TW202129416A - Photosensitive resin composition and transfer film using photosensitive resin composition in which a dry film photoresist is provided and comprising a support film and a photosensitive resin composition layer on the support film - 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 photoresist pattern forming method, a wiring pattern forming method, and the like.

In the past, the manufacture of printed wiring boards and the precision processing of metals have been carried out by photolithography. The photosensitive resin composition used in the photolithography method is classified into a negative composition that dissolves and removes the unexposed part, and a positive composition that dissolves and removes the exposed part.

It can be used when the photosensitive resin composition is coated on the substrate in the photolithography method (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 "photosensitive resin layer"), and a protective layer as needed are sequentially laminated, the photosensitive resin Method for laminating flexible resin on substrate Any of them. 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 is briefly described below. First, the protective layer is peeled off from the photosensitive resin laminate. Then, a laminating machine is used to apply the photosensitive resin layer and the supporting volume layer on the substrate such as the copper foil laminated board and the copper sputtered film in order to become the substrate, the photosensitive resin layer, and the support in this order. Then, the photosensitive resin layer is exposed via a photomask having a desired wiring pattern. Then, the support is peeled off from the laminated body after exposure, and then the non-patterned part is dissolved or dispersed by the developer, thereby forming a photoresist pattern on the substrate.

Furthermore, the substrate provided with the photoresist pattern is subjected to etching treatment, copper plating, tin-lead plating, and other plating treatments, whereby wiring patterns can also be obtained.

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

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

In Patent Document 2, for the projection exposure method, the adhesion, the resolution of the photoresist pattern, and the suppression of the generation of the photoresist edge are discussed.

For example, Patent Document 3 to Patent Document 5 disclose a photosensitive resin composition, which contains a compound having polytetramethylene oxide as a structural unit, so that a photoresist pattern can be formed even with a low exposure amount, and the formed The cured film has excellent shielding reliability and etching resistance. In addition, Patent Document 6 discloses a photosensitive resin composition that contains a compound having polyalkylene oxide as a structural unit, and can form a photoresist pattern even with a low exposure amount, and the cured film formed It has excellent shielding reliability and etching resistance. [Prior Technical 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

[The problem to be solved by the invention]

The photolithography method using the photosensitive resin composition is still required to improve the yield of the object or pattern formed by it.

In addition, the prior photosensitive resin composition has not obtained sufficient characteristics in terms of laminating properties, minimum development time, resolution, undercut (SE) amount, Cu defects, and development residue. Furthermore, there are combinations of these characteristics that are considered to be difficult to balance, and it is therefore desired to achieve a balance of various characteristics.

In view of the above, the object of the present invention is to provide a photosensitive resin composition that can improve the yield of objects or patterns formed by photolithography, and a photosensitive resin laminate and photoresist or wiring patterns using the photosensitive resin composition The formation method, and/or provide a photosensitive resin laminate that is excellent in at least one of laminating properties, minimum development time, resolution, undercut (SE) amount, Cu defects, and development residue. [Technical means to solve the problem]

The inventors of the present invention made diligent studies to solve the above-mentioned problems, and 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 non-volatile component of the photosensitive resin composition and the thickness of the photosensitive resin layer, the above-mentioned problem can be solved.

The following is an example of one aspect of the present invention. (1) A dry film photoresist, which has Support film, and A layer formed on the support film and containing a photosensitive resin composition, the photosensitive resin composition containing (A) Alkali-soluble resin, (B) Photopolymerizable compounds with ethylenically unsaturated bonds, (C) photopolymerization initiator, and (D) Dyes; The weight average molecular weight of the above component (A) calculated by gel permeation chromatography (GPC) on the above component (A) and calculated using the calibration curve of polystyrene is below 60,000, and The above-mentioned 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: a photosensitive resin layer containing the photosensitive resin composition is laminated on a support with a thickness of 25 μm. The photosensitive resin laminate is formed by laminating the photosensitive resin laminate on a copper foil laminate substrate with a thickness of 35 μm, a thickness of 1.6 mm and a through hole of 6 mm in diameter, and exposure and development. After the cured film, the support was peeled off from the cured film, and the surface of the support was peeled off at a speed of 100 mm/min to pierce the part of the photosensitive resin layer corresponding to the center of the through hole with a diameter of 2.0 mm The cylinder. (2) The dry film resist according to item 1, wherein the number of double bonds of 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 photoresist according to item 1, wherein the photosensitive resin composition contains a trifunctional or higher multifunctional monomer as the (B) component. (4) The dry film photoresist 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 epoxy alkyl group The compound as the above-mentioned (B) component. (5) The dry film photoresist as described in item 4, wherein the photosensitive resin composition further contains (B-iii) a (meth)acrylate compound having a skeleton derived from bisphenol as the bifunctional monomer. (B) Ingredients. (6) The dry film photoresist according to any one of items 1 to 5, wherein the photosensitive resin composition further contains a plasticizer. (7) The dry film photoresist according to any one of items 1 to 6, which contains a leuco dye as the dye. (8) The dry film photoresist described in any one of items 1 to 7, wherein the above-mentioned maximum point load does not reach 250 gf. (9) A dry film photoresist, which has a supporting film, and A layer formed on the support film and containing a photosensitive resin composition, the photosensitive resin composition containing (A) Alkali-soluble resin, (B) Photopolymerizable compounds having ethylenically unsaturated bonds, and (C) Photopolymerization initiator; and The above-mentioned photosensitive resin composition contains (B-ii) as a multifunctional monomer with three or more functions, a compound having a skeleton derived from dipentaerythritol but not containing an alkylene oxide group, and (B-iii) which is a bifunctional monomer, has a (meth)acrylate compound derived from a bisphenol skeleton as the (B) component. (10) The dry film photoresist as described in item 9, wherein the ratio of (B-ii)/(B-iii) above is 10 to 80% by mass. (11) The dry film photoresist as described in item 9 or 10, wherein the ratio of the above (B-ii) and the above (B-iii) in the above (B) component is 50% by mass or more. (12) The dry film photoresist according to any one of items 9 to 11, which further contains (Bi) a (meth)acrylate compound having a skeleton derived from dipentaerythritol and containing an epoxy group as the above (B) Element. (13) The dry film photoresist according to any one of items 9 to 12, wherein the above component (A) is measured by gel permeation chromatography (GPC) and calculated using a calibration curve of polystyrene The weight average molecular weight of the component (A) is 60,000 or less. (14) The dry film photoresist 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 the following puncture test is performed: on the support A photosensitive resin layer containing the photosensitive resin composition was laminated with a thickness of 25 μm to produce a photosensitive resin laminate, and the photosensitive resin laminate was laminated on a copper foil with a thickness of 35 μm and a thickness of 1.6 mm. A cured film is formed on a copper foil laminate substrate with a through hole of 6 mm in diameter, and exposed and developed to form a cured film. After that, the support is peeled off from the cured film, and the surface of the support is peeled off at a speed of 100 mm/min Pierce a cylinder with a diameter of 2.0 mm to a part of the photosensitive resin layer corresponding to the center of the through hole. (15) The dry film photoresist according to any one of items 9 to 14, wherein the number of double bonds of 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 photoresist according to any one of items 9 to 15, wherein the photosensitive resin composition further contains a plasticizer. (17) The dry film photoresist according to any one of items 9 to 16, which contains a leuco dye as the dye. (18) The dry film photoresist according to any one of items 9 to 17, wherein the above-mentioned maximum point load does not reach 250 gf. (19) A method for forming a photoresist pattern, which includes the following steps: Laminating the dry film photoresist as described in any one of items 1 to 18 on the substrate; Expose the laminated dry film photoresist; and The exposed dry film photoresist is developed. (20) A method for forming a wiring pattern, which includes the following steps: Laminating the dry film photoresist as described in any one of items 1 to 18 on the substrate; Expose the laminated dry film photoresist; Developing the exposed dry film photoresist to form a photoresist pattern; and The substrate on which the photoresist pattern has been formed is etched or plated.

The following illustrates another aspect of the present invention. (21) 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) Alkali-soluble resins that do not contain ethylenic unsaturated groups in the main chain, (B) photopolymerizable compounds having ethylenic unsaturated bonds, and (C) photopolymerization initiators; 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 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 polyoxytetramethylene oxide as a structural unit as the (D) component. (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 (E) component. (24) The photosensitive resin laminate according to any one of items 21 to 23, wherein the photosensitive resin composition has a photopolymerizable compound containing an ethylenically unsaturated bond having tetrafunctional or higher functions as the (B) component. (25) The photosensitive resin laminate according to item 22, wherein the ratio of the above-mentioned (A) component to the total of the above-mentioned (B) component and the above-mentioned (D) component [(A) component/((B) component + ( D) component)] more than 0 and 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 non-volatile component of the photosensitive resin composition exceeds 0 and is 79.0 or less. [Effects of Invention]

According to the present invention, defects in patterns formed by using the photosensitive resin composition can be suppressed, and therefore it is possible to provide an object or pattern that can be formed by photolithography with improved yield and/or lamination properties, minimum development time, A photosensitive resin laminate that is excellent in at least one of resolution, undercut (SE), Cu defects, and development residue.

Hereinafter, the form (hereinafter, abbreviated as "embodiment") for implementing the present invention will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist.

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

[An 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) Photopolymerizable compounds having ethylenically unsaturated bonds, and (C) Photopolymerization initiator. The photosensitive resin composition may contain (D) dye in addition to (A) to (C) components as needed, and may contain plasticizers, antioxidants, stabilizers, and the like.

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

(Puncture test) Prepare: support; photosensitive resin composition; copper foil laminated substrate with 35 μm thick copper foil, 1.6 mm thick copper foil with a diameter (ϕ) 6 mm through hole. A photosensitive resin layer containing a photosensitive resin composition was laminated on a support with a thickness of 25 μm to produce a photosensitive resin laminate. The photosensitive resin laminate was laminated on a copper foil laminate substrate and exposed and developed to form a cured film After that, the support is peeled off from the cured film, and the part of the photosensitive resin layer corresponding to the center of the through hole is peeled off from the surface of the support to pierce a cylinder with a diameter (ϕ) of 2.0 mm at a speed of 100 mm/min.

In the first embodiment, if the maximum point load of the cured film measured during 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 amount of side etching and the peelability are good, and the defects of the pattern can be suppressed. Therefore, the yield of the object or pattern formed by the photolithography method tends to be improved. Furthermore, a more specific method of 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 during the puncture test is related to the defects of the metal substrate, but they hope that they are not bound by theory. In the first embodiment, the maximum point load of 70 gf or more in the puncture test was found as a method for suppressing defects in objects or wiring patterns formed by the photolithography method using the photosensitive resin composition to improve yield One indicator. Regarding the maximum point load during the puncture test, from the viewpoint of further improving the yield, it is preferably 74 gf or more or 78 gf or more, and more preferably 85 gf or more. In addition, regarding the upper limit of the maximum point load during the puncture test, it is clear based on common knowledge in this technical field that the higher the better, for example, it may be less than 250 gf or less than 245 gf.

Regarding the maximum point load during the puncture test, for example, the composition of the photosensitive resin composition can be optimized, or multiple components can be used as the (B) component in the photosensitive resin composition, or two or more components can be formulated Or three or more ingredients, or optimize the type and blending ratio, and adjust to the numerical range described above.

Regarding the photosensitive resin composition of the first embodiment, from the viewpoints of improving the resolution, side etching, and peeling properties of the photoresist pattern, and suppressing pattern defects, it is preferable to include a trifunctional or higher multifunctional monomer and/ Or a bifunctional monomer is used as the (B) component. From the same point of view, as a multifunctional monomer with three or more functions, (B-ii) a compound having a skeleton derived from dipentaerythritol but not containing an alkylene oxide group is preferred, and as a bifunctional monomer, it is more Preferably (B-iii) a (meth)acrylate compound having a skeleton derived from bisphenol.

<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 epoxy alkyl groups As the above-mentioned (B) component.

If the photosensitive resin composition of the second embodiment contains both of the (Bi) component and (B-ii) as the (B) component, a photoresist formed by the photolithography method using the photosensitive resin composition The pattern resolution, undercut amount, puncture strength and peelability are good, which can suppress pattern defects, so there is a tendency to increase the yield of objects or patterns formed by photolithography.

<The third embodiment> The photosensitive resin composition of the third embodiment is characterized in that the component (B) contains: (B-ii) as a multifunctional monomer with three or more functions, a compound having a skeleton derived from dipentaerythritol but not containing an alkylene oxide group, and (B-iii) which is a bifunctional monomer has a (meth)acrylate compound derived from a bisphenol skeleton.

If the photosensitive resin composition of the third embodiment contains both of the component (B-ii) which is a trifunctional or higher polyfunctional monomer and the component (B-iii) which is a bifunctional monomer as the component (B) , The photoresist pattern formed by the photolithography method using the photosensitive resin composition has good resolution, side etching, puncture strength, and peelability, and can suppress pattern defects. Therefore, the photolithography method is used for The tendency of the yield rate of the formed object or pattern to increase.

Regarding the photosensitive resin composition of the third embodiment, from the viewpoint of improving the resolution, undercutting amount, puncture strength, and peelability of the photoresist pattern, and suppressing pattern defects, the component (B-ii)/( The ratio of the B-iii) component is 10 to 80% by mass, and/or it is preferable that the ratio of the (B-ii) component and the (B-iii) component is 50% by mass or more among the (B) components. From the same viewpoint, the (B) component of the third embodiment preferably contains the above-described (B-i) component in addition to the (B-ii) component and (B-iii) component.

The above-described features of the first, second, and third embodiments can be combined or interchanged. The photosensitive resin composition 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 for touch panels, etc., and is preferably used for Etching of substrates such as copper foil laminates and copper sputtered 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) Alkali-soluble resins are polymers that can be dissolved in alkaline solutions. In addition, (A) the alkali-soluble resin preferably has a carboxyl group, more preferably has an acid equivalent of 100 to 600, and further preferably a copolymer containing a carboxyl group-containing monomer as a copolymerization component. Furthermore, (A) alkali-soluble resin may be thermoplastic.

(A) The acid equivalent of the alkali-soluble resin is preferably 100 or more from the viewpoint 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. In addition, the acid equivalent of (A) alkali-soluble resin is more preferably 200-500, and still more preferably 250-450. Furthermore, in one aspect of the present invention, the acid equivalent refers to the mass (gram) of a polymer having 1 equivalent of carboxyl group in the molecule. For example, an automatic titration device can be used, and a 0.1 mol/L sodium hydroxide aqueous solution can be used. Measured 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 is preferably represented by the following formula (I): [Number 1]

{Where, W _i is the mass of each of the comonomers constituting the alkali-soluble resin, Tg _i is the glass transition temperature when each of the comonomers constituting the alkali-soluble resin is a homopolymer, and W _total is the alkali soluble The total mass of the resin, and n is the number of the types of comonomers constituting the alkali-soluble resin} The calculated glass transition temperature (Tg _total ) is 100°C or less. In the case of using a mixture of plural kinds of polymers as (A) alkali-soluble resin, the glass transition temperature is a value determined in the form of the average value of all polymers.

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

The Tg _{i of} representative comonomers are as follows (all are 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 of the glass transition temperature (Tg _total ) as described above is preferably a copolymer of acid monomers and other monomers.

There is no particular limitation on the lower limit _{of the glass transition temperature (Tg total} ) of (A) alkali-soluble resin determined by the above-mentioned 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 component (A) calculated by measuring at least component (A) by gel permeation chromatography (GPC) and using a calibration curve of polystyrene The average molecular weight (Mw) is 60,000 or less. (A) The Mw of the alkali-soluble resin is preferably 60,000 or less from the viewpoint of solubility in the developer. On the other hand, for the maintenance of the uniform thickness of photosensitive resin laminates such as dry film photoresist From the viewpoints of, viscosity, edge meltability, slicing property, etc., it is preferably 5,000 or more. From this viewpoint, the Mw of (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 degree of dispersion (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. In addition, (A) the alkali-soluble resin 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. The first monomer may, for example, be (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like. Among them, (meth)acrylic acid is particularly preferred.

The second monomer system is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. As the second monomer, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid may be mentioned. N-butyl ester, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid Cyclohexyl, 2-ethylhexyl (meth)acrylate, and benzyl (meth)acrylate; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile, styrene, and polymerizable Styrene derivatives (for example, methyl styrene, vinyl toluene, tertiary butoxy styrene, acetoxy styrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer, etc. )Wait. Among these, preferred are methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, and benzyl (meth)acrylate.

In addition, from the viewpoint of improving the resolution of the photoresist pattern, (A) the alkali-soluble resin preferably has an aromatic group in the side chain of its structure.

The (A) alkali-soluble resin having an aromatic group in a side chain can be prepared by using a compound having an aromatic group as the first monomer and/or second monomer. Examples of monomers having aromatic groups include: benzyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, styrene, cinnamic acid, and polymerizable styrene derivatives (For example, 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.

(A) Alkali-soluble resin 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.

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

{式中，R₁₀ 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) Photopolymerizable compound having an ethylenically unsaturated group> (B) The photopolymerizable compound having an ethylenically unsaturated group is a compound having polymerizable properties by having an ethylenically unsaturated group in its structure. In the first, second, and third embodiments, the photosensitive resin composition preferably contains a (meth)acrylate compound as the (B) component, 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): [化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 the general formula (II), the number of (meth)acrylic groups in a molecule is 4 or more from the viewpoint of obtaining sufficient cured film strength, resist shape, and resolution, which is preferable It is 5 or 6. The alkylene oxide modified (meth)acrylic acid group as the group R _{10 has been} modified, for example, by at least one member selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide, preferably To be modified by ethylene oxide and/or propylene oxide, specifically, it can be -(C ₂ H ₄ O) _m -CO-CR=CH ₂ {where R represents a hydrogen atom Or methyl, m is an integer from 1 to 30}, -(C ₃ H ₆ O) _n -CO-CR=CH ₂ {where 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 {In the formula, R represents a hydrogen atom or a methyl group, m is an integer from 1 to 30, and n is from 1 to 30 The arrangement of (C ₂ H ₄ O) _m and (C ₃ H ₆ O) _n can be alternating, random, or block).

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 having a skeleton derived from dipentaerythritol but not containing an epoxy group is used as the (B) component.

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

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

In the first and second embodiments, the photosensitive resin composition preferably contains (B- iii) A (meth)acrylate compound having a skeleton derived from bisphenol and containing an epoxy group (except for the (Bi) component).

Regarding the photosensitive resin composition of the first embodiment, it is preferable to include ( 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, it is preferable to remove the (B-ii) component and ( B-iii) In addition to the component, the component (Bi) is further included.

In the photosensitive resin composition, the mass ratio of the component (B-iii) to the total mass of the component (Bi) and the component (B-ii) is based on the point of view 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.

(Bi) The (meth)acrylate compound having a skeleton derived from dipentaerythritol and containing an alkylene oxide 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 acryl-based compound preferably has 5 and/or 6 epoxy resins in the general formula (II). Alkyl modified (meth)acrylic compound.

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), the alkylene oxide modification (methyl) _{as the base 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, pentane oxide and hexane oxide, more preferably Modified by ethylene oxide and/or modified by propylene oxide, more preferably -(C ₂ H ₄ O) _m -CO-CR=CH ₂ {where R represents a hydrogen atom or a methyl group, and m is An integer of 1-30}, -(C ₃ H ₆ O) _n -CO-CR=CH ₂ {where R represents a hydrogen atom or a methyl group, and n is an integer of 1-30}, or -(C ₂ H ₄ O) _m -(C ₃ H ₆ O) _n -CO-CR=CH ₂ {where 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 Here, R represents a hydrogen atom or a methyl group, and m is an integer of 1-30}. From the same viewpoint, in the general formula (II), the repetition number m of ethylene oxide and the repetition number n of propylene oxide are respectively preferably 3-27, more preferably 6-21, and more It is preferably in the range of 9-16.

As a specific example of the component (B-i), one can cite: • Dipentaerythritol tetra(meth)acrylate, polyethylene glycol with an average addition of 3-27 mol of ethylene oxide, • Dipentaerythritol penta(meth)acrylate, polyethylene glycol with an average addition of 3-27 mol of ethylene oxide, • Dipentaerythritol hexa(meth)acrylate, polyethylene glycol with an average addition of 3-27 mol of ethylene oxide, • Dipentaerythritol tetra(meth)acrylate, polyethylene glycol with an average addition of 3-27 mol of propylene oxide, • Dipentaerythritol penta(meth)acrylate, polyethylene glycol with an average addition of 3-27 mol of propylene oxide, • Dipentaerythritol hexa(meth)acrylate, polyethylene glycol with an average addition of 3-27 mol of propylene oxide, • Alternate, random or block addition of polyethylene glycol dipentaerythritol four, five or six ( Meth)acrylate, • Combinations of the above-exemplified compounds, etc. Among them, from the viewpoints of the resolution, the amount of side etching, the puncture strength and the peelability of the photoresist cured film, the suppression of pattern defects, and the improvement of the yield, it is preferable to add an average of 12-15 mol of ethylene oxide Dipentaerythritol hexamethacrylate of polyethylene glycol.

(B-ii) The compound having a skeleton derived from dipentaerythritol but not containing alkylene oxide can be dipentaerythritol mono or poly(meth)acrylate that has not been modified by alkylene oxide to obtain sufficient cured film strength, From the viewpoint of photoresist shape and resolution, dipentaerythritol poly(meth)acrylate that has not been modified with alkylene oxide is preferred.

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), as far as the maximum point load of the puncture test or the puncture strength of the photoresist cured film the viewpoint, preferably having 4 or more as R (meth) Bing Xixi group of _10, more preferably having 5 or 6.

When using five (meth)acrylates with 5 (meth)acrylic groups and six (meth)acrylates with 6 (meth)acrylic groups as the component (B-ii) In terms of the maximum point load of the puncture test or the puncture strength of the photoresist cured film, the mass ratio of the penta(meth)acrylate is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass or 30% to 40% by mass.

As a specific example of the component (B-ii), one can cite: • Dipentaerythritol mono(meth)acrylate, • Dipentaerythritol di(meth)acrylate, • Dipentaerythritol tri(meth)acrylate, • Dipentaerythritol tetra(meth)acrylate, • Dipentaerythritol penta(meth)acrylate, • Dipentaerythritol hexa(meth)acrylate, • A combination of at least two of the dipentaerythritol mono or poly(meth)acrylates listed above Wait. Among them, from the viewpoints of the resolution, the amount of side etching, the puncture strength and the peelability of the photoresist cured film, the suppression of pattern defects, and the improvement of the yield, a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate is preferred, Preferably, the mass ratio of the pentaacrylate in the mixture is 10% by mass, or 30% to 40% by mass.

(B-iii) Since the (meth)acrylate compound having a skeleton derived from bisphenol does not overlap with the (Bi) component, it is preferable to have a skeleton derived from bisphenol and a (meth)acrylic acid group without containing two The pentaerythritol skeleton more preferably has a skeleton derived from bisphenol, an alkylene oxide group, and a (meth)acrylic acid group.

{式中，X₁ ～X₈ 分別獨立地為氫原子或鹵素原子，較佳為X₁ ～X₈ 全部為氫原子，R₆ 及R₇ 分別獨立地表示氫原子或甲基，R₈ 及R₉ 分別獨立地表示碳數2～6之伸烷基，n₅ 及n₆ 分別獨立地為0或正整數，並且n₅ ＋n₆ 為0～20}。The component (B-iii) may be, for example, a compound represented by the following general formula (III): [化2]

{In the formula, X ₁ to X ₈ are each independently a hydrogen atom or a halogen atom, preferably X ₁ to X _{8 are} all hydrogen atoms, R ₆ and R ₇ each independently represent a hydrogen atom or a methyl group, R ₈ and R ₉ each independently represents an alkylene having 2 to 6 carbon atoms, n ₅ and n ₆ are each independently 0 or a positive integer, and n ₅ +n ₆ are 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 an ethylidene group, a propylidene group, or a butylene group, and -(R ₈ -O)- and -(R ₉ -O)- can be ethylene oxide, propylene oxide, butylene oxide, or a combination thereof.

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

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

As a specific example of ethylene oxide-modified bisphenol A having (meth)acryloyl groups at both ends, examples include: • Polyethylene glycol di(meth)acrylate made by adding an average of 1 mol of ethylene oxide to both ends of bisphenol A, • Polyethylene glycol di(meth)acrylate made by adding 2 moles of ethylene oxide to both ends of bisphenol A respectively, • Polyethylene glycol di(meth)acrylate made by adding an average of 3 moles of ethylene oxide to both ends of bisphenol A, • Polyethylene glycol di(meth)acrylate formed by adding an average of 5 mol of ethylene oxide to both ends of bisphenol A Wait. These can be used individually or in combination of 2 or more types. Among the components (B-iii) described above, in terms of resolution, undercutting amount, puncture strength, and suppressed defects of the metal substrate, it is preferable to be at both ends of bisphenol A Polyethylene glycol dimethacrylate formed by adding an average of 5 mol of ethylene oxide to the two ends of bisphenol A, respectively, adding an average of 1 mol of ethylene oxide to each end. Dimethacrylate of ethylene glycol and bisphenol A dimethacrylate.

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

Specific examples of the additional (B) component include (meth)acrylate compounds other than the (Bi) to (B-iii) components, for example: Diglycerol, di-trimethylolpropane, isocyanurate ring, etc. add polyalkylene oxide, or modify ε-caprolactone and convert the obtained alcohol into (meth)acrylate. The obtained compounds, or compounds obtained by directly reacting them with (meth)acrylic acid without modifying them with alkylene oxide or ε-caprolactone. In more detail, it is possible to use triacrylates with an average of 3 mols of ethylene oxide added to trimethylolpropane, and 3 mols of ethylene oxide with an average of 3 mols added to trimethylolpropane. Trimethacrylate, ε-caprolactone modified tris(acryloyloxyethyl) isocyanurate, etc.

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

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

When the photosensitive resin composition contains (B-ii) component and (B-iii) component, the ratio of (B-ii) component/(B-iii) component is preferably 10 to 80% by mass, more preferably It is 12 to 78% by mass. In addition, among the component (B) contained in the photosensitive resin composition, the ratio of the component (B-ii) and the component (B-iii) 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% by mass or less, or less than 100% by mass.

＜(C) Photopolymerizable initiator＞ (C) The photopolymerizable initiator is a compound that generates radicals by active light and can polymerize (B) a photopolymerizable compound having an ethylenically unsaturated group and the like. The photosensitive resin composition may contain a photopolymerization initiator generally known in this technical field as the (C) photopolymerization initiator.

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) The photopolymerization initiator may, for example, be hexaarylbiimidazole compound, N-aryl-α-amino acid compound, quinone compound, aromatic ketone compound, acetophenone compound, acetoxy Phosphine compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, 9-oxysulfur 𠮿

Compounds, dialkylaminobenzoate compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, halogen compounds, etc.

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-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl) )-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2, 4,5-Tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-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) Yl)-4,4',5,5'-tetrakis-(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 and the like. Among them, from the viewpoints of high sensitivity, resolution, and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

As the N-aryl-α-amino acid compound, for example, N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine Sour etc. In particular, N-phenylglycine has a higher sensitization effect, so it is better.

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-phenanthrenequinone, 2-methyl-1,4-naphthalene Quinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, etc.

As the aromatic ketone compound, for example, benzophenone, Michelone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino) ) Benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. As the acetophenone compound, for example, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-𠰌olinylphenyl)-butanone-1, 2-methyl -1-[4-(Methylthio)phenyl]-2-morpholinyl-acetone-1 and the like. As a commercially available product of the acetophenone compound, for example, Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals can be mentioned. From the viewpoint of use as a sensitizer and adhesiveness, 4,4'-bis(diethylamino)benzophenone is preferred.

As the phosphine oxide compound, for example, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phosphine oxide, bis(2,4,6-trimethylbenzyl)-phosphine oxide, bis (2,6-Dimethoxybenzyl)-2,4,4-trimethyl-pentyl phosphine oxide and the like. As a commercially available product of the phosphine oxide compound, for example, Lucirin TPO manufactured by BASF Corporation and Irgacure-819 manufactured by Ciba Specialty Chemicals may be mentioned.

化合物，例如可例舉：2,4-二乙基9-氧硫𠮿

、2,4-二異丙基9-氧硫𠮿

、2-氯9-氧硫𠮿

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。The benzoin compound and the benzoin ether compound may, for example, be benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, and the like. As a dialkyl ketal compound, a benzil dimethyl ketal, a benzil diethyl ketal, etc. are mentioned, for example. As 9-oxysulfur 𠮿

Compounds, for example: 2,4-diethyl 9-oxysulfur 𠮿

, 2,4-Diisopropyl 9-oxysulfur 𠮿

, 2-chloro-9-oxysulfur 𠮿

Wait. As the dialkylaminobenzoate compound, for example, ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, 4 -(Dimethylamino)benzoic acid 2-ethylhexyl ester and the like.

As the oxime ester compound, for example, 1-phenyl-1,2-propanedione-2-O-benzyloxime, 1-phenyl-1,2-propanedione-2-(O -Ethoxycarbonyl) oxime and the like. As a commercially available product of the oxime ester compound, for example, CGI-325 manufactured by Ciba Specialty Chemicals, Irgacure-OXE01, and Irgacure-OXE02 can be mentioned.

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

The pyrazoline derivative is preferably 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-third octyl-phenyl)-pyrazoline.

As the ester compound of N-arylamino acid, for example, the methyl ester of N-phenylglycine, the ethyl ester of N-phenylglycine, the n-propyl ester of N-phenylglycine , N-phenylglycine's isopropyl ester, N-phenylglycine's 1-butyl ester, N-phenylglycine's 2-butyl ester, N-phenylglycine's third butyl Ester, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, octyl ester of N-phenylglycine, etc.

As the halogen compound, for example, bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, vinyl bromide, diphenylbromomethane, benzyl bromide, dibromomethane, tribromomethyl Phenyl sulfide, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-trichloro-2, 2-bis(p-chlorophenyl)ethane, trichlorotrioxane compound, diallyl iodonium compound, etc., particularly preferably tribromomethylphenylsulfonate.

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.

(C) As the photopolymerization initiator, it is preferable to use a hexaarylbisimidazole compound. 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, it is preferable to use an aromatic ketone compound such as 4,4'-bis(diethylamino)benzophenone in combination with a hexaarylbisimidazole compound. 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% to 0.4% by mass, and the hexaaryl bisphenol 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＞ The photosensitive resin composition preferably contains a dye as the component (D) in order to impart better color rendering properties and excellent sensitivity characteristics to the photoresist cured film.

As the dye, for example, tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leuco malachite green], magenta , Phthalocyanine Green, Chrysanthine, P-fuchsin, 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 Co., Ltd.), etc. Among them, from the viewpoint of improving colorability, hue stability, and exposure contrast, leuco dyes such as diamond green and leuco crystal violet are preferred. 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% by mass or more from the viewpoint of obtaining good coloring properties. On the other hand, from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is preferably 3% by mass or less. By setting the usage ratio of the dye within this range, good color rendering and sensitivity can be achieved.

＜Other ingredients＞ It is preferable that the photosensitive resin composition contains additives, such as a plasticizer, antioxidant, and stabilizer, as needed.

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, etc. Sugar alcohol anhydride derivatives; phthalic acid esters such as diethyl phthalate; o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyl citric acid Triethyl, acetyl tri-n-propyl citrate, and acetyl tri-n-butyl citrate, propylene glycol formed by adding propylene oxide to both sides of bisphenol A, and propylene glycol in bisphenol A Ethylene oxide is added on both sides to form ethylene glycol, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, etc.

Among them, from the viewpoint of suppressing the delay of peeling time, p-toluenesulfonamide, polypropylene glycol obtained by adding an average of 3 units of propylene oxide to both ends of bisphenol A, and polyoxypropyleneglycerin are preferred. The ether is more preferably polyoxypropylene glyceryl ether, and even more preferably polyoxypropylene glyceryl ether with a weight average molecular weight of 3000, from the viewpoint of the puncture strength of the photoresist pattern, the solubility of the release sheet, or the plating resistance.

The content of the plasticizer in the photosensitive resin composition is preferably in the range of 0.1% by mass to 3% by mass, more preferably 0.15% by mass to 2% by mass. The content is preferably 0.1% by mass or more from the viewpoints of suppressing the delay of the development time, imparting flexibility to the cured film, and easy adjustment of the maximum point load obtained by the above-mentioned puncture test. On the other hand, it is preferable to set the content to 3% by mass or less from the viewpoint of suppressing insufficient hardening and edge melting.

As the antioxidant, for example, triphenyl phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (for example, Manufactured by Asahi Denka Kogyo Co., Ltd., trade name 2112), Tris(monononylphenyl) phosphite (for example, made by Asahi Denka Kogyo Co., Ltd., trade name: 1178), bis(monononylphenyl) phosphite dinonyl Phenyl ester (for example, manufactured by Asahi Denka Kogyo 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% by mass to 0.8% by mass, and more preferably in the range of 0.01% by mass to 0.3% by mass. Regarding the content of the antioxidant, it is preferably 0.01% by mass or more from the viewpoint of good performance of the hue stability of the photoresist pattern and improvement of the sensitivity of the photosensitive resin layer. On the other hand, it suppresses the color development of the photoresist pattern At the same time, from the viewpoint of expressing the hue stability well and improving the adhesion, it is preferably 0.8% by 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. As the stabilizer, for example, at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, and alkylene oxide compounds having glycidyl groups . These can be used individually by 1 type or in combination of 2 or more types.

As a radical polymerization inhibitor, for example, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tertiary butylcatechol, cuprous chloride, 2,6-bis -Tertiary butyl-p-cresol, 2,2'-methylene bis(4-methyl-6-tertiary butylphenol), 2,2'-methylene bis(4-ethyl-6 -Tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxylamine aluminum salt (For example, 3 mol aluminum salt of nitrosophenylhydroxylamine, etc. are added), diphenylnitrosamine and the like. Among them, triethylene glycol-bis[3-(3-tertiarybutyl-5-methyl-4-hydroxyphenyl)propionate] or nitrosophenyl is preferred The aluminum salt of hydroxylamine 3 mol. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

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

As carboxybenzotriazoles, for example, 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) amino vinyl carboxyl benzotriazole 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 Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, , Epolight 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2 mol adduct diglycidyl ether (for example, Epolight 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6 -Hexanediol diglycidyl ether (for example, Epolight 1600 manufactured by Kyoeisha Chemical Co., Ltd.), etc. These can be used individually by 1 type or in combination of 2 or more types.

The total content of radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, and alkylene oxide compounds having glycidyl groups in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass The range is more preferably in the range of 0.05 to 1% by mass. The total content is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition. On the other hand, from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is preferably 3 Less than mass%.

The number of double bonds of 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 in this range, the penetration strength or resolution of the coating film becomes better. On the other hand, if 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 this, the number of double bonds of the photosensitive resin composition is more preferably 4.00 mmol/g or less. The number of double bonds (number of ethylenically unsaturated bonds) of the photosensitive resin composition can be determined by the blending ratio of component (B) in the photosensitive resin composition, the molecular weight of component (B), the number of functional groups of component (B), 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 range is that the maximum point load during the puncture test is in the above range, the blending ratio of (B) component and the ratio of (B) component The molecular weight, the number of functional groups of the component (B), etc. are preferably adjusted in a preferred aspect. Such a better aspect can easily bring out the effect of the invention of this 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 resins that do not contain ethylenic unsaturated groups in the main chain, (B) photopolymerizable compounds having ethylenic unsaturated bonds, and (C) photopolymerization initiators. In addition, the photosensitive resin laminate according to another aspect of the present invention is characterized in that the acid value of the non-volatile component of the photosensitive resin composition is set to A [mgKOH/g], and the photosensitive resin composition layer is When the thickness is 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 resolution are insufficient. On the other hand, if the ratio (A/T) is greater than 90, undercutting (SE) and Cu defects are insufficient. When the ratio (A/T) is 5 or more and 90 or less, the photosensitive resin laminate has excellent lamination properties, minimum development time, resolution, undercut (SE), Cu defects, and development residue. The above-mentioned ratio (A/T) is preferably 12 (for example, 12.0) or more and less than 70, and more preferably 12 (for example, 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 group in the molecule, which is based on 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 constituting the photosensitive resin composition layer will be described.

＜(A) Alkali-soluble resin without ethylenically unsaturated group in the main chain＞ (A) Alkali-soluble resins that do not contain ethylenic unsaturated groups in the main chain are polymers that can be dissolved in alkaline solutions. In addition, (A) the alkali-soluble resin that does not contain an ethylenically unsaturated group in 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 which does not contain an ethylenic unsaturated group in a main chain may be thermoplastic.

The acid equivalent of the non-volatile component of the photosensitive resin composition containing an alkali-soluble resin without an ethylenically unsaturated group in the main chain of (A) is preferably more than 0, in terms of the development resistance of the photosensitive resin layer and the photoresist pattern From the viewpoint of resolution and adhesion, and further the viewpoint of developability and peelability of the photosensitive resin layer, the acid equivalent of the non-volatile component of the photosensitive resin composition is preferably 79.0 or less.

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

Compared with the prior art, the acid value in the above range is equivalent to the so-called "low acid value". Another aspect of the present invention has realized the "thinning of the photosensitive resin layer" and the "low acid value" in recent years when the thinning of the photosensitive resin layer is particularly required. Previously, as one of the methods for achieving high resolution (low SE), it has been known to increase the hydrophobicity of the photoresist. On the other hand, if the hydrophobicity of the photoresist is increased, the solubility in the developer is reduced, so the development time tends to be longer. In this regard, if the molecular weight of the resin is reduced to shorten the development time, there are also cases where Cu defects (film strength) are easily reduced. In contrast to these situations, another aspect of the present invention that has achieved "thinning of the photosensitive resin layer" and "low acid value" can easily achieve a balance 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) Alkali-soluble resins that do not contain ethylenic unsaturated groups in the main chain are preferably represented by the following formula (I): [Number 2]

{Where, W _i is the mass of each of the comonomers constituting the alkali-soluble resin, Tg _i is the glass transition temperature when each of the comonomers constituting the alkali-soluble resin is a homopolymer, and W _total is the alkali soluble The total mass of the resin, and n is the number of types of comonomers constituting the alkali-soluble resin} The calculated glass transition temperature (Tg _total ) is 100°C or less. When using a mixture of multiple types of polymers as an alkali-soluble resin that does not contain ethylenic unsaturated groups on the main chain of (A), the glass transition temperature is a value determined in the form of the average value of all polymers.

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

The Tg _{i of} representative comonomers are as follows (all are 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 of the above-mentioned glass transition temperature (Tg _total ) is preferably a copolymer of acid monomers and other monomers.

There is no particular limitation on the lower limit _{of the glass transition temperature (Tg total} ) of the alkali-soluble resin that does not contain an ethylenically unsaturated group in the main chain of (A) determined by the above-mentioned 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.

(A) The weight average molecular weight of the alkali-soluble resin containing no ethylenic unsaturated group in the main chain is preferably 5,000 to 500,000. Regarding (A) the weight average molecular weight of alkali-soluble resins that do not contain ethylenic unsaturated groups in the main chain, from the viewpoint of uniformly maintaining the thickness of photosensitive resin laminates such as dry film photoresists to obtain resistance to developing solutions , Is preferably 5,000 or more. On the other hand, from the viewpoint of maintaining the developability of photosensitive resin laminates such as dry film photoresist, it is preferably 500,000 or less. In addition, (A) the weight average molecular weight (Mw) of the alkali-soluble resin not containing an ethylenically unsaturated group in the main chain is more preferably 10,000 to 200,000, and still more preferably 20,000 to 100,000 or 23,000 to 50,000. Furthermore, the ratio of the above-mentioned Mw to (A) the number average molecular weight (Mn) of the alkali-soluble resin without ethylenic unsaturated groups in the main chain is the ratio of (A) the alkali-soluble resin without ethylenic unsaturated groups in the main chain The degree of dispersion (Mw/Mn) is preferably 1.0 to 6.0.

(A) The alkali-soluble resin containing no ethylenic unsaturated group in the main chain is preferably obtained by polymerizing at least one of the first monomers described below. In addition, (A) the alkali-soluble resin that does not contain an 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 the first monomer, for example, (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, β-carboxyethyl (meth)acrylate And maleic acid half ester and so on. Among these, (meth)acrylic acid is particularly preferred.

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, etc. Among them, from the viewpoint of improving the resolution of the photoresist pattern, an unsaturated aromatic compound is preferred.

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

Alkyl (meth)acrylate is a concept including both chain alkyl ester and cyclic alkyl ester. Specifically, for example, methyl (meth)acrylate and ethyl (meth)acrylate can be mentioned. , N-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, amyl (meth)acrylate, (meth) 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, etc.

As the aralkyl (meth)acrylate, for example, benzyl (meth)acrylate and the like can 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. As the polar monomer, for example, hydroxyl-containing monomers such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, pentenol, etc.; methacrylic acid 2 -Amino ethyl and other amine group-containing monomers; (meth)acrylamide, N-methylol (meth)acrylamide and other amine 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.

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

(A) Alkali-soluble resins without ethylenic unsaturated groups in the main chain can be prepared from the above-mentioned first monomer and/or second monomer by a known polymerization method, preferably addition polymerization, more preferably Radical Polymerization.

(A) The content of alkali-soluble resin in the photosensitive resin composition that does not contain an ethylenically unsaturated group in the main chain (based on the total solid content of the photosensitive resin composition; below, unless otherwise specified, then The same in each contained component) is preferably in the range of 10% by mass to 90% by mass, more preferably in the range of 20% by mass to 80% by mass, and still more preferably in the range of 30% by mass to 60% by mass. (A) The content of the alkali-soluble resin that does not contain 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. On the other hand, it is sufficient From the viewpoint of exhibiting the performance of the photoresist pattern formed by exposure as a photoresist material, it is preferably 90% by mass or less.

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

Specifically, as the component (B), for example, the second polyalkylene glycol (2) obtained by adding an average of 2 mol to 15 mol of alkylene oxide to each of both ends of bisphenol A ( Meth) acrylate, polyalkylene triol tri(meth)acrylate, which is formed by adding 3 mol to 25 mol of alkylene oxide to trimethylolpropane, by adding glycerin, trimethylolpropane Hydroxymethylpropane, pentaerythritol, diglycerol, di-trimethylolpropane, isocyanurate ring, etc. add epoxy alkyl group, or carry out ε-caprolactone modification and convert the obtained alcohol into ( The compound obtained by using meth)acrylate, or the compound obtained by directly reacting with (meth)acrylic acid without modification with epoxy alkyl group or ε-caprolactone, add average to pentaerythritol Tetra(meth)acrylate of polyols made from 4 moles to 35 moles of alkylene oxide, hexa(meth)acrylic acid, polyols made from addition of 4 to 30 moles of alkylene oxide to dipentaerythritol Ester etc. These can be used alone or in combination of two or more

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

＜(C) Photopolymerization initiator＞ (C) The photopolymerization initiator is a compound that generates radicals by active light and can polymerize (B) a photopolymerizable compound having an ethylenically unsaturated group and the like. The photosensitive resin composition may contain a photopolymerization initiator generally known in this technical field as the (C) photopolymerization initiator.

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) The photopolymerization initiator may, for example, be hexaarylbiimidazole compound, N-aryl-α-amino acid compound, quinone compound, aromatic ketone compound, acetophenone compound, acetoxy Phosphine compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, 9-oxysulfur 𠮿

Compounds, dialkylaminobenzoate compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, halogen compounds, etc.

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-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl) )-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2, 4,5-Tris-(o-chlorophenyl)-diphenylbiimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-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) Yl)-4,4',5,5'-tetrakis-(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 and the like. Among them, from the viewpoints of high sensitivity, resolution, and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

As the N-aryl-α-amino acid compound, for example, N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine Sour etc. In particular, N-phenylglycine has a higher sensitization effect, so it is better.

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-phenanthrenequinone, 2-methyl-1,4-naphthalene Quinone, 9,10-phenanthrenequinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, etc.

As the aromatic ketone compound, for example, benzophenone, Michelone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino) ) Benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc. As the acetophenone compound, for example, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-𠰌olinylphenyl)-butanone-1, 2-methyl -1-[4-(Methylthio)phenyl]-2-morpholinyl-acetone-1 and the like. As a commercially available product of the acetophenone compound, for example, Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals can be mentioned. From the viewpoint of use as a sensitizer and adhesiveness, 4,4'-bis(diethylamino)benzophenone is preferred.

As the phosphine oxide compound, for example, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phosphine oxide, bis(2,4,6-trimethylbenzyl)-phosphine oxide, bis (2,6-Dimethoxybenzyl)-2,4,4-trimethyl-pentyl phosphine oxide and the like. As a commercially available product of the phosphine oxide compound, for example, Lucirin TPO manufactured by BASF Corporation and Irgacure-819 manufactured by Ciba Specialty Chemicals may be mentioned.

化合物，例如可例舉：2,4-二乙基9-氧硫𠮿

、2,4-二異丙基9-氧硫𠮿

、2-氯9-氧硫𠮿

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。The benzoin compound and the benzoin ether compound may, for example, be benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, and the like. As a dialkyl ketal compound, a benzil dimethyl ketal, a benzil diethyl ketal, etc. are mentioned, for example. As 9-oxysulfur 𠮿

Compounds, for example: 2,4-diethyl 9-oxysulfur 𠮿

, 2,4-Diisopropyl 9-oxysulfur 𠮿

, 2-chloro-9-oxysulfur 𠮿

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

As the oxime ester compound, for example, 1-phenyl-1,2-propanedione-2-O-benzyloxime, 1-phenyl-1,2-propanedione-2-(O -Ethoxycarbonyl) oxime and the like. As a commercially available product of the oxime ester compound, for example, CGI-325 manufactured by Ciba Specialty Chemicals, Irgacure-OXE01, and Irgacure-OXE02 can be mentioned.

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

The pyrazoline derivative is preferably 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-third octyl-phenyl)-pyrazoline.

As the ester compound of N-arylamino acid, for example, the methyl ester of N-phenylglycine, the ethyl ester of N-phenylglycine, the n-propyl ester of N-phenylglycine , N-phenylglycine's isopropyl ester, N-phenylglycine's 1-butyl ester, N-phenylglycine's 2-butyl ester, N-phenylglycine's third butyl Ester, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, octyl ester of N-phenylglycine, etc.

As the halogen compound, for example, bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, vinyl bromide, diphenylbromomethane, benzyl bromide, dibromomethane, tribromomethyl Phenyl sulfide, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-trichloro-2, 2-bis(p-chlorophenyl)ethane, trichlorotrioxane compound, diallyl iodonium compound, etc., particularly preferably tribromomethylphenylsulfonate.

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 (C) photopolymerization initiator within the above-mentioned range, sufficient sensitivity can be obtained, light can be transmitted to the bottom of the photoresist sufficiently, high resolution can be obtained, and a conductive pattern can be obtained A photosensitive resin composition with excellent undercutting amount balance.

(C) As the photopolymerization initiator, it is preferable to use a hexaarylbisimidazole compound. 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, it is preferable to use an aromatic ketone compound such as 4,4'-bis(diethylamino)benzophenone in combination with a hexaarylbisimidazole compound. 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% to 0.4% by mass, and the hexaaryl bisphenol 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) Compounds with polyoxytetramethylene oxide as a structural unit＞ Compounds having polyoxytetramethylene oxide as a structural unit have higher flexibility, so they can impart moderate flexibility to the formed photoresist pattern. Thereby, it is not easy to produce defects of the photoresist film caused by the process load, so the Cu defects can also be reduced. Furthermore, the compound having polyoxytetramethylene oxide as a structural unit has high hydrophobicity, so by using it in the photosensitive resin laminate, the resolution can be improved or side erosion can be reduced. For the above reasons, it is preferable to use a compound having polyoxytetramethylene oxide as a structural unit.

Regarding compounds having polyoxytetramethylene oxide as a structural unit, for example, poly-1,4-butanediol, poly-1,4-butanediol dimethacrylate, and poly-1,4-butanediol dimethacrylate may be mentioned. Acrylate, 2,2-bis(4-((meth)acryloyloxypolytetramethyleneoxy)phenyl)propane, poly 1,4-butanediol trimethylolpropane tri(methyl) The urethane reactant of acrylate, hydroxyethyl (meth)acrylate, poly 1,4-butanediol, diisocyanate compound or triisocyanate compound, etc. Among them, a poly-1,4-butanediol dimethacrylate compound is preferred. 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 polyoxytetramethylene oxide as a structural unit in the photosensitive resin composition is preferably in the range of 0.5% to 50% by mass from the viewpoint of alkali developability, and more preferably It is in the range of 1-40% by mass.

＜(E) Compound with 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. Examples of the compound having a benzotriazole skeleton include benzotriazoles, carboxybenzotriazoles, and the like.

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

As carboxybenzotriazoles, for example, 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) amino vinyl carboxyl benzotriazole 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 having a benzotriazole skeleton 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 0.05 to 1% by mass. The total content is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition. 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% by mass or less.

In the photosensitive resin composition, the ratio [(A) component/((B) component + (D) component)] of the total of the (A) component, (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 resistance to edge fusion, the lower limit of the 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 required.

As the dye, for example, tris(4-dimethylaminophenyl)methane [leuco crystal violet], bis(4-dimethylaminophenyl)phenylmethane [leuco malachite green], magenta , Phthalocyanine Green, Chrysanthine, P-fuchsin, 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 Co., Ltd.), etc. Among them, from the viewpoint of improving colorability, hue stability, and exposure contrast, diamond green and leuco crystal violet are preferred. 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% by mass or more from the viewpoint of obtaining good coloring properties. On the other hand, from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is preferably 3% by mass or less.

As the antioxidant, for example, triphenyl phosphite (for example, manufactured by Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (for example, Manufactured by Asahi Denka Kogyo Co., Ltd., trade name 2112), Tris(monononylphenyl) phosphite (for example, made by Asahi Denka Kogyo Co., Ltd., trade name: 1178), bis(monononylphenyl) phosphite dinonyl Phenyl ester (for example, manufactured by Asahi Denka Kogyo 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% by mass to 0.8% by mass, and more preferably in the range of 0.01% by mass to 0.3% by mass. Regarding the content of the antioxidant, it is preferably 0.01% by mass or more from the viewpoint of good performance of the hue stability of the photoresist pattern and improvement of the sensitivity of the photosensitive resin layer. On the other hand, it suppresses the color development of the photoresist pattern From the viewpoint of good performance of hue stability and improvement of adhesiveness, the content is preferably 0.8% by 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.

As a radical polymerization inhibitor, for example, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tertiary butylcatechol, cuprous chloride, 2,6-bis -Tertiary butyl-p-cresol, 2,2'-methylene bis(4-methyl-6-tertiary butylphenol), 2,2'-methylene bis(4-ethyl-6 -Tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxylamine aluminum salt (For example, 3 mol aluminum salt of nitrosophenylhydroxylamine, etc. are added), diphenylnitrosamine and the like. Among them, triethylene glycol-bis[3-(3-tertiarybutyl-5-methyl-4-hydroxyphenyl)propionate] or nitrosophenyl is preferred The aluminum salt of hydroxylamine 3 mol. 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 Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (for example, , Epolight 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2 mol adduct diglycidyl ether (for example, Epolight 3002 manufactured by Kyoeisha Chemical Co., Ltd.), 1,6 -Hexanediol diglycidyl ether (for example, Epolight 1600 manufactured by Kyoeisha Chemical Co., Ltd.), etc. 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% by mass to 3% by mass, more preferably in the range of 0.05 to 1% by mass. The total content is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition. On the other hand, from the viewpoint of maintaining the sensitivity of the photosensitive resin layer, it is more preferable It is 3% by mass or less.

[Photosensitive resin composition blending liquid] 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, for example, ketones represented by acetone and methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropanol, etc. may be mentioned. It is preferable to add the solvent 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 blending solution of the present invention, a photosensitive resin laminate can be provided. The photosensitive resin laminate has a support film (support) and a layer containing the above-mentioned photosensitive resin composition formed on the support film. The photosensitive resin laminate may optionally have a protective layer on the surface on the side opposite to the support film side. 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 significantly exerting the effects of the present invention.

Among them, at least the suppression of pattern defects, the improvement of the yield of the formed object or the pattern formed by photolithography, and/or the lamination, the minimum development time, the resolution, the undercutting, the Cu defect, and the development residue From an excellent point of view, the best dry film photoresist has: Support film, and The photosensitive layer, the photosensitive layer is formed on the support film, and contains (A) Alkali-soluble resin, (B) Compounds with ethylenically unsaturated bonds, (C) photopolymerization initiator, and (D) Dyes The composition, The above component (B) contains: (B-ii) A compound having a dipentaerythritol skeleton but not having an alkylene oxide group, and (B-iii) A compound having a skeleton derived from bisphenol, Among (B) components, (B-ii) component and (B-iii) component are 50% by mass or more, and the ratio of (B-ii) component/(B-iii) component is 10 to 80% by mass. In addition, the composition of the dry film photoresist is particularly preferable when 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) is within the numerical range of the present invention. The composition of the resin laminate can be combined or interchanged.

As the support film, it is more desirable to be a transparent support film that transmits light emitted from the exposure light source. Examples of such supporting films include polyethylene terephthalate films, polyvinyl alcohol films, polyvinyl chloride films, vinyl chloride copolymer films, polyvinylidene chloride films, and vinylidene chloride copolymer films. , Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. These films can also be used if necessary.

The haze of the support film is preferably 5 or less. Regarding the thickness of the support film, it is advantageous to be thin in terms of image forming properties and economic efficiency. If the function of maintaining strength is also taken into consideration, it is preferably 10 μm to 30 μm.

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

The 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 from the photosensitive resin laminate. As the protective layer, for example, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a polyester film, etc. can be used. In addition, a release layer that can be used to peel off the protective film from the photoresist layer can also be provided to one side of the protective layer film. The release layer is usually divided into polysiloxane compounds and non-polysiloxane compounds. The so-called polysiloxane compounds can be exemplified: the two-terminal silanol polydimethylsiloxane and polymethylhydrosiloxane or polymethylsiloxane Condensation reaction type polysiloxane resin obtained by the reaction of methoxysiloxane; or dimethylsiloxane-methylvinylsiloxane copolymer or dimethylsiloxane-methylhexene Addition reaction type polysiloxane resin obtained by the reaction of base silicone copolymer and polymethylhydrosiloxane; or curing acrylic polysiloxane or epoxy-containing polysiloxane by ultraviolet light or electron beam The obtained UV-curing or electron beam-curing silicone resin; or modified silicone resin, such as epoxy modified silicone resin (polysilicon epoxy resin), polyester modified silicone resin (Polysiloxane polyester), acrylic modified polysiloxane resin (polysiloxane acrylic), phenol modified polysiloxane resin (polysiloxane phenol), alkyd modified polysiloxane resin (polysiloxane alkyd) ), melamine modified polysiloxane resin (polysiloxane melamine), etc. Examples of non-polysiloxane compounds include acid alcohol (or also called alkyd) resins, long-chain alkyl resins, acrylic resins, and polyolefin resins. The 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, there is a possibility that the appearance of the coating film will deteriorate or the coating film is not hardened enough. When the film thickness is less than 0.001 μm, there is a possibility that sufficient release properties may not be obtained. The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

[Production method of photosensitive resin laminate] The photosensitive resin laminate can be produced by sequentially laminating a photosensitive resin layer and, if necessary, a protective layer on the 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|dissolves these are mixed, and the photosensitive resin composition preparation liquid (coating liquid) of a uniform solution form is formed. Then, the coating liquid can be applied to the support film (support) using a bar coater or a roll coater, and then dried to laminate a photosensitive resin layer on the support film. A protective layer may be laminated on the photosensitive resin layer as needed to produce a photosensitive resin laminate.

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

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

Hereinafter, an example of a method of forming a photoresist and a wiring pattern using the photosensitive resin laminate and the base material will be described.

(Laminating step) The lamination step can be carried out by the following method: when the photosensitive resin laminate has a protective layer, the protective layer is peeled from the laminate, and thereafter, for example, the photosensitive resin layer is heated and press-bonded to the substrate using a laminator Surface for lamination.

As the material of the substrate used, for example, copper (Cu), stainless steel (SUS), glass, indium tin oxide (ITO), a flexible substrate laminated with a conductive thin film, etc. may be mentioned. As the conductive thin film, for example, ITO, copper, copper-nickel alloy, silver, etc. may be mentioned. Examples of the material constituting the flexible substrate include polyethylene terephthalate (PET).

The substrate used can be a form in which copper wiring is formed on a copper foil laminated board, a form of a substrate composed of only glass, and a transparent electrode formed on a transparent resin substrate (e.g., ITO, Ag nanowire substrate, etc.) ) Or metal electrodes (for example, Cu, Al, Ag, Ni, Mo, and alloys of at least two of these). In addition, the base material used may have through holes corresponding to the multilayer substrate.

From the standpoint of remarkably exerting the effects of the present invention, the substrate used is preferably a copper foil laminated substrate, more preferably a copper foil laminated with a thickness of 35 μm, a thickness of 1.6 mm and a copper foil with a diameter of 6 mm. Multilayer substrate.

The photosensitive resin layer may be laminated on only one side of the substrate surface, or may be laminated on both sides of the substrate as needed. The heating temperature during lamination is preferably 40°C to 160°C, more preferably 80°C to 120°C. By performing heating and compression bonding more than two times, the adhesion of the obtained photoresist pattern to the substrate can also be improved. When crimping is performed twice or more, a two-stage laminating machine equipped with a twin roll can be used, or the laminate of the substrate and the photosensitive resin layer can be repeatedly passed through the roll for crimping.

(Exposure step) The exposure step uses an exposure machine to expose the photosensitive resin layer. From the viewpoint of the puncture strength of the obtained photoresist film, the exposure is preferably performed after peeling the support from the photosensitive resin laminate. By performing this exposure in a pattern, a photoresist film (photoresist pattern) having a desired pattern can be obtained after the following development step. The pattern-like exposure can be performed by either a method of exposure through a photomask or a method of exposure without a photomask.

In the case of exposure through the mask, the amount of exposure is determined by the illuminance of the light source and the exposure time. The exposure level can be measured with a light meter. In the non-mask exposure, the mask is not used, and the exposure is performed on the substrate by the direct drawing device. As a light source, semiconductor lasers with wavelengths of 350 nm to 410 nm, ultra-high pressure mercury lamps, etc. can be used. During exposure without a mask, the drawing pattern can be controlled by a computer, and the amount of exposure 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, or reducing the amount of side etching, or improving the yield of the photoresist or the wiring pattern, it is preferable to perform exposure through a photomask.

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

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 with a concentration of 0.2% by mass to 2% by mass. Surfactants, defoamers, and a small amount of organic solvents to promote development can also be mixed into the alkaline aqueous solution. The temperature of the developer in the developing step is preferably kept at a fixed temperature in the range of 18°C to 40°C.

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

(Etching or plating step) The wiring pattern can be formed on the substrate by etching or plating the substrate on which the photoresist pattern is formed after the photoresist pattern is formed by the above-mentioned photoresist pattern forming method. From the viewpoint of remarkably exerting the effect 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 substrate surface that is not covered with the photoresist pattern. As an etching method, acid etching, alkaline etching, etc. can be mentioned, and it can perform 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 of these. In addition, the etching liquid may be sprayed.

The plating step can be performed by metal plating (for example, a 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 alkali than the developer to peel off the photoresist pattern from the substrate. The stripping liquid may be, for example, an aqueous solution of NaOH or KOH with a concentration of about 2% to 5% by mass and a temperature of about 40°C to 70°C.

Regarding the evaluation values of the various parameters mentioned above, as long as there is no special statement, they are based on the measurement values measured by the measurement methods in the examples described below.

As mentioned above, although the 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 explained based on examples, but the present invention is not limited to these examples.

[An aspect of the present invention] <1. Preparation of photosensitive resin composition> According to the composition shown in Table 1 (wherein, the number of each component indicates the blended amount (parts by mass) in terms of solid content), a plurality of components were mixed to prepare a photosensitive resin composition.

In addition, Table 2 shows the names of the components and the solvents used in the abbreviations in Table 1. In addition, the weight average molecular weight (Mw) shown in Table 2 means the calibration curve measured by gel permeation chromatography (GPC) using polystyrene (Shodex STANDARD SM-105 manufactured by Showa Denko Corporation) Get the weight average molecular weight. The weight average molecular weight (Mw) and number average molecular weight (Mn) can be measured using a gel permeation chromatograph manufactured by JASCO Corporation under the following conditions. Differential refractometer: RI-1530 Pump: PU-1580 Deaerator: DG-980-50 Column oven: CO-1560 String: KF-8025, KF-806M×2, KF-807 in sequence Eluent: THF (Tetrahydrofuran, tetrahydrofuran)

<2. Manufacturing of photosensitive resin laminate> Add ethanol as a solvent to the photosensitive resin composition until the solid content becomes 58% by mass, stir and mix, and use a bar coater to uniformly coat the obtained photosensitive resin composition solution to the thickness 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). Then, a 33 μm-thick polyethylene film (GF-858 manufactured by Tamapoly) was bonded on the surface of the photosensitive resin layer to obtain a photosensitive resin laminate.

＜3. Production of evaluation board＞

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

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

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

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

＜Peel off＞ Using a peeling device manufactured by Fujikiko (stock), the etched evaluation substrate is continuously processed for 30 seconds with a solid cone nozzle with a spray pressure of 0.15 MPa and a temperature of 50°C with a concentration of 3% by mass NaOH aqueous solution for 30 seconds, and the self-evaluated substrate will The photoresist pattern is stripped and removed.

＜4. Evaluation method＞

＜Image evaluation＞ A photosensitive resin laminate with a thickness of 5 μm of a photosensitive resin layer was laminated on a PET substrate with a copper layer by the method described in the above "Laminating". After 15 minutes, an evaluation substrate was obtained. A chrome glass mask with a line pattern with a width of the exposure part at a ratio of 1:1 exposes the evaluation substrate. After that, the development is carried out at twice the minimum development time, the minimum mask width normally formed with hardened resist lines is taken as the value of the resolution, and the resolution is graded as described below. Furthermore, the minimum mask width that is normally formed without the collapse of the hardened photoresist pattern or the close contact of the hardened photoresist to each other was evaluated. ◎(Significantly good): The resolution value is 3 μm or less; ○ (good): The value of the resolution exceeds 3 μm and is below 4 μm; × (bad): The value of the resolution exceeds 4 μm.

＜Side Erosion (SE) Amount＞ When evaluating the amount of side etching, a photosensitive resin laminate with a thickness of 5 μm of a photosensitive resin layer was laminated on a PET substrate with a copper layer by the method described in the above "Laminating", which was obtained after 15 minutes Evaluation substrate. After exposing the pattern of line/space=10 μm/10 μm to this laminated evaluation substrate, it was developed by the method described in the above-mentioned <Development>. First, the top width Wr (μm) of the photoresist of the pattern is measured by an optical microscope. Then, for the substrate with the line/space pattern, the dipping method is used to etch 1.5 times the minimum etching time under the conditions of an aqueous solution containing 2% by mass of hydrochloric acid and 2% by 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, a NaOH aqueous solution with a concentration of 3% by mass was used as a stripping solution, and the cured film on the substrate was peeled and removed at a temperature of 50°C to obtain a copper wire pattern. The top width Wc(μm) of the copper wire pattern was measured by an optical microscope. ). And, by the following formula: Undercutting (μm)=(Wr－Wc)÷2 Calculate the amount of side erosion and classify the amount of side erosion as described below. ◎(Significantly good): The amount of side erosion is less than 3 μm; ○ (Good): The amount of side erosion exceeds 3 μm and is less than 3.5 μm; △(Qualified): The amount of side erosion exceeds 3.5 μm and is below 4.0 μm; × (bad): The amount of side erosion exceeds 4.0 μm.

<Evaluation of Puncture Strength> As a substrate for evaluation, a substrate obtained by the following method was used: 1,008 copper foil laminate substrates with a thickness of 1.6 mm and 35 μm copper foils were formed on a copper foil laminate substrate with a thickness of 1.6 mm by surface treatment using a sandblasting brush grinder The entire surface of the substrate with a through hole 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 on one side, and use a heated roll laminator (manufactured by Asahi Kasei Co., Ltd., AL-70). ) Laminate the photosensitive resin laminate on both sides of the entire 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. Use the substrate obtained after 15 minutes of lamination. For the laminated substrate, use an exposure machine with an ultra-high pressure mercury lamp (parallel light exposure machine (manufactured by ORC MANUFACTURING, HMW-801)) with an exposure amount of 120 The evaluation substrate was exposed to mJ/cm ² and then developed by the method described in the above-mentioned <Development>. The developed substrate is subjected to humidity control overnight in a room with a temperature of 25°C and a humidity of 50%. After standing, the polyethylene terephthalate film as the support of the photosensitive resin layer was peeled off from the obtained substrate, and the surface of the support was peeled off at a speed of 100 mm/min. The part of the photosensitive resin layer corresponding to the center of the hole pierced a 2.0 mmφ cylinder, and the maximum point load was measured by Tensilon (RTM-500 manufactured by Orientec). For the part of the photosensitive resin layer corresponding to the center of the 6 mmϕ through hole, the maximum point load was measured at 10 points, and the average value of the first 5 points among these points was taken as the maximum point load of the puncture test. Evaluate the maximum point load obtained according to the following criteria. ◎(Significantly good): puncture strength is 90 gf or more; ○ (good): puncture strength is 80 gf or more and less than 90 gf; △ (passed): 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, a photosensitive resin laminate with a thickness of 5 μm of a photosensitive resin layer was laminated on a PET substrate with a copper layer by the method described in the above "Laminating", and it was made after 15 minutes The evaluation substrate. The pattern of line/space=10 μm/10 μm was exposed to this laminated evaluation substrate, and then developed by the method described in the above-mentioned <Development>. Then, for the substrate with the line/space pattern, the dipping method is used to etch 1.5 times the minimum etching time under the conditions of an aqueous solution containing 2% by mass of hydrochloric acid and 2% by mass of ferric chloride and a temperature of 30°C. 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, a NaOH aqueous solution with a concentration of 3% by mass was used as a peeling solution, and the cured film on the substrate was peeled and removed at a temperature of 50°C, and the obtained copper wire pattern was measured and observed by an optical microscope, as described below 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.

The evaluation results of Examples 1 to 13 and Comparative Examples 1 to 3 are also shown in Table 1. According to the comparison between 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 good 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 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ X ○ SE amount ○ ○ ◎ ○ ○ ○ ○ ○ ○ ○ ◎ ◎ ○ ○ △ ○ Puncture strength (gf) ○ ◎ ◎ ○ ○ ◎ ◎ ◎ ◎ △ ◎ △ ◎ X X X Cu defects ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ X X X

[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 (the ratio of pentaerythritol pentaacrylate is 10%, the molecular weight=578, the number of double bonds=5.9) Ingredient B-2 Dipentaerythritol hexamethacrylate (molecular weight = 1234, number of double bonds = 6.0) polyethylene glycol dipentaerythritol hexamethacrylate with an average addition of 13 mol of ethylene oxide Ingredient B-3 Dimethacrylate of polyethylene glycol (molecular weight = 804, number of double bonds = 2.0) by adding an average of 5 mol of ethylene oxide to both ends of bisphenol A Ingredient B-4 Triacrylate (molecular weight = 428, number of double bonds = 3.0) by adding an average of 3 mol of ethylene oxide to trimethylolpropane Ingredient B-5 ε-caprolactone modified tris(acryloxyethyl) isocyanurate (molecular weight = 765, number of double bonds = 3.0) Ingredient B-6 Dimethacrylate of polyethylene glycol (molecular weight = 452, number of double bonds = 2.0) by adding an average of 1 mol of ethylene oxide to both ends of bisphenol A Ingredient B-7 Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (the ratio of pentaacrylate is 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-tertiarybutyl-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 Table 3 to Table 5 were mixed to prepare a photosensitive resin composition. The values in Table 3 to Table 5 are the amount of solid content. In addition, Table 6 shows the name of each component and the solvent used in the abbreviations in Tables 3 to 5.

In addition, the acid value (acid equivalent) of the non-volatile component 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 the 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 the ¹ H-NMR measurement was performed. Calculate the integral value of each component in the precipitate based on the obtained area ratio of each component, and calculate the weight ratio of methacrylic acid in the precipitate (wt%) according to the following formula: Weight ratio of methacrylic acid = (A Integral value of acrylic acid)/(Total integral value derived from sediment components). Furthermore, the acid value of the non-volatile component of the photosensitive resin composition was calculated by the following formula: Acid value of the non-volatile component 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 an alkali-soluble resin is methacrylic acid. On the other hand, when the alkali-soluble resin contains an acid component different from methacrylic acid as the acid component, the acid value (acid equivalent) of the non-volatile component of the photosensitive resin composition can also be measured according to the above calculation method.

<2. Manufacturing of photosensitive resin laminate> Add the solvent acetone to the photosensitive resin composition until the solid content becomes 58% by mass, fully stir and mix, and use a bar coater to uniformly apply the photosensitive resin composition solution to the support film (support Body) 25 μm thick polyethylene terephthalate film (FB-40 manufactured by Toray; 16 μm polyethylene terephthalate film), dried in a dryer at 95°C for 5 minutes, A photosensitive resin layer (dry film) with a thickness of 1-20 μm is formed. Then, a 33 μm-thick polyethylene film (GF-858 manufactured by Tamapoly) 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 board＞ (laminated) One side peeled off the polyethylene film of the photosensitive resin laminate and the other side was laminated on a PET substrate with a copper layer at a roller temperature of 105°C using a heated roll laminator (manufactured by Asahi Kasei Microdevices (stock), AL-700). The air pressure is set to 0.35 MPa, and the lamination speed is set to 1.5 m/min.

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

(Development) Using a developing device manufactured by Fujikiko Co., Ltd., use a solid cone nozzle with a spray pressure of 0.15 MPa and spray with a 1% by mass Na ₂ CO ₃ aqueous solution at 23°C for 30 seconds to develop the unexposed part of the photosensitive resin layer Dissolve and remove. At this time, the washing step is performed using a flat nozzle with a washing spray pressure of 0.15 MPa for the same time as the developing step.

(Etching) Using the etching device manufactured by Fujikiko (stock), the solid cone nozzle is used to etch for 60 s under the conditions of spray pressure 0.15 MPa, temperature 30°C, hydrochloric acid concentration 2% by mass, and ferric chloride 2% by mass.

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

＜4. Evaluation method＞ (Graphic) The evaluation substrate obtained by laminating a photosensitive resin laminate having a thickness of 1-20 μm with a photosensitive layer of 1-20 μm by the method described in the above (laminating) was passed through the width of the exposed part and the unexposed part. A chrome glass mask with a line pattern at a ratio of 1:1 is used for exposure. After that, development was performed by the method described in the above (Development) to produce a photoresist pattern.

The minimum mask width with hardened photoresist lines normally formed is used as the value of resolution, and the resolution is classified as described below. Furthermore, the minimum mask width for the collapse of the non-hardened photoresist pattern or the close contact of the non-hardened photoresist to 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.

(Amount of Side Erosion (SE)) When evaluating the amount of side etching, use the method described in the above (Laminating) to laminate a photosensitive resin laminate with a thickness of 1-20 μm on a PET substrate with a copper layer, and then evaluate for 15 minutes Substrate. After exposing the pattern of line/space=10 μm/10 μm to this laminated evaluation substrate, it was developed by the method described in the above (Development). The top width Wr (μm) of the photoresist of the produced pattern was measured by an optical microscope.

Then, for the substrate with the line/space pattern, the dipping method is used to etch 1.5 times the minimum etching time under the conditions of an aqueous solution containing 2% by mass of hydrochloric acid and 2% by 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, a NaOH aqueous solution with a concentration of 3% by mass was used as a peeling solution, and the cured film on the substrate was peeled and removed at a temperature of 50° C., and the top width Wc (μm) of the obtained copper wire pattern was measured by an optical microscope.

And, by the following formula: Undercutting (μm)=(Wr－Wc)÷2 Calculate the amount of side erosion and classify the amount of side erosion as described below. ◎ (Significantly good): The amount of side erosion is 2.5 μm or less. ○ (good): The amount of side etching exceeds 2.5 μm and is 3.0 μm or less. △ (Pass): The amount of side erosion exceeds 3.0 μm and is 3.5 μm or less. × (bad): The amount of side erosion exceeds 3.5 μm.

(Evaluation of Copper (Cu) Defects) When evaluating the amount of side etching, a photosensitive resin laminate with a thickness of 1-20 μm in the photosensitive resin layer was laminated on a PET substrate with a copper layer by the method described in the above (Laminating), after 15 minutes The evaluation substrate. The pattern of line/space=10 μm/10 μm was exposed to this laminated evaluation substrate, and then developed by the method described in the above (Development). Then, for the substrate with the line/space pattern, the dipping method is used to etch 1.5 times the minimum etching time under the conditions of an aqueous solution containing 2% by mass of hydrochloric acid and 2% by 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, a NaOH aqueous solution with a concentration of 3% by mass was used as a peeling solution, and the cured film on the substrate was peeled and removed at a temperature of 50°C to obtain a copper wire pattern. The copper wire pattern was measured and observed by an optical microscope, and The classification 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 reduced.

(Minimum development time) Laminate a photosensitive resin laminate with a thickness of 1-20 μm on a copper foil laminate substrate with a thickness of 18 μm and a copper foil laminate with a thickness of 0.4 mm using the method described in (Laminating) above to obtain a laminate body. After the support film laminated on the photosensitive layer is removed, a 1.0% by mass sodium carbonate aqueous solution is used for spray development at 23° C. for a predetermined time.

Observe the surface of the substrate after development, take the time without remaining development residue as the minimum development time, and evaluate it according to the following criteria. ◎ (Significantly good): The minimum development time is within 15 s. ○ (good): The minimum development time is within 20 s. △(Pass): The minimum development time is within 25 s. × (bad): The minimum development time is within 30 s.

(Development residue test of photosensitive layer) Using the method described in (Laminating) above, a photosensitive resin laminate with a thickness of 1-20 μm was laminated on copper with a thickness of 0.4 mm laminated with a copper foil with a thickness of 18 μm. The foil is laminated on the substrate to obtain a laminated body. Store in a N ₂ environment at 60°C for 3 hours. Take out the stored substrate, remove the support film laminated on the photosensitive layer, and then perform spray development with a 1.0% by mass sodium carbonate aqueous solution at 23° C. and a minimum development time × 1.2 times. The surface of the substrate after development was observed, and the development residue was evaluated as described below. ○: There is no development residue on the surface of the substrate. △: A small amount of development residue was generated on the surface of the substrate. ×: Development residue is generated on the surface of the substrate.

For each example and comparative example, the composition of the photosensitive resin composition and the evaluation results of the laminate are shown in Tables 3 to 5. In addition, Table 6 shows the name of each component and the solvent used in 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 Defence points 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 divided into 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 X X X △ ◎ Resolution - - - X O SE - - - X X Cu defects - - - X X 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 (10% pentaacrylate ratio) (MA-DPH) Ingredient B-2 Dimethacrylate of polyethylene glycol (MSR-348) by adding an average of 1 mol of ethylene oxide to both ends of bisphenol A Ingredient B-3 Dimethacrylate of polyethylene glycol (MFEM-10) by adding an average of 5 mol of ethylene oxide to both ends of bisphenol A Ingredient B-4 Hexamethacrylate of polyethylene glycol (M-13MDP) obtained by adding an average of 13 mol of ethylene oxide Ingredient B-5 ε-Caprolactone modified tris(acryloyloxyethyl) isocyanurate (M-1683) Ingredient B-6 Tetramethacrylate obtained by adding an average of 15 mol of ethylene oxide to the ends of the 4 hydroxyl groups of pentaerythritol Ingredient B-7 It is the fourth one by adding an average of 9 mol of ethylene oxide to the ends 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 Shinnakamura 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

It can be seen from the table that in Comparative Examples 4 to 7 in which the ratio of acid value A to thickness T (A/T) is less than 5, the minimum development time and resolution are not sufficient. In addition, when the film thickness is 20 μm and 15 μm, the development time is 30 seconds or more and the developability is poor, so other items cannot be evaluated. On the other hand, in Comparative Example 8 where the ratio (A/T) is greater than 90, the acid value is high and PTMG (Polytetramethylene glycol, polytetramethylene glycol) is removed, and development can be performed, but due to the high acid value and the removal of PTMG, Therefore, Cu defects, resolution, and undercut (SE) are not sufficient. 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 if it is a thin film, it can be seen that the image quality tends to deteriorate. In contrast, in the embodiment where the ratio of acid value A to thickness T (A/T) is 5 or more and 90 or less, it is obtained in any one of the minimum development time, resolution, undercut, Cu defect, and development residue test A sufficiently good result. [Industrial availability]

The photosensitive resin composition, photosensitive resin laminate, and dry film photoresist of the present invention can suppress defects in patterns formed by using them, and therefore can improve the yield of objects or patterns formed by photolithography , And/or excellent in lamination, minimum development time, resolution, undercut (SE), Cu defects, and development residues, and can be widely used in the formation of photoresist patterns or wiring patterns.

Claims (27)

A dry film photoresist, which has Support film, and A layer formed on the support film and containing a photosensitive resin composition, the photosensitive resin composition containing (A) Alkali-soluble resin, (B) Photopolymerizable compounds with ethylenically unsaturated bonds, (C) photopolymerization initiator, and (D) Dyes; The weight average molecular weight of the above component (A) calculated by gel permeation chromatography (GPC) on the above component (A) and calculated using the calibration curve of polystyrene is below 60,000, and The above-mentioned 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: a photosensitive resin layer containing the photosensitive resin composition is laminated on a support with a thickness of 25 μm. The photosensitive resin laminate is formed by laminating the photosensitive resin laminate on a copper foil laminate substrate with a thickness of 35 μm, a thickness of 1.6 mm and a through hole of 6 mm in diameter, and exposure and development. After the cured film, the support was peeled off from the cured film, and the surface of the support was peeled off at a speed of 100 mm/min to pierce the part of the photosensitive resin layer corresponding to the center of the through hole with a diameter of 2.0 mm The cylinder. The dry film photoresist of claim 1, wherein the number of double bonds of the photosensitive resin composition is 1.50 mmol/g or more based on the solid content of the photosensitive resin composition. The dry film photoresist of claim 1, wherein the photosensitive resin composition contains a trifunctional or more multifunctional monomer as the (B) component. The dry film photoresist according to claim 1, wherein the photosensitive resin composition contains (B-ii) a compound having a skeleton derived from dipentaerythritol but not containing an alkylene oxide as a multifunctional monomer having a trifunctional or higher function. (B) Ingredients. The dry film photoresist of claim 4, wherein the photosensitive resin composition further contains (B-iii) a (meth)acrylate compound having a skeleton derived from bisphenol as a bifunctional monomer as the component (B) . The dry film photoresist according to any one of claims 1 to 5, wherein the photosensitive resin composition further contains a plasticizer. The dry film photoresist of any one of claims 1 to 6, which contains a leuco dye as the above-mentioned dye. Such as the dry film photoresist of any one of claims 1 to 7, wherein the above-mentioned maximum point load does not reach 250 gf. A dry film photoresist, which has Support film, and A layer formed on the support film and containing a photosensitive resin composition, the photosensitive resin composition containing (A) Alkali-soluble resin, (B) Photopolymerizable compounds having ethylenically unsaturated bonds, and (C) Photopolymerization initiator; and The above-mentioned photosensitive resin composition contains (B-ii) as a multifunctional monomer with three or more functions, a compound having a skeleton derived from dipentaerythritol but not containing an alkylene oxide group, and (B-iii) which is a bifunctional monomer, has a (meth)acrylate compound derived from a bisphenol skeleton as the (B) component. The dry film photoresist of claim 9, wherein the ratio of (B-ii)/(B-iii) above is 10 to 80% by mass. The dry film photoresist of claim 9 or 10, wherein in the above-mentioned (B) component, the ratio of the above-mentioned (B-ii) and the above-mentioned (B-iii) is 50% by mass or more. The dry film photoresist according to any one of claims 9 to 11, which further contains (B-i) a (meth)acrylate compound having a skeleton derived from dipentaerythritol and containing an epoxy group as the above-mentioned (B) component. The dry film photoresist of any one of claims 9 to 12, wherein the above component (A) is measured by gel permeation chromatography (GPC) and the above component ( A) The weight average molecular weight is less than 60,000. The dry film photoresist of any one of claims 9 to 13, wherein the above-mentioned 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: A photosensitive resin layer containing the photosensitive resin composition was laminated at 25 μm to produce a photosensitive resin laminate. The photosensitive resin laminate was laminated on a copper foil with a thickness of 35 μm and had a thickness of 1.6 mm and a diameter of 6 mm The through-hole copper foil laminate substrate is exposed and developed to form a cured film. After that, the support is peeled off from the cured film, and the surface of the support is opposed to the surface at a speed of 100 mm/min. The center of the through hole corresponds to the part of the photosensitive resin layer that pierces a cylinder with a diameter of 2.0 mm. The dry film photoresist of any one of claims 9 to 14, wherein the number of double bonds of the photosensitive resin composition is 1.50 mmol/g or more based on the solid content of the photosensitive resin composition. The dry film photoresist according to any one of claims 9 to 15, wherein the photosensitive resin composition further contains a plasticizer. The dry film photoresist of any one of claims 9 to 16, which contains a leuco dye as the above-mentioned dye. Such as the dry film photoresist of any one of claims 9 to 17, wherein the above-mentioned maximum point load does not reach 250 gf. A method for forming a photoresist pattern includes the following steps: Laminating the dry film photoresist according to any one of claims 1 to 18 on the substrate; Expose the laminated dry film photoresist; and The exposed dry film photoresist is developed. A method for forming a wiring pattern includes the following steps: Laminating the dry film photoresist according to any one of claims 1 to 18 on the substrate; Expose the laminated dry film photoresist; Developing the exposed dry film photoresist to form a photoresist pattern; and Etching or plating the substrate on which the photoresist pattern is formed. 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) Alkali-soluble resins that do not contain ethylenic unsaturated groups in the chain, (B) photopolymerizable compounds having ethylenic unsaturated bonds, and (C) photopolymerization initiators; 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 The ratio (A/T) is 5 or more and 90 or less. The photosensitive resin laminate of claim 21, wherein the photosensitive resin composition further contains a compound having polytetramethylene oxide as a structural unit as the (D) component. The photosensitive resin laminate of claim 21 or 22, wherein the photosensitive resin composition further contains a compound having a benzotriazole skeleton as the (E) component. The photosensitive resin laminate according to any one of claims 21 to 23, wherein the photosensitive resin composition has a photopolymerizable compound containing tetrafunctional or higher ethylenically unsaturated bonds as the (B) component. The photosensitive resin laminate of claim 22, wherein the ratio of the above-mentioned (A) component to the total of the above-mentioned (B) component and the above-mentioned (D) component [(A) component/((B) component + (D) component)) ] More than 0 and 1.4 or less. The photosensitive resin laminate according to any one of claims 21 to 25, wherein the weight average molecular weight of the component (A) is 20,000 or more. The photosensitive resin laminate according to any one of claims 21 to 26, wherein the acid value (acid equivalent) of the non-volatile component of the photosensitive resin composition exceeds 0 and is 79.0 or less.