TW201932984A - Photosensitive resin laminate and method for producing resist pattern especially performing exposure after peeling of the support film and reducing the defect rate - Google Patents

Abstract

The present invention provides a photosensitive resin laminate which can obtain a circuit board having a small number of defective products even when it is produced by exposure after peeling off of the support film. The present invention is a photosensitive resin laminate for use in exposure after peeling off of a support film, which is provided with the support film and a photosensitive resin composition layer containing a photosensitive resin composition arranged on the support film. The photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound reactive with a photoinitiator, and (C) a photoinitiator, which are respectively exposed according to (1) the state where the focus position is aligned with a surface of the support film using the exposure device, and the photosensitive resin composition layer is peeled off from the support film after exposure, and (2) peels off the support film, and then performs exposure in the state where the focus position is aligned with a surface of the original support film by using the exposure device, and the difference of the minimum independent thin-wire widths that can be patterned between the first and second resist patterns obtained by exposure by a specific exposure device is 5 μm or less.

Description

Photosensitive resin laminated body and manufacturing method of resist pattern

The present invention relates to a method for manufacturing a photosensitive resin laminate and a resist pattern.

In the fields of circuit board manufacturing, metal precision processing, and the like, the following methods are known: forming a specific resist pattern on a substrate, and then performing etching, plating, etc., to perform the required circuit formation or metal processing .
At this time, in order to form a resist pattern on a substrate, a photosensitive resin laminate having a photosensitive resin composition layer on a support film is widely used. This photosensitive resin laminated body is supplied more than the state where the cover film was laminated | stacked on the photosensitive resin composition layer.

The circuit board is manufactured by the following method, for example.
The cover film of the photosensitive resin laminated body is peeled off, and the photosensitive resin laminated body is laminated so that the photosensitive resin composition layer and the copper foil laminated board laminated with a rolled copper foil are in contact with each other. Next, after exposing the photosensitive resin composition layer of the photosensitive resin laminate to a pattern, uncured portions (negative-type unexposed portions and positive-type exposed portions) are developed and removed to form a resist pattern. Then, the copper foil is patterned by an appropriate method such as etching, thereby obtaining a circuit board.

The exposure of the photosensitive resin composition layer is usually performed via a support film. At this time, if the support film of the photosensitive resin laminate contains foreign matter, it is blocked during exposure due to the foreign matter, and the part to be exposed is not exposed. As a result, there is a patterning of the copper foil, that is, a defect in the wiring pattern. situation.

Patent Document 1 describes a technique for limiting the amount of particles and aggregates having a diameter of 5 μm or more contained in the support film in order to suppress defects in the wiring pattern caused by foreign matter in the support film.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] International Publication No. 2008/093643

[Problems to be solved by the invention]

As another method for avoiding a decrease in resolution caused by a foreign substance contained in the support film, a method of exposing the support film after peeling the support film after laminating a photosensitive resin laminate on a substrate is considered. In this specification, exposure after peeling a support film is called "exposure after peeling of a support film." However, the circuit board produced by exposing the support film after peeling has a problem that there are many defective products.

Therefore, an object of the present invention is to provide a photosensitive resin laminated body that can obtain a circuit board with fewer defective products even in a case where it is produced by exposing the support film after exposure.
[Technical means to solve the problem]

The inventors conducted intensive research and found that as a reason for the high number of defective products in circuit substrates produced by exposing the support film after peeling, the conventional photosensitive resin laminate was not peeled from the support film and the support film was peeled off. In the case of exposure and development under the same conditions, the shape of the resist pattern is greatly different. Furthermore, the inventors have found that by reducing the difference, the difference between the minimum line width that can be formed on the circuit substrate when the support film is peeled off and when the support film is not peeled off can be reduced, thereby reducing the Good quality.

That is, the present invention is as follows.
[1] A photosensitive resin laminated body for exposure after peeling of a supporting film, which is provided with a supporting film and a photosensitive resin composition layer, the photosensitive resin composition layer is disposed on the supporting film and contains a photosensitive resin Composition; The above-mentioned photosensitive resin composition contains: (A) an alkali-soluble polymer; (B) a compound reactive with a photoinitiator and (C) a photoinitiator; using a # 400 ground material for lamination 35 μm rolled copper foil of 0.4 mm thick copper foil laminated board was subjected to jet scraping and grinding, and was then preheated to 60 ° C. By a hot roll laminator, the roll temperature was 105 ° C, the air pressure was 0.35 MPa, and the lamination speed was 1.5. The photosensitive resin laminate is laminated on the copper foil laminate under the condition of m / min, and then exposed in accordance with any one of the following conditions (1) and (2): (1) Use an exposure device to focus the position The exposure is performed with the support film surface aligned, and the support film is peeled from the photosensitive resin composition layer after the exposure; (2) The support film is peeled off, and then the exposure device is used to align the focus position with the original support film surface. Exposure in the state; use fine The alkali alkali imager sprays a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. at twice the minimum development time to remove the unexposed parts, and the water is washed with pure water at the same time as the development time, The blade is subjected to a dewatering treatment and then subjected to hot air drying to obtain a resist pattern. In the resist pattern, a first resist pattern obtained through exposure under the above-mentioned condition (1) and a first resist pattern obtained through the above-mentioned condition (2) The difference in the patternable minimum independent fine line width of the second resist pattern obtained by the exposure is 5 μm or less, and the above exposure device is (a) an exposure device having a peak wavelength of light of 350 to 370 nm; ( b) The exposure device has a peak wavelength of 400 to 410 nm; (c) The peak wavelength of the exposed light is 360 to 380 nm and 390 to 410 nm, and the wavelength intensity ratio is 360 to 380 nm: 390 to 410 nm = 30: 70 exposure device; and (d) any one of mercury short arc lamps. [2] The photosensitive resin laminated body for exposure after peeling of the support film as described in the aspect 1, which is used to form wiring. [3] The photosensitive resin laminate for exposure after peeling of the supporting film according to the aspect 1 or 2, wherein the (A) alkali-soluble polymer includes a structure derived from at least one of acrylic acid and methacrylic acid, and (B) The compound reactive with a photoinitiator includes at least one type of cationically polymerizable compound selected from a cationic polymerizable compound having a heterocyclic structure and a vinyl ether compound, and the (C) photoinitiator includes photocationic polymerization. Initiator. [4] The photosensitive resin laminate for exposing the support film after peeling as described in the above aspect 3, wherein the compound having reactivity with the photoinitiator (B) includes a cationically polymerizable compound having a heterocyclic structure, In addition, the cationically polymerizable compound having a heterocyclic structure includes a tetraglycidyl ether compound of polyethylene glycol, polyethylene glycol, and ethylene glycol added to an average of 9 moles of pentaerythritol, and 3-ethyl-3 {[(3-ethyl At least one of oxetane-3-yl) methoxy] methyl} oxetane. [5] The photosensitive resin laminate for exposure after peeling of the support film as described in the aspect 1 or 2 above, wherein the (A) alkali-soluble polymer includes a structure derived from at least one of acrylic acid and methacrylic acid, The compound (B) reactive with a photoinitiator includes a compound containing one or more thiol groups and a compound having two or more ethylenic double bonds, and the amount of the compound containing one or more thiol groups is relative to that of the photosensitizer. The total mass of the resin composition is 6% by mass or more, and the (C) photoinitiator includes a photopolymerization initiator. [6] The photosensitive resin laminate for exposing the support film after peeling as described in the aspect 5, wherein the compound containing one or more thiol groups includes pentaerythritol tetrakis (3-mercaptobutyrate), and the above has two The compound of the above ethylenic double bond includes a compound having a bisphenol A structure and two or more ethylenic double bonds. [7] The photosensitive resin laminate for exposure after peeling of the supporting film according to any one of aspects 3 to 6, wherein the (A) alkali-soluble polymer is based on the (A) alkali-soluble polymer In addition, a monomer unit derived from a monomer having an -OH group and / or -CN group is contained in an amount of 50% by mass or more. [8] The photosensitive resin laminate according to any one of aspects 1 to 7 above, comprising a cover film disposed on a surface of the photosensitive resin composition layer on a side opposite to the support film. [9] The photosensitive resin laminated body for exposure after peeling of the supporting film according to any one of aspects 1 to 8 above, wherein the exposure light of the exposure devices of (a) to (c) above is laser light. [10] A method for producing a resist pattern, comprising: a laminating step, in which the photosensitive resin composition layer of the photosensitive resin laminate according to any one of aspects 1 to 9 described above is adhered to a substrate On the substrate; a support film peeling step to peel off the support film of the photosensitive resin laminate; an exposure step to expose the photosensitive resin laminate; and a developing step to develop the exposed photosensitive resin laminate image. [11] The method for manufacturing a resist pattern according to the aspect 10, wherein the exposure step includes exposing from the side of the photosensitive resin laminate provided with the support film. [12] A method for manufacturing a wiring substrate, comprising: a resist pattern forming step, which manufactures a substrate having a resist pattern by the method described in aspect 10 or 11 above; and a wiring forming step, which The above-mentioned substrate having a resist pattern is subjected to etching or plating to form wiring on the substrate. [Effect of the invention]

According to the present invention, there is provided a photosensitive resin laminated body that can obtain a circuit board with fewer defective products even when a circuit board is produced by exposing the support film after exposure.

Hereinafter, the form (it is also hereafter called "this embodiment") for implementing this invention is demonstrated in detail. The present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist thereof. As long as the various characteristic values of the present invention are not specifically described, they are values measured by the method described in the [Example] of the present invention or a method understood by the industry as equivalent.

<Photosensitive resin laminate>
This embodiment provides a photosensitive resin laminate including a support film and a photosensitive resin laminate for exposing the support film after the support film is peeled off. The photosensitive resin composition layer is formed on the support film. The photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound having reactivity with a photoinitiator, and (C) a photoinitiator.

The supporting film is not particularly limited, and a transparent film that transmits light emitted from an exposure light source is preferred. Examples of such a support film include a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film and cellulose derivative film. These films can also be extended as needed. 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%. As for the thickness of the film, the thinner the film, the more advantageous it is in terms of image formation and economy, but in terms of the need to maintain strength, it is preferably 10 μm to 30 μm.

In the photosensitive resin multilayer system of this embodiment, the difference between the patternable minimum independent fine line widths between the first resist pattern and the second resist pattern is 5 μm or less, and the first resist pattern is based on The second resist pattern is obtained by exposing and developing a pattern after the support film is not peeled off and developing. The second resist pattern is the same as the first pattern except that the support film is exposed and developed before the exposure. Formed under conditions. Such a photosensitive resin laminated body provides a resist pattern with a low defect rate. The photosensitive resin laminated body of this embodiment is preferably used for forming wiring. The lower limit value of the difference between the minimum independent thin line widths that can be patterned between the second resist patterns obtained by forming a pattern under the same conditions as the first pattern is not particularly limited and may be 0.01 μm or more , 0.02 μm or more, 0.3 μm or more, 0.4 μm or more, 0.5 μm or more, and 1 μm or more.

The above-mentioned first resist pattern is a 0.4 mm thick copper foil laminated layer using a # 400 ground material (for example, Sakurundum A (# 400) manufactured by Carlit Co., Ltd. or its equivalent) with a 35 μm rolled copper foil on the laminated layer. The board is subjected to jet scraping and grinding, and then preheated to 60 ° C, and heated by a hot roll laminator (such as AL-700 manufactured by Asahi Kasei Co., Ltd. or its equivalent) at a roll temperature of 105 ° C, an air pressure of 0.35 MPa, After laminating the photosensitive resin laminate at a pressing speed of 1.5 m / min, the exposure is performed in accordance with the condition (1) (that is, using the following exposure device with the focus position aligned with the surface of the support film). The photosensitive resin composition layer peeling support film) is exposed, and a precision alkali developer (for example, a precision alkali developer manufactured by Fuji Machine Engineering or its equivalent) is used to spray 1 at 30 ° C for two times the minimum development time. A resist pattern obtained by removing unexposed portions by mass% Na ₂ CO ₃ aqueous solution, washing with pure water at the same time as the development time, and performing dewatering treatment with an air knife, followed by hot air drying. In addition, in the present invention, the "supporting film surface" means a surface of the supporting film opposite to the photosensitive resin composition layer side.

The second resist pattern is performed in accordance with the condition (2) (that is, the support film is peeled off, followed by exposure using the following exposure device in a state where the focus position is aligned with the original support film surface) in place of the above condition ( Except for the exposure of 1), a resist pattern obtained by the same procedure as in the formation of the first resist pattern described above.

The above-mentioned exposure device used in the formation of the first and second resist patterns is (a) an exposure device having a peak wavelength of light of 350 to 370 nm; (b) a peak wavelength of the light of exposure to 400 to 410 nm exposure device; (c) exposure device with peak wavelengths of 360 to 380 nm and 390 to 410 nm and a wavelength intensity ratio of 360 to 380 nm: 390 to 410 nm = 30: 70; and ( d) Any one of the mercury short arc lamps.

In a preferred correspondence, the exposure light of the exposure devices of (a) to (c) above is laser light.

The present inventors have found that when the photosensitive resin laminated body is exposed and developed under the same conditions except for the presence or absence of a peeling support film, the cause of the difference in pattern shape is oxygen barrier. That is, when the support film is peeled off before exposure, the surface on the support film formation side of the photosensitive resin composition layer is exposed due to the peeling of the support film, and it comes into contact with air, and oxygen diffuses into the photosensitive resin composition layer. Due to this oxygen, free radicals generated during exposure are deactivated. As a result, the hardening by exposure becomes insufficient, and the pattern shape deteriorates compared with the case where exposure and development are performed without peeling a support film. The inventors have found that if a photosensitive resin composition layer is formed which is difficult to be hindered by oxygen as described above, a good pattern shape can be achieved.

An example of a method for obtaining a photosensitive resin composition layer that is hardly hindered by oxygen is to set the oxygen permeability of the photosensitive resin composition layer to an extremely low value.

As a method for reducing the oxygen permeability, it is possible to increase the aggregation density of molecules in the photosensitive resin composition layer (especially (A) molecules of an alkali-soluble polymer), and prepare a photosensitive resin composition layer in which oxygen is difficult to penetrate. As this method, a method of increasing the resin cohesion density by the interaction of hydrogen bonds such as -OH, -CN, and the like to reduce the gap of oxygen penetration is considered.

In addition to setting the oxygen permeability to an extremely low value, examples of a method for obtaining a photosensitive resin composition layer that is hardly hindered by oxygen include a mechanism in which the polymerization mechanism of the photosensitive resin composition is hardly affected by oxygen ( For example, a photosensitive resin composition such as cationically polymerizable and enethiol-reactive).

In the case of a cationic polymerization photosensitive resin composition using a photocationic polymerization initiator, a strong acidic substance is generated by absorbing light, thereby protonating a corresponding hetero atom to perform a polymerization reaction. During this process, free radicals are not generated and therefore are not hindered by oxygen.

In the case of a photosensitive resin composition using an enethiol reaction, polymerization is performed using a generated sulfur radical. Furthermore, a thiol group and an unsaturated vinyl group react with oxygen to generate a radical reaction that is inert to the polymerization reaction, thereby generating a sulfur radical capable of undergoing the polymerization reaction. That is, it has the effect of reviving active radicals lost due to oxygen barrier.

Furthermore, as the substance that brings about the enethiol reaction, a compound containing a thiol group is preferred, but as long as it has the effect of generating an active radical from the inert free radical, it is not limited to a compound containing a thiol group Compound.

As an indicator of the low oxygen permeability of the photosensitive resin composition and the mechanism that it is difficult to be blocked by oxygen, the smallest independent fine line width difference between the first resist pattern and the second resist pattern that can be patterned can be used. .

The compound containing a thiol group contained in the photosensitive resin composition using an enethiol reaction needs to contain one or more thiol groups, preferably one containing two or more thiols, more preferably three or more, and more preferably It contains 4 or more.

In order to suppress swelling during development, the functional group possessed by the thiol group-containing compound preferably contains a functional group having low hydrophilicity, for example, it is preferable to include an organic concept map (by Koda Shansheng, "Organic Concept Map-Basic And application- ", Sankyo Publishing House (1984)), functional groups having an I value of less than 70, more preferably containing functional groups having an I value of 65 or less. Examples of the functional group having an I value of less than 70 include -COO-, -CO-, -NCO, -O-, -SH, -S-, and the like.

Hereinafter, a suitable example of each component which comprises the photosensitive resin composition of this embodiment is demonstrated.

[(A) Alkali-soluble polymer]
(A) Alkali-soluble polymers are polymers that are soluble in alkaline substances. From the viewpoint of basic developability, the photosensitive resin composition preferably has a carboxyl group, and more preferably has a monomer unit derived from a carboxyl group-containing monomer. (A) The alkali-soluble polymer may be thermoplastic.

As a method for reducing the oxygen permeability, in a preferred embodiment, the (A) alkali-soluble polymer includes a monomer unit derived from a monomer having an -OH group and / or -CN group. When (A) an alkali-soluble polymer is obtained using a monomer (for example, acrylonitrile, vinyl alcohol, vinylphenol, etc.) having an -OH group and / or -CN group, (A) the alkali-soluble polymer can be improved Because of the intermolecular interaction, it is preferable to increase the aggregation density of the (A) alkali-soluble polymer in the photosensitive resin composition layer and reduce the oxygen permeability. As for the amount of the monomer unit derived from the monomer having an -OH group and / or -CN group, it is preferably 50% by mass or more, more preferably 60% by mass or more based on the (A) alkali-soluble polymer, and furthermore It is preferably 70% by mass or more. The amount of the monomer unit may be 100% by mass, but from the viewpoint of developability and flexibility of the photosensitive layer, it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass. %the following.

(A) The alkali-soluble polymer preferably includes a copolymer having an aromatic group, and particularly preferably includes a copolymer having an aromatic group in a side chain. Examples of such an aromatic group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The proportion of the copolymer having an aromatic group in the component (A) is preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more. And more preferably 80% by mass or more. From the viewpoint of maintaining good alkali solubility, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass.

From the viewpoint of high resolution and hydrophobicity of the resist pattern, the copolymerization ratio of (A) the comonomer having an aromatic group in the alkali-soluble polymer is preferably 20% by mass or more, more preferably It is 30% by mass or more, more preferably 40% by mass or more, more preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more. The upper limit of the copolymerization ratio is not particularly limited, but from the viewpoint of maintaining good alkali solubility, it is preferably 95% by mass or less, and more preferably 90% by mass or less.

Examples of the comonomer having an aromatic group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinylphenol, vinyltoluene, third Butoxystyrene, ethoxylated styrene, 4-vinylbenzoic acid, styrene dimer, styrene terpolymer, etc.). Among them, a monomer having aralkyl group or styrene is preferable, and a monomer having aralkyl group is more preferable.

When the comonomer having an aromatic group contains styrene, as for the copolymerization ratio of styrene in the (A) alkali-soluble polymer, from the viewpoint of high resolution and hydrophobicity of the resist pattern, It is preferably 15% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more. From the viewpoint of maintaining good alkali solubility, it is preferably 80% by mass or less, and more preferably 70% by mass. Hereinafter, it is more preferably 60% by mass or less.

Examples of the aralkyl group include a substituted or unsubstituted benzyl group, a substituted or unsubstituted benzyl group (except benzyl), and the like, and a substituted or unsubstituted benzyl group is preferred.

Examples of the comonomer having a benzyl group include a (meth) acrylate having a benzyl group, such as a benzyl (meth) acrylate, a chlorobenzyl (meth) acrylate, and the like; a vinyl group having a benzyl group Monomers such as vinyl benzyl chloride, vinyl benzyl alcohol, and the like. Among these, benzyl (meth) acrylate is preferred.

Examples of the comonomer having a phenylalkyl group (except benzyl) include phenylethyl (meth) acrylate and the like.

The copolymer having an aromatic group (particularly a benzyl group) in the side chain is preferably prepared by comparing at least one of a monomer having an aromatic group and a first monomer described below and / or a second monomer described below. It is obtained by polymerizing at least one species.

The (A) alkali-soluble polymer other than the copolymer having an aromatic group in the side chain is preferably obtained by polymerizing at least one of the following first monomers, and more preferably by polymerizing the first monomers. It is obtained by copolymerizing at least one species with at least one species of the second monomer described below.

A monomer having a carboxyl group in the first single-system molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, butenoic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half esters. Among these, (meth) acrylic acid is preferred. Further, in this specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, "(meth) acrylfluorenyl" means acrylfluorenyl or methacrylfluorenyl, and "(meth) "Acrylate" means "acrylate" or "methacrylate".

The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components of the polymer obtained by polymerizing at least one of the first monomers. From the viewpoint of good developability, the copolymerization ratio is preferably 10% by mass or more. From the viewpoint of high resolution of the resist pattern, and further from the viewpoint of chemical resistance of the resist pattern, the copolymerization ratio is preferably 50% by mass or less. Among these viewpoints, It is more preferably 35% by mass or less, further preferably 30% by mass or less, particularly preferably 25% by mass or less, and most preferably 20% by mass or less.

The second monomer is a monomer which 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, and n- (meth) acrylate Butyl ester, isobutyl (meth) acrylate, third butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic ring (Meth) acrylates such as hexyl ester, 2-ethylhexyl (meth) acrylate; vinyl alcohol esters such as vinyl acetate; and (meth) acrylonitrile.

From the viewpoint of developability, the (A) alkali-soluble polymer preferably includes a structure derived from at least one of acrylic acid and methacrylic acid.

In this embodiment, (A) the alkali-soluble polymer can be prepared by polymerizing the singular or plural monomers described above by a known polymerization method, preferably addition polymerization, more preferably radical polymerization. From the viewpoint of chemical resistance, adhesion, high resolution, or bottom shape of the resist pattern, it is preferable to include a monomer having an aralkyl group and / or styrene as the monomer. Examples include: Copolymers of acrylic acid and vinyl alcohol and styrene, copolymers of methacrylic acid and acrylonitrile and styrene, copolymers of methacrylic acid and styrene and methyl methacrylate, and the like.

As for the acid equivalent of the (A) alkali-soluble polymer (in the case where the component (A) contains a plurality of copolymers, the acid equivalent of the entire mixture), the development resistance of the photosensitive resin composition layer and the corrosion resistance From the viewpoint of resolution and adhesion of the agent pattern, it is preferably 100 or more, and from the viewpoint of the developability and peelability of the photosensitive resin composition layer, it is preferably 600 or less. (A) The acid equivalent of the alkali-soluble polymer is more preferably 200 to 500, and more preferably 250 to 450.

The weight average molecular weight of the (A) alkali-soluble polymer (when the component (A) contains a plurality of types of copolymers, the weight average molecular weight of the entire mixture thereof) is preferably 5,000 to 500,000. As for the weight average molecular weight of the (A) alkali-soluble polymer, it is preferably 5,000 or more from the viewpoint of uniformly maintaining the thickness of the dry film resist and obtaining resistance to a developing solution, and maintaining the dry film resist From the viewpoint of the developability, the viewpoint of the high resolution of the resist pattern and the shape of the bottom, and the viewpoint of the chemical resistance of the resist pattern, it is preferably 500,000 or less. (A) The weight average molecular weight of the alkali-soluble polymer is more preferably 10,000 to 200,000, further preferably 20,000 to 100,000, and particularly preferably 30,000 to 70,000. (A) The molecular weight dispersion index of the alkali-soluble polymer is preferably 1.0 to 6.0.

In this embodiment, the content of the (A) alkali-soluble polymer in the photosensitive resin composition is based on the total amount of solid components of the photosensitive resin composition (hereinafter, unless otherwise specified, it is included in each contained component The same) is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, still more preferably 30% by mass to 60% by mass, and still more preferably 35 to 55% by mass. As for the content of the (A) alkali-soluble polymer, it is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin composition layer, and the resist pattern formed by exposure is fully exerted as an anti-resistance. The viewpoint of the performance of the resist material, the viewpoint of the high resolution of the resist pattern and the shape of the bottom, and the viewpoint of the chemical resistance of the resist pattern are preferably 90% by mass or less, more preferably 70% by mass. % Or less, more preferably 60% by mass or less.

[(B) A compound reactive with a photoinitiator] (B) A compound reactive with a photoinitiator may be reacted with the following (C) according to the polymerization pattern required for the photosensitive resin composition. The combination of initiators is selected. For example, in a preferred example of the case where the photosensitive resin composition is cationically polymerizable, the compound (B) having reactivity with a photoinitiator is selected from a cationically polymerizable compound having a heterocyclic structure and vinyl ether. At least one type of compound of the compound may include a cationic polymerizable compound, and the (C) photoinitiator is a photocationic polymerization initiator or includes the same. Furthermore, in this example, it is more preferable that (A) the alkali-soluble polymer includes a structure derived from at least one of acrylic acid and methacrylic acid.

As a more preferable example, the compound having a reactivity with the photoinitiator (B) is a cationically polymerizable compound having a heterocyclic structure or includes it. Preferable examples of the cationically polymerizable compound having a heterocyclic structure include diglycidyl ether of polyethylene glycol, which is an average of 5 moles of ethylene oxide added to both ends of bisphenol A, and bisphenol A diglycidyl ether, polyethylene glycol tetraglycidyl ether with an average 9 moles of ethylene oxide added to pentaerythritol, polyethylene glycol with an average 9 moles of ethylene oxide added to trimethylolpropane Triglycidyl ethers of diols, 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane, and the like. Particularly preferred is a cationic polymerizable compound having a heterocyclic structure, a tetraglycidyl ether of polyethylene glycol with an average of 9 moles of ethylene oxide added to pentaerythritol, and 3-ethyl-3 {[(3-ethyl At least one of oxetane-3-yl) methoxy] methyl} oxetane or includes it.

Preferred examples of the vinyl ether compound include diethylene glycol monovinyl ether and the like.

In a preferable example when the photosensitive resin composition is made reactive with enethiol, the compound (B) having reactivity with a photoinitiator is a compound containing one or more thiol groups and having two or more thiol groups. The compound containing an ethylenic double bond may include the same, and the (C) photoinitiator is a photopolymerization initiator or includes the same. Furthermore, in this example, it is more preferable that (A) the alkali-soluble polymer includes a structure derived from at least one of acrylic acid and methacrylic acid.

Examples of the compound containing one or more thiol groups include pentaerythritol tetrakis (3-mercaptobutyrate) and the like. The compound containing one or more thiol groups is preferably pentaerythritol tetrakis (3-mercaptobutyrate) or includes it.

The amount of the thiol group-containing compound is preferably more than 5 mass%, more preferably 6 mass% or more, still more preferably 7 mass% or more, and still more preferably 9 mass% with respect to the total mass of the photosensitive resin composition. The above is particularly preferably 10% by mass or more, more preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and particularly preferably 70% by mass or less.

The amount of the thiol group-containing compound is, on a mass basis, preferably 0.3 times or more, more preferably 1 time or more, still more preferably 5 times or more, particularly preferably 10 times or more, with respect to the starting dose. It is preferably 100 times or less, more preferably 50 times or less, even more preferably 40 times or less, and particularly preferably 30 times or less.

<Compound having an ethylenic double bond> The compound having an ethylenic double bond which is a compound having reactivity with a photoinitiator (B) is a compound having a polymerizability because it has an ethylenically unsaturated group in its structure. Examples of such a compound include a compound obtained by adding (meth) acrylic acid to one end of a polyalkylene oxide, adding (meth) acrylic acid to one end of a polyalkylene oxide, and making the other terminal alkylene Compounds derived from etherification of allyl ethers or allyl groups (compounds of group 1); compounds having (meth) acrylfluorene groups at both ends of the alkylene oxide chain; Compounds having a (meth) acrylfluorenyl group at both ends of an alkylene oxide chain formed by bonding of an ethane chain and a propylene oxide chain, a compound modified by bisphenol A, and the like (group 2 compound); Compounds having three or more (meth) acrylfluorenyl groups in one molecule (compounds of group 3); etc.

Specific examples of the other compounds of the first group include phenoxyhexaethylene glycol mono (meth) acrylate which is a (meth) acrylate of a compound in which p-phenyl group is added with polyethylene glycol, (Meth) acrylates of compounds obtained by adding polypropylene glycol with an average of 2 moles of propylene oxide and polyethylene glycol with an average of 7 moles of ethylene oxide to nonylphenol That is, 4-n-nonylphenoxy heptaethylene glycol dipropylene glycol (meth) acrylate, polypropylene glycol with an average of 1 mol of propylene oxide, and ethylene oxide with an average of 5 mols The (meth) acrylate of a compound obtained by adding polyethylene glycol to nonylphenol is 4-n-nonylphenoxy pentaethylene glycol monopropylene glycol (meth) acrylate. The average addition is 8 Acrylic acid esters of compounds obtained by the addition of polyethylene glycol to nonylphenol by Mol are 4-n-nonylphenoxy octaethylene glycol (meth) acrylate and the like.

Specific examples of the other compounds in the second group include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, and hexaethylene glycol di (meth) acrylate. , Heptaethylene glycol di (meth) acrylate, octaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, in Polyethylene glycol (meth) acrylates such as compounds having a (meth) acrylfluorenyl group at both ends of a 12 mol ethylene oxide chain; polypropylene glycol di (meth) acrylate; polybutylene glycol di ( (Meth) acrylates and the like. Examples of the polyalkylene oxide di (meth) acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound include polypropylene glycol to which an average amount of 12 mol of propylene oxide is added, and further Dimethacrylates of glycols with an average of 3 moles of ethylene oxide added at both ends, polypropylene glycols with an average of 18 moles of propylene oxide added at both ends and an average of 15 at both ends Diethylene glycol dimethacrylate of ethylene oxide, etc.
Other examples include compounds having an ethylenic double bond at both ends of a polyalkylene glycol obtained by adding alkylene oxide to bisphenol A.

Among the compounds of the second group, the compound modified with bisphenol A is preferably used for a polymer obtained by adding alkylene oxide to bisphenol A from the viewpoint of resolvability and adhesion. A compound having an ethylenic double bond at both ends of the alkylene glycol. The ethylenic double bond in the compound is preferably contained in the compound as a (meth) acrylfluorenyl group.

For modification of bisphenol A by addition of alkylene oxide, for example, ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, and epoxy resin are known. Alkyl modification, etc. A compound having a (meth) acrylfluorenyl group at both ends of a polyalkylene glycol obtained by adding ethylene oxide to bisphenol A is preferred.

Examples of such a compound include 2,2-bis (4-((meth) acryloxyoxyethoxy) phenyl) propane (for example, NK ESTER BPE- manufactured by Shin Nakamura Chemical Industry Co., Ltd.) 200), 2,2-bis (4-((meth) propenylethoxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) propenyloxyethoxytetraethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxypentaethoxy) phenyl) propane (e.g. NK ESTER BPE-500 manufactured by Shin Nakamura Chemical Industry Co., Ltd.) Wait. Furthermore, for example, a poly (alkyl) glycol di (meth) acrylate or poly (alkyl) glycol obtained by adding an average of 2 moles of propylene oxide and an average of 6 moles of ethylene oxide to both ends of bisphenol A. The bisphenol A is bis (meth) acrylate of polyalkylene glycol which is an average of 2 moles of propylene oxide and 15 moles of ethylene oxide. Ethylene oxide modified and propylene oxide modified compounds are also preferred. From the viewpoint of improving resolution, adhesion, and flexibility, ethylene oxide and ring in compounds having a (meth) acrylfluorenyl group at both ends are modified by alkylene oxide modification of bisphenol A. The molar number of oxypropane is preferably 1 mol to 60 mol, more preferably 4 mol to 40 mol, and still more preferably 5 mol to 20 mol.

The compound of the third group is obtained by (meth) acrylation of an alcohol having a central skeleton having 3 mol or more of an alkylene group capable of adding an alkylene oxide group in the molecule. Obtained as alkoxy, such as ethoxy, propoxy, butoxy. Examples of compounds that can serve as a central skeleton include glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, and an isocyanurate ring.

More specifically, for example, trimethylolpropane ethylene oxide (EO) 3 mole modified triacrylate, trimethylolpropane EO 6 mole modified triacrylate, trimethylol EO 9 mol modified triacrylate of propyl propane, EO 12 mol modified triacrylate of trimethylolpropane and the like. Examples of such compounds include EO 3 mol modified triacrylate of glycerol (for example, A-GLY-3E manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and EO 9 mol modified triacrylate of glycerol ( For example, A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd., EO 6 mole of glycerol and propylene oxide (PO) 6 mole modified triacrylate (A-GLY-0606PE), and EO of glycerol 9 Moore PO 9 Moire modified triacrylate (A-GLY-0909PE), etc. Further examples are: 4 EO modified tetraacrylate of pentaerythritol (for example, SR-494 manufactured by Sartomer Japan), and 35 EO modified tetraacrylate of pentaerythritol (for example, NK manufactured by Shin Nakamura Chemical Industry Co., Ltd.) ESTER ATM-35E) and so on.

Examples of the compound having an ethylenic double bond include an isocyanurate compound having an ethylenic double bond. Specific examples of such compounds include, for example, ethoxylated isotricyanic acid tri (meth) acrylate, ε-caprolactone-modified tris (2- (meth) propenyloxyethyl) iso Cyanurate, triallyl isocyanurate, (EO) -modified isocyanurate-derived tris (meth) acrylate (ethylene oxide average 27 mol adduct), etc.
Commercially available such compounds can be used, and examples include UA-7100, A-9300-1CL (above manufactured by Shin Nakamura Chemical Industry Co., Ltd.); ARONIX M-327 (manufactured by Toa Kasei Corporation), and the like.

Examples of the compound having a urethane bond and an ethylenic double bond include hexamethylene diisocyanate, toluene diisocyanate, or a diisocyanate compound (for example, 2,2,4-trimethylhexamethylene) Diisocyanate) and a urethane compound of a compound having a hydroxyl group and a (meth) acrylic group in one molecule (for example, 2-hydroxypropyl acrylate, propylene glycol monomethacrylate). Specifically, it is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Blemmer PP1000 manufactured by Nippon Oil & Fat Co., Ltd.).

Examples of the compound having a phthalic acid structure and an ethylenic double bond include γ-chloro-β-hydroxypropyl-β '-(meth) acryloxyethyl-phthalate, β-hydroxyalkyl-β '-(meth) acryloxyalkyl-phthalate and the like.

In addition, as the compound having an ethylenic double bond, tricyclodecane di (meth) acrylate or 2,2-bis {4- (methacryloxypentylethoxy) cyclohexyl} propane may be included. Wait.

In the case where the compound having two or more ethylenic double bonds has a combination of a bisphenol A structure and two or more ethylenic double bonds, the crosslinking density, hydrophobicity, and reactivity can be improved, and the minimum independent thin line can be reduced. It is better in terms of wide difference. It is particularly preferable that the compound containing one or more thiol groups is pentaerythritol tetrakis (3-mercaptobutyrate) or a compound containing the same, and the compound having two or more ethylenic double bonds is a compound having a bisphenol A structure and two or more ethylenes. Compounds with a combination of sexual double bonds may include them.

The content of the compound (B) in the photosensitive resin composition that is reactive with the photoinitiator is preferably 10% by mass or more from the viewpoint of good physical properties, resolution, and adhesion of the cured film. It is 15% by mass or more, and more preferably 30% by mass or more. From the viewpoint of blending appropriate amounts of other components of the photosensitive resin composition (especially (A) alkali-soluble polymer), 90% is preferred. % Or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less.

(C) Photoinitiator
(C) A photoinitiator is a compound which polymerizes a monomer by light. The photosensitive resin composition may contain a compound generally known in the art as a (C) photoinitiator. Examples of the (C) photoinitiator include quinones, aromatic ketones, acetophenones, fluorenylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, and 9-oxysulfur. Type, dialkylaminobenzoates, oxime esters, acridines (e.g. 9-phenylacridine, bisacridylheptane, 9- (p-methylphenyl) acridine, 9- ( M-methylphenyl) acridine is preferred in terms of sensitivity, resolution and adhesion), hexaarylbiimidazole, pyrazoline compounds, coumarin compounds (e.g. 7-diethylamino-4-methyl Base coumarin is better in terms of sensitivity, resolution and adhesion), N-arylamino acid or its ester compound (e.g. N-phenylglycine in terms of sensitivity, resolution and adhesion It is preferred) and halogen compounds (such as tribromomethylphenylphosphonium). These can be used individually by 1 type or in combination of 2 or more types. Alternatively, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthienyl) -2-morpholinylpropane- 1-ketone, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, triphenylphosphine oxide, etc.

Examples of the aromatic ketones include benzophenone, Michelin [4,4'-bis (dimethylamino) benzophenone], and 4,4'-bis (diethylamino). Benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 1-hydroxy-cyclohexyl-phenylketone. These can be used individually by 1 type or in combination of 2 or more types. Among these, 4,4'-bis (diethylamino) benzophenone and 1-hydroxy-cyclohexyl-phenyl ketone are preferable from a viewpoint of adhesiveness. Furthermore, from the viewpoint of transmittance, the content of the aromatic ketones in the photosensitive resin composition is preferably in a range of 0.01% by mass to 0.5% by mass, and more preferably in a range of 0.02% by mass to 0.3% by mass.

Examples of hexaarylbiimidazole include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ', 5-tris (o-chlorophenyl) -4- (3 , 4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis (o-chlorophenyl) -5- (3,4-dimethoxyphenyl)- Diphenylbiimidazole, 2,4,5-tris (o-chlorophenyl) -diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-dimethoxy (Phenyl) -biimidazole, 2,2'-bis (2-fluorophenyl) -4,4 ', 5,5'-tetra (3-methoxyphenyl) -biimidazole, 2,2'- Bis (2,3-difluoromethylphenyl) -4,4 ', 5,5'-tetra (3-methoxyphenyl) -biimidazole, 2,2'-bis (2,4-bis (Fluorophenyl) -4,4 ', 5,5'-tetra (3-methoxyphenyl) -biimidazole, 2,2'-bis (2,5-difluorophenyl) -4,4' , 5,5'-tetra (3-methoxyphenyl) -biimidazole, 2,2'-bis (2,6-difluorophenyl) -4,4 ', 5,5'-tetra (3 -Methoxyphenyl) -biimidazole, 2,2'-bis (2,3,4-trifluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) -Biimidazole, 2,2'-bis (2,3,5-trifluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) -biimidazole, 2,2 '-Bis (2,3,6-trifluorophenyl) -4,4', 5,5'-tetra (3-methoxyphenyl) -biimidazole, 2,2'-bis (2,4 , 5-trifluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) -biimidazole, 2,2'-bis (2,4,6-trifluorophenyl) -4,4 ', 5,5'-tetra (3-methoxyphenyl) -biimidazole, 2,2'-bis ( 2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetra (3-methoxyphenyl) -biimidazole, 2,2'-bis (2,3,4 , 6-tetrafluorophenyl) -4,4 ', 5,5'-tetra (3-methoxyphenyl) -biimidazole and 2,2'-bis (2,3,4,5,6- Pentafluorophenyl) -4,4 ', 5,5'-tetrakis (3-methoxyphenyl) -biimidazole, etc. These can be used alone or in combination of two or more. From the viewpoints of high sensitivity, resolvability, and adhesion, 2- (o-chlorophenyl) -4,5-dibenzimidazole dimer is preferred.

From the standpoint of the peeling characteristics, sensitivity, resolution, or adhesion of the photosensitive resin composition layer, it is preferred that the photosensitive resin composition also contains one or two or more kinds of pyrazoline compounds as the (C) light. Initiator.

As the pyrazoline compound, for example, 1-phenyl-3- (4-third butylstyryl) -5- (4-third butylphenyl) -pyrazoline is preferred from the viewpoints described above. 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-third butylstyryl) -5- (4-third butylphenyl) -pyrazoline 1-phenyl-3- (4-biphenyl) -5- (4-third butylphenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-third octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline, 1 -Phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- (3,5-dimethoxybenzene Vinyl) -5- (3,5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3,4-dimethoxystyryl) -5- (3,4 -Dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,6-dimethoxystyryl) -5- (2,6-dimethoxyphenyl) -pyridine Oxazoline, 1-phenyl-3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,3-dimethoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,4-dimethoxybenzene Vinyl) -5- (2,4-dimethoxyphenyl) -pyrazoline, etc., more preferably It is 1-phenyl-3- (4-biphenyl) -5- (4-third butylphenyl) -pyrazoline.

Examples of the ester compound of N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, Isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, third butyl ester of N-phenylglycine , Pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, octyl ester of N-phenylglycine, and the like.

Examples of the halogen compound include bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, 1,2-dibromoethane, diphenylbromomethane, benzyl bromide, and diphenyl bromide. Methyl bromide, tribromomethylphenylphosphonium, carbon tetrabromide, tris (2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-tris Chloro-2,2-bis (p-chlorophenyl) ethane, trichloride chloride, diallyl sulfonium compound, etc., especially tribromomethylphenylsulfonium is preferred.

<Photocationic polymerizable initiator>
It is also preferable to include a photocationic polymerizable initiator. The photopolymerization initiator is one which generates a strong acid by light irradiation or heating, and protonates a heteroatom by the strong acid to start a polymerization reaction, and may include a generally known compound.

<Example of photocationic polymerizable initiator>
A cationic photopolymerizable initiator, and examples thereof include aryl sulfonium salts, aryl iodonium salt include anionic moiety comprising _{^{BF 4 -, PF 6 -,}} SbF 6 - salt of the compound.

The amount of the (C) photoinitiator in the photosensitive resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of hardening the photosensitive resin composition. It is further preferably 0.1% by mass or more, and from the viewpoint of controlling the curing of the photosensitive resin composition, it is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less.

(D) Additive The photosensitive resin composition may contain additives such as a dye, a plasticizer, an antioxidant, and a stabilizer, as necessary. For example, additives listed in Japanese Patent Laid-Open No. 2013-156369 can be used.

From the viewpoints of colorability, hue stability, and exposure contrast, the photosensitive resin composition preferably contains tris (4-dimethylaminophenyl) methane [crypto crystal violet] and / or diamond green (Hodogaya Aizen (registered trademark) (DIAMOND GREEN GH) manufactured by Chemical Co., Ltd. is used as a dye.

In this embodiment, the content of the dye in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, and more preferably 0.01% by mass to 2% by mass. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good coloring properties, and preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin composition layer.

From the viewpoint of thermal stability or storage stability of the photosensitive resin composition, it is preferable that the photosensitive resin composition contains, as a stabilizer, at least one selected from the group consisting of a radical polymerization inhibitor, For example: nitrosophenylhydroxylamine aluminum salt, p-methoxyphenol, 4-tert-butylcatechol, 4-ethyl-6-tert-butylphenol, etc .; benzotriazoles, for example: 1 -(N, N-bis (2-ethylhexyl) aminomethyl) -1,2,3-benzotriazole, 2,2 '-(((methyl-1H-benzotriazole-1 -Yl) methyl) imino) diethanol, 1- (2-di-n-butylaminomethyl) -5-carboxybenzotriazole and 1- (2-di-n-butylaminomethyl) 1: 1 mixture of 6-carboxybenzotriazole; etc .; carboxybenzotriazoles, for example: 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzene Benzotriazole, 6-carboxy-1,2,3-benzotriazole, etc .; and compounds having glycidyl groups, such as bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, neopentyl Glycidyl ether and the like. It may also contain 2-mercaptobenzimidazole, 1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 3-mercaptotriazole, 4,5-diphenyl-1,3-di Azole-2-yl, 5-amino-1H-tetrazole and the like.

In this embodiment, the total content of all stabilizers in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.01% by mass to 1% by mass, and still more preferably 0.05% by mass to 0.7. Within the mass% range. The total content of the stabilizer is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3 from the viewpoint of maintaining the sensitivity of the photosensitive resin composition layer. Mass% or less.

The additives described above can be used alone or in combination of two or more.

In a preferred aspect, the photosensitive resin laminate includes a cover film on a surface of the photosensitive resin composition layer that is opposite to the support film side. An important characteristic of the cover film is that the adhesion with the photosensitive resin composition layer is smaller than that of the support film, and it can be easily peeled off. As a cover film, a polyethylene film, a polypropylene film, etc. are preferable, for example. For example, a film having excellent peelability described in Japanese Patent Laid-Open No. 59-202457 can be used. The film thickness of the cover film 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 3 μm to 100 μm, and more preferably 5 μm to 60 μm. The smaller the thickness of the photosensitive resin composition layer is, the higher the resolution of the resist pattern is. On the other hand, the larger the thickness is, the higher the strength of the cured film is. Therefore, it can be selected according to the application.

As a method for sequentially laminating a support film, a photosensitive resin composition layer, and a cover film as necessary to produce a photosensitive resin laminate, a known method can be used. For example, a blending solution containing a photosensitive resin composition and a solvent is prepared, followed by coating on a support film with a bar coater or a roll coater and drying it, and laminating the photosensitive resin composition on the support film. A photosensitive resin composition layer formed by preparing a liquid. Furthermore, when a cover film is laminated | stacked on the photosensitive resin composition layer as needed, a photosensitive resin laminated body can be manufactured.

<Manufacturing method of resist pattern> This embodiment further provides a manufacturing method of a resist pattern including the following steps: A laminating step, which is in contact with a photosensitive resin composition layer of a photosensitive resin laminated body on a substrate; support The film peeling step peels off the supporting film of the photosensitive resin laminate; the exposure step exposes the photosensitive resin laminate; and the developing step develops the exposed photosensitive resin laminate.

First, in a laminating step, a photosensitive resin composition layer is closely adhered to a substrate using a laminator. Specifically, when the photosensitive resin laminated body has a protective layer, the protective layer is peeled off, and then the photosensitive resin composition layer of the photosensitive resin laminated body is heated and pressure-bonded to the surface of the substrate by a laminator. Laminate. Examples of the material of the substrate include copper, stainless steel (SUS), glass, and indium tin oxide (ITO). A preferred example of the substrate is a copper foil laminate.

In this embodiment, the photosensitive resin composition layer may be laminated on only one side of the surface of the substrate, or may be laminated on both sides if necessary. The heating temperature during lamination is generally 40 ° C ~ 160 ° C. In addition, the heat-pressure bonding when laminating is performed twice or more can improve the adhesion of the obtained resist pattern to the substrate. When heating and crimping, a two-stage laminator equipped with a double roll can be used, or the laminate can be crimped by repeatedly passing the laminate of the substrate and the photosensitive resin laminate through the roll.

Next, in the support film peeling step, the support film of the photosensitive resin laminate is peeled.

Next, in the exposure step, the photosensitive resin composition layer is exposed using an exposure device. Typically, the exposure step includes exposing from the side of the photosensitive resin laminated body on which the support film is provided. Typically, the exposure device is
(a) an exposure device with a peak wavelength of light of 350 to 370 nm; (b) an exposure device with a peak wavelength of light of 400 to 410 nm; (c) a peak wavelength of light of exposure to 360 to 380 nm And 390 ~ 410 nm, and an exposure device with a wavelength intensity ratio of 360 ~ 380 nm: 390 ~ 410 nm = 30: 70; and (d) any one of mercury short arc lamps. In the case of exposure through a photomask, the exposure amount is determined by the illuminance of the light source and the exposure time, and can be measured using a light meter. In the exposure step, direct imaging exposure can be performed. In the direct imaging exposure, the mask is used instead, and the substrate is exposed by a direct drawing device. When the drawing pattern is controlled by a computer, the exposure amount is determined by the illuminance of the exposure light source and the moving speed of the substrate. Exposure can be performed by projecting an image of the photomask through a lens.

Next, in the developing step, an unexposed portion or an exposed portion in the exposed photosensitive resin composition layer is removed by a developing solution using a developing device. Then, using a developing solution containing an alkaline aqueous solution, the unexposed portion or the exposed portion is developed and removed, and a resist image is obtained through a water washing step and a drying step. In the above water washing step, ion-exchanged water or water to which magnesium ions or calcium ions are added may be used.

The alkaline aqueous solution is preferably an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like. The alkaline aqueous solution is selected according to the characteristics of the photosensitive resin composition layer, and an aqueous Na ₂ CO ₃ solution having a concentration of 0.2% to 2% by mass is usually used. Surfactants, defoamers, small amounts of organic solvents used to promote development can be added to the alkaline aqueous solution. The temperature of the developing solution in the developing step is preferably kept constant within a range of 20 ° C to 40 ° C.

The resist pattern is obtained through the above steps, but a heating step may be further performed at 100 ° C to 300 ° C as necessary. By performing this heating step, the chemical resistance of the resist pattern can be improved. In the heating step, a heating furnace using hot air, infrared, or far infrared can be used.

<Manufacturing Method of Wiring Substrate> This embodiment further provides a manufacturing method of a wiring substrate including a wiring forming step. The wiring forming step is to manufacture a substrate having a resist pattern by the above-mentioned method for manufacturing a resist pattern. The substrate having the resist pattern is subjected to etching or plating to form wiring on the substrate. In the wiring formation step, the resist pattern is peeled from the substrate by an aqueous solution having an alkali stronger than the developing solution.

There is no particular limitation on the alkaline aqueous solution for peeling (hereinafter also referred to as "peeling solution"). Generally, a 2 to 5 mass% NaOH or KOH aqueous solution or an organic amine-based peeling solution is used. A small amount of water-soluble solvent can be added to the stripping solution. Examples of the water-soluble solvent include alcohols. The temperature of the peeling liquid in the peeling step is preferably within a range of 40 ° C to 70 ° C. In order to perform a SAP (Semi Additive Process), the method for manufacturing a wiring board preferably further includes a step of removing palladium from the obtained wiring board.
[Example]

Hereinafter, the present invention will be further described with examples, but the present invention is not limited to the following examples.

[Examples 1 to 12 and Comparative Examples 1 to 4]
＜ Production of photosensitive resin laminated body ＞
The composition of the photosensitive resin composition used in each Example and Comparative Example is shown in Table 1, and the details of each component name described in Table 1 are shown in Table 2. The blending amounts of each component in Table 1 are all parts by mass converted to solid components. The components A to D shown in Table 1 are mixed, and further selected from methyl ethyl ketone, ethanol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate, which have better solubility, to prepare a photosensitive resin. combination.

The obtained photosensitive resin composition was uniformly coated on a support film, that is, a polyethylene terephthalate film with a thickness of 16 μm (manufactured by Toray Co., Ltd., product name "FB40") using a bar coater. After that, it was dried in a dryer adjusted to a temperature of 95 ° C. for 5 minutes to form a photosensitive resin composition layer having a thickness of 10 μm on a support film.

Next, a 33 μm-thick polyethylene film (manufactured by Tamapoly Corporation, product name “GF-858”) was attached to the surface of the photosensitive resin composition layer on the side opposite to the support film. This obtained a photosensitive resin laminated body.

＜ Production of wiring board ＞
(Manufacture of base material)
A 0.4 mm-thick copper foil laminated board laminated with a 35 μm rolled copper foil was subjected to spray scraping and grinding using a ground material (Sakurundum A (# 400) manufactured by Carlit Japan Co., Ltd.).

(laminated)
The polyethylene film of the photosensitive resin laminate obtained in each of the examples or comparative examples was peeled, and the temperature of the roller was 105 ° C. and the pressure of 0.35 by a hot roll laminator (AL-700 manufactured by Asahi Kasei Co., Ltd.). Laminated on the above substrate under conditions of MPa and a lamination speed of 1.5 m / min to obtain a laminated substrate.

(exposure)
Regarding each Example and Comparative Example, the above-mentioned laminated substrate was exposed under the following conditions (1) and (2), respectively. The focal positions of the exposure devices of the conditions (1) and (2) are aligned with the surface of the support film.

Condition (1)
Examples 2 and 9 and Comparative Example 2 were obtained by using a direct drawing exposure apparatus (Paragon-Ultra 100 manufactured by Orbotech Co., Ltd., light source peak wavelength: 355 nm) on an unpeeled polyethylene terephthalate film. In the state, exposure is performed with an exposure amount that can obtain the smallest independent thin line.

In Example 3 and Comparative Example 3, a direct drawing exposure device (IP-8 M8000H manufactured by ADTEC Engineering, light source peak wavelength: 405 nm) was used in a state where the polyethylene terephthalate film was not peeled. It is possible to obtain the exposure of the smallest independent thin line.

Examples 1, 5, 6, 7, 8, 11, and 12 and Comparative Example 1 are exposure devices using a mercury short-arc lamp (AHD-5000R manufactured by Oak Corporation) as a light source (EXM manufactured by Oak Corporation) -1201), in a state where the polyethylene terephthalate film is not peeled off, the exposure is performed with an exposure amount capable of obtaining the smallest independent fine line.

Examples 4 and 10 and Comparative Example 4 used a direct drawing exposure machine (NuvogoF10 manufactured by Orbotech Co., Ltd., light source peak wavelength: 375 nm (30%) + 405 nm (70%)). In the state of the ethylene formate film, exposure is performed with an exposure amount that can obtain the smallest independent fine line.

Condition (2)
In the state in which the polyethylene terephthalate film is peeled off, the exposure is performed in the same order as in the above condition (1), except that the exposure is obtained with the smallest amount of independent fine lines.

(Development)
Secondly, for each laminated substrate after exposure under the above conditions (1) and (2), a precision alkali imager manufactured by Fuji Machine Works was used to spray 1% by mass of 30 ° C at twice the minimum development time. The Na ₂ CO ₃ aqueous solution was used to remove the unexposed portion. After the development, the substrate was washed with pure water at the same time as the development time, and then air-dried by an air knife, followed by hot air drying, to obtain a substrate having an evaluation hardened film having an independent thin line pattern. The minimum development time is the minimum time required until the unexposed portion of the photosensitive resin composition layer is completely dissolved and removed.

(Evaluation of independent fine line width)
Among the smallest independent thin line patterns formed on the substrate, the width of the thickest part was taken as the smallest independent thin line width, and the determination was made according to the following criteria. The results are shown in Table 1.
A: The minimum independence between the first resist pattern obtained by exposing the support film without peeling (condition (1)) and the second resist pattern obtained by exposing the support film after peeling (condition (2)) Thin line width difference is less than 3 μm
B: The minimum independence between the first resist pattern obtained by exposing the support film without peeling (condition (1)) and the second resist pattern obtained by exposing the support film after peeling (condition (2)) The difference between the fine line widths is greater than 3 μm and less than 5 μm
C: Minimum independence between the first resist pattern obtained by exposing the support film without peeling (condition (1)) and the second resist pattern obtained by exposing the support film after peeling (condition (2)) Thin line width difference greater than 5 μm

Furthermore, the photosensitive resin composition layer containing the photosensitive resin composition of Examples 1-12 was used, and the circuit board was formed by exposing and peeling a support film. Regarding the difference in wiring width between the case where a circuit substrate is produced by exposing the support film after peeling and the case where exposure is performed without peeling the support film, and the case where the circuit substrate is produced under the same conditions as the case where the support film is exposed after peeling, The examples 1 to 12 are smaller than the comparative examples 1 to 4. Therefore, regarding the defect rate of the circuit board, the examples 1 to 12 are smaller than the comparative examples 1 to 4.

P: "Paragon Ultra" made by Orbotech
I: "IP-8 M8000H" manufactured by ADTEC Engineering
E: "EXM-1201" manufactured by Oak Manufacturing
N: "NuvogoF10" manufactured by Orbotech

Table 2
[Industrial availability]

The manufacturing method of the photosensitive resin laminated body and resist pattern of this invention can be suitably used for manufacture of various circuit boards.

Claims (12)

A photosensitive resin laminate for exposing after a support film is peeled off, comprising a support film and a photosensitive resin composition layer, wherein the photosensitive resin composition layer is disposed on the support film and includes a photosensitive resin composition; The said photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a compound reactive with a photoinitiator, and (C) a photoinitiator. 35 μm rolled copper is laminated on the laminated material using a # 400 grinding material. The 0.4 mm thick copper foil laminate was spray-brazed and ground, and then pre-heated to 60 ° C. Using a hot roll laminator, the roll temperature was 105 ° C, air pressure was 0.35 MPa, and the lamination speed was 1.5 m / min. The above-mentioned photosensitive resin laminated body is laminated on the above-mentioned copper foil laminated board under the conditions, and then exposure is performed in accordance with any one of the following conditions (1) and (2): (1) using an exposure device, the focus position is aligned to support The film is exposed in a state of the film surface, and the supporting film is peeled off from the photosensitive resin composition layer after the exposure; (2) The supporting film is peeled off, and then the exposure device is used to align the focus position with the original supporting film surface. Exposure; using precision alkali The developing machine sprays a 1% by mass Na ₂ CO ₃ aqueous solution at 30 ° C. at a time twice as long as the minimum developing time to remove the unexposed portions, and the water is washed with pure water at the same time as the developing time, and is performed with an air knife. After the water removal treatment, hot air drying is performed to obtain a resist pattern. Among the resist patterns, a first resist pattern obtained by exposure to the above condition (1) and an exposure obtained from the above condition (2) are obtained. The difference in the patternable minimum independent fine line width of the second resist pattern is 5 μm or less. The above exposure device is (a) an exposure device having a peak wavelength of light of 350 to 370 nm; (b) an exposure device. An exposure device with a peak wavelength of light of 400 to 410 nm; (c) The peak wavelength of exposed light is 360 to 380 nm and 390 to 410 nm, and the wavelength intensity ratio is 360 to 380 nm: 390 to 410 nm = 30: 70 exposure device; and (d) any one of mercury short arc lamps. The photosensitive resin laminated body for exposure after peeling of the support film according to claim 1, which is used to form wiring. For example, the photosensitive resin laminated body for exposure after peeling of the supporting film of claim 1 or 2, wherein the (A) alkali-soluble polymer includes a structure derived from at least one of acrylic acid and methacrylic acid, and the above (B) and Guangqi The compound having a reactive initiator includes at least one type of cationically polymerizable compound selected from a cationic polymerizable compound having a heterocyclic structure and a vinyl ether compound, and the (C) photoinitiator includes a photocationic polymerization initiator. For example, the photosensitive resin laminate for exposure after peeling of the supporting film of claim 3, wherein the compound (B) reactive with the photoinitiator includes a cationically polymerizable compound having a heterocyclic structure, and the compound having a heterocyclic structure described above The cationic polymerizable compound includes a tetraglycidyl ether compound of polyethylene glycol, polyethylene glycol, and ethylene glycol, each of which has an average addition of 9 moles to pentaerythritol, and 3-ethyl-3 {[(3-ethyloxetane- 3-yl) methoxy] methyl} oxetane. For example, the photosensitive resin laminate for exposure after peeling of the support film of claim 1 or 2, wherein the (A) alkali-soluble polymer includes a structure derived from at least one of acrylic acid and methacrylic acid, and the above (B) and light The compound having a reactive initiator includes a compound containing one or more thiol groups and a compound having two or more ethylenic double bonds. The amount of the compound containing one or more thiol groups is relative to the total amount of the photosensitive resin composition. The mass is 6 mass% or more, and the (C) photoinitiator includes a photopolymerization initiator. For example, the photosensitive resin laminate for exposure after peeling of the supporting film of claim 5, wherein the compound containing one or more thiol groups includes pentaerythritol tetrakis (3-mercaptobutyric acid) ester, and the above having two or more ethylenic double bonds The compound includes a compound having a bisphenol A structure and two or more ethylenic double bonds. For example, the photosensitive resin laminate for exposure after peeling of the support film of claim 3, wherein the (A) alkali-soluble polymer is based on the (A) alkali-soluble polymer and contains 50% by mass or more of the polymer having- A monomer unit of an OH-based and / or -CN-based monomer. For example, the photosensitive resin laminated body for exposure after peeling of the support film of Claim 1 or 2 is provided with the cover film arrange | positioned on the surface of the said photosensitive resin composition layer on the side opposite to the said support film. For example, the photosensitive resin laminated body for exposure after peeling of the support film of claim 1 or 2, wherein the exposure light of the exposure devices of (a) to (c) above is laser light. A method for manufacturing a resist pattern includes: In the laminating step, the photosensitive resin composition layer of the photosensitive resin laminate for exposure after peeling of the supporting film according to any one of claims 1 to 9 is adhered to the substrate; A supporting film peeling step, peeling the supporting film of the photosensitive resin laminate; An exposure step of exposing the photosensitive resin laminate; and The developing step develops the exposed photosensitive resin laminate. The method for manufacturing a resist pattern according to claim 10, wherein the exposure step includes exposing from the side of the photosensitive resin laminated body on which the support film is provided. A method for manufacturing a wiring substrate, comprising: a resist pattern forming step for manufacturing a substrate having a resist pattern by a method such as claim 10 or 11; and a wiring forming step for applying a resist pattern to the above The substrate is etched or plated to form wiring on the substrate.