JP2018005250A - Method for forming resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a resist pattern excellent in resolution and adhesiveness.SOLUTION: The method for forming a resist pattern includes steps of: (1) laminating a photosensitive resin composition layer on a substrate to form a laminate of a dry film resist having the photosensitive resin composition layer and the substrate; (2) exposing the photosensitive resin composition layer of the laminate; (3) heating both the exposed photosensitive resin composition layer and the substrate under pressure by use of a press-heating mechanism; and (4) developing the exposed photosensitive resin composition layer after heating.SELECTED DRAWING: None

Description

  The present invention relates to a resist pattern forming method.

  Conventionally, a printed wiring board is generally manufactured by a photolithography method. The photolithographic method is a method in which a photosensitive resin composition is applied onto a substrate, pattern exposure is performed, and an exposed portion of the photosensitive resin composition is polymerized and cured (in the case of a negative type) or solubilized in a developer (positive). Mold) and unexposed areas (in the case of negative molds) or exposed areas (in the case of positive molds) are removed with a developer to form a resist pattern on the substrate, and etching or plating is performed to form a conductor pattern. After forming, the resist pattern is peeled off from the substrate to form a conductor pattern on the substrate.

  In the photolithography method, usually, when a photosensitive resin composition is applied onto a substrate, the photosensitive resin composition solution is applied to the substrate and dried, or a support or a photosensitive resin composition is used. A method of laminating a photosensitive resin laminate (hereinafter also referred to as “dry film resist”) in which a layer (hereinafter also referred to as “photosensitive resin composition layer”) and, if necessary, a protective layer, are sequentially laminated on a substrate. One of these is used. In the production of printed wiring boards, the latter dry film resist is often used.

A method for producing a printed wiring board using the dry film resist will be briefly described below.
First, when the dry film resist has a protective layer, for example, a polyethylene film, it is peeled off from the photosensitive resin composition layer. Next, a photosensitive resin composition layer and a support layer are laminated on a substrate such as a copper clad laminate using a laminator so that the substrate, the photosensitive resin composition layer, and the support layer are in this order. In addition, some laminating methods include a temporary attachment process. In this case, first, the temporary block is lowered to the substrate in a state where the support and the photosensitive resin composition layer are adsorbed to the temporary block by vacuum adsorption, and the photosensitive resin composition layer is temporarily bonded to the substrate. Next, after the vacuum is released, the temporary block is lifted, and at the same time when the support and the photosensitive resin composition layer are separated from the temporary block, the laminate roll comes down and lamination begins. Next, the exposed portion (for example, in the case of a negative type) is polymerized by exposing the photosensitive resin composition layer to ultraviolet rays containing i-line (365 nm) emitted from an ultrahigh pressure mercury lamp through a photomask having a wiring pattern. Harden. The support layer, such as polyethylene terephthalate, is then peeled off. Next, an unexposed portion (for example, in the case of a negative type) of the photosensitive resin composition layer is dissolved or dispersed and removed by a developer, for example, an aqueous solution having weak alkalinity, to form a resist pattern on the substrate.

  As a method for producing a metal conductor pattern using the resist pattern on the substrate thus formed, there are roughly two methods. The first method is a method in which a substrate surface not covered with a resist pattern (for example, a copper surface such as a copper-clad laminate) is removed by etching, and then the resist pattern portion is removed with an alkaline aqueous solution stronger than the developer. In this case, for the simplicity of the process, a technique (tenting method) in which a through hole (through hole) is covered with a cured film and then etched is frequently used. The second method is to perform copper plating on the same substrate surface (for example, on the copper surface), and if necessary, after further plating with solder, nickel, tin, etc., similarly, removing the resist pattern portion, Further, it is a method (plating method) for etching the substrate surface that appears (for example, a copper surface of a copper-clad laminate or the like). For etching, an acidic etching solution such as cupric chloride, ferric chloride, copper ammonia complex solution, sulfuric acid / hydrogen peroxide aqueous solution or the like is used.

With the recent miniaturization of wiring intervals in printed wiring boards, dry film resists are required to have high resolution and high adhesion in order to produce narrow pitch patterns with good yield. In order to impart high adhesion, the exposure amount is often increased, but increasing the exposure amount often sacrifices high resolution. This is because by increasing the exposure amount, the amount of radicals generated increases, and as a result, the reaction proceeds to the next line in a narrow pitch line, and the line may be formed like a bridge. is there.
Patent Document 1 describes a method for forming a resist pattern, which includes a step of exposing, heating, and developing a laminate in which a substrate, a photosensitive resin layer, and a support layer are laminated. ing.

JP 2005-266347 A

  According to the method of making the exposure amount appropriate and performing heating after exposure, there is a possibility that both high resolution and high adhesion can be satisfied. This is because the exposure amount is appropriate, the amount of radicals generated is appropriate, and the reaction of the generated radicals is a thermal reaction, which can be promoted by heat treatment. .

  However, Patent Document 1 does not mention that a pressure is applied during heating for the heat treatment method. An object of the present invention is to provide a resist pattern forming method capable of forming a narrow pitch wiring pattern and providing a resist pattern having excellent adhesion.

  In the present invention, as a result of intensive studies to solve the above problems, it has been found that the above problems can be solved by the following technical means.

｛式中、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子又はメチル基を表し、Ｘは、炭素数２〜６のアルキレン基を表し、複数存在する場合のＸは互いに同一でも異なっていてもよく、ｎ₁及びｎ₂は、それぞれ独立に、０又は正の整数であり、そしてｎ₁＋ｎ₂は、２〜４０である。｝で表される化合物を含む、上記［８］記載のレジストパターン形成方法。
［１０］ 該（Ｃ）光重合開始剤は、ヘキサアリールビスイミダゾール化合物を含む、上記［８］又は［９］に記載のレジストパターン形成方法。 [1] Each of the following steps:
(1) Laminating a photosensitive resin composition layer on a substrate to form a laminate of a dry film resist having the photosensitive resin composition layer and the substrate;
(2) a step of exposing the photosensitive resin composition layer of the laminate,
(3) A step of heating the exposed photosensitive resin composition layer and the substrate together under pressure using a pressure heating mechanism,
(4) a step of developing the exposed photosensitive resin composition layer after the heating;
A method for forming a resist pattern, comprising:
[2] The resist pattern forming method according to the above [1], wherein in the step (3), the pressure heating mechanism is a hot roll.
[3] The resist pattern forming method according to the above [1] or [2], wherein in the step (3), the heating temperature in the heating under the pressure is in the range of 50 ° C to 130 ° C.
[4] In any one of the above [1] to [3], in the step (3), a pressing force in heating under the pressing is 1.9 kg / cm to 8.6 kg / cm as a linear pressure. Resist pattern forming method.
[5] The resist pattern forming method according to any one of [1] to [4], wherein in the step (3), the pressure heating mechanism is cleaned with a clean roller before heating under the pressure.
[6] Resist pattern formation according to any one of [1] to [5], wherein heating is performed under pressure in step (3) within 3 minutes from the end of exposure in step (2). Method.
[7] The resist according to any one of [1] to [6], wherein, in the step (3), the heating time under the pressing is 1 second to 20 seconds with respect to a substrate length of 250 mm. Pattern forming method.
[8] The photosensitive resin composition layer in the step (1) has the following components based on the total solid content of the photosensitive resin composition:
(A) Alkali-soluble polymer: 10% by mass to 90% by mass,
(B) Compound having ethylenically unsaturated bond: 5% by mass to 70% by mass, and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass,
The (A) alkali-soluble polymer has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000, and the (A) alkali The method for forming a resist pattern according to any one of [1] to [7], wherein the soluble polymer has an aromatic group in a side chain.
[9] The compound (B) having an ethylenically unsaturated bond is represented by the following general formula (I):

{In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group; X represents an alkylene group having 2 to 6 carbon atoms; N ₁ and n ₂ are each independently 0 or a positive integer, and n ₁ + n ₂ is 2 to 40. } The resist pattern formation method of the said [8] description containing the compound represented by these.
[10] The resist pattern forming method according to [8] or [9], wherein the (C) photopolymerization initiator includes a hexaarylbisimidazole compound.

  ADVANTAGE OF THE INVENTION According to this invention, the formation method of a resist pattern which can form the wiring pattern of a narrow pitch and can provide the resist pattern which is excellent in adhesiveness can be provided.

  Hereinafter, an exemplary form for carrying out the present invention (hereinafter abbreviated as “this embodiment”) will be specifically described.

<Resist pattern formation method>
The present invention includes the following steps:
(1) Laminating a photosensitive resin composition layer on a substrate to form a laminate of a dry film resist having the photosensitive resin composition layer and the substrate;
(2) a step of exposing the photosensitive resin composition layer of the laminate,
(3) A step of heating the exposed photosensitive resin composition layer and the substrate together under pressure using a pressure heating mechanism,
(4) a step of developing the exposed photosensitive resin composition layer after the heating;
A method for forming a resist pattern is provided. An example of a specific method for forming a resist pattern in the present embodiment is shown below. The method of this embodiment is typically performed using a photosensitive resin laminate having a support and a photosensitive resin composition layer, and optionally a protective layer. Below, although the method using a photosensitive resin laminated body is demonstrated to an example, this invention is not limited to this.

  First, in the step (1), a laminate of a dry film resist (hereinafter sometimes simply referred to as a laminate) is formed by laminating a photosensitive resin composition layer on a substrate using a laminator or the like. Specifically, when the photosensitive resin laminate has a protective layer, after the protective layer is peeled off, the photosensitive resin composition layer is laminated on the substrate surface by thermocompression bonding with a laminator. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like. The substrate may be a metal film insulating plate. In the present embodiment, the photosensitive resin composition layer may be laminated on only one surface of the substrate surface, or may be laminated on both surfaces as necessary. The heating temperature during lamination is generally 40 ° C to 160 ° C. Moreover, the adhesiveness with respect to the board | substrate of the resist pattern obtained can be improved by performing the thermocompression bonding at the time of lamination twice or more. The thermocompression bonding may be performed using a two-stage laminator equipped with two rolls, or may be performed by repeatedly passing the laminate of the substrate and the photosensitive resin composition layer several times through the rolls. Also good.

  Next, in the step (2), the photosensitive resin composition layer is exposed to active light using an exposure machine. The exposure can be performed after peeling the support, if desired. In the case of exposing through a photomask, the exposure amount is determined by the light source illuminance and the exposure time, and may be measured using a light meter. In the exposure process, a maskless exposure method may be used. In maskless exposure, exposure is performed directly on the substrate by a drawing apparatus without using a photomask. As the light source, a semiconductor laser having a wavelength of 350 nm to 410 nm, an ultrahigh pressure mercury lamp, or the like is used. The drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the illuminance of the exposure light source and the moving speed of the substrate.

  Next, after the exposure, in the step (3), the laminate of the substrate and the exposed photosensitive resin composition layer is heated under pressure. Heating is preferably performed immediately after exposure. “Immediately” means, specifically, within 3 minutes after the exposure, specifically after the exposure is completed. This time is the time until the start of heating under pressure. The time from the end of exposure to the start of heating is more preferably within 2 minutes, further preferably within 1 minute, and is preferably as short as possible. As a pressure heating mechanism as a means for performing heating under pressure, a laminating press machine that performs processing with a single wafer for each batch or a laminating machine using a hot roll used in a laminating process can be preferably used. From the viewpoint of productivity, a hot roll capable of continuously flowing a substrate is preferable, and it is particularly preferable to use a laminator using a hot roll used in the laminating step.

  In the step (3), the heating temperature when the laminate is heated under pressure is preferably in the range of 50 ° C to 130 ° C. In the present disclosure, heating means treatment at a temperature higher than the atmospheric temperature, but a preferable heating temperature is in the above range. The heating temperature is more preferably in the range of 70 ° C to 130 ° C. The heating temperature is more preferably in the range of 90 ° C to 130 ° C. When the heating temperature is low, there is little improvement in adhesion due to heating, and when it is too high, the photosensitive resin composition layer after exposure tends to be modified, so the above range is a preferred range. In addition, the said heating temperature is the temperature of a press heating mechanism, for example, the hot roll temperature at the time of a heating, or the temperature of the press panel of a press machine.

  In the step (3), the linear pressure on the resist when the laminate is heated under pressure is preferably in the range of 1.9 kg / cm to 8.6 kg / cm. The linear pressure is more preferably in the range of 2.7 kg / cm to 8.6 kg / cm. The pressure is more preferably in the range of 3.4 kg / cm to 8.6 kg / cm. When the pressure is low, the adhesiveness between the photosensitive resin composition layer and the substrate after exposure due to the pressure tends to decrease. Moreover, when too high, the photosensitive resin composition layer of the exposed and hardened part will flow, and there exists a tendency for the target wiring pattern to be hard to be formed. Therefore, the above range is a preferable range. The said pressure can be a setting value of the press heating mechanism to be used, for example.

  When the laminate is heated under pressure in the step (3), the pressing time is preferably 1 second to 20 seconds with respect to the substrate length of 250 mm. The pressing time is more preferably 5 seconds or longer, and more preferably 15 seconds or shorter. When the pressing time is too short, there is a tendency that the adhesion is not improved, and when it is too long, the productivity tends to be lowered. Therefore, the above range is preferable.

  When the laminate is heated under pressure in the step (3), it is preferable to clean the pressure heating mechanism with a clean roller before pressing. The reason is that if the foreign matter adhered during the exposure or the flying foreign matter is present on the laminate, the foreign matter may break the wiring pattern to be formed by the exposure. is there. In order to prevent this, it is preferable to remove foreign matter with a clean roller before pressing. It is preferable to use a clean roller for removing foreign substances because it is simple and the operation time is short.

Next, after the heating under the pressing, in the step (4), the unexposed part (in the case of negative type) or the exposed part (in the case of positive type) in the photosensitive resin composition layer after exposure is developed. It removes with a developing solution using an apparatus. When there exists a support body on the photosensitive resin composition layer after exposure, this is remove | excluded. Subsequently, the unexposed portion or the exposed portion is developed and removed using a developer composed of an alkaline aqueous solution to obtain a resist image. As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is preferable. The alkaline aqueous solution is selected in accordance with the characteristics of the photosensitive resin composition layer, and an aqueous Na ₂ CO ₃ solution having a concentration of 0.2% by mass to 2% by mass is generally used. In the alkaline aqueous solution, a surfactant, an antifoaming agent, a small amount of an organic solvent for accelerating development, and the like may be mixed. In addition, it is preferable to maintain the temperature of the developing solution in a development process at a constant temperature in the range of 20 ° C to 40 ° C.

  Although a resist pattern is obtained by the above steps, in some cases, a heating step of 100 ° C. to 300 ° C. can be further performed. By performing this heating step, the chemical resistance of the resist pattern can be improved. A heating furnace of a hot air, infrared ray, far infrared ray, or the like can be used for the heating step.

  This embodiment is suitably applied in the following uses, for example.

<Conductor pattern manufacturing method>
The present embodiment includes a lamination step of laminating the photosensitive resin composition layer on a substrate such as a metal plate or a metal film insulating plate, an exposure step of exposing the photosensitive resin composition layer, and the exposed photosensitive resin composition. A developing process for obtaining a substrate on which a resist pattern is formed by removing an unexposed part or an exposed part of a physical layer with a developer, and a conductive pattern forming process for etching or plating the substrate on which the resist pattern is formed ( Also provided is a method of manufacturing a conductor pattern comprising (preferably in order). In this embodiment, the conductor pattern manufacturing method is performed by using a metal plate or a metal film insulating plate as a substrate, forming a resist pattern by the above-described resist pattern forming method, and then performing a conductor pattern forming step. In the conductor pattern forming step, a conductor pattern is formed on a substrate surface (for example, a copper surface) exposed by development using a known etching method or plating method.

<Manufacturing method of wiring board>
After producing a conductor pattern by the above-described method for producing a conductor pattern, a wiring board having a desired wiring pattern is further obtained by further performing a peeling step of peeling the resist pattern from the substrate with an aqueous solution having alkalinity stronger than that of the developer. For example, a printed wiring board) can be obtained. In the production of the wiring board, a copper-clad laminate or a flexible board is preferably used as the board. The alkaline aqueous solution for stripping (hereinafter also referred to as “stripping solution”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of 2% by mass to 5% by mass is generally used. . A small amount of a water-soluble solvent can be added to the stripping solution. As a water-soluble solvent, alcohol etc. are mentioned, for example. The temperature of the stripping solution in the stripping step is preferably in the range of 40 ° C to 70 ° C.

<Manufacture of lead frames>
A lead frame can be manufactured by forming a resist pattern by the above-mentioned resist pattern forming method using a metal plate such as copper, a copper alloy, or an iron-based alloy as a substrate and then performing the following steps. First, a step of etching the substrate exposed by development to form a conductor pattern is performed. Then, a desired lead frame can be obtained by performing a peeling process in which the resist pattern is peeled by the same method as the method for manufacturing the wiring board.

<Manufacture of a substrate having an uneven pattern>
The resist pattern formed by the resist pattern forming method can be used as a protective mask member when processing a substrate by a sandblasting method. Examples of the substrate at this time include glass, a silicon wafer, amorphous silicon, polycrystalline silicon, ceramic, sapphire, and a metal material. A resist pattern is formed on these substrates by the same method as the above resist pattern forming method. After that, a blasting material is sprayed from the formed resist pattern to cut it to a desired depth, and a resist pattern portion remaining on the substrate is removed from the substrate with an alkali stripping solution or the like. The base material which has a fine uneven | corrugated pattern on a board | substrate can be manufactured. The blast material used in the above-described sandblasting process, can be used any known, for _{example, SiC, SiO 2, Al 2} O 3, CaCO 3, ZrO, glass, having a particle diameter of about 2μm~100μm such as stainless steel particles Is commonly used.

<Manufacture of semiconductor packages>
A semiconductor package can be manufactured by using a wafer on which a large-scale integrated circuit (LSI) has been formed as a substrate and forming a resist pattern on the wafer by the resist pattern forming method, followed by the following steps. First, a step of forming a conductor pattern by performing columnar plating such as copper or solder on the opening exposed by development is performed. Then, a desired semiconductor package is obtained by performing a peeling process for peeling the resist pattern by the same method as the method for manufacturing the wiring board, and further removing a thin metal layer by etching other than the columnar plating. Can be obtained.

  In this embodiment, the photosensitive resin composition is used for the manufacture of printed wiring boards, the manufacture of lead frames for mounting IC chips, the manufacture of metal foils such as the manufacture of metal masks, ball grid arrays (BGA), or chip sizes, Manufacture of packages such as packages (CSP), manufacture of tape substrates such as chip-on-film (COF) or tape automated bonding (TAB), manufacture of semiconductor bumps, flat panels such as ITO electrodes or address electrodes, electromagnetic wave shields, etc. It can be used for manufacturing a partition of a display.

<Photosensitive resin composition and photosensitive resin laminate>
Next, exemplary aspects of the photosensitive resin composition and the photosensitive resin laminate that can be used in the method of the present embodiment will be described.

(Photosensitive resin composition)
In a preferred embodiment, as the photosensitive resin composition, a photosensitive resin composition containing (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator can be used. Moreover, in this embodiment, the photosensitive resin composition can form the photosensitive resin composition layer by applying to the arbitrary support bodies. Hereinafter, each component contained in the photosensitive resin composition will be described.

(A) Alkali-soluble polymer (A) An alkali-soluble polymer is a polymer that can be dissolved in an alkaline solution. In this embodiment, (A) the alkali-soluble polymer preferably has a carboxyl group, more preferably has an acid equivalent of 100 to 600, and contains a carboxyl group-containing monomer as a copolymerization component. More preferably, it is a copolymer. Further, (A) the alkali-soluble polymer may be thermoplastic.

  (A) The acid equivalent of the alkali-soluble polymer is preferably 100 or more from the viewpoint of the development resistance of the photosensitive resin composition layer and the resolution and adhesion of the resist pattern, while the photosensitive resin composition. From the viewpoint of developability and peelability of the physical layer, it is preferably 600 or less. The acid equivalent of (A) the alkali-soluble polymer is more preferably 200 to 500, and further preferably 250 to 450. In the present disclosure, the acid equivalent means the mass (gram) of a polymer having one equivalent of a carboxyl group in the molecule, and potentiometric titration method (for example, Hiranuma automatic titration apparatus (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.). And a method using a 0.1 mol / L sodium hydroxide aqueous solution).

  (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 or more from the viewpoint of maintaining the thickness of the dry film resist uniformly and obtaining resistance to the developer. From the viewpoint of maintaining developability, it is preferably 500,000 or less. The weight average molecular weight of the (A) alkali-soluble polymer is more preferably 10,000 to 200,000, and further preferably 40,000 to 130,000. Furthermore, it is preferable that the dispersion degree of (A) alkali-soluble polymer is 1.0-6.0.

In the present disclosure, the weight average molecular weight means a weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of polystyrene (for example, Shodex STANDARD SM-105 manufactured by Showa Denko KK). The weight average molecular weight can be measured, for example, under the following conditions using gel permeation chromatography manufactured by JASCO Corporation.
Differential refractometer: RI-1530
Pump: PU-1580
Degasser: DG-980-50
Column oven: CO-1560
Column: KF-802.5, KF-806M × 2, KF-807 in order
Eluent: THF

  (A) The alkali-soluble polymer is preferably obtained by polymerizing at least one of the first monomers described below. The (A) alkali-soluble polymer is more preferably obtained by copolymerizing at least one of the first monomers and at least one of the second monomers described below.

  The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable. In the present disclosure, “(meth) acryl” means acryl or methacryl, and “(meth) acrylate” means “acrylate” and “methacrylate”.

  The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate; vinyl acetate Esters of vinyl alcohol such as; and (meth) acrylonitrile, styrene, and polymerizable styrene derivatives such as methyl styrene, vinyl toluene, tert-butoxy styrene, acetoxy styrene, 4-vinyl Ikikosan, dimer, styrene trimer, etc.) and the like. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene and benzyl (meth) acrylate are preferable.

  In this embodiment, from the viewpoint of improving the resolution of the resist pattern, the (A) alkali-soluble polymer preferably has an aromatic group in the side chain of the structure. The (A) alkali-soluble polymer having an aromatic group in the side chain is prepared by using a compound having an aromatic group as the first monomer and / or the second monomer. be able to. Examples of the monomer having an aromatic group include benzyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, styrene, cinnamic acid, and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxy). Styrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, and the like). Among these, benzyl (meth) acrylate is preferable.

  In the present embodiment, (A) the alkali-soluble polymer is obtained by known polymerization method, preferably addition polymerization, more preferably radical polymerization of the above-mentioned first monomer or this and the second monomer. It can be prepared by polymerizing.

  In the present embodiment, the content of the (A) alkali-soluble polymer in the photosensitive resin composition (based on the total solid content of the photosensitive resin composition. Hereinafter, the same applies to each component unless otherwise specified. Is preferably in the range of 10% by mass to 90% by mass, more preferably in the range of 20% by mass to 80% by mass, and still more preferably in the range of 30% by mass to 60% by mass. (A) The content of the alkali-soluble polymer is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin composition layer, while the resist pattern formed by exposure is a resist. It is preferable that it is 90 mass% or less from a viewpoint of fully exhibiting the performance as a material.

｛式中、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子又はメチル基を表し、Ｘは、炭素数２〜６のアルキレン基を表し、複数存在する場合のＸは互いに同一でも異なっていてもよく、ｎ₁及びｎ₂は、それぞれ独立に、０又は正の整数であり、そしてｎ₁＋ｎ₂は、２〜４０である。｝で表される化合物は、解像性及び密着性が優れた感光性樹脂を得るために好ましい。 (B) Compound having an ethylenically unsaturated bond (B) A compound having an ethylenically unsaturated bond is a compound having polymerizability by having an ethylenically unsaturated group in its structure. In the present embodiment, the photosensitive resin composition has the following general formula (I) as a compound having (B) an ethylenically unsaturated bond:

{In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group; X represents an alkylene group having 2 to 6 carbon atoms; N ₁ and n ₂ are each independently 0 or a positive integer, and n ₁ + n ₂ is 2 to 40. } Is preferable in order to obtain a photosensitive resin excellent in resolution and adhesion.

Moreover, the aromatic ring in the said general formula (I) may have a hetero atom and / or a substituent. Examples of the hetero atom include a halogen atom, and the substituent includes an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and a phenacyl group. , Amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, alkylmercapto group having 1 to 10 carbon atoms, allyl group, hydroxyl group , A hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in an alkyl group, an acyl group having 1 to 10 carbon atoms in an alkyl group, an alkoxy group having 1 to 20 carbon atoms, C1-C20 alkoxycarbonyl group, C2-C10 alkylcarbonyl group, C2-C10 alkenyl group, C2-C10 N Alkylcarbamoyl group or a group containing a heterocyclic ring, or an aryl group substituted by these substituents. Moreover, these substituents may form a condensed ring, or a hydrogen atom in these substituents may be substituted with a hetero atom such as a halogen atom. Furthermore, when the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

In the general formula (I), X has preferably 2 or more carbon atoms from the viewpoint of resolution, and preferably 6 or less carbon atoms from the viewpoint of developability. More preferably, it is C2-C4. Further, n ₁ + n ₂ is preferably 2 or more from the viewpoint of developability, and preferably 40 or less from the viewpoint of resolution. N ₁ + n ₂ is more preferably 2 to 20, further preferably 2 to 15, and further preferably 2 to 10. Specific examples of the compound represented by the general formula (I) include, for example, a compound having bisphenol A modified with alkylene oxide and having (meth) acryloyl groups at both ends. There are oxide modification, butylene oxide modification, pentylene oxide modification, hexylene oxide modification and the like. Examples of the ethylene oxide-modified bisphenol A having (meth) acryloyl groups at both ends include, for example, polyethylene glycol dimethacrylate (SR-manufactured by Sartomer) in which 1 mol of ethylene oxide is added to both ends of bisphenol A on average. 348, Miwon M-249, Eternal EM-3260), diglycolate of polyethylene glycol with an average of 2 moles of ethylene oxide added to both ends of bisphenol A (manufactured by Shin-Nakamura Chemical Co., Ltd.) NK ester BPE-200) and polyethylene glycol dimethacrylate, 2,2-bis (4-((meth) acryloxytetraethoxy) obtained by adding an average of 3 moles of ethylene oxide to both ends of bisphenol A. ) Phenyl) propane, 2,2- (4-((meth) acryloxypentaethoxy) phenyl) propane (NK Nakamura Chemical Co., Ltd. NK ester BPE-500), 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl ) Propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy nonaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryl) Roxyundecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxide decaethoxy) phenyl) propane, 2,2-bis (4 ((Meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) 2,2-bis (4-(((meth) acryloxypolyethoxy) phenyl) such as pentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl) propane Examples include propane. These may be used alone or in combination of two or more. Among them, diglycolate of polyethylene glycol in which 1 mol of ethylene oxide is added to both ends of bisphenol A on average is preferable from the viewpoint of resolution.

  Moreover, in this embodiment, the photosensitive resin composition may contain not only the compound represented by the said general formula (I) but another compound as a compound which has (B) ethylenically unsaturated bond. Examples of other compounds include polyalkylene glycol di (meth) acrylate, a photopolymerizable compound having one ethylenically unsaturated bond, a (meth) acrylate compound having a urethane bond, and α, β-unsaturated polyhydric alcohol. Examples include compounds other than the above general formula (I) obtained by reacting a saturated carboxylic acid, compounds obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, phthalic acid compounds, and the like. These may be used alone or in combination of two or more.

  As polyalkylene glycol di (meth) acrylate, for example, nonaethylene glycol diacrylate, polyalkylene glycol having an average of 12 moles of propylene oxide added and an ethylene oxide added to both ends at an average of 3 moles at both ends, respectively. And dimethacrylate. From the viewpoints of adhesion and resolution, polyalkylene glycol dimethacrylate having an average of 3 moles of ethylene oxide added to both ends of polypropylene glycol with an average of 12 moles of propylene oxide added is (B). It is preferably contained in a compound having an ethylenically unsaturated bond. These may be used alone or in combination of two or more.

  Examples of the photopolymerizable compound having one ethylenically unsaturated bond include nonylphenoxypolyethyleneoxy (meth) acrylate, nonylphenoxypolypropyleneoxy (meth) acrylate, butylphenoxypolyethyleneoxy (meth) acrylate, butylphenoxypolypropyleneoxy ( And (meth) acrylate. These may be used alone or in combination of two or more.

  Examples of the (meth) acrylated compound having a urethane bond include hexamethylene diisocyanate, tolylene diisocyanate, or a diisocyanate compound (for example, 2,2,4-trimethylhexamethylene diisocyanate), a hydroxyl group in one molecule ( Examples thereof include urethane compounds obtained from compounds having a (meth) acryl group (for example, 2-hydroxypropyl acrylate, oligopropylene glycol monomethacrylate). Specifically, it is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (manufactured by NOF Corporation, Blemmer PP1000). These may be used alone or in combination of two or more.

  Examples of compounds other than the general formula (I) obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Examples include EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, and PO-modified trimethylolpropane tri (meth) acrylate. These may be used alone or in combination of two or more.

  Examples of the compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include trimethylolpropane triglycidyl ether tri (meth) acrylate, 2,2-bis (4- (meth) acryloxy- 2-hydroxy-propyloxy) phenyl and the like are fisted.

  Examples of the phthalic acid compounds include γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyalkyl-β ′-(meth) acryloloxyalkyl-o—. A phthalate etc. are mentioned. These can be used alone or in combination of two or more.

  In addition, (B) tricyclodecane di (meth) acrylate, (2,2-bis {4- (methacryloxypentaethoxy) cyclohexyl} propane, or the like may be included as a compound having an ethylenically unsaturated bond.

  In this embodiment, content of the compound which has (B) ethylenically unsaturated bond in the photosensitive resin composition becomes like this. Preferably it is the range of 5 mass%-70 mass%, More preferably, it is 20 mass%-60 It is the range of mass%, More preferably, it is the range of 30 mass%-60 mass%. (B) The content of the compound having an ethylenically unsaturated bond is preferably 5% by mass or more from the viewpoint of suppressing the curing failure of the photosensitive resin composition layer and the delay of the development time. From the viewpoint of suppressing the cold flow and the peeling delay of the cured resist, it is preferably 70% by mass or less.

(C) Photopolymerization initiator (C) The photopolymerization initiator is a compound that polymerizes a monomer by light. In the present embodiment, from the viewpoint of improving the resolution of the resist pattern and the strength of the cured resist, the photosensitive resin composition preferably includes a hexaarylbisimidazole compound as a (C) photopolymerization initiator.

  Examples of the hexaarylbisimidazole compound include hexaarylbisimidazole derivatives (hereinafter, also referred to as “triarylimidazolyl dimer” or “triarylimidazolyl dimer”).

  Examples of the hexaarylbisimidazole derivative include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer (hereinafter, “2,2′-bis (2-chlorophenyl) -4,4 ′, 5, 5'-tetraphenyl-1,1'-bisimidazole "or" 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer "), 2,2 ', 5-tris- (o- Chlorophenyl) -4- (3,4-dimethoxyphenyl) -4 ′, 5′-diphenylimidazolyl dimer, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl) -diphenyl Imidazolyl dimer, 2,4,5-tris- (o-chlorophenyl) -diphenylimidazolyl dimer, 2- (o-chlorophenyl) -bis-4,5- (3,4 Dimethoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2-fluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2 '-Bis- (2,3-difluoromethylphenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4- Difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,5-difluorophenyl) -4,4 ′, 5 , 5′-Tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,6-difluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxy Phenyl) -imidazolyl 2,2′-bis- (2,3,4-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2 ′ -Bis- (2,3,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,3 , 6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2'-bis- (2,4,6-trifluorophenyl) -4,4', 5 , 5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, 2,2′- Bis- (2,3,4,6-tetrafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer, and 2,2′-bis- (2 , 3,4,5,6-pentafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -imidazolyl dimer. These can be used alone or in combination of two or more.

  In particular, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferable for improving the resolution of the resist pattern and the strength of the cured resist.

  In the present embodiment, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is 0.05% by mass to 7% by mass from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin composition layer. %, Preferably 0.1% by mass to 6% by mass.

  In this embodiment, the photosensitive resin composition layer may contain not only a hexaarylbisimidazole compound but also other photopolymerization initiators as (C) a photopolymerization initiator. Examples of other photopolymerization initiators include acridine compounds, N-aryl amino acids, organic halogen compounds, and photosensitizers. These can be used alone or in combination of two or more.

  Acridine compounds are preferred because they give good release properties to the resin. Examples of the acridine compound include acridine, 9-phenylacridine, 1,6-bis (9-acridinyl) hexane, 1,7-bis (9-acridinyl) heptane, 1,8-bis (9-acridinyl) octane, 1,9-bis (9-acridinyl) nonane, 1,10-bis (9-acridinyl) decane, 1,11-bis (9-acridinyl) undecane, 1,12-bis (9-acridinyl) dodecane, etc. It is done. Among these, 9-phenylacridine is preferable from the viewpoint of improving the h-ray sensitivity of the photosensitive resin composition layer. Moreover, these can be used individually by 1 type or in combination of 2 or more types. Furthermore, in this embodiment, it is preferable that content of the acridine compound in the photosensitive resin composition is the range of 0.1 mass%-2 mass% from a viewpoint of obtaining favorable peeling characteristics.

  Examples of N-aryl amino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like. Among these, N-phenylglycine is preferable. These can be used alone or in combination of two or more. Moreover, in this embodiment, content of N-aryl amino acid in the photosensitive resin composition is 0.05 mass%-5 from a viewpoint of improving the peeling characteristic and / or sensitivity of the photosensitive resin composition layer. It is preferable that it is mass%, and it is more preferable that it is 0.1-2 mass%.

  Examples of the organic halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris ( 2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds and the like. Among these, tribromomethylphenyl sulfone is preferable. Moreover, these can be used individually by 1 type or in combination of 2 or more types. Furthermore, in this embodiment, the content of the organic halogen compound in the photosensitive resin composition is 0.05% by mass to 5% by mass from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin composition layer. %, Preferably 0.1% by mass to 3% by mass.

  Examples of the photosensitizer include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 1 , 4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, quinones such as 3-chloro-2-methylanthraquinone, benzophenone, Michler's ketone [4 , 4′-bis (dimethylamino) benzophenone], and aromatic ketones such as 4,4′-bis (diethylamino) benzophenone, and benzene such as benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin. Inethers, benzyl dimethyl ketal, benzyl diethyl ketal, and 1-phenyl-1,2-propanedione-2-O-benzoinoxime, and 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) ) Oxime esters such as oxime. These can be used alone or in combination of two or more.

  In this embodiment, the photosensitive resin composition can also contain a pyrazoline compound as a photosensitizer. Examples of the pyrazoline compound include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) Phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl- Phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline and the like. Among these, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline is preferable. These can be used alone or in combination of two or more.

  In the present embodiment, the content of the photosensitizer in the photosensitive resin composition is 0.05% by mass to 5% by mass from the viewpoint of improving the peeling property and / or sensitivity of the photosensitive resin composition layer. It is preferable that it is 0.1 mass%-3 mass%, and it is further more preferable that it is 0.1 mass%-1 mass%.

  In this embodiment, it is preferable that content of (C) photoinitiator in the photosensitive resin composition is 0.01 mass%-20 mass%. (C) The content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of the sensitivity of the photosensitive resin composition layer, and on the other hand, 20% by mass or less from the viewpoint of the resolution of the resist pattern. Preferably there is. The content of the (C) photopolymerization initiator is more preferably 0.1% by mass to 10% by mass, and further preferably 0.1% by mass to 6% by mass. Furthermore, as the (C) photopolymerization initiator, one of the above-listed compounds may be used alone, or two or more may be used in combination.

(D) Other component In this embodiment, it is preferable that the photosensitive resin composition contains additives, such as dye, a plasticizer, antioxidant, and a stabilizer, as desired.

  Examples of the dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green], fuchsin, phthalocyanine green, auramine base, paramadienta, crystal violet, Methyl orange, Nile blue 2B, Victoria blue, Malachite green (Hodogaya Chemical Co., Ltd., Eisen (registered trademark) MALACHITE GREEN), Basic Blue 20, Diamond Green (Hodogaya Chemical Co., Ltd., Eisen (registered trademark) DIAMOND GREEN GH) Etc. Among these, diamond green and leuco crystal violet are preferable from the viewpoint of improving colorability, hue stability and exposure contrast. These can be used alone or in combination of two or more.

  In the present embodiment, the content of the dye in the photosensitive resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably in the range of 0.01% by mass to 2% by mass. More preferably, it is the range of 0.04 mass%-1 mass%. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good colorability, and is 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin composition layer. It is preferable.

  Examples of the plasticizer include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxyethylene monomethyl ether, Glycol esters such as oxypropylene monoethyl ether and polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, citric acid Triethyl acid, triethyl acetyl citrate, tri-n-propyl acetyl citrate, and tri-n-butyl acetyl citrate Propylene glycol respectively by adding propylene oxide to both sides of the bisphenol A, and ethylene glycol obtained by adding each of ethylene oxide on either side of the Bisphenol A. These can be used alone or in combination of two or more.

  In this embodiment, content of the plasticizer in the photosensitive resin composition becomes like this. Preferably it is 0.1 mass%-50 mass%, More preferably, it is 1 mass%-20 mass%. The content of the plasticizer is preferably 0.1% by mass or more from the viewpoint of suppressing delay in the development time of the photosensitive resin composition layer and imparting flexibility to the cured film, From the viewpoint of suppressing insufficient curing and cold flow, it is preferably 50% by mass or less.

  Examples of the antioxidant include triphenyl phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris (2,4-di-tert-butylphenyl) phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd.). , Product name 2112), tris (monononylphenyl) phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., product name: 1178), bis (monononylphenyl) -dinonylphenyl phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., product) Name: 329K). These can be used alone or in combination of two or more.

  In this embodiment, content of antioxidant in the photosensitive resin composition becomes like this. Preferably it is the range of 0.01 mass%-0.8 mass%, More preferably, it is 0.01 mass%-0.00. The range is 3% by mass. The content of the antioxidant is preferably 0.01% by mass or more from the viewpoint of favorably expressing the hue stability of the resist pattern and improving the sensitivity of the photosensitive resin composition layer, It is preferably 0.8% by mass or less from the viewpoint of improving the hue stability while suppressing the color developability of the resist pattern and improving the adhesion.

  The stabilizer is preferably used from the viewpoint of improving the thermal stability and / or storage stability of the photosensitive resin composition. Examples of the stabilizer include at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, and alkylene oxide compounds having a glycidyl group. These can be used alone or in combination of two or more.

  Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt (for example, aluminum salt with 3 mol of nitrosophenylhydroxylamine added) Etc.), diphenylnitrosamine and the like. Among these, an aluminum salt added with 3 mol of nitrosophenylhydroxylamine is preferable. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole, 1- (2-di-n- Examples thereof include a 1: 1 (molar ratio) mixture of butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazole. Among these, 1: 1 (molar ratio) of 1- (2-di-n-butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazole ) A mixture is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole. These can be used alone or in combination of two or more.

  Examples of the alkylene oxide compound having a glycidyl group include neopentyl glycol diglycidyl ether (for example, Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), Bisphenol A-propylene oxide 2 mol adduct diglycidyl ether (for example, Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6-hexanediol diglycidyl ether (for example, Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.), etc. . These can be used alone or in combination of two or more.

  In this embodiment, the total content of the radical polymerization inhibitor, benzotriazoles, carboxybenzotriazoles, and alkylene oxide compounds having a glycidyl group in the photosensitive resin composition is preferably 0.001% by mass to 3%. It is the range of mass%, More preferably, it is the range of 0.05-1 mass%. The total content is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, while maintaining the sensitivity of the photosensitive resin composition layer. From the viewpoint, it is preferably 3% by mass or less.

<Photosensitive resin composition preparation solution>
In this embodiment, the photosensitive resin composition preparation liquid can be formed by adding a solvent to the photosensitive resin composition. Suitable solvents include, for example, ketones represented by methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. It is preferable to add a solvent to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid is 500 mPa · sec to 4000 mPa · sec at 25 ° C.

<Photosensitive resin laminate>
In this embodiment, the photosensitive resin laminated body which has a support body and the photosensitive resin composition layer which consists of the said photosensitive resin composition laminated | stacked on this support body can be used. If desired, the photosensitive resin laminate may have a protective layer on the side opposite to the support side of the photosensitive resin composition layer.

  The support is preferably a transparent one that transmits light emitted from the exposure light source. Examples of such a support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film. , A polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. As these films, those stretched as necessary can be used. The haze is preferably 0.01% to 5.0%, more preferably 0.01% to 2.5%, and still more preferably 0.01% to 1.0%. The thinner the film, the more advantageous in terms of image forming property and economic efficiency, but a film having a thickness of 10 to 30 μm is preferably used because the strength needs to be maintained.

  Moreover, the important characteristic of the protective layer used for the photosensitive resin laminated body is that the protective layer is smaller than the support in terms of adhesion to the photosensitive resin composition layer and can be easily peeled off. As a protective layer, a polyethylene film, a polypropylene film, etc. are preferable, for example. Further, for example, a film having excellent peelability disclosed in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

  In this embodiment, the thickness of the photosensitive resin composition layer in the photosensitive resin laminate is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. The smaller the thickness of the photosensitive resin composition layer, the higher the resolution of the resist pattern. On the other hand, the larger the thickness, the higher the strength of the cured film, so that it can be selected depending on the application.

  As a method for producing a photosensitive resin laminate by sequentially laminating a support, a photosensitive resin composition layer, and if necessary, a protective layer, a conventionally known method can be employed.

  For example, the photosensitive resin composition preparation liquid is prepared, then coated on a support using a bar coater or roll coater and dried, and the photosensitive resin composition containing the photosensitive resin composition preparation liquid is formed on the support. A resin composition layer is laminated. Furthermore, if desired, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin composition layer.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

[Examples 1 to 11 and Comparative Examples 1 to 3]
First, a method for producing samples for evaluation of Examples and Comparative Examples will be described, and then an evaluation method and evaluation results for the obtained samples will be shown.

1. Production of Evaluation Samples Evaluation samples in Examples and Comparative Examples were produced as follows.

<Preparation of photosensitive resin laminate>
A photosensitive resin composition mixed solution obtained by sufficiently stirring and mixing a photosensitive resin composition and a solvent having a composition shown in Table 2 below (where each component number indicates a blending amount (part by mass) as a solid content). The photosensitive resin composition was uniformly applied using a blade coater on the surface of a 16 μm-thick polyethylene terephthalate film (Toray Industries, Inc., FB40), which was a support film, and was placed in a dryer at 95 ° C. for 5 minutes. It dried and the uniform photosensitive resin composition layer was formed on the support film. The thickness of the photosensitive resin composition layer was 20 μm. Next, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) was bonded as a protective film on the surface of the photosensitive resin composition layer to obtain a photosensitive resin laminate. The name of the material component in the photosensitive resin composition preparation liquid represented by is as described later.

<Board surface preparation>
As a substrate for evaluation of resolution and adhesion, a 0.4 mm-thick copper-clad laminate obtained by laminating 35 μm rolled copper foil was etched with a chemical polishing liquid (CZ-8101 manufactured by Mec Co., Ltd .; product name) as an etching amount. Prepared by polishing about 0.5 μm.

<Laminate>
While peeling off the polyethylene film of the photosensitive resin laminate, the photosensitive resin laminate was applied to a copper-clad laminate that had been leveled and preheated to 60 ° C. with a hot roll laminator (Asahi Kasei Co., Ltd., AL-700). A test piece was obtained by laminating at a roll temperature of 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

<Exposure>
Using a chrome glass mask, exposure was performed with a parallel light exposure machine (HMW-801, manufactured by Oak Manufacturing Co., Ltd.) at an exposure amount of 140 mJ / cm ² .

<Post-exposure thermocompression bonding>
The copper-clad laminate on which the exposed photosensitive resin laminate is laminated is heated under pressure by laminating at a roll temperature of 105 ° C. with a hot roll laminator (Asahi Kasei Co., Ltd., AL-700). A test piece was obtained. The conditions of pressing force and laminating speed are as described in Table 1.

<Development>
After the polyethylene terephthalate film is peeled off, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for a predetermined time using a developing device manufactured by Fuji Kiko Co., Ltd. with a full cone type nozzle at a developing spray pressure of 0.15 MPa. And developed to dissolve and remove unexposed portions of the photosensitive resin composition layer. At this time, the minimum time required for completely dissolving the photosensitive resin composition layer in the unexposed portion was measured as the minimum development time, and development was performed twice as much as the minimum development time to prepare a resist pattern. At that time, as a water washing step, a flat type nozzle was used and a water washing spray pressure of 0.15 MPa was used for the same time as the development step.

2. Evaluation method <Resolution>
The evaluation board | substrate which passed 15 minutes after lamination was exposed through the chromium glass mask which has a line pattern of the ratio of 1: 1 of the width | variety of an exposed part and an unexposed part. Thereafter, post-exposure thermocompression bonding was performed under the conditions described in Table 1. Further, after that, development was performed in a time twice as long as the minimum development time, and the minimum mask width in which a cured resist line was normally formed was defined as a resolution value, and the resolution was ranked as follows. In addition, the minimum mask width | variety formed normally without the fall of a cured resist pattern or adhesion | attachment of cured resists was evaluated.
○: Resolution value is 7 μm or less;
X: The resolution value exceeds 7 μm.

<Adhesion>
The evaluation substrate 15 minutes after the lamination was exposed through a chromium glass mask having a line pattern having a width of 3 μm exposed portion and 7 μm unexposed portion, or 4 μm exposed portion and 8 μm unexposed portion. Thereafter, development was performed in a time twice as long as the minimum development time, and the ranking was made as follows depending on whether or not the cured resist line was normally formed.
A: A resist line having an exposed area of 3 μm is normally formed. ;
(Triangle | delta): The resist line of 4 micrometers of exposure parts is formed normally.
X: The resist line of the exposed part 4 μm is tilted, meandering, or does not exist on the substrate and is not normally formed.

Ｂ−１：メタクリル酸２０質量％、メタクリル酸ベンジル８０質量％の二元共重合体（重量平均分子量２５，０００、酸当量４３０）
Ｂ−２：メタクリル酸３０質量％、メタクリル酸ベンジル５０質量％、メタクリル酸シクロヘキシル２０質量％の三元共重合体（重量平均分子量３０，０００、酸当量２８７）
Ｂ−３：メタクリル酸３０質量％、スチレン５０質量％、メタクリル酸メチル２０質量％の三元共重合体（重量平均分子量５０，０００、酸当量２８７）
Ｂ−４：メタクリル酸２０質量％、メタクリル酸ベンジル８０質量％の二元共重合体（重量平均分子量５０，０００、酸当量４３０）
Ｍ−１：ペンタエリスリトールの４つの末端にそれぞれ９モルのエチレンオキシドを付加したテトラメタクリレート
Ｍ−２：ビスフェノールＡの両端にそれぞれ平均１モルずつのエチレンオキサイドを付加したポリエチレングリコールのジメタクリレート（サートマージャパン（株）製ＳＲ−３４８）
Ｍ−３：ビスフェノールＡの両端にそれぞれ平均５モルずつのエチレンオキサイドを付加したポリエチレングリコールのジメタクリレ−ト（新中村化学社製ＢＰＥ-５００、製品名）
Ｍ−４：ヘプタプロピレングリコールジメタクリレート
Ｍ−５：ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートの７：３（モル比）混合物(東亞合成製Ｍ−３０６、製品名）
Ｍ−６：トリシクロデカンジメタノールジメタクリレート（新中村化学工業（株）製ＮＫエステルＤＣＰ、製品名）
Ｍ−７：ビスフェノールＡの両端にそれぞれ平均２モルずつのエチレンオキサイドを付加したポリエチレングリコールのジメタクリレ−ト（新中村化学製ＢＰＥ−２００、製品名）
Ｉ−１：２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール二量体
Ｉ−２：４，４’−ビス（ジエチルアミノ）ベンゾフェノン
Ｄ−１：ダイアモンドグリーン
Ｄ−２：ロイコクリスタルバイオレット
Ｘ−１：１−（２−ジ-ｎ-ブチルアミノメチル）−５−カルボキシルベンゾトリアゾールと１−（２−ジ−ｎ−ブチルアミノメチル）−６−カルボキシルベンゾトリアゾールの１：１（モル比）混合物
Ｘ−２： ３−[（３−ｔｅｒｔ−ブチル）−５−メチルー４−ヒドロキシフェニル]プロパン酸２モルとトリエチレングリコール１モルとの反応で得られる縮合物
Ｘ−３：ニトロソフェニルヒドロキシルアミンが３モル付加したアルミニウム塩
Ｆ−１：メチルエチルケトン 3. Evaluation Results Table 1 shows the evaluation results of Examples 1 to 11 and Comparative Examples 1 to 3. Details of the composition in Table 1 are shown in Table 2. The meanings of the symbols in Table 2 are shown below.

B-1: Binary copolymer of 20% by mass of methacrylic acid and 80% by mass of benzyl methacrylate (weight average molecular weight 25,000, acid equivalent 430)
B-2: Ternary copolymer of 30% by mass of methacrylic acid, 50% by mass of benzyl methacrylate and 20% by mass of cyclohexyl methacrylate (weight average molecular weight 30,000, acid equivalent 287)
B-3: Ternary copolymer (methacrylic acid 30% by mass, styrene 50% by mass, methyl methacrylate 20% by mass (weight average molecular weight 50,000, acid equivalent 287)
B-4: Binary copolymer of 20% by mass of methacrylic acid and 80% by mass of benzyl methacrylate (weight average molecular weight 50,000, acid equivalent 430)
M-1: tetramethacrylate in which 9 mol of ethylene oxide is added to each of the four terminals of pentaerythritol M-2: dimethacrylate of polyethylene glycol in which 1 mol of ethylene oxide is added to each end of bisphenol A on average (Sartomer Japan) SR-348 manufactured by)
M-3: Polyethylene glycol dimethacrylate with an average of 5 moles of ethylene oxide added to each end of bisphenol A (BPE-500, product name, Shin-Nakamura Chemical Co., Ltd.)
M-4: Heptapropylene glycol dimethacrylate M-5: 7: 3 (molar ratio) mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (M-306, manufactured by Toagosei Co., Ltd., product name)
M-6: Tricyclodecane dimethanol dimethacrylate (NK Nakamura Chemical Co., Ltd. NK ester DCP, product name)
M-7: Dimethacrylate of polyethylene glycol with an average of 2 moles of ethylene oxide added to both ends of bisphenol A (BPE-200 manufactured by Shin-Nakamura Chemical, product name)
I-1: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer I-2: 4,4'-bis (diethylamino) benzophenone D-1: Diamond green D-2: Leuco crystal violet X- 1: 1 (molar ratio) mixture of 1- (2-di-n-butylaminomethyl) -5-carboxylbenzotriazole and 1- (2-di-n-butylaminomethyl) -6-carboxylbenzotriazole X-2: Condensate obtained by reaction of 2 mol of 3-[(3-tert-butyl) -5-methyl-4-hydroxyphenyl] propanoic acid and 1 mol of triethylene glycol X-3: Nitrosophenylhydroxylamine is 3 mol added aluminum salt F-1: methyl ethyl ketone

  From the results shown in Table 1, it can be seen that Examples 1 to 11 are excellent in resolution and adhesion by adopting the configuration of the present invention. In Comparative Examples 1 and 2, heating after exposure is not performed, and in Comparative Example 3, heating is performed after exposure but is not pressed. Therefore, it is possible to achieve both resolution and adhesion. could not.

  The method for forming a resist pattern according to the present invention includes the manufacture of printed wiring boards, the manufacture of lead frames for mounting IC chips, the precision processing of metal foils such as the manufacture of metal masks, the manufacture of packages such as BGA or CSP, COF or TAB, etc. The present invention can be used for the production of tape substrates, semiconductor bumps, ITO electrodes or address electrodes, and partition walls of flat panel displays such as electromagnetic wave shields.

Claims (10)

The following steps:
(1) Laminating a photosensitive resin composition layer on a substrate to form a dry film resist laminate having the photosensitive resin composition layer and the substrate;
(2) a step of exposing the photosensitive resin composition layer of the laminate,
(3) A step of heating the exposed photosensitive resin composition layer and the substrate together under pressure using a pressure heating mechanism,
(4) A step of developing the exposed photosensitive resin composition layer after the heating,
A method for forming a resist pattern, comprising:   The resist pattern forming method according to claim 1, wherein in the step (3), the press heating mechanism is a hot roll.   3. The resist pattern forming method according to claim 1, wherein, in the step (3), a heating temperature in the heating under the pressure is in a range of 50 ° C. to 130 ° C. 3.   The resist pattern formation according to any one of claims 1 to 3, wherein in the step (3), the pressing force in the heating under the pressing is 1.9 kg / cm to 8.6 kg / cm as a linear pressure. Method.   5. The resist pattern forming method according to claim 1, wherein, in the step (3), the pressure heating mechanism is cleaned with a clean roller before heating under the pressure.   The resist pattern forming method according to any one of claims 1 to 5, wherein heating is performed under pressure in the step (3) within 3 minutes from the end of exposure in the step (2).   The resist pattern forming method according to any one of claims 1 to 6, wherein in the step (3), the heating time under the pressing is 1 second to 20 seconds with respect to a substrate length of 250 mm. The photosensitive resin composition layer in the step (1) is based on the total solid content of the photosensitive resin composition, with the following components:
(A) Alkali-soluble polymer: 10% by mass to 90% by mass,
(B) Compound having ethylenically unsaturated bond: 5% by mass to 70% by mass, and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass,
The (A) alkali-soluble polymer has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000, and the (A) alkali The method for forming a resist pattern according to claim 1, wherein the soluble polymer has an aromatic group in a side chain. The compound (B) having an ethylenically unsaturated bond is represented by the following general formula (I):

{In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group; X represents an alkylene group having 2 to 6 carbon atoms; N ₁ and n ₂ are each independently 0 or a positive integer, and n ₁ + n ₂ is 2 to 40. } The resist pattern formation method of Claim 8 containing the compound represented by these.   The resist pattern forming method according to claim 8 or 9, wherein the (C) photopolymerization initiator includes a hexaarylbisimidazole compound.