WO2017168699A1 - Composition de résine photosensible, film de résine photosensible, procédé de production de produit durci, stratifié et composant électronique - Google Patents

Composition de résine photosensible, film de résine photosensible, procédé de production de produit durci, stratifié et composant électronique Download PDF

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Publication number
WO2017168699A1
WO2017168699A1 PCT/JP2016/060743 JP2016060743W WO2017168699A1 WO 2017168699 A1 WO2017168699 A1 WO 2017168699A1 JP 2016060743 W JP2016060743 W JP 2016060743W WO 2017168699 A1 WO2017168699 A1 WO 2017168699A1
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group
component
photosensitive resin
resin composition
carbon atoms
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PCT/JP2016/060743
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English (en)
Japanese (ja)
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敬司 小野
真生 成田
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日立化成株式会社
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Priority to PCT/JP2016/060743 priority Critical patent/WO2017168699A1/fr
Priority to JP2018508293A priority patent/JP7067470B2/ja
Publication of WO2017168699A1 publication Critical patent/WO2017168699A1/fr
Priority to JP2022005547A priority patent/JP2022048206A/ja
Priority to JP2023216095A priority patent/JP2024040149A/ja

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • the present disclosure relates to a photosensitive resin composition, a photosensitive resin film, a method for producing a cured product, a laminate, and an electronic component.
  • photosensitive materials are used as resists for producing conductor patterns.
  • a resist is formed using a photosensitive resin composition, and then a conductor pattern, a metal post, and the like are formed by plating. More specifically, a photosensitive layer is formed on a support (substrate) using a photosensitive resin composition, the photosensitive layer is exposed through a predetermined mask pattern, and then a conductor pattern, a metal post A resist pattern (resist) is formed by developing so that a portion for forming a film can be selectively removed (peeled). Next, a conductor such as copper is formed on the removed portion by plating, and then the resist pattern is removed, whereby a wiring board having a conductor pattern, a metal post, and the like can be manufactured.
  • a thick conductor pattern and a metal post have been produced by growing a metal plating after removing the resist pattern.
  • a thick photosensitive resist having a thickness of about 30 ⁇ m and a photosensitive layer having a thickness of about 65 ⁇ m has been used (see Patent Documents 1 and 2).
  • the conductor layer has a thickness of 150 ⁇ m by performing plating while destroying the layer existing in the direction in which selective plating growth is desired among the dilute metal ion layers with a plating solution in order to further improve the performance. Attempts have been made to make the film as thick as possible (see Patent Document 3).
  • a photosensitive resin having an excellent pattern forming property even when a thick photosensitive layer of 70 ⁇ m or more is formed. It is to provide a composition, a photosensitive resin film, a method for producing a cured product, a laminate, and an electronic component (hereinafter sometimes referred to as “photosensitive resin composition etc.”).
  • the present disclosure provides the following photosensitive resin composition and the like.
  • Component (A) a compound having a photopolymerizable functional group
  • Component (B) a photopolymerization initiator having a molar extinction coefficient with respect to light having a wavelength of 365 nm of less than 8.0 ⁇ 10 3 L / mol ⁇ cm.
  • a photosensitive resin composition having a light absorbance of less than 0.35 with respect to light having a wavelength of 365 nm when the thickness of the photosensitive resin composition is 50 ⁇ m.
  • a laminate comprising a cured product of the photosensitive resin composition according to [1].
  • An electronic component comprising a cured product of the photosensitive resin composition according to [1].
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or lower limit value of a numerical range of a certain step may be replaced with the upper limit value or lower limit value of the numerical range of another step.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • “(Meth) acrylic acid” means at least one of “acrylic acid” and “methacrylic acid” corresponding thereto, and the same applies to other similar expressions such as (meth) acrylate.
  • the photosensitive resin composition according to the embodiment of the present disclosure includes (A) component: a compound having a photopolymerizable functional group, and (B) component: wavelength 365 nm.
  • a photopolymerization initiator having a molar extinction coefficient with respect to light of less than 8.0 ⁇ 10 3 L / mol ⁇ cm, and when the thickness of the photosensitive resin composition is 50 ⁇ m
  • the photosensitive resin composition has an absorbance with respect to light having a wavelength of 365 nm of less than 0.35.
  • the “solid content” is a non-volatile content excluding volatile substances such as water and solvent contained in the photosensitive resin composition, and is volatilized when the resin composition is dried. Ingredients that remain without being included, and also include those that are liquid, syrupy, and waxy at room temperature. Here, room temperature in this specification indicates 25 ° C.
  • molar extinction coefficient it means “molar extinction coefficient with respect to light having a wavelength of 365 nm”, and when simply described as “absorbance”, “when the thickness of the photosensitive resin composition is 50 ⁇ m”. , “Absorbance with respect to light having a wavelength of 365 nm”.
  • the photosensitive resin composition of the present embodiment has an absorbance of less than 0.35 with respect to light having a wavelength of 365 nm when the thickness of the photosensitive resin composition is 50 ⁇ m.
  • the absorbance of the photosensitive resin composition is less than 0.35, for example, even when a pattern is formed with a thick photosensitive layer of 70 ⁇ m or more using the photosensitive resin composition of the present embodiment, Since light can easily pass through to the bottom (surface of the photosensitive layer on the substrate side), the pattern formability can be improved.
  • the absorbance of the photosensitive resin composition of the present embodiment can be appropriately selected from 0.30 or less, 0.25 or less, or 0.22 or less.
  • the lower limit of the absorbance can be appropriately selected from, for example, 0.001 or more, 0.005 or more, or 0.008 or more.
  • the light absorbency of the photosensitive resin composition can be suitably adjusted with the kind and content of the compound which has a photopolymerizable functional group mentioned later, a photoinitiator, an inorganic filler, etc.
  • the absorbance is, for example, an absorbance for light having a wavelength of 365 nm by using a UV-visible spectrophotometer (product name: “U-3310 Spectrophotometer”, manufactured by Hitachi High-Technologies Corporation) and using a polyethylene terephthalate film alone as a reference. Can be measured.
  • the absorbance with respect to light having a wavelength of 365 nm when the thickness of the photosensitive resin composition is 50 ⁇ m is the absorbance measured with respect to the photosensitive resin composition having a thickness other than 50 ⁇ m, based on the Lambert Beer law. It can also be obtained by conversion.
  • (A) component a compound having a photopolymerizable functional group>
  • the photopolymerizable functional group contained in the component (A) include (meth) acryloyl groups; ethylenically unsaturated groups such as alkenyl groups such as vinyl groups and allyl groups.
  • (A) component may contain the compound which has a (meth) acryloyl group as a photopolymerizable functional group from a viewpoint of improving pattern formation property.
  • the component (A) may contain a compound having a carbon-nitrogen bond from the viewpoint of improving pattern forming properties, and may contain a compound having a urethane bond as the carbon-nitrogen bond. .
  • the lower limit value of the content of the compound having a photopolymerizable functional group and a urethane bond is the solid content of the photosensitive resin composition. What is necessary is just to select suitably from 70 mass% or more, 80 mass% or more, 85 mass% or more, 90 mass% or more, or 95 mass% or more on the basis of the whole quantity.
  • the upper limit is not particularly limited in consideration of the pattern forming properties of the resulting resin composition, the coating properties, and the physical properties and characteristics required for the cured product of the resin composition, but based on the total solid content of the photosensitive resin composition Can be appropriately selected from 100% by mass or less, 99% by mass or less, 95% by mass or less, 85% by mass or less, or 80% by mass or less.
  • Examples of the compound having a (meth) acryloyl group include (meth) acrylate, and those having a urethane bond as a carbon-nitrogen bond include, for example, a (meth) acrylate having a urethane bond (hereinafter referred to as “urethane ( May be referred to as “meth) acrylate”.
  • the number of photopolymerizable functional groups of the component (A) is 1 to 24 from the viewpoint of pattern formation, and 2 to 15 or 2 from the viewpoint of stabilizing the physical properties and characteristics of the resulting cured product. It may be appropriately selected from ⁇ 12.
  • the photosensitive resin composition of the present embodiment may contain, as a component (A), a component (A1): a high molecular weight body having a photopolymerizable functional group, from the viewpoint of improving pattern formation.
  • (A2) component You may contain the low molecular weight body which has a photopolymerizable functional group.
  • (A1) component and (A2) component are demonstrated in order below.
  • the component (A1) is a high molecular weight body having a photopolymerizable functional group.
  • “High molecular weight body” means a compound having a weight average molecular weight (Mw) of 2,500 or more.
  • Mw weight average molecular weight
  • the value of the weight average molecular weight in this specification is the value measured using tetrahydrofuran (THF) by the gel permeation chromatograph (GPC) method.
  • the (A1) component has a photopolymerizable functional group that has been described as a photopolymerizable functional group contained in the above-described component (A).
  • the number of photopolymerizable functional groups contained in the component (A1) is 2 to 24 from the same viewpoint as described above, and 4 to 15 or 6 from the viewpoint of stabilizing the physical properties and characteristics of the resulting cured product. It may be appropriately selected from ⁇ 12. If the number of photopolymerizable functional groups is 2 or more, the heat resistance and rigidity of the cured product at a high temperature can be improved together with pattern formation. On the other hand, if the number of photopolymerizable functional groups is 24 or less, the rigidity of the cured product is improved and the adhesion to the substrate and the like is improved.
  • the coatability is improved, and when the resin composition after application is irradiated with light, only the surface portion is easily photocured rapidly and the inside Can suppress the phenomenon that photocuring does not proceed sufficiently. As a result, excellent resolution can be obtained, so that excellent pattern formability can be obtained even when a thick photosensitive layer is formed. Furthermore, after at least one of photocuring and heat curing is performed, the remaining unreacted photopolymerizable functional groups can be further reduced, and fluctuations in physical properties and characteristics of the obtained cured product can be further suppressed.
  • the component (A1) may include a high molecular weight polymer having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton, and the absorbance of the photosensitive resin composition. From the viewpoint of reducing the above, a high molecular weight product having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton and an alicyclic skeleton may be included.
  • Examples of the urethane (meth) acrylate as the component (A1) include a reaction product of a (meth) acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group.
  • Examples of the (meth) acrylate having a hydroxyl group include compounds having at least one hydroxyl group and at least one (meth) acryloyl group in one molecule.
  • Functional epoxy (meth) acrylate trifunctional or higher (meth) such as ditrimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc.
  • Tri- or more functional epoxy (meth) acrylates such as enolol novolac type epoxy (meth) acrylate, cresol novolac type epoxy poly (meth) acrylate, isocyanuric acid type epoxy tri (meth) acrylate; trimethylolpropane tri (meth) acrylate, ditri And hydroxypropylated compounds such as methylolpropane tetra (meth) acrylate.
  • Tri- or more functional epoxy (meth) acrylates such as enolol novolac type epoxy (meth) acrylate, cresol novolac type epoxy poly (meth) acrylate, isocyanuric acid type epoxy tri (meth) acrylate; trimethylolpropane tri (meth) acrylate, ditri And hydroxypropylated compounds such as methylolpropane tetra (meth) acrylate.
  • the (meth) acrylate ethoxylated product, propoxylated product, ethoxylated propoxylated product, and hydroxypropylated product are each, for example, an alcohol compound (or a phenol compound) that is a raw material of the (meth) acrylate. It is obtained by using as a raw material one or more ethylene oxide groups, propylene oxide groups, ethylene oxide groups and propylene oxide groups, and hydroxypropyl groups.
  • the caprolactone-modified product is obtained by using, as a raw material, a product obtained by modifying an alcohol compound (or phenol compound) that is a raw material for the (meth) acrylate with ⁇ -caprolactone.
  • Examples of the isocyanate compound having an isocyanate group include a compound having at least one isocyanate group in one molecule, and may be a compound having 1 to 3 isocyanate groups in one molecule. More specifically, aliphatic monoisocyanate compounds such as ethyl isocyanate, propyl isocyanate, butyl isocyanate, octadecyl isocyanate and 2-isocyanate ethyl (meth) acrylate; alicyclic monoisocyanate compounds such as cyclohexyl isocyanate; aromatics such as phenyl isocyanate Monoisocyanate compounds such as aliphatic monoisocyanate compounds, aliphatic diisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate; 1,3-bis (iso
  • diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, aromatic diisocyanate compounds, and multimers of these diisocyanate compounds, and in particular, hexamethylene diisocyanate.
  • Isophorone diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, and isocyanurate type multimers What is necessary is just to select suitably from isocyanurate type polyisocyanate).
  • the reaction product of the above (meth) acrylate having a hydroxyl group and an isocyanate compound has a (meth) acryloyl group as a photopolymerizable functional group and a urethane bond as a carbon-nitrogen bond.
  • a (meth) acryloyl group as a photopolymerizable functional group
  • a urethane bond as a carbon-nitrogen bond.
  • an organic group derived from (meth) acrylate having a hydroxyl group in the molecule that is, 1 to 5 (meta) which is a residue obtained by removing the hydroxyl group from the above-mentioned (meth) acrylate having a hydroxyl group.
  • An organic group having an acryloyl group), a urethane bond, and an organic group derived from the above isocyanate compound that is, a chain hydrocarbon skeleton, an oil, which is a residue obtained by removing the isocyanate group from the above isocyanate compound
  • These organic groups may be the same or different.
  • the terminal isocyanate group of a polyaddition product of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound is used.
  • a reaction product obtained by reacting a (meth) acrylate having a hydroxyl group may be included.
  • Diisocyanate compounds such as aliphatic diisocyanate compounds, alicyclic diisocyanate compounds, and aromatic diisocyanate compounds among the compounds exemplified as the isocyanate compound as the isocyanate compound having at least two isocyanate groups in one molecule used here.
  • multimers such as uretdione type dimers, isocyanurate types, biuret type trimers of these diisocyanate compounds, and the like can be mentioned.
  • the above isocyanate compounds can be used alone or in combination of two or more.
  • diol compound examples include diol compounds having 1 to 20 carbon atoms. Specific examples include ethylene glycol, diethylene glycol, propanediol, dipropylene glycol, butanediol, pentanediol, isopentylglycol, hexanediol.
  • Linear or branched saturated diol compounds such as nonanediol, decanediol, dodecanediol, dimethyldodecanediol, and octadecanediol; linear such as butenediol, pentenediol, hexenediol, methylpentenediol, and dimethylhexenediol Or branched unsaturated diol compounds; various cyclohexanediols, various cyclohexanedimethanols, various tricyclodecanedimethanols, hydrogenated bisphenol A, hydrogenated bisphenols Diol compound having an alicyclic skeleton such Lumpur F and the like.
  • the saturated diol compound and the unsaturated diol compound are collectively referred to as a diol compound having a chain hydrocarbon skeleton.
  • the above diol compounds can be used alone or in combination of two or more.
  • the diol compound having a chain hydrocarbon skeleton has 1 to 20 carbon atoms and 2 to 16 carbon atoms from the viewpoint of improving pattern forming property and increasing water resistance by increasing the glass transition point (Tg) after polymerization.
  • it may be appropriately selected from 2 to 14 saturated diol compounds, and more specifically, may be appropriately selected from ethylene glycol and octadecanediol.
  • the diol compound having an alicyclic skeleton has 5 to 20, 5 to 5 carbon atoms from the viewpoint of improving pattern formation and increasing the glass transition point (Tg) after polymerization to improve water resistance.
  • diol compounds having an alicyclic skeleton of 18 or 6 to 16 more specifically, various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, What is necessary is just to select suitably from various cyclohexane dimethanols, such as 3-cyclohexane dimethanol and 1, 4- cyclohexane dimethanol.
  • Examples of the (meth) acrylate having a hydroxyl group used herein include those exemplified as the (meth) acrylate used in the reaction product of the above-mentioned (meth) acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group. Can be mentioned.
  • reaction product obtained by reacting a (meth) acrylate having a hydroxyl group with a terminal isocyanate group of a polyaddition product of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound for example, the following general formula ( What has the structural unit represented by 3) is mentioned.
  • X 1 represents a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton
  • Y 1 represents a chain hydrocarbon skeleton or an alicyclic skeleton.
  • the component (A1) has a plurality of the above structural units, the plurality of X 1 and Y 1 may be the same or different. That is, examples of the component (A1) include those having at least one skeleton selected from the group consisting of a chain hydrocarbon skeleton, an alicyclic skeleton, and an aromatic ring skeleton.
  • Examples thereof include a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton, which is a residue excluding an isocyanate group.
  • the divalent organic group represented by X 1 may be these residues themselves, or a residue derived from an isocyanate compound derivative such as a polyaddition product of the above isocyanate compound and a diol compound. May be.
  • X 1 is a divalent organic group having an alicyclic skeleton from the viewpoint of improving pattern formation and improving the transparency, water resistance, and moisture resistance of the resin composition in a balanced manner. It may be a divalent organic group having an alicyclic skeleton, which is a residue of isophorone diisocyanate represented by 4).
  • divalent organic group having a chain hydrocarbon skeleton of Y 1 or an alicyclic skeleton a diol compound having a chain hydrocarbon skeleton exemplified as the diol compound, and a diol having an alicyclic skeleton
  • the divalent organic group having 1 to It may be appropriately selected from residues obtained by removing a hydroxyl group from 20, 2 to 16, or 2 to 14 saturated diol compounds, and more specifically, selected from residues obtained by removing a hydroxyl group from ethylene glycol and octadecandiol. do it.
  • the divalent organic group having an alicyclic skeleton is a hydroxyl group removed from a diol compound having an alicyclic skeleton having 5 to 20, 5 to 18, or 6 to 16 carbon atoms.
  • various cyclohexanediols such as 1,3-cyclohexanediol and 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol. What is necessary is just to select suitably from the residue remove
  • reaction product obtained by reacting a (meth) acrylate having a hydroxyl group with a terminal isocyanate group of a polyaddition product of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound specifically, for example, And compounds represented by the following general formulas (5) and (6).
  • n 1 and n 2 each independently represents an integer of 3 to 20.
  • isocyanate compound as the reaction product when an isocyanurate type trimer (isocyanurate type triisocyanate) which is a trimer of diisocyanate is used, for example, in the following general formulas (7) and (8): And the compounds represented.
  • n 3 and n 4 each independently represents an integer of 2 to 20.
  • Examples of commercially available products containing urethane acrylate having the structural unit represented by the general formula (3) include UN-333 (functional group number: 2, Mw: 5,000), UN-1255 (functional group number: 2, Mw: 8,000), UN-904 (functional group number: 10, Mw: 4,900), UN-2600 (functional group number: 2, Mw: 2,500), UN-6200 (functional group number: 2, Mw: 6,500), UN-9000PEP (functional group number: 2, Mw: 5,000), UN-9200A (functional group number: 2, Mw: 15,000), UN-3320HS (functional group number: 15, Mw: 4, 900), UN-6301 (number of functional groups: 2, Mw: 33,000), UN-954: (number of functional groups: 6, weight average molecular weight: 4,500), UN-953: (number of functional groups: 20, weight average) Molecular weight: 4,000 to 40,000), H-219 (number of functional groups: 9, weight average molecular weight: 25,000 to 50,000) (all are trade names, manufactured by Negami Kogyo Co
  • urethane methacrylate having the structural unit represented by the general formula (3) for example, UN-6060PTM (functional group number: 2, Mw: 6,000, trade name, manufactured by Negami Kogyo Co., Ltd.) ) And the like.
  • the number of functional groups in parentheses and Mw are the total number and weight average molecular weight of (meth) acryloyl groups contained in urethane (meth) acrylate, respectively.
  • UN-952 (number of functional groups: 10, Mw: 6,500 to 11,000) is represented by the general formula (8).
  • Examples of commercially available products containing the urethane acrylate represented include UN-905 (functional group number: 15, Mw: 40,000 to 200,000) and the like. ).
  • UN-952 is particularly preferable from the viewpoint of pattern formability and photosensitivity.
  • the total number of (meth) acryloyl groups (the number of photopolymerizable functional groups) contained in the urethane (meth) acrylate as the component (A1) is 2 to 24 in one molecule from the viewpoint of improving pattern formation and heat resistance. From the viewpoint of stabilizing the physical properties and characteristics of the resulting cured product, it may be appropriately selected from 4 to 15 or 6 to 12.
  • the weight average molecular weight of the component (A1) is 2,500 or more, and may be 3,000 or more from the viewpoint of improving the coating property and resolution of the resin composition, and further improving developability and compatibility. From the viewpoint, it may be 3,500 or more.
  • the upper limit of the weight average molecular weight may be 40,000 or less or 30,000 or less from the viewpoint of improving the coating property and resolution of the resin composition, and further developability and compatibility. From the viewpoint of improvement, it may be 20,000 or less.
  • the content of the component (A1) is 10% by mass or more and 30% by mass or more based on the total solid content of the photosensitive resin composition. Or, what is necessary is just to select suitably from 40 mass% or more. If content is 10 mass% or more, applicability
  • paintability will improve and even if it is a case where a thick photosensitive layer is formed, the outstanding pattern formation property will be obtained.
  • the upper limit of the content of the component (A1) is the solid content of the photosensitive resin composition.
  • the content of urethane (meth) acrylate in the component (A1) is 70 to 100% by mass, 80 to 100% by mass, based on the total solid content of the component (A1), from the viewpoint of improving pattern formability. 90 to 100% by mass, 95 to 100% by mass, or 100% by mass (total amount).
  • the component (A2) is a low molecular weight body having a photopolymerizable functional group.
  • the “low molecular weight body” means a compound having a weight average molecular weight of less than 2,500.
  • the photopolymerizable functional group of the component (A2) is described as the photopolymerizable functional group contained in the component (A) described above, and as a photopolymerizable functional group from the viewpoint of improving pattern formability. It may have a (meth) acryloyl group.
  • the component (A2) has at least one photopolymerizable functional group, and from the viewpoint of improving pattern formation, the number of photopolymerizable functional groups is 1 to 12, 2 to 10, or 2 to What is necessary is just to select from 6 suitably.
  • the photosensitive resin composition of the present embodiment is composed of (A2-1) component: a low molecular weight product having a photopolymerizable functional group and an isocyanuric ring, (A2-2) Component): a low molecular weight product having a photopolymerizable functional group and a urethane bond; and (A2-3) component: at least one selected from the group consisting of a low molecular weight product having a photopolymerizable functional group and an alicyclic skeleton. It may contain seeds. When the photosensitive resin composition of the present embodiment contains at least one of these, the adhesiveness of the electronic component with the substrate or the like tends to be improved, and excellent pattern formability tends to be obtained.
  • a low molecular weight substance having two or more of an isocyanuric ring, a urethane bond, and an alicyclic skeleton it is classified as the component (A2-1) if it has at least an isocyanuric ring.
  • an alicyclic skeleton are classified as component (A2-2) with priority given to having a urethane bond. That is, low molecular weight substances having an alicyclic skeleton without having an isocyanuric ring and a urethane bond are classified as the component (A2-3).
  • the component (A2-1) is a low molecular weight substance having a photopolymerizable functional group and an isocyanuric ring skeleton, and may have two or more photopolymerizable functional groups from the viewpoint of improving pattern formation. 2 to 5 photopolymerizable functional groups, 2 or 3 photopolymerizable functional groups, or 3 photopolymerizable functional groups.
  • the photopolymerizable functional group contained in the component (A2-1) has been described as the photopolymerizable functional group contained in the component (A) described above. From the viewpoint of improving pattern formation, the photopolymerizable functional group You may have a (meth) acryloyl group as a group.
  • Examples of the component (A2-1) include compounds represented by the following general formula (9).
  • R 13 , R 14 and R 15 each independently represent an alkylene group having 1 to 8 carbon atoms
  • R 16 and R 17 each independently represents a hydrogen atom or a methyl group
  • R 18 represents a hydrogen atom or a (meth) acryloyl group.
  • the alkylene group having 1 to 8 carbon atoms represented by R 13 , R 14 and R 15 may be an alkylene group having 1 to 4 carbon atoms, or an alkylene group having 1 to 3 carbon atoms. There may be.
  • the alkylene group having 1 to 8 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, an isopropylene group, an isobutylene group, a t-butylene group, a pentylene group, and a hexylene group. From the viewpoint of improving pattern formability, an ethylene group may be used.
  • R 16 and R 17 each independently represent a hydrogen atom or a methyl group, and may be a hydrogen atom from the viewpoint of improving sensitivity.
  • R 18 represents a hydrogen atom or a (meth) acryloyl group, and may be a (meth) acryloyl group from the viewpoint of improving pattern formation.
  • the compound represented by the general formula (9) may be one or more selected from the group consisting of a compound represented by the following formula (9-1) and a compound represented by the following formula (9-2).
  • a compound represented by the following formula (9-1) may be used.
  • the weight average molecular weight of the component (A2-1) is less than 2,500, and is appropriately selected from 200 to 1,500, 300 to 1,000, or 350 to 600 from the viewpoint of improving pattern formability. May be.
  • component (A2-1) a commercially available product may be used.
  • examples of commercially available products include “A-9300” (compound represented by the above formula (9-1)) manufactured by Shin-Nakamura Chemical Co., Ltd., and “M-215” manufactured by Toagosei Co., Ltd. 9-2)) and the like.
  • the component (A2-1) can be used alone or in combination of two or more.
  • the component (A2-2) is a low molecular weight body having a photopolymerizable functional group and a urethane bond, and may have two or more photopolymerizable functional groups from the viewpoint of improving pattern formation. It may have 2 to 6 photopolymerizable functional groups and may have 2 photopolymerizable functional groups.
  • the photopolymerizable functional group contained in the component (A2-2) has been described as the photopolymerizable functional group contained in the component (A) described above. From the viewpoint of improving pattern formation, the photopolymerizable functional group is included. You may have a (meth) acryloyl group as a group.
  • Examples of the component (A2-2) include a reaction product of a (meth) acrylate having a hydroxyl group and an isocyanate compound having an isocyanate group.
  • examples of the (meth) acrylate having a hydroxyl group and the isocyanate compound include a (meth) acrylate having a hydroxyl group and an isocyanate compound exemplified as those used for producing the component (A1).
  • examples of the appropriate selection from the viewpoint of improving the pattern formability are the same as those appropriately selected as those used for generating the component (A1) from the same viewpoint.
  • the component (A2-2) is a reaction in which a terminal isocyanate group of a polyaddition product of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound is reacted with a (meth) acrylate having a hydroxyl group.
  • a terminal isocyanate group of a polyaddition product of an isocyanate compound having at least two isocyanate groups in one molecule and a diol compound is reacted with a (meth) acrylate having a hydroxyl group.
  • Examples thereof include an isocyanate compound having at least two groups, a diol compound, and a (meth) acrylate having a hydroxyl group.
  • examples of the appropriate selection from the viewpoint of improving the pattern formability are the same as those appropriately selected as those used for generating the component (A1) from the same viewpoint.
  • Examples of the reaction product include urethane (meth) acrylate having a structural unit represented by the following general formula (10).
  • X 2 represents a divalent organic group having a chain hydrocarbon skeleton, an alicyclic skeleton, or an aromatic ring skeleton
  • Y 2 represents a chain hydrocarbon skeleton or an alicyclic skeleton.
  • Examples of X 2 and Y 2 are the same as X 1 and Y 1 in the general formula (3).
  • X 2 represents a divalent organic group having a chain hydrocarbon skeleton, a branched chain.
  • a divalent organic group having a skeleton-like hydrocarbon skeleton, a branched alkylene group having 2 to 12 carbon atoms, for example, a residue of the aliphatic diisocyanate compound may be appropriately selected.
  • Y 2 may be appropriately selected from a divalent organic group having an alicyclic skeleton, for example, a residue of a diol compound having the alicyclic skeleton.
  • component (A2-2) examples include urethane acrylate represented by the following general formula (11).
  • n 5 represents an integer of 1 to 4.
  • R 19 and R 20 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a plurality of R 19 and R 20 are each at least three of which are alkyl groups having 1 to 4 carbon atoms. .
  • X 2 in the general formula (10) is a residue of trimethylhexamethylene diisocyanate, which is a divalent organic group having a chain hydrocarbon skeleton, 2 has a structural unit is the residue of a divalent organic group cyclohexanedimethanol having an alicyclic skeleton, as commercially available products containing a urethane acrylate, for example, TMCH-5R (trade name, number of functional groups: 2, Mw: 950, manufactured by Hitachi Chemical Co., Ltd.).
  • the urethane (meth) acrylate which has a structural unit represented by the said General formula (10), KRM8452 (the number of functional groups: 10, Mw: 1,200, Daicel Ornex Co., Ltd. make), UN -3320HA (functional group number: 6, Mw: 1,500, manufactured by Negami Kogyo Co., Ltd.), UN-3320HC (functional group number: 6, Mw: 1,500, manufactured by Negami Kogyo Co., Ltd.), and the like.
  • the number of functional groups in parentheses and Mw are the total number and weight average molecular weight of (meth) acryloyl groups contained in urethane (meth) acrylate, respectively.
  • the weight average molecular weight of the component (A2-2) is less than 2,500, and may be 1,500 or less from the viewpoint of improving adhesion, and 1,000 or less from the viewpoint of improving resolution. There may be. On the other hand, the lower limit of the weight average molecular weight may be appropriately used according to the desired purpose, but may be 500 or more from the viewpoint of film formability.
  • Component (A2-3) is a low molecular weight substance having a photopolymerizable functional group and an alicyclic skeleton, and may have two or more photopolymerizable functional groups from the viewpoint of improving pattern formation. It may have 2 to 4 photopolymerizable functional groups, or may have 2 photopolymerizable functional groups.
  • the photopolymerizable functional group contained in the component (A2-3) has been described as the photopolymerizable functional group contained in the component (A) described above. From the viewpoint of improving pattern formation, the photopolymerizable functional group is included. You may have a (meth) acryloyl group as a group.
  • the alicyclic skeleton of the component (A2-3) is not particularly limited, and examples thereof include an alicyclic hydrocarbon skeleton having 5 to 20 carbon atoms.
  • the alicyclic hydrocarbon skeleton is at least one selected from the group consisting of a cyclopentane skeleton, a cyclohexane skeleton, a cyclooctane skeleton, a cyclodecane skeleton, a norbornane skeleton, a dicyclopentane skeleton, and a tricyclodecane skeleton. Also good.
  • a tricyclodecane skeleton may be used from the viewpoint of improving pattern formability.
  • the weight average molecular weight of the component (A2-3) is less than 2,500, may be 1,500 or less from the viewpoint of improving adhesion, and is 1,000 or less from the viewpoint of improving resolution. It may be 500 or less.
  • the lower limit of the weight average molecular weight can be appropriately used according to the desired purpose, but may be 150 or more or 200 or more from the viewpoint of film formability.
  • the component (A2-3) may be tricyclodecane dimethanol diacrylate from the viewpoint of film formation.
  • the content of the component (A2) is 3% by mass or more and 5% by mass or more based on the total solid content of the photosensitive resin composition. You may select suitably from 10 mass% or more or 20 mass% or more.
  • the content of the component (A2) is 3% by mass or more, excellent pattern formability can be obtained even when a thick photosensitive layer is formed, and excellent rigidity of the cured product can be obtained.
  • the upper limit value of the content of the component (A2) is suitably from 70% by mass or less, 60% by mass or less, or 50% by mass or less, based on the total solid content of the photosensitive resin composition. Just choose.
  • the photosensitive resin composition of this embodiment contains the component (A1) and the component (A2), the content of the component (A2) based on 100 parts by mass of the total solid content of the component (A1) From the viewpoint of improving the formability and the rigidity of the cured product, it may be appropriately selected from 20 to 120 parts by mass, 25 to 110 parts by mass, or 30 to 100 parts by mass.
  • the content of the component (A2-1) in the total solid content of the component (A2) is 15% by mass or more, 40% by mass or more, 70% by mass % Or more, 90% by mass or more, or 95% by mass or more.
  • the content of the component (A2-1) is 15% by mass or more, excellent pattern formability can be obtained even when a thick photosensitive layer is formed, and excellent rigidity of the cured product can be obtained.
  • the upper limit value of the component (A2-1) is 100% by mass or less, and 100% by mass, that is, the total amount of the component (A2) may be the component (A2-1).
  • the content of the component (A2-2) in the total solid content of the component (A2) is 20 to 100% by mass, 40 to 95% by mass, Alternatively, it may be appropriately selected from 50 to 90% by mass.
  • the content of the component (A2-3) in the total solid content of the component (A2) is 10 to 50% by mass, 15 to 40% by mass, Alternatively, it may be appropriately selected from 20 to 30% by mass.
  • the photosensitive resin composition of this embodiment contains a photopolymerization initiator having a molar extinction coefficient with respect to light having a wavelength of 365 nm of less than 8.0 ⁇ 10 3 L / mol ⁇ cm as component (B).
  • the photosensitive resin composition of the present embodiment contains the component (B) as a photopolymerization initiator, whereby the absorbance of the photosensitive resin composition can be kept low, and the bottom of the photosensitive layer (the substrate side of the photosensitive layer) Since the light can easily pass through to the surface), the pattern formability can be improved.
  • the molar extinction coefficient of the component (B) is 5.0 ⁇ 10 3 L / mol ⁇ cm or less, 3.0 ⁇ 10 3 L / mol ⁇ cm or less, 1.0 ⁇ 10 from the viewpoint of improving the pattern forming property. 3 L / mol ⁇ cm or less, 0.5 ⁇ 10 3 L / mol ⁇ cm or less, 0.2 ⁇ 10 3 L / mol ⁇ cm or less, or 0.1 ⁇ 10 3 L / mol ⁇ cm or less as appropriate Just choose.
  • the lower limit value of the molar extinction coefficient of the component (B) is not particularly limited, and may be appropriately selected from, for example, 1 L / mol ⁇ cm or more, 5 L / mol ⁇ cm or more, or 10 L / mol ⁇ cm or more.
  • the molar extinction coefficient of (B) component can be measured by the method as described in an Example using an ultraviolet visible spectrophotometer, for example.
  • the component (B) is not particularly limited as long as it has a molar extinction coefficient of less than 8.0 ⁇ 10 3 L / mol ⁇ cm and can polymerize a photosensitive resin.
  • the polymerization initiator can be appropriately selected. From the viewpoint of improving pattern formation, those that generate free radicals with actinic rays, such as acylphosphine oxides, oxime esters, aromatic ketones, quinones, alkylphenones, imidazoles, acridines, phenylglycines And photopolymerization initiators such as coumarins and coumarins.
  • the component (B) may contain at least one selected from the group consisting of alkylphenone photopolymerization initiators and acylphosphine oxide photopolymerization initiators.
  • the acylphosphine oxide photopolymerization initiator has an acylphosphine oxide group (> P ( ⁇ O) —C ( ⁇ O) — group), for example, (2,6-dimethoxybenzoyl) -2,4 , 6-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“IRGACURE-TPO” (manufactured by BASF)), ethyl-2 , 4,6-Trimethylbenzoylphenyl phosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide ("IRGACURE-819" (manufactured by BASF)), (2,5-dihydroxyphenyl) diphenylphosphine Oxide, (p-hydroxyphenyl) Diphenyl phosphine oxide, bis (p-
  • the oxime ester photopolymerization initiator is a photopolymerization initiator having an oxime ester bond.
  • 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) ( Trade name: OXE-01, manufactured by BASF)
  • 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) (trade name: OXE) -02, manufactured by BASF
  • 1-phenyl-1,2-propanedione-2- [O- (ethoxycarbonyl) oxime] (trade name: Quantacure-PDO, manufactured by Nippon Kayaku Co., Ltd.), and the like.
  • aromatic ketone photopolymerization initiator examples include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4 -Methoxy-4'-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one ("IRGACURE-651” (manufactured by BASF)), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (“IRGACURE-369” (manufactured by BASF)), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one (“IRGACURE-907” (manufactured by BASF)).
  • Examples of the quinone photopolymerization initiator include 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2 , 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, etc. It is done.
  • alkylphenone photopolymerization initiator examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin phenyl ether, 2,2-dimethoxy-1,2-diphenylethane-1- ON (“IRGACURE-651” (manufactured by BASF)), 1-hydroxy-cyclohexyl-phenyl-ketone (“IRGACURE-184” (manufactured by BASF)), 2-hydroxy-2-methyl-1-phenyl-propane- 1-one (“IRGACURE-1173” (manufactured by BASF)), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one (“IRGACURE- 2959 "(manufactured by BASF)), 2- Rhodoxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benz
  • imidazole photopolymerization initiators include 2,4,5-triarylimidazole dimers such as 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl. -1,3-diazol-2-yl] -4,5-diphenylimidazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5- Di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- And (p-methoxyphenyl) -4,5-diphenylimidazole dimer.
  • 2,4,5-triarylimidazole dimers such as 2- (2-chlorophenyl) -1- [2- (2
  • acridine photopolymerization initiator examples include 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, and the like.
  • phenylglycine photopolymerization initiator examples include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like.
  • Examples of the coumarin photopolymerization initiator include 7-amino-4-methylcoumarin, 7-dimethylamino-4-methylcoumarin, 7-diethylamino-4-methylcoumarin, and 7-methylamino-4-methylcoumarin.
  • the component (B) is at least selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (2). You may contain 1 type.
  • R 1, R 2 and R 3 are each independently a hydrogen atom, an alkyl group, or an alkoxy group having 1 to 8 carbon atoms having 1 to 8 carbon atoms
  • R 4 and R 5 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms
  • R 1 to R 5 other than a hydrogen atom are , Each may have a substituent.
  • R 6 represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an amino group
  • R 7 and R 8 each independently represents a hydrogen atom, an alkyl having 1 to 8 carbon atoms.
  • Group, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, R 7 and R 8 may be bonded to each other to form a cyclic structure having 3 to 16 carbon atoms.
  • R 6 to R 8 other than a hydroxyl group and a hydrogen atom may each have a substituent, and the amino group having a substituent is a cyclic structure having 3 to 12 carbon atoms, wherein the substituents are bonded to each other.
  • R 9 each independently contains a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or one or more atoms selected from an oxygen atom, a nitrogen atom and a sulfur atom.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.
  • the alkyl group having 1 to 8 carbon atoms represented by R 1 , R 2 and R 3 may be an alkyl group having 1 to 4 carbon atoms, or may be an alkyl group having 1 or 2 carbon atoms.
  • alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-heptyl group, an n-hexyl group, and an n-octyl group.
  • the alkoxy group having 1 to 8 carbon atoms represented by R 1 , R 2 and R 3 may be an alkoxy group having 1 to 4 carbon atoms or an alkoxy group having 1 or 2 carbon atoms.
  • alkoxy group examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, n-heptyloxy group, n-hexyloxy group, n-octyloxy and the like. Can be mentioned.
  • R 1 , R 2 and R 3 may be methyl groups from the viewpoint of improving resolution.
  • R 4 and R 5 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. .
  • the alkyl group having 1 to 8 carbon atoms and the alkoxy group having 1 to 8 carbon atoms represented by R 4 and R 5 are explained in the same manner as in the case of R 1 , R 2 and R 3 .
  • the aryl group having 6 to 12 carbon atoms represented by R 4 and R 5 may be an aryl group having 6 to 10 carbon atoms or an aryl group having 6 to 8 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.
  • R 1 to R 5 may have include, for example, a halogen atom, a carboxy group, a hydroxy group, an amino group, a mercapto group, an alkyl group having 1 to 8 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms. And aryl groups having 6 to 12 carbon atoms.
  • Alkyl group R 1 ⁇ R 5 is a substituent which may have, an alkoxy group and aryl group, alkyl group described as R 1 ⁇ R 5, are the same as those of the alkoxy group and an aryl group .
  • R 6 represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an amino group.
  • the alkoxy group represented by R 6 is explained in the same manner as in the case of R 1 , R 2 and R 3 in the general formula (1).
  • R 6 may be a hydroxyl group or a methoxy group from the viewpoint of improving pattern forming properties.
  • R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. .
  • the alkyl group, alkoxy group and aryl group represented by R 7 and R 8 are explained in the same manner as in the case of R 1 to R 5 in the general formula (1).
  • R 7 and R 8 may be bonded to each other to form a cyclic structure having 3 to 16 carbon atoms.
  • the cyclic structure may be a cyclic structure having 4 to 10 carbon atoms or a cyclic structure having 5 to 8 carbon atoms.
  • the cyclic structure may be an alicyclic structure from the viewpoint of improving pattern forming properties, and examples of the alicyclic structure include a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. These alicyclic structures may contain a carbon atom to which R 7 and R 8 are directly bonded.
  • the substituents that R 6 to R 8 may have are described in the same manner as the substituents that R 1 to R 5 in the general formula (1) may have.
  • the amino group having a substituent may be bonded to each other to form a cyclic structure having 3 to 12 carbon atoms.
  • the cyclic structure formed by the substituent of the amino group may be a cyclic structure having 3 to 10 carbon atoms or a cyclic structure having 3 to 5 carbon atoms.
  • the cyclic structure may be a 5- to 10-membered ring containing a nitrogen atom of the amino group, a 5- to 7-membered ring containing a nitrogen atom of the amino group, or a 6-membered ring containing the nitrogen atom of the amino group It may be a ring. Furthermore, these cyclic structures may contain hetero atoms other than nitrogen atoms such as oxygen atoms.
  • a specific example of the cyclic structure formed by the substituent of the amino group includes a structure represented by the following formula (2-1).
  • each R 9 independently contains one or more atoms selected from a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an oxygen atom, a nitrogen atom, and a sulfur atom. Or an organic group having 1 to 10 carbon atoms.
  • the organic group having 1 to 10 carbon atoms represented by R 9 may be an organic group having 1 to 6 carbon atoms or an organic group having 1 to 4 carbon atoms.
  • the organic group having 1 to 10 carbon atoms represented by R 9 may be a hydrocarbon group such as an alkyl group, an alkenyl group, and an aryl group.
  • alkyl group, alkenyl group and aryl group are explained in the same manner as the alkyl group, alkenyl group and aryl group represented by R 1 to R 5 in the general formula (1).
  • Examples of the organic group having 1 to 10 carbon atoms and containing an oxygen atom represented by R 9 include an alkoxy group.
  • Examples of the organic group having 1 to 10 carbon atoms containing a nitrogen atom represented by R 9 include groups represented by the above formula (2-1).
  • Examples of the organic group having 1 to 10 carbon atoms containing a sulfur atom represented by R 9 include alkylthio groups such as a methylthio group.
  • the content of the component (B) when the thickness of the photosensitive resin composition of the present embodiment is 50 ⁇ m, the amount of absorbance with respect to light having a wavelength of 365 nm is less than 0.35, the amount of 0.34 or less, .. 30 or less, 0.26 or less, or 0.22 or less.
  • the component (B) By setting the component (B) to the above content, for example, even when a pattern is formed with a thick photosensitive layer of 70 ⁇ m or more using the photosensitive resin composition of the present embodiment, the bottom of the photosensitive layer (photosensitive layer) Since the light can easily pass to the surface of the layer on the substrate side, the pattern formability can be improved.
  • the content of the component (B) is usually from 0.05 to 30% by mass, 0.2 to 20% by mass, or 0.5 to 15% by mass based on the total solid content of the photosensitive resin composition. What is necessary is just to select suitably. By setting it as the said content, the sensitivity of the photosensitive resin composition can be improved, the deterioration of a resist shape can be suppressed, and pattern formation property can be improved.
  • the content of the component (B) may be determined according to the molar extinction coefficient, molecular weight, etc. of the (B) component, and is obtained from the following formula obtained from the molar extinction coefficient, molecular weight, and content of the photopolymerization initiator.
  • the value P represented by can be selected as appropriate from the amount of 0.1 or more, 0.2 or more, or 0.3 or more, and is 3 or less, 2 or less, or 1.2 or less. What is necessary is just to select suitably from quantity. When P represented by the formula (i) is within the above range, excellent pattern formability can be obtained.
  • A The molar extinction coefficient (L / mol ⁇ cm) of the photopolymerization initiator for light having a wavelength of 365 nm
  • B Content (mass%) of the photopolymerization initiator with respect to the total amount of the photosensitive resin composition (however, when the photosensitive resin composition contains filler, the mass of filler is excluded)
  • C Molecular weight of photopolymerization initiator
  • photopolymerization initiation assistants such as secondary amines may be used alone or in combination of two or more.
  • the photosensitive resin composition of this embodiment can contain the (C) silane compound further.
  • the component (C) a known silane coupling agent can be used.
  • the component (C) can improve the adhesion of the electronic component to the substrate, and in particular, when the substrate contains silicon (for example, a glass substrate, a silicon wafer, an epoxy resin-impregnated glass cloth substrate, etc.). Is valid.
  • silane coupling agent examples include: alkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane; (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropylmethyldimethoxysilane (Meth) acryloyl group-containing alkoxysilanes such as ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1, Amine-based alkoxysilanes such as 3-dimethylbutylidene) propylamine; ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, g
  • Ureido group-containing alkoxysilanes mercapto group-containing alkoxysilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane; carbamate group-containing alkoxysilanes such as triethoxysilylpropylethylcarbamate; 3- (triethoxysilyl) And polybasic acid anhydride group-containing alkoxysilanes such as propyl succinic anhydride. These can be used alone or in combination of two or more.
  • (meth) acryloyl group-containing alkoxysilanes such as (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropylmethyldimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxy Silane coupling agents having an ethylenically unsaturated group in the molecule, such as glycidoxy group-containing alkoxysilanes such as propylmethyldiethoxysilane and glycidoxypropylmethyldiisopropenoxysilane, may be used.
  • alkoxysilanes such as (meth) acryloxypropyltrimethoxysilane, (meth) acryloxypropylmethyldimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxy Silane coupling agents having an ethylenically unsaturated group in the molecule, such as glycid
  • the content of the component (C) is 0.05 to 15% by mass, 0.1 to 10 based on the total solid content of the photosensitive resin composition. What is necessary is just to select suitably from the mass%, 0.1-7 mass%, 1-7 mass%, or 1-5 mass%. By setting it as the said content, deterioration of a resist shape can be suppressed and pattern formation property can be improved.
  • the photosensitive resin composition of the present embodiment may contain, as component (D), a high molecular weight material having a glass transition temperature of 70 to 150 ° C. and having no carbon-nitrogen bond.
  • the “high molecular weight body” has the same definition as in the component (A1).
  • the photosensitive resin composition has a tack suppressing effect.
  • the component (D) may contain an ethylenically unsaturated group from the viewpoints of pattern forming properties and tackiness. Examples of the ethylenically unsaturated group include a (meth) acryloyl group and a vinyl group.
  • the component (D) may contain a high molecular weight polymer having at least one skeleton selected from the group consisting of an alicyclic skeleton and an aromatic ring skeleton, which reduces pattern formation and reduces tackiness. From a viewpoint, you may contain the high molecular weight body which has an alicyclic skeleton.
  • the high molecular weight body having an alicyclic skeleton includes, for example, part of an acid group derived from an acid group-containing acrylic resin (d1) having no carbon-nitrogen bond and an alicyclic ring having no carbon-nitrogen bond. It can manufacture by making the epoxy group derived from a formula epoxy group containing unsaturated compound (d2) react.
  • the acid group-containing acrylic resin (d1) having no carbon-nitrogen bond include an acid having an ethylenically unsaturated group and monomers such as an ester of (meth) acrylic acid, a vinyl aromatic compound, and a polyolefin compound.
  • a copolymer obtained by copolymerizing one or two or more selected ones can be used.
  • an acid having an ethylenically unsaturated group such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, (anhydrous) maleic acid, etc. is an essential component.
  • vinyl aromatic compounds such as styrene, ⁇ -methylstyrene,
  • the acid value of the component (d1) may be 15 mg KOH / g or more, or 40 to 500 mg KOH / g. Since the component (d1) has such an acid value, a sufficient amount of acid groups remains in the component (D) even after the reaction between the component (d1) and the component (d2) described later. Become.
  • alicyclic epoxy group-containing unsaturated compound (d2) having no carbon-nitrogen bond a compound having one ethylenically unsaturated group and an alicyclic epoxy group in one molecule is preferable.
  • compounds represented by any one of the following formulas (I) to (X) can be mentioned.
  • R D1 is independently a hydrogen atom or a methyl group.
  • R D2 is independently an aliphatic saturated hydrocarbon group.
  • the aliphatic saturated hydrocarbon group represented by R D2 include a linear or branched alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 8 carbon atoms, an arylene group having 6 to 14 carbon atoms, and Examples thereof include divalent organic groups composed of these combinations.
  • Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, and a hexamethylene group.
  • Examples of the cycloalkylene group include a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.
  • Examples of the arylene group include a phenylene group and a naphthylene group.
  • the divalent organic group comprising a combination thereof, for example, -CH 2 - phenylene group -CH 2 -, - CH 2 - cyclohexylene group -CH 2 - and the like.
  • RD2 is a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, a hexamethylene group, a phenylene group, or a cyclohexylene from the viewpoints of pattern formation and reduction of tackiness.
  • the alicyclic epoxy group-containing unsaturated compound (d2) having no carbon-nitrogen bond may be a compound represented by the formula (III) from the viewpoint of pattern formation.
  • the component (D) a commercially available product may be used, and examples thereof include (ACA) Z250 (acid value 101.7 mgKOH / g, manufactured by Daicel Ornex Co., Ltd.) of the cyclomer P series.
  • (ACA) Z250 is a resin composed of three structural units represented by the following formula, which is generated by a reaction between an acid group-containing acrylic resin and an alicyclic epoxy group-containing unsaturated compound.
  • R D1 represents a hydrogen atom or a methyl group.
  • R D3 represents an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms.
  • Component (D) has a glass transition temperature of 70 to 150 ° C., but may be 100 to 150 ° C., 115 to 150 ° C., or 125 to 150 ° C.
  • the glass transition temperature of (D) component is the value measured by the following method.
  • Measurement method of glass transition temperature of component (D) As a pretreatment for the measurement, the component (D) is heated at 120 ° C. for 3 hours and then cooled to prepare a sample. Using 10 mg of the sample, the temperature was raised at a temperature range of 25 to 200 ° C. and a heating rate of 20 ° C./min under a nitrogen stream with a differential scanning calorimeter (trade name: DSC-50, manufactured by Shimadzu Corporation). And the influence of solvents and the like is eliminated. After cooling to 25 ° C., the temperature is raised again under the same conditions, and the temperature at which the baseline starts to be offset is defined as the glass transition temperature.
  • the weight average molecular weight of the component (D) may be 3,000 to 50,000, 4,000 to 40,000, or 5,000 to 30,000. . If it is 3,000 or more, the tack suppression effect tends to increase, and if it is 50,000 or less, the resolution tends to improve.
  • the content of the component (D) is the components (A1) and (D) from the viewpoints of pattern formability and tackiness. It may be 5 to 60 parts by mass, 10 to 40 parts by mass, or 10 to 30 parts by mass with respect to 100 parts by mass of the total components.
  • the photosensitive resin composition of this embodiment can contain (E) thermal radical polymerization initiator further.
  • the component (E) is not particularly limited, and examples thereof include ⁇ , ⁇ ′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, t-butylcumyl peroxide, and di-t-butyl peroxide.
  • Dialkyl peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide; 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy)- 2-methylcyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexyl) Peroxy) -3,3,5-trimethylcyclohexane and other peroxy Tar; hydroperoxide such as p-menthane hydroperoxide; diacyl peroxide such as octanoyl peroxide, lauroyl peroxide, stearyl peroxide, benzoyl peroxide; bis (4-t-butylcyclo
  • a peroxide type polymerization initiator a dialkyl peroxide type polymerization initiator, etc.
  • dicumyl peroxide can be selected.
  • component can be used individually or in combination of 2 or more types.
  • the content is 0.1 to 10% by mass, 0.2 to 5% by mass, or 0.3 to 1.% by mass based on the total solid content of the photosensitive resin composition. What is necessary is just to select suitably from 5 mass%. By setting it as the above content, the heat resistance of the photosensitive resin composition is improved, and the reliability when used as a permanent film is improved.
  • the photosensitive resin composition of the present embodiment contains (F) an inorganic filler for the purpose of further improving various properties such as adhesion between the photosensitive resin composition and the substrate, heat resistance, and rigidity of the cured product. Can do.
  • the component (F) include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), and silicon nitride (Si 3 N).
  • the average particle size of the component (F) is appropriately selected from 0.01 to 3 ⁇ m, 0.01 to 2 ⁇ m, or 0.02 to 1 ⁇ m from the viewpoint of improving adhesiveness, heat resistance, and rigidity of the cured product. That's fine.
  • the average particle diameter of the component (F) is the average particle diameter of the inorganic filler in a state dispersed in the photosensitive resin composition, and is a value obtained by measurement as follows. First, after diluting (or dissolving) the photosensitive resin composition 1,000 times with methyl ethyl ketone, using a submicron particle analyzer (trade name: N5, manufactured by Beckman Coulter, Inc.), the international standard ISO 13321 is used.
  • the particle size at an integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle size.
  • the component (F) contained in the photosensitive layer provided on the carrier film or the cured film of the photosensitive resin composition is also diluted (or dissolved) 1,000 times (volume ratio) using a solvent as described above. ) And then using the submicron particle analyzer.
  • the content of the component (F) may be appropriately selected from 10% by mass or less, 5% by mass or less, or 1% by mass or less with respect to the total solid content of the photosensitive resin composition, and the lower limit is 0. What is necessary is just to select suitably from more than mass%, and 0 mass% (it does not contain) may be sufficient.
  • the transparency of the photosensitive resin composition is improved. For example, even when a pattern is formed with a thick photosensitive layer of 70 ⁇ m or more, the photosensitive layer Since the light easily passes through to the bottom of the substrate (the surface on the substrate side of the photosensitive layer), the pattern formability is improved.
  • the photosensitive resin composition of the present embodiment further contains additives such as a sensitizer, a heat-resistant high molecular weight material, a thermal crosslinking agent, and an adhesion assistant other than the component (C) as necessary. Can do.
  • sensitizer examples include sensitization of pyrazolines, anthracenes, xanthones, oxazoles, benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, triazines, thiophenes, naphthalimides, etc. Agents. These can be used alone or in combination of two or more.
  • heat-resistant high molecular weight substance examples include polyoxazole and precursors thereof, phenol novolac, cresol novolac and other novolac resins, polyamide, which have high heat resistance and are used as engineering plastics from the viewpoint of improving processability.
  • examples include imide and polyamide. These can be used alone or in combination of two or more.
  • thermal crosslinking agent from the viewpoint of improving the rigidity of the cured product, for example, an epoxy resin, a phenol resin substituted with a methylol group and an alkoxymethyl group at the ⁇ -position, and a group consisting of a methylol group and an alkoxymethyl group at the N-position
  • an epoxy resin for example, an epoxy resin, a phenol resin substituted with a methylol group and an alkoxymethyl group at the ⁇ -position, and a group consisting of a methylol group and an alkoxymethyl group at the N-position
  • melamine resin substituted with at least one selected, urea resin, and the like These can be used alone or in combination of two or more.
  • the content of these other additives is not particularly limited as long as it does not inhibit the effect of the photosensitive resin composition of the present embodiment, and is, for example, 0 based on the total solid content of the photosensitive resin composition. It may be appropriately selected from 1 to 10% by mass, 0.3 to 5% by mass, or 0.5 to 5% by mass.
  • the contents of the component (A), the component (B), the components (C) to (F) used as desired, and other additives in the photosensitive resin composition of the present embodiment are as follows.
  • the thickness of the photosensitive resin composition is 50 ⁇ m, it is appropriately determined within a range where the absorbance with respect to light having a wavelength of 365 nm is less than 0.35.
  • a diluent can be used in the photosensitive resin composition of the present embodiment as necessary.
  • the diluent include alcohols having 1 to 6 carbon atoms such as isopropanol, isobutanol and t-butanol; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; Sulfur atom-containing compounds such as sulfoxide and sulfolane; esters such as ⁇ -butyrolactone and dimethyl carbonate; cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate And polar solvents such as esters such as propylene glycol monoethyl ether acetate. These can be used
  • the amount of the diluent used may be appropriately selected from the amount that makes the total solid content in the photosensitive resin composition 50 to 90% by mass, 60 to 80% by mass, or 65 to 75% by mass. That is, when a diluent is used, the content of the diluent in the photosensitive resin composition may be appropriately selected from 10 to 50% by mass, 20 to 40% by mass, or 25 to 35% by mass.
  • the viscosity of the photosensitive resin composition at 25 ° C. is 0.5 to 20 Pa ⁇ s, considering the ease of forming the photosensitive layer, or 1 to 10 Pa ⁇ s.
  • the photosensitive resin composition of the present embodiment comprises the above components (A), (B), components (C) to (F) used as desired, other additives, and a diluent, a roll mill, a bead mill Etc., and can be obtained by uniformly kneading and mixing.
  • the photosensitive resin composition of the present embodiment may be used as a liquid or a film.
  • the method for applying the photosensitive resin composition of the present embodiment is not particularly limited, and examples thereof include a printing method, a spin coating method, a spray coating method, a jet dispensing method, an ink jet method, and a dip coating method.
  • Various coating methods are mentioned. Among these, from the viewpoint of forming a thick photosensitive layer more easily, a printing method or a spin coating method may be selected as appropriate.
  • it can use in the form of the photosensitive resin film mentioned later, for example, In this case, a photosensitive layer of desired thickness can be formed by laminating
  • the photosensitive resin film of this embodiment has a photosensitive layer using the photosensitive resin composition of this embodiment.
  • the photosensitive resin film of this embodiment may have a carrier film.
  • the term “layer” includes not only a structure having a shape formed on the entire surface but also a structure having a shape formed on a part when observed as a plan view.
  • the photosensitive resin film of the present embodiment is formed by, for example, applying the photosensitive resin composition of the present embodiment on a carrier film by the above various coating methods to form a coating film, and then drying the coating film.
  • a photosensitive layer can be formed and manufactured.
  • the photosensitive resin composition of this embodiment contains a diluent, you may remove at least one part of this diluent in the case of drying.
  • the coating film can be dried using hot air drying, a far-infrared or near-infrared dryer, and the drying temperature ranges from 60 to 120 ° C., 70 to 110 ° C., or 90 to 110 ° C. What is necessary is just to select suitably.
  • the drying time may be appropriately selected from 1 to 60 minutes, 2 to 30 minutes, or 5 to 20 minutes. If it is dried under the above conditions, when the photosensitive resin composition of the present embodiment contains a diluent, at least a part of the diluent can be removed.
  • the carrier film examples include resin films such as polyester resin films such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), and polyolefin resin films such as polypropylene and polyethylene. From the viewpoint of improving the mechanical strength and heat resistance of the photosensitive resin film, a polyester resin film may be selected.
  • the thickness of the carrier film may be appropriately selected from 10 ⁇ m to 3 mm or 10 to 200 ⁇ m in consideration of handling properties and the like.
  • the thickness of the photosensitive layer may be appropriately selected from 1 to 500 ⁇ m, 10 to 300 ⁇ m, or 30 to 100 ⁇ m.
  • the thickness may be appropriately selected from 1 to 500 ⁇ m, 10 to 300 ⁇ m, or 30 to 100 ⁇ m.
  • the thickness By setting the thickness to 30 ⁇ m or more, for example, when forming a photosensitive layer having a thickness of 150 ⁇ m or more, the number of operations by lamination or the like can be further reduced, and by setting the thickness to 100 ⁇ m or less, the photosensitive resin film can be wound around the core. When it is wound, the deformation of the photosensitive layer due to the difference in stress between the inside and the outside of the core can be further reduced.
  • the photosensitive resin composition of this embodiment may be 70 ⁇ m or more, and the thickness exceeds 100 ⁇ m. There may be.
  • the photosensitive layer having a thickness of 70 ⁇ m or more is, for example, by bonding a film formed with a photosensitive layer on a carrier film and a film formed with a photosensitive layer on a protective layer to be described later, A photosensitive resin film having a thick photosensitive layer and a protective layer in this order can be obtained.
  • a protective layer can be laminated on the surface of the photosensitive layer opposite to the surface in contact with the carrier film.
  • a resin film such as polyethylene or polypropylene may be used.
  • the same resin film as the carrier film mentioned above may be used, and a different resin film may be used.
  • the method for producing a cured product according to the present embodiment includes a step of providing a photosensitive layer using a photosensitive resin composition or a photosensitive resin film of the present embodiment on a substrate (photosensitive layer forming step), and at least one of the photosensitive layers.
  • a step of irradiating the part with actinic rays to form a photocured portion (exposure step), and a step of removing at least a portion other than the photocured portion of the photosensitive layer to form a resin pattern (removal step) Have in order.
  • it has the process (heating process) which heat-processes the said resin pattern further as needed.
  • the method for producing a cured product according to this embodiment makes it possible to form a desired pattern.
  • a desired pattern can be formed by a thick cured product having a thickness of 70 ⁇ m or more.
  • the term “process” is not limited to an independent process, and even if it cannot be clearly distinguished from other processes, if the intended action of the process is achieved, the “process” include.
  • the photosensitive layer can be formed by applying or laminating the photosensitive resin composition or photosensitive resin film of the present embodiment on a substrate.
  • the substrate include glass substrates, silicon wafers, metal oxide insulators such as TiO 2 and SiO 2 , silicon nitride, ceramic piezoelectric substrates, and epoxy resin impregnated glass cloth substrates.
  • the photosensitive resin composition When a photosensitive resin composition is applied to a substrate to form a photosensitive layer, the photosensitive resin composition dissolved in the above diluent and in the form of a solution may be applied to the substrate, and applied as necessary. The resulting coating film may be dried. Application
  • the photosensitive layer In the case of using a photosensitive resin film, the photosensitive layer can be formed by a laminating method using a laminator or the like.
  • the thickness of the photosensitive layer provided on the substrate varies depending on the forming method (coating method or lamination method), the solid content concentration and viscosity of the photosensitive resin composition, etc., but as the lower limit of the thickness of the photosensitive layer after drying, What is necessary is just to select suitably from 10 micrometers or more, 30 micrometers or more, 50 micrometers or more, 70 micrometers or more, 100 micrometers or more, more than 100 micrometers, or 150 micrometers or more.
  • the upper limit is not particularly limited as long as the resin pattern can be formed, but may be appropriately selected from, for example, 500 ⁇ m or less, 300 ⁇ m or less, or 250 ⁇ m or less.
  • the thickness of the photosensitive layer may be appropriately selected from the above range depending on the application, and when used for an electronic component or the like, the lower limit may be appropriately selected from 70 ⁇ m or more, more than 100 ⁇ m, or 150 ⁇ m or more, and the upper limit may be 500 ⁇ m. Hereinafter, it may be appropriately selected from 300 ⁇ m or less or 250 ⁇ m or less.
  • a photosensitive layer is formed using the photosensitive resin composition of the present embodiment, so that a thick photosensitive layer can be formed.
  • a photosensitive layer having a thickness of 150 ⁇ m or more when a photosensitive layer having a thickness of 150 ⁇ m or more is formed, it is not formed by a single application (and drying if necessary) or by lamination, but is applied a plurality of times (and as necessary) until a desired thickness is obtained. Drying) or lamination may be repeated.
  • the photosensitive layer In the exposure step, at least part of the photosensitive layer provided on the substrate in the photosensitive layer forming step is irradiated with actinic rays as necessary, and the exposed portion is photocured to form a cured portion.
  • the photosensitive layer When irradiating with actinic rays, the photosensitive layer may be irradiated with actinic rays through a mask having a desired pattern.
  • LDI Laser Direct Imaging
  • DLP Digital Light Processing
  • Actinic rays may be irradiated by a direct drawing exposure method.
  • the drying conditions are not particularly limited, and may be performed at a temperature of 60 to 120 ° C. or 70 to 110 ° C. for a time of 15 seconds to 5 minutes or 30 seconds to 3 minutes.
  • the exposure dose of actinic rays may be appropriately selected from 10 to 2,000 mJ / cm 2 , 100 to 1,500 mJ / cm 2 , or 300 to 1,000 mJ / cm 2 .
  • Examples of actinic rays used include ultraviolet rays, visible rays, electron beams, and X-rays.
  • As the light source a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a halogen lamp, or the like can be used.
  • the removal step at least a part of the portion (unexposed portion) other than the cured portion of the photosensitive layer formed in the exposure step is removed to form a resin pattern.
  • the removal of the unexposed portion may be performed using a developer such as an organic solvent.
  • the organic solvent include ethanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate, N-methylpyrrolidone and the like.
  • cyclopentanone can be used from the viewpoint of development speed. These can be used alone or in combination of two or more.
  • various commonly used additives may be added to the organic solvent used as the developer.
  • alcohol such as methanol, ethanol, isopropyl alcohol, n-butyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether acetate, etc. (rinse) May be.
  • a heating process is a process employ
  • the heat treatment is preferably performed for 1 to 2 hours while selecting the heating temperature and gradually increasing the temperature.
  • the heating temperature may be appropriately selected from 120 to 240 ° C, 140 to 230 ° C, or 150 to 220 ° C. In the case where the temperature is raised stepwise, for example, at least one of around 120 ° C. and around 160 ° C., for 10 to 50 minutes, or after 20 to 40 minutes, after heat treatment, around 220 ° C. and 30 to 100 Heat treatment may be performed for a minute or for 50 to 70 minutes.
  • the thickness of the obtained resin pattern is the same as the thickness of the photosensitive layer after drying, and the lower limit is suitably 10 ⁇ m or more, 30 ⁇ m or more, 50 ⁇ m or more, 70 ⁇ m or more, 100 ⁇ m or more, more than 100 ⁇ m, or 150 ⁇ m or more. What is necessary is just to select, and what is necessary is just to select suitably from 500 micrometers or less, 300 micrometers or less, or 250 micrometers or less as an upper limit.
  • the thickness of the resin pattern may be appropriately selected from the above range depending on the application, and when used for an electronic component or the like, the lower limit may be appropriately selected from 70 ⁇ m or more, more than 100 ⁇ m, or 150 ⁇ m or more, and the upper limit may be 500 ⁇ m. Hereinafter, it may be appropriately selected from 300 ⁇ m or less or 250 ⁇ m or less.
  • the laminate of the present embodiment is provided with a cured product of the photosensitive resin composition of the present embodiment.
  • various types of substrates such as a substrate used in the method for producing the cured product and a carrier film of the photosensitive resin film, are used.
  • cured material on a support body is mentioned.
  • the cured product of the photosensitive resin composition of the present embodiment can be formed by, for example, the above-described method for producing a cured product of the present embodiment.
  • the thickness of the cured product in the laminate of the present embodiment may be appropriately selected from 10 ⁇ m or more, 30 ⁇ m or more, 50 ⁇ m or more, 70 ⁇ m or more, 100 ⁇ m or more, more than 100 ⁇ m, or 150 ⁇ m or more as the lower limit, and the upper limit is 500 ⁇ m or less, 300 ⁇ m. What is necessary is just to select suitably below or 250 micrometers or less.
  • the thickness of the cured product may be appropriately selected from the above range depending on the application, and when used for an electronic component or the like, the lower limit may be appropriately selected from 70 ⁇ m or more, more than 100 ⁇ m, or 150 ⁇ m or more, and the upper limit may be 500 ⁇ m. Hereinafter, it may be appropriately selected from 300 ⁇ m or less or 250 ⁇ m or less.
  • the cured product provided on the substrate obtained by the above-described method for producing a cured product uses the photosensitive resin composition of the present embodiment.
  • excellent pattern formability can be obtained. Therefore, for example, with the trend toward downsizing and higher performance of electronic devices, it is possible to meet the demand for electronic circuit boards that require a thick cured product to be provided in a finer pattern on the board. .
  • a decrease in yield due to a short circuit between wirings can be suppressed by using a cured product formed from the photosensitive resin composition of the present embodiment as an insulating film. it can. Therefore, the laminated body of this embodiment is used as an electronic component such as an electronic circuit board in a mobile terminal such as a mobile phone.
  • the weight average molecular weight is a value determined by GPC standard polystyrene conversion using the following apparatus, and was measured using a solution in which 0.5 mg of polymer was dissolved in 1 mL of tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • Device name HLC-8320GPC manufactured by Tosoh Corporation
  • Detector RI detector
  • Eluent THF
  • Flow rate 1 ml / min Standard material: Polystyrene
  • the absorbance of the photopolymerization initiator was measured using an ultraviolet-visible spectrophotometer (trade name: U-3010, manufactured by Hitachi High-Technologies Corporation) and a quartz cell having a thickness of 1 cm. Specifically, 0.001 g of a photopolymerization initiator was dissolved in 0.01 L of methanol to obtain a 0.1% by mass sample solution. Furthermore, the obtained 0.1 mass% sample solution was diluted 10 times and 100 times, respectively, to prepare 0.01 mass% and 0.001 mass% sample solutions, respectively. The absorbance of each sample solution at a wavelength of 365 nm was measured, and the molar extinction coefficient was calculated from the slope when the horizontal axis represents the molar concentration and the vertical axis represents the absorbance.
  • Examples 1 to 21, Comparative Examples 1 to 3 The composition is blended according to the blending composition shown in Tables 1 and 2 (the unit of numerical values in the table is parts by mass, and in the case of a solution, it is a solid content conversion amount), kneaded with a three-roll mill, and photosensitive resin composition. A product was prepared. N, N-dimethylacetamide was added so that the solid content concentration was 60% by mass to obtain a photosensitive resin composition.
  • a polyethylene terephthalate film (trade name: A-4100, manufactured by Teijin Ltd.) having a thickness of 50 ⁇ m is used as a carrier film, and the resin compositions of Examples and Comparative Examples are dried on the carrier film so that the thickness after drying becomes 50 ⁇ m. Was applied uniformly. Subsequently, the photosensitive layer was formed by heating and drying at 100 degreeC for 15 minute (s) using a hot air convection dryer, and the photosensitive resin film which has a carrier film and a photosensitive layer was produced.
  • a mask for resolution evaluation (6 types of line widths (5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m) and 5 types of line spaces (as shown in FIG. 1) as an exposed portion.
  • High-precision parallel exposure machine (Mikasa Co., Ltd.) on which an i-line filter (HB-0365 manufactured by Asahi Spectroscopy Co., Ltd.) is placed, and 30 types of patterns combined with 50 ⁇ m, 80 ⁇ m, 100 ⁇ m, 150 ⁇ m, and 200 ⁇ m) are placed. Ltd.) was used to exposure at an exposure dose of 300 mJ / cm 2 of light having a wavelength of 365 nm (i line).
  • the sample after exposure was heated after exposure for 1 minute on a hot plate at 90 ° C. Thereafter, the carrier film was removed, and development was performed by immersing in a developer (cyclopentanone) for 20 minutes.
  • the developed pattern was dried at room temperature for 30 minutes and observed with a metal microscope to evaluate the pattern formability. Evaluation was performed according to the following criteria.
  • “formable” means that the unexposed part is removed cleanly and the line part (exposed part) does not have a defect such as a fall.
  • the evaluation results are shown in Tables 1 and 2.
  • “line ( ⁇ m) / space ( ⁇ m)” described in the table has the narrowest line space among the patterns that can be formed, and among the patterns having the line space, It means the line width value ( ⁇ m) / line space value ( ⁇ m) of the pattern having the narrowest line width that could be formed.
  • Pattern A could not be formed, but a pattern having a line width of 15 ⁇ m or less and a line space of 150 to 200 ⁇ m, or a pattern having a line width of 20 to 25 ⁇ m and a line space of 50 to 100 ⁇ m could be formed. (Hereinafter, these patterns are referred to as “pattern B”).
  • C Patterns A and B could not be formed, but a pattern having a line width of 20 to 25 ⁇ m and a line space of 150 to 200 ⁇ m could be formed.
  • D Not all patterns could be formed.
  • the insulation reliability was evaluated by a high temperature and high humidity bias test.
  • the thickness obtained in Examples 1 to 21 on a comb-shaped copper electrode of TEG (Test Element Group) (trade name: WALTS-KIT EM0101JY, manufactured by WALTS, L / S 40 ⁇ m / 15 ⁇ m) as an evaluation device
  • a 50 ⁇ m photosensitive resin film was attached at 60 ° C. using a laminator so that the photosensitive layer was positioned on the comb copper electrode side.
  • the carrier film was removed after heating on a hot plate at 90 ° C. for 1 minute.
  • A-DCP Tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name, corresponding to component (A2-3))
  • TPO “IRGACURE-TPO” (trade name, manufactured by BASF) which is 2,4,6-trimethylbenzoyldiphenylphosphine oxide I-651: “IRGACURE-651” which is 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name, manufactured by BASF)
  • I-184 “IRGACURE-184” (trade name, manufactured by BASF) which is 1-hydroxy-cyclohexyl-phenyl-ketone
  • I-819 “IRGACURE-819” which is bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name, manufactured by BASF)
  • OXE-01 “IRGACURE-OXE-01” (trade name, manufactured by BASF) which is 1,2-oct

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Formation Of Insulating Films (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Polymerisation Methods In General (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)

Abstract

L'invention concerne une composition de résine photosensible qui comprend : un constituant (A), à savoir un composé ayant un groupe fonctionnel photopolymérisable ; et un constituant (B), à savoir un initiateur de photopolymérisation ayant un coefficient d'absorption molaire par rapport à la lumière ayant une longueur d'onde de 365 nm inférieur à 8,0×103 L/mol∙cm. Lorsque la composition de résine photosensible a une épaisseur de 50 µm, l'absorbance de lumière ayant une longueur d'onde de 365 nm est inférieure à 0,35.
PCT/JP2016/060743 2016-03-31 2016-03-31 Composition de résine photosensible, film de résine photosensible, procédé de production de produit durci, stratifié et composant électronique WO2017168699A1 (fr)

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PCT/JP2016/060743 WO2017168699A1 (fr) 2016-03-31 2016-03-31 Composition de résine photosensible, film de résine photosensible, procédé de production de produit durci, stratifié et composant électronique
JP2018508293A JP7067470B2 (ja) 2016-03-31 2016-03-31 感光性樹脂組成物、感光性樹脂フィルム、硬化物の製造方法、積層体、及び電子部品
JP2022005547A JP2022048206A (ja) 2016-03-31 2022-01-18 感光性樹脂組成物、感光性樹脂フィルム、硬化物の製造方法、積層体、及び電子部品
JP2023216095A JP2024040149A (ja) 2016-03-31 2023-12-21 感光性樹脂組成物、感光性樹脂フィルム、硬化物の製造方法、積層体、及び電子部品

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