TWI819260B - Photosensitive resin layer, and dry film photoresist, photosensitive element using the same - Google Patents

Photosensitive resin layer, and dry film photoresist, photosensitive element using the same Download PDF

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TWI819260B
TWI819260B TW109144461A TW109144461A TWI819260B TW I819260 B TWI819260 B TW I819260B TW 109144461 A TW109144461 A TW 109144461A TW 109144461 A TW109144461 A TW 109144461A TW I819260 B TWI819260 B TW I819260B
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photosensitive resin
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resin layer
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TW202142955A (en
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張鉉碩
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南韓商可隆工業股份有限公司
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06Hydrocarbons
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/34Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
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  • Structural Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The present disclosure relates to a photosensitive resin layer including a photopolymerizable compound and a trifunctional or higher polyfunctional (meth)acrylate compound, and having excellent substrate adhesion, and a dry film photoresist, and a photosensitive element using the same.

Description

感光樹脂層以及使用其的乾膜式光阻、感光元 件 Photosensitive resin layer and dry film photoresist and photosensitive element using it pieces

[相關申請案的交叉參考] [Cross-reference to related applications]

本申請案主張在韓國智慧財產局中於2019年12月31日提出申請的韓國專利申請案第10-2019-0179945號及於2020年7月30日提出申請的韓國專利申請案第10-2020-0095387號的權益,所述韓國專利申請案中的每一者全文併入本案供參考。 This application claims Korean Patent Application No. 10-2019-0179945 filed on December 31, 2019 and Korean Patent Application No. 10-2020 filed on July 30, 2020 in the Korean Intellectual Property Office -0095387, the full text of each of the Korean patent applications described is hereby incorporated by reference.

本揭露是有關於一種感光樹脂層、以及一種使用所述感光樹脂層的乾膜式光阻(dry film photoresist,DFR)及一種使用所述感光樹脂層的感光元件。 The present disclosure relates to a photosensitive resin layer, a dry film photoresist (DFR) using the photosensitive resin layer, and a photosensitive element using the photosensitive resin layer.

感光樹脂組成物以用於印刷電路板(printed circuit board,PCB)或引線框架(lead frame)的乾膜式光阻(dry film photoresist,DFR)、液體光阻油墨(liquid photoresist ink)或類似物的形式使用。 Photosensitive resin compositions are used in dry film photoresist (DFR), liquid photoresist ink (liquid photoresist ink) or the like for printed circuit boards (PCB) or lead frames (lead frames). form is used.

當前,乾膜式光阻不僅廣泛用於製造印刷電路板(PCB)及引線框架,而且廣泛用於製造電漿顯示面板(plasma display panel,PDP)的肋狀屏障(rib barrier)、用於其他顯示器的氧化銦錫(Indium Tin Oxide,ITO)電極、匯流排位址(bus address)電極、黑矩陣(black matrix)及類似物。 Currently, dry film photoresist is widely used not only in manufacturing printed circuit boards (PCBs) and lead frames, but also in manufacturing rib barriers for plasma display panels (PDP) and other applications. Display indium tin oxide (ITO) electrodes, bus address electrodes, black matrix (black matrix) and the like.

一般而言,此種類型的乾膜式光阻經常見於將其疊層於覆銅疊層體(copper clad laminate)上的應用中。與此相關,作為印刷電路板(PCB)的製造製程的實例,首先執行預處理製程,以便對作為PCB的原始板材料的覆銅疊層體進行疊層。預處理製程是在外層製程中以為鑽孔(drilling)、去毛刺(deburring)及表面修整(surface conditioning)等的次序執行,且表面修整或酸洗(pickling)是在內層製程中執行。在表面修整中,主要使用硬毛刷(bristle brush)及噴射浮石製程(jet pumice process),且酸洗可經歷軟蝕刻(soft etching)及5重量%(wt%)硫酸酸洗。 Generally speaking, this type of dry film photoresist is often used in applications where it is laminated on a copper clad laminate. In connection with this, as an example of a manufacturing process of a printed circuit board (PCB), a preprocessing process is first performed to laminate a copper-clad laminate as a raw board material of the PCB. The pretreatment process is performed in the order of drilling, deburring, and surface conditioning in the outer layer process, and surface conditioning or pickling is performed in the inner layer process. In surface modification, bristle brush and jet pumice process are mainly used, and pickling can undergo soft etching and 5 wt% sulfuric acid pickling.

為在已經歷預處理製程的覆銅疊層體上形成電路,一般將乾膜式光阻(在下文中稱為DFR)疊層於覆銅疊層體的銅層上。在此製程中,將DFR的光阻層疊層於銅表面上,同時使用疊層機(laminator)剝離DFR的保護膜。一般而言,疊層是以為0.5米/分鐘至3.5米/分鐘的速度、為100℃至130℃的溫度及為10磅/平方英吋(psi)至90磅/平方英吋的加熱輥壓力(heating roll pressure)執行。 In order to form a circuit on a copper-clad laminate that has undergone a pretreatment process, dry film photoresist (hereinafter referred to as DFR) is generally laminated on the copper layer of the copper-clad laminate. In this process, the DFR photoresist layer is laminated on the copper surface, and a laminator is used to peel off the DFR protective film. Generally speaking, lamination is performed at a speed of 0.5 m/min to 3.5 m/min, a temperature of 100°C to 130°C, and a heated roller pressure of 10 pounds per square inch (psi) to 90 psi. (heating roll pressure) execution.

容許將已經歷疊層製程的印刷電路板靜置15分鐘或大 於15分鐘以穩定所述板,且然後藉由上面形成有所期望電路圖案的光罩(photomask)對DFR的光阻進行曝光。當在此製程中利用紫外(ultraviolet,UV)射線照射光罩時,利用紫外射線照射的光阻藉由被照射部分中所含有的光引發劑(photoinitiator)開始聚合。首先,光阻中的氧最初被消耗,且然後活化單體被聚合以引起交聯反應。此後,在消耗大量單體的同時,聚合反應繼續進行。同時,未曝光部分以交聯反應沒有進展的狀態存在。 Allow printed circuit boards that have undergone the lamination process to rest for 15 minutes or more. The board was allowed to stabilize for 15 minutes, and the DFR photoresist was then exposed through a photomask with the desired circuit pattern formed on it. When ultraviolet (UV) rays are used to irradiate the photomask in this process, the photoresist irradiated with ultraviolet rays starts to polymerize through the photoinitiator contained in the irradiated part. First, the oxygen in the photoresist is initially consumed, and then the activated monomer is polymerized to cause a cross-linking reaction. Thereafter, the polymerization reaction continues while consuming a large amount of monomer. At the same time, the unexposed portion exists in a state where the cross-linking reaction does not progress.

接下來,執行移除光阻的未曝光部分的顯影製程。在鹼性可顯影DFR的情形中,使用為0.8重量%至1.2重量%碳酸鉀及碳酸鈉的水溶液作為顯影劑溶液(developer solution)。在此製程中,未曝光部分中的光阻在顯影劑溶液中藉由黏結劑聚合物的羧酸與顯影劑溶液之間的皂化反應被洗掉,且固化的光阻剩餘在銅表面上。 Next, a development process is performed to remove the unexposed portions of the photoresist. In the case of alkaline developable DFR, an aqueous solution of potassium carbonate and sodium carbonate at 0.8% to 1.2% by weight is used as the developer solution. In this process, the photoresist in the unexposed parts is washed away in the developer solution through the saponification reaction between the carboxylic acid of the binder polymer and the developer solution, and the cured photoresist remains on the copper surface.

接下來,端視內層製程及外層製程而定,藉由不同的製程形成電路。然而,在內層製程中,藉由蝕刻及剝離製程在板上形成電路,且在外層製程中,執行鍍覆製程及蓋孔製程(tenting process),隨後進行蝕刻及焊料剝離以形成預定電路。 Next, depending on the inner layer process and the outer layer process, the circuit is formed through different processes. However, in the inner layer process, a circuit is formed on the board through an etching and stripping process, and in the outer layer process, a plating process and a tenting process are performed, followed by etching and solder stripping to form a predetermined circuit.

近來,需要開發一種感光樹脂組成物,所述感光樹脂組成物對於超高壓汞燈或雷射直接(laser direct)曝光具有高敏感度、會增加對顯影劑溶液的耐受性且因此能夠在顯影製程中形成高密度電路,所述感光樹脂組成物具有極佳的顯色程度以用作用於設置基板曝光位置的UV標記,且會縮短固化膜的剝離時間、具有小 的剝離樣本且因此不會堵塞過濾器。 Recently, there has been a need to develop a photosensitive resin composition that has high sensitivity to ultrahigh-pressure mercury lamp or laser direct exposure, increases resistance to developer solutions, and thus can be used during development High-density circuits are formed during the process. The photosensitive resin composition has excellent color development and can be used as a UV mark for setting the exposure position of the substrate. It also shortens the peeling time of the cured film and has a small of the peeled sample and therefore does not clog the filter.

本揭露的一個目的是提供一種感光樹脂層,所述感光樹脂層可達成極佳的基板黏合力(substrate adhesion)。 An object of the present disclosure is to provide a photosensitive resin layer that can achieve excellent substrate adhesion.

本揭露的另一目的是提供一種包括所述感光樹脂層的乾膜式光阻及感光元件。 Another object of the present disclosure is to provide a dry film photoresist and photosensitive element including the photosensitive resin layer.

為達成以上目的,本文中提供一種感光樹脂層,所述感光樹脂層包含:可光聚合化合物,含有三官能或更高的多官能(甲基)丙烯酸酯化合物;以及鹼性可顯影黏結劑樹脂,其中在使用剝離試驗儀對其中將所述感光樹脂層疊層於基板上的膜樣品進行的膠帶剝離試驗(tape peeling test)期間,由以下方程式1定義的黏合力為90%或大於90%:[方程式1]黏合力(%)=(在膠帶剝離(tape peeling)試驗之後基板及感光樹脂層的表面積/在膠帶剝離(tape peeling)試驗之前感光樹脂層與基板接觸的表面積)*100。 To achieve the above purpose, this article provides a photosensitive resin layer, which includes: a photopolymerizable compound containing a trifunctional or higher polyfunctional (meth)acrylate compound; and an alkaline developable binder resin. , wherein the adhesion force defined by the following Equation 1 is 90% or greater during a tape peeling test using a peel tester on a film sample in which the photosensitive resin layer is laminated on a substrate: [Equation 1] Adhesion (%) = (surface area of the substrate and the photosensitive resin layer after the tape peeling test/surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test) * 100.

三官能或更高的多官能(甲基)丙烯酸酯化合物可具有其中三或更多個具有1至10個碳原子的環氧烷基以及三或更多個(甲基)丙烯酸酯官能基鍵合至具有1至20個碳原子的中心基的結 構。 The trifunctional or higher polyfunctional (meth)acrylate compound may have three or more epoxyalkyl groups having 1 to 10 carbon atoms and three or more (meth)acrylate functional group bonds to a central group having 1 to 20 carbon atoms structure.

三官能或更高的多官能(甲基)丙烯酸酯化合物可包括化學式2的化合物。 The trifunctional or higher polyfunctional (meth)acrylate compound may include the compound of Chemical Formula 2.

三官能或更高的多官能(甲基)丙烯酸酯化合物可包括化學式2-1的化合物。化學式2-1的化合物如下所述。 The trifunctional or higher polyfunctional (meth)acrylate compound may include the compound of Chemical Formula 2-1. The compound of Chemical Formula 2-1 is as follows.

可光聚合化合物可更包括單官能(甲基)丙烯酸酯化合物。 The photopolymerizable compound may further include a monofunctional (meth)acrylate compound.

以100重量份的單官能(甲基)丙烯酸酯化合物計,可光聚合化合物可含有100重量份或大於100重量份的多官能(甲基)丙烯酸酯化合物。 The photopolymerizable compound may contain 100 parts by weight or more of the multifunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound.

單官能(甲基)丙烯酸酯化合物可包含(甲基)丙烯酸酯,所述(甲基)丙烯酸酯包含具有1至10個碳原子的環氧烷基。 The monofunctional (meth)acrylate compound may include a (meth)acrylate containing an epoxyalkyl group having 1 to 10 carbon atoms.

單官能(甲基)丙烯酸酯化合物可包括化學式1的化合物。 The monofunctional (meth)acrylate compound may include the compound of Chemical Formula 1.

可光聚合化合物可包括:單官能(甲基)丙烯酸酯化合物,含有(甲基)丙烯酸酯,所述(甲基)丙烯酸酯含有具有1至10個碳原子的環氧烷基;以及三官能或更高的多官能(甲基)丙烯酸酯化合物,具有其中三或更多個具有1至10個碳原子的環氧烷基以及三或更多個(甲基)丙烯酸酯官能基鍵合至具有1至20個碳原子的中心基的結構。 The photopolymerizable compound may include: a monofunctional (meth)acrylate compound containing a (meth)acrylate containing an epoxyalkyl group having 1 to 10 carbon atoms; and a trifunctional or higher polyfunctional (meth)acrylate compounds having three or more epoxyalkyl groups having 1 to 10 carbon atoms and three or more (meth)acrylate functional groups bonded to Structures with a central group of 1 to 20 carbon atoms.

鹼性可顯影黏結劑樹脂可具有為20000克/莫耳(g/mol)或大於20000克/莫耳且為150000克/莫耳或小於150000克/莫耳的重量平均分子量。 The alkaline developable binder resin may have a weight average molecular weight of 20,000 grams per mole (g/mol) or greater and 150,000 g/mol or less.

以100重量份的單官能(甲基)丙烯酸酯化合物計,多官 能(甲基)丙烯酸酯化合物可以為小於100重量份的量被含有。 Based on 100 parts by weight of the monofunctional (meth)acrylate compound, the polyfunctional The (meth)acrylate compound may be contained in an amount of less than 100 parts by weight.

以100重量份的單官能(甲基)丙烯酸酯化合物計,多官能(甲基)丙烯酸酯化合物可以為30重量份或大於30重量份且為90重量份或小於90重量份的量被含有。 The polyfunctional (meth)acrylate compound may be contained in an amount of 30 parts by weight or more and 90 parts by weight or less based on 100 parts by weight of the monofunctional (meth)acrylate compound.

鹼性可顯影黏結劑樹脂可包括:第一鹼性可顯影黏結劑樹脂,包括由化學式3表示的重複單元、由化學式4表示的重複單元、由化學式5表示的重複單元、由化學式6表示的重複單元及由化學式7表示的重複單元;以及第二鹼性可顯影黏結劑樹脂,包括由化學式4表示的重複單元、由化學式5表示的重複單元及由化學式6表示的重複單元。化學式3至7如下所述。 The alkaline developable binder resin may include: a first alkaline developable binder resin including a repeating unit represented by Chemical Formula 3, a repeating unit represented by Chemical Formula 4, a repeating unit represented by Chemical Formula 5, a repeating unit represented by Chemical Formula 6 a repeating unit and a repeating unit represented by Chemical Formula 7; and a second alkaline developable binder resin including a repeating unit represented by Chemical Formula 4, a repeating unit represented by Chemical Formula 5, and a repeating unit represented by Chemical Formula 6. Chemical formulas 3 to 7 are as follows.

以100重量份的第一鹼性可顯影黏結劑樹脂計,第二鹼性可顯影黏結劑樹脂可以為500重量份或大於500重量份且為1000重量份或小於1000重量份的量被含有。 The second alkaline developable binder resin may be contained in an amount of 500 parts by weight or more and 1000 parts by weight or less based on 100 parts by weight of the first alkaline developable binder resin.

第一鹼性可顯影黏結劑樹脂的玻璃轉變溫度與第二鹼性可顯影黏結劑樹脂的玻璃轉變溫度的比率可為1:1.5或大於1:1.5且為1:5或小於1:5。 The ratio of the glass transition temperature of the first alkali developable binder resin to the glass transition temperature of the second alkali developable binder resin may be 1:1.5 or greater and 1:5 or less.

第一鹼性可顯影黏結劑樹脂的酸值與第二鹼性可顯影黏結劑樹脂的酸值的比率可為1:1.01或大於1:1.01且為1:1.5或小於1:1.5。 The ratio of the acid value of the first alkaline developable binder resin to the acid value of the second alkaline developable binder resin may be 1:1.01 or greater than 1:1.01 and 1:1.5 or less than 1:1.5.

感光樹脂層可具有為1微米或大於1微米且為1000微米或小於1000微米的厚度。 The photosensitive resin layer may have a thickness of 1 micron or more and 1000 microns or less.

感光樹脂層可具有為0.10平方公分或大於0.10平方公 分且為5.00平方公分或小於5.00平方公分的橫截面積。 The photosensitive resin layer may have a thickness of 0.10 square centimeters or greater than 0.10 square centimeters. A cross-sectional area of 5.00 square centimeters or less than 5.00 square centimeters.

本文中進一步提供一種包括含有所述感光樹脂組成物的所述感光樹脂層的乾膜式光阻。 This article further provides a dry film photoresist including the photosensitive resin layer containing the photosensitive resin composition.

本文中進一步提供一種感光元件,所述感光元件包括:聚合物基板;以及所述感光樹脂層,形成於所述聚合物基板上。 This article further provides a photosensitive element, which includes: a polymer substrate; and the photosensitive resin layer formed on the polymer substrate.

本文中進一步提供一種感光元件,所述感光元件包括:聚合物基板;以及所述感光樹脂層,形成於所述聚合物基板上,其中在使用剝離試驗儀對其中將所述感光樹脂層疊層於基板上的膜樣品進行的膠帶剝離(tape peeling)試驗期間,由以下方程式1定義的黏合力為90%或大於90%:[方程式1]黏合力(%)=(在膠帶剝離試驗之後基板及感光樹脂層的表面積/在膠帶剝離試驗之前感光樹脂層與基板接觸的表面積)*100。 This article further provides a photosensitive element, the photosensitive element comprising: a polymer substrate; and the photosensitive resin layer formed on the polymer substrate, wherein the photosensitive resin layer is laminated on the polymer substrate using a peel tester. During a tape peeling test of a film sample on a substrate, the adhesion defined by the following Equation 1 is 90% or greater: [Equation 1] Adhesion (%) = (After the tape peeling test the substrate and Surface area of the photosensitive resin layer/surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test)*100.

在下文中,將更詳細地闡述根據本揭露具體實施例的一種感光樹脂組成物、一種感光樹脂層、以及一種使用所述感光樹脂層的乾膜式光阻及感光元件。 In the following, a photosensitive resin composition, a photosensitive resin layer, a dry film photoresist and a photosensitive element using the photosensitive resin layer according to specific embodiments of the present disclosure will be described in more detail.

除非在本說明書通篇中另外詳細說明,否則本文中所使用的技術用語僅用於引用特定實施例,且不旨在限制本揭露。 Unless otherwise specified throughout this specification, technical terms used herein are used only to refer to specific embodiments and are not intended to limit the present disclosure.

除非上下文中清楚地另外指示,否則本文中所使用的單數形式「一(a/an)」及「所述」亦包括複數引用。 As used herein, the singular forms "a/an" and "the" include plural references unless the context clearly indicates otherwise.

本文中所使用的用語「包含(including)」或「包括(comprising)」詳細說明特定特徵、區、整數、步驟、動作、元件 及/或組件,但不排除不同的特定特徵、區、整數、步驟、動作、元件、組件及/或群組的存在或添加。 The terms "including" or "comprising" are used herein to specify specific features, regions, integers, steps, actions, components and/or components, but does not exclude the existence or addition of different specific features, regions, integers, steps, actions, elements, components and/or groups.

此外,包括例如「第一(first)」、「第二(second)」等序數的用語僅用於區分各個組件的目的,且不受限於所述序數。舉例而言,在不背離本揭露的範圍的條件下,第一組件可被稱為第二組件,或者相似地,第二組件可被稱為第一組件。 In addition, terms including ordinal numbers such as "first", "second", etc. are only used for the purpose of distinguishing various components and are not limited to the ordinal numbers. For example, a first component could be termed a second component, or, similarly, a second component could be termed a first component, without departing from the scope of the present disclosure.

在本說明書中,取代基的實例闡述如下,但不限於此。 In this specification, examples of substituents are set forth below, but are not limited thereto.

在本說明書中,用語「經取代的(substituted)」意指其他官能基代替化合物中的氫原子被鍵合,且欲取代的位置不受限制,只要所述位置是氫原子被取代的位置(即取代基可進行取代的位置)即可,且當二或更多者經取代時,所述二或更多個取代基可彼此相同或不同。 In this specification, the term "substituted" means that other functional groups are bonded instead of hydrogen atoms in the compound, and the position to be substituted is not limited as long as the position is the position where the hydrogen atom is substituted ( That is, the position at which the substituent may be substituted) is sufficient, and when two or more substituents are substituted, the two or more substituents may be the same or different from each other.

在本說明書中,用語「經取代或未經取代的(substituted or unsubstituted)」意指未經取代或經選自由以下組成的群組的一或多個取代基取代:氘;鹵素基;氰基;硝基;羥基;羰基;酯基;醯亞胺基;醯胺基;伯胺基;羧基;磺酸基;磺醯胺基;氧化膦基;烷氧基;芳氧基;烷基硫氧基;芳基硫氧基;烷基磺酸氧基;芳基磺酸氧基;矽烷基;硼基;烷基;環烷基;烯基;芳基;芳烷基;芳烯基;烷基芳基;烷氧基矽烷基烷基;芳基膦基;或雜環基,含有N、O及S原子中的至少一者,或者意指未經取代或經以上例示的取代基中與二或更多個取代基連結的取代基取代。舉例而言,「與二或更多個取代基連結的取代基」可為聯苯基。即,聯苯基亦 可為芳基,且可被解釋為與兩個苯基連結的取代基。 In this specification, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; halogen group; cyano group ; Nitro; hydroxyl; carbonyl; ester group; amide group; amide group; primary amine group; carboxyl group; sulfonate group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkyl sulfide Oxygen; arylsulfoxy; alkylsulfonateoxy; arylsulfonateoxy; silyl; boron; alkyl; cycloalkyl; alkenyl; aryl; aralkyl; arylalkenyl; Alkylaryl; alkoxysilylalkyl; arylphosphinoyl; or heterocyclyl, containing at least one of N, O and S atoms, or meaning unsubstituted or among the substituents exemplified above Substitution with a substituent bonded to two or more substituents. For example, the "substituent bonded to two or more substituents" may be a biphenyl group. That is, biphenyl is also Can be an aryl group and can be interpreted as a substituent bonded to two phenyl groups.

在本說明書中,記號

Figure 109144461-A0305-02-0010-45
Figure 109144461-A0305-02-0010-51
意指與另一取代基連結的鍵,且直接鍵合意指在表示為L的部分中不存在其他原子的情形。 In this manual, the notation
Figure 109144461-A0305-02-0010-45
or
Figure 109144461-A0305-02-0010-51
It means a bond to another substituent, and a direct bond means that there are no other atoms in the moiety represented by L.

在本說明書中,(甲基)丙烯酸基意欲包括丙烯酸基與甲基丙烯酸基二者。舉例而言,(甲基)丙烯酸酯意欲包括丙烯酸酯與甲基丙烯酸酯二者。 In this specification, (meth)acrylic acid groups are intended to include both acrylic acid groups and methacrylic acid groups. For example, (meth)acrylate is intended to include both acrylates and methacrylates.

在本說明書中,烷基是衍生自烷烴(alkane)的單價官能基,且可為直鏈的(linear-chain)或支鏈的(branched-chain)。直鏈烷基的碳原子數目並無特別限制,但較佳為1至20。此外,支鏈烷基的碳原子數目為3至20。烷基的具體實例包括甲基、乙基、丙基、正丙基、異丙基、丁基、正丁基、異丁基、第三丁基、第二丁基、1-甲基丁基、1-乙基丁基、戊基、正戊基、異戊基、新戊基、第三戊基、己基、正己基、1-甲基戊基、2-甲基戊基、4-甲基-2-戊基、3,3-二甲基丁基、2-乙基丁基、庚基、正庚基、1-甲基己基、辛基、正辛基、第三辛基、1-甲基庚基、2-乙基己基、2-丙基戊基、n-壬基、2,2-二甲基庚基、1-乙基丙基、1,1-二甲基丙基、異己基、2-甲基戊基、4-甲基己基、5-甲基己基、2,6-二甲基庚烷-4-基及類似物,但不限於此。烷基可為經取代或未經取代的,且當其經取代時,取代基的實例與上述者相同。 In this specification, an alkyl group is a monovalent functional group derived from an alkane, and may be linear-chain or branched-chain. The number of carbon atoms of the linear alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the number of carbon atoms of the branched alkyl group is 3 to 20. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl , 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, third pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl Base-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, octyl, n-octyl, tertiary octyl, 1 -Methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl , isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl and the like, but are not limited thereto. The alkyl group may be substituted or unsubstituted, and when it is substituted, examples of the substituents are the same as above.

在本說明書中,芳基是衍生自芳烴(arene)的單價官能基,且並無特別限制,但較佳地具有6至20個碳原子,且可為單環芳基或多環芳基。單環芳基的具體實例可包括苯基、聯苯基、三 聯苯基及類似物,但不限於此。多環芳基的具體實例可包括萘基、蒽基、菲基、芘基、苝基、

Figure 109144461-A0305-02-0011-47
基、芴基及類似物,但不限於此。芳基可為經取代或未經取代的,且當其經取代時,取代基的實例與上述者相同。 In this specification, an aryl group is a monovalent functional group derived from an arene, and is not particularly limited, but preferably has 6 to 20 carbon atoms, and can be a monocyclic aryl group or a polycyclic aryl group. Specific examples of the monocyclic aryl group may include phenyl, biphenyl, terphenyl and the like, but are not limited thereto. Specific examples of the polycyclic aromatic group may include naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylene,
Figure 109144461-A0305-02-0011-47
base, fluorenyl base and the like, but are not limited thereto. The aryl group may be substituted or unsubstituted, and when it is substituted, examples of the substituents are the same as above.

在本說明書中,伸烷基是衍生自烷烴(alkane)的二價官能基,且除伸烷基是二價官能基以外,可應用對如上定義的烷基的說明。舉例而言,伸烷基可為直鏈的或支鏈的、亞甲基、乙烯基、丙烯基、異丁烯基、第二丁烯基、第三丁烯基、伸戊基、伸己基或類似物。伸烷基可為經取代或未經取代的。 In this specification, the alkylene group is a divalent functional group derived from an alkane (alkane), and the description for the alkyl group as defined above is applicable except that the alkylene group is a divalent functional group. For example, the alkylene group may be linear or branched, methylene, vinyl, propenyl, isobutenyl, sec-butenyl, tert-butenyl, pentenyl, hexenyl or the like. things. Alkylene groups may be substituted or unsubstituted.

在本說明書中,多價官能基是其中鍵合至任意化合物的多個氫原子被移除的殘基,且舉例而言,其可為二價官能基、三價官能基及四價官能基。作為實例,衍生自環丁烷的四價官能基意指其中鍵合至環丁烷的任何四個氫原子被移除的殘基。 In this specification, a multivalent functional group is a residue in which a plurality of hydrogen atoms bonded to any compound are removed, and, for example, it may be a divalent functional group, a trivalent functional group, and a tetravalent functional group . As an example, a tetravalent functional group derived from cyclobutane means a residue in which any four hydrogen atoms bonded to cyclobutane have been removed.

在本說明書中,直接鍵合或單一鍵合意指連接至在對應位置處不存在原子或原子基團的鍵合線(bond line)上。具體而言,直接鍵合或單一鍵合意指其中在化學式中表示為Ra或Lb(其中a及b分別是為1至20的整數)的部分中不存在其他原子的情形。 In this specification, direct bonding or single bonding means connecting to a bond line where no atom or atomic group exists at the corresponding position. Specifically, direct bonding or single bonding means a situation in which no other atoms are present in the part represented by R a or L b (where a and b are respectively integers from 1 to 20) in the chemical formula.

在本說明書中,用語「(光)固化產物」或「(光)固化」意味著不僅包括其中化學結構中具有可固化或可交聯不飽和基的組分被完全固化、交聯或聚合的情形,而且包括其中此種組分被部分固化、交聯或聚合的情形。 In this specification, the term "(photo)cured product" or "(photo)cured" means not only a component in which a component having a curable or crosslinkable unsaturated group in the chemical structure is completely cured, crosslinked or polymerized situations, and includes situations in which such components are partially cured, cross-linked or polymerized.

在下文中,將更詳細地闡述本揭露。 In the following, the present disclosure will be explained in more detail.

1.感光樹脂組成物 1. Photosensitive resin composition

根據本揭露的一個實施例,可提供一種感光樹脂層,所述感光樹脂層包含:可光聚合化合物,含有三官能或更高的多官能(甲基)丙烯酸酯化合物;以及鹼性可顯影黏結劑樹脂,其中在使用剝離試驗儀對其中將所述感光樹脂層疊層於基板上的膜樣品進行的膠帶剝離(tape peeling)試驗期間,由方程式1定義的黏合力為90%或大於90%。 According to one embodiment of the present disclosure, a photosensitive resin layer may be provided, the photosensitive resin layer comprising: a photopolymerizable compound containing a trifunctional or higher polyfunctional (meth)acrylate compound; and an alkaline developable adhesive agent resin, wherein the adhesive force defined by Equation 1 is 90% or greater during a tape peeling test using a peel tester on a film sample in which the photosensitive resin layer is laminated on a substrate.

本發明者藉由實驗發現,由於一個實施例的感光樹脂層具有為90%或大於90%的由方程式1定義的黏合力,因此可確保極佳的物理性質(解析度、細線黏合力等),並完成了本揭露。 The inventor discovered through experiments that because the photosensitive resin layer of one embodiment has an adhesion force defined by Equation 1 of 90% or greater, excellent physical properties (resolution, fine line adhesion, etc.) can be ensured. , and complete this disclosure.

(1)鹼性可顯影黏結劑樹脂 (1)Alkaline developable binder resin

本揭露的感光樹脂層可包含鹼性可顯影黏結劑樹脂。 The photosensitive resin layer of the present disclosure may include an alkaline developable binder resin.

具體而言,鹼性可顯影黏結劑樹脂可包括至少二或更多種鹼性可顯影黏結劑樹脂。所述至少二或更多種鹼性可顯影黏結劑樹脂可意指由二或更多種鹼性可顯影黏結劑樹脂構成的混合物。 Specifically, the alkaline developable binder resin may include at least two or more alkaline developable binder resins. The at least two or more alkaline developable binder resins may mean a mixture composed of two or more alkaline developable binder resins.

所述至少二或更多種鹼性可顯影黏結劑樹脂可包括:第一鹼性可顯影黏結劑樹脂,包括由以下化學式3表示的重複單元、由以下化學式4表示的重複單元、由以下化學式5表示的重複單元、由以下化學式6表示的重複單元及由以下化學式7表示的重複單元;以及第二鹼性可顯影黏結劑樹脂,包括由以下化學式4表示的重複單元、由以下化學式5表示的重複單元及由以下化學式6表示的重複單元。 The at least two or more alkaline developable binder resins may include: a first alkaline developable binder resin including a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by 5, a repeating unit represented by the following Chemical Formula 6, and a repeating unit represented by the following Chemical Formula 7; and a second alkaline developable binder resin including a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5 and a repeating unit represented by the following Chemical Formula 6.

Figure 109144461-A0305-02-0013-2
Figure 109144461-A0305-02-0013-2

在化學式3中,R3"是氫,

Figure 109144461-A0305-02-0013-3
In Chemical Formula 3, R 3 " is hydrogen,
Figure 109144461-A0305-02-0013-3

在化學式4中,R3'是具有1至10個碳原子的烷基,

Figure 109144461-A0305-02-0013-4
In Chemical Formula 4, R 3 ' is an alkyl group having 1 to 10 carbon atoms,
Figure 109144461-A0305-02-0013-4

在化學式5中,R4"是具有1至10個碳原子的烷基,且R5"是具有1至10個碳原子的烷基,[化學式6]

Figure 109144461-A0305-02-0014-5
In Chemical Formula 5, R 4 " is an alkyl group having 1 to 10 carbon atoms, and R 5 " is an alkyl group having 1 to 10 carbon atoms, [Chemical Formula 6]
Figure 109144461-A0305-02-0014-5

在化學式6中,Ar是具有6至20個碳原子的芳基,

Figure 109144461-A0305-02-0014-6
In Chemical Formula 6, Ar is an aryl group having 6 to 20 carbon atoms,
Figure 109144461-A0305-02-0014-6

在化學式7中,R4'是氫,且R5'是具有1至10個碳原子的烷基。 In Chemical Formula 7, R 4 ' is hydrogen, and R 5 ' is an alkyl group having 1 to 10 carbon atoms.

具體而言,鹼性可顯影黏結劑樹脂可包括由以下構成的隨機共聚物:由以下化學式3表示的重複單元、由以下化學式4表示的重複單元、由以下化學式5表示的重複單元、由以下化學式6表示的重複單元及由以下化學式7表示的重複單元。 Specifically, the alkaline developable binder resin may include a random copolymer composed of a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5, The repeating unit represented by Chemical Formula 6 and the repeating unit represented by Chemical Formula 7 below.

Figure 109144461-A0305-02-0014-7
Figure 109144461-A0305-02-0014-7

在化學式3中,R3"是氫,

Figure 109144461-A0305-02-0015-8
In Chemical Formula 3, R 3 " is hydrogen,
Figure 109144461-A0305-02-0015-8

在化學式4中,R3'是具有1至10個碳原子的烷基,

Figure 109144461-A0305-02-0015-9
In Chemical Formula 4, R 3 ' is an alkyl group having 1 to 10 carbon atoms,
Figure 109144461-A0305-02-0015-9

在化學式5中,R4"是具有1至10個碳原子的烷基,且R5"是具有1至10個碳原子的烷基,

Figure 109144461-A0305-02-0015-10
In Chemical Formula 5, R 4 " is an alkyl group having 1 to 10 carbon atoms, and R 5 " is an alkyl group having 1 to 10 carbon atoms,
Figure 109144461-A0305-02-0015-10

在化學式6中,Ar是具有6至20個碳原子的芳基,[化學式7]

Figure 109144461-A0305-02-0016-12
In Chemical Formula 6, Ar is an aryl group having 6 to 20 carbon atoms, [Chemical Formula 7]
Figure 109144461-A0305-02-0016-12

在化學式7中,R4'是氫,且R5'是具有1至10個碳原子的烷基。 In Chemical Formula 7, R 4 ' is hydrogen, and R 5 ' is an alkyl group having 1 to 10 carbon atoms.

在化學式3至7中,具有1至10個碳原子的烷基的具體實例可包括甲基。 In Chemical Formulas 3 to 7, specific examples of the alkyl group having 1 to 10 carbon atoms may include a methyl group.

Ar是具有6至20個碳原子的芳基,且具有6至20個碳原子的芳基的具體實例可包括苯基。 Ar is an aryl group having 6 to 20 carbon atoms, and specific examples of the aryl group having 6 to 20 carbon atoms may include a phenyl group.

由化學式4表示的重複單元可為衍生自由以下化學式4-1表示的單體的重複單元。 The repeating unit represented by Chemical Formula 4 may be a repeating unit derived from a monomer represented by Chemical Formula 4-1 below.

Figure 109144461-A0305-02-0016-14
Figure 109144461-A0305-02-0016-14

在化學式4-1中,R3'是具有1至10個碳原子的烷基。在化學式4-1中,R3'的定義與針對化學式4闡述的定義相同。由化學式4-1表示的單體的具體實例可包括甲基丙烯酸(methacrylic acid, MAA)。 In Chemical Formula 4-1, R 3 ' is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 4-1, the definition of R 3 ' is the same as that set forth for Chemical Formula 4. Specific examples of the monomer represented by Chemical Formula 4-1 may include methacrylic acid (MAA).

由化學式5表示的重複單元可為衍生自由以下化學式5-1表示的單體的重複單元。 The repeating unit represented by Chemical Formula 5 may be a repeating unit derived from a monomer represented by Chemical Formula 5-1 below.

Figure 109144461-A0305-02-0017-15
Figure 109144461-A0305-02-0017-15

在化學式5-1中,R4"是具有1至10個碳原子的烷基,且R5"是具有1至10個碳原子的烷基。在化學式5-1中,R4"及R5"的定義與針對化學式5闡述的定義相同。由化學式5-1表示的單體的具體實例可包括甲基丙烯酸甲酯(methylmethacrylate,MMA)。 In Chemical Formula 5-1, R 4 " is an alkyl group having 1 to 10 carbon atoms, and R 5 " is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 5-1, the definitions of R 4 " and R 5 " are the same as those set forth for Chemical Formula 5. Specific examples of the monomer represented by Chemical Formula 5-1 may include methylmethacrylate (MMA).

由化學式6表示的重複單元可為衍生自由以下化學式6-1表示的單體的重複單元。 The repeating unit represented by Chemical Formula 6 may be a repeating unit derived from a monomer represented by Chemical Formula 6-1 below.

Figure 109144461-A0305-02-0017-16
Figure 109144461-A0305-02-0017-16

在化學式6-1中,Ar是具有6至20個碳原子的芳基。在化學式6-1中,Ar的定義與針對化學式6闡述的定義相同。由化學式6-1表示的單體的具體實例可包括苯乙烯(styrene,SM)。 In Chemical Formula 6-1, Ar is an aryl group having 6 to 20 carbon atoms. In Chemical Formula 6-1, the definition of Ar is the same as that set forth for Chemical Formula 6. Specific examples of the monomer represented by Chemical Formula 6-1 may include styrene (SM).

鹼性可顯影黏結劑樹脂可具有為30000克/莫耳或大於30000克/莫耳且為150000克/莫耳或小於150000克/莫耳的重量平均分子量,且具有為20℃或大於20℃且為150℃或小於150℃的玻璃轉變溫度。藉此,可改善乾膜式光阻的塗佈性質及跟隨性(followability)以及在電路形成之後所述光阻本身的機械強度。此外,鹼性可顯影黏結劑樹脂可具有為140毫克氫氧化鉀/克(mg KOH/g)或大於140毫克氫氧化鉀/克且為160毫克氫氧化鉀/克或小於160毫克氫氧化鉀/克的酸值。 The alkaline developable binder resin may have a weight average molecular weight of 30,000 g/mol or greater and 150,000 g/mol or less and have a weight average molecular weight of 20°C or greater and a glass transition temperature of 150°C or less. Thereby, the coating properties and followability of the dry film photoresist can be improved, as well as the mechanical strength of the photoresist itself after the circuit is formed. Additionally, the alkaline developable binder resin may have 140 milligrams of potassium hydroxide per gram (mg KOH/g) or more and 160 mg KOH/g or less. /g acid value.

此外,鹼性可顯影黏結劑樹脂可具有為20000克/莫耳或大於20000克/莫耳且為130000克/莫耳或小於130000克/莫耳的重量平均分子量,且具有為30℃或大於30℃且為160℃或小於160℃的玻璃轉變溫度。藉此,可改善乾膜式光阻的塗佈性質及跟隨性(followability)以及在電路形成之後所述光阻本身的機械強度。 In addition, the alkaline developable binder resin may have a weight average molecular weight of 20,000 g/mol or greater and 130,000 g/mol or less, and have a weight average molecular weight of 30° C. or greater 30°C and a glass transition temperature of 160°C or less. Thereby, the coating properties and followability of the dry film photoresist can be improved, as well as the mechanical strength of the photoresist itself after the circuit is formed.

本文中所使用的重量平均分子量指代藉由凝膠滲透層析法(gel permeation chromatography,GPC)量測的聚苯乙烯轉化的重量平均分子量。在量測藉由GPC量測的聚苯乙烯轉化的重量平均分子量的製程中,可使用檢測器及分析管柱(例如眾所習知的分析設備及示差折射率檢測器(differential refractive index detector)),且可使用常用的溫度條件、溶劑及流速(flow rate)。 The weight average molecular weight used herein refers to the weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC). In the process of measuring the weight average molecular weight of polystyrene conversion measured by GPC, a detector and an analytical column (such as well-known analytical equipment and a differential refractive index detector) may be used ), and commonly used temperature conditions, solvents and flow rates can be used.

量測條件的具體實例如下:將鹼性可顯影黏結劑樹脂溶解於四氫呋喃(tetrahydrofuran,THF)中,以使鹼性可顯影黏結劑樹脂在THF中具有為1.0(重量/重量(w/w))%的濃度(以固 體含量計,約0.5(重量/重量)%);使用孔徑(pore size)為0.45微米的注射器(syringe filter)過濾器進行了過濾;且然後以20微升的量注射至GPC中,四氫呋喃(THF)用作GPC的移動相(mobile phase),且流速為1.0毫升/分鐘(mL/min)。所述管柱由串聯連接的一個安捷倫PL膠(Agilent PLgel)5微米(μm)保護管(guard)(7.5×50毫米(mm))與兩個安捷倫PL膠5微米混合管(mixed)D(7.5×300毫米)配置而成,且所述量測是使用安捷倫1260無限II系統(Agilent 1260 Infinity II System)RI檢測器(RI Detector)作為檢測器在40℃下執行。 Specific examples of measurement conditions are as follows: the alkaline developable binder resin is dissolved in tetrahydrofuran (THF), so that the alkaline developable binder resin in THF has a value of 1.0 (weight/weight (w/w) )% concentration (in solid Body content, about 0.5 (weight/weight)%); filtered using a syringe filter with a pore size of 0.45 microns; and then injected into the GPC in an amount of 20 microliters, tetrahydrofuran ( THF) was used as the mobile phase of GPC, and the flow rate was 1.0 mL/min. The column is composed of an Agilent PL gel 5 micron (μm) guard (7.5 × 50 millimeters (mm)) and two Agilent PL gel 5 micron mixed tubes (mixed) D ( 7.5 × 300 mm) configured, and the measurement was performed at 40°C using the Agilent 1260 Infinity II System RI Detector as the detector.

藉由孔徑(pore size)為0.45微米的注射器過濾器(syringe filter)對其中將具有各種分子量的聚苯乙烯以0.1(重量/重量)(w/w)%的濃度溶解於四氫呋喃中的聚苯乙烯標準樣品(STD A、B、C、D)進行了過濾,且然後注射至GPC中,且使用校準曲線對鹼性可顯影黏結劑樹脂的重量平均分子量(Mw)的值進行了確定。 Polyphenyls in which polystyrenes with various molecular weights were dissolved in tetrahydrofuran at a concentration of 0.1 (weight/weight) (w/w)% were analyzed through a syringe filter with a pore size of 0.45 microns. Ethylene standards (STD A, B, C, D) were filtered and then injected into the GPC and the weight average molecular weight (Mw) value of the alkaline developable binder resin was determined using a calibration curve.

STD A(MP):791,000/27,810/945 STD A(MP):791,000/27,810/945

STD B(MP):282,000/10,700/580 STD B(MP):282,000/10,700/580

STD C(MP):126,000/4,430/370 STD C(MP):126,000/4,430/370

STD D(MP):51,200/1,920/162 STD D(MP):51,200/1,920/162

藉由示差掃描熱量計(Differential Scanning Calorimeter,DSC)(珀金-埃爾默(Perkin-Elmer),DSC-7)對參考(reference)聚合物的玻璃轉變溫度與黏結劑聚合物的玻璃轉變溫度進行了比 較。所述量測可藉由將溫度維持在20℃下達15分鐘且然後以為1℃/分鐘的速率將溫度升至200℃來執行。 The glass transition temperature of the reference polymer and the glass transition temperature of the binder polymer were measured using a Differential Scanning Calorimeter (DSC) (Perkin-Elmer, DSC-7). compared Compare. The measurement can be performed by maintaining the temperature at 20°C for 15 minutes and then increasing the temperature to 200°C at a rate of 1°C/minute.

藉由如下製程對鹼性可顯影黏結劑樹脂的酸值進行了量測:在所述製程中,對約1克鹼性可顯影黏結劑樹脂進行取樣、將其溶解於添加有兩滴1%酚酞指示劑的50毫升(ml)混合溶劑(MeOH 20%、丙酮(acetone)80%)中,且然後利用0.1當量濃度(N)KOH進行滴定以量測酸值。 The acid value of the alkaline developable binder resin was measured by the following process: In the process, approximately 1 gram of the alkaline developable binder resin was sampled and dissolved in two drops of 1% phenolphthalein indicator in 50 milliliters (ml) of a mixed solvent (MeOH 20%, acetone (80%)), and then titrated using 0.1 normal concentration (N) KOH to measure the acid value.

第一鹼性可顯影黏結劑樹脂可具有為140毫克氫氧化鉀/克或大於140毫克氫氧化鉀/克且為160毫克氫氧化鉀/克或小於160毫克氫氧化鉀/克的酸值。此外,第二鹼性可顯影黏結劑樹脂可具有為160毫克氫氧化鉀/克或大於160毫克氫氧化鉀/克且為200毫克氫氧化鉀/克或小於200毫克氫氧化鉀/克的酸值。 The first alkaline developable binder resin may have an acid value of 140 mg potassium hydroxide/gram or greater and 160 mg potassium hydroxide/gram or less. Additionally, the second alkaline developable binder resin may have an acid content of 160 mg potassium hydroxide/gram or more and 200 mg potassium hydroxide/gram or less. value.

具體而言,第一鹼性可顯影黏結劑樹脂的玻璃轉變溫度與第二鹼性可顯影黏結劑樹脂的玻璃轉變溫度的比率可為1:1.5或大於1:1.5且為1:5或小於1.5、1:1.5或大於1:1.5且為1:3或小於1:3、1:1.5或大於1:1.5且為1:2或小於1:2、1:1.5或大於1:1.5且為1:1.8或小於1:1.8、1:1.5或大於1:1.5且為1:1.75或小於1:1.75、或者1:1.6或大於1:1.6且為1:1.7或小於1:1.7。 Specifically, the ratio of the glass transition temperature of the first alkali developable binder resin to the glass transition temperature of the second alkali developable binder resin may be 1:1.5 or greater and 1:5 or less. 1.5, 1:1.5 or greater than 1:1.5 and 1:3 or less than 1:3, 1:1.5 or greater than 1:1.5 and 1:2 or less than 1:2, 1:1.5 or greater than 1:1.5 and 1:1.8 or less than 1:1.8, 1:1.5 or greater than 1:1.5 and 1:1.75 or less than 1:1.75, or 1:1.6 or greater than 1:1.6 and 1:1.7 or less than 1:1.7.

此外,第一鹼性可顯影黏結劑樹脂的酸值與第二鹼性可顯影黏結劑樹脂的酸值的比率可為1:1.01或大於1:1.01且為1:1.5或小於1:1.5、1:1.01或大於1:1.01且為1:1.25或小於1:1.25、1:1.01或大於1:1.01且為1:1.2或小於1:1.2、或者1:1.01或大於 1:1.01且為1:1.1或小於1:1.1。 In addition, the ratio of the acid value of the first alkaline developable binder resin to the acid value of the second alkaline developable binder resin may be 1:1.01 or greater than 1:1.01 and 1:1.5 or less than 1:1.5, 1:1.01 or greater than 1:1.01 and 1:1.25 or less than 1:1.25, 1:1.01 or greater than 1:1.01 and 1:1.2 or less than 1:1.2, or 1:1.01 or greater 1:1.01 and is 1:1.1 or less than 1:1.1.

同時,以1莫耳由化學式3表示的重複單元計,一個實施例的感光樹脂組成物中所含有的第一鹼性可顯影黏結劑樹脂可以為1.2莫耳或大於1.2莫耳且為3莫耳或小於3莫耳、1.2莫耳或大於1.2莫耳且為2莫耳或小於2莫耳、1.5莫耳或大於1.5莫耳且為2莫耳或小於2莫耳、或者1.5莫耳或大於1.5莫耳且為1.6莫耳或小於1.6莫耳的量包括由化學式4表示的重複單元。 Meanwhile, based on 1 mol of the repeating unit represented by Chemical Formula 3, the first alkaline developable binder resin contained in the photosensitive resin composition of one embodiment may be 1.2 mol or greater than 1.2 mol and 3 mol 1 mole or less, 1.2 mole or more than 1.2 mole and 2 mole or less, 1.5 mole or more than 1.5 mole and 2 mole or less, or 1.5 mole or An amount of more than 1.5 mole and 1.6 mole or less than 1.6 mole includes the repeating unit represented by Chemical Formula 4.

此外,以1莫耳由化學式7表示的重複單元計,一個實施例的感光樹脂組成物中所含有的第二鹼性可顯影黏結劑樹脂可以為2莫耳或大於2莫耳且為10莫耳或小於10莫耳、3莫耳或大於3莫耳且為10莫耳或小於10莫耳、3莫耳或大於3莫耳且為5莫耳或小於5莫耳、或者4莫耳或大於4莫耳且為5莫耳或小於5莫耳的量包括由化學式5表示的重複單元。 In addition, the second alkaline developable binder resin contained in the photosensitive resin composition of one embodiment may be 2 moles or greater than 2 moles and 10 moles based on 1 mole of the repeating unit represented by Chemical Formula 7. 10 moles or less, 3 moles or more and 10 moles or less, 3 moles or more than 3 moles and 5 moles or less, or 4 moles or An amount of more than 4 moles and 5 moles or less includes the repeating unit represented by Chemical Formula 5.

同時,第二鹼性可顯影黏結劑樹脂可包括由以下構成的隨機共聚物:由以下化學式4表示的重複單元、由以下化學式5表示的重複單元及由以下化學式6表示的重複單元。 Meanwhile, the second alkaline developable binder resin may include a random copolymer composed of a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5, and a repeating unit represented by the following Chemical Formula 6.

Figure 109144461-A0305-02-0021-17
Figure 109144461-A0305-02-0021-17

在化學式4中,R3'是具有1至10個碳原子的烷基。 In Chemical Formula 4, R 3 ' is an alkyl group having 1 to 10 carbon atoms.

Figure 109144461-A0305-02-0022-18
Figure 109144461-A0305-02-0022-18

在化學式5中,R4"是具有1至10個碳原子的烷基,且R5"是具有1至10個碳原子的烷基,

Figure 109144461-A0305-02-0022-19
In Chemical Formula 5, R 4 " is an alkyl group having 1 to 10 carbon atoms, and R 5 " is an alkyl group having 1 to 10 carbon atoms,
Figure 109144461-A0305-02-0022-19

在化學式6中,Ar是具有6至20個碳原子的芳基。 In Chemical Formula 6, Ar is an aryl group having 6 to 20 carbon atoms.

由化學式4表示的重複單元可為衍生自由以下化學式4-1表示的單體的重複單元。 The repeating unit represented by Chemical Formula 4 may be a repeating unit derived from a monomer represented by Chemical Formula 4-1 below.

[化學式4-1]

Figure 109144461-A0305-02-0023-20
[Chemical formula 4-1]
Figure 109144461-A0305-02-0023-20

在化學式4-1中,R3'是具有1至10個碳原子的烷基。在化學式4-1中,R3'的定義與針對化學式4闡述的定義相同。由化學式4-1表示的單體的具體實例可包括甲基丙烯酸(MAA)。 In Chemical Formula 4-1, R 3 ' is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 4-1, the definition of R 3 ' is the same as that set forth for Chemical Formula 4. Specific examples of the monomer represented by Chemical Formula 4-1 may include methacrylic acid (MAA).

由化學式5表示的重複單元可為衍生自由以下化學式5-1表示的單體的重複單元。 The repeating unit represented by Chemical Formula 5 may be a repeating unit derived from a monomer represented by Chemical Formula 5-1 below.

Figure 109144461-A0305-02-0023-21
Figure 109144461-A0305-02-0023-21

在化學式5中,R4"是具有1至10個碳原子的烷基,且R5"是具有1至10個碳原子的烷基。在化學式5-1中,R4"及R5"的定義與針對化學式5闡述的定義相同。由化學式5-1表示的單體的具體實例可包括甲基丙烯酸甲酯(MMA)。 In Chemical Formula 5, R 4 " is an alkyl group having 1 to 10 carbon atoms, and R 5 " is an alkyl group having 1 to 10 carbon atoms. In Chemical Formula 5-1, the definitions of R 4 " and R 5 " are the same as those set forth for Chemical Formula 5. Specific examples of the monomer represented by Chemical Formula 5-1 may include methyl methacrylate (MMA).

由化學式6表示的重複單元可為衍生自由以下化學式6- 1表示的單體的重複單元。 The repeating unit represented by Chemical Formula 6 may be derived from the following Chemical Formula 6- 1 represents the repeating unit of the monomer.

Figure 109144461-A0305-02-0024-22
Figure 109144461-A0305-02-0024-22

在化學式6-1中,Ar是具有6至20個碳原子的芳基。在化學式6-1中,Ar的定義與針對化學式6闡述的定義相同。由化學式6-1表示的單體的具體實例可包括苯乙烯(SM)。 In Chemical Formula 6-1, Ar is an aryl group having 6 to 20 carbon atoms. In Chemical Formula 6-1, the definition of Ar is the same as that set forth for Chemical Formula 6. Specific examples of the monomer represented by Chemical Formula 6-1 may include styrene (SM).

具體而言,第一鹼性可顯影黏結劑樹脂可以如下比率包括由化學式4表示的重複單元:由化學式5表示的重複單元:由化學式6表示的重複單元:1:(2或大於2且為5或小於5):(0.2或大於0.2且為0.9或小於0.9)、1:(2或大於2且為3或小於3):(0.5或大於0.5且為0.9或小於0.9)、1:(2.5或大於2.5且為3或小於3):(0.6或大於0.6且為0.9或小於0.9)或1:(2.75或大於2.75且為3或小於3):(0.6或大於0.6且為0.75或小於0.75)。 Specifically, the first alkaline developable binder resin may include the repeating unit represented by Chemical Formula 4 in the following ratio: the repeating unit represented by Chemical Formula 5: the repeating unit represented by Chemical Formula 6: 1: (2 or more than 2 and is 5 or less than 5): (0.2 or greater than 0.2 and 0.9 or less than 0.9), 1: (2 or greater than 2 and 3 or less than 3): (0.5 or greater than 0.5 and 0.9 or less than 0.9), 1: ( 2.5 or greater than 2.5 and 3 or less): (0.6 or greater than 0.6 and 0.9 or less than 0.9) or 1: (2.75 or greater than 2.75 and 3 or less than 3): (0.6 or greater than 0.6 and 0.75 or less 0.75).

此外,第二鹼性可顯影黏結劑樹脂可以如下比率包括由化學式4表示的重複單元:由化學式5表示的重複單元:由化學式6表示的重複單元:1:(1.1或大於1.1且為2或小於2):(0.2或大於0.2且為0.99或小於0.99)、1:(1.5或大於1.5且為2或小於2):(0.5或大於0.5且為0.99或小於0.99)或1:(1.5或大於1.5且為1.75或小於1.75):(0.75或大於0.75且為0.99或小於0.99)。 In addition, the second alkaline developable binder resin may include a repeating unit represented by Chemical Formula 4: a repeating unit represented by Chemical Formula 5: a repeating unit represented by Chemical Formula 6: 1: (1.1 or more than 1.1 and 2 or less than 2): (0.2 or greater than 0.2 and 0.99 or less than 0.99), 1: (1.5 or greater than 1.5 and 2 or less than 2): (0.5 or greater than 0.5 and 0.99 or less than 0.99) or 1: (1.5 or Greater than 1.5 and 1.75 or less than 1.75): (0.75 or greater than 0.75 and 0.99 or less than 0.99).

同時,以100重量份的第一鹼性可顯影黏結劑樹脂計, 本揭露的一個實施例的感光樹脂層可以為500重量份或大於500重量份且為1000重量份或小於1000重量份、600重量份或大於600重量份且為800重量份或小於800重量份、700重量份或大於700重量份且為800重量份或小於800重量份的量包含第二鹼性可顯影黏結劑樹脂。 At the same time, based on 100 parts by weight of the first alkaline developable binder resin, The photosensitive resin layer of an embodiment of the present disclosure may be 500 parts by weight or greater than 500 parts by weight and 1000 parts by weight or less than 1000 parts by weight, 600 parts by weight or greater than 600 parts by weight and 800 parts by weight or less, The second alkaline developable binder resin is included in an amount of 700 parts by weight or more and 800 parts by weight or less.

如上所述,由於以100重量份的第一鹼性可顯影黏結劑樹脂計,過量地添加500重量份或大於500重量份的第二鹼性可顯影黏結劑樹脂,因此可達成賦予感光樹脂疏水功能、增加對顯影劑溶液的耐受性及改善電路性質的技術效果。 As mentioned above, since 500 parts by weight or more of the second alkaline developable binder resin is excessively added based on 100 parts by weight of the first alkaline developable binder resin, it is possible to impart hydrophobicity to the photosensitive resin. function, the technical effect of increasing tolerance to developer solutions and improving circuit properties.

以固體含量計,相對於感光樹脂組成物的總重量,鹼性可顯影黏結劑樹脂以為20重量%或大於20重量%且為80重量%或小於80重量%的量被含有。當鹼性可顯影黏結劑樹脂的含量在以上範圍內時,可獲得增強電路形成之後的細線黏合力的效果。作為重量基礎的固體含量意指自感光樹脂組成物排除溶劑的其餘組分。 In terms of solid content, the alkaline developable binder resin is contained in an amount of 20% by weight or more and 80% by weight or less than 80% by weight relative to the total weight of the photosensitive resin composition. When the content of the alkaline developable binder resin is within the above range, the effect of enhancing the adhesion of thin wires after circuit formation can be obtained. The solid content on a weight basis means the remaining components excluding the solvent from the photosensitive resin composition.

相對於形成感光樹脂層的感光樹脂組成物的總重量,本揭露的鹼性可顯影黏結劑樹脂的含量可為40重量%或大於40重量%且為70重量%或小於70重量%。當相對於總感光樹脂組成物,鹼性可顯影黏結劑樹脂的含量小於40重量%時,存在由於顯影中的污染而導致例如短路等缺陷的缺點,且當鹼性可顯影黏結劑樹脂的含量超過70重量%時,存在例如黏合力及解析度等電路性質劣化的問題。 The content of the alkaline developable binder resin of the present disclosure may be 40% by weight or greater than 40% by weight and 70% by weight or less than 70% by weight relative to the total weight of the photosensitive resin composition forming the photosensitive resin layer. When the content of the alkaline developable binder resin is less than 40% by weight relative to the total photosensitive resin composition, there is a disadvantage that defects such as short circuits may occur due to contamination during development, and when the content of the alkaline developable binder resin is When the content exceeds 70% by weight, there is a problem of deterioration in circuit properties such as adhesive strength and resolution.

(2)光聚合引發劑 (2) Photopolymerization initiator

根據本揭露的感光樹脂層中所含有的光聚合引發劑是藉由UV及其他輻射(radiation)引發可光聚合單體的鏈式反應的材料,且在固化乾膜式光阻中起重要作用。 The photopolymerization initiator contained in the photosensitive resin layer according to the present disclosure is a material that initiates a chain reaction of photopolymerizable monomers through UV and other radiation (radiation), and plays an important role in curing dry film photoresist. .

可用作光聚合引發劑的化合物可包括:蒽醌衍生物,例如2-甲基蒽醌及2-乙基蒽醌;以及安息香衍生物,例如安息香甲醚、二苯甲酮、菲醌及4,4'-雙-(二甲基胺基)二苯甲酮。 Compounds that can be used as photopolymerization initiators may include: anthraquinone derivatives, such as 2-methylanthraquinone and 2-ethylanthraquinone; and benzoin derivatives, such as benzoin methyl ether, benzophenone, phenanthrenequinone and 4,4'-bis-(dimethylamino)benzophenone.

另外,可使用選自2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基雙咪唑、1-羥基環己基苯基酮、2,2-二甲氧基-1,2-二苯基乙基-1-酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代丙-1-酮、2-苄基-2-二甲基胺基-1-[4-嗎啉代苯基]丁-1-酮、2-羥基-2-甲基-1-苯基丙-1-酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、1-[4-(2-羥基甲氧基)苯基]-2-羥基-2-甲基丙-1-酮、2,4-二乙基噻噸、2-氯噻噸酮、2,4-二甲基噻噸酮、3,3-二甲基-4-甲氧基二苯甲酮、二苯甲酮、1-氯-4-丙氧基噻噸酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙-1-酮、1-(4-十二烷基苯基)-2-羥基-2-甲基丙-1-酮、4-苯甲醯基-4'-甲基二甲基硫醚、4-二甲基胺基苯甲酸、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸丁酯、4-二甲基胺基苯甲酸2-乙基己酯、4-二甲基胺基苯甲酸2-異戊酯、2,2-二乙氧基苯乙酮、苄基酮二甲基縮醛、苄基酮β-甲氧基二乙基縮醛、1-苯基-1,2-丙二肟-鄰,鄰'-(2-羰基)乙氧基醚(1-phenyl-1,2-propyldioxime-o,o'-(2-carbonyl)ethoxy ether)、鄰苯甲醯基苯甲酸甲酯、雙[4-二甲基胺基苯基]酮、4,4'-雙(二乙基 胺基)二苯甲酮、4,4'-二氯二苯甲酮、苄基、安息香、甲氧基安息香、乙氧基安息香、異丙氧基安息香、正丁氧基安息香、異丁氧基安息香、第三丁氧基安息香、對二甲基胺基苯乙酮、對第三丁基三氯苯乙酮、對第三丁基二氯苯乙酮、噻噸酮、2-甲基噻噸酮、2-異丙基噻噸酮、二苯並環庚酮、α,α-二氯-4-苯氧基苯乙酮及4-二甲基胺基苯甲酸戊酯中的化合物作為光聚合引發劑,但不限於此。 In addition, one selected from the group consisting of 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 1-hydroxycyclohexylphenylketone, 2,2-di Methoxy-1,2-diphenylethyl-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1-[4-morpholinophenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,4 ,6-trimethylbenzyldiphenylphosphine oxide, 1-[4-(2-hydroxymethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 2,4 -Diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 1- Chloro-4-propoxythioxanthone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)- 2-Hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzene Methyl formate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylamine 2-isoamyl benzoate, 2,2-diethoxyacetophenone, benzyl ketone dimethyl acetal, benzyl ketone β-methoxy diethyl acetal, 1-phenyl-1 ,2-propyldioxime-o,o'-(2-carbonyl)ethoxy ether (1-phenyl-1,2-propyldioxime-o,o'-(2-carbonyl)ethoxy ether), o-phenyldioxime Methyl benzoate, bis[4-dimethylaminophenyl]one, 4,4'-bis(diethyl) Amino)benzophenone, 4,4'-dichlorobenzophenone, benzyl, benzoin, methoxybenzoin, ethoxybenzoin, isopropoxybenzoin, n-butoxybenzoin, isobutoxy Benzoin, tert-butoxybenzoin, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methyl Compounds in thioxanthone, 2-isopropylthioxanthone, dibenzocycloheptanone, α,α-dichloro-4-phenoxyacetophenone and amyl 4-dimethylaminobenzoate As a photopolymerization initiator, it is not limited to this.

以固體含量計,相對於用於形成感光樹脂層的感光樹脂組成物的總重量,光聚合引發劑以為2重量%或大於2重量%且為10重量%或小於10重量%的量被含有。當光聚合引發劑的含量在以上範圍內時,可獲得足夠的敏感度。作為重量基礎的固體含量意指自感光樹脂組成物排除溶劑的其餘組分。 In terms of solid content, the photopolymerization initiator is contained in an amount of 2 wt% or more and 10 wt% or less with respect to the total weight of the photosensitive resin composition used to form the photosensitive resin layer. When the content of the photopolymerization initiator is within the above range, sufficient sensitivity can be obtained. The solid content on a weight basis means the remaining components excluding the solvent from the photosensitive resin composition.

當光聚合引發劑的含量小於2重量%時,光效率低,且必須應用大量曝光且因此,存在生產效率極大降低的缺點。當光聚合引發劑的含量超過10重量%時,存在膜易碎(brittle)及顯影劑溶液污染增加的問題,從而導致短路等缺陷。 When the content of the photopolymerization initiator is less than 2% by weight, the light efficiency is low, and a large amount of exposure must be applied and therefore, there is a disadvantage that the production efficiency is greatly reduced. When the content of the photopolymerization initiator exceeds 10% by weight, there are problems that the film becomes brittle and contamination of the developer solution increases, leading to defects such as short circuits.

(3)可光聚合化合物 (3) Photopolymerizable compounds

本揭露的可光聚合化合物在UV曝光之後對顯影劑溶液具有耐受性,且因此能夠形成圖案。 The photopolymerizable compounds of the present disclosure are resistant to developer solutions after UV exposure and are therefore capable of patterning.

本揭露的可光聚合化合物可包括三官能或更高的多官能(甲基)丙烯酸酯化合物。 Photopolymerizable compounds of the present disclosure may include trifunctional or higher polyfunctional (meth)acrylate compounds.

具體而言,三官能或更高的多官能(甲基)丙烯酸酯化合物可具有其中三或更多個具有1至10個碳原子的環氧烷基以及三 或更多個(甲基)丙烯酸酯官能基鍵合至具有1至20個碳原子的中心基的結構。 Specifically, the trifunctional or higher polyfunctional (meth)acrylate compound may have three or more epoxyalkyl groups having 1 to 10 carbon atoms and three A structure in which one or more (meth)acrylate functional groups are bonded to a central group having 1 to 20 carbon atoms.

更具體而言,三官能或更高的多官能(甲基)丙烯酸酯化合物可包括以下化學式2的多官能(甲基)丙烯酸酯化合物:

Figure 109144461-A0305-02-0028-23
More specifically, the trifunctional or higher polyfunctional (meth)acrylate compound may include the polyfunctional (meth)acrylate compound of the following Chemical Formula 2:
Figure 109144461-A0305-02-0028-23

在化學式2中,R4是氫或具有1至10個碳原子的烷基,R5是具有1至10個碳原子的伸烷基,R6是含有具有1至20個碳原子的中心基的p價官能基,n2是為1至20的整數,且p是取代R6的官能基的數目且是為3至10的整數。 In Chemical Formula 2, R 4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R 5 is an alkylene group having 1 to 10 carbon atoms, and R 6 is a central group containing 1 to 20 carbon atoms. For p-valent functional groups, n2 is an integer ranging from 1 to 20, and p is the number of functional groups replacing R 6 and is an integer ranging from 3 to 10.

此外,在化學式2中,n2是為1至20的整數、為1至10的整數或為1至5的整數,p意指取代R6的官能基的數目且可為3至10的整數、為3至5的整數或為3至4的整數。 Furthermore, in Chemical Formula 2, n2 is an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5, and p means the number of functional groups substituting R 6 and may be an integer of 3 to 10, is an integer from 3 to 5 or an integer from 3 to 4.

即,在化學式2中,由於意指取代R6的官能基的數目的p是為3至10的整數,因此由化學式2表示的三官能或更高的多官能(甲基)丙烯酸酯化合物可為三官能或更高的多官能(甲基)丙烯酸酯化合物。 That is, in Chemical Formula 2, since p which means the number of functional groups substituting R 6 is an integer of 3 to 10, the trifunctional or higher polyfunctional (meth)acrylate compound represented by Chemical Formula 2 can It is a trifunctional or higher polyfunctional (meth)acrylate compound.

具體而言,多官能(甲基)丙烯酸酯化合物可由以下化學 式2-1表示。 Specifically, multifunctional (meth)acrylate compounds can be formed by the following chemical Expressed in Formula 2-1.

Figure 109144461-A0305-02-0029-24
Figure 109144461-A0305-02-0029-24

在化學式2-1中,R6'是具有1至10個碳原子的三價官能基,R7至R9各自獨立地是具有1至10個碳原子的伸烷基,R10至R12各自獨立地是氫或具有1至10個碳原子的烷基,且n3至n5各自獨立地是為1至20的整數。 In Chemical Formula 2-1, R 6 ' is a trivalent functional group having 1 to 10 carbon atoms, R 7 to R 9 are each independently an alkylene group having 1 to 10 carbon atoms, and R 10 to R 12 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, and n3 to n5 are each independently an integer of 1 to 20.

在化學式2-1中,n3至n5可以是為1至20的整數、為1至10的整數或為1至5的整數。 In Chemical Formula 2-1, n3 to n5 may be an integer of 1 to 20, an integer of 1 to 10, or an integer of 1 to 5.

由化學式2表示的多官能(甲基)丙烯酸酯化合物的實例並無特別限制,但是可為例如由以下化學式B表示的T063(三羥甲基丙烷[EO]6三丙烯酸酯(Trimethylolpropane[EO]6 triacrylate))。 Examples of the polyfunctional (meth)acrylate compound represented by Chemical Formula 2 are not particularly limited, but may be, for example, T063 (Trimethylolpropane [EO] 6 triacrylate (Trimethylolpropane [EO]) represented by the following Chemical Formula B 6 triacrylate)).

Figure 109144461-A0305-02-0029-25
Figure 109144461-A0305-02-0029-25

由於一個實施例的感光樹脂組成物包括由化學式2表示的多官能(甲基)丙烯酸酯化合物,因此改善了光固化速度及固化程度、可確保對比度且可達成極佳的細線黏合力。 Since the photosensitive resin composition of one embodiment includes the multifunctional (meth)acrylate compound represented by Chemical Formula 2, the photocuring speed and degree of curing are improved, contrast can be ensured, and excellent fine line adhesion can be achieved.

同時,一個實施例的感光樹脂層可更包含單官能(甲基)丙烯酸酯化合物。 Meanwhile, the photosensitive resin layer of one embodiment may further include a monofunctional (meth)acrylate compound.

具體而言,單官能(甲基)丙烯酸酯化合物可包含(甲基)丙烯酸酯,所述(甲基)丙烯酸酯含有具有1至10個碳原子的環氧烷基。 Specifically, the monofunctional (meth)acrylate compound may include (meth)acrylate containing an epoxyalkyl group having 1 to 10 carbon atoms.

即,可光聚合化合物可包括:單官能(甲基)丙烯酸酯化合物,含有(甲基)丙烯酸酯,所述(甲基)丙烯酸酯含有具有1至10個碳原子的環氧烷基;以及三官能或更高的多官能(甲基)丙烯酸酯化合物,具有其中三或更多個具有1至10個碳原子的(甲基)丙烯酸酯官能基以及三或更多個(甲基)丙烯酸酯官能基鍵合至具有1至20個碳原子的中心基的結構。 That is, the photopolymerizable compound may include: a monofunctional (meth)acrylate compound containing a (meth)acrylate containing an epoxyalkyl group having 1 to 10 carbon atoms; and Trifunctional or higher polyfunctional (meth)acrylate compounds having three or more (meth)acrylate functional groups having 1 to 10 carbon atoms and three or more (meth)acrylic acids Structures in which the ester functionality is bonded to a central group having 1 to 20 carbon atoms.

更具體而言,單官能(甲基)丙烯酸酯化合物可包括由以下化學式1表示的單官能(甲基)丙烯酸酯化合物。 More specifically, the monofunctional (meth)acrylate compound may include a monofunctional (meth)acrylate compound represented by the following Chemical Formula 1.

Figure 109144461-A0305-02-0030-26
Figure 109144461-A0305-02-0030-26

在化學式1中,R1是氫或具有1至10個碳原子的烷基,R2是具有1至10個碳原子的伸烷基,R3是具有1至10個碳原子的烷基,且n1是為1至20的整數。 In Chemical Formula 1, R 1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R 2 is an alkylene group having 1 to 10 carbon atoms, R 3 is an alkyl group having 1 to 10 carbon atoms, And n1 is an integer from 1 to 20.

具體而言,在化學式1中,n1可以是為1至20的整數、為1至10的整數或為5至10的整數。由化學式1表示的單官能(甲基)丙烯酸酯化合物的實例並無特別限制,但是可為例如由以下化學式A表示的A040(甲氧基丙二醇[400]丙烯酸酯)。 Specifically, in Chemical Formula 1, n1 may be an integer of 1 to 20, an integer of 1 to 10, or an integer of 5 to 10. Examples of the monofunctional (meth)acrylate compound represented by Chemical Formula 1 are not particularly limited, but may be, for example, A040 (methoxypropylene glycol [400] acrylate) represented by the following Chemical Formula A.

Figure 109144461-A0305-02-0031-27
Figure 109144461-A0305-02-0031-27

由於一個實施例的感光樹脂層包含由化學式1表示的單官能(甲基)丙烯酸酯化合物,因此,由於由化學式1表示的單官能(甲基)丙烯酸酯化合物的低玻璃轉變溫度,所述感光樹脂層在乾膜式光阻的疊層溫度下具有相對大的流動性,且藉此,可達成改善對具有高表面粗糙度及非均勻性的基板的物理黏合的效果。 Since the photosensitive resin layer of one embodiment includes the monofunctional (meth)acrylate compound represented by Chemical Formula 1, the photosensitive resin layer has a low glass transition temperature due to the low glass transition temperature of the monofunctional (meth)acrylate compound represented by Chemical Formula 1. The resin layer has relatively large fluidity at the lamination temperature of the dry film photoresist, and thereby can achieve the effect of improving physical adhesion to substrates with high surface roughness and non-uniformity.

同時,以100重量份的單官能(甲基)丙烯酸酯化合物計,一個實施例的感光樹脂層可以為小於100重量份、為30重量份或大於30重量份且為90重量份或小於90重量份、50重量份或大於50重量份且為90重量份或小於90重量份、50重量份或大於50重量份且為80重量份或小於80重量份、或者50重量份或大 於50重量份且為75重量份或小於75重量份的量含有多官能(甲基)丙烯酸酯化合物。 Meanwhile, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photosensitive resin layer of one embodiment may be less than 100 parts by weight, 30 parts by weight or more than 30 parts by weight, and 90 parts by weight or less than 90 parts by weight. parts by weight, 50 parts by weight or more and 90 parts by weight or less, 50 parts by weight or more than 50 parts by weight and 80 parts by weight or less, or 50 parts by weight or more The polyfunctional (meth)acrylate compound is contained in an amount of 50 parts by weight and 75 parts by weight or less.

由於相對於單官能(甲基)丙烯酸酯化合物,一個實施例的感光樹脂層含有少量的多官能(甲基)丙烯酸酯化合物,因此會同時達成改善由化學式1表示的單官能(甲基)丙烯酸酯化合物對基板的物理黏合、確保由化學式2表示的多官能(甲基)丙烯酸酯化合物的對比度、以及改善細線黏合力,藉此表現出極佳的可顯影性,從而改善對基板的黏合及確保極佳的物理性質(解析度、細線黏合力等)。 Since the photosensitive resin layer of one embodiment contains a small amount of the multifunctional (meth)acrylate compound relative to the monofunctional (meth)acrylate compound, an improvement in the monofunctional (meth)acrylic acid represented by Chemical Formula 1 is simultaneously achieved. Physical adhesion of the ester compound to the substrate, ensuring contrast of the multifunctional (meth)acrylate compound represented by Chemical Formula 2, and improving fine line adhesion, thereby exhibiting excellent developability, thereby improving adhesion to the substrate and Ensure excellent physical properties (resolution, fine line adhesion, etc.).

以100重量份的單官能(甲基)丙烯酸酯化合物計,當一個實施例的感光樹脂層含有100重量份或大於100重量份的多官能(甲基)丙烯酸酯化合物時,可能存在對基板的黏合降低的技術問題。 When the photosensitive resin layer of one embodiment contains 100 parts by weight or more of a multifunctional (meth)acrylate compound based on 100 parts by weight of the monofunctional (meth)acrylate compound, there may be damage to the substrate. Technical issues with reduced adhesion.

同時,可光聚合化合物可包括雙官能(甲基)丙烯酸酯化合物,所述雙官能(甲基)丙烯酸酯化合物包含伸烷基二醇系二(甲基)丙烯酸酯及胺基甲酸酯系二(甲基)丙烯酸酯。 Meanwhile, the photopolymerizable compound may include a bifunctional (meth)acrylate compound including an alkylene glycol-based di(meth)acrylate and a urethane-based Di(meth)acrylate.

即,一個實施例的感光樹脂層包含可光聚合化合物,且所述可光聚合化合物可包括單官能(甲基)丙烯酸酯化合物、多官能(甲基)丙烯酸酯化合物、包括伸烷基二醇系二(甲基)丙烯酸酯及胺基甲酸酯系二(甲基)丙烯酸酯的雙官能(甲基)丙烯酸酯。 That is, the photosensitive resin layer of one embodiment includes a photopolymerizable compound, and the photopolymerizable compound may include a monofunctional (meth)acrylate compound, a multifunctional (meth)acrylate compound, or an alkylene glycol. It is a bifunctional (meth)acrylate of di(meth)acrylate and urethane di(meth)acrylate.

伸烷基二醇系二(甲基)丙烯酸酯可包括乙二醇二(甲基)丙烯酸酯(ethylene glycol di(meth)acrylate)、二乙二醇二(甲基)丙 烯酸酯(diethylene glycol di(meth)acrylate)、四乙二醇二(甲基)丙烯酸酯(tetraethylene glycol di(meth)acrylate)、丙二醇二(甲基)丙烯酸酯(propylene glycol di(meth)acrylate)、聚乙二醇二(甲基)丙烯酸酯(polyethylene glycol di(meth)acrylate)、聚丙二醇二(甲基)丙烯酸酯(polypropylene glycol di(meth)acrylate)、丁二醇二(甲基)丙烯酸酯(butylene glycol di(meth)acrylate)、乙二醇二縮水甘油醚二(甲基)丙烯酸酯(ethylene glycol diglycidyl ether di(meth)acrylate)、二乙二醇二縮水甘油醚二(甲基)丙烯酸酯(diethylene glycol diglycidyl ether di(meth)acrylate)、例如由美源特殊化工有限公司(Miwon Specialty Chemical Co.,Ltd)製造的米拉默(Miramer)M244(雙酚A(Bisphenol A)(EO)3DA、雙酚A(EO)3二丙烯酸酯(Diacrylate))、米拉默M240(雙酚A(EO)4DA、雙酚A(EO)4二丙烯酸酯)、米拉默M241(雙酚A(EO)4二甲基丙烯酸酯(Dimethacrylate))、米拉默M2100(雙酚A(EO)10DA、雙酚A(EO)10二丙烯酸酯)、米拉默M2200(雙酚A(EO)20DA、雙酚A(EO)20二丙烯酸酯)、米拉默M2101(雙酚A(EO)10二甲基丙烯酸酯)等可商業購得的產品。 Alkylene glycol di(meth)acrylates may include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate (meth)acrylate), tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate (meth)acrylate (polyethylene glycol di(meth)acrylate), polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate meth)acrylate), ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate (diethylene glycol diglycidyl ether di(meth)acrylate), such as Miramer M244 (Bisphenol A (EO) 3 DA, bisphenol A manufactured by Miwon Specialty Chemical Co., Ltd. (EO) 3 Diacrylate), Miramer M240 (Bisphenol A (EO) 4 DA, Bisphenol A (EO) 4 Diacrylate), Miramer M241 (Bisphenol A (EO) 4 Dimethacrylate), Miramer M2100 (Bisphenol A (EO) 10 DA, Bisphenol A (EO) 10 Diacrylate), Miramer M2200 (Bisphenol A (EO) 20 DA, Bisphenol A (EO) 20 diacrylate), Miramer M2101 (bisphenol A (EO) 10 dimethacrylate) and other commercially available products.

此外,KUA-1330h或類似物可用作胺基甲酸酯系二(甲基)丙烯酸酯。 In addition, KUA-1330h or the like can be used as the urethane di(meth)acrylate.

胺基甲酸酯系二(甲基)丙烯酸酯的分子量可大於現有的簡單環氧烷且具有線性結構,藉此賦予可撓性(flexibility)。此導致改善外層的乾膜式光阻(DFR)所需的蓋孔性質及作為胺基甲酸 酯丙烯酸酯的成分中的一者的多元醇的疏水性,且改善對作為強酸的鍍覆溶液的耐受性,藉此不會污染鍍覆溶液。 The molecular weight of the urethane di(meth)acrylate can be larger than the existing simple alkylene oxide and has a linear structure, thereby imparting flexibility. This results in improved hole-capping properties required for the outer dry film resist (DFR) and as a urethane The hydrophobicity of the polyol, one of the components of ester acrylate, improves the resistance to the plating solution which is a strong acid, thereby not contaminating the plating solution.

胺基甲酸酯系二(甲基)丙烯酸酯可藉由以下方式來獲得:使二異氰酸酯化合物與具有羥基的聚醚化合物或具有羥基的聚酯化合物進行反應以獲得胺基甲酸酯化合物,且然後使所獲得的胺基甲酸酯化合物與具有羥基和烯鍵式不飽和基二者的化合物進行反應。 Urethane di(meth)acrylate can be obtained by reacting a diisocyanate compound with a polyether compound having a hydroxyl group or a polyester compound having a hydroxyl group to obtain a urethane compound, And then the obtained urethane compound is reacted with a compound having both a hydroxyl group and an ethylenically unsaturated group.

具有羥基的聚醚化合物是聚醚二醇,且使用例如聚四亞甲基二醇等二醇、聚氧乙烯、聚氧丙烯及聚氧四氫呋喃。作為具有羥基的聚酯化合物,使用藉由縮合己二酸及1,4-丁二醇而獲得的化合物。 The polyether compound having a hydroxyl group is a polyether glycol, and glycols such as polytetramethylene glycol, polyoxyethylene, polyoxypropylene, and polyoxytetrahydrofuran are used. As the polyester compound having a hydroxyl group, a compound obtained by condensing adipic acid and 1,4-butanediol is used.

二異氰酸酯化合物(a-2)可包括具有二價脂肪族基(例如伸烷基)的脂肪族二異氰酸酯化合物、具有二價脂環族基(例如伸環烷基)的脂環族二異氰酸酯化合物、芳香族二異氰酸酯化合物及其異氰脲酸酯改質組分、碳二醯亞胺改質組分、滴定管改質組分(buret-modified component)及類似物。 The diisocyanate compound (a-2) may include an aliphatic diisocyanate compound having a divalent aliphatic group (such as an alkylene group), an alicyclic diisocyanate compound having a divalent alicyclic group (such as a cycloalkylene group) , aromatic diisocyanate compounds and their isocyanurate modified components, carbodiimide modified components, buret-modified components and the like.

此時,脂肪族二異氰酸酯化合物的實例包括六亞甲基異氰酸酯、三甲基六亞甲基二異氰酸酯及類似物。 At this time, examples of the aliphatic diisocyanate compound include hexamethylene isocyanate, trimethylhexamethylene diisocyanate and the like.

脂環族二異氰酸酯化合物可包括異佛爾酮二異氰酸酯、亞甲基雙(環己基)二異氰酸酯、1,3-或1,4-雙(甲基異氰酸酯)環己烷及類似物。 Alicyclic diisocyanate compounds may include isophorone diisocyanate, methylene bis(cyclohexyl)diisocyanate, 1,3- or 1,4-bis(methylisocyanate)cyclohexane, and the like.

芳香族二異氰酸酯化合物可包括2,4-甲苯二異氰酸酯、 2,6-甲苯二異氰酸酯、2,4-甲苯二異氰酸酯或2,6-甲苯二異氰酸酯的二聚聚合物、(鄰、對或間)二甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、1,5-萘二異氰酸酯及類似物。 Aromatic diisocyanate compounds may include 2,4-toluene diisocyanate, 2,6-Toluene diisocyanate, 2,4-toluene diisocyanate or dimer polymer of 2,6-toluene diisocyanate, (o-, para- or meta-)xylene diisocyanate, diphenylmethane diisocyanate, 1, 5-Naphthalene diisocyanate and the like.

所述化合物可單獨使用,或者以二或更多者的組合使用。此外,其可包括具有二或更多個異氰酸酯基的異氰酸酯化合物,例如三苯基甲烷三異氰酸酯及三(苯基異氰酸酯)硫代磷酸酯。在該些中,自提高光固化產物的可撓性及韌度(toughness)且因此改善對基板的黏合力的視角來看,脂環族二異氰酸酯化合物是較佳的。 The compounds may be used alone or in combination of two or more. Furthermore, it may include isocyanate compounds having two or more isocyanate groups, such as triphenylmethane triisocyanate and tris(phenyl isocyanate)phosphorothioate. Among these, the alicyclic diisocyanate compound is preferable from the viewpoint of improving the flexibility and toughness of the photocured product and thus improving the adhesion to the substrate.

具有羥基的聚醚化合物或聚酯化合物與二異氰酸酯化合物進行反應以製備胺基甲酸酯化合物。在以上反應中,相對於1莫耳具有羥基的聚醚化合物或聚酯化合物,二異氰酸酯化合物較佳地以為1.01至2.0的莫耳比率使用、更佳地以為1.1至2.0的莫耳比率使用。若二異氰酸酯化合物的含量小於1.01莫耳或大於2.0莫耳,則可能無法穩定地獲得兩端具有異氰酸酯基的胺基甲酸酯化合物。 A polyether compound or polyester compound having a hydroxyl group is reacted with a diisocyanate compound to prepare a urethane compound. In the above reaction, the diisocyanate compound is preferably used in a molar ratio of 1.01 to 2.0, more preferably in a molar ratio of 1.1 to 2.0 relative to 1 mol of the polyether compound or polyester compound having a hydroxyl group. If the content of the diisocyanate compound is less than 1.01 mol or more than 2.0 mol, the urethane compound having isocyanate groups at both ends may not be stably obtained.

此外,在用於合成胺基甲酸酯化合物的反應中,添加二月桂酸二丁基錫(dibutyltin dilaurate)作為催化劑是較佳的。 Furthermore, in the reaction for synthesizing the urethane compound, it is preferable to add dibutyltin dilaurate as a catalyst.

反應溫度較佳為60℃至120℃。當反應溫度小於60℃時,存在反應不會充分地繼續進行的趨勢,且當反應溫度超過120℃時,由於突然產生熱量,反應操作可能是危險的。 The reaction temperature is preferably 60°C to 120°C. When the reaction temperature is less than 60°C, there is a tendency that the reaction does not proceed sufficiently, and when the reaction temperature exceeds 120°C, the reaction operation may be dangerous due to sudden generation of heat.

用於與如此製備的胺基甲酸酯化合物反應的具有羥基和烯鍵式不飽和基二者的化合物可包括分子中具有羥基及(甲基) 丙烯醯基的化合物。該些化合物包括羥基(甲基)丙烯酸酯、羥基(甲基)丙烯酸酯-己內酯加合物或環氧烷加合物、藉由使多元醇(例如甘油)與(甲基)丙烯酸進行反應而製備的酯化合物、以及(甲基)丙烯酸縮水甘油酯-丙烯酸加合物。 Compounds having both a hydroxyl group and an ethylenically unsaturated group used for reaction with the urethane compound thus prepared may include compounds having a hydroxyl group and a (methyl) group in the molecule. Acrylyl compound. These compounds include hydroxy(meth)acrylates, hydroxy(meth)acrylate-caprolactone adducts or alkylene oxide adducts, by reacting a polyol (such as glycerol) with (meth)acrylic acid. The ester compound prepared by the reaction, and the glycidyl (meth)acrylate-acrylic acid adduct.

羥基(甲基)丙烯酸酯可包括2-羥乙基(甲基)丙烯酸酯、羥丙基(甲基)丙烯酸酯及羥基丁基(甲基)丙烯酸酯。 Hydroxy(meth)acrylates may include 2-hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, and hydroxybutyl(meth)acrylate.

羥基(甲基)丙烯酸酯-己內酯加合物可包括羥乙基(甲基)丙烯酸酯.己內酯加合物、羥丙基(甲基)丙烯酸酯.己內酯加合物、羥丁基(甲基)丙烯酸酯.己內酯加合物,且環氧烷加合物可包括羥乙基(甲基)丙烯酸酯.環氧烷加合物、羥丙基(甲基)丙烯酸酯.環氧丙烷加合物、羥丁基(甲基)丙烯酸酯.環氧丁烷加合物。 Hydroxy(meth)acrylate-caprolactone adducts may include hydroxyethyl(meth)acrylate. Caprolactone adduct, hydroxypropyl (meth)acrylate. Caprolactone adduct, hydroxybutyl (meth)acrylate. Caprolactone adduct, and the alkylene oxide adduct may include hydroxyethyl (meth)acrylate. Alkylene oxide adduct, hydroxypropyl (meth)acrylate. Propylene oxide adduct, hydroxybutyl (meth)acrylate. Butylene oxide adduct.

酯化合物可包括例如甘油單(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷單(甲基)丙烯酸酯、二三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷-環氧乙烷加合物的二(甲基)丙烯酸酯、三羥甲基丙烷-環氧丙烷加合物的二(甲基)丙烯酸酯。該些可單獨使用,或者以二或更多者的組合使用。 Ester compounds may include, for example, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane mono(meth)acrylate, acrylate, ditrimethylolpropane tri(meth)acrylate, di(meth)acrylate of trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide Adduct of di(meth)acrylate. These may be used individually or in combination of two or more.

胺基甲酸酯系二(甲基)丙烯酸酯是藉由胺基甲酸酯化合物與具有羥基和烯鍵式不飽和基二者的化合物的加成反應衍生出的化合物,且可藉由相對於1莫耳胺基甲酸酯化合物而言以為2.0至2.4的莫耳比率添加具有羥基與烯鍵式不飽和基二者的化合物且然後在60℃至90℃下使其經歷加成反應來獲得。 Urethane di(meth)acrylate is a compound derived from the addition reaction of a urethane compound and a compound having both a hydroxyl group and an ethylenically unsaturated group, and can be obtained by relatively A compound having both a hydroxyl group and an ethylenically unsaturated group is added at a molar ratio of 2.0 to 2.4 per mole of the urethane compound and then subjected to an addition reaction at 60°C to 90°C. obtain.

胺基甲酸酯系二(甲基)丙烯酸酯具有在1,000克/莫耳至60,000克/莫耳範圍內的重量平均分子量是較佳的。當重量平均分子量小於1,000克/莫耳時,難以充分地增加可撓性及韌度,因此可能無法改善對基板的黏合,且當重量平均分子量超過60,000克/莫耳時,存在顯影性質可能劣化且顯影時間可能變慢的問題。因此,根據本揭露的胺基甲酸酯系二(甲基)丙烯酸酯具有為1,000克/莫耳至60,000克/莫耳的重量平均分子量是較佳的。 The urethane di(meth)acrylate preferably has a weight average molecular weight in the range of 1,000 g/mol to 60,000 g/mol. When the weight average molecular weight is less than 1,000 g/mol, it is difficult to sufficiently increase flexibility and toughness, so adhesion to the substrate may not be improved, and when the weight average molecular weight exceeds 60,000 g/mol, there is a possibility that the development properties may be deteriorated And the development time may be slowed down. Therefore, it is preferred that the urethane di(meth)acrylate according to the present disclosure has a weight average molecular weight of 1,000 g/mol to 60,000 g/mol.

在本揭露中,具有為1,000克/莫耳至60,000克/莫耳的重量平均分子量的胺基甲酸酯系二(甲基)丙烯酸酯是以為1重量%至20重量%、較佳為1.5重量%至15重量%的量包含於感光樹脂組成物中。當具有為1,000克/莫耳至60,000克/莫耳的重量平均分子量的胺基甲酸酯系二(甲基)丙烯酸酯的含量小於1重量%時,由此產生的效果不足,且當含量超過20重量%時,可能存在曝光之後的顯影製程中顯影時間迅速地增加且亦產生大量浮渣(scum)及污泥(sludge)的缺點。 In the present disclosure, the urethane di(meth)acrylate having a weight average molecular weight of 1,000 g/mol to 60,000 g/mol is 1 to 20 wt %, preferably 1.5 The photosensitive resin composition is included in an amount of % by weight to 15% by weight. When the content of the urethane di(meth)acrylate having a weight average molecular weight of 1,000 g/mol to 60,000 g/mol is less than 1% by weight, the effect produced thereby is insufficient, and when the content When it exceeds 20% by weight, there may be disadvantages that the development time increases rapidly during the development process after exposure and a large amount of scum and sludge are generated.

以100重量份的伸烷基二醇系二(甲基)丙烯酸酯計,一個實施例的感光樹脂層可以為1重量份或大於1重量份且為50重量份或小於50重量份、1重量份或大於1重量份且為30重量份或小於30重量份、1重量份或大於1重量份且為10重量份或小於10重量份、或者1重量份或大於1重量份且為5重量份或小於5重量份的量被含有。 Based on 100 parts by weight of alkylene glycol di(meth)acrylate, the photosensitive resin layer of one embodiment may be 1 part by weight or more than 1 part by weight and 50 parts by weight or less than 50 parts by weight, 1 part by weight. 1 part by weight or more and 30 parts by weight or less, 1 part by weight or more and 10 parts by weight or less, or 1 part by weight or more than 1 part by weight and 5 parts by weight Or it is contained in an amount less than 5 parts by weight.

由於相對於100重量份的伸烷基二醇系二(甲基)丙烯酸 酯,胺基甲酸酯系二(甲基)丙烯酸酯以為1重量份或大於1重量份且為50重量份或小於50重量份的量被含有,因此一個實施例的感光樹脂組成物可達成降低例如電路性質劣化、剝離及顯影時間變化等技術效果。 Since relative to 100 parts by weight of alkylene glycol di(meth)acrylic acid The ester and urethane di(meth)acrylate are contained in an amount of 1 part by weight or more and 50 parts by weight or less, so that the photosensitive resin composition of one embodiment can be achieved Reduce technical effects such as circuit property degradation, peeling and development time changes.

具體而言,以100重量份的單官能(甲基)丙烯酸酯化合物計,一個實施例的感光樹脂層可以為500重量份或大於500重量份且為1500重量份或小於1500重量份、500重量份或大於500重量份且為1000重量份或小於1000重量份、750重量份或大於750重量份且為1000重量份或小於1000重量份、或者800重量份或大於800重量份且為900重量份或小於900重量份的量包含雙官能(甲基)丙烯酸酯化合物。 Specifically, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photosensitive resin layer of one embodiment may be 500 parts by weight or greater than 500 parts by weight and 1500 parts by weight or less than 1500 parts by weight, 500 parts by weight. 500 parts by weight or more and 1000 parts by weight or less, 750 parts by weight or more and 1000 parts by weight or less, or 800 parts by weight or more than 800 parts by weight and 900 parts by weight Or the bifunctional (meth)acrylate compound is included in an amount less than 900 parts by weight.

此外,以100重量份的多官能(甲基)丙烯酸酯化合物計,一個實施例的感光樹脂層可以為500重量份或大於500重量份且為1000重量份或小於1000重量份、500重量份或大於500重量份且為800重量份或小於800重量份、500重量份或大於500重量份且為750重量份或小於750重量份、500重量份或大於500重量份且為700重量份或小於700重量份、500重量份或大於500重量份且為600重量份或小於600重量份的量含有雙官能(甲基)丙烯酸酯化合物。 In addition, based on 100 parts by weight of the multifunctional (meth)acrylate compound, the photosensitive resin layer of one embodiment may be 500 parts by weight or greater than 500 parts by weight and 1000 parts by weight or less, 500 parts by weight or More than 500 parts by weight and 800 parts by weight or less, 500 parts by weight or more and 750 parts by weight or less, 500 parts by weight or more than 500 parts by weight and 700 parts by weight or less The bifunctional (meth)acrylate compound is contained in an amount of 500 parts by weight or more and 600 parts by weight or less.

即,以100重量份的單官能(甲基)丙烯酸酯化合物計,一個實施例的感光樹脂層可包括小於110重量份的多官能(甲基)丙烯酸酯化合物以及500重量份或大於500重量份且為1500重量 份或小於1500重量份的雙官能(甲基)丙烯酸酯化合物。 That is, based on 100 parts by weight of the monofunctional (meth)acrylate compound, the photosensitive resin layer of one embodiment may include less than 110 parts by weight of the multifunctional (meth)acrylate compound and 500 parts by weight or more than 500 parts by weight and is 1500 weight parts or less than 1500 parts by weight of a bifunctional (meth)acrylate compound.

如上所述,由於含有且同時以使得滿足以上重量範圍的方式含有單官能(甲基)丙烯酸酯化合物、多官能(甲基)丙烯酸酯化合物及雙官能(甲基)丙烯酸酯化合物,因此一個實施例的感光樹脂組成物可不僅達成對基板的極佳的黏合,而且可確保對比度及實施極佳的細線黏合力。 As described above, since a monofunctional (meth)acrylate compound, a polyfunctional (meth)acrylate compound, and a bifunctional (meth)acrylate compound are contained simultaneously in such a manner that the above weight range is satisfied, one embodiment The photosensitive resin composition of the example can not only achieve excellent adhesion to the substrate, but also ensure contrast and implement excellent fine line adhesion.

在本揭露中,以用於形成感光樹脂層的感光樹脂組成物的總重量計,單官能可光聚合化合物可以為0.1重量%或大於0.1重量%且為2.5重量%或小於2.5重量%的量被含有。 In the present disclosure, the monofunctional photopolymerizable compound may be in an amount of 0.1% by weight or more and 2.5% by weight or less than 2.5% by weight based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer. is contained.

此外,在本揭露中,以用於形成感光樹脂層的感光樹脂組成物的總重量計,多官能可光聚合化合物可以為2.6重量%或大於2.6重量%且為5.0重量%或小於5.0重量%的量被含有。 Furthermore, in the present disclosure, the multifunctional photopolymerizable compound may be 2.6% by weight or more and 5.0% by weight or less than 5.0% by weight based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer. amount is contained.

即,以用於形成感光樹脂層的感光樹脂組成物的總重量計,用於形成感光樹脂層的感光樹脂組成物可含有0.1重量%或大於0.1重量%且為2.5重量%或小於2.5重量%的單官能可光聚合化合物及2.6重量%或大於2.6重量%且為5.0重量%或小於5.0重量%的多官能可光聚合化合物。 That is, the photosensitive resin composition used to form the photosensitive resin layer may contain 0.1% by weight or more and 2.5% by weight or less than 2.5% by weight based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer. of a monofunctional photopolymerizable compound and 2.6% by weight or greater than 2.6% by weight and 5.0% by weight or less of a multifunctional photopolymerizable compound.

當以用於形成感光樹脂層的感光樹脂組成物的總重量計,單官能可光聚合化合物的含量小於0.1重量%或者多官能可光聚合化合物的含量小於2.6重量%時,由於添加由化學式1及2表示的化合物而產生的效果不足,且當單官能可光聚合化合物的含量大於2.5重量%或大於5.0重量%或者多官能可光聚合化合物的 含量大於5.0重量%時,可能存在疏水性增加的問題且因此,曝光之後的顯影製程中的顯影時間迅速地增加。 When the content of the monofunctional photopolymerizable compound is less than 0.1% by weight or the content of the multifunctional photopolymerizable compound is less than 2.6% by weight based on the total weight of the photosensitive resin composition used to form the photosensitive resin layer, due to the addition of Chemical Formula 1 The effect produced by the compounds represented by 2 and 2 is insufficient, and when the content of the monofunctional photopolymerizable compound is greater than 2.5% by weight or greater than 5.0% by weight or the content of the multifunctional photopolymerizable compound is When the content is greater than 5.0% by weight, there may be a problem of increased hydrophobicity and therefore, the development time in the development process after exposure is rapidly increased.

一個實施例的感光樹脂層是附加的可光聚合化合物,且可包含乙二醇二甲基丙烯酸酯(ethylene glycol dimethacrylate)、二乙二醇二甲基丙烯酸酯(diethylene glycol dimethacrylate)、四乙二醇二甲基丙烯酸酯(tetraethylene glycol dimethacrylate)、丙二醇二甲基丙烯酸酯(propylene glycol dimethacrylate)、聚丙二醇二甲基丙烯酸酯(polypropylene glycol dimethacrylate)、丁二醇二甲基丙烯酸酯(butylene glycol dimethacrylate)、新戊二醇二甲基丙烯酸酯(neopentyl glycol dimethacrylate)、1,6-己二醇二甲基丙烯酸酯(1,6-hexane glycol dimethacrylate)、三羥甲基丙烷三甲基丙烯酸酯(trimethyolpropane trimethacrylate)、三羥甲基丙烷三丙烯酸酯(trimethyolpropane triacrylate)、甘油二甲基丙烯酸酯(glycerin dimethacrylate)、季戊四醇二甲基丙烯酸酯(pentaerythritol dimethacrylate)、季戊四醇三甲基丙烯酸酯(pentaerythritol trimethacrylate)、二季戊四醇四甲基丙烯酸酯(dipentaerythritol pentamethacrylate)、2,2-雙(4-甲基丙烯醯氧基二乙氧基苯基)丙烷(2,2-bis(4-methacryloxydiethoxyphenyl)propane)、2,2-雙(4-甲基丙烯醯氧基聚乙氧基苯基)丙烷(2,2-bis(4-methacryloxypolyethoxyphenyl)propane)、2-羥基-3-甲基丙烯醯氧基丙基甲基丙烯酸酯(2-hydroxy-3-methacryloyloxypropyl methacrylate)、乙二醇二縮水甘油醚二甲基丙烯酸酯(ethylene glycol diglycidyl ether dimethacrylate)、二乙二醇二縮水甘油醚二甲基丙烯酸酯(diethylene glycol diglycidyl ether dimethacrylate)、鄰苯二甲酸二縮水甘油酯二甲基丙烯酸酯(phthalic acid diglycidyl ester dimethacrylate)、甘油聚縮水甘油醚聚甲基丙烯酸酯(glycerin polyglycidyl ether polymethacrylate)、含有胺基甲酸酯基的多官能(甲基)丙烯酸酯及類似物。 The photosensitive resin layer of one embodiment is an additional photopolymerizable compound and may include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, Tetraethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, butylene glycol dimethacrylate , neopentyl glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, trimethyolpropane trimethacrylate), trimethyolpropane triacrylate, glycerin dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dimethacrylate Pentaerythritol pentamethacrylate, 2,2-bis(4-methacryloxydiethoxyphenyl)propane, 2,2-bis(4-methacryloxydiethoxyphenyl)propane -Bis(4-methacryloxypolyethoxyphenyl)propane (2,2-bis(4-methacryloxypolyethoxyphenyl)propane), 2-hydroxy-3-methacryloxypolyethoxyphenyl methacrylic acid Ester (2-hydroxy-3-methacryloyloxypropyl methacrylate), ethylene glycol diglycidyl ether dimethacrylate (ethylene glycol diglycidyl ether dimethacrylate), diethylene glycol diglycidyl ether dimethacrylate, phthalic acid diglycidyl ester dimethacrylate, glycerol poly Glycerin polyglycidyl ether polymethacrylate, polyfunctional (meth)acrylates containing urethane groups and the like.

以固體含量計,相對於感光樹脂組成物的總重量,可光聚合化合物的含量可為10重量%或大於10重量%且為70重量%或小於70重量%。當可光聚合化合物的含量在以上範圍內時,可獲得增強感光度、解析度、黏合力及類似性質的效果。 In terms of solid content, the content of the photopolymerizable compound may be 10% by weight or more and 70% by weight or less than 70% by weight relative to the total weight of the photosensitive resin composition. When the content of the photopolymerizable compound is within the above range, effects of enhancing sensitivity, resolution, adhesion and similar properties can be obtained.

(4)感光樹脂組成物 (4) Photosensitive resin composition

用於形成感光樹脂層的感光樹脂組成物可包含:以固體含量計,20重量%且大於20重量%且為80重量%或小於80重量%的鹼性可顯影黏結劑樹脂、0.1重量%或大於0.1重量%且為10重量%或小於10重量%的光聚合引發劑、以及10重量%或大於10重量%且為70重量%或小於70重量%的可光聚合化合物。作為重量的基礎的固體含量意指自感光樹脂組成物排除溶劑的其餘組分。 The photosensitive resin composition used to form the photosensitive resin layer may include: based on solid content, 20% by weight and greater than 20% by weight and 80% by weight or less than 80% by weight of an alkaline developable binder resin, 0.1% by weight or More than 0.1% by weight and 10% by weight or less of a photopolymerization initiator, and 10% by weight or more than 10% by weight and 70% by weight or less of a photopolymerizable compound. The solid content on a weight basis means the remaining components excluding the solvent from the photosensitive resin composition.

感光樹脂組成物可更包含溶劑。溶劑一般選自甲基乙基酮(methyl ethyl ketone,MEK)、甲醇、THF、甲苯及丙酮,且不特別限於此,且其含量亦可根據光聚合引發劑、鹼性可顯影黏結劑樹脂及可光聚合化合物的含量來調節。 The photosensitive resin composition may further include a solvent. The solvent is generally selected from methyl ethyl ketone (MEK), methanol, THF, toluene and acetone, and is not particularly limited thereto, and its content can also be determined based on the photopolymerization initiator, alkaline developable binder resin and content of the photopolymerizable compound.

此外,感光樹脂組成物可根據需要進一步包含其他添加 劑。其他添加劑是增塑劑,且可包括:鄰苯二甲酸酯形式的鄰苯二甲酸二丁酯、鄰苯二甲酸二庚酯、鄰苯二甲酸二辛酯、鄰苯二甲酸二烯丙酯;二醇酯形式的三乙二醇二乙酸酯、四乙二醇二乙酸酯;酸醯胺形式的對甲苯磺醯胺、苯磺醯胺、正丁基苯磺醯胺;磷酸三苯酯等。 In addition, the photosensitive resin composition may further contain other additives as needed. agent. Other additives are plasticizers and may include: dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate in the form of phthalates Esters; triethylene glycol diacetate and tetraethylene glycol diacetate in the form of glycol esters; p-toluenesulfonamide, benzenesulfonamide and n-butylbenzenesulfonamide in the form of acid amide; phosphoric acid triphenyl ester etc.

在本揭露中,可添加無色染料或著色材料,以便改善感光樹脂組成物的處置性質。無色染料的實例包括三(4-二甲基胺基-2-甲基苯基)甲烷、三(4-二甲基胺基-2-甲基苯基)甲烷及螢烷染料(fluorane dye)。在該些中,當使用無色結晶紫時,對比度良好,此為較佳的。當含有無色染料時,在感光樹脂組成物中,含量可為0.1重量%或大於0.1重量%且為10重量%或小於10重量%。自表現出對比度的視角來看,0.1重量%或大於0.1重量%是較佳的,且自維持儲存穩定性的視角來看,10重量%或小於10重量%是較佳的。 In the present disclosure, a colorless dye or a coloring material may be added in order to improve the handling properties of the photosensitive resin composition. Examples of leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, and fluorane dye . Among these, when colorless crystal violet is used, the contrast is good, which is preferable. When a leuco dye is contained, the content may be 0.1% by weight or more and 10% by weight or less in the photosensitive resin composition. From the viewpoint of exhibiting contrast, 0.1% by weight or more is preferable, and from the viewpoint of maintaining storage stability, 10% by weight or less is preferable.

著色材料的實例可包括甲苯磺酸一水合物、品紅(fuchsin)、酞青綠(phthalocyanine green)、金胺鹼(auramine base)、副品紅(paramagenta)、結晶紫(Crystal violet)、甲基橙、尼羅藍2B(Nile blue 2B)、維多利亞藍(Victoria blue)、孔雀石綠(Malachite green)、鑽石綠(Diamond green)、鹼性藍20(Basic blue 20)及類似物。當包含著色材料時,以感光樹脂組成物計,所添加的量可為0.001重量%或大於0.001重量%且為1重量%或小於1重量%。當含量為0.001重量%或大於0.001重量%時,其具有改善可處置 性(handleability)的效果,且當含量為1重量%或小於1重量%時,其具有維持儲存穩定性的效果。 Examples of coloring materials may include toluenesulfonic acid monohydrate, fuchsin, phthalocyanine green, auramine base, paramagenta, crystal violet, methyl Orange, Nile blue 2B, Victoria blue, Malachite green, Diamond green, Basic blue 20 and the like. When a coloring material is included, the amount added may be 0.001% by weight or more and 1% by weight or less than 1% by weight based on the photosensitive resin composition. When the content is 0.001% by weight or greater than 0.001% by weight, it has improved disposability It has the effect of handleability, and when the content is 1% by weight or less than 1% by weight, it has the effect of maintaining storage stability.

另外,其他添加劑可更包括熱聚合抑制劑、染料、脫色劑(discoloring agent)、黏合促進劑。 In addition, other additives may further include thermal polymerization inhibitors, dyes, discoloring agents, and adhesion accelerators.

同時,在使用剝離試驗儀對其中將所述感光樹脂層疊層於基板上的膜樣品進行的膠帶剝離(tape peeling)試驗期間,由以下方程式1定義的黏合力可為90%或大於90%、為90%或大於90%且為100%或小於100%、或者95%或大於95%且為100%或小於100%。此可藉由在一個實施例的感光樹脂層中含有上述可光聚合化合物來實施。 Meanwhile, during a tape peeling test using a peel tester on a film sample in which the photosensitive resin layer is laminated on a substrate, the adhesive force defined by the following Equation 1 may be 90% or greater, It is 90% or more and 100% or less than 100%, or 95% or more and 100% or less. This can be implemented by including the above-mentioned photopolymerizable compound in the photosensitive resin layer of one embodiment.

[方程式1]黏合力(%)=(在膠帶剝離試驗之後基板及感光樹脂層的表面積/在膠帶剝離試驗之前感光樹脂層與基板接觸的表面積)*100。 [Equation 1] Adhesion (%) = (surface area of the substrate and the photosensitive resin layer after the tape peeling test/surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test)*100.

具體而言,由於一個實施例的感光樹脂層包含由化學式1表示的單官能(甲基)丙烯酸酯化合物及由化學式2表示的多官能(甲基)丙烯酸酯化合物,因此由方程式1定義的黏合力可為90%或大於90%。 Specifically, since the photosensitive resin layer of one embodiment includes a monofunctional (meth)acrylate compound represented by Chemical Formula 1 and a multifunctional (meth)acrylate compound represented by Chemical Formula 2, the adhesion defined by Equation 1 The force can be 90% or greater.

由於由方程式1定義的黏合力為90%或大於90%,因此可達成改善包括一個實施例的感光樹脂層的乾膜式光阻的基板黏合力的效果。 Since the adhesion force defined by Equation 1 is 90% or greater, the effect of improving the substrate adhesion force of the dry film photoresist including the photosensitive resin layer of one embodiment can be achieved.

具體而言,在其中將感光樹脂層疊層於基板上的膜樣品中,基板可為反向處理箔(Reverse Treated Foil,RTF)。 Specifically, in the film sample in which the photosensitive resin layer is laminated on the substrate, the substrate may be a reverse treated foil (RTF).

更具體而言,基板的表面粗糙度可為1微米或大於1微米且為10微米或小於10微米、3微米或大於3微米且為7微米或小於7微米、或者4微米或大於4微米且為6微米或小於6微米。 More specifically, the surface roughness of the substrate may be 1 micron or more and 10 microns or less, 3 microns or more and 7 microns or less, or 4 microns or more and 6 microns or less.

同時,方程式1的膠帶剝離(tape peeling)試驗可在將標準膠帶結合至其中將感光樹脂層疊層於基板上的膜樣品之後使用剝離試驗來執行。 Meanwhile, the tape peeling test of Equation 1 can be performed using a peeling test after bonding a standard tape to a film sample in which a photosensitive resin layer is laminated on a substrate.

在其中由方程式1定義的黏合力為90%或大於90%的情形中,由於相對於多官能(甲基)丙烯酸酯化合物,一個實施例的感光樹脂層含有過量的單官能(甲基)丙烯酸酯化合物,因此,由於由化學式1表示的單官能(甲基)丙烯酸酯化合物的低玻璃轉變溫度,所述感光樹脂層在乾膜式光阻的疊層溫度下具有相對大的流動性,且藉此,可達成改善對具有高表面粗糙度及非均勻性的基板的物理黏合的效果。 In the case where the adhesion force defined by Equation 1 is 90% or greater, since the photosensitive resin layer of one embodiment contains an excess of monofunctional (meth)acrylic acid relative to the multifunctional (meth)acrylate compound ester compound, therefore, the photosensitive resin layer has relatively large fluidity at the lamination temperature of the dry film type photoresist due to the low glass transition temperature of the monofunctional (meth)acrylate compound represented by Chemical Formula 1, and This can achieve the effect of improving physical adhesion to substrates with high surface roughness and non-uniformity.

2.乾膜式光阻 2. Dry film photoresist

根據本揭露的另一實施例,可提供一種包括所述一個實施例的感光樹脂層的乾膜式光阻。關於感光樹脂層的細節包括以上在所述一個實施例中闡述的所有內容。 According to another embodiment of the present disclosure, a dry film photoresist including the photosensitive resin layer of the embodiment can be provided. Details about the photosensitive resin layer include all the contents explained above in the one embodiment.

具體而言,感光樹脂層可包括一個實施例的感光樹脂組成物的乾燥產物或固化產物。乾燥產物意指藉由一個實施例的感光樹脂組成物的乾燥製程獲得的材料。固化產物意指藉由一個實施例的感光樹脂組成物的固化製程獲得的材料。 Specifically, the photosensitive resin layer may include a dried product or a cured product of the photosensitive resin composition of one embodiment. The dry product refers to the material obtained by the drying process of the photosensitive resin composition of one embodiment. The cured product means a material obtained through the curing process of the photosensitive resin composition of one embodiment.

乾膜式光阻的厚度並無特別限制,但是舉例而言,其可在為0.01微米至1毫米的範圍內自由調節。當乾膜式光阻的厚度增加或減少特定值時,在乾膜式光阻中量測的物理性質亦可改變特定數值。 The thickness of the dry film photoresist is not particularly limited, but for example, it can be freely adjusted within the range of 0.01 micron to 1 mm. When the thickness of the dry film resist increases or decreases by a specific value, the physical properties measured in the dry film resist can also change by a specific value.

乾膜式光阻可更包括基板膜及保護膜。基板膜在乾膜式光阻的製造期間充當感光樹脂層的支撐,且有利於在具有黏合強度的感光樹脂層的曝光期間的處置。 Dry film photoresist can also include substrate film and protective film. The substrate film serves as a support for the photosensitive resin layer during the fabrication of the dry film photoresist and facilitates handling during exposure of the photosensitive resin layer with adhesive strength.

各種塑膠膜可用作基板膜,且其實例可包括選自由丙烯酸膜、聚對苯二甲酸乙二醇酯(polyethylene terephthalate,PET)膜、三乙醯纖維素(triacetylcellulose,TAC)膜、聚降冰片烯(polynorbornene,PNB)膜、環烯烴聚合物(cycloolefin polymer,COP)膜及聚碳酸酯(polycarbonate,PC)膜組成的群組的至少一種塑膠膜。基板膜的厚度並無特別限制,且舉例而言,其可在為0.01微米至1毫米的範圍內自由調節。 Various plastic films may be used as the substrate film, and examples thereof may include films selected from the group consisting of acrylic films, polyethylene terephthalate (PET) films, triacetylcellulose (TAC) films, polyethylene glycol films, At least one plastic film from the group consisting of a bornene (polynorbornene, PNB) film, a cycloolefin polymer (COP) film, and a polycarbonate (PC) film. The thickness of the substrate film is not particularly limited, and for example, it can be freely adjusted in the range of 0.01 micrometer to 1 millimeter.

保護膜防止在處置期間對光阻的損壞,並起到保護感光樹脂層免受異物(例如灰塵)影響的保護覆蓋物(protective cover)的作用,且被疊層於感光樹脂層的上面未形成基板膜的背側上。保護膜用於保護感光樹脂層免受外部影響。當乾膜式光阻被應用於後處理(post-process)時,其需要容易地拆離,且其需要恰當的可釋放性(releasability)及黏合力,以使得其在儲存及分配期間變形。 The protective film prevents damage to the photoresist during handling and serves as a protective cover to protect the photosensitive resin layer from foreign matter (such as dust), and is laminated on the photosensitive resin layer without forming on the backside of the substrate membrane. The protective film is used to protect the photosensitive resin layer from external influences. When dry film photoresist is used in post-processing, it needs to be easily detachable, and it needs proper releasability and adhesion to allow it to deform during storage and distribution.

各種塑膠膜可用作保護膜,且其實例可包括選自由丙烯酸膜、聚乙烯(polyethylene,PE)膜、聚對苯二甲酸乙二醇酯(PET) 膜、三乙醯纖維素(TAC)膜、聚降冰片烯(PNB)膜、環烯烴聚合物(COP)膜及聚碳酸酯(PC)膜組成的群組的至少一種塑膠膜。保護膜的厚度並無特別限制,且舉例而言,其可在為0.01微米至1毫米的範圍內自由調節。 Various plastic films can be used as the protective film, and examples thereof can include films selected from acrylic films, polyethylene (PE) films, polyethylene terephthalate (PET) At least one plastic film from the group consisting of triacetyl cellulose (TAC) film, polynorbornene (PNB) film, cyclic olefin polymer (COP) film and polycarbonate (PC) film. The thickness of the protective film is not particularly limited, and for example, it can be freely adjusted in the range of 0.01 micron to 1 mm.

製造乾膜式光阻的方法的實例並無特別限制,且舉例而言,使用傳統塗佈方法將一個實施例的感光樹脂組成物塗佈至傳統基板膜(例如聚對苯二甲酸乙二醇酯)上,且然後進行乾燥,且將經乾燥的感光樹脂層的上表面與傳統保護膜(例如聚乙烯)進行疊層以生產出乾膜。 Examples of methods for manufacturing dry film photoresists are not particularly limited, and for example, the photosensitive resin composition of one embodiment is coated onto a traditional substrate film (such as polyethylene terephthalate glycol) using a traditional coating method. ester), and then dried, and the upper surface of the dried photosensitive resin layer is laminated with a conventional protective film (such as polyethylene) to produce a dry film.

塗佈感光樹脂組成物的方法並無特別限制,且可使用例如塗佈棒(coating bar)等方法。 The method of coating the photosensitive resin composition is not particularly limited, and a method such as a coating bar can be used.

對所塗佈的感光樹脂組成物進行乾燥的步驟可藉由例如熱空氣烘箱、熱板、熱空氣循環爐及紅外線爐等加熱工具來執行,且可在為50℃或大於50℃且為100℃或小於100℃的溫度下執行。 The step of drying the coated photosensitive resin composition can be performed by heating tools such as a hot air oven, a hot plate, a hot air circulation furnace, and an infrared furnace, and can be performed at 50°C or greater than 50°C and 100 °C or less than 100 °C.

同時,一個實施例的乾膜式光阻可具有如下特徵,即在使用剝離試驗儀對其中將感光樹脂層疊層於基板上的膜樣品進行的膠帶剝離試驗期間,由以下方程式2定義的黏合力可為90%或大於90%、為90%或大於90%且為100%或小於100%、或者95%或大於95%且為100%或小於100%。此可藉由在一個實施例的感光樹脂層中含有上述可光聚合化合物來實施。 Meanwhile, the dry film type photoresist of one embodiment may be characterized by an adhesive force defined by the following Equation 2 during a tape peel test using a peel tester on a film sample in which a photosensitive resin layer is laminated on a substrate It can be 90% or more, 90% or more and 100% or less, or 95% or more and 100% or less. This can be implemented by including the above-mentioned photopolymerizable compound in the photosensitive resin layer of one embodiment.

[方程式2] 黏合力(%)=(在膠帶剝離試驗之後乾膜式光阻的感光樹脂層與基板接觸的表面積/在膠帶剝離試驗之前乾膜式光阻的感光樹脂層與基板接觸的表面積)*100。 [Equation 2] Adhesion (%) = (surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate after the tape peeling test/surface area of the photosensitive resin layer of the dry film photoresist in contact with the substrate before the tape peeling test)*100.

關於黏合力的細節包括上述所有內容。 Details about adhesion include all of the above.

由於由方程式2定義的黏合力為90%或大於90%,因此可達成改善一個實施例的乾膜式光阻的基板黏合力的效果。 Since the adhesion force defined by Equation 2 is 90% or greater, the effect of improving the substrate adhesion force of the dry film photoresist in one embodiment can be achieved.

3.感光元件 3. Photosensitive element

根據本揭露的另一實施例,可提供一種感光元件,所述感光元件包括:聚合物基板;以及感光樹脂層,形成於所述聚合物基板上,其中在使用剝離試驗儀對其中將感光樹脂層疊層於基板上的膜樣品進行的膠帶剝離(tape peeling)試驗期間,由以下方程式1定義的黏合力為90%或大於90%:[方程式1]黏合力(%)=(在膠帶剝離試驗之後基板及感光樹脂層的表面積/在膠帶剝離試驗之前感光樹脂層與基板接觸的表面積)*100。 According to another embodiment of the present disclosure, a photosensitive element may be provided. The photosensitive element includes: a polymer substrate; and a photosensitive resin layer formed on the polymer substrate, wherein the photosensitive resin is tested using a peeling tester. During a tape peeling test of a film sample laminated to a substrate, the adhesion force defined by the following Equation 1 is 90% or greater: [Equation 1] Adhesion force (%) = (during the tape peeling test The surface area of the substrate and the photosensitive resin layer afterward/the surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test)*100.

關於黏合力的細節包括上述所有內容。 Details about adhesion include all of the above.

由於由方程式1定義的黏合力為90%或大於90%,因此可提供一種具有極佳基板黏合力的感光元件。 Since the adhesion force defined by Equation 1 is 90% or greater, a photosensitive element having excellent substrate adhesion force can be provided.

同時,感光樹脂層包括鹼性可顯影黏結劑樹脂及可光聚合化合物,且可光聚合化合物可包括由以下化學式1表示的單官能(甲基)丙烯酸酯化合物及由以下化學式2表示的多官能(甲基)丙烯酸酯化合物。 Meanwhile, the photosensitive resin layer includes an alkaline developable binder resin and a photopolymerizable compound, and the photopolymerizable compound may include a monofunctional (meth)acrylate compound represented by the following Chemical Formula 1 and a multifunctional (meth)acrylate compound represented by the following Chemical Formula 2 (meth)acrylate compounds.

Figure 109144461-A0305-02-0048-28
Figure 109144461-A0305-02-0048-28

在化學式1中,R1是氫或具有1至10個碳原子的烷基,R2是具有1至10個碳原子的伸烷基,R3是具有1至10個碳原子的烷基,且n1是為1至20的整數,

Figure 109144461-A0305-02-0048-29
In Chemical Formula 1, R 1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R 2 is an alkylene group having 1 to 10 carbon atoms, R 3 is an alkyl group having 1 to 10 carbon atoms, And n1 is an integer from 1 to 20,
Figure 109144461-A0305-02-0048-29

在化學式2中,R4是氫或具有1至10個碳原子的烷基,R5是具有1至10個碳原子的伸烷基,R6是含有具有1至20個碳原子的中心基的p價官能基,n2是為1至20的整數,且p是取代R6的官能基的數目且是為3至10的整數。 In Chemical Formula 2, R 4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R 5 is an alkylene group having 1 to 10 carbon atoms, and R 6 is a central group containing 1 to 20 carbon atoms. For p-valent functional groups, n2 is an integer ranging from 1 to 20, and p is the number of functional groups replacing R 6 and is an integer ranging from 3 to 10.

關於感光樹脂組成物的細節包括以上在所述一個實施例及另一實施例中闡述的所有內容。 Details about the photosensitive resin composition include all the contents explained above in the one embodiment and another embodiment.

即,感光樹脂層包含鹼性可顯影黏結劑樹脂及可光聚合化合物,且可光聚合化合物可包括由以下化學式1表示的單官能(甲基)丙烯酸酯化合物及由以下化學式2表示的多官能(甲基)丙烯酸酯化合物。 That is, the photosensitive resin layer includes an alkaline developable binder resin and a photopolymerizable compound, and the photopolymerizable compound may include a monofunctional (meth)acrylate compound represented by the following Chemical Formula 1 and a polyfunctional (meth)acrylate compound represented by the following Chemical Formula 2 (meth)acrylate compounds.

Figure 109144461-A0305-02-0049-31
Figure 109144461-A0305-02-0049-31

在化學式1中,R1是氫或具有1至10個碳原子的烷基,R2是具有1至10個碳原子的伸烷基,R3是具有1至10個碳原子的烷基,且n1是為1至20的整數,

Figure 109144461-A0305-02-0049-30
In Chemical Formula 1, R 1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R 2 is an alkylene group having 1 to 10 carbon atoms, R 3 is an alkyl group having 1 to 10 carbon atoms, And n1 is an integer from 1 to 20,
Figure 109144461-A0305-02-0049-30

在化學式2中,R4是氫或具有1至10個碳原子的烷基,R5是具有1至10個碳原子的伸烷基,R6是含有具有1至20個碳原子的中心基的p價官能基,n2是為1至20的整數,且p是取代 R6的官能基的數目且是為3至10的整數。 In Chemical Formula 2, R 4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R 5 is an alkylene group having 1 to 10 carbon atoms, and R 6 is a central group containing 1 to 20 carbon atoms. For p-valent functional groups, n2 is an integer ranging from 1 to 20, and p is the number of functional groups replacing R 6 and is an integer ranging from 3 to 10.

各種塑膠膜可用作保護膜,且其實例可包括選自由丙烯酸膜、聚乙烯(PE)膜、聚對苯二甲酸乙二醇酯(PET)膜、三乙醯纖維素(TAC)膜、聚降冰片烯(PNB)膜、環烯烴聚合物(COP)膜及聚碳酸酯(PC)膜組成的群組的至少一種塑膠膜。保護膜的厚度並無特別限制,且舉例而言,其可在為0.01微米至1毫米的範圍內自由調節。 Various plastic films can be used as the protective film, and examples thereof can include a film selected from the group consisting of acrylic film, polyethylene (PE) film, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film, At least one plastic film from the group consisting of polynorbornene (PNB) film, cyclic olefin polymer (COP) film and polycarbonate (PC) film. The thickness of the protective film is not particularly limited, and for example, it can be freely adjusted in the range of 0.01 micron to 1 mm.

聚合物基板的具體實例可為聚酯膜,在所述聚酯膜中,藉由單軸拉伸未拉伸的聚酯膜、將含有黏結劑樹脂及有機顆粒的塗佈溶液塗佈至其一個表面上、以及單軸拉伸其餘部分的在線塗佈方法(in-line coating method)形成抗黏連層(anti-blocking layer)。 A specific example of the polymer substrate may be a polyester film in which a coating solution containing a binder resin and organic particles is coated by uniaxially stretching an unstretched polyester film. An in-line coating method forms an anti-blocking layer on one surface and the rest of the uniaxially stretched portion.

聚合物基板一般是藉由在線塗佈方法、而非添加抗黏連劑(其一般是慮及製造期間的走料性(runnability)及捲繞特性而添加)來製造,且具有使用不損害透明度的替代性顆粒的有機顆粒層。 Polymer substrates are generally manufactured by in-line coating methods rather than adding anti-blocking agents (which are generally added taking into account runnability and winding characteristics during manufacturing), and have the advantage of being used without compromising transparency. A layer of organic particles of alternative particles.

此處,用作在慮及走料性及捲繞特性的同時不損害透明度的顆粒的有機顆粒的實例可包括例如如下有機顆粒:其中形成例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸異丁酯、甲基丙烯酸正丁酯、甲基丙烯酸正丁基甲酯、丙烯酸、甲基丙烯酸共聚物或三元共聚物的丙烯酸系顆粒、烯烴系顆粒(例如聚乙烯、聚苯乙烯或聚丙烯)、丙烯酸及烯烴系共聚物、或者均聚物顆粒且然後在所述層上塗佈另一種類型的單體的多層多組分顆粒(multi-layer multi-component particle)。 Here, examples of organic particles used as particles that do not impair transparency while taking feedability and winding characteristics into consideration may include, for example, organic particles in which, for example, methyl methacrylate, ethyl methacrylate, methyl methacrylate, etc. are formed. Acrylic particles, olefin particles (such as polyethylene, polystyrene or polyethylene) based on isobutyl acrylate, n-butyl methacrylate, n-butyl methyl methacrylate, acrylic acid, methacrylic acid copolymer or terpolymer multi-layer multi-component particles of acrylic), acrylic and olefin copolymers, or homopolymer particles and then coating another type of monomer on said layer multi-component particle).

具體而言,該些有機顆粒應為球形,且亦具有與黏結劑樹脂的折射率不同的折射率。此處,「球形」意指橢圓中的短軸(a)與長軸(b)的比率為0.5<a/b<2,且與矩形中對角線(d)的關係由d2

Figure 109144461-A0305-02-0051-48
a2+b2定義。並且,六面體中頂點之間具有最長距離的軸(f)與除a軸及b軸以外的c軸之間的關係由f2
Figure 109144461-A0305-02-0051-49
c2+a2+b2定義。顆粒的形狀應為球形,此在走料性方面是較佳的。 Specifically, the organic particles should be spherical and also have a refractive index different from that of the binder resin. Here, "spherical" means that the ratio of the minor axis (a) to the major axis (b) in the ellipse is 0.5<a/b<2, and the relationship with the diagonal (d) in the rectangle is given by d2
Figure 109144461-A0305-02-0051-48
a2+b2 definition. Furthermore, the relationship between the axis (f) with the longest distance between the vertices in the hexahedron and the c-axis other than the a-axis and b-axis is given by f2
Figure 109144461-A0305-02-0051-49
c2+a2+b2 definition. The shape of the particles should be spherical, which is better in terms of conveyability.

並且,特徵在於有機顆粒與黏結劑樹脂之間的折射率差為0.05或小於0.05。當折射率差大於0.05時,霧度增加。此意味著存在大量的散射光,且當存在大量的此種散射光時,側壁平滑效果(sidewall smoothing effect)降低。此亦取決於有機顆粒的大小及量。有機顆粒具有為約0.5微米至5微米的平均粒徑是較佳的。當其小於此值時,走料性及捲繞特性劣化,且當其大於5微米時,霧度增加,慮及掉落問題的發生,此不是較佳的。以黏結劑樹脂的總量計,有機顆粒的含量較佳為1重量%至10重量%。 Also, it is characterized in that the refractive index difference between the organic particles and the binder resin is 0.05 or less. When the refractive index difference is greater than 0.05, the haze increases. This means that there is a large amount of scattered light, and when there is a large amount of such scattered light, the sidewall smoothing effect is reduced. This also depends on the size and amount of organic particles. It is preferred that the organic particles have an average particle size of about 0.5 microns to 5 microns. When it is less than this value, the feedability and winding characteristics are deteriorated, and when it is greater than 5 microns, the haze increases, which is not preferable in view of the occurrence of drop problems. Based on the total amount of binder resin, the content of organic particles is preferably 1 to 10% by weight.

當以黏結劑樹脂的總量計,有機顆粒的含量小於1重量%時,抗黏連效果不足且易受劃傷(scratch),走料性及捲繞特性劣化,且當其超過10重量%時,可能存在霧度增加且透明度性質劣化的問題。 When the content of organic particles is less than 1% by weight based on the total amount of binder resin, the anti-adhesive effect is insufficient and susceptible to scratches, and the feeding properties and winding characteristics are deteriorated, and when it exceeds 10% by weight , there may be problems of increased haze and deterioration of transparency properties.

同時,除以上有機顆粒以外,亦可添加無機顆粒。此時,添加常用的無機抗黏連劑不是較佳的,且添加具有為100奈米或小於100奈米的粒徑的膠質二氧化矽是較佳的。以100重量份的 黏結劑樹脂計,其含量較佳為10重量份或小於10重量份。當滿足如上所述的粒徑及含量時,可防止當使用乾膜式光阻形成圖案時由抗黏連層引起的側壁缺陷或凹槽(例如凹坑)的出現。 At the same time, in addition to the above organic particles, inorganic particles can also be added. At this time, it is not preferable to add a commonly used inorganic anti-blocking agent, and it is preferable to add colloidal silica having a particle size of 100 nanometers or less. 100 parts by weight In terms of binder resin, its content is preferably 10 parts by weight or less. When the particle size and content as described above are met, the occurrence of sidewall defects or grooves (such as pits) caused by the anti-adhesion layer when patterning using dry film photoresist can be prevented.

作為充當用於將此種有機顆粒塗佈至未拉伸聚酯膜上的黏合劑的黏結劑樹脂,可使用與有機顆粒具有極佳相容性的黏結劑樹脂。此種樹脂的實例可包括:丙烯酸系樹脂,例如不飽和聚酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸異丁酯、甲基丙烯酸正丁酯、甲基丙烯酸正丁基甲酯、丙烯酸、甲基丙烯酸共聚物或三元共聚物;胺基甲酸酯系樹脂;環氧系樹脂;或者三聚氰胺系樹脂及類似物,且丙烯酸系樹脂是較佳的。 As the binder resin serving as a binder for coating such organic particles onto an unstretched polyester film, a binder resin having excellent compatibility with the organic particles can be used. Examples of such resins may include: acrylic resins such as unsaturated polyester, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, n-butyl methyl methacrylate , acrylic acid, methacrylic acid copolymer or terpolymer; urethane resin; epoxy resin; or melamine resin and the like, and acrylic resin is preferred.

可用於使用黏結劑樹脂及有機顆粒製備塗佈溶液的溶劑較佳為水。 The solvent that can be used to prepare the coating solution using the binder resin and organic particles is preferably water.

如上所述,單軸拉伸藉由熔融擠出PET粒料獲得的未拉伸聚酯膜,且然後將在黏結劑樹脂中含有有機顆粒的塗佈溶液塗佈於經單軸拉伸的膜上。所述塗佈可在經單軸拉伸的膜的至少一側上執行,且以在最終乾燥之後的厚度計,其厚度較佳為約30奈米至200奈米。若將含有有機顆粒的塗佈溶液在經單軸拉伸的膜上塗佈成厚於30奈米,則存在有機顆粒容易掉落且易受劃傷、且會產生白色粉末的問題。當塗佈成厚於200奈米時,由於塗佈溶液的黏度增加,在具有高塗佈速度的在線塗佈中,在塗佈方向上會產生塗佈條痕(coating streak)。 As described above, an unstretched polyester film obtained by melt-extruding PET pellets is uniaxially stretched, and then a coating solution containing organic particles in a binder resin is coated on the uniaxially stretched film superior. The coating may be performed on at least one side of the uniaxially stretched film, and the thickness after final drying is preferably about 30 nm to 200 nm. If the coating solution containing organic particles is applied to a uniaxially stretched film to a thickness thicker than 30 nanometers, there is a problem that the organic particles are easily dropped and scratched, and white powder is produced. When coating to a thickness thicker than 200 nm, coating streaks may occur in the coating direction during in-line coating with a high coating speed due to an increase in the viscosity of the coating solution.

透過藉由如上所述的在線塗佈方法使用不同於一般抗 黏連劑的有機顆粒進行塗佈而獲得的聚合物基板是由於顆粒層而維持走料性及捲繞特性且由於有機顆粒具有極佳透光度(light transmission)而具有極佳透明度的基板膜。 By using an in-line coating method as described above, it is different from the general resist The polymer substrate obtained by coating the organic particles of the binder is a substrate film that maintains feedability and winding characteristics due to the particle layer and has excellent transparency due to the excellent light transmission of the organic particles. .

由於感光樹脂層的疊層是在聚合物基板中含有有機顆粒的層的相對表面上執行,因此感光樹脂層以此種方式形成於含有有機顆粒的層的相對表面上。因此,當包括抗黏連劑的基板膜如之前一樣進行疊層時,不會出現凹坑狀缺陷。由於例如二氧化矽等顆粒不僅在大小上大於有機顆粒,而且分佈於整個基板膜上,因此二氧化矽的影響即使在鄰近於感光樹脂層的區域中亦顯得微不足道。 Since the lamination of the photosensitive resin layer is performed on the opposite surface of the layer containing organic particles in the polymer substrate, the photosensitive resin layer is formed on the opposite surface of the layer containing organic particles in this manner. Therefore, when the substrate film including the anti-blocking agent is laminated as before, pit-like defects do not occur. Since particles such as silicon dioxide are not only larger in size than organic particles but are also distributed throughout the substrate film, the influence of silicon dioxide is insignificant even in areas adjacent to the photosensitive resin layer.

另一方面,在用於本揭露的聚合物基板中,有機顆粒具有為0.5微米至5微米的大小,且有機顆粒層不鄰近於感光樹脂層,以使得有機顆粒的物理效果不受影響。此外,藉由使用具有極佳透光率(light transmittance)的有機顆粒,可減少側壁缺陷,且不會損害其他電路性質。 On the other hand, in the polymer substrate used in the present disclosure, the organic particles have a size of 0.5 microns to 5 microns, and the organic particle layer is not adjacent to the photosensitive resin layer so that the physical effect of the organic particles is not affected. In addition, by using organic particles with excellent light transmittance, sidewall defects can be reduced without compromising other circuit properties.

感光元件可更包括形成於感光樹脂層上的保護膜。保護膜防止在處置期間損壞感光樹脂層,且起到保護感光樹脂層免受異物(例如灰塵)影響的保護覆蓋物的作用。保護膜疊層於感光樹脂層的上面未形成聚合物基板的背側上。保護膜用於保護感光樹脂層免受外部影響。當乾膜式光阻被應用於後處理時,其需要容易地拆離,且其需要恰當的可釋放性及黏合力,以使得其在儲存及分配期間變形。 The photosensitive element may further include a protective film formed on the photosensitive resin layer. The protective film prevents damage to the photosensitive resin layer during handling and functions as a protective covering to protect the photosensitive resin layer from foreign matter such as dust. The protective film is laminated on the back side of the photosensitive resin layer on which the polymer substrate is not formed. The protective film is used to protect the photosensitive resin layer from external influences. When dry film resist is used for post-processing, it needs to be easily detachable, and it needs the right releasability and adhesion to allow it to deform during storage and distribution.

各種塑膠膜可用作保護膜,且其實例可包括選自由丙烯酸膜、聚乙烯(PE)膜、聚對苯二甲酸乙二醇酯(PET)膜、三乙醯纖維素(TAC)膜、聚降冰片烯(PNB)膜、環烯烴聚合物(COP)膜及聚碳酸酯(PC)膜組成的群組的至少一種塑膠膜。保護膜的厚度並無特別限制,且舉例而言,其可在為0.01微米至1毫米的範圍內自由調節。 Various plastic films can be used as the protective film, and examples thereof can include a film selected from the group consisting of acrylic film, polyethylene (PE) film, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film, At least one plastic film from the group consisting of polynorbornene (PNB) film, cyclic olefin polymer (COP) film and polycarbonate (PC) film. The thickness of the protective film is not particularly limited, and for example, it can be freely adjusted in the range of 0.01 micron to 1 mm.

4.電路板、顯示裝置 4. Circuit boards and display devices

根據本揭露的另一實施例,可提供一種包括含有所述一個實施例的感光樹脂組成物的感光樹脂層的電路板或顯示裝置。關於感光樹脂層的細節包括以上在所述一個實施例中闡述的所有內容。 According to another embodiment of the present disclosure, a circuit board or a display device including a photosensitive resin layer containing the photosensitive resin composition of the embodiment may be provided. Details about the photosensitive resin layer include all the contents explained above in the one embodiment.

電路板或顯示裝置的具體細節並無特別限制,且可無限制地應用各種傳統已知的技術配置。 The specific details of the circuit board or display device are not particularly limited, and various conventionally known technical configurations can be applied without limitation.

電路板或顯示裝置中所包括的感光樹脂層可為沒有開口的膜形式或具有開口的圖案形式。 The photosensitive resin layer included in the circuit board or display device may be in the form of a film without openings or in the form of a pattern with openings.

形成圖案層形式的感光樹脂的方法的實例包括將另一實施例的乾膜式光阻的感光樹脂層疊層於電路板或顯示裝置製造基板上且然後執行曝光及顯影的方法。另外,可提及一種將根據另一實施例的感光元件的感光樹脂層疊層於電路板或顯示裝置製造基板上且然後執行曝光及顯影的方法。 Examples of the method of forming the photosensitive resin in the form of a pattern layer include a method of laminating the photosensitive resin layer of the dry film type photoresist of another embodiment on a circuit board or a display device manufacturing substrate and then performing exposure and development. In addition, a method of laminating a photosensitive resin layer of a photosensitive element according to another embodiment on a circuit board or a display device manufacturing substrate and then performing exposure and development may be mentioned.

當另一實施例的乾膜式光阻或感光元件在感光樹脂層上具有保護膜時,可在將感光樹脂層疊層於電路板或顯示裝置製 造基板上的製程之前執行移除保護膜的製程。 When the dry film photoresist or photosensitive element of another embodiment has a protective film on the photosensitive resin layer, the photosensitive resin layer can be laminated on the circuit board or display device. The process of removing the protective film is performed before the process of manufacturing the substrate.

此外,當另一實施例的乾膜式光阻或感光元件具有疊層於感光樹脂層的一側上的聚合物基板或基板膜時,可進一步執行在曝光製程之後立即移除聚合物基板或基板膜的製程。 In addition, when the dry film photoresist or photosensitive element of another embodiment has a polymer substrate or substrate film laminated on one side of the photosensitive resin layer, the polymer substrate can be further removed immediately after the exposure process or Substrate film manufacturing process.

因此,電路板或顯示裝置中可包括另一實施例的乾膜式光阻或感光元件中所含有的感光樹脂層。 Therefore, the circuit board or the display device may include the dry film photoresist or the photosensitive resin layer contained in the photosensitive element of another embodiment.

根據本揭露,可提供一種可達成極佳基板黏合力的感光樹脂層、以及一種使用所述感光樹脂層的乾膜式光阻、電路板及顯示裝置。 According to the present disclosure, a photosensitive resin layer that can achieve excellent substrate adhesion, and a dry film photoresist, circuit board and display device using the photosensitive resin layer can be provided.

圖1示出在實例中量測的在膠帶剝離(tape peeling)試驗期間基板與感光樹脂層之間的黏合的光學顯微鏡影像。 Figure 1 shows an optical microscope image of the adhesion between the substrate and the photosensitive resin layer during a tape peeling test measured in the Example.

圖2示出在比較例1中量測的在膠帶剝離(tape peeling)試驗期間基板與感光樹脂層之間的黏合的光學顯微鏡影像。 2 shows an optical microscope image of the adhesion between the substrate and the photosensitive resin layer measured during a tape peeling test in Comparative Example 1.

圖3示出在比較例2中量測的在膠帶剝離(tape peeling)試驗期間基板與感光樹脂層之間的黏合的光學顯微鏡影像。 3 shows an optical microscope image of the adhesion between the substrate and the photosensitive resin layer measured during a tape peeling test in Comparative Example 2.

將藉由下面所示的實例更詳細地闡述本揭露。然而,給出該些實例僅是為示出本發明,且不旨在將本發明的範圍限於此。 The present disclosure will be explained in more detail by the examples shown below. However, these examples are given merely to illustrate the invention and are not intended to limit the scope of the invention thereto.

<製備例:鹼性可顯影黏結劑樹脂的製備><Preparation example: Preparation of alkaline developable binder resin>

製備例1Preparation Example 1

為四頸圓底燒瓶配備機械攪拌器(mechanical stirrer)及迴流裝置,且然後利用氮氣對燒瓶內部進行了吹掃。向利用氮氣吹掃的燒瓶添加了80克甲基乙基酮(methyl ethyl ketone,MEK)及7.5克甲醇(methanol,MeOH),且然後添加了0.45克偶氮二異丁腈(azobisisobutyronitrile,AIBN)並使其完全溶解。向其添加了8克丙烯酸(acrylic acid,AA)、15克甲基丙烯酸(methacrylic acid,MAA)、15克丙烯酸丁酯(butyl acrylate,BA)、52克甲基丙烯酸甲酯(methyl methacrylate,MMA)及10克苯乙烯(styrene,SM)的單體混合物作為單體,加熱至80℃,且然後聚合6小時以製備鹼性可顯影黏結劑樹脂1。 The four-neck round-bottom flask was equipped with a mechanical stirrer and a reflux device, and then the inside of the flask was purged with nitrogen. To the flask purged with nitrogen, 80 grams of methyl ethyl ketone (MEK) and 7.5 grams of methanol (MeOH) were added, and then 0.45 grams of azobisisobutyronitrile (AIBN) was added and allow it to dissolve completely. 8 grams of acrylic acid (AA), 15 grams of methacrylic acid (MAA), 15 grams of butyl acrylate (BA), and 52 grams of methyl methacrylate (MMA) were added to it. ) and 10 grams of styrene (SM) were used as monomers, heated to 80° C., and then polymerized for 6 hours to prepare an alkaline developable binder resin 1.

鹼性可顯影黏結劑樹脂1被量測為具有為71538克/莫耳的重量平均分子量、為79℃的玻璃轉變溫度、為51.4重量%的固體含量及為156.3毫克氫氧化鉀/克的酸值。 Alkaline Developable Binder Resin 1 was measured to have a weight average molecular weight of 71538 grams/mol, a glass transition temperature of 79°C, a solids content of 51.4 wt%, and 156.3 mg potassium hydroxide/gram of acid. value.

在重量平均分子量的量測條件的具體實例中,將鹼性可顯影黏結劑樹脂溶解於四氫呋喃中,以使鹼性可顯影黏結劑樹脂在THF中具有為1.0(重量/重量)%的濃度(以固體含量計,約0.5(重量/重量)%),使用孔徑(pore size)為0.45微米的注射器過濾器(syringe filter)進行了過濾,然後以為20微升的量注射至GPC中,四氫呋喃(tetrahydrofuran,THF)用作GPC的移動相,且流速為1.0毫升/分鐘。所述管柱由串聯連接的一個安捷倫PL膠 (Agilent PLgel)5微米保護管(guard)(7.5×50毫米)與兩個安捷倫PL膠5微米混合管(mixed)D(7.5×300毫米)配置而成,且所述量測是使用安捷倫1260無限II系統(Agilent 1260 Infinity II System)RI檢測器(RI Detector)作為檢測器在40℃下執行。 In a specific example of the measurement conditions of the weight average molecular weight, the alkali developable binder resin is dissolved in tetrahydrofuran so that the alkali developable binder resin has a concentration of 1.0 (weight/weight)% in THF ( Based on solid content, about 0.5 (weight/weight)%), filtered using a syringe filter with a pore size of 0.45 microns, and then injected into the GPC in an amount of 20 microliters, tetrahydrofuran ( Tetrahydrofuran (THF) was used as the mobile phase of GPC, and the flow rate was 1.0 ml/min. The column consists of an Agilent PL glue connected in series (Agilent PLgel) 5 micron guard (7.5 × 50 mm) is configured with two Agilent PL gel 5 micron mixed tubes (mixed) D (7.5 × 300 mm), and the measurement was performed using an Agilent 1260 An Agilent 1260 Infinity II System RI Detector was used as the detector and was performed at 40°C.

藉由如下製程對酸值進行了量測:在所述製程中,對約1克鹼性可顯影黏結劑樹脂進行取樣、溶解於添加有兩滴1%酚酞指示劑的50毫升混合溶劑(MeOH 20%、丙酮(acetone)80%)中,且然後利用0.1當量濃度KOH進行滴定以量測酸值。 The acid value was measured by a process in which approximately 1 gram of alkaline developable binder resin was sampled and dissolved in 50 ml of a mixed solvent (MeOH) with two drops of 1% phenolphthalein indicator. 20%, acetone (80%), and then titrate with 0.1 normal KOH to measure the acid value.

固體含量是基於在上述製備例中製備的鹼性可顯影黏結劑樹脂的重量,且對在150℃的烘箱中加熱達120分鐘之後剩餘的固體含量的重量百分比進行了量測。 The solids content is based on the weight of the alkaline developable binder resin prepared in the above preparation example, and the weight percent solids content remaining after heating in an oven at 150° C. for 120 minutes was measured.

製備例2Preparation Example 2

為四頸圓底燒瓶配備機械攪拌器(mechanical stirrer)及迴流裝置,且然後利用氮氣對燒瓶內部進行了吹掃。向利用氮氣吹掃的燒瓶添加了80克甲基乙基酮(methyl ethyl ketone,MEK)及7.5克甲醇(methanol,MeOH),且然後添加了0.9克偶氮二異丁腈(azobisisobutyronitrile,AIBN)並使其完全溶解。向其添加了25克甲基丙烯酸(methacrylic acid,MAA)、47.5克甲基丙烯酸甲酯(methyl methacrylate,MMA)及27.5克苯乙烯(styrene,SM)的單體混合物作為單體,加熱至80℃,且然後聚合6小時以製備鹼性可顯影黏結劑樹脂2(重量平均分子量:39000克/莫耳,玻璃轉變溫度:128℃,固體含量:45.6重量%,酸值:163.1毫克氫氧 化鉀/克)。 The four-neck round-bottom flask was equipped with a mechanical stirrer and a reflux device, and then the inside of the flask was purged with nitrogen. To the flask purged with nitrogen, 80 grams of methyl ethyl ketone (MEK) and 7.5 grams of methanol (MeOH) were added, and then 0.9 grams of azobisisobutyronitrile (AIBN) was added and allow it to dissolve completely. A monomer mixture of 25 grams of methacrylic acid (MAA), 47.5 grams of methyl methacrylate (MMA) and 27.5 grams of styrene (SM) was added as monomers and heated to 80 ℃, and then polymerized for 6 hours to prepare alkaline developable binder resin 2 (weight average molecular weight: 39000 g/mol, glass transition temperature: 128°C, solid content: 45.6% by weight, acid value: 163.1 mg hydrogen oxide potassium/g).

<實例及比較例:感光樹脂組成物及乾膜式光阻的製備><Examples and Comparative Examples: Preparation of photosensitive resin composition and dry film photoresist>

根據下表1中所示的組成物,將光聚合引發劑作為溶劑溶解於甲基乙基酮(MEK)中,且然後添加了光聚合化合物及鹼性可顯影黏結劑樹脂,且使用機械攪拌器混合達約1小時以製備感光樹脂組成物。 According to the composition shown in Table 1 below, the photopolymerization initiator was dissolved in methyl ethyl ketone (MEK) as a solvent, and then the photopolymerization compound and the alkaline developable binder resin were added, and mechanical stirring was used Mix for about 1 hour to prepare a photosensitive resin composition.

使用塗佈棒將所獲得的感光樹脂組成物塗佈至29微米PET膜上。使用熱空氣烘箱對所塗佈的感光樹脂組成物層進行了乾燥。此時,乾燥溫度為80℃、乾燥時間為5分鐘、且感光樹脂組成物層在乾燥之後的厚度為29微米。 The obtained photosensitive resin composition was applied to a 29-micron PET film using a coating rod. The applied photosensitive resin composition layer was dried using a hot air oven. At this time, the drying temperature was 80° C., the drying time was 5 minutes, and the thickness of the photosensitive resin composition layer after drying was 29 μm.

將保護膜(聚乙烯)疊層至經乾燥的感光樹脂組成物層上,以製備乾膜式光阻。 A protective film (polyethylene) is laminated on the dried photosensitive resin composition layer to prepare a dry film photoresist.

Figure 109144461-A0305-02-0058-32
Figure 109144461-A0305-02-0058-32
Figure 109144461-A0305-02-0059-34
Figure 109144461-A0305-02-0059-34

<實驗例><Experimental example>

藉由以下方法對實例及比較例中製備的乾膜式光阻的物理性質進行了量測,且結果示出於下表2中。 The physical properties of the dry film photoresists prepared in the Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.

1.細線黏合力(單位:微米) 1. Thin wire adhesion (unit: micron)

自在實例及比較例中製備的乾膜式光阻剝離保護膜,且使用伯東(Hakuto)MACH 610i將乾膜式光阻的感光樹脂層疊層成接觸厚度為1.0毫米的RTF(Reverse Treated Foil,反向處理箔)的銅層的在以下條件下經歷軟蝕刻的表面,藉此形成疊層體:疊層 機輥溫度為110℃、輥壓為4.0千克力/平方公分(kgf/cm3)且輥速為2.0米/分鐘。 From the dry film type photoresist peel-off protective film prepared in the examples and comparative examples, and using Hakuto MACH 610i, the photosensitive resin layer of the dry film type photoresist was laminated into an RTF (Reverse Treated Foil, Reverse Treated Foil) with a contact thickness of 1.0 mm. The surface of the copper layer of the treatment foil) was subjected to soft etching under the following conditions, thereby forming a laminate: a laminator roll temperature of 110°C, a roll pressure of 4.0 kilograms of force per square centimeter (kgf/cm 3 ) and The roller speed is 2.0 meters/minute.

在疊層於RTF(Reverse Treated Foil,反向處理箔)上的乾膜式光阻中,使用ORC FDi-3(雷射直接影像(Laser Direct Image)曝光機器)以為19毫焦/平方公分的曝光劑量利用紫外射線對細線黏合圖案(佈置成使得寬度以2微米為單位自10微米增大至58微米,且圖案間隔為400微米)進行了照射,且然後容許靜置達15分鐘。然後,剝離用於乾膜式光阻的支撐PET膜,且然後在噴霧壓力為1.5千克力/平方公分的噴霧型顯影條件下利用1.0重量% Na2CO3水溶液在30±1℃下顯影達40秒。 In the dry film photoresist laminated on RTF (Reverse Treated Foil, reverse treatment foil), the ORC FDi-3 (Laser Direct Image) exposure machine is used to achieve a photoresist temperature of 19 mJ/cm². Exposure Dosage A fine line bonding pattern (arranged so that the width increased from 10 microns to 58 microns in 2 micron increments with pattern intervals of 400 microns) was irradiated with UV rays and then allowed to stand for 15 minutes. Then, the supporting PET film for the dry film type photoresist was peeled off, and then developed using a 1.0 wt% Na 2 CO 3 aqueous solution at 30 ± 1° C. under spray type development conditions with a spray pressure of 1.5 kgf/cm2. 40 seconds.

在完成顯影的疊層體中,利用蔡司(ZEISS)阿西奧菲奧特顯微鏡(AXIOPHOT Microscope)對感光樹脂層之間的間隔的最小值進行了量測,並將所述最小值作為解析度進行了評價。可評價出:此值越小,則解析度值越佳。 In the developed laminate, the minimum value of the distance between the photosensitive resin layers was measured using a ZEISS AXIOPHOT Microscope, and the minimum value was taken as the resolution. evaluated. It can be evaluated that the smaller this value is, the better the resolution value is.

2.解析度(單位:微米) 2. Resolution (unit: micron)

自在實例及比較例中製備的乾膜式光阻剝離保護膜,且使用伯東MACH 610i將乾膜式光阻的感光樹脂層疊層成接觸厚度為1.0毫米的RTF(Reverse Treated Foil,反向處理箔)的銅層的在以下條件下經歷軟蝕刻的表面,藉此形成疊層體:疊層機輥溫度為110℃、輥壓為4.0千克力/平方公分且輥速為2.0米/分鐘。 From the dry film type photoresist peel-off protective film prepared in the examples and comparative examples, and using Bodong MACH 610i, the photosensitive resin layer of the dry film type photoresist was laminated into an RTF (Reverse Treated Foil, reverse treated foil) with a contact thickness of 1.0 mm. ), the surface of the copper layer undergoes soft etching under the following conditions, thereby forming a laminate: the laminator roller temperature is 110°C, the roller pressure is 4.0 kgf/cm2, and the roller speed is 2.0 m/min.

在疊層於RTF(Reverse Treated Foil,反向處理箔)上的乾膜式光阻中,使用ORC FDi-3(雷射直接影像曝光機器)以為19 毫焦/平方公分的曝光劑量利用紫外射線對解析度圖案(佈置成使得寬度以2微米為單位自10微米增大至58微米,且圖案間隔為400微米)進行了照射,且然後容許靜置達15分鐘。然後,剝離用於乾膜式光阻的支撐PET膜,且然後在噴霧壓力為1.5千克力/平方公分的噴霧型顯影條件下利用1.0重量% Na2CO3水溶液在30±1℃下顯影達40秒。 In the dry film photoresist laminated on RTF (Reverse Treated Foil, reverse treated foil), an ORC FDi-3 (laser direct image exposure machine) was used to utilize ultraviolet rays for an exposure dose of 19 mJ/cm2 Resolution patterns (arranged so that the width increased from 10 to 58 microns in 2 micron increments, with pattern intervals of 400 microns) were illuminated and then allowed to stand for 15 minutes. Then, the supporting PET film for the dry film type photoresist was peeled off, and then developed using a 1.0 wt% Na 2 CO 3 aqueous solution at 30 ± 1° C. under spray type development conditions with a spray pressure of 1.5 kgf/cm2. 40 seconds.

在完成顯影的疊層體中,利用蔡司(ZEISS)阿西奧菲奧特顯微鏡(AXIOPHOT Microscope)對感光樹脂層之間的間隔的最小值進行了量測,並將所述最小值作為解析度進行了評價。可評價出:此值越小,則解析度值越佳。 In the developed laminate, the minimum value of the distance between the photosensitive resin layers was measured using a ZEISS AXIOPHOT Microscope, and the minimum value was taken as the resolution. evaluated. It can be evaluated that the smaller this value is, the better the resolution value is.

3.剝離速率(單位:秒) 3. Peeling rate (unit: seconds)

自在實例及比較例中製備的乾膜式光阻剝離保護膜,且藉由伯東MACH 610i將乾膜式光阻的感光樹脂層疊層成接觸厚度為1.0毫米的RTF(Reverse Treated Foil,反向處理箔)的銅層的在以下條件下經歷軟蝕刻的表面,藉此形成疊層體:疊層機輥溫度為110℃、輥壓為4.0千克力/平方公分且輥速為2.0米/分鐘。 From the dry film photoresist peeling protective film prepared in the examples and comparative examples, and using Bodong MACH 610i, the photosensitive resin layer of the dry film photoresist was laminated into an RTF (Reverse Treated Foil) with a contact thickness of 1.0 mm. The surface of the copper layer of the foil) was subjected to soft etching under the following conditions, thereby forming the laminate, whereby the laminator roller temperature was 110° C., the roller pressure was 4.0 kgf/cm2, and the roller speed was 2.0 m/min.

在疊層於RTF(Reverse Treated Foil,反向處理箔)上的乾膜式光阻中,藉由ORC FDi-3(雷射直接影像(Laser Direct Image)曝光機器)以為19毫焦/平方公分的曝光劑量利用紫外射線對剝離圖案(50毫米×50毫米)進行了照射,且然後容許靜置達15分鐘。然後,剝離用於乾膜式光阻的支撐PET膜,且然後在噴霧壓力為1.5千克力/平方公分的噴霧型顯影條件下利用1.0重量% Na2CO3水溶液在30±1℃下顯影達40秒。 In the dry film photoresist laminated on RTF (Reverse Treated Foil, reverse treated foil), the ORC FDi-3 (Laser Direct Image) exposure machine is 19 mJ/cm2 The peeling pattern (50 mm x 50 mm) was irradiated with UV rays with an exposure dose of 100 % and then allowed to stand for 15 minutes. Then, the supporting PET film for the dry film type photoresist was peeled off, and then developed using a 1.0 wt% Na 2 CO 3 aqueous solution at 30 ± 1° C. under spray type development conditions with a spray pressure of 1.5 kgf/cm2. 40 seconds.

然後,使用3%氫氧化鈉水溶液(溫度為50℃)執行了剝離。藉由量測光固化層自銅板釋放所需的時間對剝離速率進行了評價。 Then, peeling was performed using a 3% sodium hydroxide aqueous solution (temperature: 50°C). The peeling rate was evaluated by measuring the time required for the photocured layer to be released from the copper plate.

4. RTF(Reverse Treated Foil,反向處理箔)黏合力 4. RTF (Reverse Treated Foil, reverse treated foil) adhesion

自在實例及比較例中製備的乾膜式光阻剝離保護膜,且藉由伯東MACH 610i將乾膜式光阻的感光樹脂層疊層成接觸厚度為1.0毫米的RTF(Reverse Treated Foil,反向處理箔)的在以下條件下經歷軟蝕刻的無光澤側表面(matte side surface),藉此形成疊層體:疊層機輥溫度為110℃、輥壓為4.0千克力/平方公分且輥速為2.0米/分鐘。 From the dry film photoresist peeling protective film prepared in the examples and comparative examples, and using Bodong MACH 610i, the photosensitive resin layer of the dry film photoresist was laminated into an RTF (Reverse Treated Foil) with a contact thickness of 1.0 mm. The laminate was formed from the matte side surface of the foil) which was subjected to soft etching under the following conditions: laminator roll temperature of 110°C, roll pressure of 4.0 kgf/cm2 and roll speed of 2.0 meters/minute.

自疊層體剝離用於乾膜式光阻的支撐PET膜,且然後將標準膠帶(tape)3M #610膠帶黏合至感光樹脂層,且使用SurTA剝離試驗儀(化學實驗室(ChemiLab))使3M #610膠帶經歷膠帶剝離(tape peeling)試驗,以評價RTF黏合力。結果示出於下表2中。 The supporting PET film for dry film photoresist was peeled off from the laminate, and then standard tape 3M #610 tape was bonded to the photosensitive resin layer, and a SurTA peel tester (ChemiLab) was used. 3M #610 tape undergoes tape peeling testing to evaluate RTF adhesion. The results are shown in Table 2 below.

RTF黏合力指代在膠帶剝離(tape peeling)試驗之後乾膜式光阻的感光樹脂層與基板接觸的表面積相對於在膠帶剝離(tape peeling)試驗之前乾膜式光阻的感光樹脂層與基板接觸的表面積的百分比,如以下方程式1中所示。 RTF adhesion refers to the surface area in contact between the photosensitive resin layer of the dry film photoresist and the substrate after the tape peeling test relative to the photosensitive resin layer of the dry film photoresist and the substrate before the tape peeling test. The percentage of surface area in contact, as shown in Equation 1 below.

[方程式1]黏合力(%)=(在膠帶剝離試驗之後基板及感光樹脂層的表 面積/在膠帶剝離試驗之前感光樹脂層與基板接觸的表面積)*100。 [Equation 1] Adhesion (%) = (surface of substrate and photosensitive resin layer after tape peeling test Area/surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test)*100.

Figure 109144461-A0305-02-0063-35
Figure 109144461-A0305-02-0063-35

如表2中所示,可證實出實例表現出極佳的細線黏合力及解析度,且同時,表現出顯著的RTF黏合力。與實例不同,可證實出相較於本揭露的實例而言,在不含有單官能(甲基)丙烯酸酯化合物的比較例1的情形中,RTF黏合力顯著較差。 As shown in Table 2, it can be confirmed that the example exhibits excellent fine line adhesion and resolution, and at the same time, exhibits significant RTF adhesion. Different from the examples, it can be confirmed that in the case of Comparative Example 1 which does not contain the monofunctional (meth)acrylate compound, the RTF adhesion is significantly worse compared to the examples of the present disclosure.

此外,可證實出相較於本揭露的實例而言,在不含有多官能(甲基)丙烯酸酯化合物的比較例2的情形中,細線黏合力及解析度顯著較差。 In addition, it can be confirmed that in the case of Comparative Example 2, which does not contain the multifunctional (meth)acrylate compound, the fine line adhesion and resolution are significantly poorer compared to the examples of the present disclosure.

Claims (14)

一種感光樹脂層,包含:可光聚合化合物,含有三官能或更高的多官能(甲基)丙烯酸酯化合物及單官能(甲基)丙烯酸酯化合物;以及鹼性可顯影黏結劑樹脂;其中以100重量份的所述單官能(甲基)丙烯酸酯化合物計,所述三官能或更高的多官能(甲基)丙烯酸酯化合物是以小於100重量份的量被含有,且其中在使用剝離試驗儀對其中將所述感光樹脂層疊層於基板上的膜樣品進行的膠帶剝離試驗期間,由以下方程式1定義的黏合力為90%或大於90%:[方程式1]黏合力(%)=(在所述膠帶剝離試驗之後基板及感光樹脂層的表面積)/在所述膠帶剝離試驗之前感光樹脂層與基板接觸的表面積)*100,其中所述單官能(甲基)丙烯酸酯化合物是包含以下化學式1的化合物,其中所述三官能或更高的多官能(甲基)丙烯酸酯化合物包括以下化學式2的化合物,其中所述鹼性可顯影黏結劑樹脂包括第一鹼性可顯影黏結劑樹脂以及第二鹼性可顯影黏結劑樹脂,其中所述第一鹼性可顯影黏結劑樹脂包括由以下化學式3表示的重複單元、由以下化學式4表示的重複單元、由以下化學式5 表示的重複單元、由以下化學式6表示的重複單元及由以下化學式7表示的重複單元;以及所述第二鹼性可顯影黏結劑樹脂包括由以下化學式4表示的重複單元、由以下化學式5表示的重複單元及由以下化學式6表示的重複單元,
Figure 109144461-A0305-02-0065-36
在化學式1中,R1是氫或具有1至10個碳原子的烷基,R2是具有1至10個碳原子的伸烷基,R3是具有1至10個碳原子的烷基,且n1是為1至20的整數,[化學式2]
Figure 109144461-A0305-02-0066-38
在化學式2中,R4是氫或具有1至10個碳原子的烷基,R5是具有1至10個碳原子的伸烷基,R6是含有具有1至20個碳原子的中心基的p價官能基,n2是為1至20的整數,且p是取代所述R6的官能基的數目,且是為3至10的整數,
Figure 109144461-A0305-02-0066-39
在化學式3中,R3"是氫,[化學式4]
Figure 109144461-A0305-02-0067-40
在化學式4中,R3'是具有1至10個碳原子的烷基,
Figure 109144461-A0305-02-0067-41
在化學式5中,R4"是具有1至10個碳原子的烷基,且R5"是具有1至10個碳原子的烷基,
Figure 109144461-A0305-02-0067-42
在化學式6中, Ar是具有6至20個碳原子的芳基,
Figure 109144461-A0305-02-0068-43
在化學式7中,R4'是氫,且R5'是具有1至10個碳原子的烷基。
A photosensitive resin layer comprising: a photopolymerizable compound containing trifunctional or higher polyfunctional (meth)acrylate compounds and monofunctional (meth)acrylate compounds; and an alkaline developable binder resin; wherein The trifunctional or higher polyfunctional (meth)acrylate compound is contained in an amount less than 100 parts by weight based on 100 parts by weight of the monofunctional (meth)acrylate compound, and wherein the peeling agent is used During the tape peeling test performed by the tester on a film sample in which the photosensitive resin layer is laminated on a substrate, the adhesion force defined by the following Equation 1 is 90% or greater: [Equation 1] Adhesion force (%) = (Surface area of the substrate and the photosensitive resin layer after the tape peeling test)/surface area of the photosensitive resin layer in contact with the substrate before the tape peeling test)*100, wherein the monofunctional (meth)acrylate compound is A compound of the following Chemical Formula 1, wherein the trifunctional or higher polyfunctional (meth)acrylate compound includes a compound of the following Chemical Formula 2, wherein the alkali developable binder resin includes a first alkali developable binder resin and a second alkaline developable binder resin, wherein the first alkaline developable binder resin includes a repeating unit represented by the following Chemical Formula 3, a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5 unit, a repeating unit represented by the following Chemical Formula 6, and a repeating unit represented by the following Chemical Formula 7; and the second alkaline developable binder resin includes a repeating unit represented by the following Chemical Formula 4, a repeating unit represented by the following Chemical Formula 5 and a repeating unit represented by the following Chemical Formula 6,
Figure 109144461-A0305-02-0065-36
In Chemical Formula 1, R 1 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R 2 is an alkylene group having 1 to 10 carbon atoms, R 3 is an alkyl group having 1 to 10 carbon atoms, And n1 is an integer from 1 to 20, [Chemical Formula 2]
Figure 109144461-A0305-02-0066-38
In Chemical Formula 2, R 4 is hydrogen or an alkyl group having 1 to 10 carbon atoms, R 5 is an alkylene group having 1 to 10 carbon atoms, and R 6 is a central group containing 1 to 20 carbon atoms. The p-valent functional group, n2 is an integer from 1 to 20, and p is the number of functional groups replacing R 6 , and is an integer from 3 to 10,
Figure 109144461-A0305-02-0066-39
In Chemical Formula 3, R 3 " is hydrogen, [Chemical Formula 4]
Figure 109144461-A0305-02-0067-40
In Chemical Formula 4, R 3 ' is an alkyl group having 1 to 10 carbon atoms,
Figure 109144461-A0305-02-0067-41
In Chemical Formula 5, R 4 " is an alkyl group having 1 to 10 carbon atoms, and R 5 " is an alkyl group having 1 to 10 carbon atoms,
Figure 109144461-A0305-02-0067-42
In Chemical Formula 6, Ar is an aryl group having 6 to 20 carbon atoms,
Figure 109144461-A0305-02-0068-43
In Chemical Formula 7, R 4 ' is hydrogen, and R 5 ' is an alkyl group having 1 to 10 carbon atoms.
如請求項1所述的感光樹脂層,其中所述三官能或更高的多官能(甲基)丙烯酸酯化合物具有其中三或更多個具有1至10個碳原子的環氧烷基以及三或更多個(甲基)丙烯酸酯官能基鍵合至具有1至20個碳原子的中心基的結構。 The photosensitive resin layer of claim 1, wherein the trifunctional or higher polyfunctional (meth)acrylate compound has three or more epoxyalkyl groups having 1 to 10 carbon atoms and three A structure in which one or more (meth)acrylate functional groups are bonded to a central group having 1 to 20 carbon atoms. 如請求項1所述的感光樹脂層,其中所述三官能或更高的多官能(甲基)丙烯酸酯化合物包括以下化學式2-1的化合物:[化學式2-1]
Figure 109144461-A0305-02-0069-44
在化學式2-1中,R6'是具有1至10個碳原子的三價官能基,R7至R9各自獨立地是具有1至10個碳原子的伸烷基,R10至R12各自獨立地是氫或具有1至10個碳原子的烷基,且n3至n5各自獨立地是為1至3的整數。
The photosensitive resin layer according to claim 1, wherein the trifunctional or higher polyfunctional (meth)acrylate compound includes a compound of the following Chemical Formula 2-1: [Chemical Formula 2-1]
Figure 109144461-A0305-02-0069-44
In Chemical Formula 2-1, R 6 ' is a trivalent functional group having 1 to 10 carbon atoms, R 7 to R 9 are each independently an alkylene group having 1 to 10 carbon atoms, and R 10 to R 12 Each independently is hydrogen or an alkyl group having 1 to 10 carbon atoms, and n3 to n5 are each independently an integer of 1 to 3.
如請求項1所述的感光樹脂層,其中所述單官能(甲基)丙烯酸酯化合物包含(甲基)丙烯酸酯,所述(甲基)丙烯酸酯含有具有1至10個碳原子的環氧烷基。 The photosensitive resin layer of claim 1, wherein the monofunctional (meth)acrylate compound includes (meth)acrylate containing epoxy having 1 to 10 carbon atoms. alkyl. 如請求項1所述的感光樹脂層,其中所述可光聚合化合物包括:所述單官能(甲基)丙烯酸酯化合物,含有(甲基)丙烯酸酯,所述(甲基)丙烯酸酯含有具有1至10個碳原子的環氧烷基;以及所述三官能或更高的多官能(甲基)丙烯酸酯化合物,具有其中三或更多個具有1至10個碳原子的環氧烷基以及三或更 多個(甲基)丙烯酸酯官能基鍵合至具有1至20個碳原子的中心基的結構。 The photosensitive resin layer according to claim 1, wherein the photopolymerizable compound includes: the monofunctional (meth)acrylate compound contains (meth)acrylate, and the (meth)acrylate contains an epoxyalkyl group having 1 to 10 carbon atoms; and the trifunctional or higher polyfunctional (meth)acrylate compound having three or more epoxyalkyl groups having 1 to 10 carbon atoms and three or more A structure in which multiple (meth)acrylate functional groups are bonded to a central group having 1 to 20 carbon atoms. 如請求項1所述的感光樹脂層,其中所述鹼性可顯影黏結劑樹脂具有為20000克/莫耳或大於20000克/莫耳且為150000克/莫耳或小於150000克/莫耳的重量平均分子量。 The photosensitive resin layer as claimed in claim 1, wherein the alkaline developable binder resin has an alkali density of 20,000 g/mol or greater than 20,000 g/mol and 150,000 g/mol or less than 150,000 g/mol. Weight average molecular weight. 請求項2所述的感光樹脂層,其中以100重量份的所述單官能(甲基)丙烯酸酯化合物計,所述三官能或更高的多官能(甲基)丙烯酸酯化合物是以為30重量份或大於30重量份且為90重量份或小於90重量份的量被含有。 The photosensitive resin layer according to claim 2, wherein the trifunctional or higher polyfunctional (meth)acrylate compound is 30 parts by weight based on 100 parts by weight of the monofunctional (meth)acrylate compound. It is contained in an amount of 30 parts by weight or more and 90 parts by weight or less. 如請求項1所述的感光樹脂層,其中以100重量份的所述第一鹼性可顯影黏結劑樹脂計,所述第二鹼性可顯影黏結劑樹脂是以為500重量份或大於500重量份且為1000重量份或小於1000重量份的量被含有。 The photosensitive resin layer as claimed in claim 1, wherein based on 100 parts by weight of the first alkaline developable binder resin, the second alkaline developable binder resin is 500 parts by weight or greater than 500 parts by weight. parts and is contained in an amount of 1,000 parts by weight or less. 如請求項1所述的感光樹脂層,其中所述第一鹼性可顯影黏結劑樹脂的玻璃轉變溫度與所述第二鹼性可顯影黏結劑樹脂的玻璃轉變溫度的比率為1:1.5或大於1:1.5且為1:5或小於1:5。 The photosensitive resin layer according to claim 1, wherein the ratio of the glass transition temperature of the first alkali developable binder resin to the glass transition temperature of the second alkali developable binder resin is 1:1.5 or Greater than 1:1.5 and 1:5 or less than 1:5. 如請求項1所述的感光樹脂層,其中所述第一鹼性可顯影黏結劑樹脂的酸值與所述第二鹼性可顯影黏結劑樹脂的酸值的比率為1:1.01或大於1:1.01且為1:1.5或小於1:1.5。 The photosensitive resin layer according to claim 1, wherein the ratio of the acid value of the first alkaline developable binder resin to the acid value of the second alkaline developable binder resin is 1:1.01 or greater than 1 :1.01 and 1:1.5 or less than 1:1.5. 如請求項1所述的感光樹脂層,其中所述感光樹脂層具有為1微米或大於1微米且為1000微米或小於1000微米的厚度。 The photosensitive resin layer of claim 1, wherein the photosensitive resin layer has a thickness of 1 micron or more and 1000 microns or less. 如請求項1所述的感光樹脂層,其中所述感光樹脂層具有為0.10平方公分或大於0.10平方公分且為5.00平方公分或小於5.00平方公分的橫截面積。 The photosensitive resin layer according to claim 1, wherein the photosensitive resin layer has a cross-sectional area of 0.10 square centimeters or more and 5.00 square centimeters or less. 一種包括如請求項1所述的感光樹脂層的乾膜式光阻。 A dry film photoresist including the photosensitive resin layer according to claim 1. 一種感光元件,包括:聚合物基板;以及如請求項1所述的感光樹脂層,形成於所述聚合物基板上。 A photosensitive element includes: a polymer substrate; and the photosensitive resin layer according to claim 1, formed on the polymer substrate.
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