JP2007025428A - 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 produce in a simple process by using a printing 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 to be used for forming a partition 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 partition on a substrate. The partition shows 24 to 30 mN/m critical surface tension. The ink repelling compound is concentrated on an intersurface between the partition and the outside environment, with the moiety showing compatibility with the resin binder being oriented inside the partition and the moiety showing ink repelling property being oriented outside the partition. Thereby, it is found that the partition shows appropriate ink repelling property. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a printed matter manufactured using a printing apparatus. As this printed matter, an electroluminescent element can also be illustrated, and this organic light emitting layer is formed using a printing apparatus. Moreover, a color filter can be illustrated as said printed matter, and the colored layer of this color filter is formed using a printing 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 an organic light emitting layer of the organic electroluminescence element (hereinafter referred to as an organic EL element), and representative methods include a photolithography method, a relief printing method, and the like. Various printing methods are known. The pixel pattern formation of the organic EL element by the photolithography method is to form a coating film of a photosensitive resin layer of each color on the entire substrate, and after exposing in a pattern, remove unnecessary portions of the coating film, Let it be a pixel. 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 method is used not only for organic EL elements but also for manufacturing various optical elements and electrical elements such as color filters.
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 a printing method has attracted attention. For example, when an organic EL element is manufactured by a printing method, each color can be printed at the same time by using ink containing organic light emitting materials of three colors of R, G, and B. For this reason, compared with photolithography, the ink material is hardly wasted, and at the same time, the formation process of the three-color pixels is shortened, so that it is possible to expect a reduction in environmental load and a significant cost reduction.

As described above, since the printing method can simplify the manufacturing process and reduce the cost, it is applied to the manufacture of optical elements such as organic EL elements and color filters. However, as one of the problems of the printing method, there are problems such as “mixed color” and “missing white”. Hereinafter, the case of manufacturing these optical elements will be described by taking letterpress printing 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 printed ink overflows beyond the partition. In order to solve this problem, for example, Patent Document 1 has been proposed as a method of manufacturing a color filter using a printing method. Patent Documents 2 to 3 describe that a black resin layer containing an ink repellent such as a fluorine-containing compound is formed and used as a partition wall in order to prevent ink bleeding and color mixing in the ink printing process. Yes.

“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. 1 (d), the ink repellent oozes from a part of the partition wall, and the ink 41 transferred from the plate of the printing apparatus (FIG. 1 shows an example of transfer from the relief plate). Wetting does not spread and white spots occur (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 a printing apparatus will be described with reference to Patent Documents 2 to 3. Patent Documents 2 to 3 describe a method in which a fluorine-containing material is used as an ink repellent for the partition walls of color filters and organic EL elements produced by a printing method. According to this method, color mixing due to printing 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 resin components contained in the ink, The compatibility with the solvent component 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 also been proposed a method of using a compound having a permeable perfluoroalkyl group and imparting ink repellency only to one side of the molecular chain.
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-5-93808 Japanese Patent Application No. 7-248413 JP 2003-243163 A

  The present invention has been made in order to solve the above-described problems. When a printed material is manufactured at low cost by a simple process using a printing method, the printed material has high quality and high reliability by preventing color mixing and white spots. And a method for manufacturing the same.

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 number average molecular weight of 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 walls after heating was 24 to 30 mN / m. became.
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 printed with the printing apparatus with respect to the board | substrate which has this partition, this partition showed favorable ink repellency, and color mixing and a white-out defect did not generate | occur | produce.

The present invention has been made based on such knowledge, and the invention described in claim 1 is characterized in that the invention described in claim 1 includes a substrate,
A partition that divides the surface of the substrate into a number of regions;
An ink film formed by printing on a large number of areas using a printing device;
In 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 invention according to claim 2 is the printed matter according to claim 1, wherein the site having ink repellency is a fluoroalkyl group.

The invention according to claim 3 is the printed matter according to claim 1 or 2, wherein the portion having ink repellency is a perfluoroalkyl group.

Invention of Claim 4 is a 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.

The invention according to claim 5 is the printed matter according to any one of claims 1 to 4, wherein the partition wall is a light shielding layer.

The invention according to claim 6 is the 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 a 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. The printed matter according to claim 1, wherein the printed matter is a sense element.

  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 a printed matter free from mixed colors and white spots with a high yield by a simple process using a printing 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 regions and preventing color mixing of ink applied to each of the many regions by printing.
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, when 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 walls decreases.
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. When it exceeds 30 mN / m, the ink repellency is insufficient, and a problem of white spots occurs when ink is applied later by a printing apparatus. 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), and the ink repellent agent oozes out from the side surface of the printing material (partition wall), resulting in 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 printed and formed using the printing 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 an optical material is applied later with a printing apparatus. On the other hand, if it is less than 24 mN / m, the ink repellent agent is too 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) and 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 printing device>
By the method described above, a partition having ink repellency is formed on the substrate, and ink is applied to the opening of the partition using a printing device to form an ink film. As the printing method and printing method, known printing methods such as letterpress printing, screen printing, gravure printing, and reversal printing can be used. For example, in the production of an organic electroluminescent element, a relief printing method using a flexographic plate is particularly suitable. 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 organic EL element as printed matter about embodiment of the present invention is explained 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 partition wall formation)
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 the partition walls.

(Formation of anode)
Non-alkali glass (“# 1737” manufactured by Corning) was used as the substrate 101. After forming an ITO film with a thickness of 150 nm on the substrate 101 by sputtering, the ITO film was patterned by a photolithography method and a wet etching method to form a substrate-side electrode layer 201 (FIG. 4A).

(Create partition walls)
The photosensitive resin composition A was applied on the entire surface of the substrate 101 in the form of a thin film having a thickness of 5.0 μm, and then 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 carried out with a 10% aqueous sodium carbonate solution for 30 seconds to form partition walls 301 of the resin composition (FIG. 4B). The result of measuring the critical surface tension of this resin composition is shown in Table 1 column (B). The critical surface tension obtained as a result of oven-heating the resin at 200 ° C. for 10 minutes is shown in Table 1 (C). The critical surface tension was measured by measuring the contact angle when three liquids having different surface tensions were dropped and performing Zisman plotting.

  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.

(Formation of PEDOT layer)
A 3,4-polyethylenedioxythiophene (PEDOT) aqueous solution was applied onto the substrate by a spin coating method to form a hole transport material layer (not shown).

(Formation of organic light emitting layer)
A 1.0% by weight toluene solution of polyarylene vinylene using polyarylene vinylene as an organic light emitting material was prepared as a printing ink. Using the flexographic printing proofing machine (manufactured by Matsuo Sangyo Co., Ltd.) equipped with a striped resin relief plate having a convex part of 120 μm and a concave part of 380 μm with respect to the opening of the partition wall provided on the substrate, the printing ink is Printing was performed to form an organic light emitting layer (FIG. 4C). Table 1 shows the presence or absence of color mixing and white spots in the flexographic printing process of Example 1.
Other organic light emitting materials include, for example, coumarin, perylene, pyran, anthrone, porphyrene, quinacridone, N, N′-dialkyl substituted quinacridone, naphthalimide, N, N′-diaryl substitution. Organic light-emitting materials that are soluble in organic solvents such as pyrrolopyrrole and iridium complexes, and organic light-emitting materials dispersed in polymers such as polystyrene, polymethyl methacrylate, and polyvinyl carbazole, polyarylene-based, polyarylene-based materials High molecular organic light emitting materials such as vinylene and polyfluorene are listed.

(Formation of organic EL elements)
Next, a Ca film having a thickness of 5 nm was formed on the organic light emitting medium layer 4 as the electron injection layer 51 of the sealing electrode layer. Next, an ITO film having a thickness of 100 nm was formed as the transparent electrode layer 52 on the organic light emitting medium layer 4 on which the Ca film was formed by a sputtering method. Finally, sealing was performed using a UV curable resin to obtain an organic EL element.

(Example 2)
(Preparation of photosensitive resin composition for partition wall formation)
A partition is formed on the substrate in the same manner as in Example 1 except that ink repellent C is used instead of ink repellent B, and a colored layer is printed by a printing apparatus to produce an organic EL element. did. 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 partition wall formation)
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 in place of the ink repellent agent B, and a colored layer was further formed by a printing apparatus to produce an organic EL element. . 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 partition wall formation)
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 a printing apparatus to produce an organic EL element. . 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 partition wall formation)
A partition wall 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 further formed by a printing apparatus to produce an organic EL element. . 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 partition wall formation)
A partition wall 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 further formed by a printing apparatus to produce an organic EL element. . 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 partition wall formation)
A partition wall was formed on the substrate in the same manner as in Example 1 except that the ink repellent agent G was used instead of the ink repellent agent B, and a colored layer was further formed by a printing apparatus to produce an organic EL element. . 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 a printing apparatus to produce an organic EL element. 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 a printing apparatus to produce an organic EL element. 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 a printing apparatus to produce an organic EL element. 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 a printing apparatus to produce an organic EL element. 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 a printing apparatus to produce an organic EL element. 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 a printing apparatus to produce an organic EL element. 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 a printing apparatus to produce an organic EL element. 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 printed matter which the white spot generate | occur | produced. It is explanatory drawing of an example of the printed matter which the white spot generate | occur | produced. It is sectional drawing of the printed matter of this invention. It is an example of the organic EL element produced as printed matter of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Substrate 101 ... Substrate 20 ... Resin composition 201 ... Substrate side electrode 21 ... Partition 22 ... Partition opening 23 ... Ink film 24 ... Printed matter 30 ... Ink repellent agent 301 ... Partition 401 ... Organic light emitting layer 41 ... Ink 100 ... Letterpress 501: Sealing side electrode layer

Claims (8)

A substrate,
A partition that divides the surface of the substrate into a number of regions;
An ink film formed by printing on a large number of areas using a printing device;
In 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 printed matter, wherein the ink repellent has a number average molecular weight of 40,000 to 100,000. The printed matter according to claim 1, wherein the site having ink repellency is a fluoroalkyl group. The printed matter according to claim 1 or 2, wherein the site having ink repellency is a perfluoroalkyl group. The printed matter according to any one of claims 1 to 3, wherein the site having compatibility with the resin binder includes a main chain of an alkyl group, an alkylene group, or a polyvinyl alcohol group. The printed matter according to claim 1, wherein the partition wall is a light shielding layer. The 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. 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 printed matter according to any one of claims 1 to 6.

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