JP2018031800A - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which forms a cured film particularly excellent in tent reliability.SOLUTION: The photosensitive resin composition contains a component (A): a binder polymer, a component (B): a compound having an isocyanuric ring skeleton as a photopolymerizable compound, a component (C): a photopolymerization initiator, and a component (D): a compound having at least two or more of polyethylene oxide [-(CHO)-], polypropylene oxide [-(CHO)-], and polytetramethylene oxide [-(CHO)-] (k, l and m are each 1 or more, and k+l+m is 20 or more) as structural units.SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to a photosensitive resin composition, a photosensitive element, a method for forming a resist pattern, and a method for manufacturing a printed wiring board.

  Conventionally, in the field of manufacturing printed wiring boards, a photosensitive resin composition as a resist material used for etching treatment or plating treatment, and a photosensitive resin layer obtained using the photosensitive resin composition, a support, and a protective layer Photosensitive elements having the following are widely used.

  A printed wiring board is formed by laminating the photosensitive element on a circuit-forming substrate, exposing the photosensitive resin layer in a pattern, and then removing the unexposed portion with a developer to form a resist pattern, followed by an etching process. Alternatively, after the plating process is performed to form a circuit on the substrate, the cured portion that is the exposed portion is removed from the substrate and removed.

  As the developer, an alkaline developer such as an aqueous sodium carbonate solution or an aqueous sodium hydrogen carbonate solution is mainly used from the viewpoint of environmental performance and safety. The unexposed portion of the photosensitive resin layer is removed from the substrate by the development pressure with these developers and the spray pressure of water washing. Therefore, the photosensitive resin composition is required to be capable of forming a cured film (resist pattern) having excellent tent reliability (tenting property) that is not damaged by the spray pressure of development and washing after exposure. . Further, it is necessary to improve the adhesion so that the cured film is not peeled off from the substrate by the spray pressure of development and washing with water.

  In order to improve the tent reliability, it is known to increase the strength and flexibility of a cured film formed using a photosensitive resin composition (for example, Patent Document 1).

JP 2001-117224 A JP 2006-234959 A JP 2007-1222028 A International Publication No. 2008/078483 JP 2009-69465 A International Publication No. 2010/103918

  However, even when the photosensitive resin composition described in Patent Document 1 is used, it may not be said that the tent reliability is sufficiently excellent.

  Further, in order to improve the tent reliability, there is a problem in that productivity is lowered because the peeling time becomes longer when the strength of the cured film is increased. Further, when the flexibility of the cured film is increased, there is a problem that the alkali resistance of the cured film is lowered and the resolution is lowered.

  In particular, direct drawing exposure that directly draws digital data of a pattern produced by CAD (Computer-Aided Design) called LDI (Laser Direct Imaging) method or DLP (Digital Light Processing) on a photosensitive resin composition layer by laser light. The resist material of one embodiment used in the method is required to have low exposure and alkali resistance at a low degree of cure from the viewpoint of throughput (throughput) per unit time. Therefore, a compound having a rigid skeleton is often contained. However, in order to improve the throughput per unit time (throughput), the rigid skeleton compound contained in the resist material used in the direct drawing exposure method tends to reduce the tenting property, so the direct drawing A resist material that sufficiently satisfies all of high throughput, high resolution, and high tenting properties by the exposure method has not been developed so far. For example, even when the photosensitive resin compositions described in Patent Documents 2 to 6 were used, there was room for improvement.

  Then, this indication aims at providing the photosensitive resin composition in which the tent reliability of the cured film formed is especially excellent. Further, as one embodiment, a photosensitive resin capable of forming a resist pattern even at a low exposure amount, excellent in peeling time, resolution and adhesion, and particularly excellent in tent reliability of a formed cured film. An object is to provide a composition. Moreover, it aims at providing the photosensitive element using the said photosensitive resin composition, the formation method of a resist pattern, and the manufacturing method of a printed wiring board.

Specific means for solving the above problems are as follows.
<1> (A) component: a binder polymer,
(B) component: As a photopolymerizable compound, a compound having an isocyanuric ring skeleton,
(C) component: a photopolymerization initiator,
Component (D): Polyethylene oxide [— (C ₂ H ₄ O) _k —], polypropylene oxide [— (C ₃ H ₆ O) _l —] and polytetramethylene oxide [— (C ₄ H ₈ O) _m — ] (K, l and m are 1 or more, k + l + m is 20 or more) a compound having at least two as structural units,
The photosensitive resin composition containing this.

<2> The photosensitive composition according to <1>, wherein the component (A) has a structural unit derived from (meth) acrylic acid, a structural unit derived from alkyl (meth) acrylate, and a structural unit derived from styrene. Resin composition.

<3> The component (D) is polyethylene oxide [— (C ₂ H ₄ O) _k —] and polypropylene oxide [— (C ₃ H ₆ O) _l —] (k and l are 1 or more, k + 1 is 20) The photosensitive resin composition according to <1> or <2>, including a compound having the above as a structural unit.

<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the component (D) includes a compound having a structural unit in which k + 1 + m is 30 or more.

<5> A support and a photosensitive resin layer formed on the support and formed using the photosensitive resin composition according to any one of <1> to <4>. Having a photosensitive element.

<6> Using the photosensitive resin composition according to any one of <1> to <4>, a step of forming a photosensitive resin layer on a substrate (photosensitive resin layer forming step);
Irradiating at least a part of the photosensitive resin layer with actinic rays to cure the region (exposure step);
A step (developing step) of removing an unexposed portion other than the region of the photosensitive resin layer from the substrate;
A method for forming a resist pattern having

<7> A method for producing a printed wiring board, comprising a step of etching or plating a substrate on which a resist pattern is formed by the method according to <6>.

  According to the present disclosure, it is possible to provide a photosensitive resin composition in which the tent reliability of the formed cured film is particularly excellent. Further, as one embodiment, a photosensitive resin capable of forming a resist pattern even at a low exposure amount, excellent in peeling time, resolution and adhesion, and particularly excellent in tent reliability of a formed cured film. A composition can be provided. Moreover, it becomes possible to provide the photosensitive element using the said photosensitive resin composition, the formation method of a resist pattern, and the manufacturing method of a printed wiring board.

It is an end view which shows one Embodiment of the photosensitive element of this embodiment. It is process drawing which illustrates the manufacturing method of the printed wiring board of this embodiment. It is a top view of the hole tearing number measuring substrate used for evaluation of tent reliability.

  Hereinafter, a form for carrying out this indication is explained in detail, referring to drawings if needed. However, the present disclosure is not limited to the following embodiment. In the following embodiments, it is needless to say that the constituent elements (including element steps and the like) are not necessarily indispensable unless otherwise specified and clearly considered essential in principle. This also applies to numerical values and ranges, and should not be construed to unduly limit the present disclosure. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  In this specification, “(meth) acrylic acid” means at least one of “acrylic acid” and “methacrylic acid”. The same applies to other similar expressions such as (meth) acrylate.

  In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. . Moreover, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. Furthermore, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. Further, in this specification, the term “layer” includes a structure formed in a part in addition to a structure formed in the entire surface when observed as a plan view.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment includes (A) component: binder polymer, (B) component: a compound having an isocyanuric ring skeleton as a photopolymerizable compound, (C) component: a photopolymerization initiator, Component (D): Polyethylene oxide [— (C ₂ H ₄ O) _k —], polypropylene oxide [— (C ₃ H ₆ O) _l —] and polytetramethylene oxide [— (C ₄ H ₈ O) _m — ], Wherein k, l and m are integers of 1 or more, k + 1 + m is 20 or more, and a compound having at least two as structural units. Here, k, l, and m represent the number of structural units. Therefore, an integer value is shown in a single molecule, and a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. Hereinafter, the same applies to the number of structural units. Moreover, in this specification, these components may be simply called (A) component, (B) component, (C) component, (D) component, etc.

  The said photosensitive resin composition may further contain another component as needed.

  Hereinafter, each component will be described in detail.

[(A) component: binder polymer]
The photosensitive resin composition contains at least one binder polymer as the component (A). The binder polymer has a structural unit (A1) having a structural unit derived from styrene (hereinafter sometimes simply referred to as “structural unit (A1)”) from the viewpoint of improving adhesion and developer resistance. May be. Further, from the viewpoint of improving tenting properties, the structural unit (A2) derived from alkyl (meth) acrylate (hereinafter sometimes simply referred to as “structural unit (A2)”) may be included. Further, from the viewpoint of improving developability and peelability, it may have a structural unit (A3) derived from (meth) acrylic acid (hereinafter sometimes simply referred to as “structural unit (A3)”). .

  From the viewpoint of improving developability, tenting properties, adhesion, and peelability, the binder polymer preferably has a structural unit (A1), a structural unit (A2), and a structural unit (A3).

・ Structural unit (A1)
Specific examples of the structural unit derived from styrene include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as α-methylstyrene, vinyltoluene, and p-chlorostyrene.

  When the binder polymer has a structural unit (A1), the content of the structural unit (A1) in the total solid content of the binder polymer is preferably 10 to 60% by mass, and more preferably 13 to 40% by mass. Preferably, it is 15 to 25% by mass. When the content is 10% by mass or more, the adhesion tends to be improved. When the content is 60% by mass or less, the peeling piece can be prevented from becoming large, and the peeling time can be prevented from becoming long. Tending to be improved.

・ Structural unit (A2)
The alkyl group in the alkyl (meth) acrylate may be linear or branched. Examples of the alkyl (meth) acrylate include compounds represented by the following general formula (I).
^{_{CH 2 = C (R 3)}} -COOR 4 (I)
In general formula (I), R < ³ > shows a hydrogen atom or a methyl group, R < ⁴ > shows a C1-C20 alkyl group.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁴ in the general formula (I) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Group, decyl group, undecyl group, dodecyl group and structural isomers thereof. The alkyl group having 1 to 20 carbon atoms represented by R ⁴ may have a substituent. Examples of the substituent include a hydroxyl group, an epoxy group, and a halogen group. When the alkyl group having 1 to 20 carbon atoms represented by R ⁴ has a substituent, the number of substituents and the substitution position are not particularly limited.

  The alkyl group in the alkyl (meth) acrylate preferably has 1 to 20 carbon atoms, more preferably 5 to 20 carbon atoms from the viewpoint of further improving tenting properties, and 8 carbon atoms. More preferably, it is -14.

  Examples of the compound represented by the general formula (I) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Nonyl acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

  When the binder polymer has a structural unit (A2), the content of the structural unit (A2) in the total mass of the binder polymer is 1 to 70% by mass from the viewpoint of improving adhesion, resolution, and developability. It is preferably 30 to 65% by mass, more preferably 45 to 60% by mass. By setting the content to 1% by mass or more, the tenting property of the cured film is further improved, and by setting the content to 80% by mass or less, the resolution and adhesion are further improved.

・ Structural unit (A3)
At least one of the binder polymers preferably has a carboxy group from the viewpoint of improving alkali developability. The binder polymer having a carboxyl group may have a structural unit derived from (meth) acrylic acid. The binder polymer having a carboxy group can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxy group and another polymerizable monomer. Examples of the polymerizable monomer having a carboxy group (hereinafter simply referred to as “structural unit (A3)”) include (meth) acrylic acid; α-bromoacrylic acid, α-chloroacrylic acid, β- (Meth) acrylic acid derivatives such as furyl (meth) acrylic acid and β-styryl (meth) acrylic acid; maleic acid; maleic acid derivatives such as monomethyl maleate, monoethyl maleate and monoisopropyl maleate; fumaric acid and cinnamon Examples include acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like, (meth) acrylic acid is preferable, and methacrylic acid is more preferable.

  When the binder polymer contains the structural unit (A3), the content of the structural unit (A3) is 12 to 50% by mass in the total mass of the binder polymer from the viewpoint of improving the alkali developability and developer resistance in a balanced manner. It is preferably 15 to 35% by mass, more preferably 15 to 30% by mass, from the viewpoint of superior alkali developability.

-Other structural unit The binder polymer may contain other structural units other than said (A1)-(A3). The other structural unit may be a structural unit derived from the following polymerizable monomer. Examples of the polymerizable monomer include acrylamide such as diacetone acrylamide; acrylonitrile; ethers of vinyl alcohol such as vinyl-n-butyl ether; and organic acid derivatives such as maleic anhydride. These can be used alone or in combination of two or more.

The content of other structural units in the total mass of the binder polymer is preferably 10% by mass or less, more preferably 5% by mass or less from the viewpoint of improving adhesion, resolution, and developability. More preferably, it is not substantially contained.
That is, the content of the total amount of the structural units (A1), (A2), and (A3) in the total mass of the binder polymer is preferably 90% by mass or more, and more preferably 95% by mass or more.

The binder polymer is obtained by polymerizing monomers corresponding to each structural unit. Examples of the polymerization method include radical polymerization.
In the copolymer thus obtained, each structural unit may be randomly contained in the copolymer such as a so-called random copolymer, or some specific unit such as a block copolymer. It may be a copolymer in which structural units exist in a localized manner. Each structural unit may be a single type or a plurality of types.

  Furthermore, in addition to the binder polymer containing the structural unit (A1), (A2) or (A3), another binder polymer may be used in combination. Other binder polymers are not particularly limited as long as they are soluble in an alkaline aqueous solution and can form a film. For example, acrylic resins (however, those not including the structural units (A1), (A2) and (A3)), epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins are listed. It is done. Among these, acrylic resins are preferable from the viewpoint of improving alkali developability. These can be used alone or in combination of two or more.

  Even when other binder polymer is used, the content of the structural unit (A1) in the total amount of the binder polymer nonvolatile content in the total amount of the binder polymer is preferably 10 to 60% by mass, and 13 to 40% by mass. Is more preferable, and it is still more preferable that it is 15-25 mass%. When using another binder polymer, it is preferably 10% by mass or less, and more preferably 5% by mass or less. It is more preferable that other binder polymers are not substantially contained, and it is particularly preferable that other binder polymers are not contained. In the present specification, “substantially does not contain” means less than 1% by mass, preferably 0.1% by mass or less, more preferably 0.01% by mass or less. It preferably means that it is not contained (cannot be detected), and it is more preferable.

The weight average molecular weight of the binder polymer is preferably 20,000 to 300,000, more preferably 30,000 to 200,000 from the viewpoint of improving the developer resistance and alkali developability in a balanced manner. More preferably, it is 40,000-100,000.
In addition, the weight average molecular weight in this specification is a value measured by a gel permeation chromatography method (GPC) and converted by a calibration curve prepared using standard polystyrene, and the measurement conditions are the same as in the examples. .

  The acid value of the binder polymer is preferably 120 to 200 mgKOH / g, and more preferably 150 to 170 mgKOH / g.

  The binder polymer as the component (A) can be used alone or in combination of two or more. As a binder polymer in the case of using two or more types in combination, two or more types of binder polymers comprising different copolymerization components, two or more types of binder polymers having different weight average molecular weights, two or more types of binder polymers having different degrees of dispersion, etc. Is mentioned. The dispersion degree of the binder polymer is obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).

  The content of the binder polymer as the component (A) is preferably 30 to 80 parts by mass, and 40 to 75 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). More preferably, it is more preferable to set it as 50-70 mass parts. When the content of the component (A) is within this range, the coating property of the photosensitive resin composition and the strength of the photocured product become better.

[(B) component: photopolymerizable compound]
The photosensitive resin composition includes a compound having an isocyanuric ring skeleton (“may be referred to as (B1) component”). The compound having an isocyanuric ring is not particularly limited, but preferably has 3 or more (meth) acryloyl groups in one molecule, and more preferably 3 to 6 (meth) acryloyl groups in one molecule. It is particularly preferable to have three (meth) acryloyl groups in one molecule.

  Although there is no restriction | limiting in particular as said (B1) component, For example, the compound represented by general formula (II) is mentioned preferably.

一般式（II）中のＲ¹、Ｒ²及びＲ³は、各々独立に
(−Ｘ¹−Ｏ−)_m1Ｃ(＝Ｏ)Ｃ(Ｒ⁴)＝ＣＨ₂
（式中、Ｒ⁴は水素原子又はメチル基を示し、Ｘ¹は炭素数２〜６のアルキレン基を示し、ｍ１は１〜３０である）、又は
(−ＣＨ₂)_n−ＮＨ−Ｃ(＝Ｏ)Ｏ(−Ｘ²−Ｏ−)_m2Ｃ(＝Ｏ)−Ｃ(Ｒ⁵)＝ＣＨ₂
（式中、Ｒ^５は水素原子又はメチル基を示し、Ｘ^２は炭素数２〜６のアルキレン基を示し、ｎは１〜９であり、ｍ２は１〜３０である）である。尚、ｎ、ｍ１及びｍ２は構造単位の構造単位数を示す。

R ¹ , R ² and R ³ in the general formula (II) are each independently
(—X ¹ —O—) _m1 C (═O) C (R ⁴ ) ═CH ₂
(Wherein R ⁴ represents a hydrogen atom or a methyl group, X ¹ represents an alkylene group having 2 to 6 carbon atoms, and m1 is 1 to 30), or
(—CH ₂ ) _n —NH—C (═O) O (—X ² —O—) _m ² C (═O) —C (R ⁵ ) ═CH ₂
(Wherein R ⁵ represents a hydrogen atom or a methyl group, X ² represents an alkylene group having 2 to 6 carbon atoms, n is 1 to 9, and m2 is 1 to 30). Note that n, m1, and m2 indicate the number of structural units.

Examples of the alkylene group having 2 to 6 carbon atoms in X ¹ and X ² include an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, a neopentylene group, and a hexylene group. An ethylene group is preferred. The isopropylene group is a group represented by —CH (CH ₃ ) CH ₂ —, and — (X ¹ —O) — and — in R ¹ , R ² and R ³ in the general formula (II). In (X ² —O) —, there are two types of bonding directions, a case where the methylene group is bonded to oxygen and a case where the methylene group is not bonded to oxygen. The coupling directions may be mixed. When the repeating units of-(X ¹ -O)-and-(X ² -O)-are each 2 or more, 2 or more of X ¹ and 2 or more of X ² may be the same or different. Well, when X ¹ and X ² are composed of two or more alkylene groups, two or more of — (X ¹ —O) — and — (X ² —O) — may be present randomly. However, it may exist in blocks.

  On the other hand, m1 and m2 are each independently 1-30, and are preferably 4 or more, more preferably 8 or more, and 12 or more in terms of improving tent reliability and peelability. Further preferred. Further, in terms of improving resolution, it is preferably 28 or less, more preferably 24 or less, and further preferably 20 or less.

  The photosensitive resin composition may contain other photopolymerizable compounds (sometimes referred to as “component (B2)”) other than the component (B1). The component (B2) is not particularly limited, and can be appropriately selected from commonly used photopolymerizable compounds. Examples of the photopolymerizable compound include compounds having a photopolymerizable unsaturated double bond.

  Specifically, examples of the photopolymerizable compound include polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polyethylene polypropylene glycol di (meth) acrylate; trimethylolpropane tri Multifunctional (meth) acrylates such as (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) Bisphenol A-based (meth) acrylate compounds such as propane and 2,2-bis (4-((meth) acryloxypolyethyleneoxypolypropyleneoxy) phenyl) propane; γ-chloro-β-hydroxy Cypropyl-β '-(meth) acryloyloxyethylene-o-phthalate, β-hydroxyethyl-β'-(meth) acryloyloxyethylene-o-phthalate, β-hydroxypropyl-β '-(meth) acryloyloxyethylene- phthalic acid derivatives such as o-phthalate; alkyl (meth) acrylate; and the like.

  Among these, from the viewpoint of improving adhesion and resolution, it is preferable to include at least one selected from the group consisting of a bisphenol A-based (meth) acrylate compound and a polyalkylene glycol poly (meth) acrylate, and bisphenol A It is more preferable to use at least one type (meth) acrylate compound and at least one polyalkylene glycol poly (meth) acrylate in combination, 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) More preferably, at least one of propane and at least one of polyethylene glycol poly (meth) acrylate are used in combination.

  Examples of 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethyleneoxy) phenyl) propane, 2,2- Bis (4-((meth) acryloxypentaethyleneoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypentadecaethyleneoxy) phenyl) propane may be mentioned.

  Among these, commercially available products include 2,2-bis (4- (methacryloxypentaethyleneoxy) phenyl) propane (made by Shin-Nakamura Chemical Co., Ltd., product name “BPE-500”, or Hitachi Chemical. Product name “FA-321M”) 2,2-bis (4- (methacryloxypentadecaethyleneoxy) phenyl) propane (made by Shin-Nakamura Chemical Co., Ltd., product name “BPE-1300”), etc. Can be mentioned. These can be used alone or in combination of two or more.

  When a plurality of components (B) are used in combination, the compound having two or more unsaturated double bonds capable of photopolymerization in one molecule is 75% by mass or more in the total nonvolatile content of component (B). Is preferred. (T) Tenting property, resolving power, and adhesiveness when the compound having two or more unsaturated double bonds capable of photopolymerization in one molecule is 75% by mass or more in the total nonvolatile content of the component (B). Tend to improve more.

  It is preferable that content of (B) component in the said photosensitive resin composition shall be 20-70 mass parts in 100 mass parts of total amounts of (A) component and (B) component. In terms of further improving the tent reliability and resolution, the content is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and still more preferably 30 parts by mass or more. The content is preferably 70 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 55 parts by mass or less, and even more preferably 50 parts by mass or less in that the film property is imparted and the resist shape after curing is superior. Particularly preferred.

  The content of the component (B1) in the photosensitive resin composition is preferably 1 to 30 parts by mass in 100 parts by mass of the total amount of the component (A) and the component (B). 1 mass part or more is preferable at the point which improves a tent reliability, 6 mass parts or more are more preferable, and 12 mass parts or more are still more preferable. 30 mass parts or less are preferable at the point which improves resolution, 25 mass parts or less are more preferable, and 20 mass parts or less are still more preferable.

[(C) component: photopolymerization initiator]
The said photosensitive resin composition contains at least 1 sort (s) of a photoinitiator as (C) component. There is no restriction | limiting in particular as a photoinitiator, It can select from the photoinitiator used normally, and can use it suitably. Among these, the component (C) preferably contains an acridine compound having one or two acridinyl groups in one molecule. That is, the component (C) is composed of an acridine compound having two acridinyl groups (hereinafter also referred to as “(C1) compound”) and an acridine compound having one acridinyl group (hereinafter also referred to as “(C2) compound”). It is preferable that at least one compound selected from the group consisting of:

  Examples of the compound (C1) include acridine compounds represented by the following general formula (III).

In the formula (III), R ³ represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms. R ³ is preferably an alkylene group having 2 to 20 carbon atoms, more preferably an alkylene group having 4 to 14 carbon atoms, from the viewpoint of more reliably obtaining the effect exhibited by the photosensitive resin composition.

  Examples of the compound represented by the general formula (III) include 1,2-di (9-acridinyl) ethane, 1,3-di (9-acridinyl) propane, 1,4-di (9-acridinyl). Butane, 1,5-di (9-acridinyl) pentane, 1,6-di (9-acridinyl) hexane, 1,7-di (9-acridinyl) heptane, 1,8-di (9-acridinyl) octane, 1,9-di (9-acridinyl) nonane, 1,10-di (9-acridinyl) decane, 1,11-di (9-acridinyl) undecane, 1,12-di (9-acridinyl) dodecane, 1, 14-di (9-acridinyl) tetradecane, 1,16-di (9-acridinyl) hexadecane, 1,18-di (9-acridinyl) octadecane, 1,20-di (9-acridinyl) eico Di (9-acridinyl) alkanes such as 1,3-di (9-acridinyl) -2-oxapropane; 1,5-di (9-acridinyl) -3-oxapentane; 1,3-di (9 -Acridinyl) -2-thiapropane; 1,5-di (9-acridinyl) -3-thiapentane. These are used individually by 1 type or in combination of 2 or more types.

From the standpoint of improving photosensitivity and resolution, as the (C1) compound, an acridine compound in which R ³ in the formula (III) is a heptylene group (for example, product name “N-1717” manufactured by ADEKA Corporation) ) Is preferably included.

  When the photosensitive resin composition contains the compound (C1), the content of the compound (C1) is the total amount of the component (A) and the component (B) from the viewpoint of further improving sensitivity, resolution, and adhesion. It is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, still more preferably 1 to 5 parts by mass, and 1 to 3 parts by mass with respect to 100 parts by mass. It is particularly preferred that There exists a tendency for a more favorable sensitivity, resolution, or adhesiveness to be acquired as this content is 0.1 mass part or more. When the amount is 10 parts by mass or less, a better resist shape tends to be obtained.

  Examples of (C2) compounds include acridine compounds represented by the following general formula (IV).

In formula (IV), R ⁴ represents a halogen atom, an amino group, a carboxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkylamino group having 1 to 6 carbon atoms. m shows the integer of 0-5.

  Examples of the acridine compound represented by the general formula (IV) include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine, and 9- (p-chlorophenyl) acridine. , 9- (m-chlorophenyl) acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylaminoacridine and 9-pentylaminoacridine. These are used individually by 1 type or in combination of 2 or more types.

  When the photosensitive resin composition contains the compound (C2), the content of the compound (C2) is the total amount of the component (A) and the component (B) from the viewpoint of improving sensitivity, resolution, and adhesion. It is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, still more preferably 1 to 5 parts by mass, and 1 to 3 parts by mass with respect to 100 parts by mass. It is particularly preferred that There exists a tendency for a more favorable sensitivity, resolution, or adhesiveness to be acquired as this content is 0.1 mass part or more. When the amount is 10 parts by mass or less, a better resist shape tends to be obtained.

  The photosensitive resin composition may contain a photopolymerization initiator other than the compound (C1) and the compound (C2).

Examples of photopolymerization initiators other than the (C1) compound and the (C2) compound include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4 ′. -Diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl An aromatic ketone compound such as 2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2 -Phenylanthraquinone, 2,3-diphenylanthra Quinone compounds such as quinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone; benzoin methyl ether, Benzoin ether compounds such as benzoin ethyl ether and benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer 2-mer (p-metoki) 2,4,5-triarylimidazole dimers such as phenyl) -4,5-diphenylimidazole dimer; benzyl derivatives such as benzyldimethyl ketal; 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, Substituted anthracene compounds such as 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dipentoxyanthracene; coumarin compounds; oxazole compounds; pyrazoline compounds; triarylamine compounds;
These are used individually by 1 type or in combination of 2 or more types. Moreover, it is good also as a photoinitiator combining a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and a dimethylamino benzoic acid.

  The 2,4,5-triarylimidazole dimer is a symmetric compound in which the aryl group substituents of the two 2,4,5-triarylimidazoles constituting the dimer are the same. They may be different or asymmetrical compounds.

  In the case where the photosensitive resin composition contains a photopolymerization initiator other than the (C1) compound and the (C2) compound, the content is from the viewpoint of further improving the sensitivity and the internal photocurability, (B) It is preferable that it is 0.01-10 mass parts with respect to 100 mass parts of non volatile matter total amount of a component, It is more preferable that it is 0.1-7 mass parts, 0.2-5 mass parts It is particularly preferred.

  The content of the component (C) is from 0.01 to 100 parts by mass with respect to 100 parts by mass of the nonvolatile content of the component (A) and the component (B) from the viewpoint of further improving the sensitivity, adhesion, and internal photocurability. The amount is preferably 20 parts by mass, more preferably 0.05 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass.

The photosensitive resin composition contains at least one selected from the group consisting of the compound (C1) and the compound (C2) from the viewpoint of further improving sensitivity, adhesion, and internal photocurability, and the content thereof is It is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and it is more preferable that it is 0.5-5 mass parts.
Moreover, the said photosensitive resin composition contains at least 1 sort (s) chosen from the group which consists of (C1) compound and (C2) compound from a viewpoint which improves a sensitivity, adhesiveness, and internal photocurability more, The containing It is preferable that it is 3-30 mass parts with respect to 100 mass parts of content of (D) component which the amount mentions later, and it is more preferable that it is 5-20 mass parts.

[Component (D): Polyethylene oxide _{[- (C 2 H 4 O)} k - ] and polypropylene oxide _{[- (C 3 H 6 O)} l - ] (k and l is an integer of at least 1, k + l is 20 or more) A compound having as a structural unit)
The photosensitive resin composition comprises, as component (D), polyethylene oxide [— (C ₂ H ₄ O) _k —] and polypropylene oxide [— (C ₃ H ₆ O) _l —] (k and l are integers of 1 or more). , K + 1 is 20 or more) as a structural unit. (D) A component may be used individually by 1 type or in combination of 2 or more types.

  The content of the component (D) is preferably 2% by mass or more based on the total solid content of the photosensitive resin composition, so that the resist pattern peelability and tenting properties are further improved, and preferably 3% by mass or more. Is more preferable, and 4 mass% or more is still more preferable. Similarly, when the content is 20% by mass or less, the resolution and tenting properties are further improved, which is preferably 15% by mass or less, and more preferably 10% by mass or less.

The component (D) has polyethylene oxide [— (C ₂ H ₄ O) _k —: k is 1 or more] and polypropylene oxide [— (C ₃ H ₆ O) ₁ —: 1 is 1 or more] as structural units. A compound is preferred. By containing polyethylene oxide, developability is further improved, tenting properties are further improved, and by having polypropylene oxide together, the viscosity of component (D) is further reduced and it is easy to mix with other components. Become.

  The component (D) is preferably a compound having a structural unit in which k + 1 + m is 30 or more. When k + l + m is 30 or more, the strength of the resist pattern is further improved, so that the tenting property is further improved.

[Other ingredients]
In addition, the photosensitive resin composition of the present embodiment, if necessary, a dye such as malachite green, Victoria pure blue, brilliant green, methyl violet; leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, Photochromic agent such as o-chloroaniline; Thermochromic inhibitor; Plasticizer such as p-toluenesulfonamide; Pigment; Filler; Antifoaming agent; Flame retardant; Adhesion imparting agent; Leveling agent; Other additives such as an inhibitor, a polymerization inhibitor, a fragrance, an imaging agent, and a thermal crosslinking agent may be further included.

  When the said photosensitive resin composition contains another additive, the content can be suitably selected according to the objective etc. For example, it can contain about 0.01-20 mass parts with respect to 100 mass parts of non volatile matters total of (A) component and (B) component, respectively. These can be used individually by 1 type or in combination of 2 or more types.

Moreover, the photosensitive resin composition may further contain at least one organic solvent. Organic solvents include alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as methyl cellosolve, ethyl cellosolve, and propylene glycol monomethyl ether; aromatic hydrocarbon solvents such as toluene; N, N- And aprotic polar solvents such as dimethylformamide. These may be used alone or in combination of two or more.
Content of the organic solvent contained in the said photosensitive resin composition can be suitably selected according to the objective etc. For example, it can be used as a solution having a nonvolatile content of about 30 to 60% by mass (hereinafter, a photosensitive resin composition containing an organic solvent is also referred to as “coating solution”).

  The said photosensitive resin composition can be used for formation of the photosensitive resin layer of the photosensitive element mentioned later. That is, another embodiment of the present disclosure is the use of the photosensitive resin composition for a photosensitive element. Moreover, the said photosensitive resin composition can be used for the formation method of the resist pattern mentioned later, and the manufacturing method of a printed wiring board.

<Photosensitive element>
The photosensitive element of this embodiment has a support body and the photosensitive resin layer formed using the said photosensitive resin composition provided on this support body. The said photosensitive element may have other layers, such as a protective layer, as needed.

  In FIG. 1, one Embodiment of the photosensitive element of this embodiment is shown. In the photosensitive element 10 shown in FIG. 1, the support body 2, the photosensitive resin layer 4 formed using the said photosensitive resin composition, and the protective layer 6 are laminated | stacked in this order. The photosensitive element 10 can be obtained as follows, for example. On the support 2, a coating solution which is the photosensitive resin composition containing an organic solvent is applied to form a coating layer, which is dried to form the photosensitive resin layer 4. Next, the surface opposite to the support 2 of the photosensitive resin layer 4 is covered with a protective layer 6, thereby supporting the support 2, the photosensitive resin layer 4 formed on the support 2, and the photosensitive layer. The photosensitive element 10 of this embodiment provided with the protective layer 6 laminated | stacked on the photosensitive resin layer 4 is obtained. The photosensitive element 10 does not necessarily include the protective layer 6.

  As the support 2, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used.

  The thickness of the support 2 (polymer film) is preferably 1 to 100 μm, more preferably 1 to 50 μm, and still more preferably 1 to 30 μm. When the thickness of the support body 2 is 1 μm or more, the support body 2 can be prevented from being broken when the support body 2 is peeled from the photosensitive resin layer 4. Moreover, the fall of the resolution is suppressed because it is 100 micrometers or less.

  The protective layer 6 preferably has a smaller adhesive force to the photosensitive resin layer 4 than the adhesive force of the support 2 to the photosensitive resin layer 4. A low fisheye film is preferred. Here, “fish eye” means that when a material is heat-melted, kneaded, extruded, biaxially stretched, casting method, etc., foreign materials, undissolved materials, oxidatively deteriorated materials, etc. are present in the film. It means what was taken in. That is, “low fish eye” means that the above-mentioned foreign matter or the like in the film is small.

  Specifically, as the protective layer 6, a polymer film having heat resistance and solvent resistance such as polyester such as polyethylene terephthalate, polypropylene, and polyethylene can be used. As commercial products, trade names made by Oji Paper Co., Ltd .: Alphan MA-410, E-200C (“Alphan” is a registered trademark), Shin-Etsu Film Co., Ltd. polypropylene film, Teijin Limited Product name: Polyethylene terephthalate film such as PS series such as PS-25. The protective layer 6 may be the same as the support 2.

  The thickness of the protective layer 6 is preferably 1 to 100 μm, more preferably 1 to 50 μm, and still more preferably 1 to 30 μm. When the thickness of the protective layer 6 is 1 μm or more, the protective layer 6 can be prevented from being broken when the photosensitive resin layer 4 and the support 2 are laminated on the substrate while peeling off the protective layer 6. When the thickness is 100 μm or less, the handleability is improved, and more economical benefits are easily obtained.

  Specifically, for example, the photosensitive element of the present embodiment can be manufactured as follows. A step of preparing a coating solution prepared by dissolving at least (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) a photopolymerization initiator in the organic solvent; It can be manufactured by a manufacturing method including a step of coating on and forming a coating layer, and a step of drying the coating layer and forming a photosensitive resin layer.

  Application of the coating solution onto the support 2 can be performed by a known method such as a roll coater, comma coater, gravure coater, air knife coater, die coater, bar coater or the like.

  The drying of the coating layer is not particularly limited as long as at least a part of the organic solvent can be removed from the coating layer. For example, it is preferably performed at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the photosensitive resin layer is preferably 2% by mass or less from the viewpoint of suppressing the diffusion of the organic solvent in the subsequent step.

  The thickness of the photosensitive resin layer 4 in the photosensitive element 10 can be appropriately selected depending on the intended use. The thickness after drying is preferably 1 to 200 μm, more preferably 5 to 100 μm, and more preferably 10 to 50 μm. More preferably. When this thickness is 1 μm or more, industrial coating becomes easier, and when it is 200 μm or less, the sensitivity and the photocurability of the resist bottom tend to be more sufficiently obtained.

  The photosensitive element 10 may further include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer. As these intermediate layers, the intermediate layers described in JP-A-2006-089882 and the like can also be applied in this embodiment.

  The form of the obtained photosensitive element 10 is not particularly limited. For example, it may be in the form of a sheet, or may be in the form of a roll wound around a core. When winding in roll form, it is preferable to wind up so that the support body 2 may become an outer side. Examples of the core material include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer). From the viewpoint of end face protection, it is preferable to install an end face separator on the end face of the roll-shaped photosensitive element roll thus obtained, and it is preferable to install a moisture-proof end face separator from the standpoint of edge fusion resistance. As a packaging method, it is preferable to wrap and package in a black sheet with low moisture permeability.

  The photosensitive element 10 can be suitably used, for example, in a resist pattern forming method described later.

<Method for forming resist pattern>
A resist pattern can be formed on a substrate using the photosensitive resin composition. The resist pattern forming method of this embodiment includes (i) a photosensitive resin layer forming step of forming a photosensitive resin layer on a substrate using the photosensitive resin composition, and (ii) the photosensitive resin layer. An exposure step of irradiating at least a portion of the region with actinic rays to cure the region; and (iii) removing an unexposed portion other than the region of the photosensitive resin layer from the substrate. And a developing step for forming a resist pattern composed of a cured product of the photosensitive resin composition. The method for forming the resist pattern may further include other steps as necessary.

(I) Photosensitive resin layer formation process First, the photosensitive resin layer is formed on a board | substrate using the photosensitive resin composition. As the substrate, a substrate (circuit forming substrate) including an insulating layer and a conductor layer formed on the insulating layer can be used.

  As a method for forming the photosensitive resin layer on the substrate, for example, when the photosensitive element 10 has the protective layer 6, after removing the protective layer 6, the photosensitive resin of the photosensitive element 10 is used. The layer 4 is pressure-bonded (laminated) to the substrate while being heated. Thereby, the laminated body provided with the board | substrate, the photosensitive resin layer 4, and the support body 2 in this order is obtained.

This laminating operation is preferably performed under reduced pressure from the viewpoint of adhesion and followability. It is preferable to heat the photosensitive resin layer and / or the substrate at the time of pressure bonding at a temperature of 70 to 130 ° C. The pressure bonding is preferably performed at a pressure of 0.1 to 1.0 MPa (1 to 10 kgf / cm ² ). These conditions are appropriately selected as necessary. If the photosensitive resin layer is heated to 70 to 130 ° C., it is not necessary to pre-heat the substrate in advance, but the adhesion and follow-up properties are further improved by pre-heating the circuit forming substrate. Can do.

(Ii) Exposure Step In the exposure step, at least a part of the photosensitive resin layer 4 formed on the substrate as described above is irradiated with actinic rays, so that the exposed portion irradiated with actinic rays is light. Curing forms a latent image. Examples of the actinic ray irradiation include a method of irradiating actinic rays in an image form through a negative or positive mask pattern. At this time, when the support 2 existing on the photosensitive resin layer 4 is transparent to the actinic ray, the support 2 can be irradiated with the actinic ray, and the support 2 can be applied to the actinic ray. In the case of showing light shielding properties, the photosensitive resin layer 4 is irradiated with actinic rays after the support 2 is removed.

  The light source of actinic light is not particularly limited, and conventionally known light sources such as carbon arc lamps, mercury vapor arc lamps, ultrahigh pressure mercury lamps, high pressure mercury lamps, xenon lamps, argon lasers and other solid state lasers such as YAG lasers, etc. A semiconductor laser, a gallium nitride blue-violet laser, or the like that effectively emits ultraviolet light, visible light, or the like is used. Further, a laser direct drawing exposure method may be used.

The photosensitive resin composition of this embodiment can be used suitably for a direct drawing exposure method.
That is, one of the embodiments is application of the photosensitive resin composition to a direct drawing exposure method.

(Iii) Development Step In the development step, the uncured portion of the photosensitive resin layer 4 is removed from the circuit-forming substrate by development, so that the photosensitive resin layer 4 is a cured product obtained by photocuring. A pattern is formed on the substrate. When the support 2 is present on the photosensitive resin layer 4, the support 2 is removed, and then the unexposed portion is removed (development). Development methods include wet development and dry development, and wet development is widely used.

  In the case of wet development, development is performed by a known development method using a developer corresponding to the photosensitive resin composition. Examples of development methods include dipping, paddle, spraying, brushing, slapping, scrapping, rocking immersion, etc. From the viewpoint of improving resolution, the high-pressure spraying method is most suitable. Yes. You may develop by combining these 2 or more types of methods.

  The configuration of the developer is appropriately selected according to the configuration of the photosensitive resin composition. For example, alkaline aqueous solution and organic solvent developer are mentioned.

  The alkaline aqueous solution is safe and stable when used as a developer, and has good operability. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium, or potassium hydroxide; alkali carbonates such as lithium, sodium, potassium, or ammonium carbonate or bicarbonate; potassium phosphate, sodium phosphate, and the like. Alkali metal phosphates; alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borax (sodium tetraborate), sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino 2-Hydroxymethyl-1,3-propanediol, 1,3-diamino-2-propanol, morpholine and the like are used.

Examples of the alkaline aqueous solution used for development include a dilute solution of 0.1 to 5% by mass of sodium carbonate, a dilute solution of 0.1 to 5% by mass of potassium carbonate, a dilute solution of 0.1 to 5% by mass of sodium hydroxide, A dilute solution of 1 to 5 mass% sodium tetraborate is preferred. The pH of the alkaline aqueous solution at 30 ° C. is preferably in the range of 9-11. The temperature of the alkaline aqueous solution is adjusted according to the alkali developability of the photosensitive resin layer.
In addition, pH of alkaline aqueous solution can be measured with a pH meter (for example, the electrochemical instrument company make, model number: PHL-40). As pH measurement values, standard buffer solution (phthalate pH buffer solution pH: 4.01 (25 ° C), neutral phosphate pH buffer solution pH: 6.86 (25 ° C), borate pH buffer solution After calibrating three points using a liquid pH: 9.18 (25 ° C.), the electrode is placed in an alkaline aqueous solution, and a value obtained after 2 minutes or more has elapsed and adopted.

  In the alkaline aqueous solution used for development, a small amount of a surfactant, an antifoaming agent, one or more organic solvents for accelerating development may be mixed. Examples of the organic solvent to be used include acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like. . These are used alone or in combination of two or more. When the organic solvent is included, the content of the organic solvent is preferably 2 to 90% by mass based on the alkaline aqueous solution.

  Examples of the organic solvent used in the organic solvent developer include organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. In order to prevent ignition, these organic solvents are preferably added with water in the range of 1 to 20% by mass to obtain an organic solvent developer.

The development step further includes a step of further curing the resist pattern by removing the unexposed portion and then performing heating at 60 to 250 ° C. or exposure at 0.2 to 10 J / cm ² as necessary. But you can.

<Method for manufacturing printed wiring board>
The method for manufacturing a printed wiring board according to this embodiment includes a step of forming a conductor pattern by etching or plating a substrate on which a resist pattern is formed by the resist pattern forming method. The manufacturing method of a printed wiring board may include other processes, such as a resist removal process, as needed. Etching or plating of the substrate is performed on the conductor layer of the substrate using the formed resist pattern as a mask.

  In the etching process, using the resist pattern formed on the substrate as a mask, the conductor layer of the circuit forming substrate not covered with the resist is removed by etching to form a conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. Etching solutions include cupric chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide etching solution, etc. Among these, ferric chloride solution is used because it has a better etch factor. It is preferable to use it.

  On the other hand, in the plating process, copper, solder, or the like is plated on the conductor layer of the circuit forming substrate that is not covered with the resist, using the resist pattern formed on the substrate as a mask. After the plating process, the cured resist is removed, and the conductor layer covered with the resist is etched to form a conductor pattern. The method of plating treatment may be electrolytic plating treatment or electroless plating treatment. Examples of the plating treatment include copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-throw solder plating, watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate, hard gold plating, Examples thereof include gold plating such as soft gold plating.

  After the etching process and the plating process, the resist pattern on the substrate is removed. The resist pattern can be removed using, for example, a stronger alkaline aqueous solution than the alkaline aqueous solution used in the development step. As this strongly alkaline aqueous solution, for example, a 1 to 10% by mass sodium hydroxide aqueous solution and a 1 to 10% by mass potassium hydroxide aqueous solution are used. Especially, it is preferable to use 1-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, and it is more preferable to use 1-5 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.

  When the resist pattern is removed after the plating treatment, a desired printed wiring board can be manufactured by further etching the conductor layer covered with the resist by the etching treatment to form a conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. For example, the above-described etching solution can be applied.

  The printed wiring board manufacturing method of the present embodiment can be applied not only to a single-layer printed wiring board but also to a multilayer printed wiring board, and also to a printed wiring board having a small-diameter through hole. is there.

  FIG. 2 is a diagram illustrating a conventional method for manufacturing a multilayer printed wiring board. A multilayer printed wiring board 100A shown in FIG. 2F has a wiring pattern on the surface and inside. The multilayer printed wiring board 100A is obtained by laminating a copper clad laminate, an interlayer insulating material, a metal foil, and the like, and appropriately forming a wiring pattern by an etching method, a semi-additive method, or the like.

  First, an interlayer insulating layer 103 is formed on both surfaces of a copper clad laminate 101 having a wiring pattern 102 on the surface (see FIG. 2A). The interlayer insulating layer 103 may be printed with a thermosetting composition using a screen printer or a roll coater, or a film made of the thermosetting composition is prepared in advance, and this film is printed using a laminator. It can also be attached to the surface of the wiring board. Next, an opening 104 is formed using a YAG laser or a carbon dioxide gas laser at a portion that needs to be electrically connected to the outside, and smear (residue) around the opening 104 is removed by a desmear process (FIG. 2B). )reference). Next, a seed layer 105 is formed by an electroless plating method (see FIG. 2C). A photosensitive resin composition is laminated on the seed layer 105, and a predetermined portion is exposed and developed to form a resist pattern 106 (see FIG. 2D). Next, a wiring pattern 107 is formed by electrolytic plating, the resist pattern 106 is removed by a peeling solution, and then the seed layer 105 is removed by etching (see FIG. 2E). By repeating the above and forming the solder resist 108 on the outermost surface, the multilayer printed wiring board 100A can be manufactured (see FIG. 2F).

  The photosensitive resin composition of this embodiment can be used suitably for manufacture of a printed wiring board. That is, one of the embodiments is application of the photosensitive resin composition to the production of a printed wiring board.

  Hereinafter, although the objective and advantage of this indication are concretely demonstrated by an Example, this indication is not limited to these Examples. Unless otherwise specified, “part” and “%” are based on mass.

[(A) component: binder polymer]
[Synthesis Method of (P-1)]
(Preparation of solution a-1)
Dissolve 2.0 g of azobisisobutyronitrile, which is a radical reaction initiator, in a mixed solution of polymerizable monomers (copolymerization monomers, monomers) shown in Table 1 to obtain “Solution a-1”. Prepared.

(Radical polymerization reaction)
Into a flask equipped with a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas introduction tube, 400 g of a mixed solution of 240 g of methyl cellosolve and 160 g of toluene (mass ratio 3: 2) was charged. While blowing nitrogen gas into the flask, the mixture was heated while stirring to raise the temperature to 80 ° C.

  “Solution a-1” was dropped into the above mixed solution in the flask at a constant dropping rate over 4 hours, and then the solution in the flask was stirred at 80 ° C. for 2 hours. Next, a solution obtained by further dissolving 1 g of azobisisobutyronitrile in 100 g of “solution a-1” was dropped into the solution in the flask at a constant dropping rate over 10 minutes, and then the solution in the flask was heated to 80 ° C. For 3 hours. Furthermore, the solution in the flask was heated to 90 ° C. over 30 minutes, kept at 90 ° C. for 2 hours, and then cooled to obtain a solution of the binder polymer (P-1).

  Acetone was added to the binder polymer (P-1) solution to prepare a non-volatile component (non-volatile content) of 50% by mass. The weight average molecular weight of the binder polymer (P-1) was 55,000. The weight average molecular weight was measured by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene calibration curve. The conditions for GPC are as follows.

-GPC conditions-
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd., trade name)
Column: The following three total Gelpack GL-R420
Gelpack GL-R430
Gelpack GL-R440
(The above is a product name manufactured by Hitachi Chemical Co., Ltd. (“Gelpack” is a registered trademark))
Eluent: Tetrahydrofuran Measurement temperature: 25 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., trade name)
[Synthesis Method of (P-2)]
(Preparation of solution a-2)
Dissolve 1.0 g of azobisisobutyronitrile, which is a radical reaction initiator, in a mixture of polymerizable monomers (copolymerization monomers, monomers) shown in Table 2, and add “Solution a-2”. Prepared.

  Then, radical polymerization reaction was performed like the binder polymer (P-1), and the solution of the binder polymer (P-2) was obtained. The weight average molecular weight of the binder polymer (P-2) was 100,000.

[Preparation of photosensitive resin composition]
By mixing (A) component, (B) component, (C) component, and (D) component, and 8 g of acetone, 8 g of toluene, and 8 g of methanol in the blending amounts shown in Table 3 below, Examples 1 to 7 And the solution of the photosensitive resin composition of Comparative Examples 1-4 was prepared, respectively. In addition, the compounding quantity of the binder polymer shown in Table 3 is the mass (nonvolatile content) of a non-volatile component.

Details of the materials shown in Table 3 are as follows.
P-1: Binder polymer prepared above: copolymer of methacrylic acid / methyl methacrylate / styrene (25/50/25 (mass ratio)), weight average molecular weight 55,000, acid value 163 mgKOH / g, non-volatile 50% by mass. Corresponds to component (A).

  P-2: Binder polymer prepared above: methacrylic acid / methyl methacrylate / 2-ethylhexyl acrylate (25/50/25 (mass ratio)) copolymer, weight average molecular weight 100,000, acid value 163 mg KOH / G, 50% by mass of nonvolatile content. Corresponds to component (A).

  FA-321M: bisphenol A polyoxyethylene dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name), double bond equivalent 402, k = 10, l = 0, m = 0, corresponds to component (B2).

UA-HCY-19: Urethane reaction product of polyethylene glycol monomethacrylate and hexamethylene isocyanate trimer (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Double bond equivalent 841, k = 45, l = 0, m = 0, corresponding to component (B1).
UA-21: Urethane reaction product of polyethylene glycol monomethacrylate and hexamethylene isocyanate trimer (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). k = 12, l = 0, m = 0, corresponding to component (B1).
CP-1421: Polyethylene glycol polypropylene glycol block copolymer (manufactured by Dow Chemical Company, product name Boranol CP1421). k: l = 2: 3, k + 1 is 20 or more, m = 0, and corresponds to component (D).
CP-4053: Etherified product of polyethylene glycol polypropylene glycol block copolymer and sucrose (product name: Boranol CP4053, manufactured by Dow Chemical Company). k: l = 2: 3, k + 1 is 20 or more, m = 0, and corresponds to component (D).
P-2000: Polypropylene glycol (manufactured by ADEKA, product name). k = 0, l = 35, m = 0, not applicable to component (D).
FA-137M: EO-modified trimethylolpropane trimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). k = 21, l = 0, m = 0, not applicable to component (B2).
FA-023M: polyethylene polypropylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). k = 6, l = 12, m = 0, corresponds to component (B2), not applicable to component (D).
FA-P2200M: Polypropylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). k = 0, l = 34.5, m = 0, applicable to component (B2), not applicable to component (D) N-1717: 1,7-di (9-acridinyl) heptane (ADEKA Corporation) Product name). Corresponds to component (C).
LCV: Leuco Crystal Violet (Yamada Chemical Industries, product name)
・ MKG: Malachite Green (Osaka Organic Chemical Co., Ltd., product name)

[Production of photosensitive element]
Each of the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 has a uniform thickness on a polyethylene terephthalate film (trade name “G2-16”, manufactured by Teijin Limited) having a thickness of 16 μm (support). And dried for 10 minutes with a hot air convection dryer at 100 ° C. to form a photosensitive resin layer having a thickness of 38 μm after drying. By laminating a polyethylene film (trade name “NF-13”, manufactured by Tamapoly Co., Ltd.) (protective layer) on this photosensitive resin layer by roll pressurization, a support, a photosensitive resin layer, and a protective layer The photosensitive elements according to Examples 1 to 7 and Comparative Examples 1 to 4 were stacked in this order.

[Preparation of laminated substrate for evaluation]
Subsequently, a 1.6 mm thick copper clad laminate (made by Hitachi Chemical Co., Ltd., trade name “MCL-E-67” made of glass epoxy material and copper foil (thickness 35 μm) formed on both surfaces thereof. ”(“ MCL ”is a registered trademark)) was polished with a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, washed with water, and dried with an air stream. After heating this copper clad laminated board (henceforth "a board | substrate") and heating up to 80 degreeC, the photosensitive element concerning Examples 1-7 and Comparative Examples 1-4 was made into the copper surface of the both sides of a board | substrate. The laminated substrates for evaluation were respectively prepared by laminating (lamination). Lamination is performed at a speed of 1.5 m / min using a 110 ° C. heat roll so that the photosensitive resin layer of each photosensitive element is in close contact with each copper surface of the substrate while removing the protective layer. It was. Moreover, the heat roll pressure at the time of lamination was 0.4 MPa.

[Evaluation of sensitivity]
The obtained laminated substrate for evaluation was allowed to cool to 23 ° C. Next, a phototool having a step tablet was brought into close contact with the support on the surface of the evaluation multilayer substrate. As the step tablet, a 41-step step tablet having a density region of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm × 187 mm, and each step size of 3 mm × 12 mm was used. . It exposed with respect to the photosensitive resin layer through the photo tool and support body which have such a step tablet. The exposure was performed at an exposure amount of 17 mJ / cm ² using an exposure machine (trade name “Paragon-9000 m” manufactured by Nippon Orbotech Co., Ltd.) using a semiconductor-excited solid laser as a light source.

  After the exposure, the support was peeled off from the evaluation laminate substrate to expose the photosensitive resin layer. The exposed photosensitive resin layer was sprayed (development treatment) with a 1.0 mass% sodium carbonate aqueous solution at 30 ° C. for 50 seconds to remove unexposed portions. Thus, the cured film which consists of a hardened | cured material of the photosensitive resin composition was formed in the copper surface of the laminated substrate for evaluation. By measuring the number of steps of the step tablet of the obtained cured film, the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 4 and the sensitivity (photosensitivity) of the photosensitive element obtained therefrom were evaluated. did. The higher the number of steps of the step tablet, the higher the sensitivity. The results are shown in Table 4.

[Evaluation of adhesion and resolution]
An evaluation pattern having a line width / space width of n / 3n (unit: μm, n = 5 to 30 μm and 2.5 μm intervals) is used for adhesion evaluation on the evaluation multilayer substrate, and a line for resolution evaluation is used. Phototool data having an evaluation pattern having a width / space width of 3 n / n (unit: μm, n = 5 to 30 μm and 2.5 μm intervals) was used. The exposure was performed at an exposure amount of 17 mJ / cm ² using an exposure machine (trade name “Paragon-9000 m” manufactured by Nippon Orbotech Co., Ltd.) using a semiconductor-excited solid laser as a light source. Next, development processing was performed under the same conditions as in the evaluation of the photosensitivity to remove unexposed portions. The adhesion was evaluated by the smallest value (unit: μm) of the line width in which the cured film remained by the development process. Further, the resolution was evaluated by the smallest value (unit: μm) of the space width between the line widths where the portion not photocured by the development treatment could be removed cleanly. The evaluation of adhesion and resolution is better as the numerical value is smaller. The results are shown in Table 4.

[Tent reliability]
The tent reliability was evaluated using a hole breakage number measuring substrate 40 as shown in FIG. 3 manufactured as follows. A copper-clad laminate (made by Hitachi Chemical Co., Ltd., trade name “MCL-E-67”) is connected with three independent round holes 41 and three round holes each having a diameter of 4 to 6 mm, and Three continuous holes 42 in which the interval between the round holes was gradually shortened were each produced by a die cutting machine. The burr generated when the round hole 41 and the triple hole 42 were produced was removed using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, and this was used as the substrate 40 for measuring the number of broken holes. .

  The obtained substrate for hole breakage number measurement was heated to 80 ° C., and the protective layer was peeled off from the photosensitive element obtained above so that the photosensitive resin layer faced the copper surface. 7 and Comparative Examples 1 to 4 were laminated under the conditions of 120 ° C. and 0.4 MPa to prepare laminated substrates for tent reliability evaluation.

After lamination, the laminated substrate for tent reliability evaluation was allowed to cool to 23 ° C. Subsequently, it exposed with the exposure amount of 17 mJ / cm < ² > with respect to the support body support surface using the exposure machine (Nippon Orbotec Co., Ltd. make, brand name "Paragon-9000m") which uses a semiconductor excitation solid-state laser as a light source.

  After exposure, the substrate was allowed to stand at room temperature for 15 minutes, and then the support was peeled off from the laminated substrate for tent reliability evaluation, and developed by spraying a 1% by mass aqueous sodium carbonate solution at 30 ° C. for 50 seconds. After development, the number of hole breaks of the three consecutive holes was measured, the deformed tent tear rate was calculated as the number of hole breaks with respect to the total number of three consecutive holes, and the tent reliability (%) was evaluated. The higher this number, the higher the tent reliability. The results are shown in Table 4.

[Evaluation of peelability]
It exposed using the phototool data which forms the 45-mm x 65-mm rectangular cured film for peeling property evaluation on the said laminated substrate for evaluation. The exposure was performed at an exposure amount of 16 mJ / cm ² using an exposure machine (trade name “Paragon-9000 m” manufactured by Nippon Orbotech Co., Ltd.) using a semiconductor-excited solid laser as a light source. Next, development was performed under the same conditions as in the evaluation of the photosensitivity to remove the unexposed portions.
Thereafter, 300 ml of a 3.0% NaOH aqueous solution (peeling solution) at 50 ° C. was prepared in a beaker having a capacity of 500 ml. While stirring the peeling solution at 200 min ⁻¹ using a stirring bar having a length of 30 mm, the substrate after development was immersed in the peeling solution, and the time until the cured film was separated from the substrate was measured. In addition, it can be said that peelability is so favorable that time until a cured film leaves | separates from a board | substrate is short. The results are shown in Table 4.

  From Table 4, when using the photosensitive element concerning Examples 1-6 using the photosensitive resin composition of this embodiment, and the case where the photosensitive element concerning Comparative Examples 1-4 is used in any case In comparison, it was found that the tent reliability was particularly excellent. Moreover, it turned out that Examples 1-6 show sufficiently favorable adhesiveness, resolution, peeling time, and tent reliability.

2 Support 4 Photosensitive resin layer 6 Protective layer 10 Photosensitive element 40 Hole breakage measuring substrate 41 Round hole 42 Triple hole 100A Multilayer printed wiring board 101 Copper-clad laminate 102 Wiring pattern 103 Interlayer insulating layer 104 Opening 105 Seed Layer 106 Resist pattern 107 Wiring pattern 108 Solder resist

Claims (7)

(A) component: binder polymer,
(B) component: As a photopolymerizable compound, a compound having an isocyanuric ring skeleton,
(C) component: a photopolymerization initiator,
Component (D): Polyethylene oxide [— (C ₂ H ₄ O) _k —], polypropylene oxide [— (C ₃ H ₆ O) _l —] and polytetramethylene oxide [— (C ₄ H ₈ O) _m — ] (K, l and m are 1 or more, k + l + m is 20 or more) a compound having at least two as structural units,
Containing a photosensitive resin composition.   The photosensitive resin composition according to claim 1, wherein the component (A) has a structural unit derived from (meth) acrylic acid, a structural unit derived from alkyl (meth) acrylate, and a structural unit derived from styrene. . The component (D) includes polyethylene oxide [— (C ₂ H ₄ O) _k —] and polypropylene oxide [— (C ₃ H ₆ O) ₁ —] (k and l are 1 or more, k + 1 is 20 or more). The photosensitive resin composition of Claim 1 or 2 containing the compound which has as a structural unit.   The photosensitive resin composition as described in any one of Claims 1-3 in which the said (D) component contains the compound which has a structural unit whose k + l + m is 30 or more.   The photosensitive element which has a support body and the photosensitive resin layer formed using the photosensitive resin composition as described in any one of Claims 1-4 provided on the said support body. A photosensitive resin layer forming step of forming a photosensitive resin layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 4,
An exposure step of irradiating at least a part of the photosensitive resin layer with actinic rays to cure the exposed portion;
A developing step of removing an unexposed portion other than the exposed portion of the photosensitive resin layer from the substrate;
A method for forming a resist pattern having   The manufacturing method of a printed wiring board including the process of etching or plating the board | substrate with which the resist pattern was formed by the method of Claim 6.

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