WO2009093706A1

WO2009093706A1 - Photosensitive resin laminate

Info

Publication number: WO2009093706A1
Application number: PCT/JP2009/051111
Authority: WO
Inventors: Yuzo Kotani
Original assignee: Asahi Kasei E-Materials Corporation
Priority date: 2008-01-24
Filing date: 2009-01-23
Publication date: 2009-07-30
Also published as: TWI382277B; TW200947119A; JP4825307B2; CN101952778A; JPWO2009093706A1; CN101952778B

Abstract

Disclosed is a photosensitive resin laminate which has excellent resolution and excellent adhesion to various bases such as polysilicon, amorphous silicon, copper, molybdenum, chromium and tungsten, while having good developability, excellent etching properties and excellent separability. Specifically disclosed is a photosensitive resin laminate wherein at least a supporting layer, at least one of a release layer (a), an alkali-soluble resin layer (b) and a water-soluble resin layer (c), and a photosensitive resin layer composed of a photosensitive resin composition are sequentially laminated. The photosensitive resin laminate is characterized in that the photosensitive resin composition contains 20-90% by mass of an alkali-soluble resin having a phenolic hydroxyl group, 0.01-5% by mass of a photoacid generator, 1-40% by mass of a compound having a group which is crosslinked by the action of an acid, and 1-40% by mass of a plasticizer.

Description

Photosensitive resin laminate

The present invention relates to a photosensitive resin laminate useful for manufacturing an electrode pattern or a semiconductor pattern, and an electrode pattern and a semiconductor pattern manufacturing method using the same.

The photosensitive resin laminate is also referred to as a dry film and has been widely used as a resist material for forming circuits such as printed wiring boards. The dry film is characterized by undergoing a laminating process when the photosensitive resin layer is laminated on the base material. When laminating a liquid resist on a substrate, it is necessary to apply the liquid resist to the substrate, dry it, and adjust the film thickness. However, if a dry film is used, the film thickness is adjusted uniformly in advance. By simply laminating the photosensitive resin layer on the base material, a base material on which the photosensitive resin layer is laminated can be obtained. Such a laminating process does not require a solvent, so it has little impact on the environment, can be laminated on a large area of the substrate in a lump, and has a roll-like length represented by the reel-to-reel method. It can also be laminated continuously on a scale substrate. Due to such high productivity, it has recently been proposed to apply a dry film not only to a printed wiring board but also to various other fine processing fields. For example, a lead frame, tape-automated bonding, chip-on film, and the like can be given.

The dry film contains an alkali-soluble polymer called a binder polymer. When the dry film is exposed, the photopolymerization initiator is cleaved to generate radicals. When this starts polymerization of the monomer having an unsaturated double bond and cures the exposed portion, it becomes insoluble in alkali. Thereafter, the unexposed portion is developed to form a resist pattern.

On the other hand, thin film transistors (hereinafter referred to as TFTs) are used as switching elements in devices such as liquid crystal displays and imaging sensors for image display and image capture. TFTs are currently almost always manufactured by lithography using a positive liquid resist (see Patent Document 1 below). In the positive type, a compound called photoactive compound (PAC) such as naphthoquinonediazide is insolubilized by diazo coupling with a phenolic hydroxyl group under an alkali. In the exposed portion, quinonediazide is converted to indenecarboxylic acid by a photoreaction and becomes alkali-soluble. Lithography using a positive liquid resist is characterized in that the resolution is better than that of the aforementioned dry film. However, when the opening area is large like a TFT, there is a high probability that dust on the mask or the substrate overlaps with the opening, and in the positive type, there is a high probability that a resist residue will be generated. Further, since the PAC absorbs actinic rays, the sensitivity decreases as the film thickness increases.

Further, as a negative resist having a good resolution, a chemically amplified negative liquid resist is also known (refer to Patent Document 2 and Patent Document 3 below).
Currently, in the manufacture of TFTs, for example, when used in a liquid crystal display, productivity is emphasized. Therefore, a method of mass-producing several panels on a large-area glass substrate is generally used.
Therefore, if a dry film can be used in the manufacture of TFT, a manufacturing process with extremely high productivity can be established.
JP 2006-72080 A JP-A-7-28243 JP 2003-43688 A

The object of the present invention is to have excellent resolution and adhesion to various substrates such as polysilicon, amorphous silicon, copper, molybdenum, chromium, tungsten, tantalum, etc., good developability, and etching property. And a photosensitive resin laminate excellent in releasability. Another object of the present invention is to provide a method for producing a resist pattern, a method for producing an electrode pattern, and a method for producing a semiconductor pattern, which are excellent in productivity in terms of sensitivity, development time, lamination process, and the like.

In order to solve the above problems, the present inventor has recently conducted extensive experiments and as a result, discovered that the above problems can be solved by using a photosensitive resin laminate having a specific composition, and completed the present invention. It came to do.

That is, the present invention is the following [1] to [11]:
[1] At least the support layer and the following (a) to (c):
(A) a release layer,
(B) an alkali-soluble resin layer,
(C) a water-soluble resin layer,
A photosensitive resin laminate in which at least one layer selected from the layers shown in the above and a photosensitive resin layer made of a photosensitive resin composition are sequentially laminated, and the photosensitive resin composition is phenolic 20 to 90% by mass of an alkali-soluble resin having a hydroxyl group, 0.01 to 5% by mass of a photoacid generator, 1 to 40% by mass of a compound having a group capable of crosslinking by the action of an acid, and 1 to 40% by mass of a plasticizer. The said photosensitive resin laminated body characterized by the above-mentioned.

[2] The photosensitive resin laminate according to [1], wherein the photosensitive resin composition further includes an alkali-soluble polymer having a carboxyl group.

[3] The plasticizer is represented by the following general formula (I):

{Wherein R ¹ and R ² are ethylene groups or propylene groups, R ¹ and R ² are different from each other, m1, n1, m2, and n2 are each 0 or more, and m1 + n1 + m2 + n2 is And the repeating structure of — (O—R ¹ ) — and — (O—R ² ) — may be random or block, and — (O—R ¹ ) — And the repeating structure of — (O—R ² ) — may be on the bisphenyl group side. } The photosensitive resin laminated body as described in said [1] or [2] which is a compound represented by these.

[4] A step of laminating the photosensitive resin laminate according to any one of [1] to [3] to the substrate such that the photosensitive resin layer is in contact with the substrate; A method for producing a resist pattern, comprising a step of exposing, a step of heating the exposed photosensitive resin layer, and a step of developing the heated photosensitive resin layer.

[5] The method for producing a resist pattern according to [4], wherein the step of exposing the photosensitive resin layer is a method of drawing an actinic ray.

[6] A method for producing an electrode pattern, comprising a step of performing wet etching on a portion of a base material that is not covered with the resist pattern produced by the method according to [4].

[7] A method for producing a semiconductor pattern, comprising a step of dry etching a portion of a base material that is not covered with the resist pattern produced by the method according to [4].

[8] The method for producing a resist pattern according to [4] or [5], wherein the surface of the base material in contact with the photosensitive resin layer is molybdenum.

[9] The electrode pattern manufacturing method according to [6], wherein the surface of the base material in contact with the photosensitive resin layer is molybdenum.

[10] The method for producing a resist pattern according to the above [4] or [5], wherein the surface of the substrate in contact with the photosensitive resin layer is amorphous silicon.

[11] The method for producing a resist pattern according to [4] or [5], wherein the surface of the base material in contact with the photosensitive resin layer is silicon nitride.

According to the present invention, it has excellent resolution and adhesion to various substrates such as polysilicon, amorphous silicon, copper, molybdenum, chromium, tungsten, tantalum, etc., has good developability, etching property and peeling. A photosensitive resin laminate having excellent properties is provided. Furthermore, the present invention provides a method for producing a resist pattern, a method for producing an electrode pattern, and a method for producing a semiconductor pattern, which are excellent in productivity in terms of sensitivity, development time, lamination process, and the like.

Hereinafter, the present invention will be described in detail.
The photosensitive resin laminate of the present invention has a support layer.
The support layer usually contains a lubricant to prevent blocking. Blocking refers to a phenomenon in which a gap or wrinkle is caused by friction when the support layer or the photosensitive resin laminate is pulled out or wound up. Examples of the lubricant include organic or inorganic lubricants. Examples of the organic lubricant include higher fatty acids, higher alcohols, aliphatic hydrocarbons, aliphatic amides, fatty acid metal salts, and fatty acid esters, and higher fatty acids and higher alcohols are preferable. Specific examples of higher fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, serotic acid, montanic acid, mellicic acid, celloplastic acid and the like. Specific examples of higher alcohols include pentanol, octanol, dodecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, docosanol, tetracosanol, hexacosanol, heptacosanol, octacosanol, triacontanol, oleyl Alcohol, linoleyl alcohol, linolenyl alcohol, etc. are mentioned. Examples of the inorganic lubricant include inorganic particles such as calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide. Silica particles are preferred for obtaining high transparency. Such a lubricant preferably has an average particle size of 0.01 to 0.2 μm. From the viewpoint of suppressing the drop-off of particles from the coating layer, the average particle size is preferably not more than twice the thickness of the coating layer after drying. The average particle size is preferably 0.01 μm or more from the viewpoint of easy lubrication and winding improvement.

The heat shrinkage rate at 200 ° C. for 30 minutes in the width direction of the support layer is preferably 0.01 to 4.00%. The heat shrinkage rate at 150 ° C. for 30 minutes is preferably 0.01 to 0.20%. The thermal shrinkage rate at 105 ° C. for 30 minutes is preferably 0.01 to 0.20%. The heat shrinkage rate in the width direction of the support layer is preferably not less than the above lower limit from the viewpoint of manufacturability, and is preferably not more than the above upper limit from the viewpoint of dimensional stability.

The thermal shrinkage rate at 105 ° C. for 30 minutes in the longitudinal direction of the support layer is preferably 0.30 to 0.60%, more preferably 0.35 to 0.55%. The heat shrinkage rate at 150 ° C. for 30 minutes in the longitudinal direction of the support layer is preferably 1.00 to 1.90%. The heat shrinkage rate in the longitudinal direction of the support layer at 200 ° C. for 30 minutes is preferably 3.00 to 6.50%. The heat shrinkage rate in the longitudinal direction of the support layer is preferably not less than the above lower limit from the viewpoint of ease of production, and is preferably not more than the above upper limit from the viewpoint of dimensional stability during lamination.

The heat shrinkage rate of the support layer was determined by taking 5 test pieces each having a width of 20 mm and a length of 150 mm from the longitudinal direction and the width direction of the film, attaching a mark at a distance of about 100 mm at the center, and measuring the temperature described above. A test piece is vertically suspended in a hot air circulation type thermostatic chamber maintained at ± 3 ° C., heated for 30 minutes, taken out, allowed to stand at room temperature for 30 minutes, and then the distance between the test points is measured. 1):
ΔL (%) = (L−L0) / L0 × 100 (1)
{In the formula, ΔL is the heat shrinkage rate (%), L0 is the distance between the gauge points before heating (mm), and L is the distance between the gauge points after heating (mm). }
And can be measured by calculating the average. The other conditions in the measurement of the heat shrinkage rate are based on JIS C2318-1997 (5.3.4 dimensional change).

The photosensitive resin laminate of the present invention has at least one layer selected from the following layers (a) to (c) between the support layer and the photosensitive resin layer:
(A) a release layer,
(B) an alkali-soluble resin layer,
(C) Water-soluble resin layer.

Hereinafter, the layers shown in (a) to (c) will be described in order.
(A) The release layer is a layer made of a release agent (hereinafter also referred to as a release agent) provided to improve the release property with respect to the support layer, and the treatment for providing the release layer on the support layer is separated. Also called mold processing. As the mold release treatment, for example, a mold release containing at least one resin selected from the group consisting of a silicone resin, a fluororesin, an alkyd (or alkyd) resin, a long-chain alkyl resin, an acrylic resin, and a polyolefin resin. A chemical treatment that increases the releasability by thinly coating the surface with a mold.

(A) The film thickness of the release layer is preferably 1 to 500 nm. 1 nm or more is preferable from the viewpoint of the mold release effect, and 500 nm or less is preferable from the viewpoint of transfer of the release agent to the photosensitive resin layer or migration during storage.
Examples of silicone resins include condensation reaction type silicone resins obtained by reacting silanol polydimethylsiloxane at both ends with polymethylhydrogensiloxane or polymethylmethoxysiloxane, dimethylsiloxane / methylvinylsiloxane copolymer or dimethylsiloxane / methylhexenylsiloxane copolymer. An addition reaction type silicone resin obtained by reacting a polymer with polymethylhydrogensiloxane, an ultraviolet curable type or electron beam curable type silicone resin obtained by curing an acrylic silicone or an epoxy group-containing silicone with an ultraviolet ray or an electron beam, a modified silicone resin, For example, epoxy-modified silicone resin (silicone epoxy), polyester-modified silicone resin (silicone polyester), acrylic-modified silicone resin (silicone acrylic), phenol-modified silicone Down resin (silicone phenol), alkyd-modified silicone resin (silicone alkyd), melamine-modified silicone resin (silicone melamine), and the like.

Examples of the fluororesin include fluororesins including amorphous fluororesins. Specifically, examples of the amorphous fluororesin include Lumiflon manufactured by Asahi Glass Co., Cytop manufactured by the company. Copolymer oligomers containing perfluoroalkyl group-containing (meth) acrylate and alkyl (meth) acrylate as main components include Nippon Oil & Fats Modiper F Series, Daikin Industries Unidyne, Dainippon Ink & Chemicals Examples thereof include F470 series, F480 series manufactured by the same company, F110 series manufactured by the same company, and block copolymerization is more preferable as the copolymerization. As a fluorine-type coating agent, Sumitomo 3M EGC1700 is mentioned. Examples of the fluorosurfactant include Dainippon Ink and Chemicals' MegaFace F114, the company's F410 series, the company's 440 series, the company's 450, and the company's 490 series. Examples of the fluorine-based surface treatment agent containing an electron beam or an ultraviolet curing component include Polyfox PF-3320 manufactured by Omninova Solutions, Cheminox FAMAC-8 manufactured by Unimatec. Examples of the fluorine-based surface treatment agent containing a thermosetting component include EGC1720 manufactured by Sumitomo 3M, NH-10 and NH-15 manufactured by Dainippon Ink and Chemicals, Inc. The fluorine-containing compound in the fluorine-containing compound layer may be a mixture of a plurality of types of fluorine-containing compounds. From the viewpoint of light transmittance of the fluorine-containing compound layer, amorphous fluorine resin is preferable since it has high ultraviolet light transmittance due to amorphous (see Asahi Glass Research Report 55, 2005).

The alkyd resin is also called an alkyd resin, which is a condensate of polybasic acid and polyhydric alcohol modified with fatty oil or fatty acid. Since the silicone resin may be transferred to the photosensitive resin layer, an alkyd resin may be used when it is desired to avoid such transfer of the silicone component. Moreover, it is preferable that an alkyd resin is included in a mold release layer from a viewpoint of the balance of the applicability | paintability and peelability of an oxygen interruption | blocking layer or another layer. Examples of the polybasic acid include saturated polybasic acids such as phthalic anhydride, terephthalic acid, succinic acid, adipic acid, and sebacic acid, as well as insolubles such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic anhydride. Examples thereof include saturated polybasic acid, cyclopentadiene-maleic anhydride adduct, terpene-maleic anhydride adduct, and rosin-maleic anhydride adduct. Examples of polyhydric alcohols include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, trihydric alcohols such as glycerin, trimethylolpropane, tetrahydric or higher alcohols, Examples include diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, sorbitol and the like. Examples of the modifier include soybean oil, linseed oil, tung oil, castor oil, dehydrated castor oil, coconut oil, and fatty acids thereof, stearic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid. And oils and fats such as dehydrated ricinoleic acid, natural resins such as rosin, kovar, amber, shellac, and synthetic resins such as ester gum, phenol resin, urea resin, and melamine resin. A stearic acid-modified alkyd resin and / or a cured resin of a stearic acid-modified acrylic resin and an amino resin is also preferable from the viewpoint of the balance between coatability and peelability.

The long chain alkyl resin can be any known in the art.
The acrylic resin can be any one known in the art.

Examples of the polyolefin resin include olefin thermoplastic elastomers such as ethylene propylene copolymer and ethylene octene copolymer. You may mix and use a polyethylene resin etc.

When coating with a release agent, it is preferable to coat as thin as possible as long as a release effect is obtained. After coating, the release agent can be fixed to the support layer (film) by heat or UV treatment.
Examples of the support layer that is generally available as a release-treated support layer include, for example, GS, 1031, 1020, 1010, 2010, C, 2080, 2090, 2100, E, 6040, 6010, X, manufactured by Lintec Corporation. , SK-1, and AL-5. Moreover, Teijin DuPont Co., Ltd., A-60, A-70, Mitsubishi Polyester Film Co., Ltd., T-100H, etc. may be mentioned.

(B) The alkali-soluble resin layer is a resin layer containing an alkali-soluble polymer having the same carboxyl group as the alkali-soluble polymer having a carboxyl group used in the photosensitive resin layer described in the present specification. In addition to the alkali-soluble polymer having a carboxyl group, a plasticizer is preferably included from the viewpoint of flexibility. As a plasticizer, the same plasticizer as the plasticizer used for the photosensitive resin layer can be used. In consideration of mixing of the initiator component with the photosensitive resin layer, the alkali-soluble resin layer may contain an initiator component. In this case, it is preferable to contain the same initiator as the initiator used for the photosensitive resin layer in the same mass ratio.
(B) The alkali-soluble resin layer preferably has a film thickness of 30 μm or less from the viewpoint of developability and resolution, and is preferably 3 μm or more from the viewpoint of ensuring releasability from the support layer.

(C) The water-soluble resin layer is obtained by diluting a water-soluble resin composition with water or another solvent according to the film thickness or viscosity to be applied and drying it. Other solvents can be used as long as the components of the water-soluble resin composition do not precipitate. From the viewpoints of coating properties and drying properties, those having a boiling point lower than that of water are preferable, and it is more preferable to use a mixture of water and these other solvents. Specific examples include a mixed solvent of water and ethanol or methanol, and a mixed solvent of water and methanol is preferable. In addition, a water-soluble polymer having at least vinyl alcohol as a copolymer unit is often difficult to dissolve in cold water. Therefore, if it is dispersed in cold water in advance and then heated and dissolved, it is blended with a water-soluble plasticizer. Is often easy.
The water-soluble resin composition preferably contains a water-soluble polymer having vinyl alcohol as a copolymer unit. Examples of the water-soluble polymer having vinyl alcohol as a copolymer unit include polyvinyl alcohol and its derivatives, and polyvinyl alcohol obtained by copolymerizing 1 to 20 mol% of olefin.

Polyvinyl alcohol is generally produced by alkali saponification of polyvinyl acetate. The weight average molecular weight of polyvinyl alcohol is preferably 1,000 to 100,000. The weight average molecular weight of polyvinyl alcohol is more preferably 5,000 to 50,000 from the viewpoints of oxygen barrier properties and developability. The saponification degree is preferably 50 mol% or more from the viewpoint of developability, preferably 70 mol% or more, more preferably 80 mol% or more. Examples of such polyvinyl alcohol include PVA-103, PVA-105, PVA-110, PVA-117, PVA-124, PVA-203, PVA-205, PVA-217, and PVA-220 manufactured by Kuraray Co., Ltd. , PVA-224, PVA-226, PVA-235, PVA-403, PVA-405, and PVA-420.

Examples of the polyvinyl alcohol derivative include carboxylated polyvinyl alcohol described in JP-A-63-197942.
Polyvinyl alcohol obtained by copolymerizing 1 to 20 mol% of olefin is generally produced by copolymerizing olefin and vinyl acetate and saponifying the copolymer. Examples of the olefin include ethylene, propylene, 1-hexene and the like. Ethylene is preferable from the viewpoint of copolymerization and alkali solubility. From the viewpoint of alkali solubility, the olefin copolymerization ratio is 20 mol% or less. Examples of such polyvinyl alcohol obtained by copolymerizing 1 to 20 mol% of olefin include Eval (trade name) manufactured by Kuraray Co., Ltd.

The water-soluble polymer having vinyl alcohol as a copolymer unit is preferably blended in the water-soluble resin composition at 50% by mass or more and 95% by mass or less from the viewpoint of developability and cost. More preferably, the water-soluble polymer having vinyl alcohol as a copolymer unit in the water-soluble resin composition is 60% by mass or more and 90% by mass or less.
The water-soluble resin composition preferably contains a water-soluble plasticizer from the viewpoint of releasability with the support layer.
Examples of the water-soluble plasticizer include polyvinyl pyrrolidone and derivatives thereof, water-soluble cellulose derivatives such as hydroxyethyl cellulose, polyethylene oxide, polyethylene oxide ester compounds, polyethylene oxide ether compounds such as polyethylene oxide and derivatives thereof, and vinyl ether-anhydrous maleic acid. Examples thereof include acid copolymers and water-soluble salts thereof, carboxyalkyl starch water-soluble salts, polyacrylamide, polyamide, water-soluble polyacrylic acid salts, gelatin, and polypropylene glycol.

Specific examples of polyvinylpyrrolidone include Nippon Shokubai K-15 (weight average molecular weight 40,000), K-30 (weight average molecular weight 100,000), K-85 (weight average molecular weight 900,000), K-90 ( Weight average molecular weight 1 million).
Specific examples of polyethylene oxide and derivatives thereof include polyethylene glycol having a number average molecular weight of 200 (PEG 200 manufactured by NOF Corporation), polyethylene glycol having a number average molecular weight of 300 (PEG 300 manufactured by NOF Corporation, number average molecular weight). 400 polyethylene glycol (Nippon Yushi Co., Ltd. PEG400), number average molecular weight 600 polyethylene glycol (Nippon Yushi Co., Ltd. PEG600), number average molecular weight 1000 polyethylene glycol (Nippon Yushi Co., Ltd. PEG1000) and Polyethylene glycol monomethyl ether having a number average molecular weight of 400 (Uniox M-400 manufactured by NOF Corporation), polyethylene glycol monomethyl ether having an average molecular weight of 550 (NOF Corporation) Uniox M-550), polyethylene glycol monomethyl ether (manufactured by NOF CORPORATION Uniox M-1000 is a 1000 number average molecular weight), and the like.

The weight average molecular weight of the water-soluble polymer was determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (HFIP-). 805, HFIP-803) Two in series, moving bed solvent: hexafluoroisopropanol, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) is obtained as a weight average molecular weight (polystyrene conversion).
The thickness of the water-soluble resin layer is preferably 0.1 μm or more from the viewpoint of releasability, and is preferably 10 μm or less from the viewpoint of developability.

When the photosensitive resin laminate is used in the form of a roll, a protective layer is provided for the purpose of preventing the adhesive photosensitive resin layer from being transferred to the support layer or adhering dust to the photosensitive resin layer. It can be used by being laminated on the photosensitive resin layer. The protective layer preferably has a maximum roughness (Ry) of a surface in contact with the photosensitive resin layer of 2.0 μm or less. The unevenness on the surface transferred from the protective layer may not be removed at the time of laminating, resulting in voids. From the viewpoint of suppressing this, the maximum roughness (Ry) is preferably 2.0 μm or less, and 0 from the viewpoint of manufacturability. .01 or more is preferable. The maximum roughness (Ry) is measured according to JISＪB 0601.

A polyolefin film is preferable as the film used as the protective layer. A polyethylene film, a polypropylene film, a polypropylene film, etc. are mentioned. A polyolefin film usually used as a protective film is produced by heat-melting raw materials, kneading, extruding, biaxial stretching or casting. In general, a protective film such as a polyolefin film contains undissolved and thermally deteriorated materials called fish eyes. The size of the fish eye is generally 30 to 600 μm in diameter (φ) and protrudes from the film surface at a height of 2 to 40 μm. The convex portion of the fish eye is transferred to the photosensitive resin layer to form a dent in the photosensitive resin layer, and air voids are generated on the substrate after lamination. The polyethylene film usually has a gel called fish eye, but it is preferable that the gel is less. In the case of a polyethylene film, the thickness of the protective layer is preferably 20 μm or more, more preferably 30 μm or more from the viewpoint of reducing fish eyes. The film thickness of the protective layer is preferably 50 μm or less from the viewpoint of bulkiness and handleability in the case of winding in a roll shape. In the case of a polypropylene film, the fish eye is very small and the film thickness is not particularly limited, but the film thickness of the protective layer is preferably 5 μm or more from the viewpoint of the function of protecting the photosensitive resin layer, and suppresses wrinkles during winding. In view of the above, it is preferably 25 μm or less.

Commercially available polyethylene films include GF-18, GF-818, and GF-858 manufactured by Tamapoly Co., Ltd., and polypropylene films manufactured by Oji Paper Co., Ltd., Alphan (registered trademark) E-200, E -200A.

The photosensitive resin layer constituting the photosensitive resin laminate of the present invention comprises a photosensitive resin composition, and the photosensitive resin composition comprises an alkali-soluble resin having a phenolic hydroxyl group, a photoacid generator, and an action of an acid. Containing a compound having a crosslinkable group and a plasticizer. Hereinafter, these will be described in order.
Examples of the alkali-soluble resin having a phenolic hydroxyl group include novolak resins and polyhydroxystyrene resins.

As the novolak resin, those conventionally used as a film-forming substance in a conventional positive photoresist composition can be used. The novolak resin can be obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter also simply referred to as “phenols”) and an aldehyde under an acid catalyst. Examples of phenols used in this case include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3 , 4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol The Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid are used as the acid catalyst. As the alkali-soluble novolak resin, those having a weight average molecular weight in the range of 2,000 to 20,000 with a low molecular weight region cut off are suitable.

When considering the profile shape of the resist pattern, those obtained using a phenolic compound containing 30% by weight or more of m-cresol, particularly 55 to 75% by weight of m-cresol, and the remaining The component is preferably obtained from a mixed phenolic compound containing 45 to 25% by weight of at least one selected from p-cresol, 2,5-xylenol and 3,5-xylenol.

Examples of the polyhydroxystyrene resin include polyhydroxystyrene, modified polyhydroxystyrene, hydrogenated polyhydroxystyrene, copolymers of hydroxystyrene and styrene, (meth) acrylic acid ester, maleic acid ester, and the like.
Examples of the modified polyhydroxystyrene include those obtained by reacting polyhydroxystyrene with a benzenesulfonyl chloride derivative, a naphthalenesulfonyl chloride derivative, a benzenecarbonyl chloride derivative, a naphthalenecarbonyl chloride derivative, etc. in the presence of a basic catalyst. It is done. Specific examples of the aforementioned sulfonyl chloride derivative and carbonyl chloride derivative include p-acetaminobenzenesulfonyl chloride, benzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, naphthylbenzenesulfonyl chloride, p-acetaminobenzenecarbonyl chloride, benzenecarbonyl chloride, Examples thereof include p-chlorobenzenecarbonyl chloride and naphthylbenzenecarbonyl chloride. In this case, the sulfonyl chloride derivative or the carbonyl chloride derivative is usually used at a ratio of 10 to 30 parts by weight, preferably 15 to 25 parts by weight, with respect to 100 parts by weight of polyhydroxystyrene. Such modified polyhydroxystyrene can have a weight average molecular weight in the range of 3,000 to 50,000, preferably 5,000 to 30,000.

Hydrogenated polyhydroxystyrene is obtained by hydrogenating part of the benzene ring of polyhydroxystyrene and modified polyhydroxystyrene in which part of the benzene ring is modified by a substituent. The weight average molecular weight of the hydrogenated polyhydroxystyrene is usually selected in the range of 3,000 to 30,000, preferably 5,000 to 25,000. From the viewpoint of mechanical properties and dry etching resistance, the weight average molecular weight is preferably 3,000 or more, and preferably 30,000 or less from the viewpoint of compatibility.

The alkali-soluble resin having a phenolic hydroxyl group is preferably blended in an amount of 20 to 90% by mass with respect to 100% by mass of the photosensitive resin composition. More preferably, it is 30 to 70% by mass. 20 mass% or more is preferable from a viewpoint of sensitivity, and 90 mass% or less is preferable from a viewpoint of developability.
From the viewpoint of the surface state of the resist pattern obtained after development, it is preferable to use a novolac resin or a polyhydroxystyrene resin alone as the alkali-soluble resin having a phenolic hydroxyl group.
From the viewpoint of the cross-sectional shape of the resist pattern obtained after development, an alkali-soluble resin having a phenolic hydroxyl group can be appropriately selected. For example, when a novolac resin is used, the cross-sectional shape tends to be a dome shape, and when a polyhydroxystyrene resin is used, it tends to be a rectangular shape.

The photoacid generator is a compound that generates an acid directly or indirectly by light. Specifically, 2,4-bis (trichloromethyl) -6- [2- (2-furyl) ethenyl]- s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-Ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl] -s-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-diethoxyphenyl) ) Ethenyl] -s-triazi 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3- Methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] -s-triazine, 2,4- Bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) -S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo 4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo -4methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2 -(5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) ethenyl] -4,6 - Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4-trichloromethyl (piperonyl) -6-triazine, tris (1,3-dibromo Halogen-containing triazine compounds such as propyl) -1,3,5-triazine and tris (2,3-dibromopropyl) -1,3,5-triazine and halogen-containing compounds such as tris (2,3-dibromopropyl) isocyanurate An isocyanurate compound is mentioned.

As photoacid generators, α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6 -Dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, or a compound represented by the following general formula (II):

{Wherein R ³ represents a monovalent to trivalent organic group, R ⁴ represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group; and n is 1 Indicates a natural number of ~ 3. }.
Here, the aromatic compound group refers to a group of a compound exhibiting physical and chemical properties peculiar to an aromatic compound, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, a furyl group, Examples include aromatic heterocyclic groups such as thienyl groups. These may have one or more suitable substituents on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like. Furthermore, R ³ is particularly preferably an alkyl group having 1 to 4 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group. In particular, in the compound of the formula (II), a compound in which R ³ is an aromatic compound group and R ⁴ is a lower alkyl group is preferable. The photoacid generator represented by the general formula (II) is a compound in which when n = 1, R ³ is any one of a phenyl group, a methylphenyl group and a methoxyphenyl group, and R ⁴ is a methyl group Specifically, α- (methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- ( p-methoxyphenyl) acetonitrile.

Examples of the photoacid generator include bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (2,4-dimethylphenylsulfonyl) diazomethane. Bissulfonyldiazomethanes; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate Nitrobenzyl derivatives such as pyrogallol trimesylate, pyrgallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloro Sulfonic acid esters such as tilsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methylsulfonyloxyphthalimide; diphenyliodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butyl) Onium salts such as (phenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate; benzoin tosylate, α -Benzoin tosylates such as methylbenzoin tosylate; E sulfonyl iodonium salts, triphenyl sulfonium salts, phenyl diazonium salts, benzyl carbonate and the like.

In particular, triazine compounds are preferably used because of their high performance as a photoacid generator and good solubility even when a solvent is used. Among these, the following general formula (III):

Bromo-containing triazine compounds, particularly 2,4-bis-trichloromethyl-6- (3-bromo-4methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- ( 3-Bromo-4-methoxy) styryl-s-triazine and tris (2,3-dibromopropyl) isocyanurate can be preferably used.

The photoacid generator is in the range of 0.01 to 5% by weight, preferably 0.05 to 1% by weight, more preferably 0.1 to 0.5% by weight, based on 100% by weight of the photosensitive resin composition. Can be contained. The photoacid generator is preferably 0.01% by mass or more from the viewpoint of sensitivity with respect to 100% by mass of the photosensitive resin composition, and preferably 5 parts by weight or less from the viewpoints of storage stability, resolution, and exposure margin.

As the compound having a group that crosslinks by the action of an acid, amino compounds such as melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin, and ethyleneurea-formaldehyde resin can be used. In particular, alkoxymethylated amino resins such as alkoxymethylated melamine resins and alkoxymethylated urea resins can be suitably used. The alkoxymethylated amino resin, for example, reacts a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution with lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, and isopropyl alcohol. To form an ether, and then the reaction solution is cooled and precipitated. Specific examples of the alkoxymethylated amino resin include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethylated urea resin, ethoxymethylated urea resin, and propoxymethyl. And urea-oxygenated resin, butoxymethylated urea resin, and the like. The said alkoxymethylated amino resin can be used individually or in combination of 2 or more types. In particular, an alkoxymethylated melamine resin is preferable because a dimensional change amount of the resist pattern with respect to a change in radiation dose is small and a stable resist pattern can be formed. Among these, methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin or butoxymethylated melamine resin is preferable.

Examples of the alkoxymethylated melamine resin include Nicarak MX-750, Nicarak MX-706, Nicarak MX-101, Nicarak MX-032, Nicarax MX-708, Nicarac MX-40, Nicarac MX-31, Nicarac MS-11, Nicarac MW -22, Nicalac MW-30, MW-30HM, MW-100LM, Nicalac MW-390 (all of which are manufactured by Sanwa Chemical Co., Ltd.). You may use these individually or in combination of 2 or more types. An example of the alkoxymethylated urea resin is MX-290 (manufactured by Sanwa Chemical Co., Ltd.).

The compound having a group capable of crosslinking by the action of an acid can be contained in an amount of 1 to 40% by mass, preferably 5 to 20% by mass, based on 100% by mass of the photosensitive resin composition. The compound having a group that crosslinks by the action of an acid in the photosensitive resin composition is preferably 1 part by weight or more from the viewpoint of sensitivity and etching resistance, and 40 parts by weight or less from the viewpoint of storage stability and a residue after development. Is preferred.

Examples of plasticizers include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tricitrate tri-n-propyl, A block copolymer of tri-n-butyl acetyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, polyethylene glycol polypropylene glycol (also called pluronic type) and its dialkyl ether, monoalkyl ether, etc. Can be mentioned.

Furthermore, a plasticizer represented by the following general formula (I) can be preferably used.

{Wherein R ¹ and R ² are ethylene groups or propylene groups, R ¹ and R ² are different from each other, m1, n1, m2, and n2 are each 0 or more, and m1 + n1 + m2 + n2 is And the repeating structure of — (O—R ¹ ) — and — (O—R ² ) — may be random or block, and — (O—R ¹ ) — And the repeating structure of — (O—R ² ) — may be on the bisphenyl group side. }.
The compound represented by the above general formula (I) is synthesized by adding ethylene oxide or propylene oxide to both ends of bisphenol A. m1 + n1 + m2 + n2 is 30 or less in order to obtain sufficient sensitivity and adhesion, and is 2 or more from the viewpoint of compatibility in the photosensitive resin composition and an increase in viscosity. m1 + n1 + m2 + n2 is preferably 2 to 20 and more preferably 2 to 10 from the viewpoints of resolution and adhesion. Furthermore, from the viewpoint of resolution, adhesion, cohesiveness, and phenomenon, R ³ is an ethylene group, R ⁴ is a propylene group, m1 + m2 is 0, and n1 + n2 is 2 to 10 A compound represented by the formula (I) is more preferable.

Specific examples of the compound represented by the general formula (I) include Adecanol (trademark) SDX-1569 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 0, n1 = n2 = 1]. , Adecanol ™ SDX-1570 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 0, n1 = n2 = 3], Adecanol ™ SDX-1571 [R ¹ : ethylene group, R ² = Propylene group, m1 = m2 = 0, n1 = n2 = 5], Adecanol ™ SDX-479 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 5, n1 = n2 = 0] ( Asahi Denka Co., Ltd.)
Newpol ™ BP-23P [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 0, n1 = n2 = 1], Newpol ™ BP-3P [R ¹ : ethylene group, R ² : Propylene group, m1 = m2 = 0, n1 = n2 = 1.5], Newpol ™ BP-5P [R ¹ : Ethylene group, R ² : Propylene group, m1 = m2 = 0, n1 = n2 = 2.5], New Pole ™ BPE-20T [R ¹ = ethylene group, R ² = propylene group, m1 = m2 = 1, n1 = n2 = 0], New Pole ™ BPE-60 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 3, n1 = n2 = 0], Newpol ™ BPE-100 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 5 , N1 = n2 = 0], New Pole ™ B E-180 (all manufactured by Sanyo Chemical Industries (Ltd.)) [R ^1:: ethylene group, R ² a propylene group, m1 = m2 = 9, n1 = n2 = 0],
Uniol ™ DB-400 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 0, n1 = n2 = 1.5], Uniol ™ DAB-800 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 6, n1 = n2 = 4.5,-(R ¹ -O)-and-(R ² -O)-are random], Uniol (trademark) DA-350F [R ¹ : an ethylene group, R ^2: a propylene group, m1 = m2 = 1.1, n1 = n2 = 0], UNIOL (TM) DA-400 [R ^1: an ethylene group, R ^2: a propylene group, m1 = m2 = 2 , N1 = n2 = 0], Uniol (trademark) DA-700 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 5, n1 = n2 = 0] (manufactured by NOF Corporation),
BA-P4U [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 0, n1 = n2 = 2] glycol, BA-P8 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 0, n1 = n2 = 4] glycol (made by Nippon Emulsifier Co., Ltd.) and the like.

The content of the plasticizer is preferably 1% by mass or more and 40% by mass or less in 100% by mass of the photosensitive resin composition. 1 mass% or more is preferable from the viewpoint of development speed and resolution, and 40 mass% or less is preferable from the viewpoint of resin adhesion and adhesion. More preferably, it is 5 mass% or more and 30 weight% or less.
The weight average molecular weight of the plasticizer is preferably 100 to 5,000. From the viewpoint of sublimation, it is 100 or more, and from the viewpoint of developability, it is 5,000 or less. More preferably, it is 100 to 3,000.

The photosensitive resin composition can also contain the component demonstrated below.
First, from the viewpoint of developability, an alkali-soluble polymer having a carboxyl group is preferably included. The amount of the carboxyl group is preferably 100 to 600, more preferably 250 to 450 in terms of acid equivalent. The acid equivalent means the mass of the alkali-soluble polymer having 1 equivalent of a carboxyl group therein.

The weight average molecular weight of the alkali-soluble polymer having a carboxyl group is preferably 5,000 to 500,000. The weight average molecular weight is preferably 500,000 or less from the viewpoint of resolution, and is preferably 5,000 or more from the viewpoint of peelability of the support layer after lamination or exposure. The weight average molecular weight is more preferably 5,000 to 200,000, still more preferably 5,000 to 100,000. The degree of dispersion (also referred to as molecular weight distribution) is obtained as a value obtained by dividing the weight average molecular weight by the number average molecular weight. The degree of dispersion is about 1 to 6, preferably 1 to 4.

The acid equivalent is measured by a potentiometric titration method using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., and using a 0.1 mol / L sodium hydroxide aqueous solution.
The molecular weight is gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M, KF -806M, KF-802.5) 4 in series, moving bed solvent: tetrahydrofuran, using polystyrene standard sample (use calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) as the weight average molecular weight (polystyrene conversion) It is done.

The alkali-soluble polymer having a carboxyl group can be obtained by copolymerizing one or more monomers from the following two types of monomers.
The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like.
In the present invention, (meth) acryl represents acryl and / or methacryl.

The second monomer is a non-acidic compound having one polymerizable unsaturated group in the molecule. The compound is selected so as to maintain various properties such as developability of the photosensitive resin layer, resistance to etching and plating processes, and flexibility of the cured film. Examples of the compound include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, (meth) acrylonitrile, benzyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, furfryl (meth) acrylate, tetrahydrofurfryl (meth) acrylate, Aryl (meth) acrylates such as phenoxyethyl (meth) acrylate, phenyl (meth) acrylate, cresyl (meth) acrylate, naphthyl (meth) acrylate, vinyl having a phenyl group Compounds (e.g., styrene), or the like can be used. From the viewpoint of compatibility with an alkali-soluble polymer having a phenolic hydroxyl group, benzyl (meth) acrylate is preferred.

The alkali-soluble polymer having a carboxyl group is prepared by diluting a mixture of the first monomer and the second monomer with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to synthesize by adding an appropriate amount of a radical polymerization initiator such as butyronitrile and stirring with heating. An alkali-soluble polymer having a carboxyl group can also be synthesized while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust the alkali-soluble polymer having a carboxyl group to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

The ratio of the alkali-soluble polymer having a carboxyl group to the entire photosensitive resin composition is preferably in the range of 5 to 50% by mass, more preferably 10 to 30% by mass. In the photosensitive resin composition, the alkali-soluble polymer having a carboxyl group is preferably 50% by mass or less from the viewpoint of sensitivity, and 5 from the viewpoint of the support film peelability after lamination or exposure, the developability, and the residue after development. The mass% or more is preferable.

From the viewpoint of resolution, the photosensitive resin composition may further contain an ultraviolet absorber. Examples of the ultraviolet absorber include p-aminobenzophenone, p-butylaminoacetophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p′-bis (ethylamino) benzophenone, p, p′-bis ( And dimethylamino) benzophenone [Michler's ketone], p, p′-bis (diethylamino) benzophenone, p, p′-bis (dibutylamino) benzophenone, and the like.
The cross-sectional shape of the resist pattern can be controlled by adding an ultraviolet absorber. For example, when the cross-sectional shape of the resist pattern is a dome shape, an ultraviolet absorber such as p, p′-bis (diethylamino) benzophenone can be appropriately added to make the shape close to a rectangular shape.

Hereinafter, the manufacturing method of the photosensitive resin laminated body of this invention is demonstrated as an illustration.
First, an alkali-soluble resin having a phenolic hydroxyl group, a photoacid generator, a compound having a group that is cross-linked by the action of an acid, a plasticizer, and other components as appropriate depending on the required performance, are blended into a photosensitive resin composition. Formulate. Suitable solvents used include ketones represented by methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. This is applied to the support layer using a blade coater, bar coater, roll coater, or the like, and dried to form a photosensitive resin layer. When creating a long one, a die coater, a gravure coater or the like can be used. When using a die coater, it is preferable to adjust the viscosity to be 500 to 4,000 mPa · sec at 25 ° C. In the case of using a gravure coater, it is preferable to adjust the viscosity to be 1 to 200 mPa · sec at 25 ° C. Next, a photosensitive resin laminate can be produced by laminating a protective layer.

It is also possible to laminate another resin layer on the support layer and further apply a photosensitive resin composition. Another resin layer may be exposed after peeling the support layer simply for process reasons, or when it is exposed after peeling the support layer to eliminate the influence of foreign matter on the support layer and the lubricant in the support layer. In some cases, it is provided for the purpose of blocking the base component in the air. Moreover, when the photosensitive resin layer cannot be made thick enough, it may be provided for the purpose of the photosensitive resin layer following the unevenness of the base material.

The thickness of the photosensitive resin layer can be appropriately adjusted according to the application. When used in the production of TFTs, the thickness of the photosensitive resin layer is preferably 10 μm or less from the viewpoint of electrode resolution, and preferably 0.5 μm or more from the viewpoint of etching resistance. The thickness of the photosensitive resin layer is more preferably 1 μm or more and 8 μm or less. More preferably, they are 1 micrometer or more and 5 micrometers or less.

For example, the TFT electrode can be produced as follows.
(1) The process of laminating to a base material so that a photosensitive resin layer may touch a base material When there is a protective layer in the photosensitive resin laminated body, the photosensitive resin layer of the photosensitive resin laminated body while peeling off the protective layer Is adhered to a base material obtained by laminating a metal film such as molybdenum, aluminum, neodymium, chromium, tungsten, or tantalum on a silicon wafer or glass by using a hot roll laminator.

(2) The process of exposing a photosensitive resin layer A desired electrode pattern is projected on a photosensitive resin laminated body through a glass chromium mask, and the photosensitive resin laminated body is exposed. Examples of the active light source include a high pressure mercury lamp, an ultra high pressure mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, and a xenon lamp. The exposure method includes a proximity method in which a mask is projected as it is several tens of μm above the base material, a mirror projection aligner method using a concave mirror, and a stepper method in which divided projection exposure is performed through a lens at a reduction magnification smaller than 1 ×. Alternatively, the photosensitive resin laminate may be exposed by drawing actinic rays on the photosensitive resin laminate in accordance with a pre-programmed electrode pattern. Examples of the active light source include a semiconductor laser, a semiconductor solid laser, and an ultrahigh pressure mercury lamp. Examples of the light beam scanning method include a polygon mirror method and a digital mirror device method. The support layer may be peeled off before the exposure step or may be peeled off after the exposure. From the viewpoint of resolution, it is preferable to expose the photosensitive resin layer after peeling the support layer. On the other hand, from the viewpoint of sensitivity, it is preferable to peel the support layer after exposure.

(3) The process of heating the exposed photosensitive resin layer The base material after exposure is heated with oven, a hotplate, etc. Temperature and time can be adjusted according to the sensitivity. 90 degreeC or more is preferable from a viewpoint of fully hardening the exposed photosensitive resin layer. 130 degreeC or less is preferable from a viewpoint of resolution and time control of a heating process. The heating time is preferably 10 minutes or less from the viewpoint of productivity, and preferably 15 seconds or more from the viewpoint of stability of resolution.

(4) The process of developing the heated photosensitive resin layer The unexposed part of the photosensitive resin layer is melt | dissolved or disperse | distributed and removed using an alkali developing solution, and a cured resist pattern is formed on a base material. As the alkali developer, it is preferable to use an organic alkali aqueous solution such as tetramethylammonium hydroxide in consideration of the influence on the semiconductor.

(5) Step of wet etching or dry etching In wet etching, an etching solution is sprayed from the formed resist pattern to etch the substrate not covered with the resist pattern. When the base material is molybdenum, aluminum, niobium, or the like, a mixed acid aluminum solution in which nitric acid, phosphoric acid, acetic acid, or the like is mixed can be used. When the substrate is amorphous silicon, polysilicon, silicon nitride, etc., it can be etched by dry etching, reactive ion etching, or the like.

(6) Step of peeling The resist pattern is removed from the substrate with an alkaline stripping solution. A stripping solution in which an organic amine such as monoethanolamine or triethanolamine is mixed with glycol, dimethyl sulfoxide, water, or the like can be used.

In the following examples, preferred examples of embodiments of the present invention will be specifically described.
[Examples 1 to 7, Example 10, and Comparative Examples 1 and 2]
<1. Preparation of photosensitive resin composition>
The compounds shown in Table 1 were mixed to prepare a photosensitive resin composition. The values in Table 1 are solid contents.
The symbols in the table are as shown below.
A-1: Cresol novolak resin, weight average molecular weight 10,000, molecular weight distribution about 10, m isomer: p isomer = 6: 4 (Asahi Organic Materials Co., Ltd., EP4020G (trade name))
A-2: Copolymer obtained by copolymerizing 80% by mass of benzyl methacrylate and 20% by mass of methacrylic acid, weight average molecular weight 25,000
A-3: Polyparahydroxystyrene, weight average molecular weight 20,000 (manufactured by Chemiway Corporation, Marcalinker MH-2P (trade name))
B-1: Hexamethoxymethylated melamine resin, loss on drying 1% by weight, monomer 96% by weight or more (MW-390 (trade name) manufactured by Sanwa Chemical Co., Ltd.)
C-1: 2,4-trichloromethyl (piperonyl) -6-triazine (manufactured by Nippon Sebel Hegner, Triazine PP (trade name))
C-2: p, p′-bis (diethylamino) benzophenone D-1: a compound having 3 moles of propylene glycol at both ends of bisphenol A (manufactured by Asahi Denka Kogyo Co., Ltd., polyether BPX-33 (trade name) ))
D-2: Polypropylene glycol (molecular weight 2000)

<2. Production of photosensitive resin laminate>
The above photosensitive resin composition is dissolved in a solvent (methyl ethyl ketone), and uniformly coated on the film shown in Table 1 using a blade coater, dried in a dryer at 95 ° C. for 1 minute, and 5 μm thick. The photosensitive resin layer was formed. The film shown in Table 1 was produced as follows.
As the film (a-1) having a release layer, a commercially available product (PET25X manufactured by Lintec Corporation) was used.
A film (b-1) having an alkali-soluble resin layer was produced as follows. 70% by mass of a terpolymer (weight average molecular weight 70,000, acid equivalent 344) of 65% by mass of methyl methacrylate, 25% by mass of methacrylic acid and 10% by mass of butyl acrylate, 15% by mass of B-1 and C -1 was mixed by 0.5% by mass and D-1 was mixed by 15% by mass, and dissolved in methyl ethyl ketone to prepare a uniform composition solution. This was uniformly applied to a polyester film having a thickness of 16 μm (manufactured by Toray Industries, Inc., 16QS48 (level 3)) using a blade coater and dried in a dryer at 95 ° C. for 2 minutes. An alkali-soluble resin layer was produced.
A film (c-1) having a water-soluble resin layer was produced as follows. Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., PVA-205), 90% by mass, polyethylene glycol monomethyl ether having an average molecular weight of 550 (Niox M-550 manufactured by Nippon Oil & Fats Co., Ltd.), 10% by mass, mixed with hot water To obtain a uniform water-soluble resin solution. This was uniformly applied to a 16 μm thick polyester film (manufactured by Toray Industries, Inc., 16QS48 (level 3)) using a blade coater and dried for 2 minutes in a 95 ° C. drier to obtain a thickness of 2 μm. An alkali-soluble resin layer was prepared.
For the film (d) in Table 1, a commercially available polyester film having a thickness of 19 μm (G2 manufactured by Teijin DuPont Co., Ltd.) was used as it was as a support layer, and a photosensitive resin layer was applied thereto.

<3. Creation of evaluation board>
Base material :
As a base material, a base material obtained by laminating 300 layers of Mo film on a 5-inch N-type silicon wafer was used.
Laminate:
The photosensitive resin laminate from which the protective layer was peeled off was laminated on the substrate using a laminator (MKR210 (trade name) manufactured by MCK). The conditions were laminating speed: 1.0 m / min, laminating roll temperature: 120 ° C., cylinder pressure: 0.40 MPa.
exposure:
The support layer is peeled off, and an evaluation substrate is projected at an exposure amount of 30 mJ / cm ² using an exposure machine (projection exposure apparatus UX2003SM-MS04: manufactured by Ushio Electric Co., Ltd.) having an ultrahigh pressure mercury lamp using a chromium glass photomask. Exposed. In any of Examples 1 to 7 and Examples 8 and 9 below, the support layer could be peeled off without any problem. The part exposed here becomes a cured resist.
Post-exposure heating:
After the exposure, the substrate was heated on a hot plate at 100 ° C. for 30 seconds.
developing:
When there is a support layer from the obtained evaluation substrate, the support layer is removed, and a 2.38 mass% aqueous solution of tetoramethylammonium is used as an alkali developer to perform spray development at a temperature of 30 ° C. and a spray pressure of 0.25 MPa. The unexposed part of the conductive resin layer was removed, washed with tap water and dried to obtain a resist pattern. As the developing device, an AD-1200 spin developing machine manufactured by Takizawa Sangyo Co., Ltd. was used.
etching:
The substrate on which the resist pattern was formed was etched by a dipping method at 40 ° C. for 30 seconds at Wako Pure Chemical Industries Aluminum Aluminum Solution.
Peeling:
The etched substrate was etched by a dip method, semi-clean EP-10 stripping solution manufactured by Yokohama Oil & Fat Co., Ltd., 65 ° C., 20 seconds.

<4. Evaluation>
The evaluation substrate was evaluated by the following method, and the results are summarized in Table 1 below.
Evaluation of resin adhesion to protective film:
A photosensitive resin laminate was prepared, and a polyethylene film (GF-858 (trade name) manufactured by Tamapoly Co., Ltd.) as a protective layer was hand laminated and stored at room temperature for 3 weeks. When the protective layer was peeled off, the adhesion of the resin to the surface of the protective layer was evaluated and ranked as follows.
○: Resin adhesion is not observed Δ: Resin adhesion is partially observed ×: Resin adheres as a whole

Evaluation of minimum development time:
The support layer was peeled off from the substrate on which the photosensitive resin laminate was laminated, and developed. The time from the start of development until the surface of the base material was exposed was measured and defined as the minimum development time. The minimum development time was ranked as follows.
○: Minimum development time within 60 seconds Δ: Minimum development time over 60 seconds and within 3 minutes ×: Minimum development time over 3 minutes

Resolution evaluation:
It was exposed through a chrome glass photomask having a pattern with 1: 1 lines and spaces, heated and developed. The mask width corresponding to the minimum resist pattern to be resolved was evaluated as a resolution value.
○: Resolution is 4 μm or less Δ: Resolution exceeds 4 μm, 8 μm or less ×: Resolution exceeds 8 μm

Evaluation of adhesion:
It was exposed through a chrome glass photomask having a pattern of independent lines of various widths, heated and developed. The mask width corresponding to the minimum independent resist pattern obtained without peeling was evaluated as the adhesion value.
○: Adhesiveness is 4 μm or less Δ: Adhesiveness exceeds 4 μm, 8 μm or less ×: Adhesiveness exceeds 8 μm

Evaluation of etching property:
The evaluation board | substrate obtained by evaluation of resolution was etched, and it was observed in SEM whether there was any peeling of a resist pattern.
○: No peeling of resist pattern ×: The resist pattern is peeled off and the substrate surface is exposed

Evaluation of peelability:
The resist was peeled from the evaluation substrate obtained by the evaluation of etching property, and it was confirmed by SEM whether there was any resist residue on the surface of the base material after peeling.
○: No resist residue ×: Resist residue is confirmed

Evaluation of resist pattern surface condition:
The evaluation board | substrate obtained by evaluation of resolution was observed by SEM, and the flatness of the top part and side surface of a resist pattern was observed.
○: Resist top is uniform Δ: Slight irregularities are seen on resist top and side x: Unevenness is seen on resist side and pattern linearity is impaired

[Example 8]
A resist pattern was prepared in the same manner as in Example 1 except that the exposure process was drawn by an Orbotech Paragon 9000 with an output of 8 W and an exposure amount of 30 mJ / cm ² . Both resolution and adhesion were 6 μm. There was no peeling of the resist pattern after etching, and no residue was found after the resist was peeled off.

[Example 9]
A photosensitive resin laminate was prepared and evaluated in the same manner as in Example 1 except that the protective layer was a stretched polypropylene film (Alphan E-200A (trade name) manufactured by Oji Paper Co., Ltd.).

[Example 10]
D-1: Polypropylene glycol (molecular weight 2000) instead of a compound having 3 moles of propylene glycol at both ends of bisphenol A (Asahi Denka Kogyo Co., Ltd., polyether BPX-33 (trade name)) A photosensitive resin laminate was prepared and evaluated in the same manner as in Example 1 except that was used.

[Examples 11 and 12]
The cross-sectional shape of the resist pattern was observed in Examples 11 and 12 (see Table 2 below). In Example 11, a rectangular resist pattern was obtained by using A-3 alone. In Example 12, a rectangular resist pattern was obtained by adding C-2.

[Examples 13 and 14]
As a base material, a resist pattern was prepared in the same manner as in Example 11 using an a-Si substrate in which 1500 nm of amorphous silicon was laminated on glass by a CVD method (Example 13). As a base material, a resist pattern was prepared in the same manner as in Example 11 using a SiN substrate in which 3000 nm of silicon nitride was laminated on glass by a CVD method (Example 14). In both cases, the same resolution and adhesion as in the case of using a Mo base material were obtained (see Table 3 below).

[Examples 15 and 16]
Using the photosensitive resin laminate used in Example 1, linear steps having a height of 3.5 μm, a width of 30 μm, a length of 1.5 mm, and a pitch of 300 μm were previously formed on a glass substrate. On this base material, the photosensitive resin laminate used in Example 1 was laminated along a linear step, and the occurrence of air voids was observed. Further, the linear pattern was exposed and developed so as to be orthogonal to the linear step, and the disconnection of the pattern was observed (Example 15). A similar experiment was carried out using the photosensitive resin laminate used in Example 2 (Example 16). In Example 15, the occurrence of air voids was seen beside the step, and the formed pattern was broken. In Example 16, there was no air void on the side of the step, and no disconnection of the pattern was observed.

[Comparative Example 3]
The photosensitive resin composition used in Example 1 was directly applied to a substrate by spin coating. The same substrate as that used in Example 1 was used. When the photosensitive resin laminate of Example 1 was used to laminate to a substrate, the time required for lamination was about 10 seconds. On the other hand, it took about 5 minutes to apply and dry the photosensitive resin composition by spin coating. During the spin coating and drying, it was necessary to exhaust the volatilized solvent. Moreover, the photosensitive resin composition was swelled along the edge part of a board | substrate, and the nonuniformity was seen. Radial unevenness from the center of rotation and unevenness at the portion where the substrate was sucked (chucked) were also observed.

The present invention has excellent resolution and adhesion to various substrates such as polysilicon, amorphous silicon, copper, molybdenum, chromium, tungsten, tantalum, etc., has good developability, etching property and peeling A photosensitive resin laminate having excellent properties can be provided and can be suitably used in the production of TFTs.

Claims

At least the support layer and the following (a) to (c):
(A) a release layer,
(B) an alkali-soluble resin layer,
(C) a water-soluble resin layer,
A photosensitive resin laminate in which at least one layer selected from the layers shown in the above and a photosensitive resin layer made of a photosensitive resin composition are sequentially laminated, and the photosensitive resin composition is phenolic 20 to 90% by mass of an alkali-soluble resin having a hydroxyl group, 0.01 to 5% by mass of a photoacid generator, 1 to 40% by mass of a compound having a group capable of crosslinking by the action of an acid, and 1 to 40% by mass of a plasticizer. The said photosensitive resin laminated body characterized by the above-mentioned.
The photosensitive resin laminate according to claim 1, wherein the photosensitive resin composition further comprises an alkali-soluble polymer having a carboxyl group.
The plasticizer has the following general formula (I):

{Wherein R 1 and R 2 are an ethylene group or a propylene group, and R 1 and R 2 are different from each other, m1, n1, m2, and n2 are each 0 or more, and m1 + n1 + m2 + n2 is And the repeating structure of — (O—R 1 ) — and — (O—R 2 ) — may be random or block, and — (O—R 1 ) — When - (O-R 2) - one of the repeating structure may be a bis phenyl group side. } The photosensitive resin laminated body of Claim 1 or 2 which is a compound represented by these.
A step of laminating the photosensitive resin laminate according to claim 1 or 2 on the substrate such that the photosensitive resin layer is in contact with the substrate, a step of exposing the photosensitive resin layer, and an exposed photosensitive resin. A method for producing a resist pattern, comprising a step of heating a layer and a step of developing the heated photosensitive resin layer.
The method for producing a resist pattern according to claim 4, wherein the step of exposing the photosensitive resin layer is a method of drawing actinic rays.
A method for producing an electrode pattern, comprising a step of wet etching a portion of a base material that is not covered with the resist pattern produced by the method according to claim 4.
A method for producing a semiconductor pattern, comprising a step of dry etching a portion of a base material that is not covered with the resist pattern produced by the method according to claim 4.
The method for producing a resist pattern according to claim 4 or 5, wherein the surface of the substrate in contact with the photosensitive resin layer is molybdenum.
The electrode pattern manufacturing method according to claim 6, wherein the surface of the base material in contact with the photosensitive resin layer is molybdenum.
The method for producing a resist pattern according to claim 4 or 5, wherein the surface of the base material in contact with the photosensitive resin layer is amorphous silicon.
The method for producing a resist pattern according to claim 4 or 5, wherein the surface of the base material in contact with the photosensitive resin layer is silicon nitride.