KR102458628B1 - Photosensitive resin composition, photosensitive element, method for forming resist pattern, and process for producing printed wiring board - Google Patents

Abstract

(A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: contains a photoinitiator, said (B) component is (B1) component: polyalkylene oxide [-(C) _m H _2m O) _n -: m and n each independently represent a number of 2 or more] as a structural unit, including a photopolymerizable compound having a double bond equivalent of 700 or more, The photosensitive resin composition whose content rate of the said (B1) component in a total amount is 5 mass % or more.

Description

The photosensitive resin composition, the photosensitive element, the formation method of a resist pattern, and the manufacturing method of a printed wiring board TECHNICAL FIELD

The present invention 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 a printed wiring board, a photosensitive resin composition and a photosensitive resin layer obtained by using the photosensitive resin composition as a resist material used for etching or plating, and a photosensitive element having a support and a protective layer are widely used.

In the printed wiring board, the photosensitive element is laminated on a substrate for circuit formation, the photosensitive resin layer is exposed in a pattern shape, and then the unexposed portion is removed with a developer to form a resist pattern, and an etching treatment or plating treatment is performed to the substrate. After forming a circuit thereon, it is manufactured by a method of peeling and removing a cured portion that is an exposed portion on a substrate.

As said developing solution, alkaline developing solutions, such as sodium carbonate aqueous solution and sodium hydrogencarbonate aqueous solution, are mainstream from a viewpoint of environmental property and safety|security. The unexposed part of the photosensitive resin layer is removed from a board|substrate by the spray pressure of image development by these developing solutions, and water washing. Therefore, it is calculated|required by the photosensitive resin composition that it is possible to form the cured film (resist pattern) which has the outstanding tent reliability (tenting property) which is not damaged by the spray pressure of image development and water washing after exposure.

In recent years, as an exposure method that does not require a mask, digital data of a pattern produced by a computer-aided design (CAD) called LDI (Laser Direct Imaging) method or DLP (Digital Light Processing) is used with a laser beam. Correspondence to the direct drawing exposure method which draws directly on the photosensitive resin composition layer is strongly desired. The resist material used in the direct drawing exposure method contains a compound having a rigid skeleton since it is required to have low exposure dose and low curing degree from the viewpoint of processing capacity (throughput) per unit time. However, the compound of a rigid skeleton tends to reduce the tent reliability of a cured film.

In order to improve the tent reliability of a cured film, it is effective to raise the intensity|strength of the cured film formed using the photosensitive resin composition. However, as there is a problem that the peeling time becomes longer and productivity decreases when the strength of the cured film is increased, a resist material excellent in tent reliability and peeling time while satisfying high throughput even when a direct drawing exposure method is applied has not been developed so far. For example, Japanese Patent Laid-Open No. 2006-234995, Japanese Patent Laid-Open No. 2007-122028, International Publication No. 2008/078483, Japanese Patent Application Laid-Open No. 2009-69465 and International Publication Even when the photosensitive resin composition of 2010/103918 was used, there existed room for improvement.

Then, this invention can form a resist pattern even at a low exposure dose, and an object of this invention is to provide the photosensitive resin composition excellent in tent reliability and peeling time of the cured film formed. Another object of the present invention is to provide a photosensitive element using the photosensitive resin composition, a method for forming a resist pattern, and a method for manufacturing a printed wiring board.

Specific means for solving the above problems include the following embodiments.

<1> (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: containing photoinitiator, said (B) component is (B1) component: polyalkylene oxide [ -(C _m H _2m O) _n -: 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, wherein the component (A) and the (B) ) The photosensitive resin composition whose content rate of the said (B1) component in the total amount of a component is 5 mass % or more.

<2> The component (A) contains a structural unit (A1) derived from at least one selected from the group consisting of styrene, styrene derivatives, benzyl (meth) acrylate and benzyl (meth) acrylate derivatives, The photosensitive resin composition as described in <1> whose content rate of the said structural unit (A1) in the total amount of the said (A) component is 10 mass % - 60 mass %.

The photosensitive resin composition as described in <1> or <2> in which the <3> said (B1) component contains the photopolymerizable compound which has two or more photopolymerizable double bonds in one molecule.

The photosensitivity in any one of <1>-<3> in which the <4> said (A) component further contains the structural unit (A2) derived from the alkyl (meth)acrylate which is a C5-C20 alkyl group. resin composition.

<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 is 2 The photosensitive resin composition in any one of <1>-<4> containing the photopolymerizable compound which has as a structural unit at least 1 sort(s) chosen from the group which consists of more than number].

The photosensitive resin composition in any one of <1>-<4> in which the <6> said (C)component contains the acridine compound which has (C1) compound: two acridinyl groups.

In <7> said (C)component, (C2) compound: Content of the acridine compound which has one acridinyl group is 0.3 mass with respect to 100 mass parts of total amounts of (A) component and (B) component The photosensitive resin composition in any one of <1>-<6> which is part - 1.5 mass parts.

In <8> said (C)component, (C3) compound: <1>-< whose content of N-phenylglycine is 0.1 mass part or less with respect to 100 mass parts of total amounts of (A)component and (B)component 7> The photosensitive resin composition in any one of Claims.

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 in any one of <1>-<8>.

<10> The photosensitive resin layer forming process of forming a photosensitive resin layer on a board|substrate using the photosensitive resin composition in any one of <1>-<8>, or the photosensitive element as described in <9>, The said photosensitive resin layer A method for forming a resist pattern, comprising: an exposure step of curing at least a part of the area by irradiating actinic light to the area; and a developing step of removing an unexposed portion of the photosensitive resin layer other than the area from the substrate.

<11> The manufacturing method of a printed wiring board including the process of etching or plating the board|substrate with a resist pattern by the method as described in <10>.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to form a resist pattern even at a low exposure dose, and it becomes possible to provide the photosensitive resin composition excellent in tent reliability and peeling time of the cured film formed. 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.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows one Embodiment of the photosensitive element of this invention.
It is a process chart which shows an example of the manufacturing method of the multilayer printed wiring board using the photosensitive element of this invention.
[Fig. 3] It is a top view of the board|substrate for measuring the number of hole tears used for tent reliability evaluation.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a form for carrying out the present invention will be described in detail with reference to the drawings as necessary. However, this invention is not limited to the following embodiment. In addition, in drawing, the same code|symbol shall be attached|subjected to the same element, and overlapping description is abbreviate|omitted. In addition, the dimensional ratio of a drawing is not limited to the ratio of illustration.

"(meth)acrylic acid" in this specification means at least one of "acrylic acid" and "methacrylic acid", and "(meth)acrylate" means "acrylate" and the corresponding "methacrylate" means at least one of, and "(meth)acryloyl group" means at least one of "acryloyl group" and "methacryloyl group". "Polyalkylene oxide" means a structural unit represented by [-(C _m H _2m O) _n -: m and n are each independently a number of 2 or more]. The number of structural units indicates to what extent the corresponding structural units are added in the molecule. Therefore, although an integer value is expressed for a single molecule, a rational number that is an average value is expressed as an aggregate of a plurality of types of molecules. "Non-volatile matter" refers to components in the composition other than volatile substances, such as water and an organic solvent mentioned later. Here, the substance which volatilizes points out that it is a substance whose boiling point is 155 degrees C or less under atmospheric pressure. "The total amount of (A) component" and "the total amount of (B) component" mean the total amount of non-volatile content.

As used herein, the term "process" is included in this term if the intended purpose of the process is achieved, even if it is not clearly distinguishable from other processes as well as independent processes. In addition, the numerical range indicated using "-" represents a range including the numerical value described before and after "-" as a minimum value and a maximum value, respectively. In addition, content of each component in a composition means the total amount of the said some substance which exists in a composition, unless otherwise specified, when there exist two or more substances corresponding to each component in a composition. In addition, in the numerical range described in stages in this specification, you may change the upper limit or lower limit of the numerical range of one stage with the upper limit or lower limit of the numerical range of another stage. In addition, in the numerical range described in this specification, you may change the upper limit or lower limit of the numerical range with the value shown in an Example. The term "layer" includes a configuration of a shape formed partially in addition to a configuration of a shape formed on the entire surface when viewed as a plan view. The term "stacking" refers to layering on top of each other, and two or more layers may be joined, or two or more layers may be detachable.

<Photosensitive resin composition>

The photosensitive resin composition of this embodiment contains (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photoinitiator, said (B) component is (B1) component : polyalkylene oxide [-(C _m H _2m O) _n -: 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, wherein (A ) The content rate of the said (B1) component in the total amount of a component and the said (B) component is 5 mass % or more. The said photosensitive resin composition may further contain other components as needed.

Even if the photosensitive resin composition of this invention is a low exposure amount, it is possible to form a resist pattern, and the present inventors guess as follows about the reason excellent in the tent reliability and peeling time of the cured film formed. That is, the photosensitive resin composition of this invention has a polyalkylene oxide as a structural unit, and contains the photopolymerizable compound whose double bond equivalent is 700 or more. By including a photopolymerizable compound having a highly flexible polyalkylene oxide as a structural unit, the resulting cured film (resist pattern) has moderate flexibility, so stress concentration inside the resist pattern is less likely to occur, and tent reliability is improved I think it will In addition, since the specific photopolymerizable compound has a relatively high double bond equivalent (molecular weight per photopolymerizable double bond), the crosslinking density of the formed cured film is moderately lowered, and the penetration rate of the stripper into the resist pattern is improved. . It is thought that peeling time becomes short.

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 1 sort(s) of a binder polymer as (A) component. The structure of the binder polymer is not particularly limited and may be selected from commonly used ones. A binder polymer may be used individually by 1 type, or may combine 2 or more types. As a binder polymer, the binder polymer containing the following structural unit (A1), structural unit (A2), structural unit (A3), etc. is mentioned, for example.

・Structural unit (A1)

It is preferable that at least 1 type of binder polymer contains the structural unit (A1) derived from at least 1 type selected from the group which consists of styrene, a styrene derivative, benzyl (meth)acrylate, and a benzyl (meth)acrylate derivative. . For this reason, the adhesiveness at the time of setting it as hardened|cured material can be improved, maintaining the softness|flexibility of (A) binder polymer.

From a viewpoint of making both the adhesiveness of a cured film and peeling characteristic favorable, it is preferable that the content rate of the structural unit (A1) of a binder polymer is 10 mass % - 60 mass % in the total amount of (A) component, 13 mass % It is more preferable that it is -40 mass %, It is still more preferable that it is 13 mass % - 25 mass %, It is still more preferable that it is 15 mass % - 25 mass %, It is especially preferable that it is 15 mass % - 18 mass %. When the content rate of the structural unit (A1) is 10 mass % or more, the adhesiveness of the cured film tends to improve, and when it is 60 mass % or less, it suppresses that the peeling piece becomes large, and it can suppress that the peeling time becomes long. There is a tendency for tent reliability to improve.

Specific examples of the styrene derivative include polymerizable styrene derivatives substituted at the α-position or an 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, and 4-methoxybenzyl (meth) acrylate. ) acrylate, 4-ethoxybenzyl (meth)acrylate, 4-hydroxybenzyl (meth)acrylate, 4-chlorobenzyl (meth)acrylate, etc. are mentioned.

・Structural unit (A2)

It is preferable that at least 1 sort(s) of a binder polymer contains the structural unit (A2) derived from an alkyl (meth)acrylate from a viewpoint of the tent reliability of a cured film. Linear or branched any may be sufficient as the alkyl group in alkyl (meth)acrylate, and even if it is unsubstituted, it may have a substituent. It is preferable that carbon number of an alkyl group is 1-20, It is more preferable that it is C5-C20, It is still more preferable that carbon number is 8-14. As alkyl (meth)acrylate, the compound represented by the following general formula (I) is mentioned.

CH ₂ =C(R ³ )-COOR ⁴ (I)

In the 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, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. real groups 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. A hydroxyl group, an epoxy group, a halogen group etc. are mentioned as said substituent. When the C1-C20 alkyl group represented by R< ⁴ > has a substituent, the number in particular of a substituent and a substitution position are not restrict|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) has more preferably 5 to 20 carbon atoms, and still more preferably 8 to 14 carbon atoms.

As the compound represented by the general formula (I), (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate isopropyl, (meth) acrylate n-butyl, (meth) acrylic acid tert-butyl, (meth) acrylate pentyl, (meth) acrylate hexyl, (meth) acrylate heptyl, (meth) acrylate octyl, (meth) acrylate 2-ethylhexyl, (meth) acrylate nonyl, (meth) acrylate decyl, ( and undecyl (meth)acrylate and dodecyl (meth)acrylate. These can be used individually by 1 type or in combination of 2 or more type.

When a binder polymer contains a structural unit (A2), it is preferable that the content rate of the structural unit (A2) in the total amount of (A) component is 1 mass % - 70 mass % from a viewpoint of adhesiveness, resolution, and developability. And it is more preferable that they are 30 mass % - 65 mass %, and it is still more preferable that they are 45 mass % - 60 mass %. The tent reliability of a cured film improves more by making the content rate of a structural unit (A2) 1 mass % or more, and the resolution and adhesiveness of a cured film further improve by setting it as 80 mass % or less.

・Structural unit (A3)

It is preferable that at least 1 sort(s) of a binder polymer contains the structural unit (A3) derived from the polymerizable monomer which has a carboxy group in the state 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; (meth)acrylic acid derivatives such as α-bromoacrylic acid, α-chloroacrylic acid, β-furyl (meth)acrylic acid, and β-styryl (meth)acrylic acid; maleic acid; maleic acid derivatives such as monomethyl maleate, monoethyl maleate, and monoisopropyl maleate; and fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, and propiolic acid. From a viewpoint of a sensitivity improvement, (meth)acrylic acid is preferable and methacrylic acid is more preferable.

When the binder polymer contains the structural unit (A3), from the viewpoint of the balance between alkali developability and developer resistance, the content of the structural unit (A3) in the total amount of component (A) is 12% by mass to 50% by mass. It is preferable, and it is more preferable that they are 15 mass % - 35 mass %, and it is still more preferable that they are 15 mass % - 30 mass % from the point which is more excellent in alkali developability.

・Other structural units

The binder polymer may contain other structural units other than the structural units (A1) to (A3). As a polymerizable monomer which comprises another structural unit, For example, Acrylamide, such as diacetone acrylamide; acrylonitrile; ethers of vinyl alcohol such as vinyl-n-butyl ether; Organic acid derivatives, such as maleic anhydride, are mentioned. These can be used individually by 1 type or in combination of 2 or more type.

(A) The content rate of other structural units in the total amount of component is preferably 10 mass % or less, more preferably 5 mass % or less, from the viewpoint of adhesiveness, resolution, and developability of a cured film, and does not contain substantially It is more preferable not to (for example, 0.5 mass % or less). That is, it is preferable that it is 90 mass % or more, and, as for the content rate of the sum total of structural units (A1), (A2) and (A3) in the total amount of (A) component, it is more preferable that it is 95 mass % or more, It is substantially 100 It is more preferable that it is mass % (for example, 99.5 mass % or more).

Various properties of binder polymers

A binder polymer is obtained by polymerizing the monomer corresponding to each structural unit which comprises a binder polymer. As a polymerization method, radical polymerization is mentioned. When the binder polymer is a copolymer obtained by polymerizing two or more types of monomers, each structural unit in the copolymer may be randomly included in the copolymer as in a so-called random copolymer, and monomers of the same type are continuous as in the block copolymer. The copolymer containing the structural unit formed by doing so may be sufficient. In addition, each structural unit may be a single type or a composite type may be sufficient as it.

The weight average molecular weight of the binder polymer is preferably 20,000 to 300,000, more preferably 30,000 to 200,000, still more preferably 40,000 to 100,000 from the viewpoint of the balance between developer resistance and alkali developability. The weight average molecular weight in the present specification is a value obtained by measuring by gel permeation chromatography under the same measurement conditions as those described in Examples, and converting it by a calibration curve prepared using standard polystyrene.

It is preferable that they are 120 mgKOH/g - 200 mgKOH/g, and, as for the acid value of a binder polymer, it is more preferable that they are 150 mgKOH/g - 170 mgKOH/g.

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

(A) Component is a binder polymer containing at least one of structural units (A1), (A2) or (A3), and other binder polymers that do not contain any structural units (A1), (A2) or (A3). It may be a combination with As another binder polymer, if it is soluble in aqueous alkali solution and can form a film, there will be no restriction|limiting in particular. Examples include acrylic resins (however, those that do not contain structural units (A1) (A2) (A3)), epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenolic resins. have. Especially, an acrylic resin is preferable from a viewpoint of alkali developability. These can be used individually by 1 type or in combination of 2 or more type.

(A) When component contains other binder polymer in which neither structural unit (A1), (A2), or (A3) is contained, content rate of structural unit (A1) in the total amount of (A) component is 10 mass It is preferable that they are % - 60 mass %, It is more preferable that they are 13 mass % - 40 mass %, It is more preferable that they are 15 mass % - 25 mass %. (A) When component contains another binder polymer, it is preferable that it is 10 mass % or less, and, as for the content rate of the other binder polymer in the total amount of (A) component, it is more preferable that it is 5 mass % or less. It is more preferable that other binder polymers are not substantially contained (for example, 0.5 mass % or less), and it is especially preferable that other binder polymers are not contained at all.

It is preferable to set it as 30 mass parts - 80 mass parts in 100 mass parts of total amounts of (A) component and (B) component, as for content of (A) component in the photosensitive resin composition, It is more preferable to set it as 40 mass parts - 75 mass parts And it is more preferable to set it as 50 mass parts - 70 mass parts. (A) There exists a tendency for the coating-film property of the photosensitive resin composition and the intensity|strength of a cured film to become more favorable that content of a component is this range.

[(B) component: photopolymerizable compound]

The photosensitive resin composition of this invention contains at least 1 sort(s) of a photopolymerizable compound as (B)component. (B) component has polyalkylene oxide as a structural unit, and contains at least 1 sort(s) of a photopolymerizable compound (specific photopolymerizable compound) with a double bond equivalent of 700 or more as (B1) component, (A) component and (B) ) The content rate of (B1) component in the total amount of a component is 5 mass % or more.

A photopolymerizable compound will not be restrict|limited, especially if the whole or a part is (B1) component, It can select suitably from the photopolymerizable compound normally used and can be used. As a photopolymerizable compound, the compound which has a photopolymerizable unsaturated double bond is mentioned.

-(B1) component: specific photopolymerizable compound

The photosensitive resin composition of this invention has a polyalkylene oxide as a structural unit, and contains at least 1 sort(s) of the specific photopolymerizable compound whose double bond equivalent is 700 or more. Thus, by having a highly flexible polyalkylene oxide as a structural unit, and containing the compound with a comparatively large double bond equivalent, the photosensitive resin composition which is excellent in tent reliability and can form a cured film with a short peeling time 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 a number of 2 or more). The position or number of polyalkylene oxide structural units contained in the molecule|numerator of a specific photopolymerizable compound is not specifically limited. Moreover, 2 or more types of different polyalkylene oxide structural units may be contained in one molecule. Even if there is only one type of specific photopolymerizable compound contained in the photosensitive resin composition, two or more types from which a structure is different (for example, m or n in -(C _m H _2m O) _n - has a different structural unit, respectively) A combination may be sufficient.

From the viewpoint of improving the tent reliability and peeling time of the cured film in a balanced manner, a 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 a number greater than or equal to 2], and polytetramethylene oxide [-(C ₄ H ₈ O) _n -: n is a number greater than or equal to 2] as a structural unit. it is preferable Among them, 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, and selected from the group consisting of polytetramethylene oxide. It is especially preferable to have at least 1 sort(s) as a structural unit. -(C _m H _2m O) _n in n - is preferably a number of 4 or more, more preferably a number of 19 or more, and still more preferably a number of 40 or more from the viewpoint of tent reliability and peelability. When m is 3 or more, it is preferable that it is a number of 100 or less from a developable viewpoint, It is more preferable that it is a number of 50 or less, It is more preferable that it is a number of 30 or less.

The double bond equivalent of a specific photopolymerizable compound will not be restrict|limited as long as it is 700 or more in particular. From a viewpoint of the balance of the resolution of a cured film, tent reliability, and peelability, it is preferable that the double bond equivalent of a specific photopolymerizable compound is 700-2000, It is more preferable that it is 700-1500, It is still more preferable that it is 800-1000 , it is more preferably 800 to 1500.

In the present invention, "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 whose number of photopolymerizable double bonds is 2 is the value which divided the molecular weight by 2. The double bond equivalent of the photopolymerizable compound can be increased by, for example, increasing the number of polyalkylene oxide structural units in the molecule and increasing the molecular weight.

The double bond equivalent of a photopolymerizable compound can be calculated|required by the number of g of resin required with respect to 1 mol of carbon-carbon double bonds.

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 obtained by structural analysis.

In addition, the double bond equivalent of a compound alone can be calculated|required from the value of the iodine value measured by the following method.

How to measure the iodine number:

The polyurethane compound is precisely weighed in the range of 0.25 to 0.35 g, put into a 200 ml iodine flask, 30 ml of chloroform is added, and the sample is completely dissolved. To this, 20 ml of Wijs reagent (7.9 g of iodine trichloride and 8.2 g of iodine, respectively, dissolved in 200 to 300 ml of glacial acetic acid, and the two solutions are mixed to make 1 l) were added with a hole pipette, followed by 2.5% mercuric acetate glacial acetic acid solution. After adding 10 ml, the reaction was completed by leaving it in a dark place for 20 minutes. 5 ml of a freshly prepared 20% KI solution is added thereto, and titrated with a 0.1NN _a2 S ₂ O ₃ standard solution using a 1% starch solution as an indicator. At the same time, a blank test is also performed, and the iodine value Y is calculated according to the following formula.

Iodine number Y(g/100g)=(Aml-Bml)0.1N×f×126.9×100/Sg

Double bond equivalent (g/mol)=100×253.8/Y=20000×S/((A-B)×f)

A: Number of ml of 0.1NN _a2 S ₂ O ₃ standard solution required for blank test

B: Number of ml of 0.1NN _a2 S ₂ O ₃ standard solution required for this test

f: titer of 0.1NN _a2 S ₂ O ₃ standard solution

S: number of grams of sample

The number of photopolymerizable double bonds that a specific photopolymerizable compound has is not particularly limited. From a viewpoint of reducing the resist residue in a peeling process, it is preferable that the number of photopolymerizable double bonds is two or more in one molecule. As a photopolymerizable double bond, the double bond contained in a (meth)acryloyl group is mentioned.

Examples of the specific photopolymerizable compound include an ester product of a polyalkylene glycol compound having a double bond equivalent of 700 or more and (meth)acrylic acid, a bisphenol A (meth)acrylate having a double bond equivalent of 700 or more, and a polyalkylene having a double bond equivalent of 700 or more. The reaction product (urethane compound) of glycol mono(meth)acrylate and an isocyanate compound, etc. are mentioned.

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, 2,2-bis(4-((meth)acryl) Oxypolypropyleneoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolytetramethyleneoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolyethyleneoxypolypropylene oxy) phenyl) propane and the like.

As an ester 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 , polytetramethylene glycol di(meth)acrylate, trimethylolpropane polyethylene ether tri(meth)acrylate, pentaerythritol propane polyethylene ether tetra(meth)acrylate, and the like.

As a reaction product of a polyalkylene glycol mono(meth)acrylate having a double bond equivalent of 700 or more and an isocyanate compound, 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, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, and three amounts of these isocyanates A reaction product with an isocyanate compound, such as a sieve, etc. are mentioned.

Preferred examples of the specific photopolymerizable compound include polyethylene glycol di(meth)acrylate having a molecular weight of 1400 or more, polypropylene glycol di(meth)acrylate having a molecular weight of 1400 or more, polytetramethylene glycol di(meth)acrylate having a molecular weight of 1400 or more, and a reaction product of three of polyethylene glycol mono(meth)acrylate having a molecular weight of 2100 or more and a 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 polytetramethylene glycol having a molecular weight of 1400 to 4000. The reaction product of three of di(meth)acrylate and the polyethyleneglycol mono(meth)acrylate whose molecular weight is 2100-4000, and a hexamethylene diisocyanate trimer is mentioned.

The ratio (RO content) occupied by the polyalkylene oxide structural unit in the molecule of the specific photopolymerizable compound is preferably 60 mass % or more, more preferably 65 mass % or more, still more preferably 70 mass % or more, It is more preferable that it is 75 mass % or more, and it is still more preferable that it is 85 % or more.

The content rate of a specific photopolymerizable compound is 5 mass % or more on the basis of the total amount of (A) component and (B) component, It is preferable that it is 6 mass % or more, It is more preferable that it is 12 mass % or more. Moreover, it is preferable that they are 6 mass % - 40 mass %, and it is more preferable that they are 14 mass % - 40 mass %. By making the content rate of a specific photopolymerizable compound into 5 mass % or more, a cured film becomes soft, tent reliability can be improved, and peeling time can be shortened. Moreover, resolution and adhesiveness can further be improved by setting it as 40 mass % or less. From the viewpoint of obtaining a cured film having better resolution and shorter peeling time, the content rate 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). It is preferable, and it is more preferable that they are 12 mass % - 30 mass %, It is still more preferable that they are 12 mass % - 20 mass %, It is still more preferable that they are 14 mass % - 20 mass %.

・Other photopolymerizable compounds

The photosensitive resin composition of this invention may also contain at least 1 sort(s) of photopolymerizable compounds other than a specific photopolymerizable compound as (B) component. Examples of such a photopolymerizable compound include an ester product of a polyalkylene glycol compound having a double bond equivalent of less than 700 and (meth)acrylic acid, a bisphenol A (meth)acrylate having a double bond equivalent of less than 700, and polyalkylene having a double bond equivalent of less than 700. A reaction product of glycol mono(meth)acrylate and an isocyanate compound, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethylene-o-phthalate, β-hydroxyethyl-β'-(meth) ) phthalic acid derivatives such as acryloyloxyethylene-o-phthalate and β-hydroxypropyl-β'-(meth)acryloyloxyethylene-o-phthalate, and alkyl (meth)acrylate.

When two or more types of photopolymerizable compounds are used in combination, the content of the compound having two or more photopolymerizable unsaturated double bonds in one molecule in the total amount of the two or more types of photopolymerizable compounds is preferably 75% by mass or more. . (B) When the content rate of the compound which has two or more photopolymerizable unsaturated double bonds in 1 molecule in the total amount of component is 75 mass % or more, the tent reliability of a cured film, resolution, and adhesiveness tend to improve more.

It is preferable that content of the photopolymerizable compound in the photosensitive resin composition sets it as 20 mass parts - 70 mass parts in 100 mass parts of total amounts of (A) component and (B) component. It is preferable that it is 20 mass parts or more in 100 mass parts of total amounts of (A) component and (B) component, as for content of a photopolymerizable compound from a viewpoint of improving the tent reliability and resolution of a cured film more, It is more preferable that it is 25 mass parts or more And it is more preferable that it is 30 mass parts or more. From the viewpoint of imparting good film properties to the photosensitive resin composition and improving the shape of the resist after curing, the content of the photopolymerizable compound is 70 parts by mass or less in 100 parts by mass of the total amount of the component (A) and the component (B). It is preferable, It is more preferable that it is 60 mass parts or less, It is still more preferable that it is 55 mass parts or less, It is especially preferable that it is 50 mass parts or less.

[(C)component: photoinitiator]

The said photosensitive resin composition contains at least 1 sort(s) of a photoinitiator as (C)component. The photopolymerization initiator is not particularly limited, and may be appropriately selected from commonly used photopolymerization initiators.

Especially, it is preferable that (C)component contains the acridine compound which has one or two acridinyl groups in one molecule. That is, (C)component is an acridine compound (hereinafter also referred to as "(C1) compound") having two acridinyl groups and an acridine compound having one acridinyl group (hereinafter, "( C2) It is preferable to include at least one compound selected from the group consisting of "compound"). Especially, you may contain (C1) compound from a viewpoint of improving a sensitivity, adhesiveness, resolution, peeling time, and tent reliability in a balanced way. Among these characteristics, the sensitivity and tent reliability can be improved by containing the (C1) compound.

(C1) As a compound, the acridine compound represented by the following general formula (II) is mentioned, for example.

In formula (II), R< ³ > represents a C2-C20 alkylene group, a C2-C20 oxadialkylene group, or a C2-C20 thiodialkylene group. From a viewpoint of acquiring the effect seen by the photosensitive resin composition more reliably, it is preferable that it is a C2-C20 alkylene group, and, as for R< ³ >, it is more preferable that it is a C4-C14 alkylene group.

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)hexa di(9-acridinyl)alkanes such as decane, 1,18-di(9-acridinyl)octadecane, and 1,20-di(9-acridinyl)eicosane; di(9-acridinyl)oxaalkanes such as 1,3-di(9-acridinyl)-2-oxapropane and 1,5-di(9-acridinyl)-3-oxapentane; di(9-acridinyl)thioalkanes such as 1,3-di(9-acridinyl)-2-thiapropane and 1,5-di(9-acridinyl)-3-thiapentane; can These are used individually by 1 type or in combination of 2 or more types.

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

When the said photosensitive resin composition contains (C1) compound as a photoinitiator, content of (C1) compound is 100 mass parts of total amounts of (A) component and (B) component from a viewpoint of a sensitivity, resolution, and adhesiveness. relative to, for example, 0.1 parts by mass to 10 parts by mass or 0.5 parts by mass to 5 parts by mass, preferably 0.1 parts by mass to 2 parts by mass, more preferably 0.25 parts by mass to 1.5 parts by mass, 0.35 parts by mass It is more preferable that they are parts - 1.2 mass parts, and it is especially preferable that they are 0.45 mass parts - 1 mass part.

(C1) When content of a compound is 0.1 mass part or more, there exists a tendency for a more favorable sensitivity, resolution, or adhesiveness to be acquired. When it is 10 parts by mass or less, a better resist shape tends to be obtained, and when it is 2 parts by mass or less, a more favorable resist shape tends to be obtained.

(C2) As a compound, the acridine compound represented by the following general formula (III) is mentioned, for example.

In formula (III), ^R4 represents a halogen atom, an amino group, a carboxy group, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C1-C6 alkylamino group. m represents the integer of 0-5. When m is 2 or more, some R< ⁴ > may be 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, and 9- (p-chlorophenyl)acridine, 9-(m-chlorophenyl)acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylaminoacridine and 9-pentylami and noacridine. These are used individually by 1 type or in combination of 2 or more types.

When the said photosensitive resin composition contains (C2) compound as a photoinitiator, content of (C2) compound is 100 mass parts of total amounts of (A) component and (B) component from a viewpoint of a sensitivity, resolution, and adhesiveness. For example, 0.1 parts by mass to 10 parts by mass or 0.5 parts by mass to 5 parts by mass may be sufficient, preferably 0.1 parts by mass to 2 parts by mass, more preferably 0.3 parts by mass to 1.5 parts by mass, and 0.4 parts by mass It is more preferable that they are parts - 1.2 mass parts, and it is especially preferable that they are 0.5 mass parts - 0.8 mass parts. (C2) When content of a compound is 0.1 mass part or more, there exists a tendency for a more favorable sensitivity, resolution, or adhesiveness to be acquired. When it is 10 parts by mass or less, a better resist shape tends to be obtained, and when it is 2 parts by mass or less, a more favorable resist shape tends to be obtained.

It is also preferable that the said photosensitive resin composition contains the (C3) compound represented by the following general formula (IV) as (C)component from a viewpoint of improving a sensitivity. The compound (C3) represented by the general formula (IV) can also be referred to as N-phenylglycine.

When the said photosensitive resin composition contains (C3) compound as a photoinitiator, the upper limit of (C3) compound content is 100 mass parts of total amounts of (A) component and (B) component from a viewpoint of improving resolution With respect to it, it is preferable that it is 0.1 mass part or less, It is more preferable that it is 0.07 mass part or less, It is still more preferable that it is 0.06 mass part or less. (C3) 0.01 mass part or more, 0.02 mass part or more, 0.04 mass part or more may be sufficient as the lower limit of compound content from a viewpoint of improving a sensitivity and adhesiveness. If it is 0.1 mass part or less, there exists a tendency for more favorable resolution to be acquired. Moreover, by being 0.01-0.1 mass part, a sensitivity, resolution, and adhesiveness can be improved in a balanced way.

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

Examples of the photopolymerization initiator other than the (C1) compound, the (C2) compound and the (C3) compound include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (mihiraketone), N,N' -Tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 aromatic ketone compounds such as ,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di Phenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl1,4-naphthoquinone, 2,3-dimethylanthraquinone quinone compounds, such as; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin; 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-(p-methoxyphenyl)-4 2,4,5-triaryl imidazole dimers, such as a , 5-diphenyl imidazole dimer; benzyl derivatives such as benzyl dimethyl ketal; substituted anthracene compounds such as 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dipentoxyanthracene; coumarin compounds; oxazole compounds; pyrazoline compounds; triarylamine compounds; and the like.

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 dimethylamino benzoic acid.

The 2,4,5-triarylimidazole dimer may be a compound in which the substituents of the aryl groups of the two 2,4,5-triarylimidazole constituting the dimer are identical and symmetrical. , may be different from each other and may be asymmetric compounds.

When the photosensitive resin composition contains photoinitiators other than the (C1) compound, the (C2) compound, and the (C3) compound as the component (C), the content thereof is, from the viewpoint of sensitivity and internal photocurability, (A) It is preferable that they are 0.01 mass parts - 10 mass parts with respect to 100 mass parts of total amounts of a component and (B) component, It is more preferable that they are 0.1 mass parts - 7 mass parts, It is still more preferable that they are 0.2 mass parts - 5 mass parts.

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

The photosensitive resin composition is at least one selected from the group consisting of (C1) compound and (C2) compound as (C) component, preferably (C1) compound from the viewpoint of sensitivity, adhesiveness and internal photocurability. It is included, and it is preferable that it is 0.1 mass parts - 10 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component, and, as for the content, it is more preferable that they are 0.2 mass parts - 5 mass parts.

[Other ingredients]

The photosensitive resin composition, if necessary, dyes such as malachite green, victoria pure blue, brilliant green, methyl violet; photochromic agents such as leucocrystal violet, diphenylamine, benzylamine, triphenylamine, diethylaniline and o-chloroaniline; exothermic color inhibitor; plasticizers such as p-toluenesulfonamide; pigment; fillers; antifoam; flame retardant; adhesion imparting agent; leveling agent; exfoliation accelerators; antioxidants; polymerization inhibitor; Spices; imaging agent; You may further contain other additives, such as a thermal crosslinking agent.

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 mass part - about 20 mass parts, respectively with respect to 100 mass parts of total amounts of (A) component and (B) component. These additives can be used individually by 1 type or in combination of 2 or more types.

The photosensitive resin composition may further contain at least 1 sort(s) of the organic solvent. As an organic solvent, 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; aprotic solvents such as N,N-dimethylformamide; and the like. These organic solvents may be used individually by 1 type, or may use 2 or more types together.

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 (henceforth the photosensitive resin composition containing an organic solvent is also called "coating liquid") from which a non-volatile matter becomes about 30 mass % - 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 this invention is use with respect to the photosensitive element of the said photosensitive resin composition. In addition, the said photosensitive resin composition can be used for the formation method of a resist pattern mentioned later, and a printed wiring board manufacturing method.

<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.

1, one Embodiment of the photosensitive element of this invention 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, the coating liquid which is the said photosensitive resin composition containing an organic solvent is apply|coated to form an application layer, and the photosensitive resin layer 4 is formed by drying this. Next, by covering the surface of the photosensitive resin layer 4 on the opposite side to the support 2 with the protective layer 6 , the support 2 , the photosensitive resin layer 4 formed on the support 2 , and the photosensitive resin layer (4) The photosensitive element 10 of this embodiment provided with the protective layer 6 laminated|stacked on it can be obtained. The photosensitive element 10 does not need to have the protective layer 6 .

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

It is preferable that they are 1 micrometer - 100 micrometers, as for the thickness of the support body 2 (polymer film), it is more preferable that they are 1 micrometer - 50 micrometers, It is still more preferable that they are 1 micrometer - 30 micrometers. When the thickness of the support body 2 is 1 micrometer or more and the support body 2 is peeled from the photosensitive resin layer 4, it can suppress that the support body 2 is damaged. Moreover, the resolution fall is suppressed because it is 100 micrometers or less.

As the protective layer 6 , it is preferable that the adhesive force to the photosensitive resin layer 4 is smaller than the adhesive force of the support 2 to the photosensitive resin layer 4 . Also, a film with a low fish eye is preferred. Here, the term "fish eye" means that foreign substances, undissolved substances, oxidative deterioration products, etc. contained in the material are blown into the film when the material is heat-melted and the film is manufactured by kneading, extrusion, biaxial stretching, casting, etc. it means. That is, "low fish eye" means that there are few foreign substances and the like in the film.

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. Polyethylenes such as PS series such as Alpan MA-410 and E-200C manufactured by Oji Seishi Co., Ltd., polypropylene film manufactured by Shin-Etsu Film Co., Ltd., PS-25 manufactured by Teijin Co., Ltd. A terephthalate film etc. are mentioned. In addition, the protective layer 6 may be the same as that of the support body 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 is suppressed from being damaged when the photosensitive resin layer 4 and the support body 2 are laminated on the substrate while the protective layer 6 is peeled off. tend to be able to If it is 100 micrometers or less, there exists a tendency excellent in handleability and cheapness.

The photosensitive element of this embodiment can be manufactured specifically, for example as follows. At least, (A) component: binder polymer, (B) component: photopolymerizable compound, and (C) a step of preparing a coating solution in which a photopolymerization initiator is dissolved in the organic solvent, and the coating solution is applied on the support body (2) It can manufacture by the manufacturing method containing the process of forming an application layer, and the process of drying the said application layer to form a photosensitive resin layer.

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

The drying of the application layer is not particularly limited as long as at least a part of the organic solvent can be removed from the application layer. For example, it is preferable to carry out for about 5 to 30 minutes at 70 degreeC - 150 degreeC. It is preferable that the amount of the residual organic solvent in the photosensitive resin layer obtained after drying shall be 2 mass % or less from a viewpoint of preventing the diffusion of the organic solvent in a later process.

The thickness of the photosensitive resin layer 4 in the photosensitive element 10 can be appropriately selected according to the use, and the thickness after drying is preferably 1 µm to 200 µm, more preferably 5 µm to 100 µm, , more preferably 10 μm to 50 μm. When the thickness after drying is 1 µm or more, industrial coating becomes easy, and when it is 200 µm or less, there is a tendency that the sensitivity and photocurability of the resist bottom can be sufficiently obtained.

The photosensitive element 10 may further have intermediate|middle layers, such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer, etc. As these intermediate|middle layers, the intermediate|middle layer described in Unexamined-Japanese-Patent No. 2006-098982 etc. can be applied also to this invention.

The shape of the obtained photosensitive element 10 is not particularly limited. For example, a sheet shape may be sufficient, or the shape wound up in roll shape by the core may be sufficient. When winding up in roll shape, it is preferable to wind up so that the support body 2 may become an outer side. As a material of a winding core, plastics, such as a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), etc. are mentioned. In the end face of the roll-shaped photosensitive element roll obtained in this way, it is preferable to provide an end face separator from the standpoint of end face protection, and it is preferable to provide a moisture proof end face separator from the standpoint of edge fusion resistance. As a packing method, it is preferable to wrap in a black sheet with low moisture permeability and to pack.

The photosensitive element 10 can be suitably used for the formation method of the resist pattern mentioned later, for example.

<Method of forming resist pattern>

A resist pattern may be formed on a substrate by using the photosensitive resin composition. The method for forming a resist pattern of the present embodiment includes (i) a photosensitive resin layer forming step of forming a photosensitive resin layer on a substrate using the photosensitive resin composition, (ii) in at least a part of the photosensitive resin layer, It has the exposure process of irradiating actinic light and hardening the said area|region, and (iii) the developing process of removing from the board|substrate unexposed parts other than the said area|region of the photosensitive resin layer. The formation method of the said resist pattern may further have another process as needed.

(i) Photosensitive resin layer forming process

First, a photosensitive resin layer is formed on a substrate using a photosensitive resin composition. As a board|substrate, the board|substrate (substrate for circuit formation) provided with an insulating layer and the semiconductor layer formed on the insulating layer can be used.

Formation of the photosensitive resin layer on the substrate is, for example, when the photosensitive element 10 has the protective layer 6, after the protective layer 6 is removed, the photosensitive resin layer of the photosensitive element 10 ( 4) is arranged so as to be in contact with the substrate, and is carried out by pressing (laminate) the photosensitive element 10 to the substrate while heating. Thereby, the laminated body provided with the board|substrate, the photosensitive resin layer 4, and the support body 2 in this order can be obtained.

The lamination operation is preferably performed under reduced pressure from the viewpoints of the adhesiveness and followability of the photosensitive element 10 . It is preferable to perform heating at the time of crimping|compression-bonding so that the temperature of the photosensitive resin layer 4 and a board|substrate may become 70 degreeC - 130 degreeC. In addition, it is preferable to perform crimping|compression-bonding by the pressure of 0.1 MPa - 1.0 MPa (1 kgf/cm ² - 10 kgf/cm ² ). These conditions are suitably selected as needed. In addition, when the photosensitive resin layer 4 is heated to 70° C. to 130° C., it is not necessary to preheat the substrate in advance, but the adhesion and followability of the photosensitive element 10 can be further improved by preheating the substrate. have.

(ii) exposure process

In an exposure process, by irradiating actinic light to at least one part area|region of the photosensitive resin layer 4 formed on the board|substrate as mentioned above, the exposure part irradiated with actinic light is photocured, and a latent image is formed. As an irradiation method of actinic light, the method of irradiating actinic light to an image shape through a negative type or positive type mask pattern is mentioned, for example. At this time, when the support body 2 existing on the photosensitive resin layer 4 is transparent to actinic light, the actinic light can be irradiated through the support body 2 . When the support body 2 is impermeable with respect to actinic light, after removing the support body 2, the photosensitive resin layer 4 is irradiated with actinic light.

The light source of the actinic light is not particularly limited, and conventionally known light sources, for example, carbon arc lamps, mercury vapor arc lamps, ultra-high pressure mercury lamps, high pressure mercury lamps, xenon lamps, gas lasers such as argon lasers, YAG lasers, etc. Solid-state lasers, semiconductor lasers, and gallium nitride-based blue-violet lasers that effectively emit ultraviolet and visible light are used. Moreover, you may use the laser direct drawing exposure method.

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

(iii) Development process

In the developing step, the unexposed, uncured portion of the photosensitive resin layer 4 is removed from the substrate by development. Thereby, a resist pattern in which the photosensitive resin layer 4 is a photocured cured product is formed on the substrate. When the support body 2 exists on the photosensitive resin layer 4 after exposure, after removing the support body 2, the non-hardened part is removed (development). There exist wet image development and dry image development in the image development method, and wet image development is widely used.

In the case of wet image development, it develops by a well-known image development method using the developing solution corresponding to the photosensitive resin composition. As a developing method, the method using a dip method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking|fluctuation immersion, etc. is mentioned, From a viewpoint of resolution improvement, the high pressure spray method is the most suitable. You may develop combining 2 or more types of these methods.

The structure of a developing solution is suitably selected according to the said photosensitive resin composition structure. For example, alkaline aqueous solution, organic solvent developing solution, etc. are mentioned.

When used as a developing solution, alkaline aqueous solution is safe, stable, and has favorable operability. Examples of the base of the alkaline aqueous solution include alkali hydroxides such as lithium, sodium or potassium hydroxide, carbonates of lithium, sodium, potassium or ammonium, alkali carbonates such as bicarbonate, potassium phosphate, alkali metal phosphates such as sodium phosphate, sodium pyrophosphate, and pyrophosphate Alkali metal pyrophosphates such as potassium, borax (sodium tetraborate), sodium metasilicate, tetramethylammonium hydroxide, ethanolamine, ethylenediamine, diethylenetriamine, 2-amino-2-hydroxymethyl-1,3-propane Diols, 1,3-diamino-2-propanol, morpholine and the like are used.

As an alkaline aqueous solution used for image development, 0.1 mass % - 5 mass % dilute solution of sodium carbonate, 0.1 mass % - 5 mass % dilute solution of potassium carbonate, 0.1 mass % - 5 mass % dilute solution of sodium hydroxide, 0.1 mass % - A dilute solution of 5 mass % sodium tetraborate, etc. are preferable. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11. In addition, the temperature is adjusted according to the alkali developability of the photosensitive resin composition layer.

In the alkaline aqueous solution used for image development, you may add a surface active agent, an antifoamer, the organic solvent for promoting image development, etc. in small quantities. 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. and diethylene glycol monobutyl ether. These organic solvents are used individually by 1 type or in combination of 2 or more type. When the alkaline aqueous solution contains an organic solvent, it is preferable that the content rate of the organic solvent shall be 2 mass % - 90 mass % in alkaline aqueous solution whole quantity. In addition, the temperature can be adjusted according to alkali developability.

Organic solvent Examples of the organic solvent used in the developer include 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methylisobutylketone, γ-butyrolactone, and the like. can be heard It is preferable to add water to these organic solvents in 1 mass % - 20 mass % for ignition prevention, and to set it as an organic solvent developing solution.

In the resist pattern formation method of the present embodiment, after removing the uncured portion in the developing step, heating at 60° C. to 250° C. or exposure at 0.2 J/cm ² to 10 J/cm ² is performed as needed. You may further include the process of further hardening a resist pattern.

<Printed wiring board manufacturing method>

The manufacturing method of the printed wiring board of this invention includes the process of etching or plating the board|substrate on which the resist pattern was formed by the said resist pattern formation method. Due to this, 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. The etching process or plating process of a board|substrate is performed with respect to the semiconductor layer of a board|substrate, etc. 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 the region not covered with the resist is removed by etching to form the conductor pattern. The etching method is appropriately selected according to the conductor layer to be removed. Examples of the etching solution include a cupric chloride solution, a ferric chloride solution, an alkali etching solution, and a hydrogen peroxide etching solution. Among these, it is preferable to use a ferric chloride solution at a point with an etching factor favorable.

On the other hand, in the plating process, copper, solder, or the like is plated on the conductor layer in the 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 further etched to form a conductor pattern. An electroplating process or an electroless-plating process may be sufficient as the method of a plating process. As the plating treatment, for example, copper plating such as copper sulfate plating and copper pyrophosphate plating, solder plating such as high-slow solder plating, Watt bath (nickel sulfate-nickel chloride) plating, nickel plating such as nickel sulfamate and gold plating such as hard gold plating and soft gold plating.

After the etching treatment and plating treatment, the resist pattern on the substrate is removed. The removal of the resist pattern can be performed using, for example, an aqueous solution that is more alkaline than the aqueous alkaline solution used in the above-mentioned developing step. As strong alkaline aqueous solution, 1 mass % - 10 mass % sodium hydroxide aqueous solution, 1 mass % - 10 mass % potassium hydroxide aqueous solution etc. are used, for example. 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 plating, a desired printed wiring board can be manufactured by further etching the conductor layer in the region covered with the resist by the etching treatment to form the conductor pattern. The etching treatment method is appropriately selected according to the conductor layer to be removed. For example, the etching solution described above can be applied.

The manufacturing method of the printed wiring board of this invention is applicable to manufacture of not only a single-layer printed wiring board but a multilayer printed wiring board, and is also applicable also to manufacture of the printed wiring board etc. which have a small diameter through-hole.

2 : is a figure which shows an example of the manufacturing method of the multilayer printed wiring board using the photosensitive element of this embodiment. The multilayer printed wiring board 100A shown in Fig. 2(f) has a wiring pattern on the surface and the 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, interlayer insulating layers 103 are formed on both surfaces of the copper clad laminate 101 having the wiring pattern 102 on the surface (refer to Fig. 2(a)). Even if the interlayer insulating layer 103 is formed by printing a thermosetting composition using a screen printing machine or a roll coater, a film made of the thermosetting composition is prepared in advance, and using a laminator, this film is attached to the surface of the printed wiring board. may be formed. Next, an opening 104 is formed using a YAG laser or a carbon dioxide laser at a location that needs to be electrically connected to the outside, and smear (residue) around the opening 104 is removed by desmear treatment. (see FIG. 2(b)). Next, the seed layer 105 is formed by an electroless plating method (refer to FIG. 2(c)). The photosensitive element of this embodiment is laminated on the seed layer 105, a photosensitive resin layer is formed, and a predetermined location is exposed and developed to form a resist pattern 106 (refer to Fig. 2(d)). Next, a wiring pattern 107 is formed by an electrolytic plating method, and the resist pattern 106 is removed with a stripper. Thereafter, the seed layer 105 is removed by etching (see Fig. 2(e)). By repeating the above process and forming the soldering resist 108 in the outermost surface, 100 A of multilayer printed wiring boards can be produced (refer FIG.2(f)).

The photosensitive resin composition of this embodiment can be used suitably for manufacture of a printed wiring board. That is, one of suitable embodiment of this invention is an application for printed wiring board manufacture of the said photosensitive resin composition.

Example

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In addition, unless otherwise stated, "parts" and "%" are by mass.

[(A) component: binder polymer] [synthesis method of binder polymer (P-1)] (preparation of solution a-1)

2.0 g of azobisisobutyronitrile which is a radical reaction initiator was melt|dissolved in the liquid mixture of the polymerizable monomer (copolymerization monomer, monomer) shown in Table 1, and "solution a-1" was prepared.

(Radical polymerization reaction)

To a flask equipped with a reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas introduction tube, 400 g of a liquid mixture (mass ratio 3:2) of 240 g of methylcellosolve as an organic solvent and 160 g of toluene was charged. While blowing nitrogen gas into the flask, the mixture was heated while stirring, and the temperature was raised to 80°C.

After "solution a-1" was added dropwise to the liquid mixture in the flask at a constant dropping rate over 4 hours, the solution in the flask was stirred at 80°C for 2 hours. Next, a solution in which 1 g of azobisisobutyronitrile was further dissolved in 100 g of “Solution a-1” was added dropwise to the solution in the flask over 10 minutes at a constant dropping rate, and then the solution in the flask was heated at 80° C. for 3 hours. stirred. Moreover, after heating up the solution in a flask to 90 degreeC over 30 minutes, and keeping it heat-retaining at 90 degreeC for 2 hours, by cooling, the binder polymer (P-1) solution was obtained.

Acetone was added to the binder polymer (P-1) solution, and it prepared so that a non-volatile component (non-volatile matter) might be set to 50 mass %. The weight average molecular weight of the binder polymer (P-1) was 55,000. In addition, the weight average molecular weight was measured by the gel permeation chromatography method (GPC), and was derived|led-out by converting using the analytical curve of standard polystyrene. The conditions of GPC are as showing below.

-GPC conditions-

Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)

Columns: All 3 of the following

Gelpack GL-R420

Gelpack GL-R430

Gelpack GL-R440

(above, the product name made by Hitachi Sei Co., Ltd.)

Eluent: tetrahydrofuran

Measuring temperature: 25℃

Flow: 2.05 mL/min

Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

[Method for synthesizing binder polymer (P-2)] (Preparation of solution a-2)

1.0 g of azobisisobutyronitrile which is a radical reaction initiator was melt|dissolved in the liquid mixture of the polymerizable monomer (copolymerization monomer, monomer) shown in Table 1, and "solution a-2" was prepared. Then, radical polymerization reaction was performed similarly to binder polymer (P-1), and the binder polymer (P-2) solution was obtained. The weight average molecular weight of the binder polymer (P-2) was 100,000.

[Method for synthesizing binder polymer (P-3)] (Preparation of solution a-3)

1.0 g of azobisisobutyronitrile which is a radical reaction initiator was melt|dissolved in the liquid mixture of the polymerizable monomer (copolymerization monomer, monomer) shown in Table 1, and "solution a-3" was prepared.

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

[Preparation of photosensitive resin composition]

Examples 1 to 18 and by blending component (B) and component (C), acetone 8 g, toluene 8 g, and methanol 8 g in the solution of the binder polymer obtained above in the amount (g) shown in Tables 2 and 3 below. The photosensitive resin compositions of Comparative Examples 1-6 were prepared, respectively. In addition, the compounding quantity of the binder polymer shown in Table 2 and Table 3 is the mass (non-volatile matter) of a non-volatile component.

The detail of the material shown in Table 2 and Table 3 is as follows.

<(A) component: binder polymer>

P-1: Binder polymer prepared above: methacrylic acid/methyl methacrylate/styrene (25/50/25 (mass ratio)) copolymer, weight average molecular weight 55,000, acid value 163 mgKOH/g, non-volatile content 50 mass% of methylcellosolve/toluene=6/4 (mass ratio) solution.

P-2: Binder polymer prepared above: methacrylic acid/methyl methacrylate/copolymer of acrylic acid 2-ethylhexyl (25/50/25 (mass ratio)), weight average molecular weight 100,000, acid value 163 mgKOH/g, fire Methyl cellosolve/toluene = 6/4 (mass ratio) solution of 50 mass % of volatile matter.

P-3: 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, nonvolatile matter 50 mass % methylcellosolve/toluene=6/4 (mass ratio) solution.

<(B) component: photopolymerizable compound>

FA-321M: Bisphenol A polyoxyethylene dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Double bond equivalent of 402, (B1) a non-sugar compared to component.

· UA-HCY-19: a urethane reaction product of polyethylene glycol monomethacrylate and hexamethylene isocyanate trimer (manufactured by Shin-Nakamura Chemical Co., Ltd., product name). It corresponds to the double bond equivalent of 841, (B1) component.

·FA-240M: Polyethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Double bond equivalent of 266, (B1) Non-sugar compared to component.

·FA-2200M: Polyethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Double bond equivalent of 1058, (B1) corresponds to the component.

·FA-P2100M: polypropylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Double bond equivalent 561, (B1) a non-sugar compared to the component.

·FA-2300M: polypropylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Double bond equivalent 1576, corresponding to (B1) component.

FA-PTG9M: polytetramethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Double bond equivalent of 401, (B1) a non-sugar compared to the component.

·FA-PTG28M: polytetramethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Double bond equivalent of 1085, (B1) corresponds to the component.

FA-137M: Trimethylolpropane polyethylene oxide trimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name). Double bond equivalent of 420, (B1) a non-sugar compared to component.

FA-314A: Nonylphenoxypolyethylene glycol acrylate (average value of the total amount of oxyethylene groups is 4) (manufactured by Hitachi Chemical Co., Ltd., product name). A double bond equivalent of 450, (B1) a non-sugar compared to the component.

<(C)component: photoinitiator>

-N-1717: 1,7-di(9-acridinyl)heptane (made by ADEKA Corporation, product name).

-EAB: 4,4'-bis(diethylamino)benzophenone (Hodogaya Chemical Co., Ltd. make, product name).

B-CIM: 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-2H-imidazol-2-yl] -4,5-diphenyl- 1H-imidazole (manufactured by Hodogaya Chemical Industries, Ltd., product name).

9PA: 9-phenylacridine (New Nittetsu Sumi King Chemical Co., Ltd.)

NPG: N-Phenylglycine (Sangju Kangkang Electronic New Materials Co., Ltd., product name)

<Other ingredients>

・LCV: Royco Crystal Violet (manufactured by Yamada Chemical Co., Ltd., product name)

・MKG: Malachite Green (Osaka Yuki 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 the binder polymer. "Content of structural unit (A2)" indicates the content of structural unit (A2) in the total amount of the binder polymer. "Content of structural unit (A3)" indicates 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 was coated on a 16 µm thick polyethylene terephthalate film (manufactured by Teijin Corporation, trade name "G2-16") (support) so that the thickness was uniform. It apply|coated, it dried for 10 minutes with a 100 degreeC hot-air convection type dryer, and the film thickness after drying formed the photosensitive resin layer whose film thickness is 38 micrometers. By laminating a polyethylene film protective layer (manufactured by Tama Poly Co., Ltd., trade name "NF-13") (protective layer) on this photosensitive resin layer by roll pressing, the support, the photosensitive resin layer, and the protective layer are in this order The laminated photosensitive elements according to Examples 1 to 18 and Comparative Examples 1 to 6 were respectively obtained.

[Production of laminated substrate for evaluation]

Next, the copper surface of a 1.6 mm thick copper-clad laminate (manufactured by Hitachi Chemical, trade name "MCL-E-67") made of a glass epoxy material and copper foil (thickness 35 µm) formed on both surfaces was polished. , was polished using a polishing machine (manufactured by Sanke Corporation) having a brush equivalent to #600, washed with water, and then dried with an air stream. After this copper-clad laminate (hereinafter referred to as "substrate") was heated to 80 DEG C, the photosensitive elements according to Examples 1 to 18 and Comparative Examples 1 to 6 were laminated (laminated) on the copper surfaces on both sides of the substrate. Thus, laminated substrates for evaluation were respectively produced. Lamination was performed at a speed of 1.5 m/min, using a 110°C heat roll and removing the protective layer so that the photosensitive resin layer of each photosensitive element adhered to each copper surface of the substrate. In addition, the heat roll pressure at the time of lamination was made into 0.4 Mpa.

[Evaluation of sensitivity]

The obtained laminated substrate for evaluation was left to cool to 23 degreeC. Next, the phototool which has a step tablet was closely_contact|adhered to the support body of the surface of the laminated board|substrate for evaluation. As the step tablet, a 41-stage step tablet having a density range of 0.00 to 2.00, a density step of 0.05, a tablet size of 20 mm x 187 mm, and each step size of 3 mm x 12 mm was used. Next, the photosensitive resin layer was exposed through the photo tool and support body which have a step tablet. The exposure was performed at an exposure amount of 17 mJ/cm ² using an exposure machine (manufactured by Nippon Orbotech Co., Ltd., trade name “Paragon-9000m”) using a semiconductor-excited solid-state laser as a light source.

After exposure, the support body was peeled from the laminated board|substrate for evaluation, and the photosensitive resin layer was exposed. With respect to the exposed photosensitive resin layer, the unexposed part was removed by spraying (developing process) a 30 degreeC 1.0 mass % sodium carbonate aqueous solution for 50 second. In this way, the cured film which consists of hardened|cured material of the photosensitive resin composition was formed in the copper surface of the laminated board for evaluation. By measuring the number of steps of the step tablet of the obtained cured film, the sensitivity (photosensitivity) of the photosensitive resin compositions of Examples 1-18 and Comparative Examples 1-6, and the photosensitive element obtained from them was evaluated. The higher the number of stages of this step tablet, the higher the sensitivity. The results are shown in Tables 2 and 3.

[Evaluation of adhesion and resolution]

A pattern for evaluation with a line width/space width of n/3n (unit: μm, n=5 μm to 30 μm, at intervals of 5 μm) for evaluation of adhesion on the laminate substrate for evaluation, and a line width for evaluation of resolution The phototool data each having a pattern for evaluation with a /space width of 3n/n (unit: μm, n=5 μm to 30 μm, at intervals of 5 μm) was used. Exposure was performed with the exposure amount of 17 mJ/cm< ² > using the exposure machine which uses a semiconductor-excited solid-state laser as a light source (Nippon Orbotech Co., Ltd. make, brand name "Paragon-9000m"). Next, development was performed on the same conditions as evaluation of the said photosensitivity, and the unexposed part was removed. Adhesiveness was evaluated by the minimum value (unit: micrometer) of the width|variety of the line area|region where a cured film remains by development. The resolution was evaluated by the minimum value (unit: mu m) of the width of the space between the line regions from which the portion not photocured by the developing treatment could be clearly removed. All evaluation of adhesiveness and resolution are values, so that a numerical value is small. The results are shown in Tables 2 and 3.

[tent reliability]

Tent reliability was evaluated using the board|substrate 40 for a tear number measurement as shown in FIG. 3, produced as follows, and using this. Three independent round holes 41 and three round holes are connected to a copper clad laminate (manufactured by Hitachi Sei Co., Ltd., trade name "MCL-E-67") with a hole diameter of 4 mm to 6 mm, respectively, Further, three consecutive holes 42 in which the intervals between the round holes are gradually shortened were respectively produced with a drilling machine. A burr generated when the round hole 41 and the three consecutive holes 42 are produced is removed using a polishing machine (manufactured by Sanke Corporation) having a brush equivalent to #600, and this is used for measuring the number of holes It was set as the board|substrate 40.

The obtained substrate for measuring the number of tears 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 formed on the substrate 40 for measuring the number of tears. It arrange|positions so that it may face the copper surface, it laminated|stacked on 120 degreeC and conditions of 0.4 MPa, respectively, and produced the laminated board for tent reliability evaluation, respectively.

After lamination, the laminated board for tent reliability evaluation was left to cool to 23 degreeC. Next, from the top of the support of the photosensitive element, using an exposure machine (manufactured by Nippon Orbotech Co., Ltd., trade name "Paragon-9000m") using a semiconductor-excited solid laser as a light source, exposure was performed at an exposure amount of 17 mJ/cm ² . .

After exposure, it was left to stand at room temperature for 15 minutes, then the support body was peeled off from the laminated board for tent reliability evaluation, and it developed by spraying 30 degreeC 1 mass % sodium carbonate aqueous solution for 50 second. After development, the number of tears in three consecutive holes was measured, and the release tent tear rate was calculated as the number of tears relative 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.

[Peelability evaluation]

On the said laminated board|substrate for evaluation, it exposed using the phototool data which forms a 45 mm x 65 mm rectangular cured film as an object for peelability evaluation. Exposure was performed with the exposure amount of 17 mJ/cm< ² > using the exposure machine which uses a semiconductor-excited solid-state laser as a light source (Nippon Orbotech Co., Ltd. make, brand name "Paragon-9000m"). Next, it developed under the same conditions as evaluation of the said photosensitivity, and the unexposed part was removed.

Then, 300 ml of a 50 degreeC, 3.0 mass % NaOH aqueous solution (removing liquid) was prepared in the beaker of 400 ml of capacity|capacitance. While stirring the stripper at 200 rpm using a stirrer having a length of 30 mm, the substrate after development was immersed in the stripper, and the time (unit: seconds) until the cured film detached from the substrate was measured. In addition, it evaluates that peeling time is short and peelability is favorable, so that time until a cured film falls off a board|substrate is quick. 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 are used, compared with the case where the photosensitive elements according to Comparative Examples 1 to 6 are used, even at a low exposure amount, A resist pattern exhibiting excellent tent reliability of 60% or more (more preferably 80% or more) can be formed, and the resist pattern can be peeled off in a short time of less than 80 seconds (more preferably less than 70 seconds) found out there was In addition, the resist patterns obtained in these Examples were excellent in adhesion and resolution in a well-balanced manner. As for the photosensitive element related to the comparative example, the photosensitivity was equivalent to that of the photosensitive element related to the example, but was inferior in at least either one of peeling time and tent reliability. In addition, Examples 1 to 12 using N-1717 corresponding to the (C1) compound as a photoinitiator were compared with Examples using other photoinitiators, sensitivity, adhesiveness, resolution, peeling time and tent reliability were balanced, I found it to be better.

As for the indication of Japanese Patent Application No. 2014-099629, the whole is taken in into this specification by reference. All documents, patent applications, and technical standards described in this specification are hereby incorporated by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference. .

Claims (11)

(A) component: a binder polymer;
(B) component: a photopolymerizable compound;
(C) Component: A photoinitiator is contained,
The component (B) has, as a structural unit, component (B1): polyalkylene oxide [-(C _m H _2m O) _n -: m and n are each independently a number of 2 or more], and the double bond equivalent is 700 It contains the above photopolymerizable compound,
The 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 (C) contains (C2) compound: an acridine compound having one acridinyl group, and (C3) compound: N-phenylglycine;
In said (C)component, content of the said (C2) compound is 0.3 mass part - 1.5 mass parts with respect to 100 mass parts of total amounts of (A) component and (B) component,
In said (C)component, content of the said (C3) compound 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 in which the said (B1) component has as a structural unit at least 1 sort(s) selected from the group which consists of polytetramethylene oxide [-(C ₄ H ₈ O) _n -:n is a number of 2 or more]. The method according to claim 1,
The component (A) contains a structural unit (A1) derived from at least one selected from the group consisting of styrene, styrene derivatives, benzyl (meth) acrylate and benzyl (meth) acrylate derivatives, and (A) ) The photosensitive resin composition whose content rate of the said structural unit (A1) in the total amount of a component is 10 mass % - 60 mass %. The method according to claim 1 or 2,
The photosensitive resin composition in which the said (B1) component contains the photopolymerizable compound which has two or more photopolymerizable double bonds in one molecule. The method according to claim 1 or 2,
The photosensitive resin composition in which the said (A) component further contains the structural unit (A2) derived from the alkyl (meth)acrylate which is a C5-C20 alkyl group. The method according to claim 1 or 2,
The said (C)component contains (C1) compound: the acridine compound which has two acridinyl groups, The photosensitive resin composition. The method according to claim 1 or 2,
The photosensitive resin composition whose content of the said (C3) compound is 0.01 mass parts or more and 0.07 mass parts or less with respect to 100 mass parts of total amounts of (A) component and (B) component among said (C)component. support and
The photosensitive element which has a photosensitive resin layer formed on the said support body using the photosensitive resin composition of Claim 1 or 2. A photosensitive resin layer forming step of forming a photosensitive resin layer on a substrate using the photosensitive resin composition according to claim 1 or 2;
an exposure step of irradiating at least a portion of the photosensitive resin layer with actinic light to cure the region;
and 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 on which the resist pattern was formed by the method of Claim 8. delete delete

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