JPH0899476A - Printing method for micropattern - Google Patents

Abstract

PURPOSE: To improve the release properties of ink, reproducibility of a pattern and resistance to printing by forming a releasable resin layer by means of the use of non-crystalline fluorine resin containing a cyclic structure in a method of forming a releasable resin layer on a recessed section of an intaglio, which is filled with ink and of transferring the ink to a body to be printed. CONSTITUTION: An intaglio of good release properties and resistance to printing is provided by forming a release layer 8 composed of a composition containing non-crystalline resin having a cyclic structure on an intaglio 1 provided with a recessed section 2 such as a resist pattern or the like used for the manufacture of a semiconductor circuit or the like, Photosetting ink 3 is filled in the recessed section 2 of the intaglio 1, and then beam is emitted from a light source 6 to cure an inner layer 3 in contact with the recessed section 2, and a surface layer 3b is provided with viscosity generated by the curing inhibition action by oxygen. Therefore, in the following process of transferring an ink pattern onto a bracket 5, the half-cured viscous surface layer 3b is made to adhere to the bracket 5 in a good manner to be transferred easily.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for printing a fine image with high accuracy, and in particular, a method for forming a resist pattern used for manufacturing a semiconductor device circuit, or a large-area display panel substrate. The present invention relates to surface treatment of an intaglio printing plate, which is useful in a method of forming a semiconductor device circuit or a highly accurate color filter pattern thereon.

[0002]

2. Description of the Related Art Conventionally, photolithography has been used to form a resist pattern for etching used in the manufacture of semiconductor device circuits. On the other hand, recently, the display panel has become larger, and the size of the display panel having a size of 15 inches or more has been actively developed. Therefore, also in the pattern formation of the semiconductor element circuit and the color filter pattern, it has become necessary to increase the size of the substrate and mass-produce it along with miniaturization. For such a request,
In the current photolithography, enormous cost is required for the development of a large-scale exposure device and the coating of photoresist, and the applicable size of the photomask is limited.

A resist pattern for forming a semiconductor element circuit or a color filter pattern on a panel of a large display device usually has a line width of 100 μm or less,
Regarding the position accuracy, a level of ± 1 to 10 μm is required. It is difficult to meet this requirement by the printing method by the planographic offset method, and it is necessary to use an intaglio plate. That is, it is necessary to form an ink pattern that faithfully reproduces the shape of the concave portion of the intaglio plate and completely transfer the ink pattern to the transfer target with high positional accuracy. The method of directly or indirectly transferring the pattern to the printing medium by intaglio printing is excellent in that there are few restrictions on the apparatus, the mass production effect is high, and the cost is low.

Conventionally, a method has been known in which an intaglio plate is filled with ink which is cured by light or heat, and then the ink is cured by light or heat and transferred to a printing medium (Japanese Patent Laid-Open No. 3-280416). ). As another method, the intaglio is filled with ink that is cured by light or heat, and then cured by light or heat so that at least the surface layer portion of the ink becomes semi-cured, and transferred to a printing medium, Alternatively, when transferring to a blanket as an intermediate inclusion, there is also a method of facilitating the transfer and then transferring to the printing medium (JP-A-3-19889). In addition, a release layer may be used to facilitate transfer of the ink from the intaglio plate. As the release layer, silicone resin, silicone rubber, fluororesin, polyolefin, etc. have been disclosed (JP-A-2-135348). JP-A-4-31
7005, JP-A-5-139065, JP-A-5-241175).

However, as described in JP-A-3-19889, an intaglio plate provided with a release layer is formed, and an air oxidation type printing ink, that is, an ordinary offset ink or an ink curable by ionizing radiation or When an intaglio is filled with ink that is hardened by heat, and is directly printed on a printing medium or is printed through a blanket, when printing one to several sheets, a silicone resin, a fluororesin, a silicone rubber, a polyolefin is used. The release layer consisting of etc. shows releasability to ink,
In case of printing more than 20 sheets, the releasability deteriorates,
In most cases, the hardened ink was likely to remain in the recesses of the intaglio during transfer. That is, a conventionally known release layer made of a fluororesin layer or the like has poor printing durability during printing, and the release function of the release layer is deteriorated after about 20 sheets by repeating printing. As described above, there has been no known release layer capable of forming a fine pattern with high precision and printing durability on a transfer target.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a printing method using an intaglio plate provided with a release layer by surface treatment of an intaglio plate, particularly by surface treatment with a fluorine-based releasing agent. Further, the present invention provides a surface treatment of an intaglio plate which has particularly good durability during printing and good ink releasability, and a printing method for obtaining an image in which the pattern of the intaglio plate is well reproduced by using the surface treatment. Further, the present invention provides a printing method in which the ink remains in the non-image area of the intaglio plate and does not cause stains or fog on areas other than the image area after transfer.

[0007]

The present invention has been made in view of the above-mentioned circumstances, and forms a release layer made of a composition containing an amorphous fluororesin having an annular structure in an intaglio plate. By doing so, the release layer adheres well to the intaglio plate, has a good mold release property, and provides an intaglio plate that can withstand the printing of a large number of sheets, and a method capable of printing even a fine image using the intaglio plate. It is provided. In order to form an ink pattern that faithfully reproduces the shape of the recess and to improve printing durability, at least the surface of the recess of the intaglio is surface-treated with a composition containing an amorphous fluororesin to form a release layer. When formed, it is possible to prevent the ink from remaining in the non-image area when the ink is filled in the intaglio plate by the doctor ring, and prevent the ink from remaining in the recess during transfer.

In the present invention, a release layer is formed on at least the entire surface of the concave portion of the intaglio, preferably the entire plate-making surface of the concave portion and the non-image area. As a material for the release layer, a material having a high release property that does not transfer to the ink and has no affinity with the ink is preferable. Conventionally, paraffin wax, silicone-based resin, and fluorine-based resin have been used for them. However, although there are many kinds of general fluorine-based resins, they are effective for the purpose of the present invention. The thing was not specified. In particular, regarding a fluorine-based resin, it is usually described as Teflon or simply a fluorine-type resin and is not specified at all, and nothing is mentioned about forming a thin film on the surface of the plate. Moreover, no consideration was given to the printing durability of the plate. However, when a large number of fluorine-based resins were tested, there were some that could not be applied in a thin film form to the plate, and some had poor releasability. Most of the fluororesins were not particularly good in terms of printing durability, probably because they were difficult to bond to the intaglio plate.

In the present invention, as a result of selecting a resin having a good releasability by the following evaluation method, the fluororesin having a cyclic structure is soluble in a solvent and can be applied to the surface of the intaglio plate. Therefore, the present invention has been achieved by finding out that the mold release property is good, the mold release property is good, and the printing durability of the plate is high. This fact has not been expected at all in the past, and is a very effective knowledge for easily realizing high-precision printing and improving printing durability. The releasability of the present invention was evaluated as follows. Figure 3
As shown in FIG. 3, the glass substrate 12 on which the release layer 13 is formed is fixed to the test table 20 by the vacuum suction holes 11, a certain amount of ink 14 is placed on the surface of the glass substrate 12 having the release layer 13, and the surface treatment is performed. The ink 14 is sandwiched by pressing the sensor glass 15 having a size of 10 mm × 10 mm which is not applied. Thereafter, the ink having the curing mechanism by air oxidation is used as it is, and the ink having the curing mechanism by the irradiation of electromagnetic radiation is irradiated with the electromagnetic radiation 16 from the lamp 19 on the glass substrate 12.
The ink is cured by irradiating through it, or in the case of a thermosetting ink, heat is applied to cure the ink. After that, one side of the sensor glass 15 is pulled up at a constant speed by the metal wire 17, and the force when the ink 14 and the sensor glass 15 are peeled off is measured by the force sensor 18 and expressed as a peeling force. A method for evaluating the printing durability of the release layer 13 will be described in Example 2 below.

An amorphous fluororesin having a cyclic structure shown in the following chemical formulas 1 and 2 has all of these conditions as having good releasability, in other words, low peeling force and printing durability. It was surprising to be satisfied.

[Chemical 1] In the above formula, m is an integer and n is 1 or 2.

[Chemical 2] In the above formula, x and y are integers. Conventional polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene It is difficult to form a thin film of 5 μm or less with a crystalline fluororesin such as a tetrafluoroethylene copolymer even if it is dispersed in water or an organic solvent and applied. In order to do so, it was necessary to bake at a high temperature of 200 to 450 ° C. However, it is not preferable to heat the plate for forming a fine image to a high temperature because the dimensional accuracy of the image may be deteriorated. On the other hand, the fluororesin which can be preferably used in the present invention is an amorphous fluoropolymer composed of poly (perfluoroallyl vinyl ether) shown in Chemical formula 1 or perfluorocyclopolymer shown in Chemical formula 2. . These are soluble in the solvent and 5
It can be applied as a thin film of less than μm
An excellent fluororesin film can be formed on a printing plate even when it is heated at a low temperature of ℃ or less, and the fluororesin film is characterized by strongly adhering to the plate. In addition, this fluororesin film is durable against ink components and other chemical substances, and when used as a surface treatment agent for printing plates, it is difficult for ink to adhere to the surface of the fluororesin release layer, and printing durability is improved. There is a nature. It is thought that this is because the release layer adheres well to the material of the plate where it comes into contact with the plate, and the release layer is highly crosslinked and has high strength. Among them, an amorphous fluororesin having a cyclic structure with few free double bonds, for example, CYTOP CTX-809S (trade name, manufactured by Asahi Glass Co., Ltd.) has low ink peeling force and printing durability. It is excellent. In addition, an amorphous fluororesin having a cyclic structure with a slightly free double bond, such as Cytop CTX-809M, has high adhesiveness to the plate. Top
When CTX-809S is applied, it is possible to form a release layer on the plate, which has excellent release properties and remarkably excellent printing durability.

As a method for forming the release layer on the intaglio substrate, the fluororesin is dissolved in a solvent or dispersed in a dispersant and applied to the intaglio plate. As the coating method, there are a dip method, a spin coating method, a transfer method, a spraying method, a vapor deposition method, a doctor coating method, a roll coating method, etc., and a release layer is formed by heating at room temperature or a temperature of 50 to 200 ° C. Can be formed. The thickness of the release layer is 10 nm or more and 10 μm or less, and usually 100 nm or more and 3 μm.
The following film thicknesses are suitable. The drying temperature varies depending on the thickness of the release layer, but if it is 0.5 μm or less, 80 ° C to 1 ° C.
80 ° C. is preferred. Further, in order to improve the adhesiveness between the intaglio substrate and the release layer, prior to the formation of the release layer, the intaglio surface is irradiated with a lamp that emits short-wavelength light that generates ozone in the air and then released. It has been found that the printing durability is improved by providing the mold layer. Alternatively, when a primer such as a silane coupling agent is applied to the intaglio in advance and a release layer is provided thereon, the effects of releasability and printing durability may be more excellent. At this time, it is more effective to apply the primer after irradiating with a lamp that generates ozone. More specifically, in the case of the photocurable ink described below, the release layer containing an amorphous fluororesin having a cyclic structure is more effective than the conventional release layer in releasing the ink from the intaglio plate. The printing performance was good and the printing durability of the plate was high. If the releasability of the ink is good, the transferred ink faithfully reproduces the shape of the intaglio plate, and a pattern with good image quality can be obtained.

1 and 2 are schematic sectional views showing an embodiment of the method of the present invention. In the figure, reference numeral 1 is an intaglio plate.
A desired pattern is previously formed on the intaglio plate 1 by an ordinary method such as a combination of a photolithography method and an etching method. The width of the recess 2 formed on the intaglio 1 is 1 to
The depth of the recess is 200 μm and the depth of the recess is about 1 to 20 μm, more preferably about 2 to 10 μm. Examples of the material of the intaglio plate 1 used include metals, glass, ceramics, engineering plastics, and the like. Further, for example, in order to prevent damage by the doctor 4, it is also preferable to coat the plate making surface (the surface of the shoulder portion and the concave portion) of the intaglio 1 made of these materials with a hard metal such as chromium or nickel. Examples of the coating method include a wet plating method, a sputtering method, a vacuum vapor deposition method and the like.

The material of the intaglio plate 1 may be the above-mentioned rigid material, but a flexible material such as stainless steel, phosphor bronze or low expansion iron alloy such as Invar-42 alloy is also preferably used. Also, when a press is used in the curing step and the transfer step, it is preferable to select a material having a property that the intaglio does not remain deformed when pressed and the original shape is restored. When the color filter is produced by printing, a material having a thermal expansion coefficient similar to that of the glass of the transferred material is preferable as the intaglio plate, which is also described in JP-A-5-323111. The low-expansion iron alloy has high flexibility and has the advantage that it can follow even if there is some thickness unevenness on the surface of the transfer target, but using a flatbed printing machine, Substrate 7 of body 7
When a glass substrate having a low expansion coefficient is used as a, it is preferable to use glass having substantially the same thermal expansion coefficient as the intaglio 1. The release agent of the present invention is particularly effective in the case of a glass intaglio plate. The thickness of the intaglio 1 is appropriately selected in consideration of the mechanical strength of the material.

The ink may be one that does not correspond to the general concept of ink, and may be any ink that enters the recess.
For example, ionizing radiation curable ink, electron beam curable ink, thermosetting ink, metal circuit forming ink,
Infrared curing type ink may be used. Further, the degree of curing of the curable ink by electromagnetic radiation or heat is such that the viscosity becomes higher when electromagnetic radiation is applied or heat is applied than when ink is supplied, and the shape of the concave portion can be maintained as it is. It is preferably non-fluid. A particularly preferred ink used in the method of the present invention is, for example, a photo-curable ink that is cured by irradiation with ultraviolet rays (hereinafter referred to as “UV”).
), And is an anaerobic UV ink having a curing inhibition property due to the presence of oxygen. In addition to these, visible light curable inks that undergo photocrosslinking upon irradiation with visible light can also be used. In the present invention, UV ink and the latter visible light curable ink are simply referred to as "photocurable ink".

Many photo-curable inks apply a photo-radical polymerization reaction caused by irradiation with light.
Ultraviolet light is often used as light, but near-ultraviolet light or visible light can also be used by selecting an initiator and a sensitizer. In general, the photo-curing reaction of a material that is photo-cured by a radical reaction is often obstructed by oxygen in the air and is somewhat anaerobic. Conventionally, inhibition of curing of photocurable ink by oxygen is not preferable for printability of ink, and various improvements have been made to prevent inhibition of curing by oxygen. However, one of the characteristics of the present invention is to make a fine pattern by reversely utilizing the problem of curing inhibition by air. Figure 1
In (b), when the concave portion 2 of the intaglio 1 is filled with the photocurable ink 3 and then irradiated with light from the light source 6, the inner layer 3a in contact with the concave portion 2 is cured, but the surface layer 3b has a curing inhibitory effect by oxygen. It is semi-cured and sticky due to. Next, in the step of transferring the ink pattern onto the blanket 5 in FIG. 1 (C), since the cured inner layer 3a does not have tackiness, the ink layer is transferred in the same shape from the recess 2 of the intaglio plate 1. This is convenient because ink does not remain in the recess 2. On the other hand, the semi-cured and viscous surface layer 3b has good adhesion to the blanket 5 and thus has an advantage of being convenient for transfer. The side 3b of the ink layer 3 that contacts the blanket
At this stage, the photocuring inhibition effect by air is not obtained. If an appropriate amount of second-stage light irradiation is performed in this state, the ink layer 3b on the side in contact with the blanket 5 is also hardened and easily peeled off from the blanket 5, and the subsequent FIG. In the step shown in d), the transferred body 7
Can be more favorably transferred.

As described above, the surface state of the transfer surface, that is, the surface layer 3b of the ink layer and the surface state of the peeling surface, that is, the inner layer 3a are changed by skillfully utilizing the curing inhibition property by oxygen, which has been conventionally unfavorable. In addition, it is possible to completely transfer the ink, and it is possible to print a precise pattern without applying a large pressure at the time of transfer. If the degree of radical polymerization inhibition by oxygen (anaerobic degree) is insufficient or excessive, adding anaerobic agents such as photopolymerization initiators, sensitizers, and thermal polymerization inhibitors usually used for ink The degree can be adjusted. However, when the ink is transferred to an intermediate inclusion such as a blanket and then transferred to the transfer target 7, it is easier to transfer when the adhesive layer 9 is provided on the surface of the substrate 7a of the transfer target 7. However, when an intermediate inclusion having low adhesiveness with ink such as silicone rubber is used, the ink can be transferred even if the adhesive layer is not present on the printing medium.

The photopolymerizable composition used as an ink in the present invention comprises an addition polymerizable unsaturated monomer, a photopolymerization initiator and a binder as main components as disclosed in US Pat. No. 3,549,367. To do. For details, reference can also be made to the review articles of the Journal of the Printing Society of Japan, Volume 28, pp. 200 to 214 (1991), or the Journal of the Japan Society of Adhesion, Volume 20, pp. 300 to 308.

First, as the photocrosslinkable or photopolymerizable monomer, oligomer, prepolymer, etc., ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, ethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate. , Dipentaerythritol hexaacrylate,
Acrylic or methacrylic acid esters of monohydric or polyhydric alcohols such as dipentaerythritol hexamethacrylate; (meth) acrylic acid on polyester prepolymers obtained by condensing polyhydric alcohols with monobasic acids or polybasic acids Polyester (meth) acrylate obtained by reacting the above; Polyurethane (meth) acrylate obtained by reacting a compound having a polyol group and two isocyanate groups and then reacting with (meth) acrylic acid; Bisphenol A type epoxy Resin, bisphenol F type epoxy resin, novolac type epoxy resin,
Reaction of (meth) acrylic acid with epoxy resins such as polycarboxylic acid glycidyl ester, polyol glycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin The photopolymerizable compound such as the obtained epoxy (meth) acrylate may be mentioned. Further, photopolymerizable monomers and oligomers having both a (meth) acryloyl group and a carboxyl group can be used, and specific examples of such compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, poly Reaction of (meth) acrylic acid with epoxy groups such as carboxylic acid epoxy resin, polycarboxylic acid glycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin Epoxy (meth) acrylate-carboxylic acid adduct obtained by reacting the obtained hydroxyl group with an acid anhydride; ethylene, propene, isobutylene, styrene, vinylphenol, acrylic acid ester, acrylic acid copolymerizable with maleic anhydride A compound obtained by reacting a maleic anhydride portion of a copolymer with a monomer such as amide with an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate or an acrylate having an epoxy group such as glycidyl methacrylate to form a half ester; acrylic Examples thereof include compounds in which acrylic acid is further reacted with a hydroxyl group of a copolymer of an acid, an acrylic ester and an acrylate having an alcoholic hydroxyl group such as hydroxyethyl acrylate. These photopolymerizable compounds can be used alone or in combination.

In the present invention, various photopolymerization initiators may be used alone or as a mixture, but in general, a pigment is dispersed in a photopolymerizable monomer or photopolymerizable oligomer or a photopolymerizable resin for coloring. The photopolymerizable resin requires a highly sensitive compound or composition as a photopolymerization initiator. Specific examples of such a photopolymerization initiator include benzoin ether; benzoin isobutyl ether; benzoin isopropyl ether; benzoylbenzoic acid; methyl benzoylbenzoate; 4-benzoyl-
4'-methyldiphenyl sulfide; benzyl methyl ketal; 2-n-butoxyethyl-4-dimethylaminobenzoate; 2-chlorothioxanthone; 2,4-
Diethylthioxanthone; 2,4-diisopropylthioxanthone; Dimethylaminomethylbenzoate; p-
Isoamyl dimethylaminobenzoate; 3,3′-dimethyl-4-methoxybenzophenone; 2,4-dimethylthioxanthone; 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one; 1-hydroxy Cyclohexyl phenyl ketone; 2-hydroxy-2
-Methyl-1-phenylpropan-1-one; 1- (4
-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one; isopropylthioxanthone;
2-Methyl-1- [4- (methylthio) phenyl] -2
-Morpholinopropan-1-one; 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)
-Butan-1-one, Michler's ketone, 2,2-dichloro-p-phenoxyacetophenone, phenanthrenequinone and the like can be mentioned. Further, a triazine compound containing a bismethylolaminophenyl group and a trihalomethyl group, or a derivative of the above compound in which phenyl group is replaced with bromine, and the like can also be mentioned. In particular, the compounds of this family are less colored and have a considerably higher photosensitivity.

These photopolymerization initiators are used in the range of 0.5 to 30% by weight, preferably 2 to 15% by weight, based on the photopolymerizable compound, and these are used alone or in 1 to 3 types. It can be mixed and used. Further, in the present invention, a hexaarylbisimidazole compound or a hydrogen donor may be used in combination as a photopolymerization initiator. Examples of the hexaarylbisimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′,
5,5'-Tetraphenyl bisimidazole; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra-
(3,4-methylenedioxyphenyl) -1,1'-bi-
1H-imidazole may be mentioned. As another hydrogen donor, an aromatic mercaptan compound, an aromatic amine compound, polyvinyl formal, polyvinyl butyral,
Thiohydantoin and the like can also be used.

As the resin used in the ink of the present invention, a polyester resin, a melamine resin, a urethane resin, an acrylic resin, an epoxy resin, an alkyd resin, or a partially modified resin thereof such as a melamine-modified polyester resin is used. Hexamethoxymethylol melamine and hexabutoxymethylol melamine are examples of the melamine resin that is partially cross-linked with the polyester resin. The ratio of melamine resin is polyester resin 1
It is 5 to 80 parts by weight, and particularly preferably 20 to 60 parts by weight, based on 00 parts by weight. When the amount of melamine resin is small, the cohesive force of the printing ink is not sufficiently imparted, and the ink filled in the recesses is difficult to be completely transferred to the blanket. Alternatively, ink is likely to adhere to the non-image area and stain easily. On the other hand, when the amount of the melamine resin is too large, the cohesive force becomes large, and it becomes difficult to fill the ink in the concave portions of the intaglio plate. In the present invention, an epoxy compound may be used as another resin for the purpose of improving heat resistance. The epoxy compound has a function of thermally reacting with the compound having a carboxyl group and the like and crosslinking to improve heat resistance. Specific examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, polycarboxylic acid glycidyl ester, polyol polyglycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, and triepoxy resin. Examples thereof include phenolmethane type epoxy resin and dihydroxybenzene type epoxy resin. These other resins account for 30% by weight of the photopolymerizable compound.
It is used within the following range, preferably within the range of 5 to 15%.

By using a urethane resin having a large intermolecular interaction to increase the cohesive force of the ink, the ink filled in the concave portions of the intaglio plate can be easily transferred. In order to obtain a sufficient cohesive force, a molecular chain length of a certain degree or more is required, and the average molecular weight is 3000 or more, more preferably 6000 or more and the weight average molecular weight is 10,000 or more.
The following urethane acrylates are effective. Such urethane acrylate is obtained by reacting a polyester polyol or a polyether polyol, and a hydroxyl group-containing acrylate ester with a polyisocyanate compound, Dainippon Ink and Chemicals, Inc. "Unidick",
"Gocerac" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., "Aronix" manufactured by Toa Synthetic Chemical Industry Co., Ltd., "Kayarad" manufactured by Nippon Kayaku Co., Ltd., "Evecryl" manufactured by Daicel UCB Co., Ltd., Road Far East Co., Ltd. It is also possible to appropriately select and use from "Photoglaze" manufactured by)) and other commercially available ultraviolet curable prepolymers. To obtain sufficient cohesive strength, the content of urethane acrylate required in the ink is
At least 3% or more, preferably 8% or more is suitable. The urethane acrylate that can be effectively used in the present invention is
Since the UV-curable prepolymer is a linear polymer with a relatively large molecular weight, the ink prepared by combining this with a low-viscosity UV-curable monomer alone has insufficient wettability to pigments, and when doctoring There is a problem that there is much ink stain on the non-image area. When a high acid value resin having an acid value of 100 or more, particularly preferably a natural resin-modified maleic acid resin is used in combination with the above urethane acrylate resin, the wettability to the pigment and the rheology of the ink are improved, Can solve the problem. Examples of such a high acid value resin include JP-A-59-117568, JP-A-62-53312, and JP-A-1-96273.
Acid-modified hydrocarbon resin obtained by reacting cyclopentadiene or its polymer with unsaturated carboxylic acid or its acid anhydride described in JP-A-61-26401.
Acid-modified phenol resin obtained by reacting a phenolic resin described in JP-A No. 4 with a polyvalent carboxylic acid or an acid anhydride thereof, and an ester obtained by reacting a polyvalent carboxylic acid or an acid anhydride thereof with various alcohols. Among resins, other natural resins and synthetic resins, the acid value is 100
As described above, the softening point may be in the range of 60 to 140 ° C., and particularly preferably, a natural resin-modified maleic acid resin having an acid value of 150 or more and 300 or less is suitably used.

The pigment to be used preferably has an average number particle size of 1/2 or less of the wavelength of the transmitted light in order to transmit visible light, and more preferably an average number particle size of 0.
A pigment dispersed to 2 μm or less is preferable. Further, the pigment usually uses, as a dispersant, for example, a polycaprolactone compound, a long-chain alkylpolyaminoamide compound, a polymer surfactant, or the like, and a dispersing machine such as a sand mill or a roll mill together with the pigment and the prepolymer and / or the polymer. Depending on the case, it is possible to disperse a part or all of the resin, and in some cases, to add a thermal polymerization inhibitor or a crosslinking agent such as metal soap or organic titanate for improving the cohesive force of the ink. Examples of blue pigments include phthalocyanine-based and indigo-based pigments, and red pigments include quinacridone-based pigments and perylene-based pigments.
Pyrrolo / pyrrole pigments, anthraquinone pigments, etc.
As the green pigment, halogenated phthalocyanine-based pigments can be mentioned as preferable examples. In addition, a yellow pigment may be added to adjust the hues of red and green. Further, a purple pigment may be added to adjust the hue of blue. The proportion of pigment in the ink is 5 to 5 in terms of solid content.
It is 90% by weight, more preferably 10 to 60% by weight.

When a rubber blanket is used as an intermediate inclusion for transfer, when the rubber blanket 5 is rotated while being pressed in FIG. 1 (c), the adhesive surface layer 3b of the ink 3 contacts the surface of the blanket 5, Blanket 5
The side farther away becomes the inner layer 3a of the cured ink, and the ink 3 in the recess 2 of the intaglio 1 is transferred in a complete form. Further, when the surface of the blanket 5 is slightly tacky, the surface of the surface layer 3b of the ink which is in contact with the blanket 5 may not be in a semi-cured state. In FIG. 1, for convenience of explanation, the diameter of the rubber blanket 5 is shown small, and
The layer of the ink 3 is drawn large and thick, but in reality, the diameter of the rubber blanket 5 is relatively large, so that the surface of the intaglio 1 comes into almost planar contact, and the ink 3 Is transferred to the rubber blanket as it is in the shape filled in the recess 2 of the intaglio 1. The rubber blanket used here may be any as long as it is durable against ink and has a flat surface, and in particular, silicone rubber (see JP-A-5-19116) or NBR rubber,
A blanket made of urethane rubber or the like is preferable. Particularly, a silicone rubber blanket is preferable when retransferring the transferred ink to the transfer target. Then, FIG.
The ink 3 transferred to the rubber blanket 5 in (d) is retransferred to the transfer target 7. When the surface (inner layer 3a) of the ink transferred to the blanket 5 has adhesiveness, it can be directly transferred to the substrate 7a of the transfer target 7. When the ink transferred to the blanket does not have adhesiveness, the adhesive layer 9 is uniformly formed on the substrate 7a of the transferred body 7 and then transferred.

Examples of the material for forming the pressure-sensitive adhesive layer 9 used here include adhesives or pressure-sensitive adhesives whose adhesion process is solvent-activated, heat-activated, pressure-activated, or chemically-reactive. Among these various types of pressure-sensitive adhesives, preferred are pressure-sensitive pressure-sensitive adhesives and hot-melt type pressure-sensitive adhesives. As a pressure-sensitive adhesive, a normal rubber-based or acrylic resin-based thermoplastic can be used, but if heat resistance is required or in order to avoid a small amount of pressure-sensitive adhesive flowing out in the subsequent process, thermosetting Alternatively, it is preferable to use a photocurable adhesive. Further, in this embodiment, the adhesive is applied on the transfer target substrate 7a and the ink is transferred thereon, but instead of this, for example, the recess 2 of the intaglio 1 of FIG. 1B is used.
It is also possible to apply a pressure-sensitive adhesive to the ink after the ink 3 filled in 1 is semi-cured, and then directly transfer it to the glass substrate 7a.

The thickness of the adhesive layer 9 formed of such an adhesive or an adhesive is usually 0.1 to 10 μm, preferably 0.3 to 5 μm. If the adhesive layer 9 is thinner than 0.3 μm, the adhesive force may not be sufficient. on the other hand,
If the thickness exceeds 5 μm, it may be difficult to seal the liquid crystal panel. The ink layer formed on the substrate 7a via the adhesive layer 9 is formed of a cured ink. Specifically, for example, the inks 3a and 3b previously cured on the blanket 5 are formed on the adhesive layer 9. Transfer and form. In the method of the present invention, the pressure-sensitive adhesive layer 9 may be exposed on the part of the transparent substrate 7a where the color layer is not formed. In that case, the exposed pressure-sensitive adhesive layer 9 is removed by a conventional method. Good. Examples of the removing means include a dry etching method, a wet etching method, an ozone oxidation method, a radiant energy decomposition method, and a dissolution removal method.

As described above, a precise fine pattern printed image can be obtained. In the case of a liquid crystal color filter for an LCD display, by repeating the same process four times, a fine pattern of red, green, blue and black can be obtained. Therefore, a liquid crystal color filter compatible with TFT / LCD or STN / LCD can be obtained. Can be used for. Further, the black matrix may be any method such as chromium, a method of forming a film by sputtering using chromium oxide by a sputtering method and patterning, a method of forming a pattern by photofabrication using carbon black, graphite or the like, It is also possible to form a pattern of only red, green and blue by the method of the present invention. Conversely, only the black matrix can be formed by the printing method of the present invention, and the red, green, and blue patterns can be formed by the photofabrication method. Resist inks suitable for printed circuit boards, thin film hybrid ICs, high-precision wiring resist printing for IC packages, element materials for ultra-small sensors, electrode materials, etc., such as plating resist inks, solder resist inks,
Ink for metal circuits can be applied. Further, a fine pattern can be formed by using a special resist for forming the semiconductor device circuit.

In the case of a color filter as the transferred material (printed material), a low thermal expansion glass such as borosilicate glass, borosilicate glass which has been strengthened, synthetic quartz glass,
Quartz glass, optical resin plate, polyimide, polyester,
Substrates such as polyolefins or other transparent plastic films are used. For semiconductor device circuits, a two-layer resist method is used in which polysilicon is provided on a silicon wafer as a substrate to be printed, and a photoresist film for semiconductor is used as a first layer on the polysilicon. A photoresist layer, an adhesive layer, and a print pattern are formed in this order and configured. The size of the material to be printed is not particularly limited. This is a great advantage of the present invention.

[0029]

【Example】

<Example 1> The present invention will be described in more detail below with reference to examples of the present invention. Creation of intaglio Chromium (Cr) is vapor-deposited on the entire surface of the glass substrate to a thickness of 1000Å, and then resist [Tokyo Ohka Kogyo Co., Ltd., "OFPR
-800 "] was applied to a thickness of 1.0 μm, a predetermined pattern was exposed, and development processing was performed. Next, water was added to 165 g of ceric ammonium nitrate and 42 ml of perchloric acid (70%) as an etching solution to prepare a 1 liter solution. Chromium was etched with the etching solution to form a chromium pattern. Using it as an etching resist, a mixed solution of hydrogen peroxide solution and ammonium fluoride is used as an etching solution to etch the glass to give a width of 2
A glass intaglio having a matrix pattern of 0 μm and a depth of 5 μm was produced. After that, chromium was removed with a chromium etching solution. The depth of the recess can be controlled by changing the etching time. Surface treatment of intaglio After irradiating a glass intaglio with a 200 W ozone lamp for 60 seconds from a distance of 8 cm, a fluorine compound is dissolved in a solvent so as to be 1.0% by weight, and coated on a glass substrate with a spinner. A thin release layer was formed on the glass surface by heating at 200 ° C. for 1 hour, and a surface-treated intaglio plate was prepared using 4 kinds of fluorine compounds shown in Table 1 below and 7 kinds of other fluorine polymers. Further, the surface treatment was evaluated using the above intaglio plate. As an evaluation method of releasability,
A glass substrate 12 on which a release layer 13 is formed as shown in FIG.
Is fixed on the test table 20, and a fixed amount (ink area: 0.
196 cm ² ) of ink 14 is placed, the surface of the ink 14 is pressed by pressing a sensor glass 15 of 10 mm × 10 mm which has not been surface-treated, and then the ink 14 is cured by irradiating electromagnetic radiation 16 from a lamp 19. After that, the side of the sensor glass 15 is moved at a constant speed (1.7 mm / se
The force when the photocurable ink described below was peeled off from the substrate 12 was measured by the force sensor 18 as the peeling force. The following method was adopted as the method for evaluating the printing durability of the release layer 13. That is, the measurement of the peeling force was repeated many times, and the measured value of the peeling force was 1400 g / 0.
The printing durability was evaluated by the number of times of 196 cm ² or more. The results are also shown in Table 1.

[Table 1] The column of compound name in Table 1 shows the trade name of fluororesin. Among them, No. 1 to No. 3b are products of Asahi Glass Co., Ltd., No. 4 and No. 5 are products of Shin-Etsu Chemical Co., Ltd., and No. 6 is a product of DuPont.
Further, No. 1 to No. 3b and No. 6 are amorphous fluororesins having a cyclic structure. Regarding No. 3a and No. 3b, No. 3a was applied to the plate, and then heat-dried, followed by No. 3a.
3b is applied and has a structure of a dried double film. N
o.7 is Sanyo Kasei Co., Ltd., No. 8 is Toa Gosei Co., Ltd. and No. 9
Is a fluoropolymer of 3M Co., Ltd., No. 10 and No. 11
Is a powder product of Kitamura Co., Ltd., and is considered to be a crystalline fluororesin. The CT solvent is a fluorinated solvent and is a product of Asahi Glass Co., Ltd. IPA stands for isopropanol. Printing durability was not measured for the samples having a peeling force of 1400 g or more. Regarding the coating properties, ○ means that a completely transparent film is formed, Δ means that striation, cissing or unevenness is observed in a very small part,
And x indicate that the coated surface was not good.

The photocurable inks used for measuring the ink peeling force and printing durability are shown in Table 2 below.

[Table 2] These materials were kneaded by a conventional method, and the pigment was finely dispersed with a three-roll mill. It should be noted that the pigment is added for marking, and does not have a pigment concentration for finally forming a color filter pattern. The viscosity of this ink was 25 Pa · sec at 25 ° C.

Example 2 Preparation of Blanket Silicone rubber with a thickness of 2.0 mm is double-sided tape with a diameter of 1
A blanket was prepared by affixing it to a 0 cm metal roll.
The silicone rubber had a hardness of 80 degrees and an average surface roughness of 1.6 μm. Preparation of the material to be printed (material to be transferred) A borosilicate glass having a thickness of 1.1 mm was coated with a pressure-sensitive adhesive layer coating liquid consisting of an acrylic pressure-sensitive adhesive and ethyl alcohol using a spin coater to a dry film thickness of 0.8 μm. A material to be printed having an adhesive layer was prepared.

Example 3 The intaglio prepared in Example 1 was subjected to the surface treatment of the fluororesin of No. 2 in Table 1 of Example 1 to prepare an intaglio. UV ink containing carbon black and acrylic resin varnish (viscosity 120
Pa · sec) was filled with a metal doctor at an angle of 60 ° and a speed of 100 mm / sec, and then UV light was irradiated at 100 mJ / cm ² to cure the ink, and then the ink was prepared in Example 2. A blanket roll made of silicone rubber was brought into contact with the surface-treated intaglio plate to transfer the ink to the blanket. Subsequently, the blanket roll was brought into contact with the adhesive layer on the substrate to be printed in Example 2 to transfer the ink on the blanket onto the substrate to be printed. At this time, the ink on the blanket hardly remained and was transferred onto the printing material, and a black matrix pattern having a width of 20.6 μm and a thickness of 4.4 μm was formed on the printing material. 180 ° C
After post-baking for 1 hour, a black matrix (BM) having a thickness of 4.0 μm was obtained. In the matrix pattern thus formed, partial thickening or thinning of image lines was not recognized, and the pattern surface was excellent in smoothness. Next, each of the red (R) layer, the green (G) layer, and the blue (B) layer was patterned by the intaglio offset printing method of the present invention as follows using a photocurable colored ink. First, an ink containing a red pigment was printed at a predetermined position on a glass substrate, and then further heated to cure the ink to form a red (R) layer. Similarly, each of the ink containing the green (G) layer pigment and the ink containing the blue (B) layer pigment is printed at a predetermined position on the glass substrate,
After that, it is further heated to be completely cured to form a green (G) layer and a blue (B) layer.
A GB pattern was formed. Each of the red (R) layer, the green (G) layer and the blue (B) layer was formed to a thickness of 3.7 μm by using an intaglio plate having a depth of 4.0 μm.

Further, the printed BM, R, G and B was heated at 220 ° C. for 120 minutes to completely cure the ink and the adhesive layer. According to the method of forming an RGB pattern as described above, the black matrix pattern formed in advance plays a role of a barrier, and thus a predetermined pattern can be easily obtained by RGB printing. Printing was performed using this plate, but after 300 sheets, the image on the 30th sheet was almost the same. However, it was confirmed that pinholes were formed after 500 sheets were passed.

Example 4 A UV curable ink (viscosity 45 Pa · sec) containing carbon black and phenol novolac resin, methylol melamine and a photo-acid generator, a doctor made of ceramics, an angle of 80 ° and a speed of 4
The ink was filled into the groove of the intaglio plate at a depth of 2.5 μm, which was surface-treated with No. 3a in the same manner as in Example 1 at 00 mm / sec. . Then, the ink was cured by irradiating with UV light of 100 mJ / cm ² , and the blanket roll of Example 2 was brought into contact with the intaglio plate and rotated to transfer the ink to a silicone blanket. Next, UV light is applied to the ink on the blanket.
Irradiation with mJ / cm ² completely cured the ink in the area in contact with the blanket. Subsequently, the blanket roll was brought into contact with and rotated by the material to be printed to transfer the ink to the material to be printed. At this time, the ink on the blanket is transferred onto the printing medium without remaining, and the width of the printing medium is 20 μm.
It was possible to produce a black matrix having a thickness of m and a thickness of 2 μm. The black matrix was heated at 230 ° C. for 30 minutes to completely cure it. A red color resist (CR-6000, manufactured by Fuji Hunt Co., Ltd.) by a pigment dispersion method was applied to this sample by a spin coating method, and dried at 90 ° C. for 10 minutes to form a film having a thickness of 1.4 μm. Then, image exposure was performed with ultraviolet rays, and development was performed for 40 seconds with an alkaline developer to obtain a red pattern. Similarly, color resist CG-5
A green pattern was obtained at 000 and then a blue pattern was made with CB-6000. Then 2 red, green and blue patterns
Post baking was performed by heating at 30 ° C. for 30 minutes. The film thickness after post-baking was 1.3 μm. in this way,
Conventionally, it was difficult to form a black matrix having a width of 20 μm depending on the printing method, but the present invention makes it possible to form a high-definition color filter in combination with R, G, and B patterning by the pigment dispersion method. I was able to create it.

Example 5 Copper was mechanically etched to form a grid-like recess having a line width of 20 μm, a length of 330 μm and a width of 110 μm. The whole surface was plated with chrome to form an intaglio plate. In addition, N of the cyclic amorphous fluororesin of Example 1 was added.
Surface treatment was carried out at o.6 to prepare an intaglio plate having a good releasability. A thermosetting ink containing a black pigment containing graphite as a main component and an alkyd resin varnish was filled in an intaglio plate with a doctor of urethane rubber having a hardness of 80 degrees. Then, the far-infrared lamp was irradiated on the intaglio plate to heat-harden the ink so that the surface of the ink was semi-hardened. After that, the ink was transferred to a urethane rubber blanket, and the ink pattern was retransferred from the blanket to the substrate where the acrylic adhesive was applied to the polyester film to a thickness of 0.7 μm, and then 140 ° C.
It was heated for 30 minutes to form a black matrix fine pattern. A red ink containing a red (R) pigment and a photocurable resin, a green ink containing a green (G) pigment and a photocurable resin, and a blue ink containing a blue (B) pigment and a photocurable resin Was used to form an RGB pattern in the same manner as in the case of using the photocurable ink of Example 3.
That is, first, using a red (R) ink, a red (R) pattern was formed on the material to be printed in Example 2 in the same manner as in the formation of the black matrix in Example 3. Then, a green (G) pattern was formed on the printing medium on which the red (R) pattern was formed in the same manner as in the formation of the red (R) pattern. Further, a blue (B) pattern was formed in the same manner. Then, the colored ink pattern and the adhesive layer of the material to be printed were cured by heating at 220 ° C. for 1 hour. In the RGB pattern thus formed, partial thickening or thinning of the image line was not recognized, and the smoothness of the pattern surface was significantly superior to that obtained by the conventional lithographic offset method.

<Example 6> The intaglio prepared in Example 1 was replaced with a black pigment and an acrylic resin in the grooves of the intaglio prepared by double-coating the fluororesin of No. 3a and No. 3b of Example 1. UV ink containing varnish (viscosity 120 Pa · sec)
Using a metal doctor at an angle of 60 ° and a speed of 400 mm
The ink was cured by irradiating it with UV light of 100 mJ / cm ² after filling the ink for 10 seconds. Thereafter, the blanket roll made of silicone rubber prepared in Example 2 was brought into contact with the intaglio plate to transfer the ink to the blanket. Subsequently, the blanket roll was brought into contact with the adhesive layer on the substrate to be printed in Example 2 to transfer the ink on the blanket onto the substrate to be printed. At this time, almost no ink remains on the blanket and is transferred onto the printing material, and the width of the printing material is 21 μm.
A black matrix pattern having a thickness of m and a thickness of 4.4 μm was formed. Post bake this at 200 ℃ for 1 hour,
A black matrix with a thickness of 3.8 μm was obtained.

The matrix pattern thus formed had no partial thickening or thinning of the image lines, and was excellent in smoothness of the pattern surface. Next, red (R)
Layer, green (G) layer, and blue (B) layer,
Patterning was carried out as follows by the intaglio offset printing method of the present invention. First, an ink containing a red pigment was printed at a predetermined position on a glass substrate and then heat-cured to form a red (R) layer. Similarly, each of the ink containing the green (G) layer pigment and the ink containing the blue (B) layer pigment is printed on a predetermined position of the glass substrate, and then heat-cured to cure the green (G) layer and the blue ( By forming the layer B), an RGB pattern having a predetermined arrangement was formed.
The red (R) layer, the green (G) layer, and the blue (B) layer were each 3.7 μm thick by using an intaglio plate having a depth of 4.0 μm.
formed to m. According to the method of forming an RGB pattern as described above, since a black matrix pattern formed in advance plays a role of a barrier, a predetermined pattern can be easily obtained by RGB printing. In addition, BM, R,
Even when 800 sheets of four colors of G and B were printed, the printed image was almost the same as the first 30 sheets.

[0038]

In the intaglio printing method in which the ink is transferred to the printing medium to print the pattern after the ink is filled in the depressions of the intaglio, at least the intaglio is prepared by using the amorphous fluororesin containing the annular structure. By forming the releasable resin layer on the surface of the recess, the releasability of the ink, the reproducibility of the pattern, and the printing durability can be improved.

[Brief description of drawings]

FIG. 1 shows an embodiment of a printing method of the present invention, in which (a) is a step of filling a photo-curable ink into recesses of a printing plate, (b)
FIG. 4A is a schematic longitudinal sectional view of a step of partially curing the ink of the printing plate, and FIG. 7C is a step of transferring the ink pattern to a blanket.

FIG. 2D is a schematic longitudinal sectional view of a step of transferring the ink transferred to the blanket to the transfer target in the subsequent step of the printing method shown in FIG.

FIG. 3 is a schematic vertical sectional view of an apparatus for measuring releasability.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Intaglio 2 Depression 3 Photocurable ink 3a Inner layer 3b Surface layer 4 Doctor knife 5 Blanket 6 Light source 7 Transferred material 7a Transferred substrate 8 Release layer 9 Adhesive layer 11 Vacuum suction hole 12 Glass substrate 13 Release layer 14 Ink 15 sensor glass 16 electromagnetic radiation 17 metal wire 18 force sensor 19 lamp 20 test bench

Claims (2)

[Claims] 1. A mold-releasing resin layer that adheres to an intaglio is formed on at least the surface of the intaglio provided with a pattern indent which serves as a printing image area, and the intaglio is filled with ink to form a printing medium. A printing method of transferring directly or through an intermediate inclusion, wherein the releasable resin layer is composed of a composition containing an amorphous fluororesin having a cyclic structure. 2. An intaglio plate provided with a resin layer made of a composition containing an amorphous fluororesin having the above-mentioned cyclic structure is used, and a photocurable ink is filled in the intaglio plate as the ink, and at the same time or later, ionizing radiation is used. To transfer an ink layer in which the surface layer portion of the ink is in a semi-cured state and the inside thereof is in a cured state to an intermediate inclusion, and the transferred ink image is further irradiated with ionizing radiation. The method for printing a fine pattern according to claim 1, which comprises retransferring to a material to be printed.