TW202230027A - Photosensitive resin composition and transfer film using photosensitive resin composition - Google Patents

Abstract

The purpose of the present invention is to provide a dry film photoresist that enhances the yield of forming an object or pattern with photolithography or a pattern forming method including the same; or to provide a photosensitive resin laminate that is excellent in at least one of lamination property, minimum development time, resolution, amount of side etching, Cu defect, and development residue. The present invention provides a dry film photoresist, which comprises a support film and a photosensitive resin composition layer on the support film. The photosensitive resin composition comprises (A) an alkali-soluble resin, (B) a photopolymerizable compound containing an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) a dye, wherein a maximum point load for a specific puncture test is greater than 70gf; the ingredient of component B is a polyfunctional monomer including three functional groups or bifunctional monomer; and/or with the acid value of a nonvolatile component of the photosensitive resin composition being set as A (mg/KOH/g) and the thickness of the photosensitive resin composition layer being set as T ([mu]m), the ratio (A/T) between the acid value A and the thickness T is 5-90.

Description

Photosensitive resin composition, transfer film using photosensitive resin composition

The present invention relates to a photosensitive resin composition, a photosensitive resin laminate, a dry film photoresist, a method for forming a photoresist pattern, a method for forming a wiring pattern, and the like.

Conventionally, the manufacture of printed wiring boards, the precision machining of metals, and the like have been performed by photolithography. The photosensitive resin composition used for the photolithography method is classified into a negative-type composition for dissolving and removing an unexposed part, and a positive-type composition for dissolving and removing an exposed part.

When the photosensitive resin composition is coated on the substrate in the photolithography method, it can be used (1) A method of applying a photoresist solution to a substrate and drying it, and (2) Using a photosensitive resin laminate in which a support, a layer containing a photosensitive resin composition (hereinafter, also referred to as a "photosensitive resin layer"), and an optional protective layer are sequentially laminated, and a photosensitive resin layer is used. A method of laminating a resinous resin on a substrate either. In the manufacture of printed wiring boards, the latter method is often used.

The method of forming a pattern using the above-mentioned photosensitive resin laminate will be briefly described below. First, the protective layer is peeled off from the photosensitive resin laminate. Next, the photosensitive resin layer and the support volume layer are formed on the base material such as a copper foil laminate and a copper sputtering film so as to be the order of the base material, the photosensitive resin layer, and the support using a laminator. Next, the photosensitive resin layer is exposed to light through a photomask having a desired wiring pattern. Then, a photoresist pattern is formed on a base material by peeling off a support body from the laminated body after exposure, and then dissolving or dispersing the non-pattern part by a developing solution.

Furthermore, a wiring pattern can also be obtained by subjecting the board|substrate provided with the photoresist pattern to an etching process, or a plating process, such as copper plating and tin-lead plating.

In order to form a photoresist pattern or a wiring pattern, various photosensitive resin compositions are being examined. For example, Patent Documents 1 and 2 describe photosensitive resin compositions containing a specific alkali-soluble resin, a photopolymerizable compound, and a photopolymerizable initiator.

Patent Document 1 focuses on the photoresist shape, the photosensitive resin composition excellent in the minimum development time and the exudation property, and the formation of a photoresist pattern and a wiring board using the same.

In patent document 2, regarding the projection exposure method, the adhesiveness of a photoresist pattern, the resolution, and the suppression property of the generation|occurrence|production of a photoresist edge are examined.

For example, Patent Documents 3 to 5 disclose a photosensitive resin composition that can form a photoresist pattern even at a low exposure amount by containing a compound having polytetramethylene oxide as a structural unit, and the formed The cured film has excellent shielding reliability and etching resistance. Moreover, Patent Document 6 discloses a photosensitive resin composition which can form a photoresist pattern even at a low exposure amount by containing a compound having polyalkylene oxide as a structural unit, and the cured film formed has Excellent shielding reliability and etching resistance. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 6063200 [Patent Document 2] Japanese Patent No. 6432511 [Patent Document 3] International Publication No. 2015/174467 [Patent Document 4] Japanese Patent Laid-Open No. 2018-31800 [Patent Document 5] Japanese Patent Laid-Open No. 2018-31799 [Patent Document 6] Japanese Patent No. 6673196

[Problems to be Solved by Invention]

The photolithography method using the photosensitive resin composition is still required to improve the yield of objects or patterns formed therewith.

In addition, the conventional photosensitive resin compositions have not obtained sufficient characteristics in terms of lamination property, minimum development time, resolution, amount of side etching (SE), Cu defects, and development residues. Furthermore, among these characteristics, there is a combination that is considered difficult to achieve, and therefore, it is desired to achieve a combination of various characteristics.

In view of the above circumstances, an object of the present invention is to provide a photosensitive resin composition capable of improving the yield of objects or patterns formed by photolithography, and a photosensitive resin laminate and photoresist or wiring pattern using the same A method of forming and/or providing a photosensitive resin laminate excellent in at least one of lamination properties, minimum development time, resolution, side etch (SE) amount, Cu defects, and development residues. [Technical means to solve problems]

The inventors of the present invention have made diligent studies to solve the above-mentioned problems, and as a result found that by specifying the composition of the photosensitive resin composition or the strength of the photosensitive resin composition measured by a unique test, and/ Or by specifying the relationship between the acid value of the nonvolatile component of the photosensitive resin composition and the thickness of the photosensitive resin layer, the above problems can be solved.

One aspect of the present invention is exemplified below. (1) A dry film photoresist having support membrane, and A layer formed on the support film and comprising a photosensitive resin composition containing (A) Alkali-soluble resin, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) dyes; The weight-average molecular weight of the above-mentioned component (A) calculated by measuring the above-mentioned component (A) by gel permeation chromatography (GPC) and using a calibration curve of polystyrene is 60,000 or less, and The above-mentioned photosensitive resin composition is a photosensitive resin composition having a maximum point load of 70 gf or more when a puncture test is carried out as follows: A photosensitive resin layer containing the photosensitive resin composition is laminated on a support with a thickness of 25 μm and produced. A photosensitive resin laminate is formed by laminating the photosensitive resin laminate on a copper foil laminate substrate having a copper foil having a thickness of 35 μm and having through holes having a thickness of 1.6 mm and a diameter of 6 mm, and performing exposure and development to form The hardened film was then peeled off from the hardened film, and the part of the photosensitive resin layer corresponding to the center of the through hole was punctured with a diameter of 2.0 mm at a speed of 100 mm/min from the surface on which the support was peeled off. of the cylinder. (2) The dry film resist according to item 1, wherein the number of double bonds in the photosensitive resin composition is 1.50 mmol/g or more based on the solid content of the photosensitive resin composition. (3) The dry film resist according to the item 1, wherein the photosensitive resin composition contains a trifunctional or higher polyfunctional monomer as the component (B). (4) The dry film resist as described in item 1, wherein the photosensitive resin composition contains (B-ii) as a trifunctional or more multifunctional monomer having a skeleton derived from dipentaerythritol but not containing an epoxy group The compound is used as the above-mentioned (B) component. (5) The dry film resist as described in item 4, wherein the above-mentioned photosensitive resin composition further contains (B-iii) a (meth)acrylate compound having a skeleton derived from bisphenol as a bifunctional monomer as the above-mentioned (B) Ingredient. (6) The dry film resist according to any one of items 1 to 5, wherein the photosensitive resin composition further contains a plasticizer. (7) The dry film resist according to any one of items 1 to 6, which contains a leuco dye as the above-mentioned dye. (8) The dry film photoresist according to any one of items 1 to 7, wherein the maximum point load is less than 250 gf. (9) A dry film photoresist having a support film, and A layer formed on the support film and comprising a photosensitive resin composition containing (A) Alkali-soluble resin, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator; and The above-mentioned photosensitive resin composition contains (B-ii) a compound having a skeleton derived from dipentaerythritol but not containing an epoxy group as a trifunctional or higher polyfunctional monomer, and (B-iii) which is a bifunctional monomer has a (meth)acrylate compound derived from the skeleton of a bisphenol as this (B) component. (10) The dry film resist as described in item 9, wherein the ratio of the above (B-ii)/the above (B-iii) is 10 to 80% by mass. (11) The dry film photoresist according to the item 9 or 10, wherein the ratio of the above (B-ii) and the above (B-iii) in the above (B) component is 50 mass % or more. (12) The dry film photoresist according to any one of items 9 to 11, which further comprises (B-i) a (meth)acrylate compound having a skeleton derived from dipentaerythritol and containing an epoxy group as the above (B) Element. (13) The dry film resist according to any one of items 9 to 12, wherein the component (A) is measured by gel permeation chromatography (GPC) and calculated using a calibration curve of polystyrene The weight average molecular weight of the said component (A) is 60,000 or less. (14) The dry film resist according to any one of items 9 to 13, wherein the photosensitive resin composition is a photosensitive resin composition with a maximum point load of 70 gf or more when subjected to the following puncture test: Above, a photosensitive resin layer containing the photosensitive resin composition was laminated with a thickness of 25 μm to produce a photosensitive resin layered product, and the photosensitive resin layered product was laminated on a copper foil with a thickness of 35 μm and a thickness of 1.6 mm and On the copper foil laminate substrate with a through hole with a diameter of 6 mm, exposure and development are performed to form a hardened film. After that, the support is peeled off from the hardened film, and the surface of the support is peeled off at a speed of 100 mm/min. A cylinder with a diameter of 2.0 mm was pierced into the part of the photosensitive resin layer corresponding to the center of the through hole. (15) The dry film resist according to any one of items 9 to 14, wherein the number of double bonds in the photosensitive resin composition is 1.50 mmol/g or more based on the solid content of the photosensitive resin composition . (16) The dry film resist according to any one of items 9 to 15, wherein the photosensitive resin composition further contains a plasticizer. (17) The dry film resist according to any one of items 9 to 16, which contains a leuco dye as the above-mentioned dye. (18) The dry film photoresist according to any one of items 9 to 17, wherein the maximum point load is less than 250 gf. (19) A method for forming a photoresist pattern, comprising the steps of: Laminating the dry film photoresist as described in any one of items 1 to 18 on a substrate; exposing the laminated dry film resist; and The exposed dry film resist is developed. (20) A method for forming a wiring pattern, comprising the steps of: Laminating the dry film photoresist as described in any one of items 1 to 18 on a substrate; exposing the laminated dry film photoresist; developing the exposed dry film photoresist to form a photoresist pattern; and Etching or plating is performed on the substrate on which the photoresist pattern has been formed.

Another aspect of the present invention is exemplified below. (21) A photosensitive resin laminate comprising a support and a photosensitive resin composition layer formed on the support using a photosensitive resin composition, the photosensitive resin composition comprising ( A) an alkali-soluble resin containing no ethylenically unsaturated group on the main chain, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator; and When the acid value of the non-volatile component of the photosensitive resin composition is A [mgKOH/g] and the thickness of the photosensitive resin composition layer is T [μm], the acid value A and the thickness T are The ratio (A/T) is 5 or more and 90 or less. (22) The photosensitive resin laminate according to item 21, wherein the photosensitive resin composition further contains a compound having polytetramethylene oxide as a structural unit as the component (D). (23) The photosensitive resin laminate according to item 21 or 22, wherein the photosensitive resin composition further contains a compound having a benzotriazole skeleton as the component (E). (24) The photosensitive resin laminate according to any one of Items 21 to 23, wherein the photosensitive resin composition has, as the component (B), a photopolymerizable compound containing a tetrafunctional or more ethylenically unsaturated bond. (25) The photosensitive resin laminate according to the item 22, wherein the ratio of the above-mentioned (A) component to the sum of the above-mentioned (B) component and the above-mentioned (D) component [(A)component/((B)component+( D) component)] exceeds 0 and is 1.4 or less. (26) The photosensitive resin laminate according to any one of items 21 to 25, wherein the weight average molecular weight of the component (A) is 20,000 or more. (27) The photosensitive resin laminate according to any one of items 21 to 26, wherein the acid value (acid equivalent) of the nonvolatile component of the photosensitive resin composition exceeds 0 and is 79.0 or less. [Effect of invention]

According to the present invention, the defects of the pattern formed by using the photosensitive resin composition can be suppressed, so that the yield and/or lamination property, minimum development time, A photosensitive resin laminate excellent in at least one of resolution, side etching (SE), Cu defects, and development residue.

Hereinafter, an aspect for implementing the present invention (hereinafter, abbreviated as "embodiment") will be described in detail. In addition, this invention is not limited to the following embodiment, It can variously change and implement within the range of the summary.

In addition, in this specification, "(meth)acrylic acid" means acrylic acid or methacrylic acid, "(meth)acryloyl group" means acryl group or methacryloyl group, and "(meth)acrylic acid group" "Ester" means acrylate or methacrylate.

[One aspect of the present invention] <Photosensitive resin composition> One aspect of the present invention provides a photosensitive resin composition. The photosensitive resin composition contains the following components: (A) alkali-soluble resin, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) Photopolymerization initiator. The photosensitive resin composition may contain (D) dye other than (A)-(C) component as needed, and may contain a plasticizer, an antioxidant, a stabilizer, etc., too.

<First Embodiment> The photosensitive resin composition of the first embodiment is characterized in that the dye (D) is contained in addition to the components (A) to (C), and the maximum point load measured in the puncture test described below is 70 gf above.

(Puncture Test) Preparation: support; photosensitive resin composition; copper foil laminate substrate with a thickness of 35 μm, a thickness of 1.6 mm, and a through hole with a diameter (ϕ) of 6 mm. A photosensitive resin layer containing a photosensitive resin composition was laminated with a thickness of 25 μm on a support to produce a photosensitive resin laminate, the photosensitive resin laminate was laminated on a copper foil laminate substrate, exposed to light and developed to form a cured film Then, peel off the support from the curing film, and puncture a cylinder with a diameter (ϕ) 2.0 mm on the surface of the peeled support at a speed of 100 mm/min for the part of the photosensitive resin layer corresponding to the center of the through hole.

In the first embodiment, if the maximum point load of the cured film measured in the above-mentioned puncture test is 70 gf or more, the resolution of the photoresist pattern formed by the photolithography method using the photosensitive resin composition, The undercut amount and peelability are good, and the defect of the pattern can be suppressed, so the yield rate of the object or pattern formed by the photolithography method tends to be improved. Furthermore, a more specific method for measuring the maximum point load by the puncture test will be described in detail in the examples described below.

The inventors of the present invention believe that the puncture strength of the cured film of the photosensitive resin composition in the puncture test is related to the defect of the metal substrate, but does not wish to be bound by theory. In the first embodiment, a maximum point load of 70 gf or more during a puncture test was found as a method for suppressing defects in objects or wiring patterns formed by photolithography using a photosensitive resin composition, thereby improving yield. an indicator. The maximum point load during the puncture test is preferably 74 gf or more or 78 gf or more, more preferably 85 gf or more, from the viewpoint of further improving the yield. In addition, the upper limit of the maximum point load during the puncture test is clear based on common knowledge in the technical field, and the higher the better, for example, it may be less than 250 gf or 245 gf or less.

Regarding the maximum point load during the puncture test, for example, the composition of the photosensitive resin composition can be optimized, or a plurality of components can be used as the (B) component in the photosensitive resin composition, or two or more components can be prepared Or three or more components, or by optimizing the types and blending ratios, and adjusting them within the numerical range described above.

The photosensitive resin composition of the first embodiment preferably contains a trifunctional or higher polyfunctional monomer and/ or a bifunctional monomer as the (B) component. From the same viewpoint, as the trifunctional or higher polyfunctional monomer, (B-ii) is preferably a compound having a skeleton derived from dipentaerythritol but not containing an epoxy group, and as a bifunctional monomer, is preferred. (B-iii) The (meth)acrylate compound which has a skeleton derived from a bisphenol is preferable.

<Second Embodiment> The photosensitive resin composition of the second embodiment is characterized by containing: (B-i) a (meth)acrylate compound having a skeleton derived from dipentaerythritol and containing an epoxy group, and (B-ii) Compounds having a skeleton derived from dipentaerythritol but not containing an epoxy group As said (B) component.

If the photosensitive resin composition of 2nd Embodiment contains both (B-i) component and (B-ii) as (B) component, the photoresist formed by the photolithography method using the photosensitive resin composition The resolution of the pattern, the amount of side etching, the puncture strength and the peelability are good, and the defects of the pattern can be suppressed, so the yield of the object or pattern formed by the photolithography method tends to increase.

<Third Embodiment> The photosensitive resin composition of the third embodiment is characterized in that the component (B) described above contains: (B-ii) a compound having a skeleton derived from dipentaerythritol but not containing an epoxy group as a trifunctional or higher polyfunctional monomer, and (B-iii) as a bifunctional monomer has a (meth)acrylate compound derived from the skeleton of bisphenol.

If the photosensitive resin composition of 3rd Embodiment contains both the (B-ii) component which is a trifunctional or more than trifunctional polyfunctional monomer, and the (B-iii) component which is a bifunctional monomer as (B) component , the photoresist pattern formed by the photolithography method using the photosensitive resin composition has good resolution, side etching amount, puncture strength and peelability, and can suppress the defects of the pattern. The tendency to increase the yield of formed objects or patterns.

The photosensitive resin composition of the third embodiment is preferably (B-ii) component/( The ratio of B-iii) component is 10-80 mass %, and/or it is preferable that the ratio of (B-ii) component and (B-iii) component in (B) component is 50 mass % or more. From the same viewpoint, the component (B) of the third embodiment preferably contains the component (B-i) described above in addition to the component (B-ii) and the component (B-iii).

The features described above for the first, second and third embodiments can be combined or interchanged. The photosensitive resin compositions of the first, second, and third embodiments can be used for the implementation of photolithography, the production of photosensitive resin laminates, the formation of wiring patterns of touch panels, and the like, and are preferably used in Etching of substrates such as copper foil laminates and copper sputtering films. Hereinafter, each component contained in the photosensitive resin composition of 1st, 2nd, and 3rd embodiment is demonstrated in order.

<(A) Alkali-soluble resin> (A) The alkali-soluble resin is a polymer that can be dissolved in an alkaline solution. Moreover, (A) alkali-soluble resin preferably has a carboxyl group, more preferably has an acid equivalent of 100 to 600, and is further preferably a copolymer containing a carboxyl group-containing monomer as a copolymerization component. Furthermore, the (A) alkali-soluble resin may be thermoplastic.

The acid equivalent of the (A) alkali-soluble resin is preferably 100 or more from the viewpoints of the development resistance of the photosensitive resin layer, and the resolution and adhesion of the photoresist pattern. On the other hand, the photosensitive resin From the viewpoint of the developability and peelability of the layer, it is preferably 600 or less. Moreover, 200-500 are more preferable, and, as for the acid equivalent of (A) alkali-soluble resin, 250-450 are still more preferable. Furthermore, in one aspect of the present invention, the acid equivalent refers to the mass (g) of the polymer having 1 equivalent of carboxyl groups in the molecule. Determined by potentiometric titration.

{式中，W _i為構成鹼可溶性樹脂之共聚單體各者之質量， Tg _i為構成鹼可溶性樹脂之共聚單體各者為均聚物之情形時之玻璃轉移溫度， W _total為鹼可溶性樹脂之合計質量，並且 n為構成該鹼可溶性樹脂之共聚單體之種類之數} 所求出之玻璃轉移溫度(Tg _total)為100℃以下。於使用複數種高分子之混合物作為(A)鹼可溶性樹脂之情形時，玻璃轉移溫度為以全部高分子之平均值之形式所確定之值。 (A) The alkali-soluble resin preferably has the following formula (I): [Numerical 1]

{wherein, Wi is the mass of each of the comonomers constituting the alkali-soluble resin, _Tgi is the glass transition temperature when each of the comonomers constituting the alkali-soluble resin is a homopolymer, _{and Wtotal is} the alkali-soluble The total mass of the resin, and n is the number of kinds of comonomers constituting the alkali-soluble resin} The glass transition temperature (Tg _total ) obtained is 100° C. or less. When a mixture of a plurality of polymers is used as the (A) alkali-soluble resin, the glass transition temperature is a value determined as an average value of all the polymers.

In obtaining the glass transition temperature Tg _i , as the corresponding glass transition temperature of a homopolymer containing a comonomer forming an alkali-soluble resin, "Polymer handbook, Third edition, John wiley" edited by Brandrup, J. Immergut, EH was used. & sons, 1989, p.209 Chapter VI “Glass transition temperatures of polymers””.

The _Tgi of representative comonomers are described below (all literature values). Methacrylic acid: Tg=501 K Benzyl methacrylate: Tg=327 K Methyl methacrylate: Tg=378 K Styrene: Tg=373 K 2-ethylhexyl acrylate: Tg=223 K The alkali-soluble resin having the glass transition temperature (Tg _total ) as described above is preferably a copolymer of an acid monomer and other monomers.

There is no particular limitation on the lower limit value of the glass transition temperature (Tg _total ) of the alkali-soluble resin (A) determined by the above formula (I). The glass transition temperature (Tg _total ) may be 10°C or higher, 30°C or higher, 50°C or higher, or 70°C or higher.

On the other hand, the above-mentioned (A) alkali-soluble resin is preferably the weight of the component (A) calculated by at least measuring the component (A) by gel permeation chromatography (GPC) and using a calibration curve of polystyrene The average molecular weight (Mw) is 60,000 or less. The Mw of the (A) alkali-soluble resin is preferably 60,000 or less from the viewpoint of solubility in a developer, and on the other hand, from the viewpoint of maintaining a uniform thickness of a photosensitive resin laminate such as a dry film resist , viscosity, edge meltability, sliceability, etc., it is preferably 5,000 or more. From such a viewpoint, Mw of the (A) alkali-soluble resin is more preferably 10,000 or more and 55,000 or less. Furthermore, the ratio of the above-mentioned Mw to the number average molecular weight (Mn) of the (A) alkali-soluble resin, that is, the dispersion degree (Mw/Mn) of the (A) alkali-soluble resin is preferably 1.0 to 6.0.

(A) The alkali-soluble resin is preferably obtained by polymerizing at least one of the first monomers described below. Moreover, it is more preferable that (A) alkali-soluble resin is obtained by copolymerizing at least 1 type of 1st monomer and at least 1 type of 2nd monomer mentioned later.

The first monomer is a monomer containing a carboxyl group in the molecule. As a 1st monomer, (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itonic acid, maleic anhydride, maleic acid half ester, etc. are mentioned, for example. Among these, (meth)acrylic acid is particularly preferable.

The second monomer system is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. n-Butyl, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid Cyclohexyl, 2-ethylhexyl (meth)acrylate, and benzyl (meth)acrylate; vinyl alcohol esters such as vinyl acetate; and (meth)acrylonitrile, styrene, and polymerizable Styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc. )Wait. Among these, methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, and benzyl (meth)acrylate are preferred.

Moreover, it is preferable that (A) alkali-soluble resin has an aromatic group in the side chain of the structure from a viewpoint of improving the resolution of a photoresist pattern.

(A) alkali-soluble resin which has an aromatic group in a side chain can be produced by using the compound which has an aromatic group as the said 1st monomer and/or 2nd monomer. Examples of monomers having an aromatic group include benzyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, styrene, cinnamic acid, and polymerizable styrene derivatives (For example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.) and the like. Among them, benzyl (meth)acrylate and styrene are preferred, and benzyl (meth)acrylate is more preferred.

(A) Alkali-soluble resin The above-mentioned first monomer and/or second monomer can be prepared by a known polymerization method, preferably addition polymerization, and more preferably radical polymerization.

The content of the (A) alkali-soluble resin in the photosensitive resin composition (based on the total solid content of the photosensitive resin composition; hereinafter, unless otherwise specified, it is the same in each contained component), preferably 10 The range of mass % - 90 mass % is more preferable in the range of 20 mass % - 80 mass %, and the range of 30 mass % - 60 mass % is still more preferable. The content of the (A) alkali-soluble resin is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer, and on the other hand, the photoresist pattern formed by exposure is sufficiently exerted From the viewpoint of the performance of the photoresist, it is preferably 90% by mass or less.

{式中，R ₁₀表示氫原子、(甲基)丙烯醯基、或環氧烷改性(甲基)丙烯醯基，且於1分子中包含至少4個(甲基)丙烯醯基}。 <(B) The photopolymerizable compound which has an ethylenically unsaturated group> (B) The photopolymerizable compound which has an ethylenically unsaturated group is a compound which has polymerizability by having an ethylenically unsaturated group in the structure. In the first, second and third embodiments, the photosensitive resin composition preferably contains a (meth)acrylate compound as the component (B), more preferably contains a poly(meth)acrylate compound, and more preferably It is a (meth)acrylate compound having a skeleton derived from dipentaerythritol represented by the following formula (II): [Chemical 1]

{In the formula, R ₁₀ represents a hydrogen atom, a (meth)acryloyl group, or an alkylene oxide-modified (meth)acryloyl group, and contains at least 4 (meth)acryloyl groups in one molecule}.

In general formula (II), the number of (meth)acryloyl groups in one molecule is preferably 4 or more from the viewpoint of obtaining sufficient cured film strength, photoresist shape, and resolution. 5 or 6. The alkylene oxide-modified (meth)acryloyl group as the group R ₁₀ is modified, for example, by at least one selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide, preferably In order to be modified by ethylene oxide and/or propylene oxide, specifically, it can be -(C ₂ H ₄ O) _m -CO-CR=CH ₂ {wherein, R represents a hydrogen atom or methyl group, m is an integer from 1 to 30}, -(C ₃ H ₆ O) _n -CO-CR=CH ₂ {wherein R represents a hydrogen atom or a methyl group, and n is an integer from 1 to 30}, -(C ₂ H ₄ O) _m -(C ₃ H ₆ O) _n -CO-CR=CH ₂ {wherein, R represents a hydrogen atom or a methyl group, m is an integer of 1 to 30, and n is 1 to 30 is an integer, the arrangement of (C ₂ H ₄ O) _m and (C ₃ H ₆ O) _n can be alternating, random or block} and the like.

From the viewpoint of adjusting the maximum point load of the puncture test to 70 gf or more, the photosensitive resin composition of the first embodiment preferably contains: (B-i) a (meth)acrylate compound having a skeleton derived from dipentaerythritol and containing an epoxy group, and (B-ii) A compound which has a skeleton derived from dipentaerythritol but does not contain an epoxy group as the (B) component.

Regarding the photosensitive resin composition of the second embodiment, from the viewpoints of the resolution of the photoresist cured film, the amount of side etching, the puncture strength and peelability, the suppression of pattern defects, and the improvement of the yield, it contains: (B-i) a (meth)acrylate compound having a skeleton derived from dipentaerythritol and containing an epoxy group, and (B-ii) A compound which has a skeleton derived from dipentaerythritol but does not contain an epoxy group as the (B) component.

When the photosensitive resin composition contains both the component (B-i) and the component (B-ii), the mass ratio of the two components (B-i): (B-ii) can suppress pattern defects and suppress the damage of the metal substrate. From the viewpoint of defects and yield improvement, it is preferably 8:9 to 9:7.

In the first and second embodiments, the photosensitive resin composition preferably contains (B- iii) (meth)acrylate compound (however, except (B-i) component) which has a skeleton derived from bisphenol and contains an epoxy group.

The photosensitive resin composition of the first embodiment preferably contains ( One or both of B-ii) component and (B-iii) component which is a bifunctional monomer are used as (B) component.

Regarding the photosensitive resin composition of the third embodiment, from the viewpoints of the resolution of the photoresist pattern, the amount of side etching, the puncture strength, the peelability, and the suppression of pattern defects, components other than (B-ii) and (B-ii) are preferably removed. In addition to the component B-iii), the component (B-i) is further included.

In the photosensitive resin composition, the mass ratio of the component (B-iii) to the total mass of the component (B-i) and the component (B-ii) is determined from the viewpoint of the maximum point load of the puncture test or the puncture strength of the photoresist pattern. In other words, it is preferably 0.9 to 1.8, more preferably 0.95 to 1.76.

(B-i) The (meth)acrylate compound having a skeleton derived from dipentaerythritol and containing an epoxy group may be, for example, in the general formula (II), having at least 4 alkylene oxide-modified (methyl) groups in one molecule. From the viewpoint of the maximum point load of the puncture test or the puncture strength of the photoresist cured film, the acrylyl compound preferably has 5 and/or 6 epoxy resins in 1 molecule in the general formula (II). Alkane-modified (meth)acryloyl compounds.

Moreover, regarding the component (Bi), from the viewpoint of the maximum point load of the puncture test or the puncture strength of the photoresist cured film, in the general formula (II), as the alkylene oxide modified (methyl) group R ₁₀ The acryl group is preferably modified by at least one member selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, pentene oxide and hexane oxide, more preferably Modified by ethylene oxide and/or propylene oxide, more preferably -(C ₂ H ₄ O) _m -CO-CR=CH ₂ {wherein, R represents a hydrogen atom or a methyl group, and m is An integer of 1 to 30}, -(C ₃ H ₆ O) _n -CO-CR=CH ₂ {wherein R represents a hydrogen atom or a methyl group, and n is an integer of 1 to 30}, or -(C ₂ H ₄ O) _m -(C ₃ H ₆ O) _n -CO-CR=CH ₂ {wherein, R represents a hydrogen atom or a methyl group, m is an integer from 1 to 30, n is an integer from 1 to 30, (C The arrangement of ₂ H ₄ O) _m and (C ₃ H ₆ O) _n can be alternating, random or block}, and more preferably -(C ₂ H ₄ O) _m -CO-CR=CH ₂ {formula wherein, R represents a hydrogen atom or a methyl group, and m is an integer of 1 to 30}. From the same viewpoint, in the general formula (II), the repeating number m of ethylene oxide and the repeating number n of propylene oxide are preferably 3 to 27, more preferably 6 to 21, and more preferably 3 to 27, respectively. It is preferable to be in the range of 9-16.

Specific examples of (B-i) components include: • Dipentaerythritol tetra(meth)acrylate, polyethylene glycol with an average of 3-27 moles of ethylene oxide added, • Dipentaerythritol penta(meth)acrylate, polyethylene glycol added with an average of 3-27 moles of ethylene oxide, • Dipentaerythritol hexa(meth)acrylate, polyethylene glycol with an average of 3-27 moles of ethylene oxide added, • Dipentaerythritol tetra(meth)acrylate, polyethylene glycol with an average of 3-27 moles of propylene oxide added, • Dipentaerythritol penta(meth)acrylate, polyethylene glycol with an average of 3-27 moles of propylene oxide added, • Dipentaerythritol hexa(meth)acrylate, polyethylene glycol with an average of 3-27 moles of propylene oxide added, • Di-pentaerythritol tetra-, penta- or hexa- ( meth)acrylate, • Combinations of compounds exemplified above, etc. Among them, from the viewpoints of the resolution, undercut amount, puncture strength and peelability of the photoresist cured film, as well as suppressing pattern defects and improving yield, it is preferable to add an average of 12 to 15 moles of ethylene oxide. Dipentaerythritol hexamethacrylate of polyethylene glycol of alkane.

(B-ii) The compound having a skeleton derived from dipentaerythritol but no alkylene oxide may be dipentaerythritol mono- or poly(meth)acrylate which is not modified with alkylene oxide, so as to obtain sufficient cured film strength, From the viewpoint of photoresist shape and resolution, dipentaerythritol poly(meth)acrylate which is not modified with alkylene oxide is preferable.

The component (B-ii) can be, for example, a compound having a hydrogen atom and/or a (meth)acryloyl group as R ₁₀ in the general formula (II), the maximum point load of the puncture test or the puncture strength of the photoresist cured film From a viewpoint, it is preferable to have 4 or more (meth)acryloyl groups as R ₁₀ , and it is more preferable to have 5 or 6 pieces.

In the case where penta(meth)acrylate having 5 (meth)acryloyl groups and hexa(meth)acrylate having 6 (meth)acryloyl groups are used together as the component (B-ii) In this case, the mass ratio of penta(meth)acrylate is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass or 30% by mass to 40% by mass.

Specific examples of the component (B-ii) include: • Dipentaerythritol mono(meth)acrylate, • Dipentaerythritol di(meth)acrylate, • Dipentaerythritol tri(meth)acrylate, • Dipentaerythritol tetra(meth)acrylate, • Dipentaerythritol penta(meth)acrylate, • Dipentaerythritol hexa(meth)acrylate, • Combination of at least 2 of the above-mentioned dipentaerythritol mono- or poly(meth)acrylates Wait. Among them, from the viewpoints of the resolution, side etching amount, puncture strength and peelability of the photoresist cured film, as well as suppressing pattern defects and improving yield, etc., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate is preferred, It is preferable that the mass ratio of pentaacrylate in this mixture is 10 mass %, or 30 mass % - 40 mass %.

(B-iii) Since the (meth)acrylate compound having a skeleton derived from bisphenol does not overlap with the component (B-i), it is preferable that it has a skeleton derived from bisphenol and a (meth)acryloyl group and does not contain two More preferably, the pentaerythritol skeleton has a bisphenol-derived skeleton, an alkylene oxide group, and a (meth)acryloyl group.

{式中，X ₁～X ₈分別獨立地為氫原子或鹵素原子，較佳為X ₁～X ₈全部為氫原子，R ₆及R ₇分別獨立地表示氫原子或甲基，R ₈及R ₉分別獨立地表示碳數2～6之伸烷基，n ₅及n ₆分別獨立地為0或正整數，並且n ₅＋n ₆為0～20}。 The component (B-iii) can be, for example, a compound represented by the following general formula (III): [Chemical 2]

{In the formula, X ₁ to X ₈ are each independently a hydrogen atom or a halogen atom, preferably all of X ₁ to X ₈ are hydrogen atoms, R ₆ and R ₇ are each independently a hydrogen atom or a methyl group, R ₈ and R ₉ each independently represents an alkylene group having 2 to 6 carbon atoms, n ₅ and n ₆ are each independently 0 or a positive integer, and n ₅ +n ₆ is 0 to 20}.

In the general formula (III), the alkylene group having 2 to 6 carbon atoms as R ₈ and R ₉ is preferably ethylidene, propylidene, or butylene group, and -( _R8 -O)- and -( _R9 -O)- can be individually ethylene oxide, propylene oxide, butylene oxide, or a combination of these.

In the general formula (III), preferably -(R ₈ -O)- and -(R ₉ -O)- are respectively -(C ₂ H ₄ O)-, -(C ₃ H ₆ O)-, or -(C ₂ H ₄ O) _α -(C ₃ H ₆ O) _β -{In the formula, α+β=n ₅ or n ₆ , the arrangement of (C ₂ H ₄ O) _α and (C ₃ H ₆ O) _β Can be alternating, random or block, and either _{(C2H4O)α and (C3H6O)β can be quaternary carbon side} }. The (B-iii) component containing these divalent groups is preferable from the viewpoints of the resolution, undercut amount, puncture strength, and peelability of the photoresist cured film, suppression of pattern defects, and improvement in yield. From the same viewpoint, in the general formula (III), n ₅ and n ₆ are preferably each independently a positive integer, more preferably an integer selected from 1 to 14, and n ₅ +n ₆ is preferably 2 to 20.

Specific examples of the component (B-iii) include a compound obtained by modifying bisphenol A with an alkylene oxide to introduce (meth)acryloyl groups at both ends, and a compound obtained from bisphenol A. A compound having (meth)acryloyl groups at both ends, and the like. In addition, in the case of alkylene oxide modification, there are ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentoxide modification, hexane oxide modification, and the like.

Specific examples of ethylene oxide-modified bisphenol A having (meth)acryloyl groups at both ends include: • Di(meth)acrylate of polyethylene glycol obtained by adding an average of 1 mole of ethylene oxide to both ends of bisphenol A, respectively, • Di(meth)acrylate of polyethylene glycol obtained by adding an average of 2 moles of ethylene oxide to both ends of bisphenol A, respectively. • Di(meth)acrylate of polyethylene glycol obtained by adding an average of 3 moles of ethylene oxide to both ends of bisphenol A, respectively. • Di(meth)acrylate of polyethylene glycol obtained by adding an average of 5 moles of ethylene oxide to each end of bisphenol A Wait. These may be used alone or in combination of two or more. Among the components (B-iii) described above, from the viewpoints of resolution, undercut amount, puncture strength, and suppressed defects of the metal substrate, both ends of bisphenol A are preferred. Dimethacrylate of polyethylene glycol obtained by adding an average of 5 mol of ethylene oxide to each, and a polyethylene oxide obtained by adding an average of 1 mol of ethylene oxide to both ends of bisphenol A. Ethylene glycol dimethacrylate and bisphenol A dimethacrylate.

The photosensitive resin composition may contain the photopolymerizable compound which has an ethylenically unsaturated group other than (B-i)-(B-iii) component as an additional (B) component.

Specific examples of the added (B) component include (meth)acrylate compounds other than (B-i) to (B-iii) components, for example, by paraglycerin, trimethylolpropane, pentaerythritol, Add polyalkylene oxide such as diglycerol, di-trimethylolpropane, isocyanurate ring, etc., or modify ε-caprolactone and convert the obtained alcohol into (meth)acrylate. The obtained compound, or the compound obtained by directly reacting these with (meth)acrylic acid without modification with an epoxy group or ε-caprolactone, and the like. More specifically, a triacrylate obtained by adding an average of 3 moles of ethylene oxide to each of trimethylolpropane, and an average of 3 moles of ethylene oxide added to each of trimethylolpropane can be used. The resulting trimethacrylate, ε-caprolactone modified three (acryloyloxyethyl) isocyanurate and so on.

The content of the (B) photopolymerizable compound having an ethylenically unsaturated group in the photosensitive resin composition is preferably 5 to 70% by mass, more preferably 20 to 60% by mass, and still more preferably 30% by mass Within the range of mass % to 50 mass %. (B) The content of the compound having an ethylenically unsaturated group is preferably 5 mass % or more from the viewpoint of suppressing poor curing of the photosensitive resin layer and retardation of developing time, and on the other hand, suppressing the effect of curing the photoresist From the viewpoint of peeling delay, 70 mass % or less is preferable.

The total content of the component (B-i) and the component (B-ii) in the photosensitive resin composition is preferably within a range of 5 to 25 mass %, more preferably within a range of 10 to 20 mass %. If the total content of the components (B-i) and (B-ii) is within the above numerical range, there is a tendency that the adjustment of the maximum point load in the above-mentioned puncture test becomes easy, or the defects of the pattern or the metal substrate can be suppressed, or yield improvement.

When the photosensitive resin composition contains the (B-ii) component and the (B-iii) component, the ratio of the (B-ii) component/(B-iii) component is preferably 10 to 80% by mass, more preferably It is 12-78 mass %. Moreover, among the (B) components contained in the photosensitive resin composition, the ratio of the (B-ii) component and the (B-iii) component is preferably 50% by mass or more, more preferably 55% by mass or more, The upper limit of the ratio is not limited, and may be, for example, 100 mass % or less, or less than 100 mass %.

<(C) Photopolymerizable initiator> (C) The photopolymerizable initiator is a compound which generates radicals by actinic rays and can polymerize the (B) photopolymerizable compound having an ethylenically unsaturated group. The photosensitive resin composition may contain, as the (C) photopolymerization initiator, a photopolymerization initiator generally known in the art.

化合物、二烷基胺基苯甲酸酯化合物、肟酯化合物、吖啶化合物、吡唑啉衍生物、N-芳基胺基酸之酯化合物、鹵素化合物等。(C) As a photopolymerization initiator, for example, a hexaarylbiimidazole compound, an N-aryl-α-amino acid compound, a quinone compound, an aromatic ketone compound, an acetophenone compound, an acyl group oxide can be mentioned. Phosphine compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, 9-oxosulfur

Compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, halogen compounds, and the like.

As the hexaarylbiimidazole compound, for example, 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (alias: 2,2'-bis(2-chlorophenyl)-4, 4',5,5'-tetraphenyl-1,2'-biimidazole), 2,2',5-tri-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl) )-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2, 4,5-Tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2, 3-Difluoromethylphenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorobenzene base)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4' ,5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetra -(3-Methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetra-(3-methyl) oxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl) - Biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2 ,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis -(2,4,6-Trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3 ,4,5-Tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4, 6-Tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5, 6-Pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, etc. Among them, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferable from the viewpoint of high sensitivity, resolution, and adhesion.

Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine acid etc. In particular, N-phenylglycine has a high sensitizing effect, so it is preferable.

As the quinone compound, for example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, 2,3 -Diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthalene Quinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, etc.

Examples of the aromatic ketone compound include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino) ) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-𠰌linylphenyl)-butanone-1, 2-methyl -1-[4-(Methylthio)phenyl]-2-morpholinyl-acetone-1 and the like. Examples of commercially available acetophenone compounds include Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals. From the viewpoint of use as a sensitizer and adhesiveness, 4,4'-bis(diethylamino)benzophenone is preferable.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phosphine oxide, bis(2,4,6-trimethylbenzyl)-phosphine oxide, and bis(2,4,6-trimethylbenzyl)-phosphine oxide. (2,6-Dimethoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. As a commercial item of an acylphosphine oxide compound, Lucirin TPO by BASF company, and Irgacure-819 by Ciba Specialty Chemicals company are mentioned, for example.

化合物，例如可例舉：2,4-二乙基9-氧硫

、2,4-二異丙基9-氧硫

、2-氯9-氧硫

等。 作為二烷基胺基苯甲酸酯化合物，例如可例舉：二甲胺基苯甲酸乙酯、二乙基胺基苯甲酸乙酯、乙基-對二甲胺基苯甲酸酯、4-(二甲胺基)苯甲酸2-乙基己酯等。 As a benzoin compound and a benzoin ether compound, benzoin, benzoin ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, etc. are mentioned, for example. As a dialkyl ketal compound, a benzalkonium dimethyl ketal, a benzil diethyl ketal, etc. are mentioned, for example. as 9-oxosulfur

Compound, for example: 2,4-diethyl 9-oxothio

, 2,4-diisopropyl 9-oxothio

, 2-chloro-9-oxosulfur

Wait. As the dialkylaminobenzoate compound, for example, ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, 4 - 2-ethylhexyl (dimethylamino)benzoate, etc.

As the oxime ester compound, for example, 1-phenyl-1,2-propanedione-2-O-benzyl oxime, 1-phenyl-1,2-propanedione-2-(O -Ethoxycarbonyl) oxime etc. As a commercial item of an oxime ester compound, CGI-325 by Ciba Specialty Chemicals, Irgacure-OXE01, and Irgacure-OXE02 are mentioned, for example.

The acridine compound is preferably 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine in terms of sensitivity, resolution, availability, and the like.

As the pyrazoline derivative, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4- tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline and 1-phenyl -3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline.

As the ester compound of N-arylamino acid, for example, methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, and n-propyl ester of N-phenylglycine may be mentioned. , Isopropyl N-phenylglycine, 1-butyl N-phenylglycine, 2-butyl N-phenylglycine, 3-butyl N-phenylglycine Ester, amyl ester of N-phenylglycine, hexyl N-phenylglycine, amyl N-phenylglycine, octyl N-phenylglycine, etc.

As the halogen compound, for example, bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, vinyl bromide, diphenyl bromide, benzyl bromide, dibromomethane, and tribromomethyl can be mentioned. Phenyl sulfide, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-trichloro-2, 2-bis(p-chlorophenyl)ethane, tris(II) chloride compounds, diallyl iodonium compounds, etc., particularly preferably tribromomethylphenyl sine.

The content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably 0.01% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass. By adjusting the content of the (C) photopolymerization initiator within the above range, sufficient sensitivity can be obtained, light can be sufficiently transmitted to the bottom of the photoresist, high resolution can be obtained, and a conductive pattern can be obtained. The photosensitive resin composition is excellent in the balance of the undercut amount.

As the (C) photopolymerization initiator, a hexaarylbisimidazole compound is preferably used. In this case, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass.

As the (C) photopolymerization initiator, an aromatic ketone compound such as 4,4'-bis(diethylamino)benzophenone and a hexaarylbisimidazole compound are preferably used in combination. In this case, the content of the aromatic ketone compound in the photosensitive resin composition is preferably 0.5% by mass or less, more preferably 0.01% by mass to 0.4% by mass, and the hexaarylbis in the photosensitive resin composition The content of the imidazole compound is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass.

＜(D) Dye＞ It is preferable that the photosensitive resin composition contains a dye as a (D) component, in order to provide preferable color developability and excellent sensitivity characteristic to a photoresist cured film.

Examples of dyes include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leuco malachite green], magenta , phthalocyanine green, aureine base, p-magenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (Aizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue 20 , Diamond Green (Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical (stock)) and the like. Among them, leuco dyes such as diamond green and leuco crystal violet are preferred from the viewpoint of enhancing colorability, hue stability, and exposure contrast. These can be used individually by 1 type or in combination of 2 or more types.

The content of the dye in the photosensitive resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably in the range of 0.01% by mass to 2% by mass, and still more preferably in the range of 0.04% by mass to 1% by mass. The content of the dye is preferably 0.001 mass % or more from the viewpoint of obtaining good colorability, and preferably 3 mass % or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer. By setting the usage ratio of the dye to this range, favorable color rendering properties and sensitivity can be realized.

＜Other ingredients＞ The photosensitive resin composition preferably contains additives such as a plasticizer, an antioxidant, and a stabilizer as required.

As the plasticizer, for example, polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, Polyoxyethylene monoethyl ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether and other glycol-esters; polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan oleate and other sorbitan Anhydrous sugar derivatives; phthalates such as diethyl phthalate; o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyl citric acid Triethyl ester, acetyl tri-n-propyl citrate, and acetyl tri-n-butyl citrate, propylene glycol obtained by adding propylene oxide on both sides of bisphenol A, respectively, on the side of bisphenol A Ethylene oxide, ethylene glycol, polyoxyethylene glycerol ether, polyoxypropylene glyceryl ether, etc. are added on both sides respectively.

Among them, preferred are p-toluenesulfonamide, polypropylene glycol obtained by adding an average of 3 units of propylene oxide to both ends of bisphenol A, and polyoxypropylene glycerin from the viewpoint of suppressing the delay in peeling time. The ether is more preferably polyoxypropylene glyceryl ether, more preferably polyoxypropylene glyceryl ether having a weight average molecular weight of 3,000, from the viewpoint of the puncture strength of the photoresist pattern, release sheet solubility, or plating resistance.

The content of the plasticizer in the photosensitive resin composition is preferably within a range of 0.1 to 3 mass %, more preferably 0.15 to 2 mass %. It is preferable to make this content into 0.1 mass % or more from a viewpoint of suppressing the retardation of image development time, providing flexibility to a cured film, and being easy to adjust the maximum point load by the said puncture test. On the other hand, it is preferable to make this content into 3 mass % or less from a viewpoint of suppressing insufficient hardening and edge melting.

As antioxidants, for example, triphenyl phosphite (for example, manufactured by Asahi Denka Industrial Co., Ltd., trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (for example, Manufactured by Asahi Electric Industries, Ltd., trade name: 2112), tris(mononylphenyl) phosphite (for example, manufactured by Asahi Denka Industries, trade name: 1178), bis(mononylphenyl) phosphite dinonyl Phenyl ester (for example, manufactured by Asahi Denka Industrial Co., Ltd., trade name: 329K) and the like. These can be used individually by 1 type or in combination of 2 or more types.

The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01 mass % to 0.8 mass %, more preferably in the range of 0.01 mass % to 0.3 mass %. The content of the antioxidant is preferably 0.01 mass % or more from the viewpoint of favorably expressing the hue stability of the photoresist pattern and improving the sensitivity of the photosensitive resin layer, and on the other hand, suppressing the color development of the photoresist pattern From the viewpoint of simultaneously expressing the hue stability well and improving the adhesiveness, it is preferably 0.8 mass % or less.

From the viewpoint of improving the thermal stability and/or storage stability of the photosensitive resin composition, it is preferable to use a stabilizer. Examples of the stabilizer include at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, and alkylene oxide compounds having a glycidyl group. . These can be used individually by 1 type or in combination of 2 or more types.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-diphenol -Tertiary-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6 - tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxylamine aluminum salt (For example, 3 molar aluminum salts of nitrosophenylhydroxylamine, etc. are added), diphenylnitrosoamine, and the like. Among these, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], or a nitrosophenyl group added thereto is preferable The aluminum salt of hydroxylamine 3 moles. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis(N-2-ethylhexyl)amino Methylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyl) Ethyl)aminomethylene-1,2,3-benzotriazole, 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di - 1:1 mixture of n-butylaminomethyl)-6-carboxybenzotriazole, etc. Among these, 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6- A 1:1 mixture of carboxybenzotriazoles. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N- Di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N- , N-di-2-ethylhexyl) aminovinyl carboxybenzotriazole and so on. These can be used individually by 1 type or in combination of 2 or more types.

As the alkylene oxide compound having a glycidyl group, for example, neopentyl glycol diglycidyl ether (for example, Epolight 1500NP manufactured by Kyeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, , Epolight 400E manufactured by Kyōeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-molar adduct diglycidyl ether (for example, Epolight 3002 manufactured by Kyōeisha Chemical Co., Ltd.), 1,6 - Hexylene glycol diglycidyl ether (for example, Epolight 1600 manufactured by Kyōeisha Chemical Co., Ltd.) and the like. These can be used individually by 1 type or in combination of 2 or more types.

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

The number of double bonds in the photosensitive resin composition of the first, second, and third embodiments is preferably 1.50 mmol/g or more based on the solid content of the photosensitive resin composition. By setting the number of double bonds to such a range, the puncture strength or resolution of the coating film becomes favorable. On the other hand, when the number of double bonds of the photosensitive resin composition is too high, the storage stability of the composition may be impaired. From the viewpoint of avoiding such a situation, the number of double bonds in the photosensitive resin composition is more preferably 4.00 mmol/g or less. The number of double bonds (the number of ethylenically unsaturated bonds) in the photosensitive resin composition can be determined by the compounding ratio of the (B) component in the photosensitive resin composition, the molecular weight of the (B) component, and the number of functional groups of the (B) component, etc. make adjustments. That is, it can be said that the aspect in which the number of double bonds of the photosensitive resin composition is in the above-mentioned range is the aspect in which the maximum point load at the time of the puncture test is in the above-mentioned range. A preferred aspect in which the molecular weight, the number of functional groups of the (B) component, etc. are preferably adjusted. Such a preferred aspect is easy to exert the effect of the invention of the present application.

[Another aspect of the present invention] Another aspect of the present invention provides a photosensitive resin laminate having a support and a photosensitive resin composition layer formed on the support using a photosensitive resin composition, the photosensitive resin composition comprising (A ) Alkali-soluble resin containing no ethylenically unsaturated group on the main chain, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. Furthermore, the photosensitive resin layered product of another aspect of the present invention is characterized in that the acid value of the non-volatile component of the photosensitive resin composition is A [mgKOH/g], and the photosensitive resin composition layer is characterized by: When the thickness is set to T [μm], the ratio (A/T) of the acid value A to the thickness T is 5 or more and 90 or less.

If the ratio (A/T) of the acid value A to the thickness T is less than 5 (for example, 5.0), the minimum development time and the resolution are insufficient. On the other hand, when the ratio (A/T) is more than 90, side etching (SE) and Cu defects are insufficient. When the ratio (A/T) is 5 or more and 90 or less, the photosensitive resin laminate is excellent in lamination properties, minimum development time, resolution, side etching (SE), Cu defects, and development residues. The above ratio (A/T) is preferably 12 (eg, 12.0) or more and less than 70, and more preferably 12 (eg, 12.0) or more and less than 50.

Furthermore, in another aspect of the present invention, the acid value (acid equivalent) of the non-volatile component of the photosensitive resin composition means the mass (gram) of the polymer having 1 equivalent of carboxyl groups in the molecule, and is determined according to the use The value calculated from the value measured by NMR (Nuclear Magnetic Resonance, nuclear magnetic resonance). Specifically, it is the measured value measured according to the measuring method in the examples described below. Hereinafter, each component which comprises a photosensitive resin composition layer is demonstrated.

<(A) Alkali-soluble resin containing no ethylenically unsaturated group in the main chain> (A) The alkali-soluble resin which does not contain an ethylenically unsaturated group in the main chain is a polymer which can be dissolved in an alkaline solution. In addition, (A) the alkali-soluble resin containing no ethylenically unsaturated group on the main chain preferably has a carboxyl group, more preferably has an acid equivalent of 100 to 600, and further preferably contains a carboxyl group-containing monomer as a copolymerization component. copolymer. Furthermore, (A) the alkali-soluble resin containing no ethylenically unsaturated group in the main chain may be thermoplastic.

The acid equivalent of the non-volatile component of the photosensitive resin composition comprising (A) an alkali-soluble resin that does not contain an ethylenically unsaturated group in the main chain is preferably more than 0, which is considered in terms of the development resistance of the photosensitive resin layer and the photoresist pattern. The acid equivalent of the nonvolatile content of the photosensitive resin composition is preferably 79.0 or less from the viewpoints of the resolution and adhesiveness, and further from the viewpoints of the developability and releasability of the photosensitive resin layer.

In addition, the acid value (acid equivalent) of the non-volatile component of the photosensitive resin composition comprising (A) an alkali-soluble resin that does not contain an ethylenically unsaturated group in the main chain is more preferably more than 0 and 78.0 or less, and more preferably is more than 0 and 76.0 or less.

The acid value in the above range corresponds to a so-called "low acid value" compared with the prior art. Another aspect of the present invention realizes the "thinning of the photosensitive resin layer" and the "low acid value" when the thinning of the photosensitive resin layer is particularly required in recent years. Previously, as one method for realizing high resolution (low SE), it has been known to increase the hydrophobicity of photoresist. On the other hand, if the hydrophobicity of the photoresist is increased, the solubility in the developing solution will decrease, so that the developing time tends to become longer. In this regard, if the molecular weight of the resin is reduced to shorten the development time, there is also a case where Cu defects (film strength) are easily reduced. In contrast to these cases, the other aspect of the present invention, which has achieved "thinning of the photosensitive resin layer" and "low acid value", can easily achieve a combination of various effects.

{式中，W _i為構成鹼可溶性樹脂之共聚單體各者之質量， Tg _i為構成鹼可溶性樹脂之共聚單體各者為均聚物之情形時之玻璃轉移溫度， W _total為鹼可溶性樹脂之合計質量，並且 n為構成該鹼可溶性樹脂之共聚單體之種類之數} 所求出之玻璃轉移溫度(Tg _total)為100℃以下。於使用複數種高分子之混合物作為(A)主鏈上不含乙烯性不飽和基之鹼可溶性樹脂之情形時，玻璃轉移溫度係以全部高分子之平均值之形式所確定之值。 (A) The alkali-soluble resin containing no ethylenically unsaturated group in the main chain is preferably represented by the following formula (I): [Numerical 2]

{wherein, Wi is the mass of each of the comonomers constituting the alkali-soluble resin, _Tgi is the glass transition temperature when each of the comonomers constituting the alkali-soluble resin is a homopolymer, _{and Wtotal is} the alkali-soluble The total mass of the resin, and n is the number of kinds of comonomers constituting the alkali-soluble resin} The glass transition temperature (Tg _total ) obtained is 100° C. or less. In the case of using a mixture of a plurality of polymers as (A) the alkali-soluble resin containing no ethylenically unsaturated group in the main chain, the glass transition temperature is a value determined as an average value of all the polymers.

When determining the glass transition temperature Tg _i , as the corresponding glass transition temperature of the homopolymer containing the comonomer forming the alkali-soluble resin, "Polymer handbook, Third edition, John wiley" edited by Brandrup, J. Immergut, EH was used. & sons, 1989, p.209 Chapter VI “Glass transition temperatures of polymers””.

The _Tgi of representative comonomers are as follows (all literature values). Methacrylic acid: Tg=501 K Benzyl methacrylate: Tg=327 K Methyl methacrylate: Tg=378 K Styrene: Tg=373 K 2-ethylhexyl acrylate: Tg=223 K The alkali-soluble resin having a glass transition temperature (Tg _total ) as described above is preferably a copolymer of an acid monomer and other monomers.

The lower limit value of the glass transition temperature (Tg _total ) of the alkali-soluble resin containing no ethylenically unsaturated group in the main chain of (A), which is determined by the above formula (I), is not particularly limited. The glass transition temperature (Tg _total ) may be 10°C or higher, 30°C or higher, 50°C or higher, or 70°C or higher.

(A) It is preferable that the weight average molecular weight of the alkali-soluble resin which does not contain an ethylenically unsaturated group in a main chain is 5,000-500,000. (A) The weight-average molecular weight of the alkali-soluble resin not containing an ethylenically unsaturated group in the main chain is from the viewpoint of uniformly maintaining the thickness of the photosensitive resin laminate such as dry film resist to obtain resistance to developing solutions. , preferably 5,000 or more, and on the other hand, from the viewpoint of maintaining the developability of photosensitive resin laminates such as dry film resists, preferably 500,000 or less. Moreover, (A) the weight average molecular weight (Mw) of the alkali-soluble resin which does not contain an ethylenically unsaturated group in a main chain is more preferably 10,000-200,000, More preferably, it is 20,000-100,000 or 23,000-50,000. Furthermore, the ratio of the above Mw to (A) the number average molecular weight (Mn) of the alkali-soluble resin containing no ethylenically unsaturated group on the main chain is the ratio of (A) the ratio of the alkali-soluble resin containing no ethylenically unsaturated group on the main chain. The degree of dispersion (Mw/Mn) is preferably 1.0 to 6.0.

(A) The alkali-soluble resin containing no ethylenically unsaturated group in the main chain is preferably obtained by polymerizing at least one of the first monomers described below. Further, (A) the alkali-soluble resin containing no ethylenically unsaturated group in the main chain is more preferably obtained by copolymerizing at least one of the first monomers and at least one of the second monomers described below .

The first monomer is a monomer containing a carboxyl group in the molecule. As a first monomer, (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itonic acid, maleic anhydride, (meth)acrylate β-carboxyethyl, for example, can be mentioned. And maleic acid half ester and so on. Among these, (meth)acrylic acid is especially preferable.

Examples of the second monomer include unsaturated aromatic compounds (sometimes referred to as "aromatic monomers"), alkyl (meth)acrylates, aralkyl (meth)acrylates, conjugated Diene compounds, polar monomers, crosslinkable monomers, and the like. Among these, an unsaturated aromatic compound is preferable from the viewpoint of improving the resolution of a photoresist pattern.

Examples of the unsaturated aromatic compound include benzyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, styrene, cinnamic acid, and polymerizable styrene derivatives (such as , methyl styrene, vinyl toluene, tertiary butoxy styrene, acetoxy styrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc.) and the like. Among them, benzyl (meth)acrylate and styrene are preferred, and benzyl (meth)acrylate is more preferred.

Alkyl (meth)acrylate is a concept including both a chain alkyl ester and a cyclic alkyl ester. Specifically, for example, methyl (meth)acrylate and ethyl (meth)acrylate may be mentioned. , n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, (meth)acrylate Hexyl acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, (meth)acrylate base) lauryl acrylate, n-tetradecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, and the like.

As the aralkyl (meth)acrylate, for example, benzyl (meth)acrylate etc. may be mentioned; as the conjugated diene compound, for example, 1,3-butadiene, isoprene, 2 ,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1 , 3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, etc. Examples of polar monomers include hydroxyl-containing monomers such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and pentenol; methacrylic acid 2 -Amine group-containing monomers such as aminoethyl ester; (meth)acrylamide, N-methylol (meth)acrylamide and other amide group-containing monomers; acrylonitrile, methacrylonitrile, α- Cyano group-containing monomers such as chloroacrylonitrile and α-cyanoethyl acrylate; epoxy group-containing monomers such as glycidyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate, etc.

As a crosslinkable monomer, trimethylolpropane triacrylate, divinylbenzene, etc. are mentioned, for example.

(A) The alkali-soluble resin containing no ethylenically unsaturated group on the main chain can be prepared by the above-mentioned first monomer and/or second monomer by a known polymerization method, preferably addition polymerization, more preferably Radical Polymerization.

(A) Content of the alkali-soluble resin containing no ethylenically unsaturated group on the main chain in the photosensitive resin composition (based on the total solid content of the photosensitive resin composition; hereinafter, unless otherwise specified, the It is the same in each containing component), Preferably it is the range of 10-90 mass %, More preferably, it is the range of 20-80 mass %, More preferably, it is the range of 30-60 mass %. The content of the (A) alkali-soluble resin not containing an ethylenically unsaturated group in the main chain is preferably 10% by mass or more from the viewpoint of maintaining the alkali developability of the photosensitive resin layer. From the viewpoint of exerting the performance of the photoresist pattern formed by exposure as a photoresist material, it is preferably 90 mass % or less.

<(B) Photopolymerizable compound having ethylenically unsaturated bond> (B) The photopolymerizable compound which has an ethylenically unsaturated bond is a compound which has polymerizability by having an ethylenically unsaturated bond in the structure, and this ethylenically unsaturated bond is specifically an ethylenically unsaturated group. The photosensitive resin composition should just have one or more ethylenic double bonds as (B) component. Preferably, a compound having two or more ethylenic double bonds is used.

Specifically, as the component (B), for example, polyalkylene glycol two ( Meth)acrylate, polyalkylene triol tri(meth)acrylate obtained by adding an average of 3 mol to 25 mol of alkylene oxide to trimethylolpropane, by adding glycerol, tris(meth)acrylate Methylolpropane, pentaerythritol, diglycerol, di-trimethylolpropane, isocyanurate ring, etc., add epoxy alkyl groups, or carry out ε-caprolactone modification and convert the obtained alcohol into ( A compound obtained by this method of meth)acrylate, or a compound obtained by directly reacting these with (meth)acrylic acid without modification with an alkylene oxide or ε-caprolactone, average addition to pentaerythritol Tetra(meth)acrylates of polyols obtained by adding 4 to 35 mols of alkylene oxide, polyols obtained by adding an average of 4 to 30 mols of alkylene oxides to dipentaerythritol, hexa(meth)acrylic acid esters, etc. These can be used alone or in combination of two or more

The content of the (B) photopolymerizable compound having an ethylenically unsaturated group in the photosensitive resin composition is preferably 5 to 70% by mass, more preferably 20 to 60% by mass, and still more preferably 30% by mass Within the range of mass % to 50 mass %. The content of the compound (B) having an ethylenically unsaturated group is preferably 5% by mass or more from the viewpoint of suppressing poor curing of the photosensitive resin layer and delay in developing time, and on the other hand, suppressing curing light From the viewpoint of the peeling delay of resistance, 70 mass % or less is preferable.

<(C) Photopolymerization Initiator> (C) A photopolymerization initiator is a compound which can generate|occur|produce a radical by an actinic ray, and can polymerize the photopolymerizable compound etc. which have an ethylenically unsaturated group (B). The photosensitive resin composition may contain, as the (C) photopolymerization initiator, a photopolymerization initiator generally known in the art.

化合物、二烷基胺基苯甲酸酯化合物、肟酯化合物、吖啶化合物、吡唑啉衍生物、N-芳基胺基酸之酯化合物、鹵素化合物等。(C) As a photopolymerization initiator, for example, a hexaarylbiimidazole compound, an N-aryl-α-amino acid compound, a quinone compound, an aromatic ketone compound, an acetophenone compound, an acyl group oxide can be mentioned. Phosphine compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, 9-oxosulfur

Compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, halogen compounds, and the like.

As the hexaarylbiimidazole compound, for example, 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (alias: 2,2'-bis(2-chlorophenyl)-4, 4',5,5'-tetraphenyl-1,2'-biimidazole), 2,2',5-tri-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl) )-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2, 4,5-Tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2, 3-Difluoromethylphenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorobenzene base)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5-difluorophenyl)-4,4' ,5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetra -(3-Methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetra-(3-methyl) oxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl) - Biimidazole, 2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2 ,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis -(2,4,6-Trifluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3 ,4,5-Tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4, 6-Tetrafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, and 2,2'-bis-(2,3,4,5, 6-Pentafluorophenyl)-4,4',5,5'-tetra-(3-methoxyphenyl)-biimidazole, etc. Among them, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferable from the viewpoint of high sensitivity, resolution, and adhesion.

Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine acid etc. In particular, N-phenylglycine has a high sensitizing effect, so it is preferable.

As the quinone compound, for example, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2-phenylanthraquinone, 2,3 -Diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthalene Quinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, etc.

Examples of the aromatic ketone compound include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino) ) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-𠰌linylphenyl)-butanone-1, 2-methyl -1-[4-(Methylthio)phenyl]-2-morpholinyl-acetone-1 and the like. Examples of commercially available acetophenone compounds include Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals. From the viewpoint of use as a sensitizer and adhesiveness, 4,4'-bis(diethylamino)benzophenone is preferable.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phosphine oxide, bis(2,4,6-trimethylbenzyl)-phosphine oxide, and bis(2,4,6-trimethylbenzyl)-phosphine oxide. (2,6-Dimethoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide, etc. As a commercial item of an acylphosphine oxide compound, Lucirin TPO by BASF company, and Irgacure-819 by Ciba Specialty Chemicals company are mentioned, for example.

化合物，例如可例舉：2,4-二乙基9-氧硫

、2,4-二異丙基9-氧硫

、2-氯9-氧硫

等。 作為二烷基胺基苯甲酸酯化合物，例如可例舉：二甲胺基苯甲酸乙酯、二乙基胺基苯甲酸乙酯、對二甲胺基苯甲酸乙酯、4-(二甲胺基)苯甲酸2-乙基己酯等。 As a benzoin compound and a benzoin ether compound, benzoin, benzoin ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, etc. are mentioned, for example. As a dialkyl ketal compound, a benzalkonium dimethyl ketal, a benzil diethyl ketal, etc. are mentioned, for example. as 9-oxosulfur

Compound, for example: 2,4-diethyl 9-oxothio

, 2,4-diisopropyl 9-oxothio

, 2-chloro-9-oxosulfur

Wait. As the dialkylaminobenzoate compound, for example, ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl p-dimethylaminobenzoate, 4-(diethylaminobenzoate, Methylamino) 2-ethylhexyl benzoate and the like.

As the oxime ester compound, for example, 1-phenyl-1,2-propanedione-2-O-benzyl oxime, 1-phenyl-1,2-propanedione-2-(O -Ethoxycarbonyl) oxime etc. As a commercial item of an oxime ester compound, CGI-325 by Ciba Specialty Chemicals, Irgacure-OXE01, and Irgacure-OXE02 are mentioned, for example.

The acridine compound is preferably 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine in terms of sensitivity, resolution, availability, and the like.

As the pyrazoline derivative, 1-phenyl-3-(4-tert-butyl-styryl)-5-(4- tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline and 1-phenyl -3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline.

As the ester compound of N-arylamino acid, for example, methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, and n-propyl ester of N-phenylglycine may be mentioned. , Isopropyl N-phenylglycine, 1-butyl N-phenylglycine, 2-butyl N-phenylglycine, 3-butyl N-phenylglycine Ester, amyl ester of N-phenylglycine, hexyl N-phenylglycine, amyl N-phenylglycine, octyl N-phenylglycine, etc.

As the halogen compound, for example, bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, vinyl bromide, diphenyl bromide, benzyl bromide, dibromomethane, and tribromomethyl can be mentioned. Phenyl sulfide, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-trichloro-2, 2-bis(p-chlorophenyl)ethane, tris(II) chloride compounds, diallyl iodonium compounds, etc., particularly preferably tribromomethylphenyl sine.

The content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably 0.01% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass. By adjusting the content of the (C) photopolymerization initiator within the above range, sufficient sensitivity can be obtained, light can be sufficiently transmitted to the bottom of the photoresist, high resolution can be obtained, and a conductive pattern can be obtained. A photosensitive resin composition with excellent balance of undercut amount.

As the (C) photopolymerization initiator, a hexaarylbisimidazole compound is preferably used. In this case, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass.

As the (C) photopolymerization initiator, an aromatic ketone compound such as 4,4'-bis(diethylamino)benzophenone and a hexaarylbisimidazole compound are preferably used in combination. In this case, the content of the aromatic ketone compound in the photosensitive resin composition is preferably 0.5% by mass or less, more preferably 0.01% by mass to 0.4% by mass, and the hexaarylbis in the photosensitive resin composition The content of the imidazole compound is preferably 0.1% by mass to 10% by mass, more preferably 0.5% by mass to 5% by mass.

<(D) A compound having polytetramethylene oxide as a structural unit> Since the compound having polytetramethylene oxide as a structural unit has high flexibility, it can impart moderate flexibility to the formed photoresist pattern. Thereby, defects of the photoresist film due to the process load are less likely to occur, so that Cu defects can also be reduced. Furthermore, since the compound which has polytetramethylene oxide as a structural unit is high in hydrophobicity, it can improve the resolution or reduce side etching by using it in the photosensitive resin laminated body. For the above reasons, it is preferable to use a compound having polytetramethylene oxide as a structural unit.

As a compound which has polyoxytetramethylene oxide as a structural unit, for example, poly-1,4-butanediol, poly-1,4-butanediol dimethacrylate, poly-1,4-butanediol dimethacrylate may be mentioned. Acrylates, 2,2-bis(4-((meth)acryloyloxypolytetramethyleneoxy)phenyl)propane, poly1,4-butanediol trimethylolpropane tri(methyl) Acrylate, hydroxyethyl (meth)acrylate, poly-1,4-butanediol and urethane reactant of diisocyanate compound or triisocyanate compound, etc. Among these, a poly-1,4-butanediol dimethacrylate compound is preferable. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

(D) The total content of the compound having polytetramethylene oxide as a structural unit in the photosensitive resin composition is preferably in the range of 0.5% by mass to 50% by mass from the viewpoint of alkali developability, more preferably It is the range of 1-40 mass %.

<(E) A compound having a benzotriazole skeleton> From the viewpoint of improving the thermal stability and/or storage stability of the photosensitive resin composition, it is preferable to use a compound having a benzotriazole skeleton. As a compound which has a benzotriazole skeleton, benzotriazoles, carboxybenzotriazoles, etc. are mentioned.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis(N-2-ethylhexyl)amino Methylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, bis(N-2-hydroxyl) Ethyl)aminomethylene-1,2,3-benzotriazole, 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di - 1:1 mixture of n-butylaminomethyl)-6-carboxybenzotriazole, etc. Among these, 1-(2-di-n-butylaminomethyl)-5-carboxybenzotriazole and 1-(2-di-n-butylaminomethyl)-6- A 1:1 mixture of carboxybenzotriazoles. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N- Di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N- , N-di-2-ethylhexyl) aminovinyl carboxybenzotriazole and so on. These can be used individually by 1 type or in combination of 2 or more types.

(E) The total content of the compound which has a benzotriazole skeleton in the photosensitive resin composition becomes like this. Preferably it is the range of 0.001-3 mass %, More preferably, it is the range of 0.05-1 mass %. The total content is preferably 0.001 mass % or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and on the other hand, from the viewpoint of maintaining the sensitivity or resolution of the photosensitive resin layer In other words, it is preferably 3 mass % or less.

In the photosensitive resin composition, the ratio [(A)component/((B)component+(D)component)] of the total of (A) component and (B)component and (D)component is preferably 1.4 or less. It can improve the solubility in alkaline aqueous solution, or the mechanical strength of the photoresist film, and can improve the minimum development time or Cu defects. In addition, from the viewpoint of edge fusion resistance, the lower limit of the above-mentioned ratio is preferably 0.5 or more.

＜Other ingredients＞ The photosensitive resin composition preferably contains additives such as colorants such as dyes, antioxidants, and stabilizers as necessary.

Examples of dyes include tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leuco malachite green], magenta , phthalocyanine green, aureine base, p-magenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (Aizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue 20 , Diamond Green (Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical (stock)) and the like. Among them, diamond green and leuco crystal violet are preferred from the viewpoint of enhancing colorability, hue stability, and exposure contrast. These can be used individually by 1 type or in combination of 2 or more types.

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

As antioxidants, for example, triphenyl phosphite (for example, manufactured by Asahi Denka Industrial Co., Ltd., trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (for example, Manufactured by Asahi Electric Industries, Ltd., trade name: 2112), tris(mononylphenyl) phosphite (for example, manufactured by Asahi Denka Industries, trade name: 1178), bis(mononylphenyl) phosphite dinonyl Phenyl ester (for example, manufactured by Asahi Denka Industrial Co., Ltd., trade name: 329K) and the like. These can be used individually by 1 type or in combination of 2 or more types.

The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01 mass % to 0.8 mass %, more preferably in the range of 0.01 mass % to 0.3 mass %. The content of the antioxidant is preferably 0.01 mass % or more from the viewpoint of satisfactorily expressing the hue stability of the photoresist pattern and improving the sensitivity of the photosensitive resin layer, and on the other hand, suppressing the color development of the photoresist pattern From the viewpoint of expressing the hue stability well and improving the adhesiveness at the same time, it is preferably 0.8 mass % or less.

From the viewpoint of improving the thermal stability and/or storage stability of the photosensitive resin composition, it is preferable to use a stabilizer. Examples of the stabilizer include at least one compound selected from the group consisting of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group. These can be used individually by 1 type or in combination of 2 or more types.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-diphenol -Tertiary-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6 - tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxylamine aluminum salt (For example, 3 molar aluminum salts of nitrosophenylhydroxylamine, etc. are added), diphenylnitrosoamine, and the like. Among these, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], or a nitrosophenyl group added thereto is preferable The aluminum salt of hydroxylamine 3 moles. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

As the alkylene oxide compound having a glycidyl group, for example, neopentyl glycol diglycidyl ether (for example, Epolight 1500NP manufactured by Kyeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, , Epolight 400E manufactured by Kyōeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-molar adduct diglycidyl ether (for example, Epolight 3002 manufactured by Kyōeisha Chemical Co., Ltd.), 1,6 - Hexylene glycol diglycidyl ether (for example, Epolight 1600 manufactured by Kyōeisha Chemical Co., Ltd.) and the like. These can be used individually by 1 type or in combination of 2 or more types.

The total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably in the range of 0.001 to 3 mass %, more preferably in the range of 0.05 to 1 mass %. The total content is preferably 0.001 mass % or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and on the other hand, from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is preferably It is 3 mass % or less.

[Photosensitive resin composition preparation solution] The photosensitive resin composition preparation liquid can be formed by adding a solvent to the photosensitive resin composition of this invention. As a preferable solvent, ketones represented by acetone and methyl ethyl ketone (MEK), and alcohols, such as methanol, ethanol, and isopropanol, etc. are mentioned, for example. Preferably, the solvent is added to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation liquid becomes 500 mPa·sec to 4000 mPa·sec at 25°C.

[Photosensitive resin laminate, dry film resist and transfer film] Using the photosensitive resin composition or the photosensitive resin composition preparation solution of the present invention, a photosensitive resin laminate can be provided. The photosensitive resin laminated body has a support film (support body), and the layer containing the said photosensitive resin composition formed on the support film. The photosensitive resin laminated body may have a protective layer on the surface of the side opposite to a support film side as needed. The photosensitive resin laminate is preferably a dry film photoresist or a transfer film, and more preferably a dry film photoresist, from the viewpoint of remarkably exerting the effects of the present invention.

Among them, the suppression of pattern defects, the improvement of the yield of the formation or the formation of the pattern by photolithography, and/or the lamination property, the minimum development time, the resolution, the side etching, the Cu defect, and the development residue are at least From an excellent point of view, the best dry film photoresist has: support membrane, and A photosensitive layer, the photosensitive layer is formed on the support film, and contains the (A) Alkali-soluble resin, (B) a compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, and (D) Dyes composition, Ingredient (B) above contains: (B-ii) a compound having a dipentaerythritol skeleton but not having an epoxy group, and (B-iii) a compound having a skeleton derived from bisphenol, Among (B) components, (B-ii) component and (B-iii) component are 50 mass % or more, and the ratio of (B-ii) component/(B-iii) component is 10-80 mass %. In addition, the composition of the particularly preferred dry film photoresist can be photosensitive within the range of the present invention with the ratio (A/T) of the acid value A of the non-volatile component of the photosensitive resin composition and the thickness T of the photosensitive resin layer (A/T). The constitutions of the flexible resin laminates can be combined or interchanged.

The support film is preferably a transparent support film that transmits light emitted from a self-exposure light source. As such a support film, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film may, for example, be mentioned. , Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. These films can also be overstretched as needed.

The haze of the support film is preferably 5 or less. The thickness of the support film is advantageously thin in terms of image formability and economical efficiency, and is preferably 10 μm to 30 μm in consideration of the function of maintaining strength.

The layer of the photosensitive resin composition described above (hereinafter, also referred to as a "photosensitive resin layer") may contain the photosensitive resin composition, or may be composed of the photosensitive resin composition. The film thickness of the layer of the photosensitive resin composition in the photosensitive resin laminate is preferably 0.5 μm to 25 μm from the viewpoint of the resolution of the photoresist pattern, the amount of side etching, the puncture strength, or the peelability, and more It is preferably 1 μm to 25 μm, more preferably 1 μm to 20 μm. From the same viewpoint, the upper limit of the film thickness is particularly preferably 16 μm or less, and most preferably 10 μm or less.

An important characteristic of the protective layer used in the photosensitive resin laminate is to have an appropriate adhesive force. That is, it is preferable that the adhesive force of the protective layer to the photosensitive resin layer is sufficiently smaller than the adhesive force of the support film to the photosensitive resin layer, and the protective layer can be easily peeled off from the photosensitive resin laminate. As a protective layer, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a polyester film, etc. can be used, for example. Moreover, the release layer which can be used suitably for peeling a protective film from a photoresist layer can also be provided to the single side|surface of the said protective layer film. The release layer is usually divided into polysiloxane compounds and non-polysiloxane compounds. The so-called polysiloxane compounds can be exemplified by: two-terminal silanol polydimethylsiloxane and polymethylhydrosiloxane or polymethylsiloxane. Condensation reaction type polysiloxane resin obtained by reacting dimethylsiloxane; or dimethylsiloxane-methylvinylsiloxane copolymer or dimethylsiloxane-methylhexene Addition reaction type polysiloxane resin obtained by reacting polysiloxane copolymer with polymethylhydrosiloxane; or curing acrylic polysiloxane or epoxy-containing polysiloxane by ultraviolet rays or electron beams The resulting UV-curable or electron beam-curable polysiloxane; or modified polysiloxane, such as epoxy-modified polysiloxane (polysiloxane epoxy resin), polyester-modified polysiloxane resin (polysiloxane polyester), acrylic modified polysiloxane resin (polysiloxane acrylic), phenol modified polysiloxane resin (polysiloxane phenol), alkyd modified polysiloxane resin (polysiloxane alkyd) ), melamine modified polysiloxane (polysiloxane melamine), etc. As a non-polysiloxane compound, acid alcohol (or also called alkyd) resin, long-chain alkyl resin, acrylic resin, polyolefin resin, etc. are mentioned. The film thickness of the release layer is preferably in the range of 0.001 to 2 μm, more preferably in the range of 0.005 to 1 μm, and still more preferably in the range of 0.01 to 0.5 μm. When the film thickness exceeds 2 μm, the appearance of the coating film may be deteriorated or the coating film may be insufficiently cured, and when the film thickness is less than 0.001 μm, there is a possibility that sufficient release properties cannot be obtained. As a film thickness of a protective layer, 10 micrometers - 100 micrometers are preferable, and 10 micrometers - 50 micrometers are more preferable.

[Production method of photosensitive resin laminate] The photosensitive resin laminate can be produced by sequentially laminating a photosensitive resin layer and an optional protective layer on a support film. As the method, a known method can be used. For example, the photosensitive resin composition used for the photosensitive resin layer and the solvent which melt|dissolve these are mixed, and the photosensitive resin composition preparation liquid (coating liquid) of a uniform solution form is formed. Next, the coating liquid can be applied on a support film (support) using a bar coater or a roll coater, and then dried, and a photosensitive resin layer can be laminated on the support film. A protective layer may be laminated on the photosensitive resin layer as needed to produce a photosensitive resin laminate.

[Photoresist pattern forming method] Another aspect of the present invention provides a method for forming a photoresist pattern, which includes the following steps: The step of laminating the photosensitive resin laminate of the present invention on a base material (lamination step), the step of exposing the laminated photosensitive resin laminate (exposure step), and A step (development step) of developing the exposed photosensitive resin laminate.

[Wiring pattern formation method] Another aspect of the present invention provides a wiring pattern forming method, which includes the following steps: A step (etching or plating step) of etching or plating the substrate on which the photoresist pattern is formed by the above-described photoresist pattern forming method.

Hereinafter, an example of the method of forming a photoresist and a wiring pattern using the photosensitive resin laminated body and a base material is demonstrated.

(lamination step) The lamination step can be performed by peeling off the protective layer from the laminate when the photosensitive resin laminate has a protective layer, and thereafter, for example, using a laminator to heat and crimp the photosensitive resin layer to the base material surface for lamination.

As a material of the base material to be used, for example, copper (Cu), stainless steel (SUS), glass, indium tin oxide (ITO), a flexible base material on which a conductive thin film is laminated, etc. may be mentioned. As a conductor thin film, ITO, copper, a copper-nickel alloy, silver etc. are mentioned, for example. As a material which comprises a flexible base material, a polyethylene terephthalate (PET) etc. are mentioned, for example.

The substrate used can be a form of copper wiring formed on a copper foil laminate, a form of a substrate made of only glass, or a transparent resin substrate formed with transparent electrodes (for example, ITO, Ag nanowire substrates, etc. ) or metal electrodes (for example, Cu, Al, Ag, Ni, Mo and alloys of at least two of these, etc.). Also, the substrate used may have through holes for corresponding to the multilayer substrate.

From the viewpoint of remarkably exerting the effects of the present invention, the substrate used is preferably a copper foil laminate substrate, more preferably a copper foil with a thickness of 35 μm, a thickness of 1.6 mm and a through hole with a diameter of 6 mm. Laminated substrates.

The photosensitive resin layer may be laminated on only one side of the surface of the substrate, or may be laminated on both sides of the substrate as required. The heating temperature during lamination is preferably 40°C to 160°C, more preferably 80°C to 120°C. The adhesiveness of the obtained photoresist pattern to the base material can also be improved by performing thermocompression bonding for two or more times. When performing pressure bonding two or more times, a two-stage laminator equipped with a double roller can be used, or the laminate of the base material and the photosensitive resin layer can be repeatedly passed through the rollers to perform pressure bonding.

(exposure step) The exposure process exposes the photosensitive resin layer using an exposure machine. This exposure is preferably performed after peeling the support from the photosensitive resin laminate from the viewpoint of the puncture strength of the obtained photoresist film. By performing this exposure in a pattern, a photoresist film (photoresist pattern) having a desired pattern can be obtained after undergoing the following development step. The pattern-like exposure can be performed by either a method of exposing through a mask or a method of exposure without a mask.

In the case of exposure through a mask, the exposure amount is determined by the illuminance of the light source and the exposure time. The exposure amount can be measured using a light meter. In the case of maskless exposure, exposure is performed on the substrate by a direct drawing device without using a mask. As the light source, a semiconductor laser with a wavelength of 350 nm to 410 nm, an ultra-high pressure mercury lamp, or the like can be used. In the case of maskless exposure, the drawing pattern can be controlled by a computer, and the exposure amount can be determined by the illuminance of the exposure light source and the moving speed of the substrate.

From the viewpoint of improving the resolution of the photoresist pattern, reducing the amount of side etching, or improving the yield of the photoresist or the wiring pattern, exposure through a mask is preferably performed.

(Development step) In the developing step, the non-patterned portion of the photosensitive resin layer is removed with a developing solution. In the developing step, a developer containing an alkaline aqueous solution is used, and in the case of using a negative-type photosensitive resin composition, a photoresist pattern is obtained by dissolving and removing the unexposed portion, and a positive-type photosensitive resin composition is used. In this case, a photoresist pattern is obtained by dissolving and removing the exposed portion.

As the alkaline aqueous solution, for example, an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like is preferably used. The alkaline aqueous solution can be selected according to the characteristics of the photosensitive resin composition layer, and it is preferable to use a Na ₂ CO ₃ aqueous solution having a concentration of 0.2 to 2 mass %. The alkaline aqueous solution can also be mixed with surfactants, defoaming agents, and a small amount of organic solvents for promoting development. The temperature of the developer in the developing step is preferably maintained at a fixed temperature in the range of 18°C to 40°C.

If necessary, a heating step may be performed after the developing step, and the heating step is to heat the obtained photoresist pattern at 100°C to 300°C. By performing this heating step, the chemical resistance of the photoresist pattern is sometimes improved. When heating, suitable heating furnaces such as hot air, infrared rays and far infrared rays can be used.

(etching or plating step) The wiring pattern can be formed on the substrate by performing etching or plating treatment on the substrate on which the photoresist pattern is formed after the photoresist pattern is formed by the above-described photoresist pattern forming method. From the viewpoint of remarkably exerting the effects of the present invention, it is preferable to perform at least the etching step.

The etching step can be performed according to a known etching method. For example, the etching solution is blown from above the photoresist pattern to etch the surface of the substrate that is not covered with the photoresist pattern. As an etching method, acid etching, alkaline etching, etc. are mentioned, and it can carry out by the method suitable for the photosensitive resin laminated body used. The etching solution can be, for example, an aqueous hydrochloric acid solution, an aqueous ferric chloride solution, or a mixture thereof. In addition, the etching liquid may be sprayed.

The plating step can be performed by metal plating (for example, copper sulfate plating solution) or solder plating on the surface of the substrate exposed by development according to a known plating method.

After the etching step and/or the plating step, the photosensitive resin laminate can be treated with an aqueous solution having a stronger alkalinity than the developer to peel the photoresist pattern from the substrate. The peeling liquid may be, for example, an aqueous solution of NaOH or KOH having a concentration of about 2% by mass to 5% by mass and a temperature of about 40°C to 70°C.

The evaluation values of the above-mentioned various parameters, unless otherwise specified, are the measured values measured according to the measurement methods in the examples described below.

As mentioned above, although embodiment of this invention was described, this invention is not limited to this, It can change suitably in the range which does not deviate from the summary of invention. [Example]

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

[One aspect of the present invention] <1. Preparation of photosensitive resin composition> A photosensitive resin composition was prepared by mixing a plurality of components according to the composition shown in Table 1 (wherein, the number of each component represents the compounding amount (parts by mass) in terms of solid content).

In addition, the name of each component, the solvent used, etc. which are represented by the abbreviations in Table 1 are shown in Table 2. In addition, the weight-average molecular weight (Mw) shown in Table 2 means that measured by gel permeation chromatography (GPC) using a calibration curve of polystyrene (Shodex STANDARD SM-105 manufactured by Showa Denko Co., Ltd.). The weight average molecular weight was obtained. The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be measured under the following conditions using a gel permeation chromatograph manufactured by JASCO Corporation. Differential Refractometer: RI-1530 Pump: PU-1580 Degasser: DG-980-50 Column oven: CO-1560 Column: KF-8025, KF-806M×2, KF-807 Elution solution: THF (Tetrahydrofuran, tetrahydrofuran)

<2. Manufacture of photosensitive resin laminate> Ethanol as a solvent was added to the photosensitive resin composition until the solid content reached 58% by mass, followed by stirring and mixing, and using a bar coater, the obtained solution of the photosensitive resin composition was uniformly applied to a thickness of 25 μm polyethylene terephthalate film (FB-40 manufactured by Toray; 16 μm polyethylene terephthalate film), and dried in a dryer at 95°C for 5 minutes to form a thickness 5 μm～25 μm photosensitive resin layer (dry film). Next, a polyethylene film (GF-858 manufactured by Tamapoly) with a thickness of 33 μm was bonded on the surface of the photosensitive resin layer to obtain a photosensitive resin laminate.

<3. Production of evaluation substrates>

＜Lamination＞ While peeling off the polyethylene film of the photosensitive resin laminate, the photosensitive resin laminate was laminated on the copper-coated laminate at a roll temperature of 105°C by a heating roll laminator (manufactured by Asahi Kasei Microdevices, AL-700). layer of PET substrate. The air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m/min.

<Exposure> From the laminated evaluation substrate, the polyethylene terephthalate film serving as the support of the photosensitive resin layer was peeled off, and the film was exposed by an exposure machine (parallel light exposure) with an ultra-high pressure mercury lamp using a chrome glass mask. The evaluation substrate was exposed at an exposure amount of 120 mJ/cm ² using a machine (manufactured by ORC MANUFACTURING Co., Ltd., HMW-801).

<Development> Using a developing device manufactured by Fujikiko Co., Ltd., the developed evaluation substrate was sprayed with a 1 mass % Na ₂ CO ₃ aqueous solution at 30° C. for a predetermined time using a solid cone nozzle at a spray pressure of 0.15 MPa, and the development was performed, and the development was carried out. The unexposed part of the photosensitive resin layer is dissolved and removed. At this time, the minimum time required to completely dissolve the photosensitive resin layer of the unexposed portion was measured as the minimum development time, and the photoresist pattern was produced by performing development at twice the minimum development time. At this time, the water washing step was performed using a flat nozzle with a water washing spray pressure of 0.15 MPa for the same time as the development step.

＜Etching＞ Using an etching apparatus manufactured by Fujikiko Co., Ltd., the evaluation substrate after development was carried out with an aqueous solution containing 2 mass % hydrochloric acid and 2 mass % ferric chloride at a spray pressure of 0.15 MPa and a temperature of 30° C. through a solid cone nozzle. Continue to etch for 60 seconds.

＜Peeling＞ Using a peeling device manufactured by Fujikiko Co., Ltd., the evaluation substrate after etching was continuously treated for 30 seconds with a spray pressure of 0.15 MPa and a temperature of 50° C. with an aqueous NaOH solution with a concentration of 3 mass %, and the self-evaluation substrate was Photoresist pattern lift-off removal.

<4. Evaluation method>

<Image evaluation> The evaluation substrate was obtained after 15 minutes after laminating the photosensitive resin laminate with the thickness of the photosensitive resin layer of 5 μm on the PET substrate with the copper layer by the method described in the above <Lamination>. This evaluation board|substrate was exposed to the chrome glass mask of the line pattern of the ratio of the width|variety of an exposure part. After that, development was performed for twice the minimum development time, and the minimum mask width in which the hardened photoresist lines were normally formed was used as the value of the resolution, and the resolution was graded as described below. Furthermore, the minimum mask width normally formed without the collapse of the hardened photoresist pattern or the close contact of the non-hardened photoresist with each other was evaluated. ◎ (remarkably good): the value of the resolution is 3 μm or less; ○ (good): the value of the resolution exceeds 3 μm and is 4 μm or less; × (defective): The value of the resolution exceeds 4 μm.

<Amount of side erosion (SE)> When evaluating the amount of side etching, the photosensitive resin laminate having a thickness of 5 μm of the photosensitive resin layer was laminated on the PET substrate with the copper layer by the method described in the above <Lamination>, and obtained after 15 minutes. Evaluate substrates. After the pattern of line/space = 10 μm/10 μm was exposed on the laminate evaluation substrate, development was performed by the method described in the above-mentioned <Development>. First, the photoresist top width Wr (μm) of the pattern was measured by an optical microscope. Next, the substrate with the line/space pattern was etched for 1.5 times the minimum etching time using an aqueous solution containing 2 mass % of hydrochloric acid and 2 mass % of ferric chloride at a concentration of 30° C. using a dipping method. Here, the minimum etching time refers to the minimum time required for the copper foil on the substrate to be completely dissolved and removed under the above conditions. After the above-mentioned etching, using a NaOH aqueous solution with a concentration of 3 mass % as a stripping solution, the cured film on the substrate was peeled off at a temperature of 50 ° C to obtain a copper wire pattern, and the top width Wc (μm) of the copper wire pattern was measured by an optical microscope. ). And, by the following formula: Side erosion (μm)＝(Wr－Wc)÷2 The undercut amount was calculated, and the undercut amount was graded as follows. ◎ (remarkably good): the amount of side erosion is 3 μm or less; ○ (good): the undercut amount exceeds 3 μm and is 3.5 μm or less; △ (qualified): the amount of side erosion exceeds 3.5 μm and is less than 4.0 μm; × (defective): The undercut amount exceeds 4.0 μm.

<Puncture Strength Evaluation> As a substrate for evaluation, a substrate obtained by forming 1,008 copper foil laminate substrates with a thickness of 1.6 mm of 35 μm copper foil by surface treatment using a sandblaster was used. The entire surface of the substrate with through-holes with a diameter of 6 mm is carried out. On the substrate after the entire surface, peel off the polyethylene film of the photosensitive resin laminate with a thickness of 25 μm of the photosensitive resin layer, and use a heating roll laminating machine (manufactured by Asahi Kasei Co., Ltd., AL-70 ) The photosensitive resin laminate was laminated on both sides of the full-surface substrate under the conditions of a roll temperature of 105° C., an air pressure of 0.35 MPa, and a lamination speed of 1.5 m/min. Using the substrate obtained after 15 minutes of lamination, the laminated substrate was exposed to an exposure amount of 120 using an exposure machine (parallel light exposure machine (manufactured by ORC MANUFACTURING Co., Ltd., HMW-801)) equipped with an ultra-high pressure mercury lamp. The evaluation substrate was exposed to mJ/cm ² , and then developed by the method described in the above-mentioned <Development>. The developed substrate was subjected to overnight humidity control in a room with a temperature of 25° C. and a humidity of 50%. After standing, peel off the polyethylene terephthalate film used as the support of the photosensitive resin layer from the obtained substrate, and from the surface of the peeled support at a speed of 100 mm/min and 6 mmϕ A portion of the photosensitive resin layer corresponding to the center of the hole was pierced into a cylinder of 2.0 mmϕ, and the maximum point load was measured by Tensilon (RTM-500 manufactured by Orientec). The maximum point load was measured at 10 points for the part of the photosensitive resin layer corresponding to the center of the through hole of 6 mmϕ, and the average value of the top 5 points among these was taken as the maximum point load of the puncture test. The obtained maximum point load was evaluated according to the following criteria. ◎ (remarkably good): puncture strength is 90 gf or more; ○ (good): puncture strength is 80 gf or more and less than 90 gf; △ (acceptable): puncture strength is 70 gf or more and less than 80 gf; × (bad) ): The puncture strength is less than 70 gf.

<Evaluation of copper (Cu) defects> When evaluating the amount of side etching, 15 minutes have elapsed after laminating a photosensitive resin laminate having a photosensitive resin layer thickness of 5 μm on a PET substrate with a copper layer by the method described in the above <Lamination>. evaluation substrate. This laminate evaluation substrate was exposed to a pattern of line/space = 10 μm/10 μm, and then developed by the method described in the above-mentioned <Development>. Next, the substrate with the line/space pattern was etched for 1.5 times the minimum etching time using an aqueous solution containing 2 mass % of hydrochloric acid and 2 mass % of ferric chloride at a concentration of 30° C. using a dipping method. Here, the so-called minimum etching time refers to the minimum time required for the copper foil on the substrate to be completely dissolved and removed under the above conditions. After the above-mentioned etching, the cured film on the substrate was peeled off and removed at a temperature of 50° C. using a NaOH aqueous solution with a concentration of 3 mass % as a stripping solution, and the obtained copper wire pattern was measured and observed by an optical microscope, as follows. General classification. ○: There is no defect in the copper wire pattern, and the linearity is high. ×: There is a defect in the copper wire pattern, and the linearity is low.

Table 1 also shows the evaluation results of Examples 1 to 13 and Comparative Examples 1 to 3. From the comparison of Examples 1 to 13 and Comparative Examples 1 to 3, it is considered that the photosensitive resin film having a puncture strength of 70 gf or more exhibits favorable results in suppressing copper (Cu) defects during etching.

[Table 1] Example Comparative example 1 2 3 4 5 6 7 8 9 10 11 12 13 1 2 3 Ingredient A-1 33 33 30 33 33 36 13 32 30 30 30 30 14 14 Ingredient A-2 10 10 7 10 10 17 9 7 56 twenty one twenty one Ingredient A-3 10 10 7 10 10 10 16 9 10 7 8 8 8 twenty one twenty one Ingredient A-4 36 Ingredient B-1 7 7 7 10 7 7 10 7 8 16 twenty four Ingredient B-2 9 9 9 9 9 9 8 9 9 9 8 16 9 twenty four Ingredient B-3 twenty four twenty four 16 twenty four twenty four 25 twenty three 18 25 28 25 25 25 28 35 twenty four Ingredient B-4 3 3 5 5 5 5 5 5 Ingredient B-5 3 3 Ingredient B-6 3 10 2 Ingredient B-7 7 Ingredient C-1 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Ingredient D-1 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Ingredient E-1 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 Ingredient F-1 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 Ingredient G-1 1 1 1 1 1 0.25 1 1 0.25 1 0.25 0.25 0.25 1 1 1 Number of double bonds (mmol/s) 1.98 1.98 2.53 1.98 2.08 2.05 2.07 2.38 2.05 1.66 2.50 3.01 2.00 1.46 0.92 3.24 Resolution ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ × ○ SE amount ○ ○ ◎ ○ ○ ○ ○ ○ ○ ○ ◎ ◎ ○ ○ △ ○ Puncture Strength (gf) ○ ◎ ◎ ○ ○ ◎ ◎ ◎ ◎ △ ◎ △ ◎ × × × Cu defects ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ × × ×

[Table 2] Ingredient Details Ingredient A-1 Alkali-soluble resin (methacrylic acid/methyl methacrylate/benzyl methacrylate=20/0.5/79.5, Mw=49,000) Ingredient A-2 Alkali-soluble resin (methacrylic acid/methyl methacrylate/styrene/butyl acrylate=25/10/60/5, Mw=20,000) Ingredient A-3 Alkali-soluble resin (methacrylic acid/styrene/benzyl methacrylate=25/25/50, Mw=45,000) Ingredient A-4 Alkali-soluble resin (methacrylic acid/methyl methacrylate/benzyl methacrylate=20/0.5/79.5, Mw=23,000) Ingredient B-1 Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (pentaacrylate ratio 10%, molecular weight=578, number of double bonds=5.9) Ingredient B-2 Dipentaerythritol hexamethacrylate (molecular weight = 1234, number of double bonds = 6.0) added to polyethylene glycol with an average of 13 mol of ethylene oxide Ingredient B-3 Dimethacrylate of polyethylene glycol obtained by adding an average of 5 mol of ethylene oxide to both ends of bisphenol A (molecular weight=804, number of double bonds=2.0) Ingredient B-4 Triacrylate obtained by adding an average of 3 mol of ethylene oxide to each of trimethylolpropane (molecular weight = 428, number of double bonds = 3.0) Ingredient B-5 ε-Caprolactone-modified tris(acryloyloxyethyl)isocyanurate (molecular weight=765, number of double bonds=3.0) Ingredient B-6 Dimethacrylate of polyethylene glycol obtained by adding an average of 1 mol of ethylene oxide to both ends of bisphenol A (molecular weight=452, number of double bonds=2.0) Ingredient B-7 Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (pentaacrylate ratio 30-40%) (molecular weight=578, number of double bonds=5.7) Ingredient C-1 Starter: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole Ingredient D-1 Sensitizer: 4,4'-bis(diethylamino)benzophenone Ingredient E-1 Color: Diamond Green Ingredient F-1 Polymerization inhibitor: triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] Ingredient G-1 Plasticizer: polyoxypropylene glycerol ether solvent Ethanol

[Another aspect of the present invention] <1. Preparation of photosensitive resin composition> The compounds shown in Tables 3 to 5 were mixed to prepare a photosensitive resin composition. The values in Tables 3 to 5 are the amount of solid content. In addition, Table 6 shows the name of each component, the solvent used, etc., which are represented by the abbreviations in Tables 3 to 5.

In addition, the acid value (acid equivalent) of the nonvolatile matter of the photosensitive resin composition is a value calculated from the value measured using NMR. In this Example, the photosensitive resin composition was dissolved in THF, and reprecipitation treatment was performed with n-hexane to separate the precipitate and the solution side, and the precipitate was dried. The obtained precipitate was dissolved in deuterated acetone, and ¹ H-NMR measurement was carried out. Calculate the integral value of each component in the precipitate according to the obtained area ratio of each component, and calculate the weight ratio (wt%) of methacrylic acid in the precipitate according to the following formula: Weight ratio of methacrylic acid=(methyl acrylic acid) Integral value of acrylic acid)/(Total integral value derived from precipitate components). Furthermore, the acid value of the non-volatile content of the photosensitive resin composition was calculated by the following formula: Acid value of the non-volatile content of the photosensitive resin composition = {(weight ratio of methacrylic acid × 1000 × 56/86) × precipitation weight}/weight of photosensitive resin composition dissolved in THF. The calculation method of the acid value (acid equivalent) of the said non-volatile component is an example when the acid component contained in alkali-soluble resin is methacrylic acid. On the other hand, when alkali-soluble resin contains an acid component different from methacrylic acid as an acid component, the acid value (acid equivalent) of the nonvolatile component of a photosensitive resin composition can also be measured according to the said calculation method.

<2. Manufacture of photosensitive resin laminate> The solvent acetone was added to the photosensitive resin composition until the solid content reached 58% by mass, and the mixture was sufficiently stirred and mixed, and the solution of the photosensitive resin composition was uniformly coated on a support film (supporting film) using a bar coater. body) on a polyethylene terephthalate film with a thickness of 25 μm (FB-40 manufactured by Toray; a polyethylene terephthalate film with a thickness of 16 μm), dried in a dryer at 95°C for 5 minutes, Then, a photosensitive resin layer (dry film) with a thickness of 1 to 20 μm is formed. Next, a polyethylene film (GF-858 manufactured by Tamapoly) with a thickness of 33 μm was bonded on the surface of the photosensitive resin layer to obtain a photosensitive resin laminate. The film thickness of the photosensitive resin layer was measured using a film thickness meter (ID-C112B, manufactured by Mitutoyo Corporation).

<3. Production of evaluation substrates> (laminated) While peeling off the polyethylene film of the photosensitive resin laminate, it was laminated on a PET substrate with a copper layer at a roll temperature of 105° C. by a heating roll laminator (manufactured by Asahi Kasei Microdevices, AL-700). The air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m/min.

(exposure) The support film was peeled off, and the evaluation substrate was exposed by an exposure machine (parallel light exposure machine (manufactured by ORC MANUFACTURING, HMW-801)) with an ultra-high pressure mercury lamp using a chrome glass mask.

(Development) A developing device manufactured by Fujikiko Co., Ltd. was used, and a solid cone nozzle was used to spray a 1 mass % Na ₂ CO ₃ aqueous solution at 23° C. for 30 seconds at a spray pressure of 0.15 MPa for development, and the unexposed part of the photosensitive resin layer was developed. dissolve and remove. At this time, the water washing step was treated with a flat nozzle at a water washing spray pressure of 0.15 MPa for the same time as the development step.

(etching) Using an etching device manufactured by Fujikiko Co., Ltd., etching was performed for 60 s using a solid cone nozzle under the conditions of a spray pressure of 0.15 MPa, a temperature of 30° C., a concentration of hydrochloric acid of 2% by mass, and a concentration of ferric chloride of 2% by mass.

(peel off) Using a peeling device manufactured by Fujikiko Co., Ltd., the solid cone nozzle was used to treat with a NaOH aqueous solution with a concentration of 3 mass % at a spray pressure of 0.15 MPa and a temperature of 50° C. for 30 s to perform peeling removal.

<4. Evaluation method> (pictorial) The evaluation substrate obtained by laminating a photosensitive resin laminate having a thickness of 1 to 20 μm in the photosensitive layer by the method described in the above (lamination) was passed through for 15 minutes and had a width of an exposed portion and an unexposed portion. A chrome glass mask with a line pattern in a 1:1 ratio was exposed. Then, it develops by the method described in the said (development), and produces a photoresist pattern.

The minimum mask width in which the hardened photoresist lines were normally formed was used as the value of the resolution, and the resolution was graded as described below. Furthermore, the collapse of the non-hardened photoresist pattern or the minimum mask width for which the non-hardened photoresists are in close contact with each other and normally formed was evaluated. ⊚: The value of the resolution is 2 μm or less. ○: The value of the resolution is 2 μm and 3 μm or less. ×: The value of the resolution exceeds 3 μm.

(Side Etch (SE) amount) When evaluating the amount of side etching, the evaluation was carried out 15 minutes after the photosensitive resin laminate with a thickness of 1 to 20 μm of the photosensitive resin layer was laminated on the PET substrate with the copper layer by the method described in the above (lamination). substrate. After the pattern of line/space = 10 μm/10 μm was exposed on the laminate evaluation substrate, development was performed by the method described in the above (Development). The photoresist top width Wr (μm) of the pattern produced was measured by an optical microscope.

Next, the substrate with the line/space pattern was etched for 1.5 times the minimum etching time using an immersion method with an aqueous solution containing 2 mass % of hydrochloric acid and 2 mass % of ferric chloride and a temperature of 30°C. Here, the minimum etching time refers to the minimum time required for the copper foil on the substrate to be completely dissolved and removed under the above conditions. After the above-mentioned etching, the cured film on the substrate was peeled off at a temperature of 50° C. using an aqueous NaOH solution with a concentration of 3% by mass as a stripping solution, and the top width Wc (μm) of the obtained copper wire pattern was measured by an optical microscope.

And, by the following formula: Side erosion (μm)＝(Wr－Wc)÷2 The undercut amount was calculated, and the undercut amount was graded as follows. ⊚ (remarkably good): The amount of side etching is 2.5 μm or less. ○ (good): The undercut amount exceeds 2.5 μm and is 3.0 μm or less. Δ (pass): The amount of side etching exceeds 3.0 μm and is 3.5 μm or less. × (defective): The undercut amount exceeds 3.5 μm.

(Evaluation of Copper (Cu) Defects) When evaluating the amount of side etching, a photosensitive resin laminate with a thickness of 1 to 20 μm of the photosensitive resin layer was used and laminated on the PET substrate with the copper layer by the method described in the above (lamination) for 15 minutes. evaluation substrate. This laminate evaluation substrate was exposed to a pattern of line/space=10 μm/10 μm, and then developed by the method described in the above (Development). Next, the substrate with the line/space pattern was etched for 1.5 times the minimum etching time using an aqueous solution containing 2 mass % of hydrochloric acid and 2 mass % of ferric chloride at a concentration of 30° C. using a dipping method. Here, the minimum etching time refers to the minimum time required for the copper foil on the substrate to be completely dissolved and removed under the above conditions.

After the above-mentioned etching, using a NaOH aqueous solution with a concentration of 3 mass % as a stripping solution, the cured film on the substrate was peeled and removed at a temperature of 50° C. to obtain a copper wire pattern, and the copper wire pattern was measured and observed with an optical microscope, and Ranking is performed as described below. ○: There is no defect in the copper wire pattern, and the linearity is high. △: There are some defects in the copper wire pattern, and the linearity is slightly lowered. ×: There are many defects in the copper wire pattern, and the linearity is lowered.

(minimum development time) By the method described in the above (lamination), a photosensitive resin laminate having a photosensitive layer having a thickness of 1 to 20 μm was laminated on a copper foil laminate substrate having a copper foil having a thickness of 18 μm and a thickness of 0.4 mm to obtain a laminate. body. After removing the support film laminated on the photosensitive layer, spray development was performed at 23° C. for a predetermined time using a 1.0 mass % sodium carbonate aqueous solution.

The surface of the substrate after development was observed, and the time when no development residue remained was regarded as the minimum development time, and the evaluation was performed according to the following criteria. ⊚ (remarkably good): The minimum development time is within 15 s. ○ (good): The minimum development time is within 20 s. △ (acceptable): The minimum development time is within 25 s. × (defective): The minimum development time is within 30 s.

(Development residue test of photosensitive layer) The photosensitive resin laminate having a thickness of 1 to 20 μm in the photosensitive layer was laminated on a copper foil having a thickness of 18 μm and a copper foil having a thickness of 0.4 mm by the method described in the above (lamination). onto a foil laminate substrate to obtain a laminate. Store at 60°C for 3 hours under _N2 environment. The stored substrate was taken out, and the support film laminated on the photosensitive layer was removed, and then spray development was performed at 23° C. with a 1.0 mass % sodium carbonate aqueous solution and minimum development time×1.2 times. The surface of the substrate after development was observed, and the development residue was evaluated as follows. ○: There is no development residue on the substrate surface. Δ: A small amount of development residue was generated on the surface of the substrate. ×: Development residues are generated on the surface of the substrate.

Table 3 - Table 5 show the composition of the photosensitive resin composition and the evaluation results about the layered product for each Example and Comparative Example. In addition, Table 6 shows the name of each component, the solvent used, etc., which are represented by the abbreviations in Tables 3 to 5.

[table 3] Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Ingredient A-1 20 20 20 20 20 20 20 20 20 20 20 Ingredient A-2 Ingredient A-3 20 20 20 20 20 20 20 20 20 20 20 Ingredient A-4 Ingredient A-5 Ingredient A-6 Ingredient B-1 7 7 7 7 7 7 7 7 7 7 7 Ingredient B-2 10 10 10 10 10 10 10 10 10 10 10 Ingredient B-3 10 10 10 10 10 10 10 10 10 10 10 Ingredient B-4 Ingredient B-5 Ingredient B-6 3 3 3 3 3 3 3 3 3 3 Ingredient B-7 Ingredient C-1 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Ingredient D-1 12 12 12 6 3 12 12 12 Ingredient D-2 12 Ingredient D-3 12 Ingredient D-4 12 Ingredient E-1 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 Ingredient E-2 Ingredient F-1 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 Ingredient G-1 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 Ingredient H-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Acid value (mgKOH/g) 71 68.5 68.5 73.6 76.5 68.5 68.5 68.5 68.5 68.5 68.5 Film thickness (μm) 5 5 5 5 5 3 1 7 5 5 5 Acid value/film thickness 14.2 13.7 13.7 14.7 15.3 22.8 68.5 9.8 13.7 13.7 13.7 Minimum development time △ ○ ○ ◎ ◎ ◎ ◎ △ ○ ◎ ◎ Resolution ◎ ◎ ◎ ◎ ○ ◎ ◎ ○ ◎ ◎ ◎ SE ◎ ◎ ◎ ○ ○ ◎ ○ ◎ ○ ○ ○ Cu defects ○ ○ ○ △ △ ○ ○ ○ ○ △ △ Development residue test ○ ○ △ ○ ○ ○ ○ ○ ○ ○ ○

[Table 4] Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 Example 35 Ingredient A-1 20 20 20 20 20 20 20 20 20 20 30 Ingredient A-2 20 Ingredient A-3 20 20 20 20 20 20 30 Ingredient A-4 20 Ingredient A-5 20 Ingredient A-6 20 Ingredient B-1 7 7 7 7 7 7 7 7 7 7 Ingredient B-2 10 10 10 10 10 10 10 10 10 10 10 Ingredient B-3 10 10 10 10 10 10 10 10 10 10 10 Ingredient B-4 7 Guard B-5 3 Ingredient B-6 3 3 3 3 3 3 3 3 3 Ingredient B-7 3 Ingredient C-1 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Ingredient D-1 12 12 12 12 12 12 12 12 12 12 12 Ingredient D-2 Ingredient D-3 Ingredient D-4 Ingredient E-1 0.01 0.01 0.01 0.01 0.07 0.01 0.01 0.01 0.01 Should be graded E-2 0.01 Ingredient F-1 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 Ingredient G-1 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 Ingredient H-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Acid value (mgKOH/g) 68.5 60.8 63.8 73.9 68.4 68.5 68.5 68.5 68.5 68.5 83.3 Film thickness (μm) 5 5 5 5 5 5 5 5 5 5 5 Acid value/film thickness 13.7 12.2 12.8 14.8 13.7 13.7 13.7 13.7 13.7 13.7 16.7 Minimum development time ◎ ◎ ○ ◎ ○ ○ ○ ◎ ○ ○ ◎ Resolution ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ ○ ○ SE ◎ ◎ ◎ ◎ ○ ○ ○ ○ ◎ ◎ ○ Cu defects ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Development residue test ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

[table 5] Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Ingredient A-1 20 20 40 40 40 Ingredient A-2 Ingredient A-3 20 20 40 40 40 Ingredient A-4 Ingredient A-5 Ingredient A-6 Ingredient B-1 7 7 7 7 7 Ingredient B-2 10 10 10 10 10 Ingredient B-3 10 10 10 twenty two 10 Ingredient B-4 Ingredient B-5 Ingredient B-6 3 3 3 3 3 Ingredient B-7 Ingredient C-1 2.5 2.5 2.5 2.5 2.5 Ingredient D-1 12 12 12 12 Ingredient D-2 Ingredient D-3 Ingredient D-4 Ingredient E-1 0.01 0.01 0.01 0.01 0.01 Ingredient E-2 Ingredient F-1 0.08 0.08 0.08 0.08 0.08 Ingredient G-1 0.14 0.14 0.14 0.14 0.14 Ingredient H-1 0.1 0.1 0.1 0.1 0.1 Acid value (mgKOH/g) 68.5 68.5 93.3 93.3 93.3 Film thickness (μm) 20 15 20 20 1 Acid value/film thickness 3.4 4.6 4.7 4.7 93 Minimum development time × × × △ ◎ Resolution - - - × O SE - - - × × Cu defects - - - × × Development residue test - - - ○ ○

[Table 6] Ingredient Details Ingredient A-1 Alkali-soluble resin (methacrylic acid/methyl methacrylate/benzyl methacrylate=20/0.5/79.5, Mw=49,000), acid value=130 mgKOH/g Ingredient A-2 Alkali-soluble resin (methacrylic acid/methyl methacrylate/styrene/butyl acrylate=25/10/60/5, Mw=20,000), acid value=163 mgKOH/g Ingredient A-3 Alkali-soluble resin (methacrylic acid/styrene/benzyl methacrylate=25/25/50, Mw=45,000), acid value=163 mgKOH/g Ingredient A-4 Alkali-soluble resin (methacrylic acid/methyl methacrylate/benzyl methacrylate=20/0.5/79.5, Mw=23,000), acid value=130 mgKOH/g Ingredient A-5 Alkali-soluble resin (methacrylic acid/benzyl methacrylate/cyclohexyl methacrylate=22/28/50, Mw=50,000), acid value=143 mgKOH/g Ingredient A-6 Alkali-soluble resin (acrylic acid/butyl acrylate/2-ethylhexyl acrylate/styrene/cyclohexyl methacrylate=24/0.1/0.1/73/2.8, Mw=33,000), acid value=186 mgKOH/g Ingredient B-1 Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (pentaacrylate ratio 10%) (MA-DPH) Ingredient B-2 Polyethylene glycol dimethacrylate (MSR-348) obtained by adding an average of 1 mol of ethylene oxide to each end of bisphenol A Ingredient B-3 Polyethylene glycol dimethacrylate (MFEM-10) obtained by adding an average of 5 mol of ethylene oxide to both ends of bisphenol A Ingredient B-4 Polyethylene glycol hexamethacrylate (M-13MDP) by adding an average of 13 mol of ethylene oxide Ingredient B-5 ε-Caprolactone-modified tris(acrylooxyethyl)isocyanurate (M-1683) Ingredient B-6 Tetramethacrylate obtained by adding an average of 15 mol of ethylene oxide to the end of the 4 hydroxyl groups of pentaerythritol Ingredient B-7 It is formed by adding an average of 9 mol of ethylene oxide to the end of the 4 hydroxyl groups of pentaerythritol. Ingredient C-1 IL-2: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole Ingredient D-1 FA-PTG28M polytetramethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name), molecular weight 2170 Ingredient D-2 PTMG-2000: Polytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, product name), molecular weight 2034 Ingredient D-3 FA-PTG9M: Polytetramethylene glycol dimethacrylate (manufactured by Hitachi Chemical Co., Ltd., product name), molecular weight 802 Ingredient D-4 A-PTMG65: Polytetramethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name), molecular weight 758 Ingredient E-1 1-(Dibutylamino)methyl-1H-benzotriazole-5-carboxylic acid Ingredient E-2 Carboxybenzotriazole Ingredient E-3 1-[Bis(2-ethylhexyl)aminoethyl]benzotriazole Ingredient F-1 Sensitizer: IEA: 4,4'-bis(diethylamino)benzophenone Ingredient G-1 Pigment DGH: Diamond Green Ingredient H-1 Polymerization inhibitor S-245: Triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] solvent Ethanol

As can be seen from the table, in Comparative Examples 4 to 7 in which the ratio (A/T) of the acid value A and the thickness T was less than 5, the minimum development time and the resolution were insufficient. In addition, when the film thickness was 20 μm and 15 μm, the developing time was 30 seconds or more and the developability was poor, so other items could not be evaluated. On the other hand, in Comparative Example 8 in which the ratio (A/T) was more than 90, the acid value was high and PTMG (Polytetramethylene glycol, polytetramethylene glycol) was removed, and development was possible, but since the acid value was high and PTMG was removed, Therefore, Cu defects, resolution, and side etching (SE) are insufficient. In particular, in the case of a thick film, by setting the acid value to 90 mgKOH/g or more, the resolution is relatively good, but when it is a thin film, the resolution tends to be deteriorated. On the other hand, in the examples in which the ratio of acid value A to thickness T (A/T) was 5 or more and 90 or less, the results were obtained in any of the minimum development time, resolution, side etching, Cu defects and development residue tests. sufficient good results. [Industrial Availability]

The photosensitive resin composition, the photosensitive resin laminate, and the dry film resist of the present invention can suppress the defects of the pattern formed by using them, so that the yield of the object or pattern formed by the photolithography method can be improved. , and/or excellent in lamination, minimum development time, resolution, side etch (SE) amount, Cu defects, and development residue, and can be widely used in the formation of photoresist patterns or wiring patterns.

Claims (7)

A photosensitive resin laminate, characterized in that it has a support and a photosensitive resin composition layer formed on the support using a photosensitive resin composition, the photosensitive resin composition comprising (A) a main Alkali-soluble resin containing no ethylenically unsaturated group in the chain, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator; and When the acid value of the nonvolatile component of the photosensitive resin composition is A [mgKOH/g], and the thickness of the photosensitive resin composition layer is T [μm], the acid value A and the thickness T are The ratio (A/T) is 5 or more and 90 or less. The photosensitive resin laminate according to claim 1, wherein the photosensitive resin composition further contains, as the component (D), a compound having polytetramethylene oxide as a structural unit. The photosensitive resin laminated body of Claim 1 or 2 whose said photosensitive resin composition further contains the compound which has a benzotriazole skeleton as (E) component. The photosensitive resin laminate according to claim 1 or 2, wherein the photosensitive resin composition has, as the component (B), a photopolymerizable compound containing a tetrafunctional or more ethylenically unsaturated bond. The photosensitive resin laminate according to claim 2, wherein the ratio of the above-mentioned (A) component to the sum of the above-mentioned (B) component and the above-mentioned (D) component is [(A) component/((B) component + (D) component) ] exceeds 0 and is 1.4 or less. The photosensitive resin laminated body of Claim 1 or 2 whose weight average molecular weight of the said (A) component is 20,000 or more. The photosensitive resin laminate according to claim 1 or 2, wherein the acid value (acid equivalent) of the nonvolatile component of the photosensitive resin composition exceeds 0 and is 79.0 or less.