JP2006267660A - Laminated sheet of positive photosensitive resin and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated sheet of a positive photosensitive resin suitable for use as an etching photoresist. <P>SOLUTION: The laminated sheet of a positive photosensitive resin has a cushion layer, a positive photosensitive resin layer and a cover film stacked in this order on a support film. A method for manufacturing the laminated sheet is also provided. The positive photosensitive resin layer contains a novolac type phenolic resin, an organic compound containing 1,2-naphthoquinonediazido and a thermoplastic resin required to thermally transfer the positive photosensitive resin layer to an adherend and to perform good image formation. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides a positive photoresist used on a substrate for forming a semiconductor circuit such as a TFT (thin film transistor) serving as a switching element for driving a pixel of a flat panel display such as an LCD (liquid crystal display) or a PDP (plasma display). The present invention relates to a positive-type photosensitive resin laminated sheet that is applied using a transfer method.

  The etching photoresist is a material necessary for forming semiconductor circuits such as IC and LSI, TFTs used for LCDs and PDPs, and electrode plates. The TFT array manufacturing process consists of a series of steps such as cleaning, film formation (sputtering, CVD), photolithography (resist coating, pre-baking, exposure, development, post-baking), etching, resist stripping, and ashing. .

The manufacturing process of the TFT array will be described in more detail based on the cross-sectional view of the amorphous silicon TFT shown in FIG. First, the substrate is cleaned for the purpose of 1) improving electrical conductivity, modifying the substrate surface such as improving the adhesion of the film, or removing particles such as foreign matter and dust from the substrate surface. For cleaning, brushes, ultrasonic waves, megasonics, pure water jets, and the like are used in combination depending on the application. After cleaning the glass substrate, a glass surface coat layer of SiO ₂ or Ta ₂ O ₅ is formed on the surface by sputtering or plasma CVD for the purpose of preventing Na contamination from the substrate. Subsequently, a metal material for the gate electrode is formed by a sputtering method, and patterned using photolithography to form an electrode. Next, 2) an anodic oxide film such as a silicon oxide film (SiOx) is formed as a first gate insulating film on the surface of the formed gate electrode. Thereafter, using a plasma CVD method, a silicon nitride film (SiNx) as a second gate insulating film, a hydrogenated amorphous silicon layer (a-Si: H) as a semiconductor active layer, and a SiNx 3 as a channel protective film are used. Form a layer. After forming the channel protective film, 3) an n ⁺ type amorphous silicon layer (a-Si) doped with P is formed, and the n ⁺ type and the underlying a-Si: H are etched simultaneously to form an island-like pattern Form. 4) A transparent electrode film (ITO) is formed by sputtering to form a pixel electrode pattern. 5) A metal film is formed by sputtering and patterned to provide a source electrode and a drain electrode. The n ⁺ a-Si in between is removed by etching. 6) Finally, SiNx is deposited as a protective film, and the peripheral electrode terminal portion is exposed to complete the TFT array. Wiring materials used for metal electrode films such as gate electrodes, source electrodes, drain electrodes, scanning lines, storage capacitor electrodes, signal lines, and pixel electrodes provided by sputtering are tantalum (Ta), molybdenum (Mo), Metals such as tungsten (W), titanium (Ti), chromium (Cr), and aluminum (Al), and alloys thereof such as molybdenum tantalum (MoTa) and molybdenum tungsten (MoW) are used.

  Next, an example of using an etching photoresist used for manufacturing a general TFT array will be described below. In the first step of photolithography, a metal film is formed in advance, a liquid photoresist is applied to a cleaned glass substrate, and prebaking is performed to form a photoresist film. Subsequently, an actinic ray such as ultraviolet light is applied to the photoresist film through a photomask to perform pattern exposure. After developing this with a developing solution to form a pattern, it is hardened by post-baking to improve the adhesion to the substrate. Then, using the formed photoresist pattern as a mask, the underlying metal film is removed by etching to form a metal film pattern. Finally, the photoresist film remaining on the metal film pattern is peeled and removed to obtain a pattern of only the metal film. There are two types of photoresist used: negative and positive. Rubber-type negative photoresists are known in the past, but since an organic solvent is required for the developer, a positive photoresist that can be developed with an alkaline solution is more widely used because it is easier to process the waste developer. It has been. Further, the positive photoresist is characterized in that the dimensional change of the pattern image due to swelling during development is extremely small and the resolution is high, and the acid resistance, etching resistance and heat resistance are excellent. For the application of the photoresist, a so-called spin coating method has been employed in which a liquid photoresist is dropped onto a substrate, and the substrate is rotated to shake off excess photoresist by centrifugal force.

  There are two methods of etching, wet etching and dry etching, which are properly used according to the purpose. In wet etching, an acid solution such as hydrochloric acid, nitric acid, phosphoric acid, or hydrofluoric acid is used as an etchant. On the other hand, dry etching uses fluorine radicals, chlorine radicals, or other active chemical species or ions generated by plasma decomposition of gases such as carbon tetrafluoride, sulfur hexafluoride, hydrogen chloride, boron trichloride in vacuum. It etches silicon-based thin films such as a-Si: H and SiNx and metal films.

  With the trend toward larger and higher definition flat panel displays in recent years, etching photoresists used in the manufacture of TFTs and electrode plates are required to have higher sensitivity, uniformity, and resist reduction. Adhesion and dry etching resistance (heat resistance) are required. In particular, resolution and film thickness uniformity are becoming increasingly demanding as glass substrates become larger.

  The spin coating method for applying a photoresist is a simple method, but there is a lot of excess liquid photoresist and the yield of the photoresist is poor, coating unevenness is likely to occur, and the uniformity of the dry resist film thickness at the central and peripheral portions of the substrate It is difficult to improve the resolution of the circuit by causing liquid accumulation in the uneven parts of the stacked circuit when the process is repeated, and liquid photoresist contains organic solvent, so the cost of maintaining a clean environment and drying equipment etc. There are problems such as high.

  As the size of glass substrates increases, these problems of the spin coating method become more serious issues, and improvement of the photoresist coating method is being studied. For example, slit coaters have been developed for the purpose of making the film thickness distribution of the conventional spin coating method uniform and improving the resist saving. Although there is a direction that is being put into practical use as a technology that can also handle a large substrate of 1870 mm × 2200 mm, the response to a large substrate is still not common. Also, with this technique, the difference in film thickness between the central part and the peripheral part is smaller than in the spin coating method, and the uniformity of the photoresist film thickness in the substrate is improved, but it is still formed in the TFT array manufacturing process. There is a problem that a liquid pool is generated in the uneven portion of the electrode of about 2 μm.

  On the other hand, a photoresist dry film in which a photoresist is uniformly applied in advance on a film is widely used in the field of printed wiring boards. This film has a structure in which a negative photoresist capable of alkali development is applied in a thickness of 10 to 80 μm on a plastic film having a thickness of 16 to 38 μm and protected by a plastic film having a thickness of 16 to 25 μm. When this film is used, since the photoresist film is thick, it is possible to embed the photoresist film evenly without entraining bubbles in the uneven part of the electrode of about 2 μm, and development using an alkaline solution is possible. However, in the field of printed wiring boards, the resolution is 30 to 300 μm, and it cannot be applied to the TFT array manufacturing field that requires a resolution of 2 to 10 μm.

  In addition, a film provided with a negative photoresist layer is adhered to a glass substrate by thermal lamination, and the negative photoresist layer is patterned on the substrate to color a color filter or overcoat layer for LCD or the like. A method for forming a colorless pattern is disclosed in Japanese Patent No. 2794242 (Patent Document 1), Japanese Patent No. 28773889 (Patent Document 2), Japanese Patent Laid-Open No. 10-97061 (Patent Document 3), Japanese Patent Laid-Open No. 10-206888. (Patent Document 4). These are structures in which a thermoplastic resin layer, an intermediate layer, and a negative photoresist layer are sequentially applied and dried on a support film in advance. When this method is used, a negative photoresist layer with a thickness of 1 to 5 μm can be transferred at a high speed onto a 2 μm thick glass substrate with irregularities, but the resolution is limited due to the negative type. was there.

  At present, most liquid positive photoresists used in the manufacture of TFT arrays are composed mainly of novolac-type phenolic resins and organic compounds containing 1,2-naphthoquinonediazide as photosensitive components. It is. When this composition is applied and dried on a support film, a positive type photoresist film can be formed on the film, but the film is fragile because it contains a novolac type phenol resin as a main component, and the sheet is wound up, When the film is deformed when it is handled, or when it is thermocompression bonded to the glass substrate in the process, there is a problem that the photoresist film is cracked and damaged. In addition, when a laminated sheet is slit to a specified product width, the positive photoresist layer at the end of the sheet touched by the slit blade is finely cracked and scattered as chips. For this reason, the chips are mixed into the sheet over the process of commercializing and using the laminated sheet, which causes a problem in manufacturing the TFT array. Further, since the photoresist film does not have flexibility or adhesiveness, the photoresist film cannot be attached to the substrate even if it is thermocompression bonded to the glass substrate.

  In order to solve these problems, Japanese Patent Application Laid-Open No. 2002-341525 (Patent Document 5) discloses a transfer material comprising a temporary support / thermoplastic resin layer / intermediate layer / photoresist layer / protective film. There has been proposed a method in which a positive photoresist layer is formed on a substrate by a transfer method by peeling between photoresist layers. In this method, an intermediate layer is required because the thermoplastic resin layer, the intermediate layer, and the photoresist layer are sequentially coated on the temporary support. When the intermediate layer is directly coated with a photoresist layer on the thermoplastic resin layer, the thermoplastic resin layer is easy to dissolve in the diluent contained in the photoresist layer paint, causing a troublesome mixture between the two. It is provided in order to prevent the separation between the two layers. Further, in this case, although depending on the material of the intermediate layer and the thermoplastic resin layer, a diluent such as an organic solvent contained in the composition to be the photoresist layer paint passes through the intermediate layer or the intermediate layer during drying. The thermoplastic resin layer is eroded and as a result, the flatness of the surface may be impaired, and it is difficult to obtain a uniform film thickness of the photoresist layer.

  Furthermore, when a general positive type liquid photoresist is applied on the thermoplastic resin layer to form a resist film, the novolac type phenolic resin, which is brittle in film quality, is the main component of the paint, so it remains at the time of coating film formation. There may be a problem that the film of the photoresist layer cracks over time due to stress or dimensional change after formation.

Japanese Patent No. 2794242 Japanese Patent No. 2873889 JP-A-10-97061 JP-A-10-206888 JP 2002-341525 A

  As a result of intensive studies to solve such problems, the present inventors have found that an organic compound containing a 1,2-naphthoquinonediazide sulfonic acid ester group, a novolac type phenol resin, and a thermoplastic resin having an alkali-soluble carboxyl group. The inventors have found that the above problems can be solved by devising a sheet in which a positive photosensitive resin layer having a composition containing a resin is laminated and a method for producing the positive photosensitive resin laminated sheet, and have completed the present invention.

That is, the present invention
(1) A laminate in which a cover film, at least one positive photosensitive resin layer, a cushion layer, and a support film are laminated in this order, and the cushion layer is made of a thermoplastic resin, and the positive photosensitive resin A positive photosensitive resin characterized in that the resin layer contains, as a photosensitive component, an organic compound having a 1,2-naphthoquinonediazide sulfonic acid ester group, a novolac-type phenol resin, and a thermoplastic resin having an alkali-soluble carboxyl group. Resin laminated sheet.
(2) The positive photosensitive resin layer is peelable between the cover film and the cushion layer, and the adhesive force between the positive photosensitive resin layer and the cover film is such that the positive photosensitive resin layer and the cushion are The positive-type photosensitive resin laminated sheet according to (1) above, which is lower than the adhesive strength of the layer.
(3) In the above (1) or (2), the photosensitive component contained in the positive photosensitive resin layer is an organic compound containing two or more 1,2-naphthoquinonediazide sulfonic acid ester groups Positive photosensitive resin laminate sheet.
(4) The positive photosensitive resin layer is 5-30 parts by weight of an organic compound containing 1,2-naphthoquinonediazide sulfonic acid ester group, 40-70 parts by weight of a novolac phenolic resin, and 5-40 parts by weight of alkali. The positive photosensitive resin laminated sheet according to any one of (1) to (3) above, which contains a thermoplastic resin having a soluble carboxyl group, and the thickness of the positive photosensitive resin layer is 0.5 to 3 μm.
(5) The positive photosensitive resin laminated sheet according to (1) to (4) above, wherein the novolac type phenolic resin contained in the positive photosensitive resin layer has a weight average molecular weight in the range of 2000 to 20000.
(6) The thermoplastic resin having an alkali-soluble carboxyl group contained in the positive photosensitive resin layer has a weight average molecular weight of 1000 to 30000, a softening temperature of 80 ° C. or less, and an acid value of 30 to 300 mg. The positive-type photosensitive resin laminated sheet according to any one of (1) to (5) above, which is -KOH / g.
(7) The positive type of (1) to (6) above, wherein the thermoplastic resin constituting the cushion layer has a softening temperature of 30 to 90 ° C., and the cushion layer has a thickness of 5 to 40 μm. Photosensitive resin laminated sheet.
(8) Positive photosensitivity comprising an organic compound containing a 1,2-naphthoquinonediazide sulfonic acid ester group as a photosensitive component on one side of the cover film, a novolak type phenol resin, and a thermoplastic resin having an alkali-soluble carboxyl group. Film (A) coated and dried with resin layer, film (B) coated with cushion layer made of thermoplastic resin on one side of support film, positive photosensitive resin layer surface of film (A) and film (B) ) The method for producing a positive-type photosensitive resin laminated sheet according to any one of (1) to (7), wherein the cushion layer surface is bonded.
(9) The cover film is peeled off from the positive photosensitive resin layer from the positive photosensitive resin laminated sheet of (1) to (7), and the surface of the positive photosensitive resin layer is the surface of the glass substrate. After the film is attached while being heated and pressurized, the support film is peeled and removed between the cushion layer and the positive photosensitive resin layer, and only the positive photosensitive resin layer is transferred to the glass substrate. A circuit pattern is formed on the glass substrate by performing photolithography (pre-baking, pattern exposure with actinic light, development with alkaline aqueous solution, post-baking) and etching (wet etching with acid solution or dry etching with plasma gas) on the conductive resin layer. Is formed, and the positive photosensitive resin pattern remaining on the substrate is removed by a stripping solution.

  According to the present invention, it is possible to form a positive photosensitive resin layer that is a thin film and has a uniform film thickness on a glass substrate.

  FIG. 1 shows an aspect of the configuration of the positive photosensitive resin laminate sheet of the present invention, and each layer shown in FIG. 1 will be described below.

  The positive photosensitive resin laminate sheet of the present invention is a laminate in which a cushion layer, a positive photosensitive resin layer, and a cover film are laminated in this order on a support film. The positive photosensitive resin layer and the cushion layer on the support film are separately applied and dried, and then heated and pressurized so as to oppose the cushion layer and the positive photosensitive resin layer, and then heat laminated. It is characterized by sticking together and manufacturing.

  In the present invention, it is not necessary to provide a layer such as an intermediate layer between the cushion layer and the positive photosensitive resin layer. When a cushion layer / positive photosensitive resin layer is provided on a support by a coating method, an intermediate layer is required to facilitate peeling of the cushion layer and the positive photosensitive resin layer. On the other hand, since the organic solvent in the positive photosensitive resin coating attacks the cushion layer and the intermediate layer, it is difficult to obtain a uniform positive photosensitive resin layer. On the other hand, in the present invention, the cushion layer is formed on the support film and the positive photosensitive resin layer is separately formed on the cover film, and then bonded together to support film / cushion layer / positive photosensitive resin. Since the layer / cover film structure is used, the surface of the cushion layer is not dissolved by the solvent and the flatness is not impaired, and a positive photosensitive resin layer having a uniform film thickness and high patterning accuracy can be obtained.

  When the positive photosensitive resin layer is applied directly on the cushion, the cushion layer is easily dissolved in a diluent such as an organic solvent contained in the positive photosensitive resin layer paint. It is provided in order to prevent a troublesome mixture from occurring and the separation between the two layers becoming impossible. In this case, although depending on the material of the intermediate layer and the cushion layer, a diluent such as an organic solvent contained in the composition that becomes the positive photosensitive resin layer paint passes through the intermediate layer or the intermediate layer during drying. In some cases, the cushion layer is eroded, and as a result, the flatness of the surface is impaired, and it is difficult to obtain the film thickness uniformity of the positive photosensitive resin layer.

  The method of using the positive photosensitive resin laminate sheet of the present invention is as follows. First, the cover film is peeled off and removed from the positive photosensitive resin layer, and the surface of the positive photosensitive resin layer is placed on the surface of the glass substrate with a thermal laminator. Then, the support film is peeled and removed between the cushion layer and the positive photosensitive resin layer. After that, the positive photosensitive resin layer transferred to the glass substrate is subjected to photolithography (pre-baking, pattern exposure with actinic rays, development with alkaline aqueous solution, post-baking) and etching (wet etching with acid solution or dry etching with plasma gas) ) To form a circuit pattern on the glass substrate. Finally, the positive photosensitive resin pattern remaining on the substrate is removed with a stripping solution.

  As the cover film 1, a conventionally known plastic film can be used. Examples thereof include polyethylene terephthalate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, and cellulose triacetate. In particular, a polyethylene terephthalate (PET) film having high mechanical strength and excellent thermal stability, or a polypropylene film (OPP film) inexpensive and excellent in releasability is preferable. Although the thickness of a cover film does not have a restriction | limiting in particular, 25-75 micrometers thickness is preferable. This is because the product form of the positive photosensitive resin laminated sheet, that is, when it is finished into a roll product, the rigidity of the laminated sheet becomes high when the cover film is a film with a thickness exceeding 75 μm, In the slitting operation, the cover film is lifted so that air enters between the cover film and the positive photosensitive resin layer, or the product weight per unit length is heavy, making it difficult to manufacture a long wound product. This is because adverse effects such as an increase in cost are expected. On the other hand, when a film thinner than 25 μm is used, there is an adverse effect that the film is deformed by heat when the positive photosensitive resin layer is applied and dried or heat laminated.

  In order to further stabilize the peelability between the base material of the cover film and the positive photosensitive resin layer, it is preferable to provide a release layer. Examples of the resin used for the release layer include a urethane resin, a melamine resin, a silicon resin, or a copolymer or mixture thereof. The coating thickness of the release layer is not particularly limited, but a coating thickness of 0.5 to 2.0 μm is preferable.

  When using a substrate having peelability such as a polypropylene film (OPP film), it is not necessary to provide a release layer. You may use the plastic film in which peelability was previously provided with mold release agents, such as a silicon system, a modified silicon system, and a fluorine system.

  The positive photosensitive resin layer 2 is a coating film composed of an organic compound containing a 1,2-naphthoquinonediazide sulfonic acid ester group as a photosensitive component, a novolac phenolic resin, and an alkali-soluble thermoplastic resin. .

  A composition of an organic compound containing 1,2-naphthoquinonediazide and a novolac type phenol resin has been well known as a photodegradable alkali-soluble positive photosensitive material. The 1,2-naphthoquinone diazide before being exposed to actinic rays such as ultraviolet rays is not dissolved in an alkaline solution, and when a certain amount of 1,2-naphthoquinone diazide is added to a novolac type phenol resin, The dried membrane does not dissolve in the alkaline solution. Thus, 1,2-naphthoquinonediazide has a function of suppressing the alkali solubility of the novolak type phenol resin. On the other hand, when 1,2-naphthoquinone diazide is exposed to actinic rays such as ultraviolet rays, naphthoquinone diazide undergoes photolysis and transfer reaction to produce a ketene compound. When this ketene comes into contact with water, indene carboxylic acid is produced, so that it becomes soluble in an alkaline solution. In the case of a dry film in which an organic compound containing 1,2-naphthoquinonediazide is blended with a novolak-type phenol resin, the solubility of the novolac-type phenolic resin in the alkali solution is higher than that of a single substance due to the photolysis of the aforementioned 1,2-naphthoquinonediazide. And the dissolution is promoted.

  Therefore, 1,2-naphthoquinone diazide has both extreme functions of novolak-type phenolic resin, ie, an alkaline dissolution inhibiting effect (before exposure to actinic rays such as ultraviolet rays) and an alkali dissolution promoting effect (after exposure to actinic rays such as ultraviolet rays). Therefore, it is excellent as a positive photosensitive material. Further, it exhibits high resolving power by development with an alkaline solution after exposure, and is used for the production of semiconductors such as IC and LSI, and circuit substrates such as LCDs. In addition, novolak type phenolic resin has high heat resistance due to the structure having many aromatic rings against plasma dry etching, and naphthoquinone diazide type photosensitizer and novolac type phenolic resin as resist materials that can withstand the heating process. A large number of positive photoresists containing bismuth have been developed and put to practical use, and have achieved great results.

  The organic compound containing 1,2-naphthoquinonediazide that can be used in the positive photosensitive resin layer of the present invention includes a polyhydric phenol compound having a hydroxyl group, 1,2-naphthoquinonediazidesulfonic acid, or a halide thereof. It has a general structure obtained by the esterification reaction. For example, as the polyhydric phenol compound, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2 ′ , 3,4,4′-pentahydroxybenzophenone, 2,3,3 ′, 4,4′-pentahydroxybenzophenone and other benzophenones, gallic acid alkyl esters, bis (2-hydroxy-2-methylphenyl) methane Bis (2,6-dimethyl-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (2,4-dihydroxyphenyl) methane, 2,2-bis (2,4- Dihydroxyphenyl) propane, bis (2,4-dimethyl-3-hydroxyphenyl) methane, (4- Bis ((poly) hydroxyphenyl) such as (roxyphenyl) (2,3,4-hydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2- (2,3,4-hydroxy40droxyphenyl) propane Examples include alkanes, polyhydroxytriphenylalkanes, polyhydroxybenzopyrans, polyhydroxyindanes, polyhydroxycoumarones, polyhydroxyphthalides, polyhydroxycoumarins, polynuclear phenols and the like.

  Examples of 1,2-naphthoquinone diazide sulfonic acid or halide include 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-naphthoquinone diazide-5-sulfonic acid, and 1,2-naphthoquinone diazide-6. -Sulphonic acid and the like, and 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-6-sulfonyl chloride, and the like.

  In the present invention, an organic compound having two or more 1,2-naphthoquinonediazide sulfonic acid ester groups in the molecule is suitable for achieving good developability, sensitivity and resolution. In use, the compound is not limited to a compound having a single type of structure, and a compound having a plurality of structures may be used as a mixture. The organic compound containing 1,2-naphthoquinonediazide is not particularly limited, but 2,3,4-trihydroxybenzophenone or 2,3,4,4′-tetrahydroxybenzophenone and 1,2-naphthoquinone- (2) -diazide-4-sulfonic acid, 1,2-naphthoquinone- (2) -diazide-5-sulfonic acid or 1,2-naphthoquinone- (2) -diazido-6-sulfonic acid esterified product, etc. Particularly preferred.

  The novolak type phenol resin that can be used in the positive photosensitive resin layer of the present invention is obtained by reacting phenols with aldehydes or ketones in the presence of an acid and a base and condensing them. Examples of phenols used in this case include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, propylphenol, o-butylphenol, m -Butylphenol, p-butylphenol, octylphenol, nonylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3, 5-xylenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 3, 4,5-trimethylphenol, p-phenylphenol, halogenated phenol, hydroquinone, catechol , Resorcinol, pyrogallol, alpha-naphthol, such as β- naphthol or bisphenol A and the like. These phenols can be used alone or in combination of two or more.

  Examples of aldehydes and ketones include alkylaldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, propyl aldehyde, butyraldehyde, isobutyraldehyde, isovaleraldehyde, hexyl aldehyde and octyl aldehyde, and acrolein and crotonaldehyde. Hydroxybenzaldehydes such as saturated alkyl aldehydes, salicylaldehyde, parahydroxybenzaldehyde, benzaldehyde, 2-fluorobenzaldehyde, 3-fluorobenzaldehyde, 4-fluorobenzaldehyde, 2,4-difluorobenzaldehyde, 2,6-difluorobenzaldehyde, 3, Aromatic aldehydes such as 4-difluorobenzaldehyde and phthalaldehyde, Affectation - le, dialdehydes such as glutaraldehyde, acetone, and the like ketones such as methyl ethyl ketone. These aldehydes and ketones can be used alone or in admixture of two or more.

The novolak type phenol resin used in the present invention preferably has a weight average molecular weight in the range of 1000 to 40,000. When the molecular weight is less than the lower limit, the heat resistance is inferior, and when the molecular weight exceeds the upper limit, the effect of improving the sensitivity and heat resistance as a photoresist may be reduced. In the present invention, a novolac type phenol resin having a weight average molecular weight in the range of 2000 to 20000 is particularly preferred. Courtroom Next, the positive photosensitive resin layer of the present invention must be properly adhered to the cover film and the cushion layer at the time of manufacture, and must be firmly adhered to the substrate as the adherend at the time of use. It must exhibit the property that the part exposed to light is dissolved in an alkaline solution. Furthermore, an alkali-soluble thermoplastic resin having a carboxyl group is added to the positive photosensitive resin layer for the purpose of imparting flexibility and flexibility.

  Examples of the thermoplastic resin having an alkali-soluble carboxyl group include acrylic acid ester, methacrylic acid ester, acrylic acid amide, methacrylic acid amide, methacrylic acid acrylamide, N-substituted acrylamide, N-substituted methacrylamide, and acrylonitrile. It is a resin obtained by polymerizing an acrylic monomer alone, or by copolymerizing two or more kinds or other monomers. Copolymers include ethylene and acrylate copolymers, styrene and (meth) acrylate copolymers, vinyltoluene and (meth) acrylate copolymers, poly (meth) acrylate esters, and ( Examples include (meth) acrylic acid ester copolymers such as (meth) butyl acrylate and vinyl acetate, copolymers of (meth) acrylic acid and ethylenically unsaturated group-containing monomers, and saponified products thereof.

  The alkali-soluble thermoplastic resin suitable for the present invention is a resin having a carboxyl group as described above, having a weight average molecular weight in the range of 1000 to 50000, a softening point of 80 ° C. or less, and an acid value. It is preferable that it is 30-300 mg-KOH / g. When these conditions are not met, the softness and flexibility of the positive photosensitive resin layer, and further the adhesion is not sufficient, and cracking of the positive photosensitive resin layer is suppressed, It becomes difficult to obtain a strong adhesive force to the adherend. Depending on the molecular weight, if the acid value is lower than the lower limit, the solubility in the alkali solution is impaired and development residues are likely to occur. Conversely, if the acid value exceeds the upper limit, the alkali solubility is too strong. Good patterning becomes difficult. Particularly preferred alkali-soluble thermoplastic resins have a weight average molecular weight of 1,000 to 30,000.

  Further, the composition of the positive photosensitive resin layer of the present invention is obtained by using an organic compound containing 1,2-naphthoquinonediazide in order to obtain characteristics such as good developability, resolution, heat resistance, and a high residual film ratio in the unexposed area. The amount is preferably 5 to 30 parts by weight, 40 to 70 parts by weight of the novolac type phenol resin, and 5 to 40 parts by weight of the alkali-soluble thermoplastic resin. The thickness of the positive photosensitive resin layer is suitably 0.5 to 3 μm in order to obtain good characteristics. As a method for forming the positive photosensitive resin layer, a normal coating method using a blade coater, an air knife coater, a roll coater, a curtain coater, a slot die coater, a bar coater, a rod blade coater, a gravure coater, or the like may be used. The coating film can be dried by a method of drying and solidifying with hot air or infrared rays.

  The cushion layer is disclosed in JP 2001-43796 A, JP 2003-346648 A, JP 2003-346649 A, JP 2004-82658 A, JP 2004-86089 A, JP 2004-87416 A. When transferring onto a pattern formed on an adherend in the method of using a transfer material as disclosed in Japanese Patent Laid-Open No. 2004-87417, a photosensitive resin layer or a photosensitive inorganic layer is surely placed between the patterns. It is necessary to embed and transfer to. Since the electrode pattern formed on the glass substrate is usually 1 to 2 μm thick, it is necessary to cushion the positive photosensitive resin layer properly between the patterns or between the uneven parts of the pattern, depending on the material properties. The layer thickness should be at least about 2 to 4 times the electrode pattern thickness. If the thickness of the cushion layer is thinner than this, it becomes difficult to transfer the pattern reliably between the patterns or to the uneven portions of the pattern without gaps, and the bottom of the pattern, that is, the side of the electrode pattern rising from the adherend surface and the adherend surface is difficult. Air retention (tenting) occurs between them, which tends to cause transfer failure. Therefore, the thickness of the cushion layer is preferably 2 to 100 μm, and particularly preferably 5 to 40 μm. If the thickness of the cushion layer exceeds 100 μm, it depends on the thermal conductivity of the resin used, but the heat conduction speed from the heat roll decreases during the transfer operation, so the cushion layer cannot be sufficiently softened and the pre-formed electrode pattern It becomes difficult to transfer so as to embed a new positive photosensitive resin layer in the space or in the uneven portion of the pattern.

  Therefore, the function of the cushion layer has a function of assisting the transfer of the positive photosensitive resin layer to the adherend. In the case of transfer to a surface having relatively high flatness such as a plate glass, if the cushion layer has a certain degree of thermal softening and elasticity, it can be stably transferred to the glass surface. However, if the positive photosensitive resin layer is transferred onto the adherend provided with the already formed pattern, it becomes difficult to embed a new positive photosensitive resin layer evenly between the already provided patterns or between the uneven portions. . Therefore, it is more preferable to use a resin having high deformability and elasticity for the cushion layer. For the cushion layer, a thermoplastic resin that deforms with good response when externally heated and stress is applied and maintains a certain degree of hardness when there is no external heating or stress is suitable for the cushion layer.

  Preferable materials for the cushion layer include, for example, acrylate copolymer, saponified ethylene and acrylate copolymer, saponified styrene and acrylate copolymer, ethylene vinyl acetate copolymer, ethylene ethyl Examples include acrylate copolymers, styrene and isoprene, butadiene copolymers, polyester resins, and thermoplastic resins such as polyolefin resins. These resins can be used alone, mixed in an appropriate formulation, or laminated in an appropriate combination. If necessary, a plasticizer may be added. These thermoplastic resins are more preferable when the dried coating film has resistance to an organic solvent.

  The thermoplastic resin used for the cushion layer is measured using a thermomechanical analyzer (TMA) similar to the method for measuring the softening temperature of resin defined in JIS K 7196, and the softening temperature at that time is 30. It is preferable that it is -90 degreeC.

  Moreover, it is possible to internally add a wax-like releasable component into the cushion layer. Depending on the type of resin used for the cushion layer, the release of the positive photosensitive resin layer is stabilized by the internal addition of a release component, and the effect of making the transfer of the phosphor layer to the adherend easier is demonstrated. it can. Furthermore, various additions such as a coupling agent, a dehydrating agent, a leveling agent, an antifoaming agent or an antifoaming agent, a surfactant, a coloring dye, a coloring pigment, an ultraviolet absorber, and a water resistance agent are added to the cushion layer as necessary. An agent may be blended.

  As a method for forming the cushion layer, a blade coater, an air knife coater, a roll coater, a curtain coater, a slot die coater, a bar coater, a rod blade coater, a gravure coater, etc., or a heat-melted resin is used. An extrusion method, an inflation method, an extrusion laminating method, or the like, which is extruded from a mold die, can be used. When the coating method is used, a method of drying and solidifying the coating film with hot air or infrared rays is used.

4 is a support film. As the support film, a conventionally known plastic film similar to that shown in the description of the cover film can be used. The thickness of the support film is not particularly limited, but 25 to 150 μm is appropriate. If the thickness is less than 25 μm, workability deteriorates, and curling occurs remarkably when the antistatic layer and the cushion layer are applied, which is not preferable. When the thickness exceeds 150 μm, not only is it difficult to produce a roll-shaped product, but also the positive photosensitive resin laminate sheet and the adherend are heated and pressure-bonded by a hot roll in the attaching operation to the adherend. Since the heat conduction speed to the mold type photosensitive resin layer decreases, good adhesiveness can be obtained unless measures such as increasing the heat roll temperature, lowering the transfer speed, or sufficiently heating the adherend are obtained. It becomes impossible. Since this is not preferable from the viewpoint of workability and economy, the thickness of the support is preferably as thin as possible. Particularly preferably, a thickness of 40 to 75 μm is suitable as the support film.
Note that an antistatic layer 5 may be provided to prevent dust from being mixed due to peeling charging. The surface resistance value of the plastic film is preferably 10 ⁶ to 10 ⁹ Ω / □ by the measurement method specified in JIS K 6911. For this reason, it is preferable to use an antistatic film or a film provided with the antistatic layer 5 in advance. Furthermore, in order to improve the adhesiveness with the cushion layer, a plastic film in which adhesiveness is previously provided on the opposite surface to which the antistatic layer is provided may be used.

  In the configuration of the positive-type photosensitive resin laminated sheet shown in FIG. 1, the peelability between the layers is a very important factor in transferring the positive-type photosensitive resin layer to the adherend. That is, the two positive photosensitive resin layers and the adherend are preferably firmly bonded, and it is required that the positive photosensitive resin layer cannot be easily peeled off from the adherend.

  Further, it is preferable that the positive photosensitive resin layer 2 is easily peeled off from the cushion layer 3, and the peeling force should be made as light as possible in order to facilitate the adhesion of the positive photosensitive resin layer to the adherend. However, on the other hand, when the peeling force between the positive photosensitive resin layer 2 and the cushion layer 3 is too light, the positive photosensitive resin can be simply bent or curved when handling the positive photosensitive resin laminated sheet. When the layer 2 is peeled off or the cover film 1 is peeled off, the positive photosensitive resin layer 2 is transferred onto the cover film. Therefore, a peeling force greater than a certain value is required between the positive photosensitive resin layer 2 and the cushion layer 3. The preferable peeling force is in the range of 5 to 40 g / 50 mm width.

  Regarding the peeling force between the cover film 1 and / or the release layer provided on the cover film 1 and the positive photosensitive resin layer 2, the cover film can be easily used when the positive photosensitive resin laminated sheet is used. It is required that 1 can be peeled off. When the peeling force is too large, the cover film 1 cannot be peeled off and the positive photosensitive resin laminated sheet itself cannot be used. In the configuration of FIG. 1, when only the peeling force protrudes and is large, there is a problem that the positive photosensitive resin layer 2 is transferred onto the cover film as described above. On the other hand, if the peeling force is too light, the cover sheet is easily bent by bending or bending the laminated sheet slightly, so that air enters between the cover film and the positive photosensitive resin layer. This event causes intrusion of dust, dust, etc. into the sheet, which becomes a factor that hinders the transferability of the laminated sheet. Accordingly, a certain range of peeling force is required between the cover film 1 and / or the release layer provided on the cover film 1 and the positive photosensitive resin layer 2. The preferable peeling force is in the range of 1 to 10 g / 50 mm width.

  It is necessary that the peeling force between the cushion layer 3 and the support 4 does not peel when using the positive photosensitive resin laminated sheet. When peeling between the two, the cushion layer 3 is transferred to the adherend so as to cover the positive photosensitive resin layer 2, so that the positive photosensitive resin layer cannot be developed during patterning. This is because of concern.

  As described above, it is preferable to rank the peel strength between the layers. That is, (small) 1-2 peel force <2-3 peel force <3-4 peel force <2-adherend peel force (large).

  However, when the cushion layer 3 and the positive photosensitive resin layer 2 are applied in this order on the support 4, the peeling force between 2-3 cannot be controlled. This is because the diluent contained in the coating material of the positive photosensitive resin layer 2 dissolves or invades the surface of the cushion layer 3, so that the positive photosensitive resin layer is not peeled off from the cushion layer 3 or is difficult to peel off. Furthermore, even if it can be peeled off, the surface of the cushion layer is affected by the diluent and sufficient flatness cannot be obtained, so that it becomes difficult to obtain a positive photosensitive resin layer having a uniform film thickness.

  Therefore, a sheet FIG. 2- (a) in which the positive photosensitive resin layer 2 is applied and dried on the cover film 1 and a sheet FIG. 2- (b) in which the cushion layer 3 is applied and dried on the support 4 are separately provided. It is easier than the coating method to control the peeling force between 2-3 by heating, pressurizing and heat laminating and pasting so that the cushion layer and the positive photosensitive resin layer face each other. .

  That is, after overlapping the sheet shown in FIG. 2- (a) and the sheet shown in FIG. 2- (b) so that the coated surfaces face each other, between two rolls including at least one heatable roll. The positive photosensitive resin sheet is bonded by passing through the both sheets and pressing the nip between the rolls. Since the positive photosensitive resin layer and the cushion layer are softened by heating, the positive photosensitive resin layer adheres to the cushion layer and is integrated as a positive photosensitive resin sheet when pressure bonded. The adhesive force of the sheet | seat of FIG. 2- (a) and FIG. 2- (b) can be adjusted with the lamination conditions (heating temperature, the bonding speed, the bonding pressure) when bonding both.

  Under temperature conditions that apply excessive heat more than necessary at the time of bonding, wrinkles occur on the positive-type photosensitive resin sheet bonded due to heat shrinkage of the cushion layer as well as heat shrinkage of the cover film and support. Or because the positive photosensitive resin layer and the cushion layer are firmly bonded to each other, the positive photosensitive resin layer cannot be peeled off from the cushion layer. Furthermore, when pressure is applied under a temperature condition higher than the melting temperature of the resin used for the cushion layer, the resin of the cushion layer protrudes from the cover film and the support and adheres to the roll used for bonding. In some cases, the positive photosensitive resin sheet may be caught in a roll. Conversely, if the heating temperature is so low that it does not reach the required temperature, the cushioning layer becomes insufficiently softened in the positive photosensitive resin layer, so that the positive photosensitive resin layer and the cushion layer are not bonded, Even if it can be bonded, the adhesive force between the positive photosensitive resin layer and the cushion layer becomes insufficient, and when the cover film is peeled off, the positive photosensitive resin layer remains on the cover film side as it is. It becomes easy.

The range of the bonding speed is 0.5 to 30 m / min, and the pressing condition is preferably 0.1 to 2.0 MPa as the actual pressure. When the pressure condition is less than 0.1 MPa, the positive pressure-sensitive photosensitive resin layer and the cushion layer are weak in thermocompression bonding force, so that it is not possible to realize a bonding property sufficient to bond the two layers. Although the upper limit pressure is not particularly recognized as the pressurizing condition, it is possible to pressurize as long as the adhesive force between the positive photosensitive resin layer and the cushion layer is not impaired. The heating conditions are preferably 60 to 200 ° C., considering the cushioning layer material, the bonding speed, and the practical range of the bonding pressure. The adhesive force between the positive photosensitive resin layer and the cushion layer can be adjusted within the range of the aforementioned lamination conditions (heating temperature, bonding speed, bonding pressure), the heating temperature is high, and the bonding speed is high. However, it increases as the bonding pressure increases.
[Action]
The manufacturing method of the positive photosensitive resin sheet which this invention provides is characterized by manufacturing by bonding a positive photosensitive resin layer and a cushion layer on heating and pressurizing conditions. When a positive photosensitive resin layer is applied on an adherend using a positive photosensitive resin sheet produced by this method, the peelability of the cover film, transferability to the adherend, patterning accuracy, etching It has been confirmed that it exhibits good performance as a positive resist material such as characteristics.

  Further, if the production method of the present invention is used, since the positive photosensitive resin layer is applied on the cover film, there is no adverse effect caused by the diluent when applied on the cushion layer, so that the film thickness is flatter. It is possible to form a positive photosensitive resin layer with good uniformity.

  Hereinafter, the features of the present invention will be described in more detail using examples, but the present invention is not limited to the examples shown here. A film having the structure shown in FIG. 1 was produced as follows.

[Example 1]
(1) A 50 μm-thick polypropylene film (OPP film) was used as the cover film. After coating the positive photosensitive resin layer forming photosensitive solution 1 having the following composition on this OPP film using a Mayer bar, drying is performed at 100 ° C. for 2 minutes in a hot air circulating dryer. A positive photosensitive resin layer having a thickness of 1.5 μm was formed.
<Positive photosensitive resin layer forming photosensitive solution 1>
・ Photosensitive organic compound 20 parts by weight (2,3,4,4′-tetrakis {1,2-naphthoquinone- (2) -diazido-5-sulfonyl} benzophenone)
・ Novolak type phenol resin (weight average molecular weight: 13000) 64 parts by weight ・ Acrylic resin 16 parts by weight (manufactured by Toagosei Co., Ltd .: Alfon UC-3000, weight average molecular weight: 10000, softening temperature: 36 ° C., acid value: 74 mg- KOH / g)
・ 0.3 parts by weight of leveling agent (Dainippon Ink & Chemicals, Inc .: MegaFac R08-MH)
The liquid concentration was adjusted to 10% by weight with a diluent (methyl ethyl ketone / cyclohexanone = 70/30 weight ratio).

(2) A 75 μm-thick polyethylene terephthalate (PET) film (with an antistatic layer on the back surface: surface resistance of 10 ⁸ Ω / □) was used as a support, and a 20 μm-thick low-density polyethylene resin was extruded into this by laminating. This was applied to form a cushion layer.

(3) Sheet lamination After the sheets obtained in (1) and (2) were stacked so that the positive photosensitive resin layer surface of (1) and the cushion layer surface of (2) face each other, they were nipped with a laminator. . Both films were bonded and integrated in a heated and pressurized state to obtain a positive photosensitive resin laminated sheet. The pasting conditions are shown below.
Bonding temperature: 100 ° C., bonding pressure: 0.3 MPa, bonding speed: 2 m / min

[Example 2]
(1) A positive photosensitive resin layer having a thickness of 1.5 μm was formed in the same manner as in Example 1 except that the photosensitive solution 2 having the following composition was used.
<Positive photosensitive resin layer forming photosensitive solution 2>
・ Photosensitive organic compound 23 parts by weight
2,3,4,4′-tetrakis {1,2-naphthoquinone- (2) -diazide-5-sulfonyl} benzophenone / novolak type phenol resin (weight average molecular weight: 8800) 61 parts by weight / acrylic resin 16 parts by weight (Toagosei Co., Ltd .: Alfon UC-3000, weight average molecular weight: 10000, softening temperature: 36 ° C., acid value: 74 mg-KOH / g)
・ 0.3 parts by weight of leveling agent (Dainippon Ink Chemical Co., Ltd .: MegaFac R08-MH)
The liquid concentration was adjusted to 10% by weight with a diluent (methyl ethyl ketone / cyclohexanone = 70/30 weight ratio).

(2) A cushion layer having a thickness of 20 μm was formed in the same manner as in Example 1 except that an ethylene-vinyl acetate copolymer containing 14% by weight of vinyl acetate was used.

(3) Sheet bonding The sheets obtained in (1) and (2) were bonded in the same manner as in Example 1 to obtain a positive-type photosensitive resin laminated sheet.

[Example 3]
(1) Using a photosensitive solution 3 having the following composition, a 1.5 μm thick positive photosensitive resin layer was formed on a 25 μm thick PET film previously treated with modified silicon in the same manner as in Example 1.
<Positive photosensitive resin layer forming photosensitive solution 3>
・ Photosensitive organic compound 25 parts by weight (2,3,4-tris {1,2-naphthoquinone- (2) -diazido-5-sulfonyl} benzophenone)
-Novolak type phenol resin (weight average molecular weight: 11000) 53 parts by weight-Acrylic resin 22 parts by weight (manufactured by Toagosei Co., Ltd .: Alfon UC-3000, weight average molecular weight: 10000, softening temperature: 36 ° C, acid value: 74 mg- KOH / g)
・ 0.3 parts by weight of leveling agent (Dainippon Ink & Chemicals, Inc .: MegaFac R08-MH)
The liquid concentration was adjusted to 10% by weight with a diluent (methyl ethyl ketone / cyclohexane = 70/30 weight ratio).

(2) On a 75 μm-thick PET film (with an antistatic layer on the back surface: surface resistance value 10 ⁸ Ω / □), a cushion layer forming resin solution 1 having the following composition was applied using a Mayer bar: Thereafter, drying was performed at 140 ° C. for 2 minutes in a hot air circulation dryer to form a cushion layer having a thickness of 18 μm.
<Cushion layer forming resin liquid 1>
・ Polyolefin resin 70 parts by weight (Sumitomo Seika Co., Ltd .: Xyxen L)
・ Polyolefin resin 30 parts by weight (Sumitomo Seika Co., Ltd .: Xyxen N)
The liquid concentration was adjusted to 20% by weight with a diluent (water).

(3) Sheet bonding The sheets obtained in (1) and (2) were bonded in the same manner as in Example 1 to obtain a positive-type photosensitive resin laminated sheet.

[Example 4]
A positive photosensitive resin laminated sheet was obtained in the same manner as in Example 3 except that the positive photosensitive resin layer forming photosensitive solution 4 having the following composition was used.
<Positive photosensitive resin layer forming photosensitive solution 4>
・ Photosensitive organic compound 28 parts by weight (2,3,4-tris {1,2-naphthoquinone- (2) -diazido-5-sulfonyl} benzophenone)
・ Novolak type phenolic resin (weight average molecular weight: 4300) 51 parts by weight • Acrylic resin 21 parts by weight (manufactured by Toagosei Co., Ltd .: Alfon UC-3000, weight average molecular weight: 10000, softening temperature: 36 ° C., acid value: 74 mg- KOH / g)
・ 0.3 parts by weight of leveling agent (Dainippon Ink & Chemicals, Inc .: MegaFac R08-MH)
The liquid concentration was adjusted to 10% by weight with a diluent (methyl ethyl ketone / cyclohexanone = 70/30 weight ratio).

[Example 5]
A positive photosensitive resin laminated sheet was obtained in the same manner as in Example 3 except that the positive photosensitive resin layer forming photosensitive solution 5 having the following composition was used and the thickness of the cushion layer was 10 μm.
<Positive type photosensitive resin layer forming photosensitive solution 5>
・ Photosensitive organic compound 28 parts by weight (2,3,4-tris {1,2-naphthoquinone- (2) -diazido-5-sulfonyl} benzophenone)
・ Novolak type phenol resin (weight average molecular weight: 5800) 58 parts by weight ・ Acrylic resin 14 parts by weight (manufactured by Toagosei Co., Ltd .: Alfon UC-3000, weight average molecular weight: 10000, softening temperature: 36 ° C., acid value: 74 mg- KOH / g)
・ 0.3 parts by weight of leveling agent (Dainippon Ink & Chemicals, Inc .: MegaFac R08-MH)
The liquid concentration was adjusted to 10% by weight with a diluent (methyl ethyl ketone / cyclohexanone = 70/30 weight ratio).

[Example 6]
A positive photosensitive resin laminated sheet was obtained in the same manner as in Example 5 except that the positive photosensitive resin layer forming photosensitive solution 6 having the following composition was used.
<Positive photosensitive resin layer forming photosensitive solution 6>
・ Photosensitive organic compound 30 parts by weight (2,3,4-tris {1,2-naphthoquinone- (2) -diazido-5-sulfonyl} benzophenone)
・ Novolak type phenolic resin (weight average molecular weight: 4200) 42 parts by weight ・ Novolac type phenolic resin (weight average molecular weight: 3300) 14 parts by weight ・ Acrylic resin 14 parts by weight (manufactured by Toagosei Co., Ltd .: Alfon UC-3000, weight average) (Molecular weight: 10000, softening temperature: 36 ° C., acid value: 74 mg-KOH / g)
・ 0.3 parts by weight of leveling agent (Dainippon Ink & Chemicals, Inc .: MegaFac R08-MH)
The liquid concentration was adjusted to 10% by weight with a diluent (methyl ethyl ketone / cyclohexanone = 70/30 weight ratio).

[Example 7]
(1) A positive photosensitive resin layer having a thickness of 1.5 μm was formed in the same manner as in Example 3 except that the positive photosensitive resin layer forming photosensitive solution 7 having the following composition was used.
<Positive photosensitive resin layer forming photosensitive solution 7>
・ Photosensitive organic compound 25 parts by weight (2,3,4,4′-tetrakis {1,2-naphthoquinone- (2) -diazide-5-sulfonyl} benzophenone)
・ Novolak type phenol resin (weight average molecular weight: 11000) 53 parts by weight ・ Acrylic resin 22 parts by weight (Johnson Polymer Co., Ltd .: John Krill 682, weight average molecular weight: 1700, softening temperature: 58 ° C., acid value: 238 mg-KOH / G)
・ 0.3 parts by weight of leveling agent (Dainippon Ink & Chemicals, Inc .: MegaFac R08-MH)
The liquid concentration was adjusted to 10% by weight with a diluent (methyl ethyl ketone / cyclohexanone = 70/30 weight ratio).

(2) On a 75 μm-thick PET film (an antistatic layer was provided on the back surface: surface resistance value 10 ⁸ Ω / □), a cushion layer forming resin solution 2 having the following composition was applied using a Meyer bar. Thereafter, drying was performed at 140 ° C. for 2 minutes in a hot-air circulating dryer to form a 10 μm thick cushion layer.
<Cushion layer forming resin liquid 2>
-100 parts by weight of ethylene vinyl acetate resin (manufactured by Toho Chemical Industry Co., Ltd .: Hitech S-3127)
The liquid concentration was adjusted to 20% by weight with a diluent (water).

(3) Sheet bonding The sheets obtained in (1) and (2) were bonded in the same manner as in Example 1 to obtain a positive-type photosensitive resin laminated sheet.

[Example 8]
A positive photosensitive resin laminated sheet was obtained in the same manner as in Example 7 except that the positive photosensitive resin layer forming photosensitive solution 8 having the following composition was used.
<Positive photosensitive resin layer forming photosensitive solution 8>
・ Photosensitive organic compound 25 parts by weight (2,3,4,4′-tetrakis {1,2-naphthoquinone- (2) -diazide-5-sulfonyl} benzophenone)
・ Novolak type phenolic resin (weight average molecular weight: 11000) 55 parts by weight ・ Acrylic resin 20 parts by weight (manufactured by Johnson Polymer Co., Ltd .: John Kuryl 586, weight average molecular weight: 4600, softening temperature: 50 ° C., acid value: 108 mg-KOH / G)
・ 0.3 parts by weight of leveling agent (Dainippon Ink & Chemicals, Inc .: MegaFac R08-MH)
The liquid concentration was adjusted to 10% by weight with a diluent (methyl ethyl ketone / cyclohexanone = 70/30 weight ratio).

[Example 9]
A positive photosensitive resin laminated sheet was obtained in the same manner as in Example 7 except that the positive photosensitive resin layer forming photosensitive solution 9 having the following composition was used.
<Positive type photosensitive resin layer forming photosensitive solution 9>
・ Photosensitive organic compound 25 parts by weight (2,3,4,4′-tetrakis {1,2-naphthoquinone- (2) -diazide-5-sulfonyl} benzophenone)
・ Novolak type phenolic resin (weight average molecular weight: 11000) 58 parts by weight ・ Acrylic resin 17 parts by weight (manufactured by Johnson Polymer Co., Ltd .: Jonkrill 67, weight average molecular weight: 12500, softening temperature: 53 ° C., acid value: 213 mg-KOH / G)
・ 0.3 parts by weight of leveling agent (Dainippon Ink & Chemicals, Inc .: MegaFac R08-MH)
The liquid concentration was adjusted to 10% by weight with a diluent (methyl ethyl ketone / cyclohexanone = 70/30 weight ratio).

[Comparative Example 1]
Using the photosensitive solution 1 for forming a positive photosensitive resin layer shown in Example 1, a positive photosensitive resin having a thickness of 1.5 μm was formed in the same manner as in Example 1 on a PET film having a thickness of 25 μm previously treated with modified silicon. A resin layer was formed. An OPP film was covered as a cover film on the positive photosensitive resin layer to obtain a positive photosensitive resin laminated sheet.

[Comparative Example 2]
On the cushion layer shown in Example 3, the positive photosensitive resin layer forming photosensitive solution 1 shown in Example 1 was applied using a Meyer bar, and then heated at 100 ° C. in a hot air circulating drier. Drying for 1 minute was performed to form a positive photosensitive resin layer having a thickness of 1.5 μm. A 25 μm thick PET film previously treated with modified silicon was covered as a cover film on this positive photosensitive resin layer to obtain a positive photosensitive resin laminated sheet.

[Comparative Example 3]
A positive photosensitive resin laminated sheet was obtained in the same manner as in Example 3 except that the positive photosensitive resin layer forming photosensitive solution 10 having the composition shown below was used.
<Positive photosensitive resin layer forming photosensitive solution 10>
・ Photosensitive organic compound 20 parts by weight (2,3,4-tris {1,2-naphthoquinone- (2) -diazido-5-sulfonyl} benzophenone)
・ Novolak-type phenolic resin (weight average molecular weight: 11000) 80 parts by weight ・ Leveling agent 0.3 parts by weight (Dainippon Ink and Chemicals Co., Ltd .: Megafuck R08-MH)
The liquid concentration was adjusted to 10% by weight with a diluent (methyl ethyl ketone / cyclohexanone = 70/30 weight ratio).

[Comparative Example 4]
A positive photosensitive resin laminated sheet was obtained in the same manner as in Example 3 except that the positive photosensitive resin layer forming photosensitive solution 11 having the following composition was used.
<Positive photosensitive resin layer forming photosensitive solution 11>
・ Photosensitive organic compound 20 parts by weight (2,3,4-tris {1,2-naphthoquinone- (2) -diazido-5-sulfonyl} benzophenone)
・ Novolak type phenolic resin (weight average molecular weight: 11000) 32 parts by weight ・ Acrylic resin 48 parts by weight (manufactured by Toagosei Co., Ltd .: Alfon UC-3000, weight average molecular weight: 10000, softening temperature: 36 ° C., acid value: 74 mg- KOH / g)
・ 0.3 parts by weight of leveling agent (Dainippon Ink & Chemicals, Inc .: MegaFac R08-MH)
The liquid concentration was adjusted to 10% by weight with a diluent (methyl ethyl ketone / cyclohexanone = 70/30 weight ratio).

[Comparative Example 5]
A positive photosensitive resin laminated sheet was obtained in the same manner as in Example 3, except that the positive photosensitive resin layer forming photosensitive solution 12 having the following composition was used.
<Positive type photosensitive resin layer forming photosensitive solution 12>
・ Photosensitive organic compound 25 parts by weight (2,3,4-tris {1,2-naphthoquinone- (2) -diazido-5-sulfonyl} benzophenone)
・ Novolak type phenolic resin (weight average molecular weight: 11000) 53 parts by weight ・ Acrylic resin 22 parts by weight (manufactured by Shin-Nakamura Chemical Co., Ltd .: PSY-1934, weight average molecular weight: 104000, softening temperature: 40 ° C., acid value: 0 mg -KOH / g)
・ 0.3 parts by weight of leveling agent (Dainippon Ink & Chemicals, Inc .: MegaFac R08-MH)
The liquid concentration was adjusted to 10% by weight with a diluent (methyl ethyl ketone / cyclohexanone = 70/30 weight ratio).

  Table 1 shows the characteristics of the positive-type photosensitive resin laminated sheets obtained in Examples and Comparative Examples. The softening temperature of the resin was measured in a penetration mode using TMA2940 type manufactured by TA Instruments. The test pieces were prepared by applying and drying various thermoplastic resins on a polyethylene terephthalate film (PET film) having a thickness of 50 μm so that the film thickness after drying was 20 μm. As shown in FIG. 4, the test piece having a size of 10 mm × 10 mm was placed on a quartz glass table and pressed with a quartz glass probe having a diameter of 2 mm, and a load of 20 g was applied to the probe during the measurement. The test piece and the probe were heated from 0 ° C. to 150 ° C. at a heating rate of 20 ° C./min while maintaining a constant load, and the movement of the probe with respect to the temperature was recorded. Since the probe moves so as to sink into the resin due to the softening of the resin, the softening temperature of the resin is read from the inflection point of the movement of the probe as shown in FIG.

  The weight average molecular weight of the resin is measured using gel permeation chromatography (GPC measurement) and is calculated based on a calibration curve created from measurement of a polystyrene standard sample.

  Further, the characteristics of the positive photosensitive resin laminated sheets obtained in Examples and Comparative Examples were evaluated as follows, and the results are shown in Table 2.

First, a 1 mm-thick glass substrate on which a 1 μm-thick metal chromium film pattern is formed in advance using an existing technique such as sputtering is sufficiently washed with pure water, and then the cover film is formed with a positive photosensitive resin layer. The surface of the positive photosensitive resin layer is placed so as to face the surface of the chromium metal film, and the pressure of 3 kgf / cm ² is applied using a thermal laminator in which the surface temperature of the rubber roll is heated to 120 ° C. The film was stuck at a speed of 1000 mm / min while being pressurized. Then, the support film was peeled and removed between the cushion layer and the positive photosensitive resin layer, and the positive photosensitive resin layer was transferred onto the glass substrate. At this time, the transfer surface and the cross-section were observed with a microscope, and the positive photosensitive resin layer was marked as “◯” when it was embedded without involving bubbles in the step of the metal film pattern, and “X” when it was not sufficiently embedded.

Then, the positive photosensitive resin layer which is transferred to the glass substrate using an ultra-high pressure mercury lamp perform pattern exposure 20 mJ / cm ² or 30mJ / cm ^2, 2.38% tetramethylammonium hydroxide maintained at 25 ° C. ( Development was performed for 30 seconds using a TMAH solution as a developer. The pattern image formed on the glass substrate was observed for pattern formation using an electron microscope and a laser microscope, and the presence or absence of a resin residue (development residue) remaining in the exposed portion, and the quality was evaluated. The pattern formation state is ○ if the pattern used for the mask is well formed, △ if the shape is broken, × if the pattern is not formed, and the development residue is that the exposed area is completely dissolved and removed. ○ if there is residue, × if there is residue. In addition, the thickness of the resin layer with the positive photosensitive resin layer transferred to the glass substrate (before treatment) and the thickness of the pattern formed on the unexposed area (after treatment) were measured, and the remaining film ratio of the pattern was It was calculated as follows.

Pattern remaining film ratio (%) = (pattern thickness after treatment) / (resin layer thickness before treatment) × 100
Subsequently, after thoroughly washing and rinsing the glass substrate on which the resin layer pattern is formed with pure water, the metal chromium film is etched using 16% concentration diammonium cerium (IV) nitrate. Patterning was performed. Then, the pattern image formed on the glass substrate was observed for the pattern formation state using an electron microscope and a laser microscope, and the quality was evaluated. If a new metal chrome film pattern is satisfactorily formed by etching in a place where the positive photosensitive resin layer formed on the glass substrate does not remain, it is marked as ◯, and if a new pattern cannot be formed, it is marked as x. .

  Based on the above-described evaluation method, in Comparative Example 1, since no cushion layer was provided, bubbles remained at the step between the metal film and the glass surface, and satisfactory transferability was not obtained, and the metal film pattern was not formed. It was. In Comparative Example 2, since the positive type photosensitive resin layer forming photosensitive solution was directly applied onto the cushion layer, the support film could not be peeled and removed between the cushion layer and the positive type photosensitive resin layer. The positive photosensitive resin layer could not be transferred to. Further, in the same manner as in Comparative Example 2 using an acrylic resin or EVA-based copolymer for the cushion layer, when the positive photosensitive resin layer forming photosensitive solution is directly applied on the cushion layer, the cushion layer The cushion layer was dissolved without solvent resistance. Furthermore, even if the degree of dissolution is weak and the positive photosensitive resin layer can be peeled off, the film thickness distribution of the positive photosensitive resin layer varies widely, and the film thickness uniformity targeted by the present invention is achieved. Was far from complete. In Comparative Example 3, although a positive photosensitive resin layer can be formed, flexibility and flexibility are poor, and the resin layer is cracked during a sticking operation to a glass substrate, and good transfer to the substrate is not possible. It was. In Comparative Example 4, the amount of the thermoplastic resin component in the positive photosensitive resin layer was large, the flexibility and flexibility were excellent, and the transfer property to the glass substrate was very good. The pattern was not able to be formed by dissolving in the developer up to the unexposed area on the substrate. In Comparative Example 5, the transfer property of the positive photosensitive resin layer was good, but contrary to Comparative Example 4, the alkali solubility was poor and a residue was generated in the exposed area.

  When a series of photolithography was performed on the comparative examples using the positive-type photosensitive resin laminated sheets shown in Examples 1 to 9, all had good metal chromium film patterns as shown in Table 2. Was able to be formed. From this, the usefulness of the present invention is clear.

It is sectional drawing which shows the structure of the positive type photosensitive resin laminated sheet which concerns on this invention. It is sectional drawing which shows the structure by the side of the cover film before bonding. It is sectional drawing which shows the structure by the side of the support body film before bonding. Cross-sectional view of substrate showing outline of TFT array manufacturing process Conceptual diagram showing a method for measuring the softening temperature of a resin by thermomechanical analysis (TMA) Measurement example of softening temperature of resin by thermomechanical analysis (TMA)

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Cover film 2 Positive type photosensitive resin layer 3 Cushion layer 4 Support body 5 Glass surface coat layer 6 Gate electrode 7 Silicon oxide film 8 Silicon nitride film 9 Hydrogenated amorphous silicon layer 10 Channel protective film 11 n ⁺ type amorphous silicon layer 12 Pixel electrode 13 Source electrode 14 Drain electrode 15 Protective film

Claims (9)

A laminate in which a cover film, at least one positive photosensitive resin layer, a cushion layer, and a support film are laminated in this order, and the cushion layer is made of a thermoplastic resin, and the positive photosensitive resin layer is A positive-type photosensitive resin laminate sheet comprising an organic compound having a 1,2-naphthoquinonediazide sulfonic acid ester group as a photosensitive component, a novolak-type phenol resin, and a thermoplastic resin having an alkali-soluble carboxyl group . The positive photosensitive resin layer is peelable between the cover film and the cushion layer, and the adhesive force between the positive photosensitive resin layer and the cover film is the adhesion between the positive photosensitive resin layer and the cushion layer. The positive photosensitive resin laminated sheet according to claim 1, wherein the positive photosensitive resin laminated sheet is lower than the force. 3. The positive photosensitive resin according to claim 1, wherein the photosensitive component contained in the positive photosensitive resin layer is an organic compound having two or more 1,2-naphthoquinonediazide sulfonic acid ester groups. Laminated sheet. The positive photosensitive resin layer is 5 to 30 parts by weight of an organic compound having a 1,2-naphthoquinonediazide sulfonic acid ester group, 40 to 70 parts by weight of a novolac type phenol resin, and 5 to 40 parts by weight of an alkali-soluble compound. The positive photosensitive resin laminated sheet according to any one of claims 1 to 3, comprising a thermoplastic resin having a carboxyl group, wherein the positive photosensitive resin layer has a thickness of 0.5 to 3 µm. The positive photosensitive resin laminated sheet according to any one of claims 1 to 4, wherein the novolac type phenolic resin contained in the positive photosensitive resin layer has a weight average molecular weight in the range of 2000 to 20000. The thermoplastic resin having an alkali-soluble carboxyl group contained in the positive photosensitive resin layer has a weight average molecular weight of 1000 to 30000, a softening temperature of 80 ° C. or less, and an acid value of 30 to 300 mg-KOH / g. The positive photosensitive resin laminate sheet according to claim 1, wherein the positive photosensitive resin laminate sheet is provided. The positive photosensitive film according to any one of claims 1 to 6, wherein the thermoplastic resin constituting the cushion layer has a softening temperature of 30 to 90 ° C and a thickness of the cushion layer of 5 to 40 µm. Resin laminated sheet. A positive photosensitive resin layer comprising an organic compound having a 1,2-naphthoquinonediazide sulfonic acid ester group as a photosensitive component, a novolac type phenolic resin, and a thermoplastic resin having an alkali-soluble carboxyl group on one side of the cover film. Using the film (A) formed by coating and drying, and the film (B) formed by coating and drying a cushion layer made of a thermoplastic resin on one side of the support film, the positive type of the film (A) A method for producing a positive-type photosensitive resin laminate sheet, comprising bonding a photosensitive resin layer surface and a cushion layer surface of the film (B). The cover film is peeled and removed from the positive photosensitive resin layer from the positive photosensitive resin laminated sheet according to claim 1, and the surface of the positive photosensitive resin layer is heated and pressurized on the surface of the glass substrate. After sticking, the support film is peeled and removed between the cushion layer and the positive photosensitive resin layer, and only the positive photosensitive resin layer is transferred to the glass substrate, and a photo is transferred to the positive photosensitive resin layer. Lithography (pre-baking, pattern exposure with actinic light, development with alkaline aqueous solution, post-baking) and etching (wet etching with acid solution or dry etching with plasma gas) are performed to form a circuit pattern on the glass substrate. A method for producing a circuit pattern, wherein a positive photosensitive resin pattern remaining on the top is removed with a stripping solution.

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