface. When it exceeds 40 mN / m, the applicability of the resin composition deteriorates.

  Then, the board | substrate with which the photosensitive resin composition was apply | coated to one side is exposed using the mask of a partition pattern. The substrate is developed with a developing solution to remove unnecessary photosensitive resin composition, and partition walls are formed on the substrate. When the critical surface tension of the applied resin composition is 30 to 40 mN / m or less, the ink repellent agent is appropriately concentrated on the surface during development, so that development at the lower part of the resin composition proceeds as compared with the upper part. As a result, since the partition wall has an inversely tapered shape, there is an effect that the shape of the ink film ejected and formed using the ink ejecting apparatus becomes flat. Thereafter, the partition wall is heated at 100 to 250 ° C. for about 3 to 60 minutes.

  In order to optimize the critical surface tension of the partition walls, the photosensitive resin composition is preferably adjusted to have a critical surface tension in the range of 24 to 30 mN / m after being heated under specific heating conditions. If it exceeds 30 mN / m, the ink repellency of the photosensitive resin composition is insufficient, and a problem of color mixing occurs when the optical material is later ejected by an ink ejection device. On the other hand, if it is less than 24 mN / m, the ink repellent agent is excessively concentrated on the surface of the photosensitive resin composition (partition wall), so that the ink repellent agent oozes out from the side surface of the photosensitive resin composition (partition wall), resulting in white spots. Arise. The specific heating condition is a case where the temperature of a hot plate, a hot air furnace, a far-infrared furnace, etc. is set to around 180 ° C. and heated for 10 minutes as in the case of the printing material.

<Ink film formation by ink ejection device>
By the above method, a partition having ink repellency is formed on the substrate, and ink is ejected to the opening of the partition using an ink ejection device to form an ink film. As an ink discharge device, there are a piezo conversion method and a heat conversion method depending on the discharge method, and the piezo conversion method is particularly preferable. It is preferable to use an apparatus in which the ink particleization frequency is about 5 to 100 KHz, the nozzle diameter is about 5 to 80 μm, a plurality of heads are arranged, and a number of nozzles are incorporated in one head. In addition, a known ink discharge device can be used. After the ink film is formed, the ink solvent can be dried and cured as necessary by heating.

<Photosensitive resin composition>
As a monomer applied to the photosensitive resin composition, a monomer having a vinyl group or an allyl group, an oligomer, or a molecule having a vinyl group or an allyl group at the terminal or side chain can be used. Specifically, (meth) acrylic acid and salts thereof, (meth) acrylic acid esters, (meth) acrylamides, maleic anhydride, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers, vinyl esters, N -Vinyl heterocycles, allyl ethers, allyl esters, and derivatives thereof. Suitable compounds include, for example, relatively low molecular weight polyfunctional acrylates such as pentaerythritol triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta and hexaacrylate. it can. These monomers may be used alone or in combination of two or more. The amount of the monomer can be in the range of 1 to 200 parts by weight, preferably 50 to 150 parts by weight with respect to 100 parts by weight of the binder resin.

  Examples of the photopolymerization initiator include benzophenone compounds such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, and 4,4′-bis (diethylamino) benzophenone. In addition, as photopolymerization initiators, 1-hydroxycyclohexyl acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one An acetophenone derivative such as can also be used. Further, thioxanthone derivatives such as thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone may be used. Moreover, anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and chloroanthraquinone may be used. In addition, benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether can also be used. Further, acylphosphine derivatives such as phenylbis- (2,4,6-trimethylbenzoyl) -phosphine oxide, 2- (o-chlorophenyl) -4,5-bis (4′-methylphenyl) imidazolyl dimer Lophine isomers such as N-arylglycine such as N-phenylglycine, organic azides such as 4,4′-diazidochalcone, 3,3 ′, 4,4′-tetra (tert-butylperoxycarboxy) Examples include benzophenone and quinonediazide group-containing compounds. These photopolymerization initiators may be used alone or in combination of two or more. The quantity of a photoinitiator can take the range of 0.1-50 weight part with respect to 100 weight part of binder resin, Preferably it is 1-20 weight part.

  Hereinafter, the example which manufactured the color filter as ink discharge printed matter about embodiment of this invention is demonstrated in detail. In addition, the number average molecular weight (Mn) described in the examples was measured by a GPC method using a Shodex column of Showa Denko KK, and expressed as a conversion value based on a calibration curve of a polystyrene standard sample.

(Purification of ink repellent)
(Purification of ink repellent B)
An ink repellent agent “Modiper F2020” (manufactured by NOF Corporation) (hereinafter referred to as “ink repellent agent A” in this example) is prepared by using a diethyl ether: hexane = 1: 1 solution as a precipitating agent, and a reprecipitation method. The ink repellent agent B was obtained after purification 3 times. The average molecular weight (Mn) of the ink repellent A before purification was 35,000. The average molecular weight (Mn) of the ink repellent B after purification was 40000.
(Purification of ink repellent C)
The ink repellent agent “Modiper F2020” (manufactured by NOF Corporation) was purified by reprecipitation three times using diethyl ether: hexane = 3: 1 solution as a precipitating agent, and ink repellent agent C was obtained. The average molecular weight (Mn) of the ink repellent A before purification was 35,000. The average molecular weight (Mn) of the ink repellent C after purification was 43,000.
(Purification of ink repellent D)
The ink repellent agent “Modiper F2020” (manufactured by NOF Corporation) was purified by performing the reprecipitation method three times using diethyl ether as a precipitating agent to obtain ink repellent agent D. The average molecular weight (Mn) of the ink repellent A before purification was 35,000. The average molecular weight (Mn) of the purified ink repellent D was 50,000.
(Purification of ink repellent E)
The ink repellent agent “Modiper F2020” (manufactured by Nippon Oil & Fats) was purified by performing the reprecipitation method three times using a p-xylene: diethyl ether = 1: 1 solution as a precipitating agent, and ink repellent agent E was obtained. The average molecular weight (Mn) of the ink repellent A before purification was 35,000. The average molecular weight (Mn) of the purified ink repellent E was 58,000.
(Purification of ink repellent F)
The ink repellent agent “Modiper F2020” (manufactured by Nippon Oil & Fats) was purified by reprecipitation three times using p-xylene as a precipitating agent, and ink repellent agent F was obtained. The average molecular weight (Mn) of the ink repellent A before purification was 35,000. The average molecular weight (Mn) of the purified ink repellent F was 70000.
(Purification of ink repellent G)
The ink repellent agent “Modiper F2020” (manufactured by Nippon Oil & Fats) was purified by performing a reprecipitation method three times using hexane as a precipitating agent to obtain an ink repellent agent G. The average molecular weight (Mn) of the ink repellent A before purification was 35,000. The average molecular weight (Mn) of the purified ink repellent G was 37000.

Example 1
(Preparation of photosensitive resin composition for black matrix)
Binder resin; V259 (Nippon Steel Chemical Co., Ltd.) 100g
Compound having an unsaturated double bond; 1.65 g of pentaerythritol tetraacrylate
Photopolymerization initiator; oxime photopolymerization initiator (CGI-124 manufactured by Ciba Specialty Chemicals) 4.95 g
Dispersant: Commercial solution (manufactured by Mikuni Dye Co., Ltd.) EX-2906 159 g in which a black pigment is dispersed in a solvent together with a dispersant
Solvent: 201 g of propylene glycol monoethyl ether acetate
Leveling agent; BYK-330 (by Big Chemie) 0.003g
Each component was mixed in the above ratio to obtain a photosensitive resin composition. Furthermore, a ratio of 0.1 wt% of the ink repellent agent B to the photosensitive resin composition with respect to the total solid content weight (the total weight excluding the solvent weight of the solvent and the dispersant in the photosensitive resin composition). Was added and stirred to prepare a photosensitive resin composition used for forming a black matrix (partition wall).

(Create a black matrix)
Non-alkali glass (Corning “# 1737”) was used as the substrate. The photosensitive resin composition was applied on the entire surface of the substrate in the form of a thin film having a thickness of 2.0 μm.

The substrate was pre-baked. Thereafter, using a photomask having a lattice pattern, exposure was performed at 50 mJ / cm ² with an ultrahigh pressure mercury lamp. Development processing was performed with a 10% aqueous sodium carbonate solution for 30 seconds to form a partition pattern of the resin composition.

  This substrate was placed in an oven and heat-cured at 180 ° C. for 10 minutes. Table 1 shows the results of measuring the critical surface tension and the contact angle with respect to the colored ink (surface tension 30 mN / m) of the partition wall thus prepared. Since the OD value (optical density) of the partition wall of the color filter produced in Example 1 is good and has sufficient light shielding properties, it was confirmed that both can be used as a light shielding layer. The critical surface tension was measured by measuring the contact angle when three liquids having different surface tensions were dropped and performing Zisman plotting.

The OD value was obtained from the following equation from the incident light intensity I ₀ and transmitted light intensity I of a 1 μm sample.
OD = -log (I / I ₀ )

(Colored ink adjustment)
Methacrylic acid 20 parts by weight Methyl methacrylate 10 parts by weight Butyl methacrylate 55 parts by weight Hydroxyethyl methacrylate 15 parts by weight Butyl lactate 300 parts by weight Add 0.75 parts by weight of azobisisobutylnitrile under nitrogen atmosphere and add 5 parts at 70 ° C. An acrylic copolymer resin was obtained by reaction over time. The obtained acrylic copolymer resin was diluted with propylene glycol monomethyl ether acetate so that the resin concentration was 10% by weight to obtain a diluted solution of the acrylic copolymer resin.

  19.0 g of pigment and 0.9 g of polyoxyethylene alkyl ether as a dispersant were added to 80.1 g of this diluted solution, and kneaded with three rolls to obtain red, green and blue colored varnishes. . As a red pigment, Pigment Red 177, Pigment Green 36 as a green pigment, and Pigment Blue 15 as a blue pigment were used.

  Propylene glycol monomethyl ether acetate is added to each colored varnish so that the pigment concentration is 12 to 15% by weight and the viscosity is 15 cps, and red, green, and blue colored inks are obtained. It was.

(Production of color filter)
Red, green, and blue colored inks are used for the black matrix openings provided on the substrate, and the colored ink is ejected by an ink ejection device equipped with a 12 pl, 180 dpi head. Each colored layer of green (G) and blue (B) was formed. Table 1 shows the presence or absence of color mixing and white spots in the ink ejection process of Example 1. In Example 1, ΔEab (color difference) was good, and it was found that the color filter was a good color filter with little color unevenness. ΔEab (color difference) was measured with a microanalyzer.

(Example 2)
(Preparation of photosensitive resin composition for black matrix)
A partition was formed on the substrate in the same manner as in Example 1 except that ink repellent C was used instead of ink repellent B, and a colored layer was formed by an ink discharge device to produce a color filter. . As in Example 1, Table 1 shows the critical surface tension of the partition walls, the contact angle with the colored ink (30 mN / m), color mixture, presence or absence of white spots, and the like.

(Example 3)
(Preparation of photosensitive resin composition for black matrix)
A partition wall was formed on the substrate in the same manner as in Example 1 except that the ink repellent agent D was used instead of the ink repellent agent B, and a colored layer was formed by an ink ejection device to produce a color filter. . As in Example 1, Table 1 shows the critical surface tension of the partition walls, the contact angle with the colored ink (30 mN / m), color mixture, presence or absence of white spots, and the like.

Example 4
(Preparation of photosensitive resin composition for black matrix)
A partition wall was formed on the substrate in the same manner as in Example 1 except that ink repellent E was used instead of ink repellent B, and a colored layer was formed by an ink ejection device to produce a color filter. . As in Example 1, Table 1 shows the critical surface tension of the partition walls, the contact angle with the colored ink (30 mN / m), color mixture, presence or absence of white spots, and the like.

(Example 5)
(Preparation of photosensitive resin composition for black matrix)
A partition was formed on the substrate in the same manner as in Example 1 except that the ink repellent agent F was used instead of the ink repellent agent B, and a colored layer was formed by an ink discharge device to produce a color filter. . As in Example 1, Table 1 shows the critical surface tension of the partition walls, the contact angle with the colored ink (30 mN / m), color mixture, presence or absence of white spots, and the like.

(Comparative Example 1)
(Preparation of photosensitive resin composition for black matrix)
A partition was formed on the substrate in the same manner as in Example 1 except that the ink repellent agent A was used instead of the ink repellent agent B, and a colored layer was formed by an ink discharge device to produce a color filter. . As in Example 1, Table 1 shows the critical surface tension of the partition walls, the contact angle with the colored ink (30 mN / m), color mixture, presence or absence of white spots, and the like.

(Comparative Example 2)
(Preparation of photosensitive resin composition for black matrix)
A partition was formed on the substrate in the same manner as in Example 1 except that the ink repellent G was used instead of the ink repellent B, and a color layer was formed by an ink discharge device to produce a color filter. . As in Example 1, Table 1 shows the critical surface tension of the partition walls, the contact angle with the colored ink (30 mN / m), color mixture, presence or absence of white spots, and the like.

(Example 6)
Instead of adding the ink repellent agent B at a ratio of 0.2 wt% with respect to the total solid weight (total weight excluding the solution weight of the solvent and the dispersant), the ink repellent agent B is added at a ratio of 0.20 wt%. Except for the addition, partition walls were formed on the substrate in the same manner as in Example 1, and further a colored layer was formed by an ink discharge device to produce a color filter. As in Example 1, Table 2 shows the critical surface tension of the partition walls, the contact angle with respect to the colored ink (30 mN / m), color mixture, presence or absence of white spots, and the like.

(Example 7)
Instead of adding the ink repellent B at a ratio of 0.2 wt% with respect to the total solid weight (total weight excluding the solution weight of the solvent and the dispersant), the ink repellent C is added at a ratio of 0.20 wt%. Except for the addition, partition walls were formed on the substrate in the same manner as in Example 1, and further a colored layer was formed by an ink discharge device to produce a color filter. As in Example 1, Table 2 shows the critical surface tension of the partition walls, the contact angle with respect to the colored ink (30 mN / m), color mixture, presence or absence of white spots, and the like.

(Example 8)
Instead of adding the ink repellent agent B at a ratio of 0.2 wt% with respect to the total solid weight (total weight excluding the solution weight of the solvent and the dispersant), the ink repellent agent D was added at a ratio of 0.20 wt%. Except for the addition, partition walls were formed on the substrate in the same manner as in Example 1, and further a colored layer was formed by an ink discharge device to produce a color filter. As in Example 1, Table 2 shows the critical surface tension of the partition walls, the contact angle with respect to the colored ink (30 mN / m), color mixture, presence or absence of white spots, and the like.

Example 9
Instead of adding the ink repellent agent B at a ratio of 0.2 wt% with respect to the total solid weight (total weight excluding the solution weight of the solvent and the dispersant), the ink repellent agent E is added at a ratio of 0.20 wt%. Except for the addition, partition walls were formed on the substrate in the same manner as in Example 1, and further a colored layer was formed by an ink discharge device to produce a color filter. As in Example 1, Table 2 shows the critical surface tension of the partition walls, the contact angle with respect to the colored ink (30 mN / m), color mixture, presence or absence of white spots, and the like.

(Example 10)
Instead of adding the ink repellent agent B at a ratio of 0.2 wt% with respect to the total solid weight (total weight excluding the solution weight of the solvent and the dispersant), the ink repellent agent F is added at a ratio of 0.20 wt%. Except for the addition, partition walls were formed on the substrate in the same manner as in Example 1, and further a colored layer was formed by an ink discharge device to produce a color filter. As in Example 1, Table 2 shows the critical surface tension of the partition walls, the contact angle with respect to the colored ink (30 mN / m), color mixture, presence or absence of white spots, and the like.

(Comparative Example 3)
Instead of adding the ink repellent agent B at a ratio of 0.2 wt% with respect to the total solid weight (total weight excluding the solution weight of the solvent and the dispersant), the ink repellent agent A is added at a ratio of 0.20 wt%. Except for the addition, partition walls were formed on the substrate in the same manner as in Example 1, and further a colored layer was formed by an ink discharge device to produce a color filter. As in Example 1, Table 2 shows the critical surface tension of the partition walls, the contact angle with respect to the colored ink (30 mN / m), color mixture, presence or absence of white spots, and the like.

(Comparative Example 4)
Instead of adding the ink repellent agent B at a ratio of 0.2 wt% with respect to the total solid weight (total weight excluding the solution weight of the solvent and the dispersant), the ink repellent agent G is added at a ratio of 0.20 wt%. Except for the addition, partition walls were formed on the substrate in the same manner as in Example 1, and further a colored layer was formed by an ink discharge device to produce a color filter. As in Example 1, Table 2 shows the critical surface tension of the partition walls, the contact angle with respect to the colored ink (30 mN / m), color mixture, presence or absence of white spots, and the like.

It is explanatory drawing of an example of the ink discharge printed matter in which the white spot generate | occur | produced. It is explanatory drawing of an example of the ink discharge printed matter in which the white spot generate | occur | producing. It is sectional drawing of the ink discharge printed matter of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Board | substrate 20 ... Resin composition 21 ... Partition 22 ... Partition opening 23 ... Ink film 24 ... Ink ejection printed matter 30 ... Ink repellent 41 ... Ink 100 ... Ink ejection part

Claims (8)

A substrate,
A partition that divides the surface of the substrate into a number of regions;
An ink film ejected and formed using an ink ejection device on the multiple areas;
In the ink discharge printed matter having
The partition wall is made of an ink repellent material containing a resin binder and an ink repellent agent,
This ink repellent agent is a compound having a part exhibiting compatibility with the resin binder and a part having ink repellency,
The partition wall has a critical surface tension of 24 to 30 mN / m,
The number average molecular weight of the ink repellent agent is 40,000 to 100,000. The ink discharge printed matter according to claim 1, wherein the site having ink repellency is a fluoroalkyl group. The ink-discharge printed matter according to claim 1 or 2, wherein the site having ink repellency is a perfluoroalkyl group. The ink discharge printed matter according to any one of claims 1 to 3, wherein the part having compatibility with the resin binder includes a main chain of an alkyl group, an alkylene group, or a polyvinyl alcohol group. The ink ejection printed matter according to claim 1, wherein the partition wall is a light shielding layer. The ink discharge printed matter according to claim 5, wherein the partition is a light shielding layer including a black light shielding member. 7. The substrate according to claim 1, wherein the substrate is a transparent substrate, the ink film is a colored layer formed of an ink containing a colorant, and a color filter having a plurality of colored layers. The ink discharge printed matter according to any one of the above. The substrate is a transparent substrate, the ink film is an organic light-emitting layer formed of an ink containing an organic light-emitting material, and is an organic electroluminescent element having a plurality of colors of organic light-emitting layers. The ink discharge printed matter according to any one of claims 1 to 6.

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