JP2009056625A - Planographic printing plate, its manufacturing method, and printed matter using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a planographic printing plate, its manufacturing method and printed matter using the planographic printing plate that can easily, inexpensively and rapidly manufacture a printing plate having high resolution and clearness of streaks of an ink receiving part and obtaining printed matter of high quality. <P>SOLUTION: The planographic printing plate 100 has a plate pattern on a support base material comprising an ink-philic part corresponding to a streak section and an ink repellent part corresponding to a non-streak section. The surface of the support base material 10 is formed of at least a substrate layer 120, and an inactive layer 160 forming the ink-philic part and an adsorption layer 110 forming the ink repellent part are formed on the substrate layer 120. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a field in which a fine pattern needs to be printed, specifically to a technique for printing a wiring pattern or the like in the manufacture of electrical parts, electronic parts, etc., and in particular, printing of the wiring pattern etc. The present invention relates to a lithographic printing plate used for printing, a method for producing the same, and printed matter using the same.

  Conventionally, a photolithography method and a vacuum process method have been used to form electronic components such as circuit boards and display devices. In recent years, with the advancement of electronic technology, the size of elements has become smaller and the pattern forming elements has been required to be miniaturized accordingly. Therefore, compared to conventional manufacturing methods using photoresists, methods for manufacturing fine patterns using various printing methods have been proposed for productivity, cost, high accuracy, large area, and further miniaturization. ing.

  As a technique for forming a fine pattern of the electronic circuit, a lithographic printing method can be mentioned. This lithographic printing method is generally spread as an offset printing method, and the normal offset printing method uses immiscibility of water and oil, and forms a hydrophilic part and an oleophilic part on the printing plate surface. In printing, first, water called dampening water is given to the hydrophilic portion of the lithographic plate to impart resilience to the oil-based ink, and then the ink is supplied to the lithographic plate to adhere the ink only to the oleophilic portion. Once transferred to the blanket, it is transferred again to the substrate and printed.

  Since such a lithographic printing method is difficult to control fountain solution, an offset printing method that does not use fountain solution, that is, a dry lithographic printing method has been developed. This basically uses an oil repellent part and an oleophilic part, and ink adheres only to the lipophilic part and does not adhere to the oil repellent part. This oil-repellent part is generally composed of an organic silicone compound or an organic fluorine compound, and a part of these compounds existing on a metal plate such as aluminum is removed by an appropriate means to expose the oleophilic part to expose the ink receiving part. To form a lithographic printing plate. A photochemical means is generally used as a method for removing the oil-repellent part. For example, photosensitivity is imparted to the oil-repellent part layer, the oil-repellent part layer is exposed to light and the exposed part is photocured to form the oil-repellent part, while the unexposed part is developed with a solvent or the like. There is a method of removing and forming a lipophilic part.

  In addition, a general photosensitive resin layer such as a diazonium compound is disposed below the oil-repellent part layer (silicone rubber layer), the exposed part is cured and stored, and the unexposed part is developed and removed to remove the upper oil-repellent part. There is also a method of removing the oleophilic part to expose the lipophilic part.

Furthermore, a method for attaching toner using an electrophotographic method for a simple printing plate has been proposed. In addition, there is a method in which a silicone layer applied to the entire surface of a substrate is locally broken to expose the substrate surface, and ink is attached to the exposed portion (see, for example, Patent Document 1). Furthermore, there is a dry lithographic material in which a chemical foaming agent is blended in a lipophilic thermosoftening material layer and / or an oil repellent material layer (see, for example, Patent Document 2).
The above prior art documents are shown below.
Japanese Patent Publication No.42-21879 JP-A-1-192555

  However, the above-described method for producing a dry planographic printing plate by photochemical means has a problem that the plate making process is complicated, an expensive apparatus and a long plate making time are required, and further, the handling of the developer is required. is doing. In addition, the higher the resolution of the printed pattern is tens of μm or less, the more difficult it is to form a plate, and defects such as sharpness of the image area (linearity of lines) and non-image area scumming occur. There is a problem that makes it easier to do.

  In addition, the dry lithographic printing plate manufacturing method applying the above-described electrophotographic method for the simplified printing plate is a simple, inexpensive, and rapid plate making method. Since the oil-repellent substance is essentially poor in affinity with other substances, there is a problem that toner adhesion (fixation) is poor, unstable and printing durability is poor.

  Also, the method of locally destroying the silicone layer has a problem that a complicated and expensive apparatus and a long plate making time are required due to irradiation of an electron beam or a laser beam, discharge destruction, or the like. Furthermore, in the case of a chemical foaming agent blended, gas is generated by utilizing thermal decomposition, so that it gradually decomposes during storage, and if the foaming aid distribution is not uniform, the degree of foaming depending on the location However, there is a drawback that image formation defects such as background stains and wrinkles occur, and it is difficult to stably produce a plate material, which has a serious industrial problem. In addition, some foaming agents contain harmful components in the generated gas and those that generate harmful as a by-product, which has a serious problem from the work environment. .

  The present invention solves the problems of the prior art, and the problem is that the image line of the ink receiving portion has high resolution and sharpness, and a high-quality printed matter can be obtained. An object of the present invention is to provide a lithographic printing plate that can be produced simply, inexpensively and rapidly, a method for producing the same, and a printed matter using the same.

  In order to achieve the above object in the present invention, first, in the invention of claim 1, the plate pattern on the support substrate has a parent ink portion corresponding to the image line portion and an ink repellent portion corresponding to the non-image line portion. The surface of the support substrate is at least a base layer, and an inert layer forming the parent ink portion and an adsorption layer forming the ink repellent portion are formed on the base layer. The lithographic printing plate is characterized by this.

  The invention according to claim 2 is a lithographic printing plate in which a plate pattern on a support substrate comprises a parent ink part corresponding to an image line part and an ink repellent part corresponding to a non-image line part, wherein the support base A lithographic printing plate characterized in that the surface of the material is at least an inactive layer forming the parent ink part, and an adsorption layer forming the ink repellent part is formed on the inactive layer through a base layer. It is a thing.

  According to a third aspect of the present invention, the underlayer is made of a metal oxide, the inert layer is made of a metal or a resin, and the adsorption layer is a combination of a silane coupling agent. The planographic printing plate according to 1 or 2 is used.

  The invention according to claim 4 is characterized in that the silane coupling agent is one or more compounds selected from compounds represented by the following formulas (1), (2), and (3). The planographic printing plate according to claim 3 is used.

（式（１）中、Ｒ¹ は独立してアルキル基、シクロアルキル基、フェニル基であり、アルキル基、シクロアルキル基、フェニル基は全フッ素化もしくは部分フッ素化されていても
よい。また、式（１）中、Ｘ¹ 、Ｘ² 、Ｘ³ は独立して塩素、臭素、ヨウ素などのハロゲンもしくはアルコキシ基である。）

(In formula (1), R ¹ is independently an alkyl group, a cycloalkyl group, or a phenyl group, and the alkyl group, cycloalkyl group, or phenyl group may be fully fluorinated or partially fluorinated. In formula (1), X ¹ , X ² and X ³ are each independently a halogen such as chlorine, bromine or iodine or an alkoxy group.)

（式（２）中、Ｒ¹ 、Ｒ² は独立してアルキル基、シクロアルキル基、フェニル基であり、アルキル基、シクロアルキル基、フェニル基は全フッ素化もしくは部分フッ素化されていてもよい。また、式（１）中、Ｘ¹ 、Ｘ² は独立して塩素、臭素、ヨウ素などのハロゲンもしくはアルコキシ基である。）

(In Formula (2), R ¹ and R ² are independently an alkyl group, a cycloalkyl group, and a phenyl group, and the alkyl group, cycloalkyl group, and phenyl group may be fully fluorinated or partially fluorinated. In formula (1), X ¹ and X ² are each independently a halogen or alkoxy group such as chlorine, bromine or iodine.)

（式（３）中、Ｒ¹ 、Ｒ² 、Ｒ³ は独立してアルキル基、シクロアルキル基、フェニル基であり、アルキル基、シクロアルキル基、フェニル基は全フッ素化もしくは部分フッ素化されていてもよい。また、式（１）中、Ｘ¹ は独立して塩素、臭素、ヨウ素などのハロゲンもしくはアルコキシ基である。）
また、請求項５の発明では、前記下地層は金属でなり、前記不活性層は金属酸化物もしくは樹脂でなり、前記吸着層はチオアルキル化合物でなる組合せであることを特徴とする請求項１または２記載の平版印刷版としたものである。

(In the formula (3), R ¹ , R ² and R ³ are independently an alkyl group, a cycloalkyl group and a phenyl group, and the alkyl group, cycloalkyl group and phenyl group are fully fluorinated or partially fluorinated. In formula (1), X ¹ is independently a halogen such as chlorine, bromine or iodine or an alkoxy group.
In the invention of claim 5, the underlayer is made of metal, the inert layer is made of metal oxide or resin, and the adsorption layer is a combination of thioalkyl compounds. 2 is a planographic printing plate.

  In the invention of claim 6, the lithographic printing plate according to claim 5, wherein the thioalkyl compound is at least one compound selected from compounds represented by the following formula (4): Is.

（式（４）中、Ｒ¹ は独立してアルキル基、シクロアルキル基、フェニル基であり、アルキル基、シクロアルキル基、フェニル基は全フッ素化もしくは部分フッ素化されていてもよい。Ｒ² は独立して水素、アルキル基、シクロアルキル基、フェニル基であり、アルキル基、シクロアルキル基、フェニル基は全フッ素化もしくは部分フッ素化されていてもよい。また、式中、ｎは１から３までの間で選択される整数である。）
また、請求項７の発明では、上記請求項１記載の平版印刷版の製造方法であって、下地層上への不活性層をフォトリソグラフィー法で形成し、該不活性層が形成されていない下地層への吸着層を気相もしくは液相法で形成することを特徴とする平版印刷版の製造方法としたものである。

(In the formula (4), R ¹ is an alkyl group independently, a cycloalkyl group, a phenyl group, an alkyl group, a cycloalkyl group, a phenyl group which may be perfluorinated or partially fluorinated .R ² Is independently hydrogen, an alkyl group, a cycloalkyl group, or a phenyl group, and the alkyl group, cycloalkyl group, or phenyl group may be fully fluorinated or partially fluorinated. An integer selected between 3 and 3.)
The invention according to claim 7 is the method for producing a lithographic printing plate according to claim 1, wherein the inactive layer on the underlayer is formed by a photolithography method, and the inactive layer is not formed. A method for producing a lithographic printing plate is characterized in that the adsorption layer on the underlayer is formed by a gas phase or liquid phase method.

  The invention of claim 8 is the method for producing a lithographic printing plate according to claim 2, wherein the underlayer on the inactive layer is formed by a photolithography method, and the adsorption layer on the underlayer is formed. It is a method for producing a lithographic printing plate characterized by being formed by a gas phase or liquid phase method.

  Furthermore, the invention of claim 9 is a printed matter using the planographic printing plate according to any one of claims 1 to 6.

  Since this invention is the above structure, there exist the following effects.

That is, according to the invention according to claim 7, in the lithographic printing plate manufacturing method according to claim 1, the inactive layer is formed on the underlayer by photolithography, and the inactive layer is formed. A high-resolution, high-definition plate can be easily, inexpensively and rapidly formed by forming the adsorption layer on an untreated underlayer by a gas phase or liquid phase method that performs self-selection on the underlayer. A lithographic printing plate that can be provided.

  According to the invention according to claim 8, in the lithographic printing plate manufacturing method according to claim 2, the underlayer is formed on the inactive layer by a photolithography method, and the underlayer is formed on the underlayer. Provided is a lithographic printing plate capable of easily, inexpensively and rapidly forming a plate having high resolution and high sharpness by forming the adsorption layer by a gas phase or liquid phase method which performs self-selection on the underlayer. be able to.

  The best mode for carrying out the present invention will be described below in detail with reference to the drawings.

<Configuration of planographic printing plate>
As the configuration of the lithographic printing plate of the present invention, for example, as shown in FIG. 1, an inert layer 160 that forms a parent ink portion and a suction layer that forms an ink repellent portion on a support base 10 that is entirely composed of a base layer 120. 110 is formed. Although not particularly shown, the underlayer may be formed on a sheet-like or flexible support substrate. When printing, the inactive layer 160 forming the parent ink portion corresponds to the image portion of the printed matter, and the adsorption layer 110 forming the ink repellent portion corresponds to the non-image portion of the printed matter.

  Further, as another configuration of the lithographic printing plate of the present invention, for example, as shown in FIG. 2, an underlayer 120 and an ink repellent portion are formed on a support substrate 10 composed of an inactive layer 160 that entirely forms a parent ink portion. An adsorption layer 110 is formed. Although not particularly shown, the inert layer may be formed on a sheet-like or flexible supporting substrate. When printing, the inactive layer 160 forming the parent ink portion corresponds to the image portion of the printed matter, and the adsorption layer 110 forming the ink repellent portion corresponds to the non-image portion of the printed matter.

  The adsorption layer 110 is preferably selectively adsorbed on the underlayer 120, and more preferably, the adsorption layer 110 is chemically adsorbed on the underlayer 120 from the viewpoint of printing resistance. In order for the adsorption layer 110 to be chemically adsorbed to the underlayer 120, an appropriate combination of both is important. The combination shown in Table 1 below from Cited Reference 1 can be used as the combination in which the adsorption layer 110 and the underlayer 120 are chemically adsorbed.

  In the present invention, the foundation layer 120 is composed of a metal oxide, the inert layer 160 is composed of a metal or a resin, and the adsorption layer 110 is composed of a silane coupling agent, and the foundation layer. A second combination in which 120 is made of metal, the inactive layer 160 is made of a metal oxide or resin, and the adsorption layer 110 is made of a thioalkyl compound can be selected.

＜平版印刷版の製造方法＞
本発明の平版印刷版の形成工程の一例について図４を用いて説明する。

<Method for producing planographic printing plate>
An example of the process for forming a lithographic printing plate according to the present invention will be described with reference to FIG.

[Step 1]
For example, as shown in FIG. 4A, a film of the inactive layer 160 is formed on the entire surface of the supporting base material 10 which is entirely the base layer 120, and is patterned as shown in FIG. 4B. Thus, the inactive layer 160 forming the parent ink portion is formed. This film is formed by sputtering, resistance heating vapor deposition, EB vapor deposition, laser ablation, ion plating, CVD and other dry processes, spray coating, bar coating, dip coating, die coating, cap coating, spin coating, roll coating, applicator, After forming the liquid film of the base layer material by a wet process such as gravure coating, the film can be formed by heat treatment or the like. Further, imprinting, photolithography, cutting, or the like can be used as the patterning method, but the photolithography method is preferable from the viewpoint of patterning accuracy and the remaining film on the bottom of the recess.

[Step 2]
Subsequently, as shown in FIG. 4C, the adsorption layer 110 is formed on the base layer 120 on which the inactive layer 160 is not formed by patterning. The adsorption layer 110 is formed by exposing the substrate to the material vapor of the adsorption layer in a wet process such as a dipping method, a dip method, or a spin coating method using a solution in which the material of the adsorption layer is dissolved in water or an organic solvent. A dry process can be used. Since the adsorption layer 110 is adsorbed to the base layer 120 in a self-aligning manner, it is possible to easily form a plate with high positional accuracy of the adsorption layer 110. In this way, an example of the lithographic printing plate 100 of the present invention can be obtained.

  Another example of the process for forming a lithographic printing plate according to the present invention will be described with reference to FIG.

[Step 1]
For example, as shown in FIG. 5A, a film of the base layer 120 is formed on the entire surface of the support base material 10 that is entirely composed of the inactive layer 160, and is patterned as shown in FIG. 5B. To do. The film formation method of this underlayer 120 is a dry process such as sputtering, resistance heating vapor deposition, EB vapor deposition, laser ablation, ion plating, CVD, spray coating, bar coating, dip coating, die coating, cap coating, spin coating, roll After forming the liquid film of the underlayer material by a wet process such as coating, applicator, or gravure coating, film formation can be performed by heat treatment or the like. Further, imprinting, photolithography, cutting, or the like can be used as a patterning method for the underlayer 120, but photolithography is preferable in terms of patterning accuracy and a remaining film at the bottom of the recess.

[Step 2]
Subsequently, as illustrated in FIG. 5C, the adsorption layer 110 is formed on the patterned base layer 120. The adsorption layer 110 is formed by exposing the substrate to the material vapor of the adsorption layer in a wet process such as a dipping method, a dip method, or a spin coating method using a solution in which the material of the adsorption layer is dissolved in water or an organic solvent. A dry process can be used. Since the adsorption layer 110 is adsorbed to the base layer 120 in a self-aligning manner, it is possible to easily form a plate with high positional accuracy of the adsorption layer 110. In this way, another example of the planographic printing plate 100 of the present invention can be obtained.

<Materials of planographic printing plates>
Hereinafter, materials constituting the planographic printing plate of the present invention will be described.

  As the underlayer 120, metal oxide such as silicon dioxide, alumina, kaolin, mica, talc, clay, alumina, wollastonite, potassium titanate, titanium oxide, zinc oxide, tin oxide, chromium oxide, zirconium oxide, indium oxide, etc. Alternatively, metals such as Au, Ag, Cu, Pt, Pd, Rh, Ru, Fe, Co, Cr, Al, Zn, Ti, Mn, Mo, W, Zr, and alloys selected from these can be used.

  The adsorption layer 110 can be composed of a silane coupling agent, and the silane coupling agent is selected from the group consisting of compounds represented by the following formulas (1), (2), and (3). Preferably, the compound is one or more compounds.

（式（１）中、Ｒ¹ は独立してアルキル基、シクロアルキル基、フェニル基であり、アル
キル基、シクロアルキル基、フェニル基は全フッ素化もしくは部分フッ素化されていてもよい。また、式（１）中、Ｘ¹ 、Ｘ² 、Ｘ³ は独立して塩素、臭素、ヨウ素などのハロゲンもしくはアルコキシ基である。）

(In formula (1), R ¹ is independently an alkyl group, a cycloalkyl group, or a phenyl group, and the alkyl group, cycloalkyl group, or phenyl group may be fully fluorinated or partially fluorinated. In formula (1), X ¹ , X ² and X ³ are each independently a halogen such as chlorine, bromine or iodine or an alkoxy group.)

（式（２）中、Ｒ¹ 、Ｒ² は独立してアルキル基、シクロアルキル基、フェニル基であり、アルキル基、シクロアルキル基、フェニル基は全フッ素化もしくは部分フッ素化されていてもよい。また、式（１）中、Ｘ¹ 、Ｘ² は独立して塩素、臭素、ヨウ素などのハロゲンもしくはアルコキシ基である。）

(In Formula (2), R ¹ and R ² are independently an alkyl group, a cycloalkyl group, and a phenyl group, and the alkyl group, cycloalkyl group, and phenyl group may be fully fluorinated or partially fluorinated. In formula (1), X ¹ and X ² are each independently a halogen or alkoxy group such as chlorine, bromine or iodine.)

（式（３）中、Ｒ¹ 、Ｒ² 、Ｒ³ は独立してアルキル基、シクロアルキル基、フェニル基であり、アルキル基、シクロアルキル基、フェニル基は全フッ素化もしくは部分フッ素化されていてもよい。また、式（１）中、Ｘ¹ は独立して塩素、臭素、ヨウ素などのハロゲンもしくはアルコキシ基である。）
上記シランカップリング剤として、具体的には、イソブチルトリメトキシシラン、トリメチルメトキシシラン、シクロヘキシルメチルジメトキシシラン、ｎ−デシルトリメトキシシラン、ジイソプロピルジメトキシシラン、ｎ−プロピルトリメトキシシラン、ジイソブチルジメトキシシラン、ｎ−オクチルメトキシシロキサン、エチルトリメトキシシラン、ジメチルジメトキシシラン、ｎ−オクチルトリエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、ｎ−ヘキシルトリメトキシシラン、ｎ−ヘキシルトリエトキシシラン、ジメチルエトキシシラン、n−オクタデシルトリメトキシシラン、トリメチルプロポキシシラン、トリメチルイソプロポキシシラン、フェノキシトリメチルシラン、シクロヘキロキシトリメチルシラン、ヘキシルトリクロロシラン、ヘプチルトリクロロラン、オクチルトリクロロシラン、ノニルトリクロロシラン、デシルトリクロロシラン、オクタデシルトリクロロシランなどのアルキル基や、シクロヘキシルトリメトキシシラン、ジシクロペンチルジメトキシシラン、(シクロプロピルメチル)ジメチルメトキシシラン、シクロヘキシルトリクロロシランなどのシクロアルキル基を有するアルコキシシランや、ジメトキシメチル−３，３，３−トリフルオロプロピルシラン、３，３，３−トリフルオロプロピルトリメトキシシラン、２−(ノナデカフルオロノニル)エチルトリエトキシシラン、３，３，３−トリフルオロプロピルトリエトキシシラン、(ペンタフルオロフェニル)トリエトキシシラン、８，８，８−トリフルオロオクチルトリエトキシシラン、２−(ヘニコサフルオロデシル)エチルトリエトキシシラン、(４−フルオロフェニル)トリメトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−ペルフルオロデシルトリクロロシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロオクチルトリクロロシラン、３，３，３−トリフルオロプロピルトリクロロシラン、ヘニコサフルオロデシルトリクロロシラン、４−フルオロベンジルトリクロロシランなどのフッ素化されたアルコキシシランなどを例として挙げることが出来るがこれに限定されない。

(In the formula (3), R ¹ , R ² and R ³ are independently an alkyl group, a cycloalkyl group and a phenyl group, and the alkyl group, cycloalkyl group and phenyl group are fully fluorinated or partially fluorinated. In formula (1), X ¹ is independently a halogen such as chlorine, bromine or iodine or an alkoxy group.
Specific examples of the silane coupling agent include isobutyltrimethoxysilane, trimethylmethoxysilane, cyclohexylmethyldimethoxysilane, n-decyltrimethoxysilane, diisopropyldimethoxysilane, n-propyltrimethoxysilane, diisobutyldimethoxysilane, n- Octylmethoxysiloxane, ethyltrimethoxysilane, dimethyldimethoxysilane, n-octyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, dimethylethoxysilane, n- Octadecyltrimethoxysilane, trimethylpropoxysilane, trimethylisopropoxysilane, phenoxytrimethylsilane, cyclohexoxytrimethyl Alkyl groups such as silane, hexyltrichlorosilane, heptyltrichlorosilane, octyltrichlorosilane, nonyltrichlorosilane, decyltrichlorosilane, octadecyltrichlorosilane, cyclohexyltrimethoxysilane, dicyclopentyldimethoxysilane, (cyclopropylmethyl) dimethylmethoxysilane, Alkoxysilanes having a cycloalkyl group such as cyclohexyltrichlorosilane, dimethoxymethyl-3,3,3-trifluoropropylsilane, 3,3,3-trifluoropropyltrimethoxysilane, 2- (nonadecafluorononyl) ethyl Triethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, (pentafluorophenyl) triethoxysilane, 8,8,8-trifluorooctyl Ethoxysilane, 2- (Henicosafluorodecyl) ethyltriethoxysilane, (4-fluorophenyl) trimethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane, 1H, 1H, 2H, 2H-perfluorooctyl Examples include, but are not limited to, fluorinated alkoxysilanes such as trichlorosilane, 3,3,3-trifluoropropyltrichlorosilane, henicosafluorodecyltrichlorosilane, and 4-fluorobenzyltrichlorosilane.

  The adsorption layer 110 can be composed of a thioalkyl compound, and the thioalkyl compound is preferably one or more compounds selected from compounds represented by the following formula (4).

（式（４）中、Ｒ¹ は独立してアルキル基、シクロアルキル基、フェニル基であり、アルキル基、シクロアルキル基、フェニル基は全フッ素化もしくは部分フッ素化されていてもよい。Ｒ² は独立して水素、アルキル基、シクロアルキル基、フェニル基であり、アルキ
ル基、シクロアルキル基、フェニル基は全フッ素化もしくは部分フッ素化されていてもよい。また、式中、ｎは１から３までの間で選択される整数である。）
上記チオアルキル化合物として、具体的には、1-ブタンチオール、シクロヘキサンチオール、1-デカンチオール、1-ドデカンチオール、1-ヘプタンチオール、1-オクタデカンチオール、1-ヘキサデカンチオール、1-ノナンチオール、４‐ｔｅｒｔ‐ブチルシクロヘキサノンジチオアセタール、シクロヘキサンチオール、４‐ｔｅｒｔ‐ブチルシクロヘキサンチオール、シクロペンタンチオール、p-フルオロベンゼンメタンチオール、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロデカン-1-チオール、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロオクタンチオール、４−(トリフルオロメチル)ベンゼンチオール、４−（トリフルオロメチル）−２，３，５，６−テトラフルオロベンゼンチオール、１２，１２，１２−トリフルオロドデカン‐１‐チオール、１，１−ビス（トリフルオロメチル）−２，２，２−トリフルオロエタンチオール、６−（ヘプタデカフルオロオクチル）−１−ヘキサンチオール、４，４，５，５，６，６，７，７，８，８，９，９，１０，１０，１１，１１，１２，１２，１３，１３，１３−ヘニコサフルオロトリデカン−１−チオール、５，５，６，６，７，７，８，８，９，９，１０，１０，１０−トリデカフルオロデカン−１−チオール、３，３，４，４，５，５，６，６，７，７，８，８，９，９，１０，１０，１１，１１，１２，１２，１３，１３，１３−トリコサフルオロトリデカン−１−チオール、トリコサフルオロウンデカン−１−チオール、４−チアヘプタン二酸ジドデシル、ジシクロヘキシルスルフィド、ジブチルスルフィド、ジイソアミルスルフィド、ジドデシルスルフィド、ジヘキシルスルフィド、ジシクロヘキシルペルスルフィド、ジヘキサデシルペルスルフィド、ビス（ペンタフルオロフェニル）ペルジスルフィド、ジヘキシルペルトリスルフィド、ジヘプチルペルトリスルフィド、ジデシルペルトリスルフィド、ジノナデシルペルトリスルフィド、ビス（トリフルオロメチル）トリスルファンなどのジスルフィド、トリスルフィドなどのチオアルキル化合物を例として挙げることが出来るがこれに限定されない。このように、アルキル基やフッ化アルキル基を有する低表面エネルギーの表面を与える材料を吸着層に用いると、吸着層へのインクの付着が抑制される。

(In the formula (4), R ¹ is an alkyl group independently, a cycloalkyl group, a phenyl group, an alkyl group, a cycloalkyl group, a phenyl group which may be perfluorinated or partially fluorinated .R ² Is independently hydrogen, an alkyl group, a cycloalkyl group, or a phenyl group, and the alkyl group, cycloalkyl group, or phenyl group may be fully fluorinated or partially fluorinated. An integer selected between 3 and 3.)
Specific examples of the thioalkyl compound include 1-butanethiol, cyclohexanethiol, 1-decanethiol, 1-dodecanethiol, 1-heptanethiol, 1-octadecanethiol, 1-hexadecanethiol, 1-nonanethiol, 4- tert-Butylcyclohexanone dithioacetal, cyclohexanethiol, 4-tert-butylcyclohexanethiol, cyclopentanethiol, p-fluorobenzenemethanethiol, 1H, 1H, 2H, 2H-perfluorodecane-1-thiol, 1H, 1H, 2H , 2H-perfluorooctanethiol, 4- (trifluoromethyl) benzenethiol, 4- (trifluoromethyl) -2,3,5,6-tetrafluorobenzenethiol, 12,12,12-trifluorododecane-1 -Thiol, 1, -Bis (trifluoromethyl) -2,2,2-trifluoroethanethiol, 6- (heptadecafluorooctyl) -1-hexanethiol, 4,4,5,5,6,6,7,7,8 , 8,9,9,10,10,11,11,12,12,13,13,13-Henicosafluorotridecan-1-thiol, 5,5,6,6,7,7,8,8 , 9, 9, 10, 10, 10-tridecafluorodecane-1-thiol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10, 10,11,11,12,12,13,13,13-tricosafluorotridecan-1-thiol, tricosafluoroundecan-1-thiol, 4-thiaheptanedioic acid dododecyl, dicyclohexyl sulfide, dibutyl sulfide, diisoamyl Sulfide Didodecyl sulfide, dihexyl sulfide, dicyclohexyl persulfide, dihexadecyl persulfide, bis (pentafluorophenyl) perdisulfide, dihexyl pertrisulfide, diheptyl pertrisulfide, didecyl pertrisulfide, dinonadecyl pertrisulfide, Examples thereof include, but are not limited to, disulfides such as bis (trifluoromethyl) trisulfane and thioalkyl compounds such as trisulfide. As described above, when a material that provides a low surface energy surface having an alkyl group or an alkyl fluoride group is used for the adsorption layer, the adhesion of ink to the adsorption layer is suppressed.

  Since the lithographic printing plate constructed in this way can selectively form an adsorption layer on the underlayer using the patterned inert layer as a mask, a plate with high positional accuracy of the ink-repellent part comprising the adsorption layer can be obtained. It can be formed easily. In addition, since the inactive layer is formed by a photolithography method similar to that for semiconductor devices and LCDs, a clear pattern of image lines can be formed with high resolution. Therefore, it is possible to supply a lithographic plate capable of forming a high-detail and high-quality printed matter.

  The inert layer 160 includes silicon dioxide, alumina, kaolin, mica, talc, clay, alumina, wollastonite, potassium titanate, titanium oxide, zinc oxide, tin oxide, chromium oxide, zirconium oxide, indium oxide, and the like. Metal oxides such as Au, Ag, Cu, Pt, Pd, Rh, Ru, Fe, Co, Cr, Al, Zn, Ti, Mn, Mo, W, Zr and alloys selected from these, acrylic , Polyimide, benzocyclobutene, epoxy, silicone, polymethyl methacrylate, urethane, polyvinyl alcohol, methoxymethylated nylon, polyamide, polybutadiene, unsaturated polyester, oxetane, vinyl ether, and other photosensitive resins and polymer alloys that combine these resins However, the present invention is not limited to this. The photosensitive resin can be used in either a positive photosensitive mechanism or a negative photosensitive mechanism.

Further, as the support base material 10, a glass base material such as quartz glass, crystal glass, soda lime glass, borosilicate glass, a metal base material such as stainless steel, aluminum or copper, a wafer base material composed of silicon or the like. Polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyetherimide, polyetheretherketone, polyetherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cycloolefin polymer, polyolefin, polyvinyl chloride, liquid crystal Materials such as polymers, epoxy resins, phenol resins, urea resins, melamine resins, and silicone resins can be used. Polymer alloys combining these resins and glass epoxy groups It can be a plastic substrate, such as a multilayer structure film of one or more multi-layer structure formed by laminating a combination of the resin material.
<Manufacture of printed materials using lithographic printing plates>
Production of a printed matter using an example of the lithographic printing plate of the present invention obtained in this way will be described with reference to FIGS.

  The lithographic printing plate 100 of the present invention is used as a lithographic printing plate. First, for example, as shown in FIG. 6A, the lithographic printing plate 100 is brought into contact with the inking mechanism 540 to adhere the ink 541 to the inactive layer 160 of the lithographic printing plate 100. Next, as shown in FIG. 6B, the lithographic printing plate 100 is brought into contact with the substrate to be printed 550, and the ink 541 is transferred to the substrate to be printed 550, whereby the printed material 500 can be obtained. At this time, the ink 541 on the planographic printing plate 100 may be transferred entirely or partially to the printing substrate 550.

  Further, for example, as shown in FIG. 7A, first, the planographic printing plate 100 is brought into contact with the inking mechanism 540 to adhere the ink 541 to the inert layer 160 that forms the concave portion of the planographic printing plate 100. Next, as shown in FIG. 7B, the lithographic printing plate 100 is brought into contact with the substrate to be printed 550, and the ink 541 is transferred to the substrate to be printed 550, whereby the printed material 500 can be obtained. At this time, the ink 541 on the planographic printing plate 100 may be transferred entirely or partially to the printing substrate 550.

  The ink 541 used in the lithographic printing method using the lithographic printing plate may be adjusted according to the type of printed matter to be produced, such as gold, silver, copper, nickel, platinum, palladium, rhodium, ITO, tin oxide, Metals such as zinc oxide, inorganic conductive inks with various additives added to the metal oxide fine particle dispersion as needed, and organic conductives in which PEDOT / PSS, polyaniline, polypyrrole, etc. are dissolved in water or organic solvents Examples include, but are not limited to, ink, ink obtained by dissolving or dispersing an organic electroluminescence (EL) material in an organic solvent, a pigment dispersion for a color filter, an etching resist, and the like.

  Further, the substrate to be printed 550 on which an image is formed by transferring an ink film can be appropriately selected according to the target printed matter. When manufacturing electronic parts, polyethylene terephthalate (PET), polyimide, polyethersulfone (PES), polyethylene naphthalate (PEN), polycarbonate, plastic materials such as glass epoxy substrates, glass substrates such as quartz, silicon wafers, etc. Can be mentioned. It is also possible to select a flexible base material such as a film according to the environment in which the printed material is used. In this case, continuous printing is performed using a long base material to improve production efficiency. Is preferred.

  Examples of the printed material 500 manufactured by the manufacturing method using the planographic printing plate of the present invention include a circuit board, a thin film transistor substrate, a color filter, a printed wiring board, an organic electroluminescence element, and a component-embedded substrate. The thin film transistor substrate includes a plurality of thin film transistors in an array corresponding to the pixels, and can be used as a display member that needs to be turned on and off for each pixel such as a liquid crystal display.

In addition, as an image pattern printed using the planographic printing plate of the present invention, for example, an electrode provided in a thin film transistor substrate, a capacitor electrode, wiring, etc., a colored layer provided in a color filter, an electrode provided in an organic electroluminescence element In the case of a printed wiring board with a built-in element, an organic electroluminescence layer, a printed wiring board, or a passive element / active element such as a capacitor electrode, a dielectric layer, a resistive element electrode, a resistor, an inductor, or a transistor component Examples thereof include etching resists for forming elements and circuit boards.

  Specific examples of the present invention will be described below.

<Example 1>
A PEN film having a size of 100 mm × 100 mm and a thickness of 0.1 mm was used as a supporting substrate. A SiO ₂ film was formed on one side of the PEN film by vapor deposition to obtain a 50 nm underlayer. Cr was vapor-deposited on the entire surface of the SiO ₂ film to form an inactive layer of 30 nm, and this inactive layer was patterned by a photolithography method to obtain a patterned inactive layer forming a parent ink portion.

  Next, a support in which the inert layer obtained above is formed in a solution obtained by dissolving fluoroalkylsilane (manufactured by GE Toshiba Silicone Co., Ltd .: trade name TSL8233) in isopropyl alcohol as a silane coupling agent to 0.5% by weight. The substrate was dipped for 10 minutes and then dried at 120 ° C. for 10 minutes to form an adsorption layer on the surface of the underlayer to produce a lithographic printing plate.

In addition, the plate pattern formed above is 100 units in a unit of 10 units × 10 units in a 100 mm square region at the center of the glass plate, with the pattern schematically shown in FIGS. 3A and 3B as one unit. Units were arranged. The image pattern corresponding to the pattern sparse portion 270 is a 250 μm × 250 μm square, and the image pattern corresponding to the pattern dense portion 211 is a 140 μm × 210 μm rectangle. The line / space width between the pattern sparse part and the pattern dense part is 5 μm / 5 μm.
<Ink 1>
As an ink to be used, a conductive ink was prepared by dissolving a silver particle aqueous dispersion having an average particle diameter of 20 nm so that the silver particles were 20 parts by weight and the water was 80 parts by weight.

  Next, the conductive ink adjusted as described above was applied to a glass substrate used as a support for the inking mechanism with a bar coater to form a conductive ink film. Subsequently, the lithographic printing plate obtained above was brought into close contact with the ink film of the inking mechanism and then peeled to form an ink film on the plate surface of the lithographic printing plate. Subsequently, the lithographic printing plate on which the ink of the image portion is formed on the plate surface and the soda lime glass substrate having a thickness of 0.7 mm and a size of 100 mm × 100 mm used as the substrate side to be printed are peeled off. Then, the ink film on the planographic printing plate was transferred to the printing substrate side. Next, this was heat-processed at 200 degreeC for 30 minutes, and the printed matter provided with the electroconductive pattern was produced.

<Example 2>
Example except that thioalkyl compound (manufactured by Fluorous Technologies: 1H, 1H, 2H, 2H-perfluorooctane-1-thiol) was used as the material for the adsorption layer, gold was used as the underlayer, and SiO ₂ was used as the inert layer. A lithographic printing plate was produced in the same manner as in Example 1, and a printed matter using this was obtained in the same manner as in Example 1.

<Example 3>
A lithographic printing lithographic plate was produced in the same manner as in Example 1 except that the color filter coloring ink prepared as described below was used as the ink, and a printed material was produced using the lithographic printing plate.
<Ink 2>
First, a red pigment dispersion was prepared with the following composition.
[Red pigment dispersion]
-Red pigment C.I. I. Pigment Red 254 (“Ilgar For Red B-CF” manufactured by Ciba Specialty Chemicals) 18 parts by weight C.I. I. Pigment Red 177 (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals) 2 parts by weight Acrylic varnish (solid content 20%) 108 parts by weight (red coloring ink)
Thereafter, a mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 5 μm filter to obtain a red colored ink.
-100 parts by weight of the above red pigment dispersion-Methylated methylol melamine (manufactured by Sanyo Kasei Kogyo Co., Ltd .: trade name MW-30) ... 20 parts by weight-Leveling agent (manufactured by Dainippon Ink & Chemicals Co., Ltd .: trade name Megafuck F- 483SF) ... 1 part by weight, propylene glycol monomethyl ether ... 85 parts by weight, propylene glycol monomethyl ether acetate ... 45 parts by weight The red colored ink thus prepared was applied to the blanket in the same manner as in Example 1 and the non-image part was removed. -Transfer to the substrate to be printed was performed and an ink pattern was applied on the glass substrate to obtain a printed matter.

<Example 4>
A PEN film having a size of 100 mm × 100 mm and a thickness of 0.1 mm was used as a supporting substrate that is entirely composed of an inert layer. On one side of this PEN film, Cr was deposited by vapor deposition to obtain a 50 nm underlayer. Next, SiO ₂ used as an inert layer was deposited on the Cr film to a thickness of 30 nm by vapor deposition, and the SiO ₂ film was patterned by a photolithography method.

  Next, after immersing the base material obtained above for 10 minutes in a solution obtained by dissolving fluoroalkylsilane (manufactured by GE Toshiba Silicone Co., Ltd .: trade name TSL8233) in isopropyl alcohol as a silane coupling agent to 0.5 wt%, By drying at 120 ° C. for 10 minutes, an adsorption layer was formed on the surface of the underlayer to obtain a lithographic printing plate.

  A printed matter was obtained in the same manner as in Example 1 except that the lithographic printing plate obtained above was used.

<Example 5>
Example 4 except that a thioalkyl compound (Fluorous Technologies: 1H, 1H, 2H, 2H-perfluorooctane-1-thiol) was used as the material for the adsorption layer, gold was used as the underlayer, and SiO ₂ was used as the inert layer. A lithographic printing plate was produced in the same manner as above, and a printed material was obtained in the same manner as in Example 4 using this.

<Example 6>
A lithographic printing plate was produced in the same manner as in Example 4 except that the ink used for printing was the same as that used in Example 3, and this was used in the same manner as in Example 4. A printed material was obtained.

  Below, the comparative example of this invention is demonstrated.

<Comparative Example 1>
A printed matter was obtained in the same manner as in Example 1 except that a conventional wet lithographic plate was used.

  Table 2 shows the results of observing the conductive patterns of the printed materials obtained in Examples 1 to 6 and Comparative Example 1 with an optical microscope.

上記表２より、実施例１〜６に於ける平版印刷版のように非画線部に対応する撥インク部に吸着層が施されていることによる効果として、得られた導電性パターンは、パターン密部から疎部にかけて画像の形成は良好であった。これに対し比較例１に於ける従来の湿式平版では、特にパターン密部における画像の欠けや非画像部の汚れ、画線の不鮮明さが顕著に見られた。

From the above Table 2, the conductive pattern obtained as an effect by the adsorption layer being applied to the ink repellent part corresponding to the non-image part as in the lithographic printing plates in Examples 1 to 6, Image formation was good from the pattern dense part to the sparse part. On the other hand, in the conventional wet lithographic plate in Comparative Example 1, image chipping in the dense pattern portion, stains in the non-image portion, and unclear image lines were noticeable.

  Therefore, as an example of utilization of the lithographic printing plate according to the present invention, in an electronic component requiring a fine pattern such as a display device such as a circuit board, liquid crystal, organic EL, and electronic paper, a conductor, an insulator, a dielectric, a magnetic Body, semiconductor, resistor, luminescent material, resist, printing plate used when forming color filters by printing and its manufacturing method and circuit board manufactured by the printing plate, display of liquid crystal, organic EL, electronic paper, etc. It is used for electronic parts that require fine patterns such as devices.

It is explanatory drawing which represented one Embodiment of the lithographic printing plate of this invention by the side cross section. It is explanatory drawing which represented another embodiment of the lithographic printing plate of this invention in the side cross section. An example of a lithographic printing plate according to the present invention will be described, wherein (a) is a plan view thereof and (b) is a schematic cross-sectional view of the A-A ′ plane of (a). BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 illustrates an example of a process for producing a lithographic printing plate according to the present invention, in which (a) is a side sectional view of a process of forming an inactive layer on the entire surface of a base layer, and (b) is an inactive layer. Is a side sectional view of the step of patterning, (c) is a side sectional view of the step of forming the adsorption layer, FIG. 2 is a diagram illustrating another example of the process for producing a lithographic printing plate according to the present invention, wherein (a) is a side sectional view of a process of forming an inactive layer on the entire surface of the underlayer, and (b) It is a side sectional view of the step of patterning the active layer, (c) is a side sectional view of the step of forming the adsorption layer, The process of producing a printed matter using an example of the lithographic printing plate of the present invention will be described, wherein (a) is a side sectional view of the process of attaching ink to the lithographic printing plate from the inking mechanism, (b ) Is a side sectional view of a step of printing on a substrate to be printed. Explaining the process of producing a printed matter using another example of the lithographic printing plate of the present invention, (a) is a side sectional view of the process of attaching ink to the lithographic printing plate from the inking mechanism, (B) is a sectional side view of the process of printing on the substrate to be printed.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Base material 100 ... Lithographic printing plate 110 ... Adsorption layer 120 ... Inactive layer 160 ... Underlayer 211 ... Pattern dense part 270 ... Pattern sparse part 500 ... Printed matter 540 ... Inking mechanism 541 ... Ink 550 ... Printed substrate

Claims (9)

  A lithographic printing plate in which a plate pattern on a supporting substrate is composed of a parent ink portion corresponding to an image portion and an ink repellent portion corresponding to a non-image portion, and the surface of the supporting substrate is at least an underlayer The lithographic printing plate is characterized in that an inactive layer forming the parent ink portion and an adsorption layer forming the ink repellent portion are formed on the underlayer.   A lithographic printing plate in which a plate pattern on a supporting substrate is composed of a parent ink portion corresponding to an image portion and an ink repellent portion corresponding to a non-image portion, and the surface of the supporting substrate is at least the parent ink portion A lithographic printing plate comprising: an inactive layer comprising: an adsorbing layer comprising the ink-repellent portion formed on the inactive layer through an underlayer.   The lithographic printing plate according to claim 1 or 2, wherein the underlayer is made of a metal oxide, the inactive layer is made of metal or resin, and the adsorption layer is made of a silane coupling agent. The lithographic printing plate according to claim 3, wherein the silane coupling agent is one or more compounds selected from compounds represented by the following formulas (1), (2), and (3).

(In formula (1), R ¹ is independently an alkyl group, a cycloalkyl group, or a phenyl group, and the alkyl group, cycloalkyl group, or phenyl group may be fully fluorinated or partially fluorinated. In formula (1), X ¹ , X ² and X ³ are each independently a halogen such as chlorine, bromine or iodine or an alkoxy group.)

(In Formula (2), R ¹ and R ² are independently an alkyl group, a cycloalkyl group, and a phenyl group, and the alkyl group, cycloalkyl group, and phenyl group may be fully fluorinated or partially fluorinated. In formula (1), X ¹ and X ² are each independently a halogen or alkoxy group such as chlorine, bromine or iodine.)

(In the formula (3), R ¹ , R ² and R ³ are independently an alkyl group, a cycloalkyl group and a phenyl group, and the alkyl group, cycloalkyl group and phenyl group are fully fluorinated or partially fluorinated. In formula (1), X ¹ is independently a halogen such as chlorine, bromine or iodine or an alkoxy group.   3. The lithographic printing plate according to claim 1, wherein the underlayer is made of metal, the inactive layer is made of metal oxide or resin, and the adsorption layer is made of a thioalkyl compound. 6. The lithographic printing plate according to claim 5, wherein the thioalkyl compound is one or more compounds selected from compounds represented by the following formula (4).

(In the formula (4), R ¹ is an alkyl group independently, a cycloalkyl group, a phenyl group, an alkyl group, a cycloalkyl group, a phenyl group which may be perfluorinated or partially fluorinated .R ² Is independently hydrogen, an alkyl group, a cycloalkyl group, or a phenyl group, and the alkyl group, cycloalkyl group, or phenyl group may be fully fluorinated or partially fluorinated. An integer selected between 3 and 3.)   2. The method for producing a lithographic printing plate according to claim 1, wherein an inactive layer on the underlayer is formed by photolithography, and an adsorption layer on the underlayer on which the inactive layer is not formed is formed in a gas phase. Alternatively, a method for producing a lithographic printing plate, which is formed by a liquid phase method.   The method for producing a lithographic printing plate according to claim 2, wherein the underlayer on the inert layer is formed by a photolithography method, and the adsorption layer on the underlayer is formed by a gas phase or a liquid phase method. A process for producing a lithographic printing plate characterized by the above.   A printed matter using the planographic printing plate according to any one of claims 1 to 6.

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