KR20230161863A - Photosensitive resin composition, photosensitive element, and method for producing a laminate - Google Patents

Abstract

A photosensitive resin composition containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a hydrogen donor, wherein the photopolymerizable compound includes a compound having a ditrimethylolpropane skeleton. A photosensitive element (1) comprising a support (2) and a photosensitive resin layer (3) disposed on the support (2), wherein the photosensitive resin layer (3) contains the photosensitive resin composition described above.

Description

Photosensitive resin composition, photosensitive element, and method for producing a laminate

This disclosure relates to a photosensitive resin composition, a photosensitive element, a method for producing a laminate, etc.

In the production of a laminate that can be used as a wiring board, a resist pattern is formed to obtain desired wiring. A resist pattern can be formed by exposing and developing a photosensitive resin layer obtained using a film-like photosensitive resin composition. As a photosensitive resin composition, various compositions are being examined. For example, in Patent Document 1 below, a photosensitive resin composition containing an anthracene derivative is described.

Patent Document 1: International Publication No. 2007/004619

The cured product pattern used as a resist pattern is formed, for example, by photocuring (exposure) a photosensitive resin layer disposed on a substrate, and then developing and removing the uncured portion (unexposed portion) of the photosensitive resin layer. Then, after treatment (for example, plating treatment) is applied to the portion of the substrate where the cured product pattern is not formed, the cured product pattern is peeled off (removed). In this case, from the viewpoint of efficiency, etc., it is required to shorten the peeling time required for peeling the hardened portion.

One aspect of the present disclosure aims to provide a photosensitive resin composition capable of shortening the peeling time of the cured portion. Another aspect of the present invention aims to provide a photosensitive element using the photosensitive resin composition. Another aspect of the present invention aims to provide a method for manufacturing a laminate using the photosensitive resin composition described above.

One aspect of the present disclosure is a photosensitive resin composition comprising a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a hydrogen donor, wherein the photopolymerizable compound includes a compound having a ditrimethylolpropane skeleton. It's about.

According to such a photosensitive resin composition, the peeling time of the cured portion of the photosensitive resin composition can be shortened.

Another aspect of the present disclosure relates to a photosensitive element comprising a support and a photosensitive resin layer disposed on the support, wherein the photosensitive resin layer includes the photosensitive resin composition described above.

Another aspect of the present disclosure includes a process of disposing a photosensitive resin layer on a substrate using the photosensitive resin composition described above or the photosensitive element described above, and a process of photocuring a portion of the photosensitive resin layer; A laminate comprising a step of removing an uncured portion of the photosensitive resin layer to form a cured product pattern, and a step of forming a metal layer on at least a portion of the portion of the substrate where the cured product pattern is not formed. It relates to a manufacturing method.

According to one aspect of the present disclosure, a photosensitive resin composition capable of shortening the peeling time of the cured portion can be provided. According to another aspect of the present invention, a photosensitive element using the photosensitive resin composition can be provided. According to another aspect of the present invention, a method for manufacturing a laminate using the photosensitive resin composition described above can be provided. According to another aspect of the present invention, application of the photosensitive resin composition or photosensitive element to the formation of a resist pattern can be provided. According to another aspect of the present invention, application of the photosensitive resin composition or photosensitive element to the manufacture of a wiring board can be provided.

1 is a schematic cross-sectional view showing an example of a photosensitive element.
Figure 2 is a schematic diagram showing an example of a method for manufacturing a laminate.

Hereinafter, embodiments of the present disclosure will be described in detail.

“A or more” in a numerical range means A, and a range exceeding A. “A or less” in the numerical range means A and the range less than A. In the numerical range described in steps in this specification, the upper or lower limit of the numerical range at a certain level can be arbitrarily combined with the upper or lower limit of the numerical range at another level. In the numerical range described in this specification, the upper or lower limit of the numerical range may be replaced with the value shown in the examples. “A or B” may include either A or B, or may include both. Unless otherwise specified, the materials exemplified in this specification can be used individually or in combination of two or more types. The content of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified, when multiple substances corresponding to each component exist in the composition. The term "membrane" includes not only the shaped structure formed on the entire surface when observed in plan view, but also the shaped structure formed on a part of the surface. The word "process" is included in this term not only as an independent process, but also when the intended effect of the process is achieved even if it cannot be clearly distinguished from other processes. “(meth)acrylate” means at least one of acrylate and the corresponding methacrylate. The same applies to other similar expressions such as “(meth)acrylic acid”. Unless otherwise specified, the “alkyl group” may be linear, branched, or cyclic.

In this specification, “(poly)oxyalkylene group” means at least one of an oxyalkylene group and a polyoxyalkylene group (a group in which two or more alkylene groups are linked by an ether bond). The same applies to other similar expressions such as “(poly)oxyethylene group” and “(poly)oxypropylene group”. “EO modified” means a compound having a (poly)oxyethylene group. “PO modified” means a compound having a (poly)oxypropylene group. “EO·PO modified” means a compound having a (poly)oxyethylene group and/or a (poly)oxypropylene group.

In this specification, "solid content of the photosensitive resin composition" refers to the non-volatile content excluding volatile substances (water, solvent, etc.) in the photosensitive resin composition. That is, “solid content” refers to components (components other than the solvent) that remain without volatilizing when the photosensitive resin composition is dried, and also includes liquid, syrup, or wax components at room temperature (25°C).

<Photosensitive resin composition and cured material>

The photosensitive resin composition according to the present embodiment includes (A) a binder polymer (component (A)), (B) a photopolymerizable compound (component (B)), (C) a photopolymerization initiator (component (C)), (D) It contains a hydrogen donor (component (D)), and the photopolymerizable compound includes a compound having a ditrimethylolpropane skeleton. The photosensitive resin composition according to this embodiment can be used, for example, as a negative photosensitive resin composition.

The photosensitive resin composition according to this embodiment has photocurability, and a cured product can be obtained by photocuring the photosensitive resin composition. The cured product according to the present embodiment is a cured product (photocured product) of the photosensitive resin composition according to the present embodiment. The cured product according to the present embodiment may be in the form of a pattern (cured product pattern) or may be a resist pattern. The minimum or maximum value of the visible light transmittance (for example, visible light transmittance at a thickness of 5.0 μm) of the photosensitive resin composition and the cured product according to the present embodiment is 90% or less, less than 90%, 85% or less, or 80%. It may be less than %. As the visible light transmittance, for example, the transmittance in the wavelength range of 400 to 700 nm can be used.

The thickness of the cured product according to this embodiment may be 1 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, or 25 μm or more. The thickness of the cured product according to this embodiment may be 100 μm or less, 80 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, or 25 μm or less. From these viewpoints, the thickness of the cured product according to the present embodiment may be 1 to 100 μm, 10 to 50 μm, or 15 to 40 μm.

According to the photosensitive resin composition according to the present embodiment, the peeling time required for peeling (removing) the cured portion (exposed portion) of the photosensitive resin composition can be shortened. According to the photosensitive resin composition according to the present embodiment, for example, the peeling time of the cured portion of the photosensitive resin composition when the cured portion is immersed in a 3.0 mass% NaOH aqueous solution (50°C) can be shortened.

According to the photosensitive resin composition according to this embodiment, excellent sensitivity to actinic rays can be obtained. According to the photosensitive resin composition according to the present embodiment, uncured portions can be well removed by developing treatment, and excellent resolution can be obtained. According to the photosensitive resin composition according to the present embodiment, it is possible to ensure that the cured portion remains well during development treatment, and excellent adhesion can be obtained.

The photosensitive resin composition according to this embodiment contains a binder polymer as (A) component. Examples of the component (A) include acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, and phenol resin. Acrylic resin is a resin having a compound having a (meth)acryloyl group ((meth)acrylic acid compound) as a monomer unit, and includes styrene-based resin, epoxy-based resin, amide-based resin, amide-epoxy-based resin, Alkyd resins and phenolic resins belong to acrylic resins.

The component (A) may contain an acrylic resin from the viewpoint of easily shortening the peeling time of the hardened portion and from the viewpoint of easy obtaining of excellent sensitivity, resolution, and adhesion. The content of the acrylic resin is 50% by mass or more, 50% by mass, based on the total mass of component (A), from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of ease of obtaining excellent sensitivity, resolution, and adhesion. %, 70% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, or substantially 100% by mass (an embodiment in which component (A) is substantially composed of acrylic resin). do.

Examples of compounds having a (meth)acryloyl group include (meth)acrylic acid and (meth)acrylic acid ester. As (meth)acrylic acid ester, (meth)acrylic acid alkyl ((meth)acrylic acid alkyl ester, excluding compounds corresponding to (meth)acrylic acid cycloalkyl), (meth)acrylic acid cycloalkyl ((meth)acrylic acid cycloalkyl ester) , aryl (meth)acrylic acid ((meth)acrylic acid aryl ester), (meth)acrylamide compounds (diacetone acrylamide, etc.), (meth)acrylic acid glycidyl ester, and styryl (meth)acrylic acid.

Component (A) may have (meth)acrylic acid as a monomer unit from the viewpoint of easily shortening the peeling time of the hardened portion and from the viewpoint of being easy to obtain excellent sensitivity, resolution, and adhesion.

When component (A) has (meth)acrylic acid as a monomer unit, the content of the monomer unit of (meth)acrylic acid is adjusted from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easy to obtain excellent sensitivity, resolution, and adhesion. , it may be within the following range based on the total amount of monomer units constituting component (A). The content of the monomer unit of (meth)acrylic acid is 1% by mass or more, 5% by mass or more, 10% by mass or more, 12% by mass or more, 15% by mass or more, 18% by mass or more, 20% by mass or more, or 25% by mass. It may be more than %. The content of the monomer unit of (meth)acrylic acid may be 50 mass% or less, less than 50 mass%, 45 mass% or less, 40 mass% or less, 35 mass% or less, or 30 mass% or less. From these viewpoints, the content of the monomer unit of (meth)acrylic acid may be 1 to 50 mass%, 10 to 45 mass%, or 15 to 40 mass%.

Component (A) may have an alkyl (meth)acrylate as a monomer unit from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of being easy to obtain excellent sensitivity, resolution, and adhesion. Examples of the alkyl group of alkyl (meth)acrylate include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., and the alkyl group is , various structural isomers may be used. The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is 1 to 4, 1 to 3, 2 to 3, or It can be 1 or 2.

The alkyl group of alkyl (meth)acrylate may have a substituent. Examples of the substituent include hydroxy group, amino group, epoxy group, furyl group, halogeno group (fluoro group, chloro group, bromo group, etc.). (A) Components include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3 (meth)acrylic acid. -Tetrafluoropropyl, α-chloro(meth)acrylic acid, α-bromo(meth)acrylic acid, etc. are mentioned.

Component (A) may have hydroxyalkyl (meth)acrylate as a monomer unit from the viewpoint of ease of shortening the peeling time of the cured portion and of ease of obtaining excellent sensitivity, resolution, and adhesion. Examples of hydroxyalkyl (meth)acrylate include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, ( Meth) hydroxyhexyl acrylate, etc. can be mentioned.

Content of alkyl (meth)acrylate monomer units when component (A) has alkyl (meth)acrylate as a monomer unit, or when component (A) has hydroxyalkyl (meth)acrylate as a monomer unit The content of the monomer unit of hydroxyalkyl (meth)acrylate in the monomer unit constituting component (A) is determined from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of ease of obtaining excellent sensitivity, resolution, and adhesion. It may be within the following range based on the total amount of the unit. The content of the above-mentioned monomer units may be 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 2 mass% or more, or 3 mass% or more. The content of the above-mentioned monomer units may be 20 mass% or less, 18 mass% or less, 15 mass% or less, 12 mass% or less, 10 mass% or less, 8 mass% or less, 5 mass% or less, or 3 mass% or less. do. From these viewpoints, the content of the above-mentioned monomer units may be 0.1 to 20 mass%, 0.5 to 10 mass%, or 1 to 8 mass%.

Component (A) may have aryl (meth)acrylate as a monomer unit from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of being easy to obtain excellent sensitivity, resolution, and adhesion. Examples of aryl (meth)acrylate include benzyl (meth)acrylate, phenyl (meth)acrylate, and naphthyl (meth)acrylate.

When the component (A) has aryl (meth)acrylate as a monomer unit, the content of the aryl (meth)acrylate monomer unit is adjusted from the viewpoint of easily shortening the peeling time of the cured portion and obtaining excellent sensitivity, resolution, and adhesion. From a simple point of view, the range below may be acceptable based on the total amount of monomer units constituting component (A). The content of the monomer unit of aryl (meth)acrylate may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, or 20% by mass or more. The content of the monomer unit of aryl (meth)acrylate is 50 mass% or less, less than 50 mass%, 45 mass% or less, 40 mass% or less, 35 mass% or less, 30 mass% or less, 25 mass% or less, or 20 mass% or less. It may be less than mass%. From these viewpoints, the content of the monomer unit of aryl (meth)acrylate may be 1 to 50 mass%, 5 to 40 mass%, or 10 to 30 mass%.

Component (A) may have a styrene compound as a monomer unit from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of being easy to obtain excellent sensitivity, resolution, and adhesion. Examples of styrene compounds include styrene and styrene derivatives. Styrene derivatives include vinyltoluene and α-methylstyrene. Component (A) may have hydroxyalkyl (meth)acrylate and a styrene compound as monomer units from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of ease of obtaining excellent sensitivity, resolution, and adhesion.

When the component (A) has a styrene compound as a monomer unit, the content of the monomer unit of the styrene compound is adjusted from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easy to obtain excellent sensitivity, resolution, and adhesion, (A) It may be within the following range based on the total amount of monomer units constituting the component. The content of the monomer unit of the styrene compound is 10 mass% or more, 20 mass% or more, 25 mass% or more, 30 mass% or more, 35 mass% or more, 40 mass% or more, 45 mass% or more, 47 mass% or more, Alternatively, it may be 50% by mass or more. The content of the monomer unit of the styrene compound is 90 mass% or less, 85 mass% or less, 80 mass% or less, 75 mass% or less, 70 mass% or less, 65 mass% or less, 60 mass% or less, 55 mass% or less, Alternatively, it may be 50% by mass or less. From these viewpoints, the content of the monomer unit of the styrene compound is 10 to 90 mass%, 30 to 90 mass%, 40 to 90 mass%, 50 to 90 mass%, 10 to 70 mass%, 30 to 70 mass%, It may be 40 to 70 mass%, 50 to 70 mass%, 10 to 50 mass%, 30 to 50 mass%, or 40 to 50 mass%.

(A) Component may have other monomers as monomer units. Examples of such monomers include vinyl alcohol ethers (vinyl-n-butyl ether, etc.), (meth)acrylonitrile, maleic acid, maleic anhydride, maleic acid monoester (monomethyl maleate, monoethyl maleate) , monoisopropyl maleate, etc.), fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid, etc.

In component (A), the content of monomer units of the monomer having a carbazole ring is 0.1 mol% or less, less than 0.1 mol%, or 0.01 mol% or less, based on the total amount of monomer units constituting component (A). It may be 0.001 mol% or less, or substantially 0 mol%. (A) Component does not need to contain a binder polymer having a carbazole ring. That is, the photosensitive resin composition according to this embodiment does not need to contain a binder polymer having a carbazole ring.

The acid value of the component (A) may be within the following range from the viewpoint of easily shortening the peeling time of the hardened portion and from the viewpoint of ease of obtaining excellent sensitivity, resolution, and adhesion. (A) The acid value of the component is 80 mgKOH/g or more, 90 mgKOH/g or more, 100 mgKOH/g or more, more than 100 mgKOH/g, 120 mgKOH/g or more, 140 mgKOH/g or more, 150 mgKOH/g or more, 160 mgKOH/g or more, It may be more than 170mgKOH/g. The acid value of the component (A) may be 250 mgKOH/g or less, 240 mgKOH/g or less, 230 mgKOH/g or less, 210 mgKOH/g or less, 200 mgKOH/g or less, or 180 mgKOH/g or less. From these viewpoints, the acid value of component (A) may be 80 to 250 mgKOH/g, 100 to 230 mgKOH/g, or 150 to 200 mgKOH/g. The acid value of component (A) can be adjusted depending on the content of monomer units (for example, monomer units of (meth)acrylic acid) constituting component (A). (A) The acid value of component can be measured by the method described in the Examples. When the measurement object is a solution obtained by mixing component (A) with volatile components such as a synthetic solvent or dilution solvent, the acid value can be calculated using the following formula. (A) When mixing the component with volatile components such as synthetic solvent or diluting solvent, before accurately weighing, heat for 1 to 4 hours at a temperature at least 10°C higher than the boiling point of the volatile component to remove the volatile component. You can then measure the acid value.

Acid value=0.1×Vf×56.1/(Wp×I/100)

[Wherein, Vf represents the appropriate amount (unit: mL) of KOH (potassium hydroxide) aqueous solution, Wp represents the mass (unit: g) of the solution containing the component (A) to be measured, and I is, It represents the ratio (unit: mass%) of non-volatile matter in the solution containing the component (A) to be measured.]

The weight average molecular weight (Mw) of the component (A) may be within the following range from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of ease of obtaining excellent sensitivity, resolution, and adhesion. The weight average molecular weight of component (A) may be 10,000 or more, 20,000 or more, 25,000 or more, 30,000 or more, or 35,000 or more. The weight average molecular weight of component (A) may be 100,000 or less, 80,000 or less, 70,000 or less, 70,000 or less, 65,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, or 35,000 or less. From these viewpoints, the weight average molecular weight of component (A) may be 10,000 to 100,000, 20,000 to 50,000, or 30,000 to 40,000.

The number average molecular weight (Mn) of the component (A) may be within the following range from the viewpoint of easily shortening the peeling time of the hardened portion and from the viewpoint of ease of obtaining excellent sensitivity, resolution, and adhesion. The number average molecular weight of the component (A) may be 5000 or more, 10000 or more, 12000 or more, 15000 or more, or 16000 or more. The number average molecular weight of component (A) may be 50,000 or less, 40,000 or less, 35,000 or less, 30,000 or less, 25,000 or less, 20,000 or less, or 16,000 or less. From these viewpoints, the number average molecular weight of component (A) may be 5000 to 50000, 10000 to 25000, or 15000 to 20000.

The dispersion degree (weight average molecular weight/number average molecular weight) of the component (A) may be within the following range from the viewpoint of easily shortening the peeling time of the hardened portion and from the viewpoint of ease of obtaining excellent sensitivity, resolution, and adhesion. (A) The dispersion degree of component may be 1.0 or more, 1.5 or more, 1.8 or more, 2.0 or more, or 2.1 or more. The dispersion degree of component (A) may be 3.0 or less, 2.8 or less, 2.5 or less, 2.3 or less, or 2.2 or less. From these viewpoints, the dispersion degree of component (A) may be 1.0 to 3.0, 1.5 to 2.5, or 1.8 to 2.3.

The weight average molecular weight and number average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. More specifically, it can be measured under the conditions described in the examples. For compounds with low molecular weight, if it is difficult to measure the weight average molecular weight and number average molecular weight using the above-mentioned measurement methods, the molecular weight may be measured by another method and the average value may be calculated.

The content of component (A) may be in the following range based on the total solid content of the photosensitive resin composition from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easy to obtain excellent sensitivity, resolution, and adhesion. The content of component (A) may be 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, 45 mass% or more, or 50 mass% or more from the viewpoint of excellent film formability. . The content of component (A) may be 90 mass% or less, 80 mass% or less, 75 mass% or less, 70 mass% or less, 65 mass% or less, 60 mass% or less, or 55 mass% or less. From these viewpoints, the content of component (A) may be 10 to 90 mass%, 30 to 70 mass%, or 40 to 60 mass%.

The content of component (A) is as follows with respect to 100 parts by mass of the total amount of component (A) and component (B) from the viewpoint of ease of shortening the peeling time of the hardened portion and of ease of obtaining excellent sensitivity, resolution, and adhesion. It may be in the range of . The content of component (A) is, from the viewpoint of excellent film formability, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 45 parts by mass or more, 50 parts by mass or more, or 55 parts by mass or more. It may be more than parts by mass. The content of component (A) may be 90 parts by mass or less, 80 parts by mass or less, 75 parts by mass or less, 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less. From these viewpoints, the content of component (A) may be 10 to 90 parts by mass, 30 to 70 parts by mass, or 40 to 60 parts by mass.

The photosensitive resin composition according to this embodiment contains a photopolymerizable compound as the (B) component, and the photopolymerizable compound contains a compound having a ditrimethylolpropane skeleton. The photopolymerizable compound is a compound that is polymerized by light, and may be, for example, a compound having an ethylenically unsaturated bond.

The component (B) may contain a (meth)acrylic acid compound having a ditrimethylolpropane skeleton from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easy obtaining excellent sensitivity, resolution, and adhesion.

The number of (meth)acryloyl groups (total of acryloyl groups and methacryloyl groups) in the (meth)acrylic acid compound having a ditrimethylolpropane skeleton is from the viewpoint of easily shortening the peeling time of the cured portion, and , from the viewpoint of easy to obtain excellent sensitivity, resolution and adhesion, the range below may be sufficient. The number of (meth)acryloyl groups may be 2 or more, 3 or more, or 4 or more. The number of (meth)acryloyl groups may be 8 or less, 7 or less, 6 or less, 5 or less, or 4 or less. From these viewpoints, the number of (meth)acryloyl groups may be 2 to 8, 3 to 6, or 4.

Compounds having a ditrimethylolpropane skeleton have a (poly)oxyalkylene group (e.g., polyoxyalkylene group) from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of being easy to obtain excellent sensitivity, resolution, and adhesion. lene group) or at least one selected from the group consisting of a (poly)oxyethylene group and a (poly)oxypropylene group. The compound having a ditrimethylolpropane skeleton may have a polyoxyethylene group from the viewpoint of making it particularly easy to shorten the peeling time of the hardened portion and making it easy to obtain particularly excellent sensitivity. The compound having a ditrimethylolpropane skeleton may have a polyoxypropylene group, especially from the viewpoint of easily obtaining excellent resolution and adhesion.

The number of oxyalkylene groups (total per molecule), the number of oxyethylene groups, or the number of oxypropylene groups in the compound having a ditrimethylolpropane skeleton may be within the following ranges. The number of the above-mentioned groups is 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more from the viewpoint of easily shortening the peeling time of the hardened portion and easy to obtain excellent sensitivity and adhesion. It may be 12 or more, 15 or more, 18 or more, or 20 or more. The number of the above-mentioned groups may be 30 or less, 25 or less, 20 or less, 18 or less, 15 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less from the viewpoint of easy to obtain excellent sensitivity and resolution. do. In these terms, the numbers of the above-mentioned groups are 1 to 30, 4 to 20, 8 to 20, 12 to 20, 16 to 20, 4 to 16, 8 to 16, 12 to 16, 4 to 12, 8 to 12. , or it may be 4 to 8.

The molecular weight of the compound having a ditrimethylolpropane skeleton is 250 or more, 300 or more, 400 or more, 500 or more, and 600 or more from the viewpoint of easily shortening the peeling time of the cured portion and easy to obtain excellent sensitivity and adhesion. , 650 or more, 700 or more, 800 or more, 1000 or more, 1050 or more, 1100 or more, 1200 or more, or 1400 or more. The molecular weight of the compound having a ditrimethylolpropane skeleton may be 1500 or more, 1600 or more, or 1700 or more, especially from the viewpoint of easily obtaining excellent resolution and adhesion. The molecular weight of the compound having a ditrimethylolpropane skeleton is 10000 or less, 10000 or less, 8000 or less, 6000 or less from the viewpoint of easily shortening the peeling time of the cured portion and easy to obtain excellent sensitivity, resolution and adhesion. , may be 5000 or less, 3000 or less, 2000 or less, or 1800 or less. The molecular weight of the compound having a ditrimethylolpropane skeleton may be 1700 or less, 1600 or less, or 1500 or less from the viewpoint of particularly easy to shorten the peeling time of the cured portion and especially easy to obtain excellent sensitivity. The molecular weight of the compound having a ditrimethylolpropane skeleton may be 1400 or less, 1200 or less, 1100 or less, 1050 or less, 1000 or less, 800 or less, or 700 or less from the viewpoint of easily obtaining excellent resolution. From these viewpoints, the molecular weight of the compound having the ditrimethylolpropane skeleton is 250 to 10000, 500 to 5000, 600 to 2000, 800 to 2000, 1200 to 2000, 1500 to 2000, 600 to 1500, 800 to 1500, It may be 1200-1500, 600-1200, 800-1200, or 600-800.

The content of the compound having a ditrimethylolpropane skeleton is based on the total mass of component (B) from the viewpoint of easy to shorten the peeling time of the cured portion and easy to obtain excellent sensitivity, resolution, and adhesion. It may be within the following range. The content of the compound having a ditrimethylolpropane skeleton may be 1% by mass or more, 3% by mass or more, 5% by mass or more, 8% by mass or more, 10% by mass or more, or 11% by mass or more. The content of the compound having a ditrimethylolpropane skeleton is 50 mass% or less, less than 50 mass%, 40 mass% or less, 30 mass% or less, 20 mass% or less, 18 mass% or less, 15 mass% or less, or , may be 12% by mass or less. From these viewpoints, the content of the compound having a ditrimethylolpropane skeleton may be 1 to 50 mass%, 5 to 30 mass%, or 8 to 20 mass%.

The content of the compound having a ditrimethylolpropane skeleton is as follows based on the total solid content of the photosensitive resin composition from the viewpoint of ease of shortening the peeling time of the cured portion and of ease of obtaining excellent sensitivity, resolution, and adhesion. It may be in the range of . The content of the compound having a ditrimethylolpropane skeleton is 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 2 mass% or more, 3 mass% or more, 4 mass% or more, or 4.5 mass% or more. You can continue. The content of the compound having a ditrimethylolpropane skeleton is 20% by mass or less, 15% by mass or less, 10% by mass or less, 8% by mass or less, 6% by mass or less, 5% by mass or less, or less than 5% by mass. You can continue. From these viewpoints, the content of the compound having a ditrimethylolpropane skeleton is 0.1 to 20 mass%, 1 to 20 mass%, 3 to 20 mass%, 0.1 to 10 mass%, 1 to 10 mass%, 3 to It may be 10 mass%, 0.1 to 8 mass%, 1 to 8 mass%, 3 to 8 mass%, 0.1 to 5 mass%, 1 to 5 mass%, or 3 to 5 mass%.

The content of the compound having a ditrimethylolpropane skeleton is the total amount of component (A) and component (B) from the viewpoint of easy to shorten the peeling time of the hardened part and easy to obtain excellent sensitivity, resolution, and adhesion. The range below may be applicable to 100 parts by mass. The compound having a ditrimethylolpropane skeleton is 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, 4.5 parts by mass or more, or 5 parts by mass or more. It may be more than parts by mass. The content of the compound having a ditrimethylolpropane skeleton may be 20 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 6 parts by mass or less, or 5 parts by mass or less. From these viewpoints, the content of the compound having a ditrimethylolpropane skeleton is 0.1 to 20 parts by mass, 1 to 20 parts by mass, 3 to 20 parts by mass, 5 to 20 parts by mass, 0.1 to 10 parts by mass, 1 to 10 parts by mass. 10 parts by mass, 3 to 10 parts by mass, 5 to 10 parts by mass, 0.1 to 8 parts by mass, 1 to 8 parts by mass, 3 to 8 parts by mass, 5 to 8 parts by mass, 0.1 to 5 parts by mass, 1 to 5 parts by mass 2, or 3 to 5 masses may be added.

(B) Component may contain a compound that does not have a ditrimethylolpropane skeleton. Compounds that do not have a ditrimethylolpropane skeleton include bisphenol A-type (meth)acrylic acid compounds, EO-modified di(meth)acrylate, PO-modified di(meth)acrylate, and EO·PO-modified di(meth)acrylate. , polyalkylene glycol di(meth)acrylate (polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.), EO modified polyalkylene glycol di(meth)acrylate Rate, PO modified polyalkylene glycol di(meth)acrylate, EO·PO modified polyalkylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri. (meth)acrylate, EO modified trimethylol propain tri(meth)acrylate, PO modified trimethylol propain tri(meth)acrylate, EO·PO modified trimethylol propain tri(meth)acrylate, Tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, EO modified pentaerythritol tetra(meth)acrylate, PO modified pentaerythritol tetra(meth)acrylate, EO· PO modified pentaerythritol tetra(meth)acrylate, EO modified dipentaerythritol hexa(meth)acrylate, PO modified dipentaerythritol hexa(meth)acrylate, EO·PO modified dipentaerythritol hexa(meth)acrylate Acrylate, nonylphenoxypolyethyleneoxyacrylate, phthalic acid-based compounds, alkyl (meth)acrylate, photopolymerizable compounds (oxetane compounds, etc.) having at least one cationic polymerizable cyclic ether group in the molecule.

The component (B) is a bisphenol A type (meth)acrylic acid compound (a compound having a ditrimethylolpropane skeleton) from the viewpoint of easily shortening the peeling time of the hardened portion and from the viewpoint of easy to obtain excellent sensitivity, resolution, and adhesion. may be included). As bisphenol A type (meth)acrylic acid compounds, 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane (2,2-bis(4-((meth)acryloxypentaethoxy) )phenyl)propane, etc.), 2,2-bis(4-((meth)acryloxypolypropoxy)phenyl)propane, 2,2-bis(4-((meth)acryloxypolybutoxy)phenyl )propane, 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane, etc. Component (B) is 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl from the viewpoint of easy to shorten the peeling time of the hardened part and easy to obtain excellent sensitivity, resolution, and adhesion. ) propane may be included, and 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane may be included.

The content of the bisphenol A type (meth)acrylic acid compound is as follows based on the total mass of component (B) from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of ease of obtaining excellent sensitivity, resolution, and adhesion. It may be a range. The content of the bisphenol A type (meth)acrylic acid compound may be 50 mass% or more, more than 50 mass%, 60 mass% or more, 65 mass% or more, 70 mass% or more, or 75 mass% or more. The content of bisphenol A type (meth)acrylic acid compound is 99 mass% or less, 97 mass% or less, 95 mass% or less, 92 mass% or less, 90 mass% or less, 89 mass% or less, 85 mass% or less, or 80 mass% or less. It may be less than mass%. From these viewpoints, the content of the bisphenol A type (meth)acrylic acid compound may be 50 to 99 mass%, 60 to 95 mass%, or 70 to 90 mass%.

The content of the bisphenol A type (meth)acrylic acid compound is within the following range based on the total solid content of the photosensitive resin composition from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of ease of obtaining excellent sensitivity, resolution, and adhesion. It's okay. The content of the bisphenol A type (meth)acrylic acid compound may be 1% by mass or more, 5% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more. . The content of bisphenol A type (meth)acrylic acid compound is 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, or 35% by mass or less. It may be less than mass%. From these viewpoints, the content of the bisphenol A type (meth)acrylic acid compound is 1 to 70 mass%, 10 to 70 mass%, 20 to 70 mass%, 30 to 70 mass%, 1 to 50 mass%, 10 to 50 mass%. %, 20-50 mass%, 30-50 mass%, 1-40 mass%, 10-40 mass%, 20-40 mass%, or 30-40 mass% may be sufficient.

The content of component (B) may be in the following range based on the total solid content of the photosensitive resin composition from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easy to obtain excellent sensitivity, resolution, and adhesion. The content of component (B) may be 10 mass% or more, 15 mass% or more, 20 mass% or more, 25 mass% or more, 30 mass% or more, 35 mass% or more, or 40 mass% or more. (B) The content of component may be 90 mass% or less, 80 mass% or less, 70 mass% or less, 65 mass% or less, 60 mass% or less, 55 mass% or less, 50 mass% or less, or 45 mass% or less. do. From these viewpoints, the content of component (B) is 10 to 90 mass%, 20 to 90 mass%, 30 to 90 mass%, 40 to 90 mass%, 10 to 70 mass%, 20 to 70 mass%, 30 to It may be 70 mass%, 40-70 mass%, 10-50 mass%, 20-50 mass%, 30-50 mass%, or 40-50 mass%.

The content of component (B) is as follows with respect to 100 parts by mass of the total amount of component (A) and component (B) from the viewpoint of ease of shortening the peeling time of the hardened portion and of ease of obtaining excellent sensitivity, resolution, and adhesion. It may be in the range of . The content of component (B) may be 10 parts by mass or more, 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more. The content of component (B) may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, 50 parts by mass or less, or 45 parts by mass or less. From these viewpoints, the content of component (B) is 10 to 90 parts by mass, 20 to 90 parts by mass, 30 to 90 parts by mass, 40 to 90 parts by mass, 10 to 70 parts by mass, 20 to 70 parts by mass, 30 to 30 parts by mass. It may be 70 parts by mass, 40 to 70 parts by mass, 10 to 50 parts by mass, 20 to 50 parts by mass, 30 to 50 parts by mass, or 40 to 50 parts by mass.

The photosensitive resin composition according to this embodiment contains a photopolymerization initiator as (C) component.

(C) As a component, hexaarylbiimidazole compound; Benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1- [4-(4-morpholinyl)phenyl]-1-butanone, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, 2-methyl-1-[4 Aromatic ketones such as -(methylthio)phenyl]-2-morpholino-propanone-1; Quinone compounds such as alkylanthraquinone; Benzoin ether compounds such as benzoin alkyl ether; Benzoin compounds such as benzoin and alkylbenzoin; Benzyl derivatives such as benzyl dimethyl ketal; Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; Bis(2,6-dimethylbenzoyl)-2,4,4-trimethyl-pentylphosphine oxide; (2,4,6-trimethylbenzoyl)ethoxyphenylphosphine oxide, etc. can be mentioned.

Component (C) may contain a hexaarylbiimidazole compound from the viewpoint of easily shortening the peeling time of the hardened portion and from the viewpoint of easy to obtain excellent sensitivity, resolution, and adhesion. The aryl group in the hexaarylbiimidazole compound may be a phenyl group or the like. The hydrogen atom bonded to the aryl group in the hexaarylbiimidazole compound may be substituted with a halogen atom (chlorine atom, etc.).

The hexaarylbiimidazole compound may be a 2,4,5-triarylimidazole dimer. Examples of 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(o-chlorophenyl)-4,5-bis. -(m-methoxyphenyl)imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, etc. The hexaarylbiimidazole compound is 2-(o-chlorophenyl)-4,5-diphenylimide from the viewpoint of easy to shorten the peeling time of the hardened part and easy to obtain excellent sensitivity, resolution, and adhesion. It may contain a sol dimer, or it may contain 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

The content of the hexaarylbiimidazole compound is 50% by mass or more based on the total amount of component (C) from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easy to obtain excellent sensitivity, resolution, and adhesion. , more than 50% by mass, 70% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, or substantially 100% by mass (component (C) is substantially hexaarylbiimide An aspect consisting of a polyazole compound) may be used.

The content of component (C) may be in the following range based on the total solid content of the photosensitive resin composition from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easy to obtain excellent sensitivity, resolution, and adhesion. (C) The content of component may be 0.1 mass% or more, 0.5 mass% or more, 1 mass% or more, 2 mass% or more, 3 mass% or more, 4 mass% or more, 5 mass% or more, or 5.5 mass% or more. do. The content of component (C) may be 20 mass% or less, 15 mass% or less, 12 mass% or less, 10 mass% or less, 8 mass% or less, 7 mass% or less, or 6 mass% or less. From these viewpoints, the content of component (C) may be 0.1 to 20 mass%, 1 to 10 mass%, or 3 to 8 mass%.

The content of component (C) is as follows with respect to 100 parts by mass of the total amount of component (A) and component (B) from the viewpoint of ease of shortening the peeling time of the hardened part and of ease of obtaining excellent sensitivity, resolution and adhesion. It may be in the range of . (C) The content of component is 0.1 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, 3 parts by mass or more, 4 parts by mass or more, 5 parts by mass or more, 5.5 parts by mass or more, or, It may be 6 parts by mass or more. The content of component (C) may be 20 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, 10 parts by mass or less, 8 parts by mass or less, 7 parts by mass or less, or 6 parts by mass or less. From these viewpoints, the content of component (C) may be 0.1 to 20 parts by mass, 1 to 10 parts by mass, or 3 to 8 parts by mass.

The photosensitive resin composition according to the present embodiment contains a hydrogen donor (excluding the compounds corresponding to the (A) component, (B) component, or (C) component) as the (D) component. Examples of the hydrogen donor include bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, leuco crystal violet, and N-phenylglycine.

The content of component (D) is as follows with respect to 100 parts by mass of the total amount of component (A) and component (B) from the viewpoint of ease of shortening the peeling time of the hardened portion and of ease of obtaining excellent sensitivity, resolution, and adhesion. It may be in the range of . The content of component (D) may be 0.1 part by mass or more, 0.2 part by mass or more, 0.3 part by mass or more, 0.4 part by mass or more, or 0.5 part by mass or more. The content of component (D) may be 5 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, 1.5 parts by mass or less, 1 part by mass or less, 0.8 parts by mass or less, 0.7 parts by mass or less, or 0.5 parts by mass or less. do. From these viewpoints, the content of component (D) may be 0.1 to 5 parts by mass, 0.2 to 1 part by mass, or 0.3 to 0.8 parts by mass.

The photosensitive resin composition according to this embodiment may contain an anthracene compound as the (E) component. (E) Component can be used as an anthracene-based sensitizer (photosensitizer). (E) Components include 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 9,10-diethoxyanthracene. The component (E) may contain 9,10-dibutoxyanthracene from the viewpoint of easily shortening the peeling time of the hardened portion and from the viewpoint of easy to obtain excellent sensitivity, resolution, and adhesion.

The content of component (E) may be in the following range based on the total solid content of the photosensitive resin composition from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of ease of obtaining excellent sensitivity, resolution, and adhesion. (E) The content of the component may be 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, 0.2 mass% or more, 0.3 mass% or more, 0.4 mass% or more, 0.5 mass% or more, or 0.55 mass% or more. do. (E) The content of the component is 5 mass% or less, 3 mass% or less, 2 mass% or less, 1.5 mass% or less, 1 mass% or less, less than 1 mass%, 0.8 mass% or less, 0.7 mass% or less, or, It may be 0.6% by mass or less. From these viewpoints, the content of component (E) is 0.01 to 5 mass%, 0.1 to 5 mass%, 0.3 to 5 mass%, 0.5 to 5 mass%, 0.01 to 1 mass%, 0.1 to 1 mass%, 0.3 to 1 mass%, 0.5~1 mass%, 0.01 mass% or more but less than 1 mass%, 0.1 mass% or more but less than 1 mass%, 0.3 mass% or more but less than 1 mass%, 0.5 mass% or more but less than 1 mass%, 0.01~0.8 mass %, 0.1 to 0.8 mass %, 0.3 to 0.8 mass %, or 0.5 to 0.8 mass %.

The content of component (E) is as follows with respect to 100 parts by mass of the total amount of component (A) and component (B) from the viewpoint of easy to shorten the peeling time of the hardened part and easy to obtain excellent sensitivity, resolution and adhesion. It may be in the range of . (E) The content of the component is 0.01 parts by mass or more, 0.05 parts by mass or more, 0.1 parts by mass or more, 0.2 parts by mass or more, 0.3 parts by mass or more, 0.4 parts by mass or more, 0.5 parts by mass or more, 0.6 parts by mass or more, or, It may be 0.65 parts by mass or more. The content of component (E) may be 5 parts by mass or less, 3 parts by mass or less, 2 parts by mass or less, 1.5 parts by mass or less, 1 part by mass or less, less than 1 part by mass, 0.8 parts by mass or less, or 0.7 parts by mass or less. do. From these viewpoints, the content of component (E) is 0.01 to 5 parts by mass, 0.1 to 5 parts by mass, 0.3 to 5 parts by mass, 0.5 to 5 parts by mass, 0.01 to 1 part by mass, 0.1 to 1 part by mass, 0.3 to 5 parts by mass. 1 part by mass, 0.5 to 1 part by mass, 0.01 to less than 1 part by mass, 0.1 to 1 part by mass, 0.3 to 1 part by mass, 0.5 to 1 part by mass, 0.01 to 0.8 mass parts, 0.1 to 0.8 parts by mass, 0.3 to 0.8 parts by mass, or 0.5 to 0.8 parts by mass.

The photosensitive resin composition according to this embodiment may contain a polymerization inhibitor as the (F) component. Component (F) suppresses polymerization in unexposed areas during resist pattern formation and tends to improve resolution. As a polymerization inhibitor, t-butylcatechol (e.g., 4-t-butylcatechol), hindered amine (e.g., 2,2,6,6-tetramethyl-4-hydroxypiperidine-1) -oxyl), 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, etc.

The content of component (F) may be within the following range with respect to 100 parts by mass of the total amount of component (A) and component (B). (F) The content of the component is, from the viewpoint of easy to obtain excellent sensitivity and resolution, 0.001 part by mass or more, 0.003 part by mass or more, 0.005 part by mass or more, 0.01 part by mass or more, 0.015 part by mass or more, 0.02 part by mass or more. , may be 0.025 parts by mass or more. The content of component (F) may be 0.1 part by mass or less, 0.05 part by mass or less, 0.04 part by mass or less, or 0.03 part by mass or less from the viewpoint of easily obtaining excellent sensitivity and adhesion. From these viewpoints, the content of component (F) may be 0.001 to 0.1 parts by mass, 0.005 to 0.05 parts by mass, or 0.01 to 0.04 parts by mass.

The photosensitive resin composition according to this embodiment may contain an organic solvent. Examples of organic solvents include methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N,N-dimethylformamide, propylene glycol monomethyl ether, and the like.

The photosensitive resin composition concerning this embodiment may contain other components other than the components mentioned above. Other ingredients include dyes (malachite green, etc.), photosensitizers (excluding anthracene compounds), tribromophenyl sulfone, photochromic agents, exothermic color inhibitors, plasticizers (p-toluenesulfonamide, etc.), pigments, fillers, and anti-foaming agents. , flame retardants, stabilizers (light stabilizers, etc.), adhesion imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, heat crosslinking agents, etc.

In the photosensitive resin composition according to the present embodiment, the content of aluminum powder (aluminum particles), the content of aluminum alloy powder (alloy powder containing aluminum; aluminum alloy particles), or the total amount of aluminum powder and aluminum alloy powder is: Based on the total solid content of the photosensitive resin composition, it may be 20% by mass or less, less than 20% by mass, 10% by mass or less, 1% by mass or less, 0.1% by mass or less, 0.01% by mass or less, or substantially 0% by mass. . The photosensitive resin composition according to the present embodiment does not need to contain at least one selected from the group consisting of aluminum powder (aluminum particles) and aluminum alloy powder (aluminum alloy particles).

<Photosensitive element>

The photosensitive element according to the present embodiment includes a support and a photosensitive resin layer disposed on the support, and the photosensitive resin layer contains the photosensitive resin composition according to the present embodiment. The photosensitive element according to this embodiment may be provided with a protective layer disposed on the photosensitive resin layer. The photosensitive element according to this embodiment may be provided with a cushion layer, an adhesive layer, a light absorption layer, a gas barrier layer, etc. The photosensitive element may be in the form of a sheet or may be in the form of a photosensitive element roll wound around a core.

1 is a schematic cross-sectional view showing an example of a photosensitive element. As shown in FIG. 1, the photosensitive element 1 includes a support (support film) 2, a photosensitive resin layer 3 disposed on the support 2, and a photosensitive resin layer 3 disposed on the photosensitive resin layer 3. It is provided with a protective layer (protective film) 4. The photosensitive resin layer 3 consists of the photosensitive resin composition according to this embodiment.

The photosensitive element 1 can be obtained, for example, by the following procedure. First, a photosensitive resin layer (3) is formed on the support (2). The photosensitive resin layer 3 can be formed, for example, by drying an application layer formed by applying a photosensitive resin composition containing an organic solvent. Next, the protective layer (4) is disposed on the photosensitive resin layer (3).

Each of the support and the protective layer may be a polymer film having heat resistance and solvent resistance, and may be a polyester film (polyethylene terephthalate film, etc.), a polyolefin film (polyethylene film, polypropylene film, etc.), or a hydrocarbon-based polymer (polyolefin film, etc.). excluded), etc. The type of film constituting the protective layer and the type of film constituting the support may be the same or different from each other.

The thickness of the support may be 1 μm or more, 5 μm or more, 10 μm or more, or 15 μm or more from the viewpoint of easily suppressing breakage of the support when peeling the support from the photosensitive resin layer. The thickness of the support may be 100 μm or less, 50 μm or less, 30 μm or less, or 20 μm or less from the viewpoint of easy exposure when exposing through the support. From these viewpoints, the thickness of the support may be 1 to 100 μm.

The thickness of the protective layer is 1 μm or more, 5 μm or more, 10 μm or more, or 15 μm or more from the viewpoint of easily suppressing damage to the protective layer when laminating the photosensitive resin layer and support on the substrate while peeling off the protective layer. You can continue. The thickness of the protective layer may be 100 μm or less, 50 μm or less, or 30 μm or less from the viewpoint of easily improving productivity. From these viewpoints, the thickness of the protective layer may be 1 to 100 μm.

The thickness of the photosensitive resin layer (thickness after drying; when the photosensitive resin composition contains an organic solvent, thickness after volatilizing the organic solvent) may be within the following range. The thickness of the photosensitive resin layer may be 1 μm or more, 5 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, or 25 μm or more from the viewpoint of easy coating of the photosensitive resin composition and easy productivity improvement. The thickness of the photosensitive resin layer may be 100 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, or 25 μm or less from the viewpoint of easily obtaining excellent adhesion and resolution. From these viewpoints, the thickness of the photosensitive resin layer is 1 to 100 μm, 5 to 100 μm, 10 to 100 μm, 20 to 100 μm, 1 to 50 μm, 5 to 50 μm, 10 to 50 μm, 20 to 50 μm, 1 to 30 μm, 5 to 30 μm. , 10 to 30 μm, or 20 to 30 μm.

<Method for manufacturing laminate>

The method for manufacturing a laminate according to the present embodiment includes a photosensitive resin layer disposition step of disposing the photosensitive resin layer on a base material (for example, a substrate) using the photosensitive resin composition or photosensitive element according to the present embodiment, and photosensitive water. An exposure process of photocuring (exposing) a portion of the base layer, a development process of removing the uncured portion (unexposed portion) of the photosensitive resin layer to form a cured product pattern, and the portion of the substrate where the cured product pattern is not formed. A metal layer forming process is provided to form a metal layer on at least a portion of the. The laminate according to the present embodiment is obtained by the method for manufacturing a laminate according to the present embodiment, and may be a wiring board (for example, a printed wiring board). The laminate according to the present embodiment includes a substrate, a cured product pattern (cured product according to the present embodiment) disposed on the substrate, and at least a portion of the substrate where the cured product pattern is not formed. It may be an aspect provided with a metal layer.

In the photosensitive resin layer arrangement process, the photosensitive resin layer consisting of the photosensitive resin composition according to this embodiment is disposed on the base material. For example, the photosensitive resin layer may be formed by applying and drying the photosensitive resin composition on a substrate, or may be formed by removing the protective layer from the photosensitive element and then pressing the photosensitive resin layer of the photosensitive element to the substrate while heating.

In the exposure process, actinic light may be irradiated with a mask placed on the photosensitive resin layer, and areas of the photosensitive resin layer other than the area where the mask is placed may be exposed and photocured. LDI may be performed without using a mask. A part of the photosensitive resin layer may be exposed and photocured by irradiating actinic light in a desired pattern using a direct drawing exposure method such as an exposure method or a DLP exposure method. As a light source of actinic light, an ultraviolet light source or a visible light source may be used, such as a carbon arc lamp, mercury vapor arc lamp, high-pressure mercury lamp, ultra-high pressure mercury lamp, xenon lamp, gas laser (argon laser, etc.), and solid-state laser (YAG laser, etc.). , semiconductor lasers, etc.

The development method in the development process may be, for example, wet development or dry development. Wet development can be performed using a developer corresponding to the photosensitive resin composition, for example, by a method such as a dip method, a puddle method, a spray method, brushing, slapping, scrubbing, or shaking immersion. The developing solution is appropriately selected depending on the structure of the photosensitive resin composition, and may be an alkaline developing solution or an organic solvent developing solution.

Alkaline developers include alkali hydroxides such as hydroxide of lithium, sodium, or potassium; Alkali carbonates such as carbonates or bicarbonates of lithium, sodium, potassium or ammonium; Alkali metal phosphates such as potassium phosphate and sodium phosphate; Alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate; borax; sodium metasilicate; tetramethylammonium hydroxide; Ethanolamine; ethylenediamine; diethylenetriamine; 2-amino-2-hydroxymethyl-1,3-propanediol; 1,3-diamino-2-propanol; It may be an aqueous solution containing a base such as morpholine.

The organic solvent developer is an organic solvent such as 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone. It may be contained.

The metal layer in the metal layer formation process may be, for example, a metallic copper layer. The metal layer can be formed, for example, by performing plating treatment. The plating treatment may be one or both of electrolytic plating treatment and electroless plating treatment.

The method for manufacturing a laminate according to the present embodiment may include a step of further curing the resist pattern by heating at 60 to 250° C. or exposure at 0.2 to 10 J/cm ² after the development step.

The method for manufacturing a laminate according to the present embodiment may include a step of removing the cured product pattern after the metal layer forming step. The cured product pattern can be removed, for example, by performing development using a strong alkaline aqueous solution, such as an immersion method or a spray method.

Figure 2 is a schematic diagram showing an example of a method for manufacturing a laminated body (method for manufacturing a wiring board). In an example of a method for manufacturing a laminate, first, as shown in Figure 2 (a), a base material (for example, For example, a substrate for circuit formation) (10) is prepared. The conductor layer 10b may be, for example, a metallic copper layer.

Next, as shown in FIG. 2(b), the photosensitive resin layer 12 is disposed on the conductor layer 10b of the substrate 10 (photosensitive resin layer disposition step). In the photosensitive resin layer arrangement process, the photosensitive resin layer 12 is disposed on the conductor layer 10b of the base material 10 using the photosensitive resin composition or photosensitive element according to the present embodiment.

Next, as shown in FIG. 2(c), actinic light L is irradiated with the mask 14 disposed on the photosensitive resin layer 12, and the mask 14 in the photosensitive resin layer 12 is irradiated. The area other than the area where is placed is exposed to photocuring.

Next, after removing the mask 14, as shown in (d) of FIG. 2, areas other than the photocured portion (uncured portion) in the photosensitive resin layer are removed from the substrate 10 by development, and A resist pattern 12a consisting of a flowering portion (cured product of the photosensitive resin layer) is formed.

Next, as shown in FIG. 2(e), a wiring layer (metal layer) 16 is formed in a portion of the conductor layer 10b of the substrate 10 where the resist pattern 12a is not formed. The wiring layer 16 may be formed of the same material as the conductor layer 10b, or may be formed of a different material.

Next, as shown in FIG. 2(f), the resist pattern 12a is removed and the conductor layer 10b provided at a position corresponding to the resist pattern 12a is removed to form the conductor layer 10c. do. As a result, a wiring board 18 is obtained including the conductor layer 10c and the wiring layer 16 disposed on the insulating layer 10a. The conductor layer 10b can be removed by etching. The etching solution is appropriately selected depending on the type of the conductor layer 10b, and may be, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or a hydrogen peroxide etching solution.

Example

Hereinafter, the present disclosure will be described in more detail through examples, but the present disclosure is not limited to these examples.

<Synthesis of binder polymer>

A solution (a) was prepared by mixing 27 parts by mass of methacrylic acid, 3 parts by mass of 2-hydroxyethyl methacrylate, 20 parts by mass of benzyl methacrylate, 50 parts by mass of styrene, and 0.9 parts by mass of azobisisobutyronitrile. ) was prepared. Solution (b) was prepared by dissolving 0.5 parts by mass of azobisisobutyronitrile in 50 parts by mass of a mixed solution of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene. After adding 500 g of a mixed solution of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene to a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas introduction tube, the mixture was stirred while spraying nitrogen gas into the flask, The temperature was raised to ℃. After the solution (a) was dropped into the flask described above for 4 hours at a constant dropping rate, the solution in the flask was stirred at 80°C for 2 hours. Next, solution (b) was dropped into the flask described above for 10 minutes at a constant dropping rate, and then the solution in the flask was stirred at 80°C for 3 hours. Additionally, the solution in the flask was heated to 90°C for 30 minutes, kept at 90°C for 2 hours, then stirring was stopped and cooled to room temperature (25°C) to obtain a binder polymer solution. The non-volatile content (solid content) of the binder polymer solution was 56% by mass.

The acid value of the binder polymer was 176 mgKOH/g. The acid value was measured in the following procedure. First, 1 g of the binder polymer, the object of acid value measurement, was precisely weighed and then 30 g of acetone was added to the binder polymer to uniformly dissolve it to obtain a solution. Next, an appropriate amount of phenolphthalein, an indicator, was added to the solution, and then titration was performed using a 0.1N KOH (potassium hydroxide) aqueous solution. The acid value was obtained by calculating the mass (unit: mg) of KOH required to neutralize the acetone solution of the binder polymer.

The weight average molecular weight (Mw) of the binder polymer was 35,000 and the number average molecular weight (Mn) was 16,000. The weight average molecular weight and number average molecular weight were measured by gel permeation chromatography (GPC) under the following conditions and derived by conversion using a standard polystyrene calibration curve.

(GPC conditions)

Pump: Hitachi L-6000 type (made by Hitachi Seisakusho Co., Ltd., brand name)

Columns: A total of 3 below (made by Showa Denko Materials Co., Ltd., brand name)

Gelpack GL-R440

Gelpack GL-R450

Gelpack GL-R400M

Eluent: tetrahydrofuran

Measurement temperature: 40℃

Flow rate: 2.05mL/min

Detector: Hitachi L-3300 type RI (made by Hitachi Seisakusho Co., Ltd., brand name)

<Preparation of photosensitive resin composition>

(Example 1)

100 parts by mass of a solution of the above-mentioned binder polymer (binder polymer (non-volatile matter): 56 parts by mass), EO-modified ditrimethylolpropane tetramethacrylate (EO group: 4 (sum value), molecular weight: 698, Toho 5 parts by mass of Kagaku Kogyo Co., Ltd., and propylene glycol monomethyl of 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (EO average 10 mol adduct, molecular weight: 804) 35 parts by mass of (PO)(EO)(PO) modified dimethacrylate (EO average of 6 mol and PO average of 12 mol adducts (combined value), Molecular weight: 1114, manufactured by Showa Denko Materials Co., Ltd., brand name: FA-024M) 4 parts by mass, photopolymerization initiator (2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra 6 parts by mass of phenyl-1,2'-biimidazole, BCIM, manufactured by Hampford, 0.5 parts by mass of a hydrogen donor (Leuco Crystal Violet, LCV, manufactured by Yamada Chemical Industry Co., Ltd.), and a sensitizer (9,10-di) Butoxyanthracene, DBA, manufactured by Kawasaki Kasei Kogyo Co., Ltd.) 0.65 parts by mass, polymerization inhibitor A (4-t-butylcatechol, manufactured by DIC Corporation, brand name: DIC-TBC) 0.015 parts by mass, polymerization inhibitor B ( 0.01 parts by mass of Asahi Denka Kogyo Co., Ltd., brand name: LA-7RD), 0.02 parts by mass of dye (malachite green, MKG, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.), and additive A (carboxybenzotriazole, 5-amino-1H) - A mixture of tetrazole and methoxypropanol; 0.5 parts by mass of Sanwa Kasei Co., Ltd., brand name: SF-808H) and 1 part by mass of additive B (light stabilizer, Showa Denko Materials Co., Ltd., brand name: FA711MM) are mixed. By doing so, a photosensitive resin composition was prepared.

(Example 2)

EO-modified ditrimethylolpropane tetramethacrylate (EO group: 4 (sum value)) was replaced with EO-modified ditrimethylolpropane tetramethacrylate (EO group: 12 (sum value), molecular weight: 1050, Doho. A photosensitive resin composition was prepared in the same manner as in Example 1 except that it was changed to (manufactured by Kagaku Kogyo Co., Ltd.).

(Example 3)

EO-modified ditrimethylolpropane tetramethacrylate (EO group: 4 (sum value)) was replaced with EO-modified ditrimethylolpropane tetramethacrylate (EO group: 20 (sum value), molecular weight: 1402, Doho. A photosensitive resin composition was prepared in the same manner as in Example 1 except that it was changed to (manufactured by Kagaku Kogyo Co., Ltd.).

(Example 4)

EO modified ditrimethylolpropane tetramethacrylate (EO group: 4 (sum value)) was mixed with PO modified ditrimethylolpropane tetramethacrylate (PO group: 20 (sum value), molecular weight: 1762, Doho. A photosensitive resin composition was prepared in the same manner as in Example 1 except that it was changed to (manufactured by Kagaku Kogyo Co., Ltd.).

(Example 5)

EO modified ditrimethylolpropane tetramethacrylate (EO group: 4 (sum value)) is mixed with (EO)(PO) modified ditrimethylolpropane tetramethacrylate (EO group: 12 (sum value), A photosensitive resin composition was prepared in the same manner as in Example 1 except that it was changed to PO group: 8 (sum value), manufactured by Toho Chemical Industry Co., Ltd.).

(Comparative Example 1)

EO-modified ditrimethylolpropane tetramethacrylate (EO group: 4 (total value)) is changed to EO-modified bisphenol A dimethacrylate (molecular weight: 1686, manufactured by Miwon, product name: Miramer M2301), and BCIM's A photosensitive resin composition was prepared in the same manner as in Example 1, except that the usage amount was changed to 5 parts by mass, the usage amount of 4-t-butylcatechol was changed to 0.01 parts by mass, and the usage amount of malachite green was changed to 0.01 parts by mass. did.

(Comparative Example 2)

EO modified ditrimethylolpropane tetramethacrylate (EO group: 4 (combined value)) was mixed with 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane (ethylene oxide average of 12 mol and Propylene oxide adduct with an average of 4 mol, molecular weight: 1125, manufactured by Showa Denko Materials Co., Ltd., product name: FA-3200MY), the amount of BCIM used was changed to 5 parts by mass, and the amount of 4-t-butylcatechol used was changed to 0.01. A photosensitive resin composition was prepared in the same manner as in Example 1, except that the amount was changed to 0.01 parts by mass and the amount of malachite green used was changed to 0.01 parts by mass.

(Comparative Example 3)

EO-modified ditrimethylolpropane tetramethacrylate (EO group: 4 (total value)) was replaced with EO-modified urethane methacrylate (molecular weight: 692, manufactured by Shinnakamura Chemical Industry Co., Ltd., brand name: UA-1137). , the amount of BCIM used was changed to 5 parts by mass, the amount of 4-t-butylcatechol used was changed to 0.01 parts by mass, and the amount of malachite green used was changed to 0.01 parts by mass. By doing so, a photosensitive resin composition was prepared.

<Production of photosensitive elements>

A polyethylene terephthalate film (manufactured by Toray Corporation, brand name "FS-31") with a thickness of 16 μm was prepared as a support. After applying the above-described photosensitive resin composition on a support so that the thickness was uniform, it was sequentially dried with a hot air convection dryer at 80°C and 120°C to form a photosensitive resin layer (thickness after drying: 25 μm). By bonding a polyethylene film (manufactured by Tama Poly Co., Ltd., brand name "NF-15") as a protective layer to this photosensitive resin layer, a photosensitive element was obtained comprising a support, a photosensitive resin layer, and a protective layer in that order.

<Production of laminate>

A copper-clad laminate (substrate, manufactured by Showa Denko Materials Co., Ltd., brand name: MCL-E-67) having copper foil (thickness: 35 μm) disposed on both sides of a glass epoxy material was washed with air after pickling and water washing. It was dry. Next, the copper-clad laminate is heated to 80°C, and then the copper-clad laminate, the photosensitive resin layer, and the support are formed by laminating the above-described photosensitive element so that the photosensitive resin layer is in contact with the copper surface while peeling off the protective layer. A laminate prepared in the order was obtained. Laminating was performed using a heat roll at 110°C, a compression pressure of 0.4 MPa, and a roll speed of 1.0 m/min.

<Evaluation>

(Sensitivity)

After placing a 41-step tablet (manufactured by Showa Denko Materials Co., Ltd.) on the support of the above-described laminate, a straight exposure machine (manufactured by Via Mechanics Co., Ltd., brand name) using a blue-violet laser diode with a wavelength of 405 nm as a light source was used. : DE-1UH), the photosensitive resin layer was exposed through the support at an exposure amount (irradiation energy amount) such that the remaining number of steps after development of the 41-step tablet was 15 steps. At this time, sensitivity (light sensitivity) was evaluated based on the exposure amount (unit: mJ/cm ² ). The results are shown in Table 1. The smaller the exposure amount, the better the sensitivity.

(resolution)

After placing a 41-step tablet (manufactured by Showa Denko Materials Co., Ltd.) on the support of the above-mentioned laminate, a straight exposure machine (manufactured by Via Mechanics Co., Ltd., product name: DE-1UH) using a blue-violet laser diode with a wavelength of 405 nm as a light source is used. ), a drawing pattern with a line width (L)/space width (S) (hereinafter referred to as "L/S") of 3x/x (x=1 to 20, unit: μm, 1μm interval) is created. Using this, exposure (drawing) was performed on the photosensitive resin layer through the support at an exposure amount (irradiation energy amount) such that the number of remaining stages after development of the 41-stage tablet was 15 stages.

After exposure, the support was peeled from the laminate to expose the photosensitive resin layer, and the unexposed portion was removed by spraying a 1.0% by mass aqueous sodium carbonate solution at 30°C for twice the minimum development time. After development, the space portion (unexposed portion) is removed without residue, and the line portion (exposed portion) is formed without meandering or damage. Resolution is evaluated based on the minimum value of the space width in the resist pattern. did. The results are shown in Table 1. The smaller this number, the better the resolution.

The above-mentioned minimum development time was evaluated in advance in the following procedure. First, the above-described laminate was cut into a rectangular shape (12.5 cm x 4 cm), and then the support was peeled off to obtain a test piece. Next, using a 1.0 mass% sodium carbonate aqueous solution at 30°C, the unexposed photosensitive resin layer in the test piece was spray developed at a pressure of 0.18 MPa, and it was visually confirmed that the unexposed photosensitive resin layer was completely removed. The shortest time was obtained as the minimum development time (MD).

(adhesion)

After placing a 41-step tablet (manufactured by Showa Denko Materials Co., Ltd.) on the support of the above-mentioned laminate, a straight exposure machine (manufactured by Via Mechanics Co., Ltd., product name: DE-1UH) using a blue-violet laser diode with a wavelength of 405 nm as a light source is used. ), using a drawing pattern with L/S of In both cases, exposure (drawing) was performed on the photosensitive resin layer through the support.

After exposure, the support was peeled from the laminate to expose the photosensitive resin layer, and the unexposed portion was removed by spraying a 1.0% by mass aqueous sodium carbonate solution at 30°C for twice the minimum development time. After development, adhesion was evaluated based on the minimum value of the line width in the resist pattern in which the space portion (unexposed portion) was removed without residue and the line portion (exposed portion) was formed without meandering or damage. The results are shown in Table 1. The smaller this value, the better the adhesion.

(Peeling characteristics)

A peeling test was conducted using the above-described laminates of Examples 1 to 5 and Comparative Examples 1 to 3. Using the above-described laminate, a vertical exposure machine (manufactured by Via Mechanics Co., Ltd., brand name: DE-1UH) using a blue-violet laser diode with a wavelength of 405 nm as a light source was applied at the same exposure amount (irradiation energy amount) as the above-mentioned resolution evaluation. , exposure (drawing) was performed on the photosensitive resin layer through the support.

After exposure, the support was peeled from the laminate to expose the photosensitive resin layer. Then, a test specimen was obtained by developing in the same manner as the evaluation of resolution described above. Next, the above-described test specimen was immersed in a 3.0% by mass NaOH aqueous solution heated to 50°C in a thermostat, and the peeling time until the photosensitive resin layer after development was completely peeled off (removed) was measured. The results are shown in Table 1. A shorter peeling time means better peeling characteristics.

[Table 1]

One… photosensitive element
2… support
3, 12… photosensitive resin layer
4… protective layer
10… write
10a… insulating layer
10b, 10c... conductor layer
12a… resist pattern
14… mask
16… wiring layer
18… wiring board
L… active rays

Claims (13)

Contains a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a hydrogen donor,
A photosensitive resin composition in which the photopolymerizable compound contains a compound having a ditrimethylolpropane skeleton. In claim 1,
A photosensitive resin composition wherein the binder polymer has a styrene compound as a monomer unit. In claim 2,
A photosensitive resin composition wherein the content of the monomer units of the styrene compound is 20% by mass or more based on the total amount of monomer units constituting the binder polymer. In claim 2 or claim 3,
A photosensitive resin composition wherein the binder polymer further has aryl (meth)acrylate as a monomer unit. The method according to any one of claims 1 to 4,
A photosensitive resin composition in which the compound having a ditrimethylolpropane skeleton includes a (meth)acrylic acid compound having a ditrimethylolpropane skeleton. In claim 5,
A photosensitive resin composition wherein the number of (meth)acryloyl groups in the (meth)acrylic acid compound is 4. The method according to any one of claims 1 to 6,
A photosensitive resin composition in which the compound having the ditrimethylolpropane skeleton has a polyoxyalkylene group. In claim 7,
A photosensitive resin composition wherein the number of polyoxyalkylene groups is 4 to 20. The method according to any one of claims 1 to 8,
A photosensitive resin composition in which the content of the compound having the ditrimethylolpropane skeleton is 0.1 to 20 parts by mass with respect to 100 parts by mass of the total amount of the binder polymer and the photopolymerizable compound. The method according to any one of claims 1 to 9,
A photosensitive resin composition further containing an anthracene compound. In claim 10,
A photosensitive resin composition in which the content of the anthracene compound is 0.01% by mass or more and less than 1% by mass based on the total solid content of the photosensitive resin composition. Equipped with a support and a photosensitive resin layer disposed on the support,
A photosensitive element in which the photosensitive resin layer contains the photosensitive resin composition according to any one of claims 1 to 11. A step of disposing a photosensitive resin layer on a substrate using the photosensitive resin composition according to any one of claims 1 to 11, or the photosensitive element according to claim 12,
A process of photocuring a portion of the photosensitive resin layer;
A process of forming a cured pattern by removing the uncured portion of the photosensitive resin layer;
A method for producing a laminate, comprising a step of forming a metal layer on at least a portion of the substrate where the cured product pattern is not formed.

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