JPWO2015174468A1 - Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method - Google Patents

Abstract

(A) component: a binder polymer, (B) component: a photopolymerizable compound, and (C) component: a photopolymerization initiator, wherein the (B) component is (B1) component: polyalkylene oxide [-(CmH2mO) n-: where m and n are each independently a number of 2 or more] as a structural unit, including a photopolymerizable compound having a double bond equivalent of 700 or more, the component (A) and the component The photosensitive resin composition whose content rate of the said (B1) component in the total amount of (B) component is 5 mass% or more.

Description

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

  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. .

  Furthermore, recently, as an exposure method that does not require a mask, digital data of a pattern produced by CAD (Computer-Aided Design), called LDI (Laser Direct Imaging) method or DLP (Digital Light Processing), is photosensitive by laser light. There is a strong demand for a direct drawing exposure method for drawing directly on the resin composition layer. The resist material used in the direct drawing exposure method requires a low exposure amount and alkali resistance at a low degree of cure from the viewpoint of throughput per unit time (throughput). There are many cases. However, rigid skeletal compounds tend to reduce the tent reliability of the cured film.

  In order to improve the tent reliability of the cured film, it is effective to increase the strength of the cured film formed using the photosensitive resin composition. However, when the strength of the cured film is increased, the peeling time becomes longer and the productivity is lowered.As described above, even if the direct drawing exposure method is applied, the high throughput is satisfied and the tent reliability and the peeling time are improved. Until now, no excellent resist material has been developed. For example, the photosensitive resin compositions described in JP-A-2006-234959, JP-A-2007-1222028, International Publication No. 2008/078483, JP-A-2009-69465 and International Publication No. 2010-103918 are used. Even when used, there was room for improvement.

  Therefore, an object of the present invention is to provide a photosensitive resin composition that can form a resist pattern even at a low exposure amount and is excellent in tent reliability and peeling time of a formed cured film. 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-described problems include the following embodiments.
<1> Component (A): Binder polymer, Component (B): Photopolymerizable compound, Component (C): Photopolymerization initiator, The component (B) is the component (B1): polyalkylene oxide: have a _{[- - (C m H 2m O} ) n m, n each independently 2 or more numbers] as a structural unit, comprising a photopolymerizable compound is a double bond equivalent is more than 700, The photosensitive resin composition whose content rate of the said (B1) component in the total amount of the said (A) component and the said (B) component is 5 mass% or more.
<2> The component (A) includes a structural unit (A1) derived from at least one selected from the group consisting of styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative, The photosensitive resin composition as described in <1> whose content rate of the said structural unit (A1) in the total amount of A) component is 10 mass%-60 mass%.
<3> The photosensitive resin composition according to <1> or <2>, wherein the component (B1) includes a photopolymerizable compound having two or more photopolymerizable double bonds in one molecule.
<4> Any one of <1> to <3>, wherein the component (A) further includes a structural unit (A2) derived from an alkyl (meth) acrylate that is an alkyl group having 5 to 20 carbon atoms. The photosensitive resin composition according to item.
<5> The component (B1) is polyethylene oxide [— (C ₂ H ₄ O) _n —: n is a number of 2 or more] and polytetramethylene oxide [— (C ₄ H ₈ O) _n —: n The photosensitive resin composition as described in any one of <1>-<4> containing the photopolymerizable compound which has at least 1 type selected from the group which consists of 2 or more] as a structural unit.
<6> The photosensitive resin composition according to any one of <1> to <4>, wherein the component (C) includes an acridine compound having two (C1) compounds: acridinyl groups.
<7> In the component (C), the content of the (C2) compound: acridine compound having one acridinyl group is 0.3 mass with respect to 100 mass parts of the total amount of the component (A) and the component (B). The photosensitive resin composition as described in any one of <1>-<6> which is a part-1.5 mass parts.
<8> In the component (C), the content of the (C3) compound: N-phenylglycine is 0.1 parts by mass or less with respect to 100 parts by mass of the total amount of the component (A) and the component (B). The photosensitive resin composition as described in any one of <1>-<7>.
The photosensitive element which has a <9> support body and the photosensitive resin layer formed on the said support body using the photosensitive resin composition as described in any one of <1>-<8>.
<10> The photosensitive resin which forms a photosensitive resin layer on a board | substrate using the photosensitive resin composition as described in any one of <1>-<8>, or the photosensitive element as described in <9>. A layer forming step, an exposure step of irradiating at least a part of the photosensitive resin layer with actinic rays to cure the region, and an unexposed portion other than the region of the photosensitive resin layer from the substrate. And a developing step for removing the resist pattern.
<11> 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 <10>.

  According to the present invention, it is possible to form a resist pattern even at a low exposure amount, and it is possible to provide a photosensitive resin composition excellent in tent reliability and peeling time of a formed cured film. 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 invention. It is process drawing which shows an example of the manufacturing method of the multilayer printed wiring board using the photosensitive element of this invention. It is a top view of the hole tearing number measuring substrate used for evaluation of tent reliability.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. 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”, and “(meth) acrylate” means at least one of “acrylate” and “methacrylate” corresponding thereto. The “(meth) acryloyl group” means at least one of “acryloyl group” and “methacryloyl group”. A "polyalkylene oxide", _{[- (C m H 2m O)} n -: m, n is a number of 2 or more independently] means a structural unit represented by. The number of structural units indicates how much the corresponding structural unit is added in the molecule. Therefore, an integer value is shown for a single molecule, but a rational number that is an average value is shown as an aggregate of a plurality of types of molecules. “Nonvolatile content” refers to components in the composition other than water and volatile substances such as organic solvents described below. Here, the volatile substance refers to a substance having a boiling point of 155 ° C. or lower under atmospheric pressure. “Total amount of component (A)” and “total amount of component (B)” mean the total amount of non-volatile content only.

  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. In addition, in the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples. The term “layer” includes a configuration formed in a part in addition to a configuration formed in the entire surface when observed as a plan view. The term “stacked” indicates that the layers are stacked, and two or more layers may be bonded, or two or more layers may be detachable.

<Photosensitive resin composition>
The photosensitive resin composition of the present embodiment contains (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) component: photopolymerization initiator, and the (B) component, (B1) component: polyalkylene oxide _{[- (C m H 2m O)} n -: m, n are each independently 2 or more numbers] has as a structural unit, a double bond equivalent of 700 or more Including a certain photopolymerizable compound, the content of the component (B1) in the total amount of the component (A) and the component (B) is 5% by mass or more. The said photosensitive resin composition may further contain another component as needed.

Regarding the reason why the photosensitive resin composition of the present invention can form a resist pattern even at a low exposure amount, and the reason why the formed cured film is excellent in tent reliability and peeling time, the present inventors have as follows. I guess. That is, the photosensitive resin composition of the present invention includes a photopolymerizable compound having polyalkylene oxide as a structural unit and having a double bond equivalent of 700 or more. By containing a photopolymerizable compound having a highly flexible polyalkylene oxide as a structural unit, the formed cured film (resist pattern) has appropriate flexibility, so that stress concentration hardly occurs inside the resist pattern, The tent reliability is expected to improve. In addition, since the specific photopolymerizable compound has a relatively high double bond equivalent (molecular weight per photopolymerizable double bond), the crosslink density of the formed cured film is moderately lowered and peeled off. It is considered that the penetration rate of the liquid into the resist pattern is improved and the peeling time is shortened.
Hereinafter, each component of the photosensitive resin composition of this invention is demonstrated in detail.

[(A) component: binder polymer]
The photosensitive resin composition contains at least one binder polymer as the component (A). The structure of the binder polymer is not particularly limited and can be selected from those usually used. A binder polymer may be used individually by 1 type, or may combine 2 or more types. Examples of the binder polymer include binder polymers containing the following structural unit (A1), structural unit (A2), structural unit (A3) and the like.

・ Structural unit (A1)
It is preferable that at least one of the binder polymers includes a structural unit (A1) derived from at least one selected from the group consisting of styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative. Thereby, adhesiveness when it is set as hardened | cured material can be improved, maintaining the softness | flexibility of (A) binder polymer.

  From the standpoint of improving both the adhesion and the peeling property of the cured film, the content of the structural unit (A1) in the binder polymer is 10% by mass to 60% by mass in the total amount of the component (A). Preferably, the content is 13% by mass to 40% by mass, more preferably 13% by mass to 25% by mass, still more preferably 15% by mass to 25% by mass, and further preferably 15% by mass to 18% by mass. It is particularly preferable that the content is mass%. When the content of the structural unit (A1) is 10% by mass or more, the adhesion of the cured film tends to be improved. When the content is 60% by mass or less, the peeling piece is prevented from becoming large, and the peeling time is increased. Prolonging can be suppressed and tent reliability tends to be improved.

Specific examples of the styrene derivative include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as α-methylstyrene, vinyltoluene, and p-chlorostyrene.
Specific examples of the benzyl (meth) acrylate derivative include 4-methylbenzyl (meth) acrylate, 4-ethylbenzyl (meth) acrylate, 4-tert-butylbenzyl (meth) acrylate, 4-methoxybenzyl (meth) acrylate, Examples include 4-ethoxybenzyl (meth) acrylate, 4-hydroxybenzyl (meth) acrylate, and 4-chlorobenzyl (meth) acrylate.

・ Structural unit (A2)
At least one of the binder polymers preferably includes a structural unit (A2) derived from alkyl (meth) acrylate from the viewpoint of tent reliability of the cured film. The alkyl group in the alkyl (meth) acrylate may be either linear or branched, and may be unsubstituted or may have a substituent. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 5 to 20 carbon atoms, and still more preferably 8 to 14 carbon atoms. 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 represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group. The alkyl group represents a linear or branched alkyl group having 1 to 20 carbon atoms.

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 be unsubstituted or 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.

From the viewpoint of further improving the tent reliability of the cured film, the alkyl group represented by R ⁴ in the general formula (I) preferably has 5 to 20 carbon atoms, and has 8 to 14 carbon atoms. Is more preferable.

  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 contains the structural unit (A2), the content of the structural unit (A2) in the total amount of the component (A) is 1% by mass to 70% by mass from the viewpoints of adhesion, resolution, and developability. It is preferable that it is 30 mass%-65 mass%, and it is still more preferable that it is 45 mass%-60 mass%. When the content of the structural unit (A2) is 1% by mass or more, the tent reliability of the cured film is further improved, and when the content is 80% by mass or less, the resolution and adhesion of the cured film are further improved.

・ Structural unit (A3)
At least one of the binder polymers preferably includes a structural unit (A3) derived from a polymerizable monomer having a carboxy group from the viewpoint of alkali developability. The binder polymer containing the structural unit (A3) 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 include (meth) acrylic acid; α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid and the like ( (Meth) acrylic acid derivatives; maleic acid; maleic acid derivatives such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate; fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, etc. Can be mentioned. From the viewpoint of improving sensitivity, (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) in the total amount of the component (A) is 12% by mass to 50% by mass from the viewpoint of the balance between alkali developability and developer resistance. It is preferable that it is more preferable, and it is more preferably 15% by mass to 35% by mass, and further preferably 15% by mass to 30% by mass from the viewpoint of superior alkali developability.

-Other structural unit The binder polymer may contain other structural units other than structural unit (A1)-(A3). Examples of the polymerizable monomer constituting the other structural unit 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. It is done. These can be used alone or in combination of two or more.

  The content of other structural units in the total amount of component (A) is preferably 10% by mass or less, preferably 5% by mass or less, from the viewpoints of adhesion, resolution, and developability of the cured film. Is more preferable, and it is still more preferable not to contain substantially (for example, it is 0.5 mass% or less). That is, the total content of the structural units (A1), (A2) and (A3) in the total amount of the component (A) is preferably 90% by mass or more, and more preferably 95% by mass or more. More preferably, the content is substantially 100% by mass (for example, 99.5% by mass or more).

-Various characteristics of a binder polymer A binder polymer is obtained by polymerizing the monomer corresponding to each structural unit which comprises a binder polymer. Examples of the polymerization method include radical polymerization. When the binder polymer is a copolymer obtained by polymerizing two or more monomers, each structural unit in the copolymer is randomly contained in the copolymer like a so-called random copolymer. Alternatively, it may be a copolymer including a structural unit in which monomers of the same type are continuously formed, such as a block copolymer. Each structural unit may be a single type or a plurality of types.

  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 the balance between developer resistance and alkali developability. More preferably, it is from 1,000 to 100,000. The weight average molecular weight in the present specification is a value measured by a gel permeation chromatography method under the same measurement conditions as described in Examples and converted by a calibration curve prepared using standard polystyrene.

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

  (A) The binder polymer contained in a component can be used individually by 1 type or in combination of 2 or more types. Examples of combinations of two or more types of binder polymers include two or more types of binder polymers having different types and ratios of copolymer components, two or more types of binder polymers having different weight average molecular weights, and two or more types having different degrees of dispersion. The combination of a binder polymer etc. are mentioned. The degree of dispersion of the binder polymer is a value obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).

  Component (A) is a binder polymer containing at least one of structural units (A1), (A2) or (A3), and another binder not containing any of structural units (A1), (A2) or (A3) A combination with a polymer may also be used. Other binder polymers are not particularly limited as long as they are soluble in an alkaline aqueous solution and can form a film. Examples thereof include 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. Of these, acrylic resins are preferred from the viewpoint of alkali developability. These can be used alone or in combination of two or more.

  When component (A) contains another binder polymer that does not contain any of structural units (A1), (A2), or (A3), the content of structural unit (A1) in the total amount of component (A) is 10% by mass. It is preferably ˜60% by mass, more preferably 13% by mass to 40% by mass, and further preferably 15% by mass to 25% by mass. When the component (A) contains another binder polymer, the content of the other binder polymer in the total amount of the component (A) is preferably 10% by mass or less, and more preferably 5% by mass or less. It is further preferred that the other binder polymer is substantially not contained (for example, 0.5% by mass or less), and it is particularly preferred that no other binder polymer is contained at all.

  The content of the component (A) in the photosensitive resin composition is preferably 30 parts by mass to 80 parts by mass, and 40 parts by mass to 75 parts by mass in 100 parts by mass of the total amount of the components (A) and (B). It is more preferable to set it as a mass part, and it is still more preferable to set it as 50 mass parts-70 mass parts. When the content of the component (A) is within this range, the coating properties of the photosensitive resin composition and the strength of the cured film tend to be better.

[(B) component: photopolymerizable compound]
The photosensitive resin composition of the present invention contains at least one photopolymerizable compound as the component (B). The component (B) has a polyalkylene oxide as a structural unit and has a double bond equivalent of 700 or more. At least one photopolymerizable compound (specific photopolymerizable compound) is included as the component (B1), and the content of the component (B1) in the total amount of the components (A) and (B) is 5% by mass or more.

  The photopolymerizable compound is not particularly limited as long as all or part thereof is the component (B1), and can be appropriately selected from commonly used photopolymerizable compounds. Examples of the photopolymerizable compound include compounds having a photopolymerizable unsaturated double bond.

Component (B1): specific photopolymerizable compound The photosensitive resin composition of the present invention comprises at least one specific photopolymerizable compound having a polyalkylene oxide as a structural unit and having a double bond equivalent of 700 or more. Including. By including a compound having such a flexible polyalkylene oxide as a structural unit and a relatively large double bond equivalent, a photosensitive film capable of forming a cured film having excellent tent reliability and a short peeling time. Resin composition can be obtained.

In the present invention, “polyalkylene oxide” means a structural unit represented by — (C _m H _2m O) _n — (m and n are each independently 2 or more). The position or number of the polyalkylene oxide structural unit contained in the molecule of the specific photopolymerizable compound is not particularly limited. Two or more different polyalkylene oxide structural units may be contained in one molecule. It is only one particular photopolymerizable compound contained in the photosensitive resin composition, different structures (e.g., - having at m or n is different structural units each _{- (C m H 2m O)} n) Two or more combinations may be used.

From the viewpoint of improving the tent reliability and the peeling time of the cured film in a well-balanced manner, the specific photopolymerizable compound is polyethylene oxide [— (C ₂ H ₄ O) _n —: n is a number of 2 or more], polypropylene oxide [— _{(C 3 H 6 O) n} -: n is 2 or more numbers], and polytetramethylene oxide _{[- (C 4 H 8 O)} n -: at least n is selected from the group consisting of 2 or more numbers] It is preferable to have one kind as a structural unit. Among these, from the viewpoint of further improving the tent reliability of the cured film, it is more preferable to have as a structural unit at least one selected from the group consisting of polyethylene oxide and polytetramethylene oxide, from the group consisting of polytetramethylene oxide. It is particularly preferable to have at least one selected as a structural unit. _N in — (C _m H _2m O) _n — is preferably a number of 4 or more, more preferably a number of 19 or more, and a number of 40 or more from the viewpoint of tent reliability and peelability. More preferably it is. When m is 3 or more, the number is preferably 100 or less, more preferably 50 or less, and still more preferably 30 or less from the viewpoint of developability.

  The double bond equivalent of the specific photopolymerizable compound is not particularly limited as long as it is 700 or more. From the viewpoint of the balance of resolution, tent reliability and peelability of the cured film, the double bond equivalent of the specific photopolymerizable compound is preferably 700 to 2000, more preferably 700 to 1500, More preferably, it is 800-1000, and still more preferably 800-1500.

  In the present invention, the “double bond equivalent” is a numerical value obtained by dividing the molecular weight of the photopolymerizable compound by the number of photopolymerizable double bonds per molecule. The double bond equivalent of the photopolymerizable compound can be easily adjusted by selecting the molecular weight of the photopolymerizable compound, the number of photopolymerizable double bonds, and the like. For example, the double bond equivalent of polytetramethylene glycol di (meth) acrylate having 2 photopolymerizable double bonds is a value obtained by dividing the molecular weight by 2. The double bond equivalent of the photopolymerizable compound can be increased, for example, by increasing the number of polyalkylene oxide structural units in the molecule and increasing the molecular weight.

The double bond equivalent of the photopolymerizable compound can be determined by the number of grams of resin required for 1 mol of the carbon-carbon double bond.
That is, it can be calculated from the molecular weight measurement result by the method described in Examples and the number of carbon-carbon double bonds per molecule determined by structural analysis.
Further, the double bond equivalent of the compound alone can be determined from the value of iodine value measured by the following method.
Method for measuring iodine value:
The polyurethane compound is precisely weighed in the range of 0.25 to 0.35 g, placed in a 200 ml iodine flask, and 30 ml of chloroform is added to completely dissolve the sample. To this was added exactly 20 ml of Wijs reagent (iodine trichloride 7.9 g and iodine 8.2 g in 200-300 ml glacial acetic acid, then mixed to make 1 l) with a whole pipette. After adding 10 ml of 5% mercuric acetic acid glacial acetic acid solution, the reaction is completed by leaving it in the dark for 20 minutes. 20% KI solution freshly prepared to which was added 5 ml, with 1% starch solution as an _indicator, titrated with _{0.1N-N a2} S 2 _{O 3} standard solution. At the same time, a blank test is also performed and the iodine value Y is calculated by the following formula.
Iodine value Y (g / 100 g) = (Aml−Bml) 0.1 N × f × 126.9 × 100 / Sg
Double bond equivalent (g / mol) = 100 × 253.8 / Y = 20000 × S / ((A−B) × f)
A: Check _{0.1N-N a2} S 2 _O required for the test ₃ ml Number of standard solution B: This test requires a _{0.1N-N a2} S 2 _{O 3} standard solution (ml) f: 0.1N- N _a2 S ₂ O ₃ standard solution titer S: g number of samples

  The number of photopolymerizable double bonds that the specific photopolymerizable compound has is not particularly limited. From the viewpoint of reducing resist residues in the peeling step, the number of photopolymerizable double bonds is preferably 2 or more in one molecule. Examples of the photopolymerizable double bond include a double bond contained in a (meth) acryloyl group.

  Specific photopolymerizable compounds include esterified products of polyalkylene glycol compounds having a double bond equivalent of 700 or more and (meth) acrylic acid, bisphenol A (meth) acrylates having a double bond equivalent of 700 or more, double Examples include a reaction product (urethane compound) of a polyalkylene glycol mono (meth) acrylate having a bond equivalent of 700 or more and an isocyanate compound.

  Examples of the bisphenol A (meth) acrylate having a double bond equivalent of 700 or more include 2,2-bis (4-((meth) acryloxypolyethyleneoxy) phenyl) propane and 2,2-bis (4-(( (Meth) acryloxypolypropyleneoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolytetramethyleneoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethyleneoxy) And polypropyleneoxy) phenyl) propane.

  As an esterified product of a polyalkylene glycol compound having a double bond equivalent of 700 or more and (meth) acrylic acid, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate, Examples thereof include polytetramethylene glycol di (meth) acrylate, trimethylolpropane polyethylene ether tri (meth) acrylate, pentaerythritol propane polyethylene ether tetra (meth) acrylate and the like.

  Examples of the reaction product of polyalkylene glycol mono (meth) acrylate having a double bond equivalent of 700 or more and an isocyanate compound include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene polypropylene glycol mono (meth) Two or three polyalkylene glycol mono (meth) acrylates such as acrylate and polytetramethylene glycol mono (meth) acrylate, and isocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and trimers of these isocyanates And the like.

  Preferred examples of the specific photopolymerizable compound include polyethylene glycol di (meth) acrylate having a molecular weight of 1400 or higher, polypropylene glycol di (meth) acrylate having a molecular weight of 1400 or higher, polytetramethylene glycol di having a molecular weight of 1400 or higher. There can be mentioned a reaction product of (meth) acrylate and three of polyethylene glycol mono (meth) acrylate having a molecular weight of 2100 or more and hexamethylene diisocyanate trimer.

  More preferable examples of the specific photopolymerizable compound include polyethylene glycol di (meth) acrylate having a molecular weight of 1400 to 4000, polypropylene glycol di (meth) acrylate having a molecular weight of 1400 to 4000, and poly having a molecular weight of 1400 to 4000. Mention may be made of a reaction product of tetramethylene glycol di (meth) acrylate and three polyethylene glycol mono (meth) acrylates having a molecular weight of 2100 to 4000 and hexamethylene diisocyanate trimer.

  The proportion of the polyalkylene oxide structural unit in the molecule of the specific photopolymerizable compound (RO content) is preferably 60% by mass or more, more preferably 65% by mass or more, and 70% by mass or more. More preferably, it is more preferably 75% by mass or more, and further preferably 85% or more.

  The content of the specific photopolymerizable compound is 5% by mass or more, preferably 6% by mass or more, and preferably 12% by mass or more based on the total amount of the component (A) and the component (B). Further preferred. Moreover, it is preferable that it is 6 mass%-40 mass%, and it is more preferable that it is 14 mass%-40 mass%. By setting the content of the specific photopolymerizable compound to 5% by mass or more, the cured film becomes flexible, the tent reliability can be improved, and the peeling time can be shortened. Moreover, by setting it as 40 mass% or less, resolution and adhesiveness can further be improved. From the viewpoint of obtaining a cured film that is more excellent in resolution and shorter in peeling time, the content of the specific photopolymerizable compound is 10% by mass to 30% by mass based on the total amount of the component (A) and the component (B). %, More preferably 12% by mass to 30% by mass, still more preferably 12% by mass to 20% by mass, and still more preferably 14% by mass to 20% by mass.

-Other photopolymerizable compound The photosensitive resin composition of this invention may contain at least 1 sort (s) of photopolymerizable compounds other than a specific photopolymerizable compound as (B) component. As such a photopolymerizable compound, a polyalkylene glycol compound having a double bond equivalent of less than 700 and an esterified product of (meth) acrylic acid, a bisphenol A-based (meth) acrylate having a double bond equivalent of less than 700, Reaction product of polyalkylene glycol glycol mono (meth) acrylate and isocyanate compound having a double bond equivalent of less than 700, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethylene-o-phthalate, β- Phthalic acid derivatives such as hydroxyethyl-β ′-(meth) acryloyloxyethylene-o-phthalate, β-hydroxypropyl-β ′-(meth) acryloyloxyethylene-o-phthalate, alkyl (meth) acrylate, etc. It is done.

  When two or more photopolymerizable compounds are used in combination, inclusion of a compound having two or more photopolymerizable unsaturated double bonds in one molecule in the total total amount of two or more photopolymerizable compounds The rate is preferably 75% by mass or more. (T) The tent reliability and resolution of the cured film are such that the content of the compound having two or more photopolymerizable unsaturated double bonds in one molecule in the total amount of component (B) is 75% by mass or more. And there exists a tendency for adhesiveness to improve more.

  It is preferable that content of the photopolymerizable compound in the photosensitive resin composition shall be 20 mass parts-70 mass parts in 100 mass parts of total amounts of (A) component and (B) component. From the viewpoint of further improving the tent reliability and resolution of the cured film, the content of the photopolymerizable compound is preferably 20 parts by mass or more in 100 parts by mass of the total amount of the component (A) and the component (B). 25 parts by mass or more, more preferably 30 parts by mass or more. From the viewpoint of imparting good film properties to the photosensitive resin composition and from the viewpoint of improving the shape of the resist after curing, the content of the photopolymerizable compound is 100 mass of the total amount of the component (A) and the component (B). It 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 particularly preferably 50 parts by mass or less.

[(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: Among these, from the viewpoint of improving the sensitivity, adhesion, resolution, peeling time, and tent reliability in a balanced manner, the compound (C1) may be contained. Among these properties, the sensitivity and tent reliability can be improved by containing the compound (C1).

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

In the formula (II), 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, and 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 (II) 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) Ai Di (9-acridinyl) alkanes such as Sun; di (9-acridinyl) such as 1,3-di (9-acridinyl) -2-oxapropane, 1,5-di (9-acridinyl) -3-oxapentane Oxalkane; Di (9-acridinyl) thioalkane such as 1,3-di (9-acridinyl) -2-thiapropane and 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 (II) 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) as a photopolymerization initiator, the content of the compound (C1) is from the viewpoint of sensitivity, resolution, and adhesion, and the components (A) and (B) For example, it may be 0.1 to 10 parts by mass or 0.5 to 5 parts by mass, and preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the total amount of components. 0.25 parts by mass to 1.5 parts by mass, more preferably 0.35 parts by mass to 1.2 parts by mass, and 0.45 parts by mass to 1 part by mass. Particularly preferred.
When the content of the (C1) compound is 0.1 parts by mass or more, better sensitivity, resolution, or adhesion tends to be obtained. When the amount is 10 parts by mass or less, a better resist shape tends to be obtained, and when the amount is 2 parts by mass or less, a tendency to obtain a better resist shape is remarkable.

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

In formula (III), 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. When m is 2 or more, the plurality of R ⁴ may be the same or different.

  Examples of the acridine compound represented by the general formula (III) include 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine, 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 (C2) compound as a photopolymerization initiator, the content of the (C2) compound is (A) and (B) from the viewpoint of sensitivity, resolution and adhesion. For example, it may be 0.1 to 10 parts by mass or 0.5 to 5 parts by mass, and preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the total amount of components. 0.3 parts by mass to 1.5 parts by mass, more preferably 0.4 parts by mass to 1.2 parts by mass, and further preferably 0.5 parts by mass to 0.8 parts by mass. It is particularly preferred. When the content of the (C2) compound is 0.1 parts by mass or more, better sensitivity, resolution, or adhesion tends to be obtained. When the amount is 10 parts by mass or less, a better resist shape tends to be obtained, and when the amount is 2 parts by mass or less, a tendency to obtain a better resist shape is remarkable.

  From the viewpoint of improving sensitivity, the photosensitive resin composition preferably also contains a (C3) compound represented by the following general formula (IV) as the component (C). The (C3) compound represented by the general formula (IV) can be said to be N-phenylglycine.

  When the photosensitive resin composition contains the (C3) compound as a photopolymerization initiator, the upper limit value of the content of the (C3) compound is the component (A) and the component (B) from the viewpoint of improving resolution. The total amount of components is preferably 0.1 parts by mass or less, more preferably 0.07 parts by mass or less, and still more preferably 0.06 parts by mass or less. (C3) 0.01 mass part or more, 0.02 mass part or more, and 0.04 mass part or more may be sufficient from the viewpoint of improving a sensitivity and adhesiveness. There exists a tendency for better resolution to be acquired as it is 0.1 mass part or less. Moreover, a sensitivity, resolution, and adhesiveness can be improved with sufficient balance by being 0.01-0.1 mass part.

  The said photosensitive resin composition may contain photoinitiators other than the said (C1), (C2) compound, and (C3) compound as (C) component.

As photopolymerization initiators other than the (C1) compound, the (C2) compound and the (C3) compound, 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 Aromatic ketone compounds such as-(methylthio) phenyl] -2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3 -Benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenyl Quinone compounds such as nthraquinone, 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, 2- (p- 2,4,5-triarylimidazole dimer such as methoxyphenyl) -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, 9,10-dipentoxyanthracene; coumarin compounds; oxazole compounds; pyrazoline compounds; triarylamine compounds;
These photoinitiators can be 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 substituents of the aryl groups of two 2,4,5-triarylimidazoles constituting the dimer are the same. They may be different or asymmetrical compounds.

  When the photosensitive resin composition contains a photopolymerization initiator other than the (C1) compound, the (C2) compound and the (C3) compound as the component (C), the content thereof is a viewpoint of sensitivity and internal photocurability. From 0.01 part by weight to 10 parts by weight, more preferably from 0.1 part by weight to 7 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). More preferably, it is 0.2-5 mass parts.

  (C) Content of a component is 0.01 mass part-20 mass parts with respect to a total amount of 100 mass parts of (A) component and (B) component from a viewpoint of a sensitivity, adhesiveness, and internal photocurability. It is preferable that it is 0.05 mass part-10 mass parts, and it is still more preferable that it is 0.1 mass part-5 mass parts.

  The photosensitive resin composition is at least one selected from the group consisting of the compound (C1) and the compound (C2) as the component (C), preferably (C1), from the viewpoints of sensitivity, adhesion, and internal photocurability. ) Compound, and the content thereof is preferably 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B), and 0.2 parts by mass to 5 parts by mass. It is more preferable that

[Other ingredients]
If necessary, the photosensitive resin composition is a dye such as malachite green, Victoria pure blue, brilliant green, methyl violet; leuco crystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline, o-chloroaniline, etc. Photo-coloring agent; thermal coloring inhibitor; plasticizer such as p-toluenesulfonamide; pigment; filler; antifoaming agent; flame retardant; adhesion-imparting agent; leveling agent; Other additives such as an agent, 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 be contained in an amount of about 0.01 to 20 parts by mass per 100 parts by mass of the total amount of component (A) and component (B). These additives can be used alone or in combination of two or more.

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 organic solvents 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 (hereinafter, a photosensitive resin composition containing an organic solvent is also referred to as “coating liquid”) having a nonvolatile content of about 30 mass% to 60 mass%.

  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 invention 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 invention has a support body and the photosensitive resin layer formed on the said support body using the said photosensitive resin composition. The said photosensitive element may have other layers, such as a protective layer, as needed.

  FIG. 1 shows an embodiment of the photosensitive element of the present invention. 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 resin. The photosensitive element 10 of this embodiment provided with the protective layer 6 laminated | stacked on the layer 4 is obtained. The photosensitive element 10 may not have 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 μm to 100 μm, more preferably 1 μm to 50 μm, and still more preferably 1 μm 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. Also, a low fish eye film is preferred. Here, “fish eye” means that foreign materials, undissolved materials, oxidation degradation products, etc. contained in the material are produced when the film is produced by heat melting, kneading, extruding, biaxial stretching, casting method, etc. It means what was taken into the film. 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. Examples of commercially available products include polyethylene terephthalate films such as Alphan MA-410 and E-200C manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and PS series such as PS-25 manufactured by Teijin Limited. Can be mentioned. The protective layer 6 may be the same as the support 2.

  The thickness of the protective layer 6 is preferably 1 μm to 100 μm, more preferably 1 μm to 50 μm, and still more preferably 1 μm to 30 μm. When the thickness of the protective layer 6 is 1 μm or more, the protective layer 6 tends to 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 handling property and the inexpensiveness tend to be excellent.

  Specifically, the photosensitive element of this embodiment can be manufactured as follows, for example. 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 using 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 preferable to carry out at 70 to 150 ° C. for about 5 to 30 minutes. After drying, the amount of the remaining organic solvent in the obtained photosensitive resin layer is preferably 2% by mass or less from the viewpoint of preventing 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 μm to 200 μm, more preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm. More preferably. When the thickness after drying is 1 μm or more, industrial coating becomes easy. When the thickness is 200 μm or less, the sensitivity and the photocurability of the resist bottom tend to be 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 the present invention.

  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 part of the region with actinic rays to cure the region; and (iii) a development step of removing an unexposed portion other than the region of the photosensitive resin layer from the substrate. 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.

  For example, when the photosensitive element 10 has the protective layer 6, the photosensitive resin layer 4 is formed on the substrate after the protective layer 6 is removed and then the photosensitive resin layer 4 of the photosensitive element 10 is formed. It arrange | positions so that it may contact | connect a board | substrate and it carries out by crimping | bonding (laminating) the photosensitive element 10 to a board | substrate, heating. Thereby, the laminated body provided with the board | substrate, the photosensitive resin layer 4, and the support body 2 in this order is obtained.

The laminating operation is preferably performed under reduced pressure from the viewpoint of adhesion and followability of the photosensitive element 10. Heating at the time of pressure bonding is preferably performed so that the temperature of the photosensitive resin layer 4 and the substrate is 70 ° C to 130 ° C. The pressure bonding is preferably performed at a pressure of 0.1 MPa to 1.0 MPa (1 kgf / cm ^{2 to} 10 kgf / cm ² ). These conditions are appropriately selected as necessary. If the photosensitive resin layer 4 is heated to 70 ° C. to 130 ° C., it is not necessary to pre-heat the substrate in advance, but the pre-heat treatment of the substrate can improve the adhesion and followability of the photosensitive element 10. Further improvement can be achieved.

(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 method 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 transmissive to actinic rays, actinic rays can be irradiated through the support 2. In the case where the support 2 is impermeable to actinic rays, 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 preferred embodiment of the present invention is an application of the photosensitive resin composition to a direct drawing exposure method.

(Iii) Development Step In the development step, the uncured uncured portion of the photosensitive resin layer 4 is removed from the substrate by development. Thereby, the resist pattern which is the hardened | cured material which the photosensitive resin layer 4 photocured is formed on a board | substrate. When the support 2 exists on the photosensitive resin layer 4 after the exposure, the support 2 is removed, and then the uncured portion is removed (developed). 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 the developing method include a method using a dipping method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, etc., and the high pressure spray method is most suitable from the viewpoint of improving resolution. . You may develop by combining 2 or more types of these methods.

  The configuration of the developer is appropriately selected according to the configuration of the photosensitive resin composition. Examples thereof include an alkaline aqueous solution and an organic solvent developer.

  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 carbonates and bicarbonates, potassium phosphates and sodium phosphates. 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% by mass to 5% by mass of sodium carbonate, a dilute solution of 0.1% by mass to 5% by mass of potassium carbonate, and 0.1% by mass to 5% by mass of sodium hydroxide. A dilute solution of 0.1 mass% to 5 mass% of sodium tetraborate is preferred. The pH of the alkaline aqueous solution is preferably in the range of 9-11. The temperature is adjusted in accordance with the alkali developability of the photosensitive resin composition layer.

  A small amount of a surfactant, an antifoaming agent, an organic solvent for accelerating development, and the like may be added to the alkaline aqueous solution used for development. Examples of the organic solvent added to the alkaline aqueous solution 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. Etc. These organic solvents are used alone or in combination of two or more. When alkaline aqueous solution contains the organic solvent, it is preferable that the content rate of the organic solvent shall be 2 mass%-90 mass% in the whole quantity of alkaline aqueous solution. Moreover, the temperature can be adjusted according to alkali developability.

  Examples of the organic solvent used in the organic solvent developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. It is preferable to add an organic solvent developer to these organic solvents in order to prevent ignition by adding water in the range of 1% by mass to 20% by mass.

The method for forming a resist pattern of the present embodiment, after removing the uncured portions, heating or exposure of 0.2J ^/ cm ² ~10J ^/ cm 2 of 60 ° C. to 250 DEG ° C. optionally carried out in the developing step By this, you may further include the process of further hardening a resist pattern.

<Method for manufacturing printed wiring board>
The manufacturing method of the printed wiring board of this invention includes the process of etching or plating the board | substrate with which the resist pattern was formed by the formation method of the said resist pattern. Thereby, a conductor pattern is formed. 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 in a region 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. Examples of the etching solution include cupric chloride solution, ferric chloride solution, alkaline etching solution, hydrogen peroxide etching solution and the like. In these, it is preferable to use a ferric chloride solution from a point with a favorable etch factor.

  On the other hand, in the plating process, copper, solder, or the like is plated on the conductor layer in a region not covered with the resist, using the resist pattern formed on the substrate as a mask. After the plating process, the resist is removed, and the conductor layer in the region 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 the strong alkaline aqueous solution, for example, a 1% by mass to 10% by mass sodium hydroxide aqueous solution, a 1% by mass to 10% by mass potassium hydroxide aqueous solution, or the like is used. Especially, it is preferable to use 1 mass%-10 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, and it is more preferable to use 1 mass%-5 mass% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.

  When the resist pattern is removed after the plating process is performed, a desired printed wiring board can be manufactured by further etching the conductor layer in the region covered with the resist by the etching process to form the 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 invention 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. .

  FIG. 2 is a diagram illustrating an example of a method for producing a multilayer printed wiring board using the photosensitive element of the present embodiment. 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). Even if the interlayer insulating layer 103 is formed by printing a thermosetting composition using a screen printer or a roll coater, a film made of the thermosetting composition is prepared in advance, and this film is formed using a laminator. You may affix and form on the surface of a printed wiring board. Next, an opening 104 is formed using a YAG laser or a carbon dioxide gas laser in a place 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). The photosensitive element of this embodiment is laminated on the seed layer 105 to form a photosensitive resin layer, 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, and the resist pattern 106 is removed by a peeling solution. Thereafter, the seed layer 105 is removed by etching (see FIG. 2E). By repeating the above steps 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 preferred embodiments of the present invention is application of the photosensitive resin composition to the production of a printed wiring board.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

[(A) Component: Binder Polymer] [Synthesis Method of Binder Polymer (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 the nitrogen gas was blown into the flask, the mixture was heated while stirring to raise the temperature to 80 ° C.

  After dropping “Solution a-1” at a constant dropping rate over 4 hours to the above mixed solution in the flask, 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 (manufactured by Hitachi, Ltd.)
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.)
Eluent: Tetrahydrofuran Measurement temperature: 25 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

[Synthesis Method of Binder Polymer (P-2)] (Preparation of Solution a-2)
Dissolve 1.0 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-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.

[Synthesis Method of Binder Polymer (P-3)] (Preparation of Solution a-3)
Dissolve 1.0 g of azobisisobutyronitrile, which is a radical reaction initiator, in a mixture of polymerizable monomers (copolymerization monomers, monomers) shown in Table 1 to obtain “Solution a-3”. Prepared.

  Then, radical polymerization reaction was performed similarly to binder polymer (P-1), and the solution of binder polymer (P-3) was obtained. The weight average molecular weight of the binder polymer (P-3) was 30,000.

[Preparation of photosensitive resin composition]
In the binder polymer solution obtained above, the components (B) and (C), acetone 8 g, toluene 8 g, and methanol 8 g were blended in the blending amounts (g) shown in Tables 2 and 3 below. The photosensitive resin composition of Examples 1-18 and Comparative Examples 1-6 was prepared, respectively. In addition, the compounding quantity of the binder polymer shown in Table 2 and Table 3 is the mass (nonvolatile content) of a non-volatile component.

  Details of the materials shown in Tables 2 and 3 are as follows.

<(A) component: Binder polymer>
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 A 50% by weight methyl cellosolve / toluene = 6/4 (mass ratio) solution.

  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, methyl cellosolve / toluene = 6/4 (mass ratio) solution having a nonvolatile content of 50% by mass.

  P-3: a copolymer of methacrylic acid / benzyl methacrylate / methyl methacrylate / styrene (30/25/5/40 (mass ratio)), weight average molecular weight 30,000, acid value 196 mgKOH / g, non-volatile content 50 mass% methyl cellosolve / toluene = 6/4 (mass ratio) solution.

<(B) component: photopolymerizable compound>
FA-321M: Bisphenol A polyoxyethylene dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Not applicable to double bond equivalent 402, component (B1).
UA-HCY-19: Urethane reaction product of polyethylene glycol monomethacrylate and hexamethylene isocyanate trimer (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). Equivalent to double bond equivalent 841, component (B1).
FA-240M: polyethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Not applicable to double bond equivalent 266, component (B1).
FA-2200M: polyethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Equivalent to double bond equivalent 1058, component (B1).
FA-P2100M: Polypropylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Not applicable to double bond equivalent 561, component (B1).
FA-2300M: Polypropylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Equivalent to double bond equivalent 1576, component (B1).
FA-PTG9M: polytetramethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Not applicable to double bond equivalent 401, component (B1).
FA-PTG28M: polytetramethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Equivalent to double bond equivalent 1085, component (B1).
FA-137M: trimethylolpropane polyethylene oxide trimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Double bond equivalent 420, not applicable to component (B1).
FA-314A: nonylphenoxypolyethylene glycol acrylate (average number of oxyethylene groups is 4) (product name, manufactured by Hitachi Chemical Co., Ltd.). Double bond equivalent 450, not applicable to component (B1).

<(C) component: photopolymerization initiator>
N-1717: 1,7-di (9-acridinyl) heptane (manufactured by ADEKA, product name).
EAB: 4,4′-bis (diethylamino) benzophenone (product name, manufactured by Hodogaya Chemical Co., Ltd.).
B-CIM: 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-2H-imidazol-2-yl] -4,5-diphenyl-1H-imidazo -Le (Hodogaya Chemical Co., Ltd., product name).
・ 9PA: 9-phenylacridine (Nippon Steel & Sumikin Chemical Co., Ltd.)
・ NPG: N-Phenylglycine (Changzhou Powerful Electronic New Material Co., Ltd., product name)

<Other ingredients>
LCV: Leuco Crystal Violet (product name, manufactured by Yamada Chemical Co., Ltd.)
・ MKG: Malachite Green (Osaka Organic Chemical Co., Ltd., product name)

  In Tables 2 and 3, “content of structural unit (A1)” represents the content of structural unit (A1) in the total amount of binder polymer. “Content of structural unit (A2)” represents the content of structural unit (A2) in the total amount of the binder polymer. “Content of structural unit (A3)” represents the content of structural unit (A3) in the total amount of the binder polymer.

[Production of photosensitive element]
Each of the photosensitive resin compositions of Examples 1 to 18 and Comparative Examples 1 to 6 has a uniform thickness on a polyethylene terephthalate film (trade name “G2-16”, manufactured by Teijin Ltd.) 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 protective layer (manufactured by Tamapoly Co., Ltd., trade name “NF-13”) (protective layer) on this photosensitive resin layer by roll pressurization, a support, a photosensitive resin layer, The photosensitive element concerning Examples 1-18 and Comparative Examples 1-6 with which the protective layer was laminated | stacked in this order was obtained, respectively.

[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”) composed of a glass epoxy material and copper foil (thickness 35 μm) formed on both surfaces thereof. The copper surface was polished using a polishing machine (manufactured by Sankei Co., Ltd.) having a brush equivalent to # 600, washed with water, and then dried with an air stream. After heating this copper clad laminated board (henceforth a "board | substrate") and heating up at 80 degreeC, the photosensitive element concerning Examples 1-18 and Comparative Examples 1-6 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. . Next, the photosensitive resin layer was exposed through a phototool having a step tablet and a support. 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 18 and Comparative Examples 1 to 6 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 Tables 2 and 3.

[Evaluation of adhesion and resolution]
An evaluation pattern having a line width / space width of n / 3n (unit: μm, n = 5 μm to 30 μm at 5 μm intervals) for evaluation of adhesion on the evaluation multilayer substrate, and line width / Phototool data having an evaluation pattern having a space width of 3 n / n (unit: μm, n = 5 μm to 30 μm and 5 μm interval) 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. Adhesion was evaluated by the minimum value (unit: μm) of the width of the line area where the cured film remained after development. The resolution was evaluated by the minimum value (unit: μm) of the width of the space between the line regions where the portion not photocured by the development process could be removed cleanly. The evaluation of adhesion and resolution is better as the numerical value is smaller. The results are shown in Tables 2 and 3.

[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 3 independent round holes 41 and 3 round holes each having a diameter of 4 mm 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., the protective layer was peeled off from the photosensitive elements according to Examples 1 to 18 and Comparative Examples 1 to 6, and the photosensitive resin layer was for hole breakage number measurement. Arranged so as to face the copper surface of the substrate 40 and laminated under the conditions of 120 ° C. and 0.4 MPa, respectively, a laminated substrate for tent reliability evaluation was produced.

After lamination, the laminated substrate for tent reliability evaluation was allowed to cool to 23 ° C. Next, exposure is performed from above the support of the photosensitive element with an exposure amount of 17 mJ / cm ² using an exposure machine (Japan Orbotech Co., Ltd., trade name “Paragon-9000m”) using a semiconductor-excited solid laser as a light source. did.

  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 Tables 2 and 3.

[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 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.
Then, 300 ml of 3.0 mass% NaOH aqueous solution (peeling liquid) was prepared at 50 ° C. in a beaker having a capacity of 400 ml. While the peeling solution was stirred at 200 rpm using a stirring bar having a length of 30 mm, the developed substrate was immersed in the peeling solution, and the time (unit: second) until the cured film was separated from the substrate was measured. In addition, it is evaluated that the longer the time until the cured film is separated from the substrate, the shorter the peeling time and the better the peelability. The results are shown in Tables 2 and 3.

  As shown in the above evaluation results, when the photosensitive elements according to Examples 1 to 18 using the photosensitive resin composition of the present invention were used, the photosensitive elements according to Comparative Examples 1 to 6 were used in any case. Compared with the case where it is used, a resist pattern showing excellent tent reliability of 60% or more (more preferably 80% or more) can be formed even at a low exposure amount, and less than 80 seconds (more preferably 70%). It was found that the resist pattern can be peeled off in a short time (less than seconds). Further, the resist patterns obtained in these examples were excellent in adhesion and resolution in a well-balanced manner. Regarding the photosensitive element according to the comparative example, the photosensitivity was the same as that of the photosensitive element according to the example, but at least one of the peeling time and the tent reliability was inferior. Further, Examples 1 to 12 using N-1717 corresponding to the compound (C1) as the photopolymerization initiator are more sensitive, adhesive, resolution and peeling than the examples using other photopolymerization initiators. It was found that time and tent reliability were better balanced.

  The disclosure of Japanese Patent Application No. 2014-099629 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims (11)

(A) component: binder polymer,
(B) component: a photopolymerizable compound;
(C) component: containing a photoinitiator,
The component (B), (B1) component: polyalkylene oxide _{[- (C m H 2m O)} n -: m, n are each independently 2 or more numbers] has as a structural unit, a double bond equivalent Including a photopolymerizable compound having 700 or more,
The photosensitive resin composition whose content rate of the said (B1) component in the total amount of the said (A) component and the said (B) component is 5 mass% or more.   The component (A) includes a structural unit (A1) derived from at least one selected from the group consisting of styrene, a styrene derivative, benzyl (meth) acrylate, and a benzyl (meth) acrylate derivative, and the component (A) The photosensitive resin composition of Claim 1 whose content rate of the said structural unit (A1) in the total amount of is 10 mass%-60 mass%.   The photosensitive resin composition of Claim 1 or Claim 2 in which the said (B1) component contains the photopolymerizable compound which has 2 or more of photopolymerizable double bonds in 1 molecule.   The said (A) component further contains the structural unit (A2) derived from the alkyl (meth) acrylate which is a C5-C20 alkyl group, It is any one of Claims 1-3. Photosensitive resin composition. The component (B1) is polyethylene oxide [— (C ₂ H ₄ O) _n —: n is a number of 2 or more] and polytetramethylene oxide [— (C ₄ H ₈ O) _n —: n is 2 or more. The photosensitive resin composition as described in any one of Claims 1-4 containing the photopolymerizable compound which has at least 1 type selected from the group which consists of a number as a structural unit.   The photosensitive resin composition as described in any one of Claims 1-5 in which the said (C) component contains the acridine compound which has two (C1) compounds: acridinyl group.   In the component (C), the content of the (C2) compound: acridine compound having one acridinyl group is 0.3 parts by mass to 1 part with respect to 100 parts by mass of the total amount of the component (A) and the component (B). The photosensitive resin composition as described in any one of Claims 1-6 which is 0.5 mass part.   Content of (C3) compound: N-phenylglycine in said (C) component is 0.1 mass part or less with respect to 100 mass parts of total amounts of (A) component and (B) component, The photosensitive resin composition as described in any one of Claims 1-7. A support;
The photosensitive element which has the photosensitive resin layer formed on the said support body using the photosensitive resin composition as described in any one of Claims 1-8. The photosensitive resin layer formation process which forms a photosensitive resin layer on a board | substrate using the photosensitive resin composition as described in any one of Claims 1-8, or the photosensitive element of Claim 9. When,
An exposure step of irradiating at least a part of the photosensitive resin layer with actinic rays to cure the region;
A developing step of removing an unexposed portion other than the region of the photosensitive resin layer from the substrate.   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 10.