JP7287581B2 - Photosensitive resin composition, photosensitive element, and method for producing laminate - Google Patents

Description

TECHNICAL FIELD The present disclosure relates to a photosensitive resin composition, a photosensitive element, a method for producing a laminate, and the like.

In manufacturing 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 photosensitive resin composition. Various compositions have been studied as the photosensitive resin composition. For example, Patent Document 1 below describes a photosensitive resin composition containing an anthracene derivative.

WO2007/004619

A cured product pattern used as a resist pattern is obtained, for example, by photocuring (exposing) a photosensitive resin layer disposed on a substrate, and then developing and removing an uncured portion (unexposed portion) of the photosensitive resin layer. It is formed by Then, after the portion of the substrate where the cured product pattern is not formed is treated (for example, plating), 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 cured portion.

An object of one aspect of the present disclosure is to provide a photosensitive resin composition capable of shortening the peeling time of the cured portion. Another object of the present invention is to provide a photosensitive element using the photosensitive resin composition. Another object of the present invention is to provide a method for producing a laminate using the photosensitive resin composition described above.

One aspect of the present disclosure contains a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a hydrogen donor, and the photopolymerizable compound includes a compound having a ditrimethylolpropane skeleton. It relates to a flexible resin composition.

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 contains the photosensitive resin composition described above. .

Another aspect of the present disclosure includes a step of disposing a photosensitive resin layer on a substrate using the above-described photosensitive resin composition or the above-described photosensitive element, and partially removing the photosensitive resin layer a step of photocuring; a step of removing an uncured portion of the photosensitive resin layer to form a cured product pattern; and a step of forming a laminate.

According to one aspect of the present disclosure, it is possible to provide a photosensitive resin composition capable of shortening the peeling time of the cured portion. According to another aspect of the present invention, it is possible to provide a photosensitive element using the photosensitive resin composition. According to another aspect of the present invention, it is possible to provide a method for producing a laminate using the photosensitive resin composition described above. According to another aspect of the present invention, it is possible to provide application of the photosensitive resin composition or photosensitive element to formation of a resist pattern. According to another aspect of the present invention, it is possible to provide application of the photosensitive resin composition or photosensitive element to the production of wiring boards.

1 is a schematic cross-sectional view showing an example of a photosensitive element; FIG. It is a schematic diagram which shows an example of the manufacturing method of a laminated body.

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 a numerical range means A and a range less than A. In the numerical ranges described stepwise in this specification, the upper limit or lower limit of the numerical range in one step can be arbitrarily combined with the upper limit or lower limit of the numerical range in another step. In the numerical ranges described herein, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples. "A or B" may include either A or B, or may include both. The materials exemplified in this specification can be used singly or in combination of two or more unless otherwise specified. 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 there are multiple substances corresponding to each component in the composition. The term "layer" includes not only a shape structure formed over the entire surface but also a shape structure formed partially when viewed as a plan view. The term "process" is included in the term not only as an independent process, but also as long as the intended action of the process is achieved even if it is not clearly distinguishable from other processes. "(Meth)acrylate" means at least one of acrylate and its corresponding methacrylate. The same applies to other similar expressions such as "(meth)acrylic acid". An "alkyl group" may be linear, branched or cyclic, unless otherwise specified.

As used herein, a "(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.

As used herein, the term "solid content of the photosensitive resin composition" refers to the non-volatile content of the photosensitive resin composition excluding volatile substances (water, solvent, etc.). That is, the term “solid content” refers to components (components other than the solvent) that remain without volatilizing when the photosensitive resin composition dries, and includes components that are liquid, starch syrup-like, or wax-like at room temperature (25° C.).

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

The photosensitive resin composition according to the present embodiment is photocurable, and a cured product can be obtained by photocuring the photosensitive resin composition. The cured product according to this embodiment is a cured product (photocured product) of the photosensitive resin composition according to this embodiment. The cured product according to the present embodiment may be patterned (cured product pattern) or may be a resist pattern. The minimum or maximum visible light transmittance of the photosensitive resin composition and the cured product (e.g., visible light transmittance at a thickness of 5.0 μm) according to the present embodiment is 90% or less, less than 90%, or 85%. or less, or 80% or less. 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 this 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 when the cured portion of the photosensitive resin composition is immersed in a 3.0% by 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, the uncured portion can be satisfactorily removed by development processing, and excellent resolution can be obtained. According to the photosensitive resin composition according to the present embodiment, it is possible to leave the cured portion satisfactorily in development processing, and excellent adhesion can be obtained.

The photosensitive resin composition according to this embodiment contains a binder polymer as component (A). Component (A) includes acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, and the like. The acrylic resin is a resin having a compound ((meth)acrylic acid compound) having a (meth)acryloyl group as a monomer unit, and includes styrene resins, epoxy resins, and amide resins having the monomer unit. , amidoepoxy resins, 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 cured portion and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. The content of the acrylic resin is 50 mass based on the total mass of the component (A) from the viewpoint of easily shortening the peeling time of the cured part and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. % or more, 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 ((A) component is substantially It may be a mode) made of an acrylic resin.

(Meth)acryloyl group-containing compounds include (meth)acrylic acid and (meth)acrylic acid esters. (Meth)acrylates include alkyl (meth)acrylates (alkyl (meth)acrylates; excluding compounds corresponding to cycloalkyl (meth)acrylates), cycloalkyl (meth)acrylates ((meth) cycloalkyl acrylate), aryl (meth)acrylate (aryl (meth)acrylate), (meth)acrylamide compounds (diacetone acrylamide, etc.), glycidyl (meth)acrylate, styryl (meth)acrylic acid, etc. is mentioned.

The component (A) may have (meth)acrylic acid as a monomer unit from the viewpoint of easily shortening the peeling time of the cured portion, and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. .

When the component (A) has (meth)acrylic acid as a monomer unit, the content of the monomer unit of (meth)acrylic acid is from the viewpoint of easily shortening the peeling time of the cured part, and excellent sensitivity , from the viewpoint of easily obtaining resolution and adhesion, the total amount of the monomer units constituting the component (A) may be within the following ranges. The content of the monomer units 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, Alternatively, it may be 25% by mass or more. The content of the monomer units of (meth)acrylic acid may be 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less. . From these viewpoints, the content of the (meth)acrylic acid monomer unit may be 1 to 50% by mass, 10 to 45% by mass, or 15 to 40% by mass.

Component (A) has 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 easily obtaining excellent sensitivity, resolution and adhesion. good. Examples of the alkyl group of alkyl (meth)acrylate include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group and dodecyl group. and the alkyl groups may be of various structural isomers. The number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is 1 to 4, 1 to 3 from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. , 2-3, or 1-2.

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

Component (A) has a hydroxyalkyl (meth)acrylate as a monomer unit from the viewpoint of easily shortening the peeling time of the cured part and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. you can Hydroxyalkyl (meth)acrylates include hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, Hydroxyhexyl (meth)acrylate and the like can be mentioned.

(A) content of alkyl (meth)acrylate monomer units when component (A) has alkyl (meth)acrylate as a monomer unit, or component (A) contains hydroxyalkyl (meth)acrylate The content of the monomer unit of hydroxyalkyl (meth)acrylate in the case of having it as a monomer unit is from the viewpoint of easily shortening the peeling time of the cured part, and excellent sensitivity, resolution and adhesion. From the viewpoint of ease of use, the following ranges may be used based on the total amount of the monomer units constituting component (A). The content of the monomer units described above may be 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, or 3% by mass or more. The content of the above monomer units is 20% by mass or less, 18% by mass or less, 15% by mass or less, 12% by mass or less, 10% by mass or less, 8% by mass or less, 5% by mass or less, or 3% by mass. % or less. From these points of view, the content of the above monomer units may be 0.1 to 20% by mass, 0.5 to 10% by mass, or 1 to 8% by mass.

Component (A) has an aryl (meth)acrylate as a monomer unit from the viewpoint of easily shortening the peeling time of the cured part and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. good. Aryl (meth)acrylates include benzyl (meth)acrylate, phenyl (meth)acrylate, and naphthyl (meth)acrylate.

When the component (A) has an aryl (meth)acrylate as a monomer unit, the content of the monomer unit of the aryl (meth)acrylate is such that the peeling time of the cured portion is easily shortened, and an excellent From the viewpoint of easily obtaining the sensitivity, resolution and adhesion, the total amount of the monomer units constituting the component (A) may be within the following ranges. The content of the monomer units of the 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 units of the aryl (meth)acrylate is 50% by mass or less, less than 50% by mass, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, and 25% by mass or less. , or 20% by mass or less. From these viewpoints, the content of the monomer units of the aryl (meth)acrylate may be 1 to 50% by mass, 5 to 40% by mass, or 10 to 30% by mass.

The component (A) may contain 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 easily obtaining excellent sensitivity, resolution and adhesion. Styrene compounds include styrene and styrene derivatives. Examples of styrene derivatives include vinyltoluene and α-methylstyrene. Component (A) is a monomer unit of hydroxyalkyl (meth)acrylate and a styrene compound from the viewpoint of easily shortening the peeling time of the cured part and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. may have as

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

(A) A component may have another monomer as a monomer unit. Such monomers include vinyl alcohol ethers (vinyl-n-butyl ether, etc.), (meth)acrylonitrile, maleic acid, maleic anhydride, maleic acid monoesters (monomethyl maleate, monoethyl maleate, maleic monoisopropyl acid, etc.), fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid, propiolic acid and the like.

In component (A), the content of the monomer units of the monomer having a carbazole ring is 0.1 mol% or less and 0.1 mol% based on the total amount of the monomer units constituting component (A). It may be less than, 0.01 mol % or less, 0.001 mol % or less, or substantially 0 mol %. Component (A) may not 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 fall within the following ranges from the viewpoints of easily shortening the peeling time of the cured portion and from the viewpoints of easily obtaining excellent sensitivity, resolution and adhesion. The acid value of component (A) is 80 mgKOH/g or more, 90 mgKOH/g or more, 100 mgKOH/g or more, 100 mgKOH/g or more, 120 mgKOH/g or more, 140 mgKOH/g or more, 150 mgKOH/g or more, 160 mgKOH/g or more, or , 170 mg KOH/g or more. The acid value of 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 80-250 mgKOH/g, 100-230 mgKOH/g, or 150-200 mgKOH/g. The acid value of component (A) can be adjusted by adjusting the content of the monomer units (for example, the monomer units of (meth)acrylic acid) constituting component (A). The acid value of component (A) can be measured by the method described in Examples. When measuring a solution obtained by mixing the component (A) with a volatile matter such as a synthetic solvent or a dilution solvent, the acid value can be calculated by the following formula. When blending the component (A) in a mixed state with a volatile component such as a synthetic solvent or a dilution solvent, heat for 1 to 4 hours at a temperature higher than the boiling point of the volatile component by 10°C or more before precisely weighing to volatilize. It is also possible to measure the acid value after removing the minute.
Acid value = 0.1 x Vf x 56.1/(Wp x I/100)
[Wherein, Vf represents the titration amount (unit: mL) of the KOH (potassium hydroxide) aqueous solution, Wp represents the mass (unit: g) of the solution containing the component (A) to be measured, and I indicates the percentage of non-volatile matter in the solution containing the component (A) to be measured (unit: % by mass). ]

The weight average molecular weight (Mw) of 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 easily 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, less than 70,000, 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 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 easily obtaining excellent sensitivity, resolution and adhesion. Component (A) may have a number average molecular weight of 5,000 or more, 10,000 or more, 12,000 or more, 15,000 or more, or 16,000 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 5,000 to 50,000, 10,000 to 25,000, or 15,000 to 20,000.

The degree of dispersion (weight average molecular weight/number average molecular weight) of the component (A) is within the following range from the viewpoint of easily shortening the peeling time of the cured portion, and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. can be Component (A) may have a dispersity of 1.0 or more, 1.5 or more, 1.8 or more, 2.0 or more, or 2.1 or more. Component (A) may have a dispersity of 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 component (A) may have a dispersity of 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 standard polystyrene calibration curve. More specifically, it can be measured under the conditions described in Examples. If it is difficult to measure a compound having a low molecular weight by the above weight average molecular weight and number average molecular weight measurement methods, the molecular weight can be measured by another method and the average value can be calculated.

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

The content of component (A) is from the viewpoint of easily shortening the peeling time of the cured part, and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion, the total amount of component (A) and component (B) is 100 It may be in the following range with respect to parts by mass. From the viewpoint of excellent film formability, the content of component (A) is 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 It may be 55 parts by mass or more. 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 component (B), and the photopolymerizable compound contains a compound having a ditrimethylolpropane skeleton. The photopolymerizable compound is a compound polymerized by light, and may be, for example, a compound having an ethylenically unsaturated bond.

Component (B) contains 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 easily obtaining excellent sensitivity, resolution and adhesion. good.

The number of (meth)acryloyl groups (total of acryloyl groups and methacryloyl groups) in the (meth)acrylic acid compound having a ditrimethylolpropane skeleton is easy to shorten the peeling time of the cured part, and excellent sensitivity and resolution. From the viewpoint of easily obtaining properties and adhesion, the following ranges may be used. 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 points of view, the number of (meth)acryloyl groups may be 2-8 or 3-6, and may be 4.

Compounds having a ditrimethylolpropane skeleton, from the viewpoint of easily shortening the peeling time of the cured portion, and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion, a (poly) oxyalkylene group (e.g. ), and may have at least one selected from the group consisting of (poly)oxyethylene groups and (poly)oxypropylene groups. The compound having a ditrimethylolpropane skeleton may have a polyoxyethylene group from the viewpoint of particularly easily shortening the peeling time of the cured portion and from the viewpoint of particularly easily obtaining excellent sensitivity. A compound having a ditrimethylolpropane skeleton may have a polyoxypropylene group 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 groups is 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easily obtaining excellent sensitivity and adhesion. It may be 10 or more, 12 or more, 15 or more, 18 or more, or 20 or more. From the viewpoint of easily obtaining excellent sensitivity and resolution, the number of the above groups is 30 or more, 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 may be: From these points of view, the numbers of the groups mentioned above 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 It may be 12, or 4-8.

The molecular weight of the compound having a ditrimethylolpropane skeleton is 250 or more, 300 or more, 400 or more, 500 or more, 600 or more from the viewpoint of easily shortening the peeling time of the cured part and from the viewpoint of easily obtaining 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 from the viewpoint of easily obtaining excellent resolution and adhesion. The molecular weight of the compound having a ditrimethylolpropane skeleton is 10,000 or less, less than 10,000, 8,000 or less, and 6,000 from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easily obtaining excellent sensitivity, resolution, and adhesion. 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 1,700 or less, 1,600 or less, or 1,500 or less, from the viewpoint of particularly easily shortening the peeling time of the cured portion and from the viewpoint of particularly easily obtaining 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 a 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, 1200 to It may be 1500, 600-1200, 800-1200, or 600-800.

The content of the compound having a ditrimethylolpropane skeleton is based on the total mass of the component (B) from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. may be in 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% by mass or less, less than 50% by mass, 40% by mass or less, 30% by mass or less, 20% by mass or less, 18% by mass or less, 15% by mass or less, or 12% by mass. % by mass or less. From these viewpoints, the content of the compound having a ditrimethylolpropane skeleton may be 1 to 50% by mass, 5 to 30% by mass, or 8 to 20% by mass.

The content of the compound having a ditrimethylolpropane skeleton is the total solid content of the photosensitive resin composition, from the viewpoint of easily shortening the peeling time of the cured part, and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. may be in the following ranges based on The content of the compound having a ditrimethylolpropane skeleton is 0.1% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, 3% by mass or more, 4% by mass or more; It may be 5% by mass or more. 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 From these viewpoints, the content of the compound having a ditrimethylolpropane skeleton is 0.1 to 20% by mass, 1 to 20% by mass, 3 to 20% by mass, 0.1 to 10% by mass, 1 to 10% by mass. , 3 to 10% by mass, 0.1 to 8% by mass, 1 to 8% by mass, 3 to 8% by mass, 0.1 to 5% by mass, 1 to 5% by mass, or 3 to 5% by mass you can

The content of the compound having a ditrimethylolpropane skeleton is the component (A) and the component (B) from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. It may be in the following range with respect to 100 parts by mass of the total amount. 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, Alternatively, it may be 5 parts by mass or more. 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, and 0.1 to 10 parts by mass. , 1 to 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 weight, 1 to 5 parts by weight, or 3 to 5 parts by weight.

(B) The component may contain a compound that does not have a ditrimethylolpropane skeleton. Compounds not having a ditrimethylolpropane skeleton include bisphenol A type (meth)acrylic acid compounds, EO-modified di(meth)acrylates, PO-modified di(meth)acrylates, EO/PO-modified di(meth)acrylates, polyalkylene Glycol di(meth)acrylate (polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.), EO-modified polyalkylene glycol di(meth)acrylate, 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 trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, EO/PO-modified trimethylolpropane 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, nonylphenoxy Polyethylene oxyacrylate, phthalic acid compounds, alkyl (meth)acrylates, photopolymerizable compounds (oxetane compounds, etc.) having at least one cationically polymerizable cyclic ether group in the molecule, and the like.

Component (B) is a bisphenol A type (meth)acrylic acid compound (ditrimethylolpropane skeleton) from the viewpoint of easily shortening the peeling time of the cured part, and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. except for compounds with As the bisphenol A type (meth)acrylic acid compound, 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 and the like. Component (B) is a 2,2-bis(4-((meth)acryloxy poly ethoxy)phenyl)propane and may include 2,2-bis(4-((meth)acryloxypentaethoxy)phenyl)propane.

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

The content of the bisphenol A type (meth)acrylic acid compound is the solid content of the photosensitive resin composition from the viewpoint of easily shortening the peeling time of the cured part, and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. It may be in the following ranges based on the total amount. The content of the bisphenol A type (meth)acrylic acid compound is 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. can be The content of the 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. From these viewpoints, the content of the bisphenol A type (meth)acrylic acid compound is 1 to 70% by mass, 10 to 70% by mass, 20 to 70% by mass, 30 to 70% by mass, 1 to 50% by mass, 10 ~50% by weight, 20-50% by weight, 30-50% by weight, 1-40% by weight, 10-40% by weight, 20-40% by weight, or 30-40% by weight.

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

The content of component (B) is from the viewpoint of easily shortening the peeling time of the cured part, and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion, the total amount of component (A) and component (B) is 100. It may be in the following range with respect to parts by mass. 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 70 parts by weight, 40 to 70 parts by weight, 10 to 50 parts by weight, 20 to 50 parts by weight, 30 to 50 parts by weight, or 40 to 50 parts by weight.

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

Component (C) includes hexaarylbiimidazole compounds; 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- Aromatic ketones such as [4-(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; bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; bis(2,6-dimethylbenzoyl)-2,4,4-trimethyl-pentylphosphine oxide; 6-trimethylbenzoyl)ethoxyphenylphosphine oxide and the like.

The component (C) may contain a hexaarylbiimidazole compound from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. The aryl group in the hexaarylbiimidazole compound may be a phenyl group or the like. A hydrogen atom bonded to an aryl group in the hexaarylbiimidazole compound may be substituted with a halogen atom (such as a chlorine atom).

The hexaarylbiimidazole compound may be a 2,4,5-triarylimidazole dimer. Examples of the 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m- methoxyphenyl)imidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and the like. The hexaarylbiimidazole compound is 2-(o-chlorophenyl)-4,5-diphenylimidazole from the viewpoint of easily shortening the peeling time of the cured part and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. Dimers may be included and may include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

The content of the hexaarylbiimidazole compound is 50 based on the total amount of the component (C) from the viewpoint of easily shortening the peeling time of the cured part and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. % by mass or more, 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 and a hexaarylbiimidazole compound).

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

The content of component (C) is, from the viewpoint of easily shortening the peeling time of the cured part, and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion, the total amount of component (A) and component (B) is 100. It may be in the following range with respect to parts by mass. The content of component (C) 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. It may be 5 parts by mass or more, or 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 compounds corresponding to component (A), component (B), or component (C)) as component (D). Hydrogen donors include bis[4-(dimethylamino)phenyl]methane, bis[4-(diethylamino)phenyl]methane, leucocrystal violet, N-phenylglycine and the like.

The content of component (D) is from the viewpoint of easily shortening the peeling time of the cured part, and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion, the total amount of component (A) and component (B) is 100. It may be in the following range with respect to parts by mass. The content of component (D) may be 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, or 0.5 parts by mass or more. The content of component (D) is 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 mass part or less, 0.8 parts by mass or less, 0.7 parts by mass or less, Alternatively, it may be 0.5 parts by mass or less. 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 component (E). The (E) component can be used as an anthracene-based sensitizer (photosensitizer). Component (E) includes 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene and the like. The (E) component may contain 9,10-dibutoxyanthracene from the viewpoint of easily shortening the peeling time of the cured portion and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion.

The content of the component (E) is based on the total solid content of the photosensitive resin composition, from the viewpoint of easily shortening the peeling time of the cured part, and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion. It may be in the following range. The content of component (E) is 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, 0.2% by mass or more, 0.3% by mass or more, 0.4% by mass or more , 0.5% by mass or more, or 0.55% by mass or more. The content of component (E) is 5% by mass or less, 3% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, less than 1% by mass, 0.8% by mass or less, 0.8% by mass or less. It may be 7% by mass or less, or 0.6% by mass or less. From these viewpoints, the content of component (E) is 0.01 to 5% by mass, 0.1 to 5% by mass, 0.3 to 5% by mass, 0.5 to 5% by mass, 0.01 to 1% by mass, 0.1 to 1% by mass, 0.3 to 1% by mass, 0.5 to 1% by mass, 0.01% by mass or more and less than 1% by mass, 0.1% by mass or more and less than 1% by mass, 0.3% by mass or more and less than 1% by mass, 0.5% by mass or more and less than 1% by mass, 0.01 to 0.8% by mass, 0.1 to 0.8% by mass, 0.3 to 0.8% by mass %, or 0.5 to 0.8 mass %.

The content of component (E) is from the viewpoint of easily shortening the peeling time of the cured part, and from the viewpoint of easily obtaining excellent sensitivity, resolution and adhesion, the total amount of component (A) and component (B) is 100. It may be in the following range with respect to parts by mass. The content of component (E) 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 0.65 parts by mass or more. The content of component (E) is 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, or 0.8 parts by mass or less, or It may be 0.7 parts by mass or less. 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 1 part by mass, 0.5 to 1 part by mass, 0.01 part by mass or more and less than 1 part by mass, 0.1 part by mass or more and less than 1 part by mass, 0.3 parts by mass or more and less than 1 part by mass, 0.5 parts by mass or more and less than 1 part by mass, 0.01 to 0.8 parts by mass, 0.1 to 0.8 parts by mass, 0.3 to 0.8 parts by mass parts, or 0.5 to 0.8 parts by mass.

The photosensitive resin composition according to this embodiment may contain a polymerization inhibitor as the component (F). The component (F) suppresses polymerization in unexposed areas during resist pattern formation, and tends to improve resolution. Polymerization inhibitors include t-butylcatechol (eg 4-t-butylcatechol), hindered amines (eg 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl), 4-hydroxy-2, 2,6,6-tetramethylpiperidine-N-oxyl and the like.

The content of component (F) may be within the following range with respect to 100 parts by mass of the total amount of components (A) and (B). From the viewpoint of easily obtaining excellent sensitivity and resolution, the content of component (F) is 0.001 parts by mass or more, 0.003 parts by mass or more, 0.005 parts by mass or more, 0.01 parts by mass or more, It may be 0.015 parts by mass or more, 0.02 parts by mass or more, or 0.025 parts by mass or more. The content of component (F) is 0.1 parts by mass or less, 0.05 parts by mass or less, 0.04 parts by mass or less, or 0.03 parts by mass or less from the viewpoint of easily obtaining excellent sensitivity and adhesion. can be 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. 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 according to this embodiment may contain components other than the components described above. Other ingredients include dyes (malachite green, etc.), photosensitizers (excluding anthracene compounds), tribromophenyl sulfone, photocoloring agents, thermal coloring inhibitors, plasticizers (p-toluenesulfonamide, etc.), and pigments. , fillers, antifoaming agents, flame retardants, stabilizers (light stabilizers, etc.), adhesion imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal cross-linking agents, and the like.

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 sum of aluminum powder and aluminum alloy powder The amount is 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, based on the total solid content of the photosensitive resin composition, Alternatively, it may be substantially 0% by mass. The photosensitive resin composition according to this embodiment may not contain at least one selected from the group consisting of aluminum powder (aluminum particles) and aluminum alloy powder (aluminum alloy particles).

<Photosensitive element>
A photosensitive element according to this 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 this embodiment. The photosensitive element according to this embodiment may comprise a protective layer disposed on the photosensitive resin layer. The photosensitive element according to this embodiment may comprise a cushion layer, an adhesive layer, a light absorbing layer, a gas barrier layer, and the like. The photosensitive element may be in the form of a sheet, or in the form of a photosensitive element roll wound around a core.

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

The photosensitive element 1 can be obtained, for example, by the following procedure. First, the photosensitive resin layer 3 is formed on the support 2 . The photosensitive resin layer 3 can be formed, for example, by drying a coating layer formed by applying a photosensitive resin composition containing an organic solvent. Next, a protective layer 4 is arranged 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, such as a polyester film (polyethylene terephthalate film, etc.), a polyolefin film (polyethylene film, polypropylene film, etc.), a hydrocarbon-based polymer (polyolefin film, etc.). excluding film). The type of film forming the protective layer and the type of film forming the support may be the same or different.

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 the support is peeled off 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 favorable exposure when exposed through the support. From these points of view, 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 It may be 15 μm or more. 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 points of view, the protective layer may have a thickness of 1 to 100 μm.

The thickness of the photosensitive resin layer (the thickness after drying; when the photosensitive resin composition contains an organic solvent, the thickness after volatilizing the organic solvent) may be within the following range. The thickness of the photosensitive resin layer is 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 improvement of productivity. can be 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, It may be 5-30 μm, 10-30 μm, or 20-30 μm.

<Method for manufacturing laminate>
The method for producing a laminate according to the present embodiment includes a photosensitive resin layer placement step of placing a photosensitive resin layer on a substrate (for example, a substrate) using the photosensitive resin composition or the photosensitive element according to the present embodiment. Then, an exposure step of photocuring (exposing) a portion of the photosensitive resin layer, a developing step of removing the uncured portion (unexposed portion) of the photosensitive resin layer to form a cured product pattern, and a substrate and a metal layer forming step of forming a metal layer on at least a portion of the portion where the cured product pattern is not formed. The laminate according to this embodiment is obtained by the method for producing a laminate according to this embodiment, and may be a wiring board (for example, a printed wiring board). The laminate according to this embodiment includes a substrate, a cured product pattern (cured product according to this embodiment) arranged on the substrate, and at least one part of the substrate where the cured product pattern is not formed. and a metal layer disposed on the part.

In the photosensitive resin layer disposing step, a photosensitive resin layer made of the photosensitive resin composition according to the present embodiment is disposed on the substrate. For example, the photosensitive resin layer may be formed by applying and drying a photosensitive resin composition on a substrate, and after removing the protective layer from the photosensitive element, heating the photosensitive resin layer of the photosensitive element. It may be formed by pressing against the base material while holding.

In the exposure step, an actinic ray is irradiated with a mask placed on the photosensitive resin layer, and a region other than the region where the mask is placed in the photosensitive resin layer may be exposed and photocured. Instead, a part of the photosensitive resin layer may be exposed and photocured by irradiating actinic rays in a desired pattern by a direct writing exposure method such as an LDI exposure method or a DLP exposure method. As a light source for actinic rays, an ultraviolet light source or a visible light source may be used, and carbon arc lamps, mercury vapor arc lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, gas lasers (argon lasers, etc.), solid-state lasers (YAG lasers, etc.). , and semiconductor lasers.

The development method in the development step may be, for example, wet development or dry development. Wet development can be carried out by using a developer corresponding to the photosensitive resin composition, for example, by a dipping method, a paddle method, a spray method, brushing, slapping, scrubbing, rocking immersion, or the like. The developer is appropriately selected according to the constitution of the photosensitive resin composition, and may be an alkaline developer or an organic solvent developer.

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

The organic solvent developer may contain organic solvents such as 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methylisobutylketone and γ-butyrolactone.

The metal layer in the metal layer forming step may be, for example, a metal copper layer. The metal layer can be formed by plating, for example. 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 includes a step of further curing the resist pattern by heating at 60 to 250° C. or exposing at 0.2 to 10 J/cm ² after the developing step. you can

The method for manufacturing a laminate according to this embodiment may include a step of removing the cured product pattern after the metal layer forming step. The cured product pattern can be removed by, for example, developing with a strong alkaline aqueous solution by an immersion method, a spray method, or the like.

FIG. 2 is a schematic diagram showing an example of a method for manufacturing a laminate (method for manufacturing a wiring board). In one example of the method for manufacturing a laminate, first, as shown in FIG. prepare. The conductor layer 10b may be, for example, a metallic copper layer.

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

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

Next, after removing the mask 14, as shown in FIG. A resist pattern 12a made of (a cured product of a photosensitive resin layer) is formed.

Next, as shown in FIG. 2E, a wiring layer (metal layer) 16 is formed on 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 made of the same material as the conductor layer 10b, or may be made of a different material.

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

EXAMPLES The present disclosure will be described in more detail below with reference to Examples, but the present disclosure is not limited to these Examples.

<Synthesis of binder polymer>
Solution (a) 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. A solution (b) was prepared by dissolving 0.5 parts by mass of azobisisobutyronitrile in 50 parts by mass of a mixture of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene. 500 g of a mixture of 30 parts by mass of methyl cellosolve and 20 parts by mass of toluene was added to a flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel, and nitrogen gas inlet tube, and then stirred while blowing nitrogen gas into the flask. and the temperature was raised to 80°C. After the solution (a) was dropped into the flask over 4 hours at a constant dropping rate, the solution in the flask was stirred at 80° C. for 2 hours. Next, the solution (b) was added dropwise into the flask over 10 minutes at a constant dropping rate, and then the solution in the flask was stirred at 80°C for 3 hours. Further, the temperature of the solution in the flask was raised to 90°C over 30 minutes, and the temperature was maintained at 90°C for 2 hours, then stirring was stopped and the solution was 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 by the following procedure. First, 1 g of a binder polymer whose acid value is to be measured was accurately weighed, and then 30 g of acetone was added to the binder polymer to uniformly dissolve the binder polymer to obtain a solution. Then, after adding an appropriate amount of phenolphthalein as an indicator to the solution, 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 binder polymer had a weight average molecular weight (Mw) of 35,000 and a number average molecular weight (Mn) of 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 (manufactured by Hitachi, Ltd., trade name)
Columns: The following three columns (manufactured by Showa Denko Materials Co., Ltd., trade name)
Gelpack GL-R440
Gelpack GL-R450
Gelpack GL-R400M
Eluent: Tetrahydrofuran Measurement temperature: 40°C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd., trade name)

<Preparation of photosensitive resin composition>
(Example 1)
100 parts by mass of the binder polymer solution described above (binder polymer (non-volatile): 56 parts by mass), EO-modified ditrimethylolpropane tetramethacrylate (EO group: 4 (total value), molecular weight: 698, manufactured by Toho Chemical Industry Co., Ltd. ) and 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (EO average 10 mol adduct, molecular weight: 804) propylene glycol monomethyl ether (manufactured by Showa Denko Materials Co., Ltd., trade name : FA-321M) 35 parts by mass, (PO) (EO) (PO) modified dimethacrylate (EO average 6 mol and PO average 12 mol adduct (total value), molecular weight: 1114, manufactured by Showa Denko Materials Co., Ltd., product Name: FA-024M) 4 parts by mass, and a photopolymerization initiator (2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, BCIM , Hampford) 6 parts by mass, a hydrogen donor (Leuco Crystal Violet, LCV, Yamada Chemical Co., Ltd.) 0.5 parts by mass, a sensitizer (9,10-dibutoxyanthracene, DBA, Kawasaki Kasei Kogyo Co., Ltd.) 0.65 parts by mass, polymerization inhibitor A (4-t-butylcatechol, DIC Corporation, trade name: DIC-TBC) 0.015 parts by mass, polymerization inhibitor B (Asahi Denka Kogyo Co., Ltd., trade name: LA-7RD) 0.01 parts by mass, dye (malachite green, MKG, manufactured by Osaka Organic Chemical Industry Co., Ltd.) 0.02 parts by mass, additive A (carboxybenzotriazole, 5 -Amino-1H-tetrazole and a mixture of methoxypropanol; manufactured by Sanwa Kasei Co., Ltd., trade name: SF-808H) 0.5 parts by mass, and additive B (light stabilizer, manufactured by Showa Denko Materials Co., Ltd., A photosensitive resin composition was prepared by mixing 1 part by mass of FA711MM (trade name).

(Example 2)
EO-modified ditrimethylolpropane tetramethacrylate (EO groups: 4 (total value)) was changed to EO-modified ditrimethylolpropane tetramethacrylate (EO groups: 12 (total value), molecular weight: 1050, manufactured by Toho Chemical Industry Co., Ltd.) A photosensitive resin composition was prepared in the same manner as in Example 1 except for

(Example 3)
EO-modified ditrimethylolpropane tetramethacrylate (EO group: 4 (total value)) was changed to EO-modified ditrimethylolpropane tetramethacrylate (EO group: 20 (total value), molecular weight: 1402, manufactured by Toho Chemical Industry Co., Ltd.) A photosensitive resin composition was prepared in the same manner as in Example 1 except for

(Example 4)
EO-modified ditrimethylolpropane tetramethacrylate (EO group: 4 (total value)) was changed to PO-modified ditrimethylolpropane tetramethacrylate (PO group: 20 (total value), molecular weight: 1762, manufactured by Toho Chemical Industry Co., Ltd.) A photosensitive resin composition was prepared in the same manner as in Example 1 except for

(Example 5)
EO-modified ditrimethylolpropane tetramethacrylate (EO group: 4 (total value)) (EO) (PO)-modified ditrimethylolpropane tetramethacrylate (EO group: 12 (total value), PO group: 8 (total value), Toho A photosensitive resin composition was prepared in the same manner as in Example 1, except that the resin was changed to (manufactured by Kagaku Kogyo Co., Ltd.).

(Comparative example 1)
EO-modified ditrimethylolpropane tetramethacrylate (EO group: 4 (total value)) was changed to EO-modified bisphenol A dimethacrylate (molecular weight: 1686, manufactured by Miwon, trade name: Miramer M2301), and the amount of BCIM used was changed to 5 mass. parts, 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. A photosensitive resin composition was prepared.

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

(Comparative Example 3)
EO-modified ditrimethylolpropane tetramethacrylate (EO group: 4 (total value)) was changed to EO-modified urethane methacrylate (molecular weight: 692, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: UA-1137), and 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. A photosensitive resin composition was prepared by carrying out.

<Preparation of photosensitive element>
A polyethylene terephthalate film (manufactured by Toray Industries, Inc., trade name "FS-31") having a thickness of 16 μm was prepared as a support. After coating the above-mentioned photosensitive resin composition on the support so that the thickness is uniform, the photosensitive resin layer (thickness after drying) is obtained by sequentially drying in a hot air convection dryer at 80 ° C. thickness: 25 μm). A polyethylene film (manufactured by Tamapoly Co., Ltd., trade name "NF-15") was laminated as a protective layer to this photosensitive resin layer to obtain a photosensitive element comprising a support, a photosensitive resin layer and a protective layer in this order. .

<Production of laminate>
A copper clad laminate (substrate, manufactured by Showa Denko Materials Co., Ltd., trade name: MCL-E-67) provided with copper foil (thickness: 35 μm) arranged on both sides of a glass epoxy material is subjected to pickling and After washing with water, it was dried in an air stream. Next, after heating the copper-clad laminate to 80 ° C., while peeling off the protective layer, by laminating the above-mentioned photosensitive element so that the photosensitive resin layer is in contact with the copper surface, the copper-clad laminate, the photosensitive A laminate comprising a flexible resin layer and a support in this order was obtained. Lamination was carried out using heat rolls at 110° C. at a pressure of 0.4 MPa and a roll speed of 1.0 m/min.

<Evaluation>
(sensitivity)
After placing a 41-stage step tablet (manufactured by Showa Denko Materials Co., Ltd.) on the support of the above laminate, a direct exposure machine (manufactured by Via Mechanics Co., Ltd., (trade name: DE-1UH), the photosensitive resin layer was exposed through the support at an exposure amount (irradiation energy amount) such that the number of steps remaining after development of the 41-step tablet was 15 steps. The sensitivity (photosensitivity) was evaluated based on the amount of exposure (unit: mJ/cm ² ) at this time. Table 1 shows the results. It means that the lower the exposure amount, the better the sensitivity.

(Resolution)
After placing a 41-stage step tablet (manufactured by Showa Denko Materials Co., Ltd.) on the support of the above laminate, a direct exposure machine (manufactured by Via Mechanics Co., Ltd., Product name: DE-1UH), line width (L) / space width (S) (hereinafter referred to as "L / S") is 3x / x (x = 1 to 20, unit: μm, 1 μm interval) Using the drawing pattern, the photosensitive resin layer is exposed (drawn) through the support at an exposure amount (irradiation energy amount) such that the number of remaining steps after development of the 41-step tablet is 15 steps. rice field.

After exposure, the support is peeled off from the laminate to expose the photosensitive resin layer, and an unexposed area is removed by spraying a 1.0% by mass sodium carbonate aqueous solution at 30° C. for twice the minimum development time. Removed. After development, the space portion (unexposed portion) is removed without residue, and the line portion (exposed portion) is formed without meandering or chipping. evaluated. Table 1 shows the results. A smaller value means better resolution.

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

(Adhesion)
After placing a 41-stage step tablet (manufactured by Showa Denko Materials Co., Ltd.) on the support of the above laminate, a direct exposure machine (manufactured by Via Mechanics Co., Ltd., Product name: DE-1UH), using a drawing pattern with L/S of x/3x (x = 1 to 20, unit: μm, 1 μm interval), the number of remaining steps after development of a 41-step tablet is 15. The photosensitive resin layer was exposed (drawn) through the support with stepped exposure amounts (irradiation energy amounts).

After exposure, the support is peeled off from the laminate to expose the photosensitive resin layer, and an unexposed area is removed by spraying a 1.0% by mass sodium carbonate aqueous solution at 30° C. for twice the minimum development time. Removed. After development, the space portion (unexposed portion) is removed without residue, and the line portion (exposed portion) is formed without meandering or chipping. bottom. Table 1 shows the results. A smaller value means better adhesion.

(Peeling property)
A peel test was performed using the above laminates of Examples 1-5 and Comparative Examples 1-3. Using the above-mentioned laminate, a direct exposure machine (manufactured by Via Mechanics Co., Ltd., trade name: DE-1UH) using a blue-violet laser diode with a wavelength of 405 nm as a light source is exposed in the same manner as the above-mentioned resolution evaluation. The amount (irradiation energy amount) of the photosensitive resin layer was exposed (drawn) through the support.

After exposure, the photosensitive resin layer was exposed by peeling the support from the laminate. Then, a test sample was obtained by developing in the same manner as in the evaluation of resolution described above. Next, the test piece was immersed in a 3.0% by mass NaOH aqueous solution heated to 50° C. in a constant temperature bath, and the peeling time until the photosensitive resin layer after development was completely peeled off (removed). was measured. Table 1 shows the results. It means that the shorter the peeling time, the better the peeling properties.

DESCRIPTION OF SYMBOLS 1... Photosensitive element 2... Support body 3, 12... Photosensitive resin layer 4... Protective layer 10... Base material 10a... Insulating layer 10b, 10c... Conductor layer 12a... Resist pattern 14... Mask , 16... Wiring layer, 18... Wiring substrate, L... Active ray.

Claims (13)

containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a hydrogen donor,
The photopolymerizable compound contains a compound having a ditrimethylolpropane skeleton,
A photosensitive resin composition in which the compound having a ditrimethylolpropane skeleton has a polyoxyalkylene group (provided that it includes a radically polymerizable component , an initiator composition, a sensitizing dye, and a polymer main chain, and the polymer A radiation-sensitive composition comprising a polymeric binder having a carbazole derivative represented by structure (I) below attached to the main chain, aluminum powder and/or aluminum alloy powder, an alkali-soluble polymer, and light and a photosensitive composition characterized by containing a polymerization initiator, a solvent, and a compound represented by the following formula (1)).

(wherein Y is a direct bond or linking group, and R ¹ -R ⁸ are independently hydrogen or alkyl, alkenyl, aryl, halo, cyano, alkoxy, acyl, acyloxy, or carboxylate groups or any adjacent R ¹ -R ⁸ groups can be taken together to form a carbocyclic or heterocyclic group or a fused aromatic ring.)

(In Formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms; R ² represents an n-divalent organic group; ^{R 3} _represents a propylene group; n ₁ represents 1 to 23; , _n2 represents an integer from 2 to 12.) containing a binder polymer, a photopolymerizable compound, a photopolymerization initiator, and a hydrogen donor,
The photopolymerizable compound contains a compound having a ditrimethylolpropane skeleton,
A photosensitive resin composition in which the compound having a ditrimethylolpropane skeleton has a polyoxyalkylene group (provided that aluminum powder and/or aluminum alloy powder, an alkali-soluble polymer, a photopolymerization initiator, a solvent, and the following formula ( 1) except the photosensitive composition characterized by containing the compound represented by ).

(In Formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms; R ² represents an n-divalent organic group; ^{R 3} _represents a propylene group; n ₁ represents 1 to 23; , _n2 represents an integer from 2 to 12.) 3. The photosensitive resin composition according to claim 1 , wherein the number of said polyoxyalkylene groups is 4-20. 4. The photosensitive resin composition according to any one of claims 1 to 3 , wherein the binder polymer has a styrene compound as a monomer unit. 5. The photosensitive resin composition according to claim 4 , wherein the content of monomer units of said styrene compound is 20% by mass or more based on the total amount of monomer units constituting said binder polymer. 6. The photosensitive resin composition according to claim 4 , wherein the binder polymer further has an aryl (meth)acrylate as a monomer unit. The photosensitive resin composition according to any one of claims 1 to 6 , wherein the compound having a ditrimethylolpropane skeleton comprises a (meth)acrylic acid compound having a ditrimethylolpropane skeleton. The photosensitive resin composition according to claim 7 , wherein the (meth)acrylic acid compound has four (meth)acryloyl groups. 9. Any one of claims 1 to 8 , wherein the content of the compound having a ditrimethylolpropane skeleton is 0.1 to 20 parts by mass with respect to 100 parts by mass as the total amount of the binder polymer and the photopolymerizable compound. The photosensitive resin composition according to . The photosensitive resin composition according to any one of claims 1 to 9 , further comprising an anthracene compound. The photosensitive resin composition according to claim 10 , wherein 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. comprising a support and a photosensitive resin layer disposed on the support;
A photosensitive element, wherein the photosensitive resin layer comprises 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 step of photocuring a portion of the photosensitive resin layer;
removing the uncured portion of the photosensitive resin layer to form a cured product pattern;
and forming a metal layer on at least part of a portion of the substrate where the cured product pattern is not formed.

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