TW201932307A - Photosensitive resin laminate - Google Patents

Photosensitive resin laminate Download PDF

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TW201932307A
TW201932307A TW107145555A TW107145555A TW201932307A TW 201932307 A TW201932307 A TW 201932307A TW 107145555 A TW107145555 A TW 107145555A TW 107145555 A TW107145555 A TW 107145555A TW 201932307 A TW201932307 A TW 201932307A
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support film
photosensitive resin
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TW107145555A
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TWI700183B (en
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宮崎純
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日商旭化成股份有限公司
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    • 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
    • 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
    • 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
    • G03F7/20Exposure; Apparatus therefor
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/02Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

Provided is a photosensitive resin laminate which prevents generation of resist projection, which provides a preferable resist pattern shape, and with which good productivity can be obtained. A photosensitive resin laminate according to one embodiment of the present invention is provided with a support film and a photosensitive resin composition layer formed on the support film, wherein the support film contains fine particles, and includes a region where the total area ratio of optical anomaly regions is not more than 300 ppm when observation is made in an area of 13.5 mm2 of the support film using an epi-illumination-type laser microscope.

Description

感光性樹脂積層體Photosensitive resin laminate

本發明係關於一種感光性樹脂積層體。The present invention relates to a photosensitive resin laminate.

於個人電腦、行動電話等電子設備中,為了安裝零件、半導體等,可使用印刷配線板等。作為印刷配線板等之製造用抗蝕劑,先前,業界使用於支持膜上積層感光性樹脂組合物層,進而於該感光性樹脂組合物層上視需要積層保護膜而成之感光性樹脂積層體之所謂幹膜光阻(以下,有時亦稱為DF)。作為感光性樹脂組合物層,目前,通常為使用弱鹼性水溶液作為顯影液之鹼性顯影型者。於使用DF製作印刷配線板等時,例如經過以下之步驟。於DF具有保護膜之情形時,首先剝離保護膜。其後,於銅箔積層板或可撓性基板等永久電路製作用基板上使用貼合機等層壓DF,並通過配線圖案掩膜等進行曝光。其次,視需要剝離支持膜,利用顯影液將未硬化部分(例如若為負型則為未曝光部分)之感光性樹脂組合物層溶解或分散去除,於基板上形成硬化抗蝕圖案(以下,有時亦簡稱為抗蝕圖案)。In electronic devices such as personal computers and mobile phones, printed wiring boards, etc. can be used for mounting parts, semiconductors, etc. As a resist for manufacturing printed wiring boards, etc., in the past, the industry used a photosensitive resin composition layer in which a photosensitive resin composition layer was laminated on a support film, and a protective film was optionally laminated on the photosensitive resin composition layer. The so-called dry film photoresist (hereinafter sometimes referred to as DF). As the photosensitive resin composition layer, at present, it is generally an alkaline development type using a weakly alkaline aqueous solution as a developing solution. When manufacturing printed wiring boards using DF, for example, the following steps are performed. When the DF has a protective film, first peel off the protective film. Thereafter, the DF is laminated on a substrate for permanent circuit production such as a copper foil laminate or a flexible substrate using a laminator or the like, and exposed through a wiring pattern mask or the like. Next, if necessary, the support film is peeled off, and the photosensitive resin composition layer of the uncured portion (for example, the unexposed portion if it is negative) is dissolved or dispersed with a developer to form a cured resist pattern on the substrate (hereinafter, (Sometimes also referred to as a resist pattern).

於抗蝕圖案形成後,形成電路之製程大致分成2個方法。第一種方法為於對未經抗蝕圖案覆蓋之基板面(例如銅箔積層板之銅面)進行蝕刻去除後,利用強於顯影液之鹼性水溶液去除抗蝕圖案部分之方法(蝕刻法)。第二種方法為於對上述基板面進行銅、焊料、鎳、錫等之鍍覆處理後,以與第一種方法同樣之方式去除抗蝕圖案部分,進而對露出之基板面(例如銅箔積層板之銅面)進行蝕刻之方法(鍍覆法)。於蝕刻中可使用氯化銅、氯化鐵、銅氨錯合物溶液等。近年來,隨著電子設備之小型化及輕量化,印刷配線板之微細化及高密度化不斷發展,於如上所述之製造步驟中要求提供高解像性、良好之線寬再現性等之高性能DF。After the resist pattern is formed, the process of forming the circuit is roughly divided into two methods. The first method is to remove the resist pattern part by using an alkaline aqueous solution stronger than the developer after etching and removing the substrate surface not covered by the resist pattern (for example, the copper surface of the copper foil laminate) (etching method) ). The second method is to apply copper, solder, nickel, tin, etc. to the above substrate surface, and then remove the resist pattern portion in the same way as the first method, and then to the exposed substrate surface (such as copper foil) The copper surface of the laminate) is etched (plating method). Copper chloride, ferric chloride, copper ammonia complex solution, etc. can be used for etching. In recent years, with the miniaturization and weight reduction of electronic equipment, the miniaturization and high density of printed wiring boards have been continuously developed. In the above-mentioned manufacturing steps, high resolution and good line width reproducibility are required. High performance DF.

於專利文獻1中記載有如下感光性元件,其係具備支持膜、與形成於該支持膜上之包含感光性樹脂組合物之層者,且上述支持膜之霧度為0.01~2.0%,該支持膜中所含之直徑5 μm以上之粒子及直徑5 μm以上之凝聚物之總數為5個/mm2 以下,上述包含感光性樹脂組合物之層含有(A)黏合劑聚合物、(B)具有乙烯性不飽和鍵之光聚合性化合物及(C)光聚合起始劑,且上述包含感光性樹脂組合物之層之厚度為3~30 μm,且其目的在於減少抗蝕劑之缺損。
[先前技術文獻]
[專利文獻]
Patent Document 1 describes a photosensitive element including a support film and a layer formed on the support film that contains a photosensitive resin composition, and the haze of the support film is 0.01 to 2.0%. The total number of particles with a diameter of 5 μm or more and aggregates with a diameter of 5 μm or more contained in the support film is 5 particles / mm 2 or less. The above-mentioned layer containing the photosensitive resin composition contains (A) a binder polymer, (B ) A photopolymerizable compound having an ethylenically unsaturated bond and (C) a photopolymerization initiator, and the thickness of the layer containing the photosensitive resin composition is 3 to 30 μm, and its purpose is to reduce the defect of the resist .
[Prior Technical Literature]
[Patent Literature]

[專利文獻1]國際公開第2008/093643號[Patent Literature 1] International Publication No. 2008/093643

[發明所欲解決之問題][Problems to be solved by the invention]

上述專利文獻1為了減少抗蝕劑之缺損,著眼於直徑5 μm以上之微粒子之數量。然而,本案之發明者進行努力研究,結果發現,作為抗蝕劑之形狀異常之原因,除考慮微粒子本身以外,亦考慮支持膜內之微粒子以外之光學異常區域(例如異常折射率區域)。專利文獻1雖然著眼於直徑5 μm以上之微粒子之數量,但未著眼於支持膜內之微粒子以外之光學異常區域。若支持膜中之光學異常區域較多,則產生如下等曝光控制不良:產生光之散射、繞射等,光照射至原本不欲照射光之部分,或異物遮住曝光之光,曝光之光未照射至原本欲照射曝光之光之場所。因此種曝光控制不良,存在產生抗蝕劑突起,無法獲得所需之抗蝕圖案形狀之情形。專利文獻1未著眼於此種抗蝕劑突起之產生,現狀為未能獲得可避免抗蝕劑突起之感光性樹脂積層體。The above Patent Document 1 focuses on the number of fine particles with a diameter of 5 μm or more in order to reduce the defect of the resist. However, the inventors of the present application conducted intensive studies and found that as the cause of the abnormal shape of the resist, in addition to the fine particles themselves, optical abnormal regions (eg, abnormal refractive index regions) other than the fine particles in the supporting film are also considered. Although Patent Document 1 focuses on the number of fine particles having a diameter of 5 μm or more, it does not focus on optically abnormal regions other than fine particles in the support film. If there are many optical abnormal areas in the support film, the following exposure control defects will occur: light scattering, diffraction, etc., the light is irradiated to the part that does not want to be irradiated, or a foreign object blocks the exposed light, the exposed light It has not been irradiated to the place where the light to be exposed was originally intended. Therefore, this kind of exposure control is poor, and there are cases where resist protrusions occur and the desired resist pattern shape cannot be obtained. Patent Document 1 does not focus on the generation of such resist protrusions, and the current situation is that a photosensitive resin laminate that can avoid resist protrusions cannot be obtained.

本發明之一態樣之目的在於解決上述課題,提供一種避免抗蝕劑突起,形成良好之抗蝕圖案形狀之感光性樹脂積層體。
[解決問題之技術手段]
An object of one aspect of the present invention is to solve the above-mentioned problems and provide a photosensitive resin laminate in which a resist pattern is avoided and a good resist pattern shape is formed.
[Technical means to solve the problem]

本發明者為了解決上述課題而進行努力研究並反覆進行實驗。其結果為,發現於一態樣中,藉由以下之技術手段,可解決該課題。In order to solve the above-mentioned problems, the present inventors have made intensive research and conducted experiments repeatedly. As a result, it was found that in one aspect, the problem can be solved by the following technical means.

即,本發明包含以下之態樣。
[1]一種感光性樹脂積層體,其係具備支持膜、與形成於上述支持膜上之感光性樹脂組合物層者,且
上述支持膜包含微粒子,包含利用落射型雷射顯微鏡於13.5 mm2 之面積中觀測上述支持膜時之光學異常區域之合計面積比率為300 ppm以下之區域。
[2]如上述態樣1中所記載之感光性樹脂積層體,其中上述支持膜包含利用落射型雷射顯微鏡於13.5 mm2 之面積中觀測上述支持膜時之光學異常區域之合計面積比率為200 ppm以下之區域。
[3]如上述態樣1中所記載之感光性樹脂積層體,其中上述支持膜包含利用落射型雷射顯微鏡於13.5 mm2 之面積中觀測上述支持膜時之光學異常區域之合計面積比率為100 ppm以下之區域。
[4]如上述態樣1中所記載之感光性樹脂積層體,其中上述支持膜包含利用落射型雷射顯微鏡於13.5 mm2 之面積中觀測上述支持膜時之光學異常區域之合計面積比率為50 ppm以下之區域。
[5]如上述態樣1至4中任一項所記載之感光性樹脂積層體,其中上述支持膜以質量基準計,包含微粒子10 ppm以上。
[6]一種感光性樹脂積層體,其係具備支持膜、與形成於上述支持膜上之感光性樹脂組合物層者,且
上述支持膜包含微粒子,
上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑0.5 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量以數量平均計成為1200個以下之區域。
[7]如上述態樣6中所記載之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑0.5 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量以數量平均計成為1000個以下之區域。
[8]如上述態樣6中所記載之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑0.5 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為900個以下之區域。
[9]如上述態樣6中所記載之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑0.5 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為500個以下之區域。
[10]如上述態樣6中所記載之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑0.5 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為200個以下之區域。
[11]如上述態樣6至10中任一項所記載之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑1.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為500個以下之區域。
[12]如上述態樣11中所記載之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑1.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為300個以下之區域。
[13]如上述態樣11中所記載之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑1.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為100個以下之區域。
[14]如上述態樣11中所記載之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑1.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為50個以下之區域。
[15]如上述態樣6至14中任一項所記載之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑2.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為200個以下之區域。
[16]如上述態樣15中所記載之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑2.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為100個以下之區域。
[17]如上述態樣15中所記載之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑2.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為50個以下之區域。
[18]如上述態樣15中所記載之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑2.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為10個以下之區域。
[19]如上述態樣1至18中任一項所記載之感光性樹脂積層體,其中上述微粒子之折射率與上述支持膜之主區域之折射率的折射率差為0.2以下。
[20]如上述態樣19中所記載之感光性樹脂積層體,其中上述微粒子之折射率與上述支持膜之主區域之折射率的折射率差為0.1以下。
[21]如上述態樣19中所記載之感光性樹脂積層體,其中上述微粒子之折射率與上述支持膜之主區域之折射率的折射率差為0.05以下。
[22]如上述態樣19中所記載之感光性樹脂積層體,其中上述微粒子之折射率與上述支持膜之主區域之折射率的折射率差為0.02以下。
[23]如上述態樣1至22中任一項所記載之感光性樹脂積層體,其中上述光學異常區域包含空腔。
[24]如上述態樣1至23中任一項所記載之感光性樹脂積層體,其中上述光學異常區域包含與上述支持膜之主區域配向性不同之區域。
[25]如上述態樣1至24中任一項所記載之感光性樹脂積層體,其中上述光學異常區域包含與上述支持膜之主區域結晶性不同之區域。
[26]如上述態樣1至25中任一項所記載之感光性樹脂積層體,其係線寬/間隙寬為20/20(μm)以下之配線形成用。
[27]如上述態樣26中所記載之感光性樹脂積層體,其係線寬/間隙寬未達10/10(μm)之配線形成用。
[28]一種印刷配線板中之抗蝕圖案之製造方法,其使用如上述態樣1至27中任一項所記載之感光性樹脂積層體。
[29]如上述態樣28中所記載之方法,其係利用半加成法進行。
[30]如上述態樣28或29中所記載之方法,其中上述抗蝕圖案之線寬/間隙寬未達10/10(μm)。
[31]一種感光性樹脂積層體,其係具備支持膜、與形成於上述支持膜上之感光性樹脂組合物層者,且
於直接使用繪圖曝光機於基板上形成線寬/間隙寬為8/8(μm)之抗蝕圖案之情形時,於支持膜之感光性樹脂組合物層側之表面對焦時之線寬、與自該表面沿厚度方向朝400 μm基板內側偏移時之線寬之差為1.8 μm以下。
[發明之效果]
That is, the present invention includes the following aspects.
[1] A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film, and the support film contains fine particles, including an epitaxy laser microscope at 13.5 mm 2 An area where the total area ratio of the optically abnormal areas when the above-mentioned supporting film is observed in the area is 300 ppm or less.
[2] The photosensitive resin laminate as described in the above aspect 1, wherein the total area ratio of the optically abnormal region when the support film includes the optically abnormal region when the support film is observed in an area of 13.5 mm 2 using an epi-type laser microscope is Areas below 200 ppm.
[3] The photosensitive resin laminate as described in the above aspect 1, wherein the total area ratio of the optically abnormal region when the support film includes the optically abnormal region when the support film is observed in an area of 13.5 mm 2 using an epi-laser laser microscope is Areas below 100 ppm.
[4] The photosensitive resin laminate as described in the above aspect 1, wherein the total area ratio of the optically abnormal region when the support film includes the optically abnormal region when the support film is observed in an area of 13.5 mm 2 using an epi-laser laser microscope is Areas below 50 ppm.
[5] The photosensitive resin laminate according to any one of the above aspects 1 to 4, wherein the support film contains 10 ppm or more of fine particles on a mass basis.
[6] A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film, and the support film contains fine particles,
The support film has a diameter of 0.5 μm or more contained in the area of 13.5 mm 2 of the support film, and the number of particles that are in contact with a region other than the particles of the optically abnormal region is 1200 on average The following areas.
[7] The photosensitive resin laminate as described in the above aspect 6, wherein the support film has the above-mentioned fine particles having a diameter of 0.5 μm or more contained in an area of 13.5 mm 2 of the support film, which is different from the optical abnormality The number of microparticles in the area other than the microparticles in the area is equal to or less than 1000 in average.
[8] The photosensitive resin laminate as described in aspect 6 above, wherein the support film has the above-mentioned fine particles having a diameter of 0.5 μm or more contained in an area of 13.5 mm 2 of the support film, which is different from the optical abnormality The number of particles in the area other than the particles in the area is less than 900.
[9] The photosensitive resin laminate as described in the above aspect 6, wherein the support film has the above-mentioned fine particles having a diameter of 0.5 μm or more contained in an area of 13.5 mm 2 of the support film, which is different from the optical abnormality The number of particles in the area other than the particles in the area is 500 or less.
[10] The photosensitive resin laminate as described in the above aspect 6, wherein the support film has the above-mentioned fine particles having a diameter of 0.5 μm or more contained in an area of 13.5 mm 2 of the support film, which is different from the optical abnormality The number of particles in the area other than the particles in the area is 200 or less.
[11] The photosensitive resin laminate according to any one of the above aspects 6 to 10, wherein the support film has the fine particles having a diameter of 1.0 μm or more contained in an area of 13.5 mm 2 of the support film The number of particles that are in contact with the area other than the particles in the optically abnormal area becomes an area of 500 or less.
[12] The photosensitive resin laminate as described in aspect 11 above, wherein the support film has the above-mentioned fine particles having a diameter of 1.0 μm or more contained in an area of 13.5 mm 2 of the support film, which is different from the optical abnormality The number of particles in the area other than the particles in the area is 300 or less.
[13] The photosensitive resin laminate as described in the above aspect 11, wherein the support film has the above-mentioned fine particles having a diameter of 1.0 μm or more contained in an area of 13.5 mm 2 of the support film, which is different from the optical abnormality The number of particles in the area other than the particles in the area is less than 100.
[14] The photosensitive resin laminate as described in the above aspect 11, wherein the support film has the above-mentioned fine particles having a diameter of 1.0 μm or more contained in an area of 13.5 mm 2 of the support film, which is different from the optical abnormality The number of particles in the area other than the particles in the area is less than 50.
[15] The photosensitive resin laminate according to any one of the above aspects 6 to 14, wherein the support film has the fine particles having a diameter of 2.0 μm or more contained in an area of 13.5 mm 2 of the support film The number of particles that are in contact with the areas other than the particles in the optically abnormal area becomes 200 or less.
[16] The photosensitive resin laminate as described in aspect 15 above, wherein the support film has the above-mentioned fine particles having a diameter of 2.0 μm or more contained in an area of 13.5 mm 2 of the support film, which is different from the optical abnormality The number of particles in the area other than the particles in the area is less than 100.
[17] The photosensitive resin laminate as described in aspect 15 above, wherein the support film has the above-mentioned fine particles having a diameter of 2.0 μm or more contained in an area of 13.5 mm 2 of the support film, which is different from the optical abnormality The number of particles in the area other than the particles in the area is less than 50.
[18] The photosensitive resin laminate as described in the above aspect 15, wherein the support film has the above-mentioned fine particles having a diameter of 2.0 μm or more contained in an area of 13.5 mm 2 of the support film, which is different from the optical abnormality The number of particles in the area other than the particles in the area is 10 or less.
[19] The photosensitive resin laminate according to any one of the above aspects 1 to 18, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.2 or less.
[20] The photosensitive resin laminate as described in aspect 19 above, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.1 or less.
[21] The photosensitive resin laminate as described in aspect 19 above, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.05 or less.
[22] The photosensitive resin laminate as described in aspect 19 above, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.02 or less.
[23] The photosensitive resin laminate according to any one of the above aspects 1 to 22, wherein the optical abnormal region includes a cavity.
[24] The photosensitive resin laminate according to any one of the above aspects 1 to 23, wherein the optically abnormal region includes a region that is different in alignment from the main region of the support film.
[25] The photosensitive resin laminate according to any one of the above aspects 1 to 24, wherein the optically abnormal region includes a region having a crystallinity different from the main region of the support film.
[26] The photosensitive resin laminate according to any one of the above aspects 1 to 25, which is used for wiring formation having a line width / gap width of 20/20 (μm) or less.
[27] The photosensitive resin laminate as described in the above aspect 26, which is used for wiring formation where the line width / gap width is less than 10/10 (μm).
[28] A method for manufacturing a resist pattern in a printed wiring board using the photosensitive resin laminate as described in any one of the above aspects 1 to 27.
[29] The method described in the above aspect 28 is performed by a semi-additive method.
[30] The method as described in the above aspect 28 or 29, wherein the line width / gap width of the resist pattern is less than 10/10 (μm).
[31] A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film, and a line width / gap width of 8 is formed on a substrate directly using a drawing exposure machine In the case of a resist pattern of / 8 (μm), the line width when the surface on the photosensitive resin composition layer side of the support film is in focus, and the line width when shifted from the surface toward the inside of the 400 μm substrate in the thickness direction The difference is less than 1.8 μm.
[Effect of invention]

根據本發明之一態樣,可提供一種避免抗蝕劑突起,形成良好之抗蝕圖案形狀之感光性樹脂積層體。According to one aspect of the present invention, it is possible to provide a photosensitive resin laminate in which a resist pattern is avoided and a good resist pattern shape is formed.

以下,對用以實施本發明之例示之形態(以下,簡稱為「實施形態」)詳細地進行說明。再者,本發明並不限定於以下之實施形態,可於其主旨之範圍內進行各種變化而實施。Hereinafter, an exemplary embodiment for implementing the present invention (hereinafter, simply referred to as "embodiment") will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist thereof.

[感光性樹脂積層體]
本實施形態提供一種感光性樹脂積層體,其具備支持膜、與形成於該支持膜上之感光性樹脂組合物層。本實施形態中,利用落射型雷射顯微鏡於13.5 mm2 之面積中觀測支持膜時之光學異常區域之合計面積比率為300 ppm以下。
[Photosensitive resin laminate]
The present embodiment provides a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film. In this embodiment, the total area ratio of the optically abnormal regions when the support film is observed in an area of 13.5 mm 2 using an epi-laser microscope is 300 ppm or less.

作為支持膜,較佳為使自曝光之光源發出之光透過之透明之支持膜。作為此種支持膜,例如可列舉:聚對苯二甲酸乙二酯膜、聚乙烯醇膜、聚氯乙烯膜、氯乙烯共聚物膜、聚偏二氯乙烯膜、偏二氯乙烯共聚膜、聚甲基丙烯酸甲酯共聚物膜、聚苯乙烯膜、聚丙烯腈膜、苯乙烯共聚物膜、聚醯胺膜、纖維素衍生物膜等。該等膜視需要亦可使用進行延伸者。As the support film, a transparent support film that transmits light emitted from the exposed light source is preferred. Examples of such a supporting film include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, Polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, cellulose derivative film, etc. These films can also be used as extenders as needed.

又,支持膜可為單層構造,亦可為積層有由複數種組成形成之樹脂層之多層構造。於多層構造之情形時,可存在防靜電層。於如2層構造或3層構造之多層構造之情形時,例如可採用於一面A上形成含有微粒子之樹脂層,且於另一面B上,(1)與面A同樣地含有微粒子、(2)含有少於面A之微粒子、(3)含有較面A微細之微粒子、(4)不含微粒子等構造。於(2)、(3)、(4)之構造之情形時,較佳為於面B側形成感光性樹脂組合物層。此時,若於面A側存在含有微粒子之樹脂層,則就膜之滑動性等觀點而言較佳。In addition, the support film may have a single-layer structure or a multi-layer structure in which a resin layer formed of a plurality of kinds of layers is laminated. In the case of a multilayer structure, an antistatic layer may be present. In the case of a multi-layer structure such as a two-layer structure or a three-layer structure, for example, a resin layer containing fine particles may be formed on one side A, and on the other side B, (1) containing fine particles, (2) ) Contains less particles than face A, (3) contains finer particles than face A, (4) does not contain fine particles, etc. In the case of the structures of (2), (3) and (4), it is preferable to form the photosensitive resin composition layer on the surface B side. At this time, if there is a resin layer containing fine particles on the surface A side, it is preferable from the viewpoint of film slidability and the like.

於支持膜中,利用落射型雷射顯微鏡於13.5 mm2 之面積中觀測時之光學異常區域之合計面積比率為300 ppm以下,更佳為250 ppm以下,更佳為200 ppm以下,更佳為150 ppm以下,更佳為100 ppm以下,更佳為80 ppm以下,更佳為70 ppm以下,更佳為60 ppm以下,更佳為50 ppm以下,更佳為40 ppm以下,更佳為20 ppm以下,更佳為10 ppm以下。上述合計面積比率越小,為了減少遮光、異常之折射或繞射等,於抗蝕劑突起之避免方面越有利。由於抗蝕劑突起(尤其是於半加成法(SAP)中)帶來配線之缺損,導致偏離配線之規定電阻值、進而電路之可靠性降低(即信號(正弦波)之紊亂),故而避免抗蝕劑突起於獲得電路之良好之可靠性之方面較有利。利用落射型雷射顯微鏡於13.5 mm2 之面積中觀測支持膜時之光學異常區域之合計面積比率可為1 ppm以上,亦可為5 ppm以上、10 ppm以上、20 ppm以上。In the support film, the total area ratio of the optical anomaly area when observed in an area of 13.5 mm 2 using an epi-laser microscope is 300 ppm or less, more preferably 250 ppm or less, more preferably 200 ppm or less, more preferably 150 ppm or less, more preferably 100 ppm or less, more preferably 80 ppm or less, more preferably 70 ppm or less, more preferably 60 ppm or less, more preferably 50 ppm or less, more preferably 40 ppm or less, more preferably 20 ppm or less, more preferably 10 ppm or less. The smaller the above-mentioned total area ratio, the more advantageous it is in avoiding resist protrusions in order to reduce shading, abnormal refraction, diffraction, and the like. Resist protrusions (especially in the semi-additive method (SAP)) cause defects in the wiring, resulting in deviations from the specified resistance value of the wiring, and the reliability of the circuit is reduced (that is, the disturbance of the signal (sine wave)) Avoiding the protrusion of the resist is more advantageous in obtaining good reliability of the circuit. The total area ratio of the optically abnormal regions when the support film is observed in an area of 13.5 mm 2 using an epi-laser microscope can be 1 ppm or more, or 5 ppm, 10 ppm, or 20 ppm.

本發明之光學異常區域之面積與微粒子之數量係指於支持膜之厚度之中心2 μm之區域中觀測之光學異常區域之面積與微粒子之數量,於支持膜為多層構造之情形時,係指於多層構造整體之厚度之中心2 μm之區域中測定之光學異常區域之面積與微粒子之數量。The area of the optical abnormal area and the number of fine particles of the present invention refer to the area of the optical abnormal area and the number of fine particles observed in the area of 2 μm in the center of the thickness of the support film. In the case where the support film has a multilayer structure, it means The area of the optically abnormal region and the number of fine particles measured in the region with a thickness of 2 μm at the center of the overall thickness of the multilayer structure.

以下,對在支持膜之厚度中心2 μm之區域中測定光學異常區域之面積及微粒子之數量之原因進行說明。
本件發明者進行努力研究,結果發現光之散射、繞射、遮光等主要因素為光學異常區域。於本發明中,所謂光學異常區域係與支持膜之主區域(構成支持膜之樹脂)光學物性不同之區域(具體而言,反射率或折射率不同於主區域,或散射、繞射等光學現象較主區域更強地產生之區域)。光學異常區域可包含由微粒子所引起之遮光部分、與微粒子以外之光學異常區域(例如具有不同於微粒子及支持膜之主區域之折射率之異常折射率區域)之兩者。光學異常區域之例為配向性及/或結晶性不同於支持膜之主區域之區域、空氣之區域、空氣以外之氣體之區域、幾乎不存在氣體之空腔區域等。例如,於在支持膜之製造步驟中進行延伸之情形時,因於支持膜內存在微粒子等原因,存在產生延伸條件於微粒子之附近不同於其他區域之區域之情形。該區域由於配向性及/或結晶性不同於其他區域,故而折射率不同於其他區域。又,於支持膜之製造步驟中,因於支持膜內存在微粒子等原因,有可能產生空氣之區域、空氣以外之氣體之區域、空腔區域。該區域之折射率不同於其他區域。異常折射率區域等光學異常區域多數情況下存在於微粒子之附近,但未必存在於微粒子之附近。光學異常區域由於折射率等不同於周圍之主區域,故而於利用光學顯微鏡等進行視認時,於光學異常區域與主區域之間光進行散射、折射,故而看起來較明亮等呈現方式不同於主區域。因光學異常區域(尤其是異常折射率區域)之產生原因,光學異常區域不易於支持膜之表面產生,而容易於支持膜之內部產生,故而於本發明中,於支持膜之厚度中心2 μm之區域中測定光學異常區域之面積及微粒子之數量。
Hereinafter, the reason for measuring the area of the optically abnormal region and the number of fine particles in the region of 2 μm in the thickness center of the support film will be described.
The inventors of this article conducted intensive research and found that the main factors of light scattering, diffraction, shading and other optical abnormal areas. In the present invention, the so-called optical anomaly area is an area having different optical properties from the main area of the support film (the resin constituting the support film) (specifically, the reflectivity or refractive index is different from the main area, or optical properties such as scattering and diffraction (Area where the phenomenon occurs more strongly than the main area). The optical anomaly region may include both a light-shielding portion caused by fine particles and an optical anomaly region other than the fine particles (for example, an abnormal refractive index region having a refractive index different from that of the main region of the fine particles and the support film). Examples of optically abnormal regions are regions where the alignment and / or crystallinity is different from the main region of the supporting film, the region of air, the region of gas other than air, the cavity region where almost no gas exists, and so on. For example, in the case of stretching in the manufacturing process of the support film, there may be cases where the extension condition is in a region different from other regions near the particles due to the presence of particles in the support film. This region is different from other regions due to the alignment and / or crystallinity, so the refractive index is different from other regions. In addition, in the manufacturing process of the support film, due to the presence of fine particles in the support film and the like, there may be a region where air is generated, a region other than air, and a cavity region. The refractive index of this area is different from other areas. Optical abnormal regions such as abnormal refractive index regions often exist in the vicinity of fine particles, but they do not necessarily exist in the vicinity of fine particles. The optical anomaly area is different from the surrounding main area due to refractive index, so when visually recognized with an optical microscope, etc., the light is scattered and refracted between the optical anomaly area and the main area, so it looks brighter, etc. region. Due to the generation of optical abnormal regions (especially abnormal refractive index regions), the optical abnormal regions are not easily generated on the surface of the support film, but are easily generated inside the support film. Therefore, in the present invention, the thickness center of the support film is 2 μm The area of the optical abnormal area and the number of fine particles are measured in the area.

作為減少光學異常區域之方法,較有用的是提高微粒子表面對於構成支持膜材料之親和性之方法(例如於支持膜為PET(Polyethylene Terephthalate,聚對苯二甲酸乙二酯)膜之情形時,利用芳香族系聚合物塗覆微粒子表面之方法);於支持膜之雙軸延伸後再次以支持膜之玻璃轉移溫度以上之溫度對膜進行熱壓接處理,使光學異常區域(尤其是異常折射率區域)消失之方法等。於支持膜為PET膜之情形時,熱壓接處理之溫度例如可為約180~250℃。As a method to reduce the optical abnormal area, it is more useful to increase the affinity of the surface of the microparticles to the material constituting the support film (for example, when the support film is a PET (Polyethylene Terephthalate) film, The method of coating the surface of the microparticles with an aromatic polymer); after biaxial extension of the support film, the film is thermocompression-bonded again at a temperature above the glass transition temperature of the support film to cause abnormal optical regions (especially abnormal refraction) Rate area) disappearing method, etc. When the support film is a PET film, the temperature of the thermocompression bonding process may be, for example, about 180 to 250 ° C.

光學異常區域之合計面積之測定方法係如下所述。於落射型雷射顯微鏡(Olympus製造之OLS-4100)之物鏡之上部插入偏光濾光器(OLS4000-QWP)。其次於雷射顯微鏡之載置台上使用多孔質吸附板(Universal Giken製造之65F-HG)及真空泵而水平地吸引固定切斷為30 mm×30 mm之支持膜樣品。利用物鏡50倍之雷射光量60(雷射波長為405 nm)觀測進行了吸引固定之支持膜。此時,將支持膜之厚度方向之中心2 μm之區域規定為測定區域,並於測定區域259 μm×260 μm中以測定部位數200點進行測量(因此,測定區域合計成為0.259 mm×0.26 mm×200=13.5 mm2 )。The method for measuring the total area of the optically abnormal area is as follows. A polarizing filter (OLS4000-QWP) was inserted above the objective lens of an epi-laser microscope (OLS-4100 manufactured by Olympus). Secondly, a porous adsorption plate (65F-HG manufactured by Universal Giken) and a vacuum pump were used on the mounting table of the laser microscope to horizontally attract and fix the support membrane sample cut to 30 mm × 30 mm. The support film was attracted and fixed by observation with an objective lens 50 times the laser light amount 60 (laser wavelength is 405 nm). At this time, the area of 2 μm in the center of the thickness direction of the supporting film was defined as the measurement area, and the measurement area was measured at 200 points in the measurement area 259 μm × 260 μm (therefore, the total measurement area becomes 0.259 mm × 0.26 mm × 200 = 13.5 mm 2 ).

將所測量之圖像內之最大光量之像素與最小光量之像素之光量差分成4096等級(最大光量之值為4095,最小光量之值成為0)。製作將圖像內之像素之光量分佈圖表化而成之直方圖(橫軸:光量之等級(最小值0、最大值4095)、縱軸:像素之個數)。將自所製作之直方圖之存在2個之下擺部之值較大之下擺部之值加上400等級所得之等級設為閾值,將所測量之圖像二值化,對光量大於閾值之像素之面積進行合計,並將該合計面積設為光學異常區域之合計面積。算出光學異常區域之合計面積相對於測量面積之比率。The difference between the light quantity of the maximum light quantity pixel and the minimum light quantity pixel in the measured image is 4096 levels (the maximum light quantity value is 4095, and the minimum light quantity value is 0). Create a histogram that graphs the light intensity distribution of pixels in the image (horizontal axis: light intensity level (minimum value 0, maximum value 4095), vertical axis: number of pixels). Set the value obtained from the existence of the two hem parts of the histogram to be greater than the value of the hem part plus 400 levels as the threshold value, binarize the measured image, and count the pixels whose light intensity is greater than the threshold value The total area is calculated as the total area of the optically abnormal area. Calculate the ratio of the total area of the optical abnormal area to the measurement area.

圖1係對光學異常區域之合計面積之測定方法進行說明之圖。圖1中表示例示之直方圖。直方圖之α、β之點表示於測量畫面內光量α(以最大光量之值為4095,最小光量之值成為0之方式利用4096等級進行標準化)之像素存在β個。將自直方圖較大之下擺部(由於光量0之處亦計數為下擺部,故而存在2個之下擺部之一者成為光量0之處)加上400等級所得之等級設為閾值。若利用閾值將具有閾值以上之光量之像素(典型而言為幾個像素左右而極少)二值化(即,將低於閾值之光量之像素設為黑,將高於閾值之光量之像素設為白),則於黑色之測量畫面之中存在幾個像素之白色之點。該白色之點係與遮光部分即,藉由支持膜內之微粒子或其他光學異常區域(例如異常折射率區域)反射落射型雷射顯微鏡之雷射之部分相對應。將上述測定設為利用Olympus製造之OLS-4100之雷射顯微鏡模式之測定。FIG. 1 is a diagram illustrating a method of measuring the total area of optically abnormal regions. An example histogram is shown in FIG. 1. The points of α and β in the histogram indicate that there are β pixels in the measurement screen where the amount of light α (the value of the maximum light amount is 4095 and the value of the minimum light amount becomes 0 is standardized by the 4096 level). The level obtained by adding 400 levels to the lower hem of the histogram (where the amount of light 0 is also counted as the hem, so one of the two hem portions becomes the position of the amount of light 0) is added to the threshold. If the threshold is used to binarize pixels with a light amount above the threshold (typically a few pixels and few), that is, pixels with a light amount below the threshold are set to black, pixels with a light amount above the threshold are set to Is white), there are a few pixels of white dots in the black measurement frame. The white point corresponds to the light-shielding portion, that is, the portion that reflects the laser light of the epi-type laser microscope by the particles or other optically abnormal regions (such as the abnormal refractive index region) in the supporting film. The above measurement was set to the measurement using the laser microscope mode of OLS-4100 manufactured by Olympus.

其次,微粒子之數量之測定方法係如下所述。
於測定光學異常區域之合計面積後,將落射型雷射顯微鏡(Olympus製造之OLS-4100)切換為光學顯微鏡模式。其後,於測定區域259 μm×260 μm中測定與和藉由目測利用雷射顯微鏡模式確認之遮光部分之位置(即微粒子之位置)相對應之微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子之數量及其直徑。即,利用光學顯微鏡模式藉由目測觀察利用雷射顯微鏡模式計數為白色之點(遮光部分)之部位,確認白色之點是否為與微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子,進而,藉由目測測定其直徑。
以測定部位數200點實施(即,於0.259 mm×0.26 mm×200=13.5 mm2 之面積內實施)同樣之測定,並對微粒子之每一直徑算出其合計數。於微粒子並非完全之球體之情形時,將微粒子之最長之寬度設為該微粒子之直徑。
圖2係對微粒子數之利用雷射顯微鏡模式之測定進行說明之圖,白色之點相當於遮光部分。又,圖3係對微粒子數之利用光學顯微鏡模式之測定進行說明之圖。
暫時設為圖2之白虛線區域之場所與圖3之白虛線區域之場所相對應。於該情形時,於相當於圖2之白虛線區域之區域中存在1個與微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子。於利用雷射顯微鏡模式觀測之白色之點(遮光範圍)所有部位利用光學顯微鏡模式對其進行觀測,並測定與微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子之數量及其直徑。亦存在利用雷射顯微鏡模式觀測之白色之點(遮光範圍)並非與微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子之情形。
Next, the method of measuring the number of fine particles is as follows.
After measuring the total area of the optical abnormal area, the epi-laser microscope (OLS-4100 manufactured by Olympus) was switched to the optical microscope mode. After that, in the measurement area 259 μm × 260 μm, an optical abnormal area (for example, an abnormal refractive index area) other than fine particles corresponding to the position of the light-shielding portion (that is, the position of fine particles) confirmed by the laser microscope mode is measured. ) The number of connected particles and their diameter. That is, using the optical microscope mode, by visually observing the part counted as the white point (light-shielding portion) by the laser microscope mode, it is confirmed whether the white point is in contact with an optical abnormal region (such as an abnormal refractive index region) other than fine particles The microparticles are further measured for their diameter by visual observation.
The measurement was performed at 200 points (ie, within an area of 0.259 mm × 0.26 mm × 200 = 13.5 mm 2 ), and the total number of particles was calculated for each diameter. When the particle is not a complete sphere, the longest width of the particle is set as the diameter of the particle.
Fig. 2 is a diagram for explaining the measurement of the number of fine particles using a laser microscope mode, and the white dot corresponds to the shading part. 3 is a diagram explaining the measurement of the number of fine particles using the optical microscope mode.
The place temporarily set as the white dotted line area of FIG. 2 corresponds to the place of the white dotted line area of FIG. 3. In this case, there is one fine particle that is in contact with an optically abnormal region (such as an abnormal refractive index region) other than fine particles in the region corresponding to the white dotted line region in FIG. 2. Observe all parts of the white point (shading range) observed by the laser microscope mode using the optical microscope mode, and measure the number of fine particles and their contact with the optical abnormal area (such as the abnormal refractive index area) other than the fine particles diameter. There are also cases where the white point (shading range) observed by the laser microscope mode is not in contact with an optically abnormal region (such as an abnormal refractive index region) other than the particles.

若支持膜完全不含微粒子,則於將感光性樹脂積層體捲繞於輥之情形時難以獲得充分之捲取性,故而於本實施形態中,支持膜包含微粒子。微粒子之含量並無特別限制,相對於支持膜,以質量比計,較佳為5~1,000 ppm,更佳為10~800 ppm,尤佳為20~500 ppm。If the support film does not contain fine particles at all, it is difficult to obtain sufficient windability when the photosensitive resin laminate is wound around a roller. Therefore, in this embodiment, the support film contains fine particles. The content of the microparticles is not particularly limited, and it is preferably 5 to 1,000 ppm, more preferably 10 to 800 ppm, more preferably 20 to 500 ppm in terms of mass ratio relative to the support film.

作為支持膜中所含之微粒子,例如存在無機微粒子或有機微粒子,存在潤滑劑、添加劑之凝聚物、混入至原料中之異物、於製造步驟上混入之異物等。作為微粒子之具體例,可列舉:碳酸鈣、磷酸鈣、氧化矽(二氧化矽)、高嶺土、滑石、二氧化鈦、氧化鋁(alumina)、硫酸鋇、氟化鈣、氟化鋰、沸石、硫化鉬等無機粒子、交聯高分子粒子、草酸鈣等有機粒子等。該等可為單獨,亦可為兩種以上之組合。As the fine particles contained in the support film, for example, there are inorganic fine particles or organic fine particles, there are agglomerates of lubricants, additives, foreign substances mixed into the raw materials, foreign substances mixed in the manufacturing process, and the like. Specific examples of fine particles include calcium carbonate, calcium phosphate, silica (silica), kaolin, talc, titanium dioxide, alumina (alumina), barium sulfate, calcium fluoride, lithium fluoride, zeolite, and molybdenum sulfide Inorganic particles such as inorganic particles, cross-linked polymer particles, calcium oxalate, etc. These can be individual or a combination of two or more.

微粒子係根據常法而調配至支持膜中。於製造將遮光部分之合計面積設為特定範圍之支持膜時,例如可列舉利用過濾器(例如2.0 μm以下之網眼之過濾器)對材料樹脂進行過濾等方法。越使過濾器之網眼變細,又,越增加材料樹脂通過過濾器之次數,材料樹脂中之微粒子之數量越少,微粒子之大小越小,遮光部分之合計面積越減小。The microparticles are formulated into the support film according to the usual method. When manufacturing a support film whose total area of the light-shielding portion is within a specific range, for example, a method of filtering a material resin with a filter (for example, a mesh filter of 2.0 μm or less) may be mentioned. The finer the mesh of the filter, and the more the number of times the material resin passes through the filter, the smaller the number of fine particles in the material resin, the smaller the size of the fine particles, and the smaller the total area of the shading part.

就抑制抗蝕劑突起之產生之觀點而言,微粒子之折射率與支持膜之主區域之折射率的折射率差較佳為0.2以下,更佳為0.18以下,更佳為0.15以下,更佳為0.12以下,更佳為0.1以下,更佳為0.08以下,更佳為0.05以下,更佳為0.04以下,更佳為0.03以下,更佳為0.02以下,尤佳為0.01以下。若微粒子與支持膜之折射率差較小,則有光之散射減少之傾向。於本發明中,所謂「支持膜之主區域」係指於支持膜之光學異常區域以外之區域中占支持膜之大部分之區域。由於感光性樹脂積層體用之支持膜之折射率典型而言為1.4~1.7左右,故而作為減小微粒子與支持膜之折射率差之方法,可列舉使用折射率為相同程度者作為微粒子。支持膜之折射率較佳為1.4~1.7,更佳為1.5~1.7。
再者,本案說明書中之折射率係指波長589 nm下之折射率。
From the viewpoint of suppressing the generation of resist protrusions, the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is preferably 0.2 or less, more preferably 0.18 or less, even more preferably 0.15 or less, more preferably It is 0.12 or less, more preferably 0.1 or less, more preferably 0.08 or less, more preferably 0.05 or less, more preferably 0.04 or less, more preferably 0.03 or less, more preferably 0.02 or less, particularly preferably 0.01 or less. If the difference in refractive index between the microparticles and the support film is small, there is a tendency for the scattering of light to decrease. In the present invention, the so-called "main region of the support film" refers to a region that occupies most of the support film in the region other than the optically abnormal region of the support film. Since the refractive index of the support film for the photosensitive resin laminate is typically about 1.4 to 1.7, as a method of reducing the refractive index difference between the microparticles and the support film, those having the same refractive index can be used as the microparticles. The refractive index of the support film is preferably 1.4 to 1.7, more preferably 1.5 to 1.7.
Furthermore, the refractive index in the specification of this case refers to the refractive index at a wavelength of 589 nm.

作為減少支持膜內之微粒子之數量之方法,可例示使用通過了去除微粒子之過濾器之膜材料而製造支持膜之方法等。例如,於欲減少直徑0.5 μm以上之微粒子之數量之情形時,只要使用去除直徑0.5 μm以上之微粒子之過濾器即可。再者,於使用此種過濾器後,其後添加微粒子,藉此可使微粒子之數量增加至所需之範圍內而調整微粒子數。As a method of reducing the number of fine particles in the support membrane, a method of manufacturing a support membrane using a membrane material that has passed through a filter for removing fine particles can be exemplified. For example, when it is desired to reduce the number of particles with a diameter of 0.5 μm or more, it is sufficient to use a filter that removes particles with a diameter of 0.5 μm or more. Furthermore, after using such a filter, particles are added thereafter, thereby increasing the number of particles to a desired range and adjusting the number of particles.

由於光學異常區域係尤其使光進行散射、繞射等之區域,故而若微粒子與微粒子以外之光學異常區域接近地存在,則光之散射變得顯著而欠佳。因此,較佳為減少存在於微粒子以外之光學異常區域(例如異常折射率區域)之附近之微粒子數。Since the optically abnormal region is a region where light is scattered, diffracted, etc., if the microparticles and the optically abnormal regions other than the microparticles are close to each other, the scattering of light becomes significant and poor. Therefore, it is preferable to reduce the number of fine particles existing in the vicinity of optically abnormal regions (for example, abnormal refractive index regions) other than fine particles.

就減少由支持膜中之微粒子所引起之遮光之影響之觀點而言,較佳為具有支持膜之13.5 mm2 之面積中所含之直徑0.5 μm以上之微粒子之中,與具有不同於支持膜之主區域之光學物性(例如折射率)之微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子之數量較佳為成為1500個以下、較佳為成為1200個以下、較佳為成為1000個以下、較佳為成為900個以下、較佳為成為800個以下、較佳為成為700個以下、較佳為成為600個以下、較佳為成為500個以下、較佳為成為400個以下、較佳為成為300個以下、更佳為成為200個以下、更佳為成為100個以下、進而較佳為成為80個以下、進而較佳為成為50個以下、進而較佳為成為30個以下、尤佳為成為10個以下之區域。關於該直徑0.5 μm以上之微粒子之直徑,並無特別之上限,可為10 μm以下,可為8 μm以下,可為5 μm以下,可為4.5 μm以下,可為4 μm以下,可為3.5 μm以下,亦可為3 μm以下。From the viewpoint of reducing the influence of shading caused by the fine particles in the support film, it is preferable that the fine particles with a diameter of 0.5 μm or more contained in the area of 13.5 mm 2 having the support film have a difference from the support film. The number of microparticles in the optical abnormal region (e.g., abnormal refractive index region) other than the microparticles of the main region whose optical properties (e.g. refractive index) are in contact is preferably 1500 or less, preferably 1200 or less, 1000 or less, preferably 900 or less, preferably 800 or less, preferably 700 or less, preferably 600 or less, preferably 500 or less, preferably 400 Or less, preferably 300 or less, more preferably 200 or less, more preferably 100 or less, more preferably 80 or less, further preferably 50 or less, and even more preferably Less than 30, especially good to become less than 10 regions. There is no particular upper limit on the diameter of the particles with a diameter of 0.5 μm or more, which can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, 3.5 less than or equal to 3 μm.

較佳之一態樣提供一種感光性樹脂積層體,其係具備支持膜、與形成於該支持膜上之感光性樹脂組合物層者,且
支持膜包含微粒子,且包含於利用落射型雷射顯微鏡於13.5 mm2 之面積中觀測該支持膜時之光學異常區域之合計面積比率為300 ppm以下之區域,且
支持膜具有該支持膜之13.5 mm2 之面積中所含之直徑0.5 μm以上之微粒子之中,與光學異常區域之微粒子以外之區域相接之微粒子之數量以數量平均計成為1200個以下之區域。
又,於上述態樣之代替或與上述態樣之組合之感光性樹脂積層體中,於直接使用繪圖曝光機於基板上形成線寬/間隙寬為8/8(μm)之抗蝕圖案之情形時,於支持膜之感光性樹脂組合物層側之表面對焦時之線寬、與自該表面沿厚度方向朝400 μm基板內側偏移時之線寬之差為1.8 μm以下。
A preferred aspect provides a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film, and the support film includes fine particles and is included in an epi-type laser microscope The total area ratio of the optically abnormal regions when the support film is observed in an area of 13.5 mm 2 is an area of 300 ppm or less, and the support film has particles with a diameter of 0.5 μm or more contained in the area of 13.5 mm 2 of the support film Among them, the number of fine particles in contact with the area other than the fine particles in the optical abnormal area becomes an area of 1200 or less on average.
In addition, in a photosensitive resin laminate in which the above-mentioned aspect is replaced or combined with the above-mentioned aspect, a resist pattern having a line width / gap width of 8/8 (μm) is formed on the substrate directly using a drawing exposure machine In this case, the difference between the line width when the surface on the photosensitive resin composition layer side of the support film is in focus and the line width when shifted from the surface toward the inside of the substrate of 400 μm in the thickness direction is 1.8 μm or less.

再者,於本發明中,所謂直徑為特定值之微粒子,係指包含直徑為該特定值之一次粒子、與一次粒子之凝聚物之直徑為該特定值之一次粒子凝聚物。再者,於一次粒子並非完全之球體之情形時,將一次粒子之最長之寬度設為該一次粒子之直徑。又,於一次粒子凝聚物並非完全之球體之情形時,將一次粒子凝聚物之最長之寬度設為該一次粒子凝聚物之直徑。例如於直徑0.5 μm以上之微粒子中包含直徑為0.5 μm以上之一次粒子、與為直徑0.5 μm以下之一次粒子之凝聚物且直徑為0.5 μm以上之一次粒子凝聚物。In addition, in the present invention, the fine particles having a specific value of diameter refer to a primary particle agglomerate including primary particles having a specific value of the diameter and an aggregate of primary particles having a specific value of the diameter. Furthermore, when the primary particles are not complete spheres, the longest width of the primary particles is set as the diameter of the primary particles. In addition, when the primary particle aggregate is not a complete sphere, the longest width of the primary particle aggregate is set as the diameter of the primary particle aggregate. For example, fine particles having a diameter of 0.5 μm or more include primary particles having a diameter of 0.5 μm or more, and aggregates of primary particles having a diameter of 0.5 μm or less, and primary particles having a diameter of 0.5 μm or more.

光學異常區域於利用光學顯微鏡模式進行觀測時,由於呈現方法(光之透過、反射)不同於其周圍之主區域,故而可如圖3般利用光學顯微鏡藉由目測觀測微粒子是否與微粒子以外之光學異常區域(例如異常折射率區域)相接。When the optical anomaly area is observed in the optical microscope mode, since the presentation method (transmission and reflection of light) is different from the main area around it, the optical microscope can be used to visually observe whether the microparticles and the optical particles other than the microparticles as shown in FIG. 3 The abnormal regions (for example, the abnormal refractive index regions) are in contact.

再者,於在支持膜中測定微粒子之數量時,若存在具有本實施形態之特定之態樣中所規定之微粒子數之部位,則感光性樹脂積層體包含於該特定之態樣之感光性樹脂積層體中。即,於即便於在某部位進行測定時不滿足規定之微粒子數,亦於在其他部位進行測定時滿足規定之微粒子數之情形時,該感光性樹脂積層體包含於該特定之態樣之感光性樹脂積層體中。In addition, when measuring the number of fine particles in the support film, if there is a part having the number of fine particles specified in the specific aspect of this embodiment, the photosensitive resin laminate is included in the sensitivity of the specific aspect In the resin laminate. That is, even when the specified number of fine particles is not satisfied at the time of measurement at a certain site, and when the specified number of fine particles is satisfied at the time of measurement at another site, the photosensitive resin laminate is included in the photosensitive of the specific aspect Resin laminate.

於較佳之態樣中,支持膜之總面積之中,較佳為5%以上、較佳為10%以上、較佳為20%以上、較佳為30%以上、較佳為50%以上、更佳為60%以上、更佳為70%以上、更佳為80%以上、更佳為90%以上、尤佳為約100%(即實質上整個區域)為於本實施形態之特定之態樣中所規定之特定之光學異常區域、或具有特定之微粒子(遮光面積、直徑及微粒子數)之區域。In a preferred aspect, the total area of the supporting film is preferably 5% or more, preferably 10% or more, preferably 20% or more, preferably 30% or more, preferably 50% or more, More preferably, it is 60% or more, more preferably 70% or more, more preferably 80% or more, more preferably 90% or more, and particularly preferably about 100% (that is, substantially the entire area) is a specific state in this embodiment. Specified optical abnormal area specified in the sample, or area with specific particles (shading area, diameter and number of particles).

就良好地獲得感光性樹脂積層體之輥捲取性之觀點而言,支持膜包含微粒子。又,支持膜可具有13.5 mm2 之面積中所含之直徑0.5 μm以上之微粒子之中,與具有不同於支持膜之主區域之光學物性(例如折射率)之微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子之數量較佳為成為1個以上、更佳為成為3個以上、進而較佳為成為5個以上之區域。關於該直徑0.5 μm以上之微粒子之直徑,並無特別之上限,可為10 μm以下,可為8 μm以下,可為5 μm以下,可為4.5 μm以下,可為4 μm以下,可為3.5 μm以下,亦可為3 μm以下。The support film contains fine particles from the viewpoint of obtaining good rollability of the photosensitive resin laminate. In addition, the support film may have an optical abnormality region (for example, other than particles having an optical property (for example, refractive index) different from the main region of the support film among particles with a diameter of 0.5 μm or more contained in an area of 13.5 mm 2 (for example (Abnormal refractive index region) The number of fine particles in contact is preferably one or more, more preferably three or more, and still more preferably five or more regions. There is no particular upper limit on the diameter of the particles with a diameter of 0.5 μm or more, which can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, 3.5 less than or equal to 3 μm.

於本實施形態中,支持膜可具有13.5 mm2 之面積中所含之直徑1.0 μm以上之微粒子之中,與具有不同於支持膜之主區域之光學物性(例如折射率)之微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子之數量較佳為成為500個以下、更佳為成為400個以下、更佳為成為300個以下、更佳為成為200個以下、進而較佳為成為100個以下、進而較佳為成為80個以下、進而較佳為成為50個以下、進而較佳為成為30個以下、尤佳為成為10個以下之區域。關於該直徑1.0 μm以上之微粒子之直徑,並無特別之上限,可為10 μm以下,可為8 μm以下,可為5 μm以下,可為4.5 μm以下,可為4 μm以下,可為3.5 μm以下,亦可為3 μm以下。In this embodiment, the support film may have optical properties other than the particles having a diameter of 1.0 μm or more contained in an area of 13.5 mm 2 and particles having optical properties (such as refractive index) different from the main region of the support film The number of fine particles in contact with the abnormal region (e.g., abnormal refractive index region) is preferably 500 or less, more preferably 400 or less, more preferably 300 or less, more preferably 200 or less, and more preferably In order to be 100 or less, more preferably 80 or less, still more preferably 50 or less, still more preferably 30 or less, and particularly preferably 10 or less. There is no particular upper limit for the diameter of the fine particles with a diameter of 1.0 μm or more, which can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, 3.5 less than or equal to 3 μm.

就良好地獲得感光性樹脂積層體之輥捲取性之觀點而言,支持膜包含微粒子。又,支持膜可具有13.5 mm2 之面積中所含之直徑1.0 μm以上之微粒子之中,與具有不同於支持膜之主區域之光學物性(例如折射率)之微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子之數量較佳為成為1個以上、更佳為成為3個以上、進而較佳為成為5個以上之區域。關於該直徑1.0 μm以上之微粒子之直徑,並無特別之上限,可為10 μm以下,可為8 μm以下,可為5 μm以下,可為4.5 μm以下,可為4 μm以下,可為3.5 μm以下,亦可為3 μm以下。The support film contains fine particles from the viewpoint of obtaining good rollability of the photosensitive resin laminate. In addition, the support film may have an optical abnormality region (for example, other than particles having an optical property (e.g. refractive index) different from the main region of the support film among particles having a diameter of 1.0 μm or more contained in an area of 13.5 mm 2 (e.g. (Abnormal refractive index region) The number of fine particles in contact is preferably one or more, more preferably three or more, and still more preferably five or more regions. There is no particular upper limit for the diameter of the fine particles with a diameter of 1.0 μm or more, which can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, 3.5 less than or equal to 3 μm.

於本實施形態中,支持膜可具有13.5 mm2 之面積中所含之直徑2.0 μm以上之微粒子之中,與具有不同於支持膜之主區域之光學物性(例如折射率)之微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子之數量以10部位之數量平均計,較佳為成為200個以下、更佳為成為180個以下、更佳為成為150個以下、更佳為成為120個以下、進而較佳為成為100個以下、進而較佳為成為80個以下、進而較佳為成為50個以下、進而較佳為成為30個以下、尤佳為成為10個以下之區域。關於該直徑2.0 μm以上之微粒子之直徑,並無特別之上限,可為10 μm以下,可為8 μm以下,可為5 μm以下,可為4.5 μm以下,可為4 μm以下,可為3.5 μm以下,亦可為3 μm以下。In this embodiment, the support film may have an optical property other than the particles having a diameter of 2.0 μm or more contained in an area of 13.5 mm 2 and particles having optical properties (such as refractive index) different from the main region of the support film The number of fine particles in contact with the abnormal region (for example, the abnormal refractive index region) is averaged at the number of 10 parts, preferably 200 or less, more preferably 180 or less, more preferably 150 or less, more preferably 120 or less, more preferably 100 or less, further preferably 80 or less, still more preferably 50 or less, still more preferably 30 or less, particularly preferably 10 or less . There is no particular upper limit on the diameter of the fine particles with a diameter of 2.0 μm or more, which can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, 3.5 less than or equal to 3 μm.

就良好地獲得感光性樹脂積層體之輥捲取性之觀點而言,支持膜包含微粒子。又,支持膜可具有13.5 mm2 之面積中所含之直徑2.0 μm以上之微粒子之中,與具有不同於支持膜之主區域之光學物性(例如折射率)之微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子之數量較佳為1個以上、更佳為成為3個以上、進而較佳為成為5個以上之區域。關於該直徑2.0 μm以上之微粒子之直徑,並無特別之上限,可為10 μm以下,可為8 μm以下,可為5 μm以下,可為4.5 μm以下,可為4 μm以下,可為3.5 μm以下,亦可為3 μm以下。The support film contains fine particles from the viewpoint of obtaining good rollability of the photosensitive resin laminate. In addition, the support film may have an optical anomaly region (for example, other than particles having an optical property (e.g. refractive index) different from the main region of the support film among particles having a diameter of 2.0 μm or more contained in an area of 13.5 mm 2 (e.g. (Abnormal refractive index region) The number of fine particles in contact is preferably one or more, more preferably three or more, and still more preferably five or more regions. There is no particular upper limit on the diameter of the fine particles with a diameter of 2.0 μm or more, which can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, 3.5 less than or equal to 3 μm.

又,本實施形態提供一種感光性樹脂積層體,其係具備支持膜、與形成於該支持膜上之感光性樹脂組合物層者,且
支持膜包含微粒子,
支持膜具有13.5 mm2 之面積中所含之直徑0.5 μm以上之微粒子之中,與具有不同於支持膜之主區域之光學物性(例如折射率)之微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子之數量以10部位之數量平均計成為1500個以下之區域。與該光學異常區域相接之微粒子之數量以10部位之數量平均計可為1200個以下,可為1000個以下,可為800個以下,可為500個以下,可為300個以下,亦可為100個以下。
於該感光性樹脂積層體中,上述13.5 mm2 之面積中所含之與作為微粒子以外之光學異常區域之異常折射率區域相接,且與支持膜之主區域之折射率差較佳為0.2以下、較佳為0.15以下、較佳為0.10以下、更佳為0.05以下、更佳為0.03以下、更佳為0.02以下、更佳為0.01以下之直徑0.5 μm以上之微粒子之數量可為1個以上,可為10個以上,亦可為50個以上。
與異常折射率區域相接之微粒子之數量較佳為較少,但只要為與支持膜之主區域之折射率差較小之微粒子,則光之散射之不良情況較小。又,微粒子之存在可提供感光性樹脂積層體之滑動性之提高之優點,有助於將感光性樹脂積層體捲繞於輥之情形時之優異之捲取性。
關於該直徑0.5 μm以上之微粒子之直徑,並無特別之上限,可為10 μm以下,可為8 μm以下,可為5 μm以下,可為4.5 μm以下,可為4 μm以下,可為3.5 μm以下,亦可為3 μm以下。
Furthermore, this embodiment provides a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film, and the support film contains fine particles,
The support film has an optical anomaly region (such as an abnormal refractive index) other than the microparticles having a diameter of 0.5 μm or more contained in an area of 13.5 mm 2 other than those having optical properties (such as refractive index) different from the main region of the support film Area) The number of particles in contact with each other becomes an area of 1500 or less based on the average number of 10 parts. The number of fine particles in contact with the optically abnormal region can be 1200 or less, 1000 or less, 800 or less, 500 or less, 300 or less, on the average of 10 parts. Less than 100.
In the photosensitive resin laminate, the area included in the above 13.5 mm 2 area is in contact with the abnormal refractive index region which is an optical abnormal region other than fine particles, and the refractive index difference from the main region of the support film is preferably 0.2 The following, preferably 0.15 or less, preferably 0.10 or less, more preferably 0.05 or less, more preferably 0.03 or less, more preferably 0.02 or less, more preferably 0.01 or less, the number of fine particles of 0.5 μm or more may be one The above may be 10 or more, or 50 or more.
The number of fine particles in contact with the abnormal refractive index region is preferably small, but as long as the fine particles have a small refractive index difference from the main region of the support film, the defect of light scattering is small. In addition, the presence of fine particles provides the advantage of improving the slidability of the photosensitive resin laminate, and contributes to the excellent windability when the photosensitive resin laminate is wound around a roller.
There is no particular upper limit on the diameter of the particles with a diameter of 0.5 μm or more, which can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, 3.5 less than or equal to 3 μm.

又,本實施形態提供一種感光性樹脂積層體,其係具備支持膜、與形成於該支持膜上之感光性樹脂組合物層者,且
支持膜包含微粒子,
支持膜具有13.5 mm2 之面積中所含之直徑1.0 μm以上之微粒子之中,與具有不同於支持膜之主區域之光學物性(例如折射率)之微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子之數量成為500個以下之區域。與該光學異常區域相接之微粒子之數量可為400個以下,可為300個以下,可為250個以下,可為200個以下,可為150個以下,可為100個以下,可為80個以下,可為50個以下,可為30個以下,可為10個以下,亦可為5個以下。
Furthermore, this embodiment provides a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film, and the support film contains fine particles,
The support film has an optical anomaly region (such as an abnormal refractive index) other than microparticles having a diameter of 1.0 μm or more contained in an area of 13.5 mm 2 and an optical property (such as a refractive index) different from the main region of the support film Area) The number of connected particles becomes an area of less than 500. The number of microparticles in contact with the optical anomaly region may be 400 or less, 300 or less, 250 or less, 200 or less, 150 or less, 100 or less, or 80 Less than 50, less than 30, less than 10, or less than 5.

於該感光性樹脂積層體中,上述13.5 mm2 之面積中所含之與作為微粒子以外之光學異常區域之異常折射率區域相接,且與支持膜之主區域之折射率差較佳為0.2以下、較佳為0.15以下、較佳為0.10以下、更佳為0.05以下、更佳為0.03以下、更佳為0.02以下、更佳為0.01以下之直徑1.0 μm以上之微粒子之數量以10部位之數量平均計可為1個以上,可為5個以上,亦可為10個以上。
關於該直徑1.0 μm以上之微粒子之直徑,並無特別之上限,可為10 μm以下,可為8 μm以下,可為5 μm以下,可為4.5 μm以下,可為4 μm以下,可為3.5 μm以下,亦可為3 μm以下。
In the photosensitive resin laminate, the area included in the above 13.5 mm 2 area is in contact with the abnormal refractive index region which is an optical abnormal region other than fine particles, and the refractive index difference from the main region of the support film is preferably 0.2 The following, preferably 0.15 or less, preferably 0.10 or less, more preferably 0.05 or less, more preferably 0.03 or less, more preferably 0.02 or less, more preferably 0.01 or less, and the number of fine particles with a diameter of 1.0 μm or more is 10 The average number can be more than 1, more than 5, or more than 10.
There is no particular upper limit for the diameter of the fine particles with a diameter of 1.0 μm or more, which can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, 3.5 less than or equal to 3 μm.

又,本實施形態提供一種感光性樹脂積層體,其係具備支持膜、與形成於該支持膜上之感光性樹脂組合物層者,且
支持膜包含微粒子,
支持膜具有13.5 mm2 之面積中所含之直徑2.0 μm以上之微粒子之中,與具有不同於支持膜之主區域之光學物性(例如折射率)之微粒子以外之光學異常區域(例如異常折射率區域)相接之微粒子之數量成為200個以下之區域。與該光學異常區域相接之微粒子之數量更佳可為180個以下,更佳可為150個以下,更佳可為120個以下,進而較佳可為100個以下,進而較佳可為80個以下,進而較佳可為50個以下,進而較佳可為30個以下,尤佳可為10個以下。
Furthermore, this embodiment provides a photosensitive resin laminate including a support film and a photosensitive resin composition layer formed on the support film, and the support film contains fine particles,
The support film has an optical anomaly region (such as an abnormal refractive index) other than microparticles having a diameter of 2.0 μm or more contained in an area of 13.5 mm 2 and other than particles having optical properties (such as refractive index) different from the main region of the support film Area) The number of connected particles becomes an area of less than 200. The number of microparticles in contact with the optically abnormal region is more preferably 180 or less, more preferably 150 or less, more preferably 120 or less, further preferably 100 or less, and even more preferably 80 Less than, more preferably 50 or less, still more preferably 30 or less, particularly preferably 10 or less.

於該感光性樹脂積層體中,上述13.5 mm2 之面積中所含之與作為微粒子以外之光學異常區域之異常折射率區域相接,且與支持膜之主區域之折射率差較佳為0.2以下、較佳為0.15以下、較佳為0.10以下、更佳為0.05以下、更佳為0.03以下、更佳為0.02以下、更佳為0.01以下之直徑2.0 μm以上之微粒子之數量以10部位之數量平均計可為1個以上,可為5個以上,亦可為10個以上。
關於該直徑2.0 μm以上之微粒子之直徑,並無特別之上限,可為10 μm以下,可為8 μm以下,可為5 μm以下,可為4.5 μm以下,可為4 μm以下,可為3.5 μm以下,亦可為3 μm以下。
In the photosensitive resin laminate, the area included in the above 13.5 mm 2 area is in contact with the abnormal refractive index region which is an optical abnormal region other than fine particles, and the refractive index difference from the main region of the support film is preferably 0.2 The following, preferably 0.15 or less, preferably 0.10 or less, more preferably 0.05 or less, more preferably 0.03 or less, more preferably 0.02 or less, more preferably 0.01 or less, and the number of fine particles with a diameter of 2.0 μm or more take 10 places The average number can be more than 1, more than 5, or more than 10.
There is no particular upper limit on the diameter of the fine particles with a diameter of 2.0 μm or more, which can be 10 μm or less, 8 μm or less, 5 μm or less, 4.5 μm or less, 4 μm or less, 3.5 less than or equal to 3 μm.

就抑制曝光時之光散射之觀點而言,支持膜較佳為霧度5%以下者,更佳為2%以下,進而較佳為1.5%以下,尤佳為1.0%以下。就同樣之觀點而言,與感光層相接之面之表面粗糙度Ra較佳為30 nm以下,更佳為20 nm以下,尤佳為10 nm以下。From the viewpoint of suppressing light scattering during exposure, the support film is preferably one having a haze of 5% or less, more preferably 2% or less, further preferably 1.5% or less, and particularly preferably 1.0% or less. From the same viewpoint, the surface roughness Ra of the surface in contact with the photosensitive layer is preferably 30 nm or less, more preferably 20 nm or less, and particularly preferably 10 nm or less.

支持膜之厚度越薄越有利於提高圖像形成性及經濟性,但為了維持感光性樹脂積層體之強度,可較佳地使用10 μm~30 μm者。The thinner the thickness of the support film, the better the image formability and economy. However, in order to maintain the strength of the photosensitive resin laminate, 10 μm to 30 μm can be preferably used.

感光性樹脂積層體中所使用之保護層之重要之特性為與感光性樹脂組合物層之密接力充分地小於支持層,可容易地剝離。例如,聚乙烯膜或聚丙烯膜可較佳地用作保護層。又,亦可使用日本專利特開昭59-202457號公報所示出之剝離性優異之膜。保護層之膜厚較佳為10 μm~100 μm,更佳為10 μm~50 μm。An important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesive force with the photosensitive resin composition layer is sufficiently smaller than that of the support layer and can be easily peeled off. For example, polyethylene film or polypropylene film can be preferably used as a protective layer. In addition, a film having excellent peelability as shown in Japanese Patent Laid-Open No. 59-202457 can also be used. The film thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

存在於聚乙烯膜表面存在稱為魚眼之凝膠之情形。於使用具有魚眼之聚乙烯膜作為保護層之情形時,存在該魚眼被轉印至感光性樹脂組合物層之情形。若魚眼被轉印至感光性樹脂組合物層,則存在於層壓時夾帶空氣而成為空隙之情形,而導致抗蝕圖案之缺損。就防止魚眼之觀點而言,作為保護層之材質,較佳為延伸聚丙烯。作為具體例,可列舉王子製紙股份有限公司製造之ALPHAN E-200A。There is a case where a gel called fisheye exists on the surface of the polyethylene film. In the case of using a polyethylene film having a fisheye as a protective layer, the fisheye may be transferred to the photosensitive resin composition layer. If the fish eyes are transferred to the photosensitive resin composition layer, air may be trapped during lamination and become voids, which may cause defects in the resist pattern. From the viewpoint of preventing fish eyes, the material of the protective layer is preferably extended polypropylene. Specific examples include ALPHAN E-200A manufactured by Oji Paper Co., Ltd.

感光性樹脂積層體中之感光性樹脂組合物層之厚度於用途方面雖有所不同,但較佳為1 μm~300 μm,更佳為3 μm~100 μm,尤佳為5 μm~60 μm,最佳為10 μm~30 μm。感光性樹脂組合物層之厚度越薄越提高解像度,又,越厚越提高膜強度。Although the thickness of the photosensitive resin composition layer in the photosensitive resin laminate differs in use, it is preferably 1 μm to 300 μm, more preferably 3 μm to 100 μm, and particularly preferably 5 μm to 60 μm , The best is 10 μm ~ 30 μm. The thinner the thickness of the photosensitive resin composition layer, the higher the resolution, and the thicker the layer, the higher the film strength.

其次,對感光性樹脂積層體之製造方法進行說明。Next, a method of manufacturing the photosensitive resin laminate will be described.

作為依序積層支持膜及感光性樹脂組合物層、以及視需要之保護層而製作感光性樹脂積層體之方法,可採用已知之方法。例如,將感光性樹脂組合物層中所使用之感光性樹脂組合物與溶解其之溶劑混合而製成均勻之溶液,首先使用棒式塗佈機或輥式塗佈機塗佈於支持膜上,繼而進行乾燥而去除上述溶劑,藉此可於支持膜上積層包含感光性樹脂組合物之感光性樹脂組合物層。繼而藉由視需要將保護層層壓於感光性樹脂組合物層上,可製作感光性樹脂積層體。As a method of sequentially laminating the support film, the photosensitive resin composition layer, and the protective layer as needed to produce a photosensitive resin laminate, a known method can be used. For example, the photosensitive resin composition used in the photosensitive resin composition layer and the solvent in which it is dissolved are mixed to make a uniform solution, and firstly applied on the support film using a bar coater or roll coater Then, drying is performed to remove the above-mentioned solvent, whereby the photosensitive resin composition layer containing the photosensitive resin composition can be laminated on the support film. Then, by laminating the protective layer on the photosensitive resin composition layer as necessary, a photosensitive resin laminate can be produced.

[感光性樹脂組合物]
於本實施形態中,感光性樹脂組合物較佳為包含(A)鹼溶性高分子、(B)具有乙烯性不飽和雙鍵之化合物、及(C)光聚合起始劑。感光性樹脂組合物以該感光性樹脂組合物之全部固形物成分質量基準計,較佳為包含(A)鹼溶性高分子:10質量%~90質量%;(B)具有乙烯性不飽和雙鍵之化合物:5質量%~70質量%;及(C)光聚合起始劑:0.01質量%~20質量%。以下,依序說明各成分。
[Photosensitive resin composition]
In the present embodiment, the photosensitive resin composition preferably contains (A) an alkali-soluble polymer, (B) a compound having an ethylenically unsaturated double bond, and (C) a photopolymerization initiator. The photosensitive resin composition preferably contains (A) alkali-soluble polymer: 10% by mass to 90% by mass based on the mass basis of the total solid content of the photosensitive resin composition; (B) has an ethylenically unsaturated double Bond compound: 5 mass% to 70 mass%; and (C) photopolymerization initiator: 0.01 mass% to 20 mass%. Hereinafter, each component will be described in order.

<(A)鹼溶性高分子>
於本發明中,(A)鹼溶性高分子包含容易溶於鹼性物質中之高分子。更具體而言,(A)鹼溶性高分子中所含之羧基之量以酸當量計為100~600,較佳為250~450。所謂酸當量係指於其分子中具有1當量之羧基之聚合物之質量(單位:克)。(A)鹼溶性高分子中之羧基係為了對感光性樹脂組合物層賦予對於鹼性水溶液之顯影性及剝離性所必需。就提高耐顯影性、解像性、及密接性之觀點而言,較佳為將酸當量設為100以上。並且,更佳為將酸當量設為250以上。另一方面,就提高顯影性及剝離性之觀點而言,較佳為將酸當量設為600以下。並且,更佳為將酸當量設為450以下。於本發明中,酸當量係使用電位差滴定裝置,並藉由在0.1 mol/L之NaOH水溶液中進行滴定之電位差滴定法而測定之值。
<(A) Alkali-soluble polymer>
In the present invention, (A) the alkali-soluble polymer includes a polymer that is easily soluble in an alkaline substance. More specifically, the amount of carboxyl groups contained in (A) the alkali-soluble polymer is 100 to 600, preferably 250 to 450 in terms of acid equivalent. The acid equivalent refers to the mass (unit: gram) of a polymer having 1 equivalent of carboxyl groups in its molecule. (A) The carboxyl group in the alkali-soluble polymer is necessary for imparting developability and peelability to the alkaline aqueous solution to the photosensitive resin composition layer. From the viewpoint of improving development resistance, resolution, and adhesion, it is preferable to set the acid equivalent to 100 or more. Furthermore, it is more preferable to set the acid equivalent to 250 or more. On the other hand, from the viewpoint of improving developability and peelability, it is preferable to set the acid equivalent to 600 or less. Furthermore, it is more preferable to set the acid equivalent to 450 or less. In the present invention, the acid equivalent is a value measured by a potentiometric titration device and a potentiometric titration method performed in a 0.1 mol / L NaOH aqueous solution.

(A)鹼溶性高分子之重量平均分子量較佳為5,000~500,000。就提高解像性及顯影性之觀點而言,較佳為將重量平均分子量設為500,000以下。更佳為將重量平均分子量設為100,000以下,進而較佳為設為60,000以下,尤佳為設為50,000以下。另一方面,就控制顯影凝聚物之性狀、以及製成感光性樹脂積層體之情形時之邊緣熔融性及切屑性等未曝光膜之性狀之觀點而言,較佳為將重量平均分子量設為5,000以上。更佳為將重量平均分子量設為10,000以上,進而較佳為設為20,000以上。所謂邊緣熔融性,係指於製成感光性樹脂積層體並捲取為卷狀之情形時,感光性樹脂組合物層(即包含感光性樹脂組合物之層)自卷之端面之溢出容易性之程度。所謂切屑性,於利用切割器切斷未曝光膜之情形時,係指切屑之容易飛散程度。若該切屑附著於感光性樹脂積層體之上表面等,則於其後之曝光步驟等中轉印至遮罩,而導致不良品。(A)鹼溶性高分子之分散度較佳為1.0~6.0,更佳為1.0~5.0,進而較佳為1.0~4.0,進而較佳為1.0~3.0。(A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. From the viewpoint of improving resolution and developability, the weight average molecular weight is preferably 500,000 or less. More preferably, the weight average molecular weight is 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developing agglomerate and the properties of the unexposed film such as edge meltability and chipping properties when made into a photosensitive resin laminate, the weight average molecular weight is preferably set to Above 5,000. More preferably, the weight average molecular weight is 10,000 or more, and further preferably 20,000 or more. The edge melting property refers to the ease of overflow of the photosensitive resin composition layer (that is, the layer containing the photosensitive resin composition) from the end surface of the roll when the photosensitive resin laminate is formed and wound into a roll shape Degree. The so-called chipping property refers to the degree of easy flying of chips when the unexposed film is cut by a cutter. If the swarf adheres to the upper surface of the photosensitive resin laminate or the like, it is transferred to the mask in the subsequent exposure step and the like, resulting in defective products. (A) The degree of dispersion of the alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, still more preferably 1.0 to 4.0, further preferably 1.0 to 3.0.

於本實施形態中,關於感光性樹脂組合物,就抑制曝光時之焦點位置偏移時之線寬變粗或解像度之惡化之觀點而言,較佳為包含具有芳香族烴基之單體成分作為(A)鹼溶性高分子者。再者,作為此種芳香族烴基,例如可列舉經取代或未經取代之苯基、或經取代或未經取代之芳烷基。關於該(A)鹼溶性高分子中之具有芳香族烴基之單體成分之含有比率,將全部單體成分之合計質量作為基準,較佳為20質量%以上,更佳為40質量%以上,進而較佳為50質量%以上,尤佳為55質量%以上,最佳為60質量%以上。作為上限,並無特別限定,較佳為95質量%以下,更佳為80質量%以下。再者,含有複數種(A)鹼溶性高分子之情形時之具有芳香族烴基之單體成分之含有比率係以重量平均值之形式求出。In the present embodiment, regarding the photosensitive resin composition, it is preferable that the monomer component having an aromatic hydrocarbon group be included as the monomer component having an aromatic hydrocarbon group from the viewpoint of suppressing the thickening of the line width when the focal position shifts during exposure or the deterioration of the resolution (A) Those with alkali-soluble polymers. In addition, examples of such an aromatic hydrocarbon group include substituted or unsubstituted phenyl, and substituted or unsubstituted aralkyl. Regarding the content ratio of the monomer component having an aromatic hydrocarbon group in the (A) alkali-soluble polymer, based on the total mass of all monomer components as a reference, it is preferably 20% by mass or more, and more preferably 40% by mass or more, Furthermore, it is preferably 50% by mass or more, particularly preferably 55% by mass or more, and most preferably 60% by mass or more. The upper limit is not particularly limited, but is preferably 95% by mass or less, and more preferably 80% by mass or less. In addition, when a plurality of (A) alkali-soluble polymers are contained, the content ratio of the monomer component having an aromatic hydrocarbon group is obtained as a weight average value.

作為上述具有芳香族烴基之單體,例如可列舉:具有芳烷基之單體、苯乙烯、及可聚合之苯乙烯衍生物(例如甲基苯乙烯、乙烯基甲苯、第三丁氧基苯乙烯、乙醯氧基苯乙烯、4-乙烯基苯甲酸、苯乙烯二聚物、苯乙烯三聚物等)。其中,較佳為具有芳烷基之單體、或苯乙烯。Examples of the monomer having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives (such as methylstyrene, vinyltoluene, and third butoxybenzene) Ethylene, ethoxylated styrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.). Among them, a monomer having an aralkyl group or styrene is preferred.

作為芳烷基,可列舉經取代或未經取代之苯基烷基(苄基除外)、或經取代或未經取代之苄基等,較佳為經取代或未經取代之苄基。Examples of the aralkyl group include substituted or unsubstituted phenylalkyl (except benzyl), substituted or unsubstituted benzyl, and the like, and preferably substituted or unsubstituted benzyl.

作為具有苯基烷基之共聚單體,可列舉(甲基)丙烯酸苯基乙酯等。Examples of the comonomer having a phenylalkyl group include phenylethyl (meth) acrylate.

作為具有苄基之共聚單體,可列舉:具有苄基之(甲基)丙烯酸酯例如(甲基)丙烯酸苄酯、(甲基)丙烯酸氯代苄酯等;具有苄基之乙烯基單體例如乙烯基苄基氯、乙烯基苄醇等。其中較佳為(甲基)丙烯酸苄酯。Examples of the comonomer having a benzyl group include (meth) acrylates having a benzyl group such as benzyl (meth) acrylate and chlorobenzyl (meth) acrylate; vinyl monomers having a benzyl group; For example, vinyl benzyl chloride, vinyl benzyl alcohol, etc. Among them, benzyl (meth) acrylate is preferred.

含有具有芳香族烴基之單體成分之(A)鹼溶性高分子較佳為使藉由使具有芳香族烴基之單體、與下述第一單體之至少1種及/或下述第二單體之至少1種進行聚合而獲得。The (A) alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group is preferably such that the monomer having an aromatic hydrocarbon group and at least one of the following first monomers and / or the following second monomers At least one monomer is obtained by polymerization.

不含具有芳香族烴基之單體成分之(A)鹼溶性高分子較佳為藉由使下述第一單體之至少1種進行聚合而獲得,更佳為藉由使第一單體之至少1種與下述第二單體之至少1種進行共聚而獲得。The (A) alkali-soluble polymer that does not contain a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one of the following first monomers, more preferably by using It is obtained by copolymerizing at least one type with at least one of the following second monomers.

第一單體係於分子中具有羧基之單體。作為第一單體,例如可列舉:(甲基)丙烯酸、反丁烯二酸、肉桂酸、丁烯酸、伊康酸、4-乙烯苯甲酸、順丁烯二酸酐、順丁烯二酸半酯等。該等之中,較佳為(甲基)丙烯酸。The first monomer has a carboxyl group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, maleic acid Half ester etc. Among these, (meth) acrylic acid is preferable.

再者,於本說明書中,所謂「(甲基)丙烯酸」係指丙烯酸或甲基丙烯酸,所謂「(甲基)丙烯醯基」係指丙烯醯基或甲基丙烯醯基,且所謂「(甲基)丙烯酸酯」係指「丙烯酸酯」或「甲基丙烯酸酯」。In addition, in this specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid, and "" (meth) acryl acetyl "means propylene acetyl or methacryl acetyl, and" ( "Meth) acrylate" means "acrylate" or "methacrylate".

關於第一單體之共聚比率,將全部單體成分之合計質量作為基準,較佳為10~50質量%。就表現出良好之顯影性之觀點、控制邊緣熔融性等觀點而言,較佳為將該共聚比率設為10質量%以上,更佳為15質量%以上,進而較佳為20質量%以上。就抗蝕圖案之高解像性及下擺部形狀之觀點而言,進而就抗蝕圖案之耐化學品性之觀點而言,較佳為將該共聚比率設為50質量%以下,於該等觀點中,更佳為35質量%以下,進而較佳為30質量%以下,尤佳為27質量%以下。The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components. From the viewpoint of showing good developability and controlling the edge meltability, the copolymerization ratio is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. From the viewpoint of the high resolution of the resist pattern and the shape of the hem portion, and further from the viewpoint of the chemical resistance of the resist pattern, it is preferable to set the copolymerization ratio to 50% by mass or less. From a viewpoint, it is more preferably 35% by mass or less, further preferably 30% by mass or less, and particularly preferably 27% by mass or less.

第二單體係為非酸性,且於分子中具有至少1個聚合性不飽和基之單體。作為第二單體,例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯等(甲基)丙烯酸酯類;乙酸乙烯酯等乙烯醇之酯類;以及(甲基)丙烯腈等。其中,較佳為(甲基)丙烯酸甲酯、(甲基)丙烯酸2-乙基己酯、及(甲基)丙烯酸正丁酯。The second monomer system is a non-acidic monomer with at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (meth) acrylic acid. Butyl ester, isobutyl (meth) acrylate, third butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid ring (Meth) acrylates such as hexyl ester and 2-ethylhexyl (meth) acrylate; vinyl alcohol esters such as vinyl acetate; and (meth) acrylonitrile. Among them, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate are preferred.

就抑制曝光時之焦點位置偏移時之線寬變粗或解像度之惡化之觀點而言,較佳為含有具有芳烷基之單體、及/或苯乙烯作為單體。例如,較佳為包含甲基丙烯酸、甲基丙烯酸苄酯及苯乙烯之共聚物、包含甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸苄酯及苯乙烯之共聚物等。From the viewpoint of suppressing the thickening of the line width or the deterioration of the resolution when the focal position shifts during exposure, it is preferable to contain a monomer having an aralkyl group and / or styrene as the monomer. For example, a copolymer containing methacrylic acid, benzyl methacrylate, and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene, etc. are preferable.

(A)鹼溶性高分子可單獨使用一種,或亦可混合兩種以上而使用。於混合兩種以上而使用之情形時,較佳為混合兩種包含具有芳香族烴基之單體成分之鹼溶性高分子而使用,或混合包含具有芳香族烴基之單體成分之鹼溶性高分子、與不含具有芳香族烴基之單體成分之鹼溶性高分子而使用。於後者之情形時,包含具有芳香族烴基之單體成分之鹼溶性高分子之使用比率相對於(A)鹼溶性高分子之全部,較佳為50質量%以上,更佳為70質量%以上,較佳為80質量%以上,更佳為90質量%以上。(A) The alkali-soluble polymer may be used alone or in combination of two or more. In the case of mixing two or more kinds, it is preferable to mix and use two types of alkali-soluble polymers containing a monomer component having an aromatic hydrocarbon group, or to mix an alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group , Used with alkali-soluble polymers that do not contain monomer components with aromatic hydrocarbon groups. In the latter case, the use ratio of the alkali-soluble polymer containing the monomer component having an aromatic hydrocarbon group is preferably 50% by mass or more, and more preferably 70% by mass or more with respect to the total of (A) the alkali-soluble polymer. It is preferably 80% by mass or more, and more preferably 90% by mass or more.

(A)鹼溶性高分子之合成較佳為藉由如下方法而進行:向利用丙酮、甲基乙基酮、異丙醇等溶劑稀釋上述中所說明之單數或複數種單體所得之溶液中,適量添加過氧化苯甲醯、偶氮異丁腈等自由基聚合起始劑,並進行加熱攪拌。亦存在一面將混合物之一部分滴加至反應液中,一面進行合成之情形。反應結束後,亦存在進而添加溶劑而調整為所需之濃度之情形。作為合成方法,除溶液聚合以外,亦可使用塊狀聚合、懸浮聚合、或乳化聚合。(A) The synthesis of the alkali-soluble polymer is preferably carried out by a method of diluting the singular or plural monomers described above with a solvent such as acetone, methyl ethyl ketone, isopropyl alcohol, etc. , Add appropriate amount of radical polymerization initiators such as benzoyl peroxide, azoisobutyronitrile, and heat and stir. There is also a case where a part of the mixture is added dropwise to the reaction solution to synthesize. After the reaction is completed, a solvent may be further added to adjust to a desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization can also be used.

(A)鹼溶性高分子之玻璃轉移溫度Tg之重量平均值Tgtotal 較佳為30℃以上且135℃以下。Tgtotal 係藉由下述實施例中所記載之方法而算出。於感光性樹脂組合物中,藉由使用具有135℃以下之Tgtotal 之(A)鹼溶性高分子,可抑制曝光時之焦點位置偏移時之線寬變粗或解像度之惡化。就該觀點而言,(A)鹼溶性高分子之Tgtotal 更佳為120℃以下,進而較佳為115℃以下,更佳為110℃以下,進而較佳為105℃以下,尤佳為110℃以下。又,就提高耐邊緣熔融性之觀點而言,較佳為使用具有30℃以上之Tgtotal 之(A)鹼溶性高分子。就該觀點而言,(A)鹼溶性高分子之Tgtotal 更佳為40℃以上,進而較佳為50℃以上,尤佳為60℃以上。(A) The weight average Tg total of the glass transition temperature Tg of the alkali-soluble polymer is preferably 30 ° C or more and 135 ° C or less. Tg total is calculated by the method described in the following examples. In the photosensitive resin composition, by using the (A) alkali-soluble polymer having a Tg total of 135 ° C. or less, it is possible to suppress the line width from becoming thicker or the resolution from deteriorating when the focal position shifts during exposure. From this point of view, (A) the Tg total of the alkali-soluble polymer is more preferably 120 ° C. or lower, further preferably 115 ° C. or lower, more preferably 110 ° C. or lower, still more preferably 105 ° C. or lower, particularly preferably 110 Below ℃. In addition, from the viewpoint of improving the edge melting resistance, it is preferable to use an (A) alkali-soluble polymer having a Tg total of 30 ° C. or higher. From this point of view, (A) the Tg total of the alkali-soluble polymer is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, and particularly preferably 60 ° C. or higher.

(A)鹼溶性高分子相對於感光性樹脂組合物之全部固形物成分質量之比率較佳為10質量%~90質量%之範圍,更佳為30質量%~70質量%,進而較佳為40質量%~60質量%。就控制顯影時間之觀點而言,較佳為將(A)鹼溶性高分子相對於感光性樹脂組合物之比率設為90質量%以下。另一方面,就提高耐邊緣熔融性之觀點而言,較佳為將(A)鹼溶性高分子相對於感光性樹脂組合物之比率設為10質量%以上。(A) The ratio of the alkali-soluble polymer to the total solid content of the photosensitive resin composition is preferably in the range of 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, and further preferably 40% by mass to 60% by mass. From the viewpoint of controlling the development time, it is preferable to set the ratio of (A) alkali-soluble polymer to the photosensitive resin composition to 90% by mass or less. On the other hand, from the viewpoint of improving the edge melting resistance, it is preferable to set the ratio of (A) alkali-soluble polymer to the photosensitive resin composition to 10% by mass or more.

<(B)具有乙烯性不飽和雙鍵之化合物>
(B)具有乙烯性不飽和雙鍵之化合物就硬化性及與(A)鹼溶性高分子之相溶性之觀點而言,較佳為包含於分子內具有(甲基)丙烯醯基之化合物。(B)化合物中之(甲基)丙烯醯基之數量只要為1個以上即可。
< (B) Compounds with ethylenically unsaturated double bonds >
(B) The compound having an ethylenically unsaturated double bond is preferably a compound having a (meth) acryloyl group contained in the molecule from the viewpoint of curability and compatibility with (A) an alkali-soluble polymer. (B) The number of (meth) acryloyl groups in the compound may be one or more.

作為具有1個(甲基)丙烯醯基之(B)化合物,例如可列舉:於聚環氧烷之一末端加成(甲基)丙烯酸而成之化合物;或於聚環氧烷之一末端加成(甲基)丙烯酸,且使另一末端烷基醚化或烯丙基醚化而成之化合物;鄰苯二甲酸系化合物等,就剝離性或硬化膜柔軟性之觀點而言較佳。Examples of the (B) compound having one (meth) acryloyl group include: a compound obtained by adding (meth) acrylic acid to one end of polyalkylene oxide; or one end of one polyalkylene oxide A compound obtained by adding (meth) acrylic acid and alkylating or alkylating the other terminal; a phthalic acid-based compound, etc. is preferred from the viewpoint of releasability or flexibility of the cured film .

作為此種化合物,例如可列舉:
作為於苯基上加成聚乙二醇而成之化合物之(甲基)丙烯酸酯之苯氧基六乙二醇單(甲基)丙烯酸酯、
作為將加成有平均2莫耳之環氧丙烷之聚丙二醇、與加成有平均7莫耳之環氧乙烷之聚乙二醇加成於壬基苯酚上而成之化合物之(甲基)丙烯酸酯之4-正壬基苯氧基七乙二醇二丙二醇(甲基)丙烯酸酯、
作為將加成有平均1莫耳之環氧丙烷之聚丙二醇、與加成有平均5莫耳之環氧乙烷之聚乙二醇加成於壬基苯酚上而成之化合物之(甲基)丙烯酸酯之4-正壬基苯氧基五乙二醇單丙二醇(甲基)丙烯酸酯、
作為將加成有平均8莫耳之環氧乙烷之聚乙二醇加成於壬基苯酚上而成之化合物之丙烯酸酯之4-正壬基苯氧基八乙二醇(甲基)丙烯酸酯(例如東亞合成股份有限公司製造,M-114)等。
Examples of such compounds include:
Phenoxyhexaethylene glycol mono (meth) acrylate as a (meth) acrylate of a compound formed by adding polyethylene glycol to phenyl,
As a compound obtained by adding polypropylene glycol added with an average of 2 moles of propylene oxide to polyethylene glycol added with an average of 7 moles of ethylene oxide to nonylphenol (methyl ) Acrylate 4-n-nonylphenoxy heptaethylene glycol dipropylene glycol (meth) acrylate,
As a compound obtained by adding polypropylene glycol added with an average of 1 mole of propylene oxide and polyethylene glycol added with an average of 5 moles of ethylene oxide to nonylphenol (methyl ) Acrylate 4-n-nonylphenoxypentaethylene glycol monopropylene glycol (meth) acrylate,
4-n-nonylphenoxy octaethylene glycol (methyl) as an acrylate of a compound obtained by adding polyethylene glycol added with an average of 8 moles of ethylene oxide to nonylphenol Acrylic ester (for example, M-114 manufactured by East Asia Synthetic Co., Ltd.), etc.

又,若包含γ-氯-β-羥丙基-β'-甲基丙烯醯氧乙基-鄰苯二甲酸酯,則除上述觀點以外,就感度、解像性、密接性之觀點而言亦較佳。In addition, if γ-chloro-β-hydroxypropyl-β'-methacryloxyethyl-phthalate is included, in addition to the above viewpoints, from the viewpoint of sensitivity, resolution, and adhesion Words are also better.

作為於分子內具有2個(甲基)丙烯醯基之化合物,例如可列舉:於環氧烷鏈之兩末端具有(甲基)丙烯醯基之化合物、或於環氧乙烷鏈與環氧丙烷鏈藉由無規或嵌段鍵結而成之環氧烷鏈之兩末端具有(甲基)丙烯醯基之化合物等。Examples of the compound having two (meth) acryloyl groups in the molecule include compounds having (meth) acryloyl groups at both ends of the alkylene oxide chain, or ethylene oxide chains and epoxy Compounds having (meth) acryloyl groups at both ends of the alkylene oxide chain formed by random or block bonding of the propane chain.

作為此種化合物,例如除四乙二醇二(甲基)丙烯酸酯、五乙二醇二(甲基)丙烯酸酯、六乙二醇二(甲基)丙烯酸酯、七乙二醇二(甲基)丙烯酸酯、八乙二醇二(甲基)丙烯酸酯、九乙二醇二(甲基)丙烯酸酯、十乙二醇二(甲基)丙烯酸酯、於12莫耳之環氧乙烷鏈之兩末端具有(甲基)丙烯醯基之化合物等聚乙二醇(甲基)丙烯酸酯等以外,可列舉聚丙二醇二(甲基)丙烯酸酯、聚丁二醇二(甲基)丙烯酸酯等。作為於化合物中包含環氧乙烷基與環氧丙烷基之聚環氧烷二(甲基)丙烯酸酯化合物,例如可列舉:於加成有平均12莫耳之環氧丙烷之聚丙二醇之兩末端分別進而加成平均3莫耳之環氧乙烷而成之二醇之二甲基丙烯酸酯、於加成有平均18莫耳之環氧丙烷之聚丙二醇之兩末端分別進而加成平均15莫耳之環氧乙烷而成之二醇之二甲基丙烯酸酯、FA-023M、FA-024M、FA-027M(製品名,日立化成工業製造)等。該等就柔軟性、解像性、密接性等觀點而言較佳。Examples of such compounds include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, and heptaethylene glycol di (meth) acrylate. Base) acrylate, octaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, ethylene oxide in 12 moles In addition to polyethylene glycol (meth) acrylates such as compounds having (meth) acryloyl groups at both ends of the chain, polypropylene glycol di (meth) acrylate and polybutylene glycol di (meth) acrylic acid can be cited. Ester etc. Examples of the polyalkylene oxide di (meth) acrylate compound containing ethylene oxide and propylene oxide in the compound include two of polypropylene glycols added with an average of 12 moles of propylene oxide. Dimethacrylates of diols added with an average of 3 moles of ethylene oxide at the ends, and an average of 15 at both ends of polypropylene glycol added with an average of 18 moles of propylene oxide Dimethacrylate of diol made from mole ethylene oxide, FA-023M, FA-024M, FA-027M (product name, manufactured by Hitachi Chemical Industry), etc. These are preferable from the viewpoints of flexibility, resolution, and adhesion.

作為於分子內具有2個(甲基)丙烯醯基之化合物之另一例,就解像性及密接性之觀點而言,較佳為藉由對雙酚A進行環氧烷改性而於兩末端具有(甲基)丙烯醯基之化合物。
具體而言,可使用下述通式(I):
As another example of a compound having two (meth) acryloyl groups in the molecule, from the viewpoint of resolution and adhesion, it is preferable to modify the bisphenol A by alkylene oxide A compound having a (meth) acryloyl group at the end.
Specifically, the following general formula (I) can be used:

[化1]

{式中,R1 及R2 分別獨立地表示氫原子或甲基,A為C2 H4 ,B為C3 H6 ,n1及n3分別獨立地為1~39之整數,且n1+n3為2~40之整數,n2及n4分別獨立地為0~29之整數,且n2+n4為0~30之整數,-(A-O)-及-(B-O)-之重複單元之排列可為無規亦可為嵌段。並且,於嵌段之情形時,-(A-O)-與-(B-O)-中之任一者可為雙苯基側}
所表示之化合物。
[Chem 1]

{In the formula, R 1 and R 2 independently represent a hydrogen atom or a methyl group, A is C 2 H 4 , B is C 3 H 6 , n1 and n3 are each independently an integer from 1 to 39, and n1 + n3 is 2 Integer of ~ 40, n2 and n4 are independently integers of 0-29, and n2 + n4 are integers of 0-30, the arrangement of the repeating units of-(AO)-and-(BO)-may be random or Block. Moreover, in the case of a block, any of-(AO)-and-(BO)-may be a bisphenyl side}
The compound represented.

例如,就解像性、密接性之方面而言,較佳為於雙酚A之兩端分別加成有平均各5莫耳之環氧乙烷之聚乙二醇之二甲基丙烯酸酯、於雙酚A之兩端分別加成有平均各2莫耳之環氧乙烷之聚乙二醇之二甲基丙烯酸酯、於雙酚A之兩端分別加成有平均各1莫耳之環氧乙烷之聚乙二醇之二甲基丙烯酸酯。For example, in terms of resolution and adhesion, it is preferable to add polyethylene glycol dimethacrylate with an average of 5 moles of ethylene oxide to both ends of bisphenol A, Dimethacrylate of polyethylene glycol with an average of 2 moles of ethylene oxide added to both ends of bisphenol A, respectively, with an average of 1 mole of each added to both ends of bisphenol A Dimethacrylate of polyethylene glycol of ethylene oxide.

又,上述通式(I)中之芳香環可使用具有雜原子及/或取代基之化合物。In addition, as the aromatic ring in the general formula (I), a compound having a hetero atom and / or a substituent can be used.

作為雜原子,例如可列舉鹵素原子等,並且作為取代基,可列舉:碳數1~20之烷基、碳數3~10之環烷基、碳數6~18之芳基、苯甲醯甲基、胺基、碳數1~10之烷基胺基、碳數2~20之二烷基胺基、硝基、氰基、羰基、巰基、碳數1~10之烷基巰基、芳基、羥基、碳數1~20之羥基烷基、羧基、烷基之碳數為1~10之羧基烷基、烷基之碳數為1~10之醯基、碳數1~20之烷氧基、碳數1~20之烷氧基羰基、碳數2~10之烷基羰基、碳數2~10之烯基、碳數2~10之N-烷基胺甲醯基或包含雜環之基、或經該等取代基取代之芳基等。該等取代基可形成縮合環,或該等取代基中之氫原子可經鹵素原子等雜原子取代。於通式(I)中之芳香環具有複數個取代基之情形時,複數個取代基可相同亦可不同。Examples of the hetero atom include a halogen atom and the like, and examples of the substituent include a C 1-20 alkyl group, a C 3-10 cycloalkyl group, a C 6-18 aryl group, and benzoyl Methyl group, amino group, C1-C10 alkylamine group, C2-C20 dialkylamine group, nitro group, cyano group, carbonyl group, mercapto group, C1-C10 alkyl mercapto group, aromatic Group, hydroxyl group, hydroxyalkyl group having 1-20 carbon atoms, carboxyl group, carboxyalkyl group having 1-10 carbon atoms, alkyl group having 1-10 carbon atoms, alkyl group having 1-20 carbon atoms Oxygen group, alkoxycarbonyl group having 1 to 20 carbon atoms, alkylcarbonyl group having 2 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, N-alkylamine carboxamide group having 2 to 10 carbon atoms or containing hetero group Ring groups, or aryl groups substituted with these substituents, etc. These substituents may form a condensed ring, or the hydrogen atoms in these substituents may be substituted with hetero atoms such as halogen atoms. In the case where the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

作為於分子內具有3個以上(甲基)丙烯醯基之化合物,可藉由將具有3莫耳以上之分子內可加成環氧烷基之基作為中心骨架,並將於其上加成伸乙氧基、伸丙氧基、伸丁氧基等伸烷氧基所獲得之醇製成(甲基)丙烯酸酯而獲得。於該情形時,作為可成為中心骨架之化合物,例如可列舉:甘油、三羥甲基丙烷、季戊四醇、二季戊四醇、異氰尿酸酯環等。作為該等化合物,例如可列舉:三(甲基)丙烯酸酯例如乙氧基化甘油三(甲基)丙烯酸酯、乙氧基化異三聚氰酸三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯(例如,就柔軟性、密接性、滲出抑制之觀點而言,較佳為於三羥甲基丙烷上加成平均21莫耳之環氧乙烷而成之三甲基丙烯酸酯、於三羥甲基丙烷上加成平均30莫耳之環氧乙烷而成之三甲基丙烯酸酯)等;四(甲基)丙烯酸酯例如二-三羥甲基丙烷四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯等;五(甲基)丙烯酸酯例如二季戊四醇五(甲基)丙烯酸酯等;六(甲基)丙烯酸酯例如二季戊四醇六(甲基)丙烯酸酯等。就解像性、密接性、抗蝕劑下擺部形狀之觀點而言,較佳為具有3個以上(甲基)丙烯醯基之化合物,若為具有3個以上甲基丙烯醯基之化合物則更佳。As a compound having 3 or more (meth) acryloyl acetyl groups in the molecule, a group having 3 or more moles of an alkylene oxide group as the central skeleton can be added to the compound Alcohols obtained from alkoxy groups such as ethoxylated, propoxylated, butoxylated, etc. are obtained as (meth) acrylates. In this case, examples of the compound that can become the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate ring. Examples of such compounds include tri (meth) acrylates such as ethoxylated glycerin tri (meth) acrylate, ethoxylated isocyanurate tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. Methacrylic acid ester, trimethylolpropane tri (meth) acrylate (for example, from the viewpoint of flexibility, adhesion, and bleed suppression, it is preferable to add an average of 21 mol to trimethylolpropane Trimethacrylate made from ethylene oxide in the ear, trimethacrylate made by adding an average of 30 moles of ethylene oxide to trimethylolpropane), etc .; tetra (meth) acrylic acid Esters such as di-trimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, etc .; penta (meth) acrylates such as dipentaerythritol penta (meth) Group) acrylate and the like; hexa (meth) acrylates such as dipentaerythritol hexa (meth) acrylate and the like. From the viewpoint of resolution, adhesion, and the shape of the resist hem, a compound having 3 or more (meth) acryloyl groups is preferred, and a compound having 3 or more methacryloyl groups Better.

作為四(甲基)丙烯酸酯,較佳為季戊四醇四(甲基)丙烯酸酯。季戊四醇四(甲基)丙烯酸酯可為於季戊四醇之4個末端加成有合計1~40莫耳之環氧基之四(甲基)丙烯酸酯等。As tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate is preferred. The pentaerythritol tetra (meth) acrylate may be a tetra (meth) acrylate having an epoxy group added to the four ends of pentaerythritol at a total of 1 to 40 moles.

作為六(甲基)丙烯酸酯,較佳為於二季戊四醇之6個末端加成有合計1~40莫耳之環氧乙烷之六(甲基)丙烯酸酯、於二季戊四醇之6個末端加成有合計1~20莫耳之ε-己內酯之六(甲基)丙烯酸酯。As the hexa (meth) acrylate, it is preferable to add hexa (meth) acrylate having a total of 1 to 40 moles of ethylene oxide to the 6 ends of dipentaerythritol, and add to the 6 ends of dipentaerythritol Hexa (meth) acrylate with a total of 1-20 moles of ε-caprolactone is formed.

上述中所說明之(甲基)丙烯酸酯化合物可分別獨立地使用或進行組合而使用。感光性樹脂組合物可含有其他化合物作為(B)具有乙烯性不飽和鍵之化合物。作為其他化合物,可列舉:具有胺基甲酸酯鍵之(甲基)丙烯酸酯、使α,β-不飽和羧酸與多元醇進行反應而獲得之化合物、使α,β-不飽和羧酸與含縮水甘油基之化合物進行反應而獲得之化合物、1,6-己二醇二(甲基)丙烯酸酯等。The (meth) acrylate compounds described above can be used independently or in combination. The photosensitive resin composition may contain other compounds as (B) a compound having an ethylenically unsaturated bond. Examples of other compounds include (meth) acrylates having a urethane bond, compounds obtained by reacting α, β-unsaturated carboxylic acids with polyols, and α, β-unsaturated carboxylic acids. A compound obtained by reacting with a glycidyl group-containing compound, 1,6-hexanediol di (meth) acrylate, etc.

(B)具有乙烯性不飽和雙鍵之化合物相對於感光性樹脂組合物之全部固形物成分質量之比率較佳為5質量%~70質量%。就感度、解像性及密接性之觀點而言,較佳為將該比率設為5質量%以上。更佳為將該比率設為20質量%以上,進而較佳為設為30質量%以上。另一方面,就抑制邊緣熔融及硬化抗蝕劑之剝離延遲之觀點而言,較佳為將該比率設為70質量%以下。更佳為將該比率設為50質量%以下。(B) The ratio of the compound having an ethylenically unsaturated double bond to the mass of the total solid content of the photosensitive resin composition is preferably 5% by mass to 70% by mass. From the viewpoints of sensitivity, resolution, and adhesion, it is preferable to set the ratio to 5% by mass or more. More preferably, the ratio is 20% by mass or more, and further preferably 30% by mass or more. On the other hand, from the viewpoint of suppressing the edge melting and the peeling delay of the hardened resist, the ratio is preferably set to 70% by mass or less. More preferably, the ratio is set to 50% by mass or less.

<(C)光聚合起始劑>
(C)光聚合起始劑係利用光使單體聚合之化合物。感光性樹脂組合物包含於本技術領域中通常已知之化合物作為(C)光聚合起始劑。
< (C) Photopolymerization initiator >
(C) The photopolymerization initiator is a compound that uses light to polymerize the monomer. The photosensitive resin composition contains a compound generally known in the art as the (C) photopolymerization initiator.

感光性樹脂組合物中之(C)光聚合起始劑之總含量較佳為0.01~20質量%之範圍內,更佳為0.05質量%~10質量%之範圍內,進而較佳為0.1質量%~7質量%之範圍內,尤佳為0.1質量%~6質量%之範圍內。關於(C)光聚合起始劑之總含量,就獲得充分之感度之觀點而言,較佳為0.01質量%以上,就使光充分地透過至抗蝕劑底面,獲得良好之高解像性之觀點而言,較佳為20質量%以下。The total content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 0.05 to 10% by mass, and further preferably 0.1% by mass % To 7% by mass, particularly preferably 0.1% to 6% by mass. The total content of the (C) photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity to sufficiently transmit light to the bottom surface of the resist to obtain good high resolution From a viewpoint, it is preferably 20% by mass or less.

作為(C)光聚合起始劑,可列舉:醌類、芳香族酮類、苯乙酮類、醯基氧化膦類、安息香或安息香醚類、二烷基縮酮類、9-氧硫 類、二烷基胺基苯甲酸酯類、肟酯類、吖啶類(例如,就感度、解像性、密接性之觀點而言,較佳為9-苯基吖啶、雙吖啶基庚烷、9-(對甲基苯基)吖啶、9-(間甲基苯基)吖啶),進而可列舉:六芳基聯咪唑、吡唑啉化合物、蒽化合物(例如,就感度、解像性、密接性之觀點而言,較佳為9,10-二丁氧基蒽、9,10-二乙氧基蒽)、香豆素化合物(例如,就感度、解像性、密接性之觀點而言,較佳為7-二乙基胺基-4-甲基香豆素)、N-芳基胺基酸或其酯化合物(例如,就感度、解像性、密接性之觀點而言,較佳為N-苯基甘胺酸)、及鹵素化合物(例如三溴甲基苯基碸)等。該等可單獨使用一種或組合兩種以上而使用。除此以外,亦可使用2,2-二甲氧基-1,2-二苯乙烷-1-酮、2-甲基-1-(4-甲基噻吩基)-2-嗎啉基丙烷-1-酮、2,4,6-三甲基苯甲醯基-二苯基氧化膦、三苯基氧化膦。Examples of the (C) photopolymerization initiator include quinones, aromatic ketones, acetophenones, acetylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, and 9-oxysulfide , Dialkylaminobenzoates, oxime esters, acridines (for example, from the viewpoint of sensitivity, resolution, and adhesion, 9-phenylacridine, bisacridinyl are preferred Heptane, 9- (p-methylphenyl) acridine, 9- (m-methylphenyl) acridine), further exemplified: hexaarylbiimidazole, pyrazoline compound, anthracene compound (for example, sensitivity , From the viewpoint of resolution and adhesion, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene), coumarin compounds (for example, in terms of sensitivity, resolution, From the viewpoint of adhesion, 7-diethylamino-4-methylcoumarin), N-arylamino acid or its ester compound (for example, in terms of sensitivity, resolution, adhesion) From a viewpoint, N-phenylglycine acid), a halogen compound (for example, tribromomethyl phenylbenzene), etc. are preferable. These can be used alone or in combination of two or more. In addition, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthienyl) -2-morpholinyl can also be used Propane-1-one, 2,4,6-trimethylbenzyl-diphenylphosphine oxide, triphenylphosphine oxide.

作為芳香族酮類,例如可列舉:二苯甲酮、米其勒酮[4,4'-雙(二甲基胺基)二苯甲酮]、4,4'-雙(二乙基胺基)二苯甲酮、4-甲氧基-4'-二甲基胺基二苯甲酮。該等可單獨使用一種或組合兩種以上而使用。該等之中,就密接性之觀點而言,較佳為4,4'-雙(二乙基胺基)二苯甲酮。進而,就透過率之觀點而言,感光性樹脂組合物中之芳香族酮類之含量較佳為0.01質量%~0.5質量%之範圍內,進而較佳為0.02質量%~0.3質量%之範圍內。As aromatic ketones, for example, benzophenone, Michler's ketone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamine Group) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone. These can be used alone or in combination of two or more. Among these, from the viewpoint of adhesion, 4,4′-bis (diethylamino) benzophenone is preferred. Furthermore, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably in the range of 0.01% by mass to 0.5% by mass, and more preferably in the range of 0.02% by mass to 0.3% by mass Inside.

作為六芳基聯咪唑之例,可列舉:2-(鄰氯苯基)-4,5-二苯基聯咪唑、2,2',5-三-(鄰氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基聯咪唑、2,4-雙-(鄰氯苯基)-5-(3,4-二甲氧基苯基)-二苯基聯咪唑、2,4,5-三-(鄰氯苯基)-二苯基聯咪唑、2-(鄰氯苯基)-雙-4,5-(3,4-二甲氧基苯基)-聯咪唑、2,2'-雙-(2-氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,3-二氟甲基苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,4-二氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,5-二氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,6-二氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,3,4-三氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,3,5-三氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,3,6-三氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,4,5-三氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,4,6-三氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,3,4,5-四氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、2,2'-雙-(2,3,4,6-四氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑、及2,2'-雙-(2,3,4,5,6-五氟苯基)-4,4',5,5'-四-(3-甲氧基苯基)-聯咪唑等,該等可單獨使用一種或組合兩種以上而使用。就高感度、解像性及密接性之觀點而言,較佳為2-(鄰氯苯基)-4,5-二苯基咪唑二聚物。Examples of hexaarylbiimidazole include 2- (o-chlorophenyl) -4,5-diphenylbiimidazole, 2,2 ', 5-tri- (o-chlorophenyl) -4- ( 3,4-dimethoxyphenyl) -4 ', 5'-diphenylbiimidazole, 2,4-bis- (o-chlorophenyl) -5- (3,4-dimethoxyphenyl ) -Diphenylbiimidazole, 2,4,5-tris- (o-chlorophenyl) -diphenylbiimidazole, 2- (o-chlorophenyl) -bis-4,5- (3,4-di Methoxyphenyl) -biimidazole, 2,2'-bis- (2-fluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3-difluoromethylphenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, 2,2'- Bis- (2,4-difluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,5- Difluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,6-difluorophenyl) -4 , 4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4-trifluorophenyl) -4,4', 5 , 5'-tetra- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,5-trifluorophenyl) -4,4 ', 5,5'-tetra -(3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,6-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methyl Oxyphenyl) -biimidazole, 2,2'-bis- (2,4,5-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxy Phenyl) -biimidazole, 2,2'-bis- (2,4,6-trifluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -bi Imidazole, 2,2'-bis- (2,3,4,5-tetrafluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, 2 , 2'-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, and 2,2 '-Bis- (2,3,4,5,6-pentafluorophenyl) -4,4', 5,5'-tetra- (3-methoxyphenyl) -biimidazole, etc. Used alone or in combination of two or more. From the viewpoints of high sensitivity, resolution and adhesion, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer is preferred.

於本實施形態中,關於感光性樹脂組合物中之六芳基雙咪唑化合物之含量,就提高感光性樹脂組合物層之剝離特性及/或感度之觀點而言,較佳為0.05質量%~7質量%之範圍內,更佳為0.1質量%~6質量%之範圍內,進而較佳為1質量%~5質量%之範圍內。In the present embodiment, the content of the hexaarylbisimidazole compound in the photosensitive resin composition is preferably 0.05% by mass from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin composition layer Within the range of 7% by mass, it is more preferably within the range of 0.1% by mass to 6% by mass, and further preferably within the range of 1% by mass to 5% by mass.

就感光性樹脂組合物層之剝離特性或感度、解像性、密接性之觀點而言,感光性樹脂組合物較佳為亦包含吡唑啉化合物作為光敏劑。From the viewpoint of peeling characteristics, sensitivity, resolution, and adhesion of the photosensitive resin composition layer, the photosensitive resin composition preferably also contains a pyrazoline compound as a photosensitizer.

作為吡唑啉化合物,就上述觀點而言較佳,例如可列舉:1-苯基-3-(4-第三丁基-苯乙烯基)-5-(4-第三丁基-苯基)-吡唑啉、1-(4-(苯并唑-2-基)苯基)-3-(4-第三丁基-苯乙烯基)-5-(4-第三丁基-苯基)-吡唑啉、1-苯基 -3-(4-聯苯基)-5-(4-第三丁基-苯基)-吡唑啉、1-苯基-3-(4-聯苯基)-5-(4-第三辛基-苯基)-吡唑啉、1-苯基-3-(4-異丙基苯乙烯基)-5-(4-異丙基苯基)-吡唑啉、1-苯基-3-(4-甲氧基苯乙烯基)-5-(4-甲氧基苯基)-吡唑啉、1-苯基-3-(3,5-二甲氧基苯乙烯基)-5-(3,5-二甲氧基苯基)-吡唑啉、1-苯基-3-(3,4-二甲氧基苯乙烯基)-5-(3,4-二甲氧基苯基)-吡唑啉、1-苯基-3-(2,6-二甲氧基苯乙烯基)-5-(2,6-二甲氧基苯基)-吡唑啉、1-苯基-3-(2,5-二甲氧基苯乙烯基)-5-(2,5-二甲氧基苯基)-吡唑啉、1-苯基-3-(2,3-二甲氧基苯乙烯基)-5-(2,3-二甲氧基苯基)-吡唑啉、1-苯基-3-(2,4-二甲氧基苯乙烯基)-5-(2,4-二甲氧基苯基)-吡唑啉等。該等之中,更佳為1-苯基-3-(4-聯苯基)-5-(4-第三丁基-苯基)-吡唑啉。The pyrazoline compound is preferable from the above viewpoint, and examples thereof include 1-phenyl-3- (4-third butyl-styryl) -5- (4-third butyl-phenyl ) -Pyrazoline, 1- (4- (benzo Oxazol-2-yl) phenyl) -3- (4-third butyl-styryl) -5- (4-third butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-third butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-third octyl -Phenyl) -pyrazoline, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylphenyl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- (3,5-dimethoxystyryl) -5- (3,5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3,4-dimethoxystyryl) -5- (3,4-dimethoxybenzene Group) -pyrazoline, 1-phenyl-3- (2,6-dimethoxystyryl) -5- (2,6-dimethoxyphenyl) -pyrazoline, 1-benzene Yl-3- (2,5-dimethoxystyryl) -5- (2,5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,3-di Methoxystyryl) -5- (2,3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2,4-dimethoxystyryl) -5- (2,4-dimethoxyphenyl) -pyrazoline and so on. Among these, 1-phenyl-3- (4-biphenyl) -5- (4-third butyl-phenyl) -pyrazoline is more preferable.

於本實施形態中,關於感光性樹脂組合物中之光敏劑之含量,就提高感光性樹脂組合物層之剝離特性及/或感度之觀點而言,較佳為0.05質量%~5質量%之範圍內,更佳為0.1質量%~3質量%之範圍內。In the present embodiment, the content of the photosensitizer in the photosensitive resin composition is preferably 0.05% by mass to 5% by mass from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin composition layer Within the range, it is more preferably within a range of 0.1% by mass to 3% by mass.

<(D)酚衍生物>
於本實施形態中,感光性樹脂組合物較佳為進而包含(D)酚衍生物。作為(D)酚衍生物,例如可列舉:對甲氧基苯酚、對苯二酚、鄰苯三酚、第三丁基鄰苯二酚、2,6-二-第三丁基-對甲酚、2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)、2,2'-亞甲基雙(4-乙基-6-第三丁基苯酚)、2,6-二-第三丁基 -4-甲基苯酚、2,5-二-第三戊基對苯二酚、2,5-二-第三丁基對苯二酚、2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)、雙(2-羥基-3-第三丁基-5-乙基苯基)甲烷、三乙二醇-雙[3-(3-第三丁基-5-甲基-4-羥基苯基)丙酸酯]、1,6-己二醇-雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、季戊四醇-四[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、2,2-硫代-二伸乙基雙[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、十八烷基-3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯、N,N'-六亞甲基雙(3,5-二-第三丁基-4-羥基-苯丙醯胺)、3,5-二-第三丁基-4-羥基苄基膦酸二乙酯、1,3,5-三甲基-2,4,6-三(3,5-二-第三丁基-4-羥基苄基)苯、三-(3,5-二-第三丁基-4-羥基苄基)-異氰尿酸酯、4,4'-硫代雙(6-第三丁基-間甲酚)、4,4'-亞丁基雙(3-甲基-6-第三丁基苯酚)、1,1,3-三(2-甲基-4-羥基-5-第三丁基苯基)丁烷、苯乙烯化苯酚(例如川口化學工業股份有限公司製造、Antage SP)、三苄基苯酚(例如川口化學工業股份有限公司製造,TBP,具有1~3個苄基之苯酚)、聯苯酚等。就可抑制曝光時之焦點位置偏移時之線寬變粗或解像度之惡化之觀點而言,較佳含有(D)酚衍生物,就同樣之觀點而言,較佳為受阻苯酚或聯苯酚。又,就同樣之觀點而言,(D)酚衍生物較佳為具有2個以上之苯酚核。
< (D) phenol derivatives >
In the present embodiment, the photosensitive resin composition preferably further contains (D) a phenol derivative. Examples of (D) phenol derivatives include p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol Phenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-pentyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 2,2 '-Methylenebis (4-methyl-6-tert-butylphenol), bis (2-hydroxy-3-tert-butyl-5-ethylphenyl) methane, triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) propionate, N, N'-hexamethylene bis (3,5-di-t-butyl-4-hydroxy-phenylpropionamide), 3,5-di-t-butyl- Diethyl 4-hydroxybenzylphosphonate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl ) Benzene, tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 4,4'-thiobis (6-tert-butyl-m-cresol) , 4,4'-butylene bis (3-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) Butane, styrenated phenol (for example, manufactured by Kawaguchi Chemical Industry Co., Ltd., Antage SP), tribenzylphenol (for example, manufactured by Kawaguchi Chemical Industry Co., Ltd., TBP, phenol having 1 to 3 benzyl groups), biphenol Wait. From the viewpoint of suppressing the thickening of the line width or the deterioration of the resolution when the focal position shifts during exposure, it is preferable to contain (D) phenol derivatives, and from the same viewpoint, it is preferably hindered phenol or biphenol . In addition, from the same viewpoint, the (D) phenol derivative preferably has two or more phenol cores.

(D)酚衍生物相對於感光性樹脂組合物之全部固形物成分質量之比率較佳為0.001質量%~10質量%。該比率就可抑制曝光時之焦點位置偏移時之線寬變粗或解像度之惡化之觀點而言,較佳為0.001質量%以上,更佳為0.005質量%以上,進而較佳為0.01質量%以上,更佳為0.05質量%以上,尤佳為0.1質量%以上。另一方面,該比率就感度降低較少之方面及解像性之提高之方面而言,較佳為10質量%以下,更佳為5質量%以下,進而較佳為3質量%以下,尤佳為2質量%以下,最佳為1.5質量%以下。(D) The ratio of the phenol derivative to the total solid content of the photosensitive resin composition is preferably 0.001% by mass to 10% by mass. This ratio is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and even more preferably 0.01% by mass in terms of suppressing the thickening of the line width or the deterioration of the resolution when the focal position shifts during exposure. The above is more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. On the other hand, the ratio is preferably not more than 10% by mass, more preferably not more than 5% by mass, and even more preferably not more than 3% by mass in terms of a small decrease in sensitivity and an improvement in resolution. It is preferably 2% by mass or less, and most preferably 1.5% by mass or less.

<添加劑>
感光性樹脂組合物視需要可含有染料、塑化劑、抗氧化劑、穩定劑等添加劑。例如可使用日本專利特開2013-156369號公報中所列舉之添加劑。
<Additives>
The photosensitive resin composition may contain additives such as dyes, plasticizers, antioxidants, and stabilizers as needed. For example, the additives listed in Japanese Patent Laid-Open No. 2013-156369 can be used.

(染料及著色物質)
於本實施形態中,感光性樹脂組合物視需要可進而含有選自由染料(例如隱色染料、螢光黃母體染料等)及著色物質所組成之群中之至少1種。
(Dyes and coloring substances)
In this embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of dyes (for example, leuco dyes, fluorescent yellow matrix dyes, etc.) and coloring substances, if necessary.

作為著色物質,例如可列舉:品紅、酞菁綠、金黃胺鹼、對品紅、結晶紫、甲基橙、尼祿藍2B、維多利亞藍、孔雀綠(例如Hodogaya化學股份有限公司製造之Aizen(註冊商標) MALACHITE GREEN)、鹼性藍20、鑽石綠(例如Hodogaya化學股份有限公司製造之Aizen(註冊商標) DIAMOND GREEN GH)。關於感光性樹脂組合物中之著色物質之含量,於將感光性樹脂組合物之全部固形物成分質量設為100質量%時,較佳為0.001質量%~1質量%。就提高感光性樹脂組合物之操作性之觀點而言,較佳為將該含量設為0.001質量%以上。另一方面,就感光性樹脂組合物之保存穩定性之觀點而言,較佳為將該含量設為1質量%以下。Examples of the coloring substance include magenta, phthalocyanine green, auramine, para-magenta, crystal violet, methyl orange, Nero blue 2B, Victoria blue, and malachite green (e.g., Aizen manufactured by Hodogaya Chemical Co., Ltd.) (Registered trademark) MALACHITE GREEN), basic blue 20, diamond green (for example, Aizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). The content of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass when the mass of the total solid content of the photosensitive resin composition is 100% by mass. From the viewpoint of improving the handleability of the photosensitive resin composition, the content is preferably 0.001% by mass or more. On the other hand, from the viewpoint of storage stability of the photosensitive resin composition, the content is preferably set to 1% by mass or less.

感光性樹脂組合物藉由含有染料而使曝光部分顯色,故而就視認性之方面而言較佳,又,於檢査機等讀取用於曝光之對位標記物之情形時,曝光部與未曝光部之對比度較大者容易進行識別而較有利。就該觀點而言,作為較佳之染料,可列舉隱色染料及螢光黃母體染料。The photosensitive resin composition contains the dye to make the exposed portion color, so it is preferable from the viewpoint of visibility. In addition, when the alignment mark used for exposure is read by an inspection machine or the like, the exposure portion and Those with greater contrast in unexposed areas are easier to identify and more advantageous. From this viewpoint, preferred dyes include leuco dyes and fluorescent yellow matrix dyes.

作為隱色染料,可列舉三(4-二甲基胺基苯基)甲烷[隱色結晶紫]、雙(4-二甲基胺基苯基)苯甲烷[隱色孔雀綠]等。尤其是就對比度變得良好之觀點而言,較佳為使用隱色結晶紫作為隱色染料。關於感光性樹脂組合物中之隱色染料之含量,相對於感光性樹脂組合物之全部固形物成分質量較佳為0.1質量%~10質量%。就使曝光部分與未曝光部分之對比度變得良好之觀點而言,較佳為將該含量設為0.1質量%以上。該含量更佳為設為0.2質量%以上,尤佳為設為0.4質量%以上。另一方面,就維持保存穩定性之觀點而言,較佳為將該含量設為10質量%以下。該含量更佳為設為5質量%以下,尤佳為設為2質量%以下。Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leuco malachite green], and the like. In particular, from the viewpoint that the contrast becomes good, it is preferable to use leuco crystal violet as the leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass relative to the mass of the total solid content of the photosensitive resin composition. From the viewpoint of improving the contrast between the exposed portion and the unexposed portion, the content is preferably set to 0.1% by mass or more. The content is more preferably 0.2% by mass or more, and particularly preferably 0.4% by mass or more. On the other hand, from the viewpoint of maintaining storage stability, the content is preferably 10% by mass or less. The content is more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

又,就使密接性及對比度最佳化之觀點而言,較佳為於感光性樹脂組合物中,組合隱色染料與於(C)光聚合起始劑中已說明之鹵素化合物而使用。於將隱色染料與該鹵素化合物併用之情形時,關於感光性樹脂組合物中之該鹵素化合物之含量,於將感光性樹脂組合物之全部固形物成分質量設為100質量%時,就維持感光層中之色相之保存穩定性之觀點而言,較佳為0.01質量%~3質量。In addition, from the viewpoint of optimizing adhesion and contrast, it is preferable to use a leuco dye in combination with the halogen compound described in (C) Photopolymerization Initiator in the photosensitive resin composition. When the leuco dye is used in combination with the halogen compound, the content of the halogen compound in the photosensitive resin composition is maintained when the mass of the total solid content of the photosensitive resin composition is 100% by mass From the viewpoint of storage stability of the hue in the photosensitive layer, it is preferably 0.01% by mass to 3% by mass.

(其他添加劑)
為了提高熱穩定性及保存穩定性,感光性樹脂組合物可進而含有選自由自由基聚合抑制劑、苯并三唑類、及羧基苯并三唑類所組成之群中之至少1種化合物。
(Other additives)
In order to improve thermal stability and storage stability, the photosensitive resin composition may further contain at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles.

作為自由基聚合抑制劑,例如可列舉:萘胺、氯化亞銅、亞硝基苯基羥基胺鋁鹽、二苯基亞硝基胺等。為了不損及感光性樹脂組合物之感度,較佳為亞硝基苯基羥基胺鋁鹽。Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, aluminum salts of nitrosophenylhydroxylamine, and diphenylnitrosoamine. In order not to impair the sensitivity of the photosensitive resin composition, the aluminum salt of nitrosophenylhydroxylamine is preferred.

作為苯并三唑類,例如可列舉:1,2,3-苯并三唑、1-氯-1,2,3-苯并三唑、雙(N-2-乙基己基)胺基亞甲基-1,2,3-苯并三唑、雙(N-2-乙基己基)胺基亞甲基-1,2,3-甲苯基三唑、雙(N-2-羥基乙基)胺基亞甲基-1,2,3-苯并三唑等。Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, and bis (N-2-ethylhexyl) amino Methyl-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl ) Amino methylene-1,2,3-benzotriazole and so on.

作為羧基苯并三唑類,例如可列舉:4-羧基-1,2,3-苯并三唑、5-羧基-1,2,3-苯并三唑、N-(N,N-二-2-乙基己基)胺基亞甲基羧基苯并三唑、N-(N,N-二-2-羥基乙基)胺基亞甲基羧基苯并三唑、N-(N,N-二-2-乙基己基)胺基伸乙基羧基苯并三唑等。Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di -2-ethylhexyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N -Di-2-ethylhexyl) aminoethylethylcarboxybenzotriazole and the like.

關於自由基聚合抑制劑、苯并三唑類、及羧基苯并三唑類之合計含量,於將感光性樹脂組合物之全部固形物成分質量設為100質量%時,較佳為0.01質量%~3質量%,更佳為0.05質量%~1質量%。就對感光性樹脂組合物賦予保存穩定性之觀點而言,較佳為將該含量設為0.01質量%以上。另一方面,就維持感度,抑制染料之脫色之觀點而言,較佳為將該含量設為3質量%以下。The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% by mass when the total solid content of the photosensitive resin composition is 100% by mass. ~ 3% by mass, more preferably 0.05% by mass to 1% by mass. From the viewpoint of imparting storage stability to the photosensitive resin composition, the content is preferably 0.01% by mass or more. On the other hand, from the viewpoint of maintaining sensitivity and suppressing discoloration of the dye, it is preferable to set the content to 3% by mass or less.

於本實施形態中,感光性樹脂組合物可進而含有雙酚A之環氧化合物類。作為雙酚A之環氧化合物類,例如可列舉利用聚丙二醇修飾雙酚A,將末端環氧化而成之化合物等。In this embodiment, the photosensitive resin composition may further contain epoxy compounds of bisphenol A. Examples of epoxy compounds of bisphenol A include compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the terminal.

於本實施形態中,感光性樹脂組合物可進而含有塑化劑。作為塑化劑,例如可列舉:鄰苯二甲酸酯類(例如鄰苯二甲酸二乙酯等)、鄰甲苯磺醯胺、對甲苯磺醯胺、檸檬酸三丁酯、檸檬酸三乙酯、乙醯檸檬酸三乙酯、乙醯檸檬酸三正丙酯、乙醯檸檬酸三正丁酯、聚乙二醇、聚丙二醇、聚乙二醇烷基醚、聚丙二醇烷基醚等。又,可列舉:ADEKA NOL SDX-1569、ADEKA NOL SDX-1570、ADEKA NOL SDX-1571、ADEKA NOL SDX-479(以上為旭電化股份有限公司製造)、Newpol BP-23P、Newpol BP-3P、Newpol BP-5P、Newpol BPE-20T、Newpol BPE-60、Newpol BPE-100、Newpol BPE-180(以上為三洋化成股份有限公司製造)、Uniol DB-400、Uniol DAB-800、Uniol DA-350F、Uniol DA-400、Uniol DA-700(以上為日本油脂股份有限公司製造)、BA-P4U Glycol、BA-P8 Glycol(以上為日本乳化劑股份有限公司製造)等具有雙酚骨架之化合物。In this embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of plasticizers include phthalates (such as diethyl phthalate), o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, and triethyl citrate , Triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, etc. In addition, ADEKA NOL SDX-1569, ADEKA NOL SDX-1570, ADEKA NOL SDX-1571, ADEKA NOL SDX-479 (above manufactured by Asahi Denka Co., Ltd.), Newpol BP-23P, Newpol BP-3P, Newpol BP-5P, Newpol BPE-20T, Newpol BPE-60, Newpol BPE-100, Newpol BPE-180 (above manufactured by Sanyo Chemical Co., Ltd.), Uniol DB-400, Uniol DAB-800, Uniol DA-350F, Uniol Compounds having a bisphenol skeleton such as DA-400, Uniol DA-700 (above manufactured by Nippon Oil & Fats Co., Ltd.), BA-P4U Glycol, BA-P8 Glycol (above manufactured by Nippon Emulsifier Co., Ltd.), etc.

關於感光性樹脂組合物中之塑化劑之含量,相對於感光性樹脂組合物之全部固形物成分質量,較佳為1質量%~50質量%,更佳為1質量%~30質量%。就抑制顯影時間之延遲,且對硬化膜賦予柔軟性之觀點而言,較佳為將該含量設為1質量%以上。另一方面,就抑制硬化不足及冷流之觀點而言,較佳為將該含量設為50質量%以下。The content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass, and more preferably 1% by mass to 30% by mass relative to the mass of the total solid content of the photosensitive resin composition. From the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film, the content is preferably 1% by mass or more. On the other hand, from the viewpoint of suppressing insufficient hardening and cold flow, the content is preferably 50% by mass or less.

[溶劑]
感光性樹脂組合物可溶解於溶劑中而以感光性樹脂組合物調合液之形態用於感光性樹脂積層體之製造。作為溶劑,可列舉酮類、醇類等。上述酮類係以甲基乙基酮(MEK)、丙酮為代表。上述醇類係以甲醇、乙醇、及異丙醇為代表。溶劑較佳為於感光性樹脂積層體之製造時,以如塗佈於支持層上之感光性樹脂組合物調合液於25℃下之黏度成為500 mPa・s~4,000 mPa・s之量添加至感光性樹脂組合物中。
[Solvent]
The photosensitive resin composition can be dissolved in a solvent and used in the production of a photosensitive resin laminate in the form of a photosensitive resin composition blending solution. Examples of the solvent include ketones and alcohols. The above ketones are represented by methyl ethyl ketone (MEK) and acetone. The above alcohols are represented by methanol, ethanol, and isopropanol. The solvent is preferably added to the photosensitive resin laminate when it is added in such an amount that the viscosity of the photosensitive resin composition mixing liquid applied on the support layer at 25 ° C becomes 500 mPa · s to 4,000 mPa · s In the photosensitive resin composition.

<抗蝕圖案之形成方法>
其次,說明使用本實施形態之感光性樹脂積層體而製造抗蝕圖案之方法之一例。該方法可包括如下步驟:層壓步驟,其係將感光性樹脂積層體積層於基板;曝光步驟,其係使該感光性樹脂積層體之感光性樹脂組合物曝光;及顯影步驟,其係將該感光性樹脂組合物層之未曝光部顯影去除。作為抗蝕圖案,例如可列舉:印刷配線板、半導體元件、印刷版、液晶顯示器面板、可撓性基板、引線框架基板、COF(薄膜覆晶)用基板、半導體封裝用基板、液晶用透明電極、液晶用TFT(Thin Film Transistor,薄膜電晶體)用配線、PDP(電漿顯示器面板)用電極等圖案。由於本實施形態之感光性樹脂積層體具有抗蝕劑突起之良好之避免之優點,故而例如對線寬/間隙寬為20/20(μm)以下、或線寬/間隙寬未達10/10(μm)等高精細之配線形成用尤其有用。作為本實施形態之感光性樹脂積層體可應用之線寬/間隙寬(μm),並無特別限制,例如為15/15(μm)以下,較佳為10/10(μm)以下,進而較佳為9.5/9.5(μm)以下,尤佳為9.0/9.0(μm)以下。作為線寬/間隙寬(μm)之下限值,並無特別限制,可為3/3(μm)以上、4/4(μm)以上、或5/5(μm)以上。又,本實施形態之感光性樹脂積層體因上述優點而尤其對利用半加成法(SAP)之配線形成用較有用。SAP法可藉由常法實施,例如可使用絕緣樹脂層與銅層(例如包含鈀作為觸媒之無電解銅鍍覆層)之積層體,藉由已知之鍍覆法進行配線形成。作為一例,如下所述般說明印刷配線板之製造方法。
<Method of forming resist pattern>
Next, an example of a method of manufacturing a resist pattern using the photosensitive resin laminate of this embodiment will be described. The method may include the following steps: a laminating step, which is to layer the photosensitive resin layer on the substrate; an exposure step, which is to expose the photosensitive resin composition of the photosensitive resin laminate; and a developing step, which is to The unexposed portion of the photosensitive resin composition layer is developed and removed. Examples of the resist pattern include printed wiring boards, semiconductor elements, printing plates, liquid crystal display panels, flexible substrates, lead frame substrates, substrates for COF (film on chip), substrates for semiconductor packages, and transparent electrodes for liquid crystals , Wiring for liquid crystal TFT (Thin Film Transistor, thin film transistor), electrode for PDP (plasma display panel), etc. Since the photosensitive resin laminate of this embodiment has the advantage of avoiding resist protrusions well, for example, if the line width / gap width is 20/20 (μm) or less, or the line width / gap width is less than 10/10 (μm) is particularly useful for forming high-definition wiring. The line width / gap width (μm) applicable to the photosensitive resin laminate of the present embodiment is not particularly limited, for example, it is 15/15 (μm) or less, preferably 10/10 (μm) or less, and further It is preferably 9.5 / 9.5 (μm) or less, and particularly preferably 9.0 / 9.0 (μm) or less. The lower limit of the line width / gap width (μm) is not particularly limited, and may be 3/3 (μm) or more, 4/4 (μm) or more, or 5/5 (μm) or more. In addition, the photosensitive resin laminate of the present embodiment is particularly useful for wiring formation using the semi-additive method (SAP) due to the above advantages. The SAP method can be implemented by a conventional method. For example, a laminate of an insulating resin layer and a copper layer (for example, an electroless copper plating layer containing palladium as a catalyst) can be used, and wiring can be formed by a known plating method. As an example, a method of manufacturing a printed wiring board will be described as follows.

印刷配線板係經過以下之各步驟而製造。
(1)層壓步驟
首先,於層壓步驟中,使用貼合機於基板上形成感光性樹脂組合物層。具體而言,於感光性樹脂積層體具有保護層之情形時,於剝離保護層後,利用貼合機將感光性樹脂組合物層加熱壓接至基板表面而進行層壓。作為基板之材料,例如可列舉:銅、不鏽鋼(SUS)、玻璃、氧化銦錫(ITO)等。
The printed wiring board is manufactured through the following steps.
(1) Lamination step First, in the lamination step, a photosensitive resin composition layer is formed on the substrate using a laminator. Specifically, in the case where the photosensitive resin laminate has a protective layer, after the protective layer is peeled off, the photosensitive resin composition layer is heated and pressure-bonded to the surface of the substrate by a laminator to be laminated. Examples of the material of the substrate include copper, stainless steel (SUS), glass, and indium tin oxide (ITO).

於本實施形態中,感光性樹脂組合物層可僅層壓至基板表面之單面、或視需要層壓至雙面。層壓時之加熱溫度通常為40℃~160℃。又,藉由進行2次以上層壓時之加熱壓接,可提高所獲得之抗蝕圖案對於基板之密接性。於加熱壓接時,可藉由使用具備雙聯輥之二段式貼合機、或使基板與感光性樹脂組合物層之積層物重複數次通過輥而進行壓接。In this embodiment, the photosensitive resin composition layer may be laminated to only one side of the substrate surface, or to both sides as necessary. The heating temperature during lamination is usually 40 ° C to 160 ° C. In addition, by performing heat and pressure bonding when laminating two or more times, the adhesion of the obtained resist pattern to the substrate can be improved. In the case of heating and pressure bonding, the pressure bonding can be performed by using a two-stage laminating machine equipped with a double-roller, or by repeatedly passing the laminate of the substrate and the photosensitive resin composition layer through the roller several times.

(2)曝光步驟
於本步驟中,藉由如下曝光方法使感光性樹脂組合物層曝光:使具有所需之配線圖案之掩膜密接於支持層上,並使用活性光源進行之曝光方法;利用作為所需之配線圖案之繪圖圖案之直接繪圖進行之曝光方法;或藉由使光罩之像通過透鏡而進行投影之曝光方法。本實施形態之感光性樹脂組合物之優點於利用繪圖圖案之直接繪圖進行之曝光方法、或使光罩之像通過透鏡而進行投影之曝光方法中更顯著,於利用繪圖圖案之直接繪圖進行之曝光方法中尤其顯著。
(2) Exposure step In this step, the photosensitive resin composition layer is exposed by the following exposure method: an exposure method in which a mask having a desired wiring pattern is closely attached to the support layer and using an active light source; As the exposure method of direct drawing of the drawing pattern of the required wiring pattern; or the exposure method of projecting by passing the image of the photomask through the lens. The advantages of the photosensitive resin composition of this embodiment are more prominent in the exposure method using direct drawing of the drawing pattern or the exposure method of projecting the image of the reticle through the lens, and the direct drawing using the drawing pattern This is particularly noticeable in the exposure method.

(3)顯影步驟
於本步驟中,於曝光後,剝離感光性樹脂組合物層上之支持層,繼而使用鹼性水溶液之顯影液將未曝光部顯影去除,藉此於基板上形成抗蝕圖案。
(3) Development step In this step, after exposure, the support layer on the photosensitive resin composition layer is peeled off, and then the unexposed portion is developed and removed using an alkaline aqueous solution developer, thereby forming a resist pattern on the substrate .

使用Na2 CO3 或K2 CO3 之水溶液作為鹼性水溶液。鹼性水溶液係根據感光性樹脂組合物層之特性而適當加以選擇,較佳為約0.2質量%~約2質量%之濃度且約20℃~約40℃之Na2 CO3 水溶液。An aqueous solution of Na 2 CO 3 or K 2 CO 3 is used as an alkaline aqueous solution. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin composition layer, and is preferably a Na 2 CO 3 aqueous solution having a concentration of about 0.2% by mass to about 2% by mass and about 20 ° C to about 40 ° C.

可經過上述(1)~(3)之各步驟而獲得抗蝕圖案。於該等步驟後,視情形,亦可進而進行約100℃~約300℃之加熱步驟。藉由實施該加熱步驟,可進一步提高耐化學品性。加熱可使用熱風、紅外線、或遠紅外線之方式之加熱爐。又,該加熱步驟可於曝光步驟後實施。The resist pattern can be obtained through the above steps (1) to (3). After these steps, if necessary, a heating step of about 100 ° C to about 300 ° C may be further performed. By performing this heating step, the chemical resistance can be further improved. Heating can be done by means of hot air, infrared, or far infrared. In addition, this heating step can be implemented after the exposure step.

(4)蝕刻步驟或鍍覆步驟
對藉由顯影露出之基板表面(例如銅箔積層板之銅面)進行蝕刻或鍍覆,而製造導體圖案。
(4) Etching step or plating step The substrate surface exposed by development (for example, the copper surface of the copper foil laminate) is etched or plated to produce a conductor pattern.

(5)剝離步驟
其後,利用具有強於顯影液之鹼性之水溶液自基板上剝離抗蝕圖案。關於剝離用之鹼性水溶液,並無特別限制,較佳為約2質量%~約5質量%之濃度、且約40~約70℃之溫度之NaOH或KOH之水溶液。亦可向剝離液中添加少量之水溶性溶劑。
(5) After the stripping step, the resist pattern is stripped from the substrate using an aqueous solution having a stronger alkalinity than the developer. The alkaline aqueous solution for peeling is not particularly limited, and preferably an aqueous solution of NaOH or KOH having a concentration of about 2% by mass to about 5% by mass and a temperature of about 40 to about 70 ° C. A small amount of water-soluble solvent can also be added to the stripping solution.

本實施形態之感光性樹脂積層體係適於印刷配線板、可撓性基板、引線框架基板、COF用基板、半導體封裝用基板、液晶用透明電極、液晶用TFT用配線、PDP用電極等中之抗蝕圖案或導體圖案之製造之感光性樹脂積層體。The photosensitive resin lamination system of this embodiment is suitable for printed wiring boards, flexible substrates, lead frame substrates, COF substrates, semiconductor package substrates, transparent electrodes for liquid crystals, wiring for TFTs for liquid crystals, electrodes for PDPs, etc. A photosensitive resin laminate for the manufacture of resist patterns or conductor patterns.

再者,關於上述各種參數,只要無特別說明,則係依據下述實施例中之測定方法或本領域業者理解為與其同等之方法而進行測定。
[實施例]
In addition, as long as there is no special description about the above-mentioned various parameters, they are measured according to the measurement methods in the following examples or methods understood by those skilled in the art as equivalent to them.
[Example]

其次,列舉實施例及比較例更具體地說明本實施形態。然而,本實施形態只要不脫離其主旨,則並不限定於以下之實施例。實施例中之物性係藉由以下之方法而進行測定。Next, the present embodiment will be described more specifically with examples and comparative examples. However, this embodiment is not limited to the following embodiments as long as it does not deviate from the gist. The physical properties in the examples were measured by the following methods.

表示實施例及比較例之評價用樣品之製作方法、以及對所獲得之樣品之評價方法及其評價結果。The manufacturing method of the sample for evaluation of an Example and a comparative example, the evaluation method of the obtained sample, and its evaluation result are shown.

<實施例1~3及比較例1>
1.感光性樹脂組合物之製備
藉由使作為(A)鹼溶性高分子之甲基丙烯酸/甲基丙烯酸苄酯共聚物(聚合比20/80(質量比)、酸當量430、重量平均分子量5萬)47質量份、
作為(B)光聚合起始劑之4,4'-雙(二乙基胺基)二苯甲酮0.1質量份及2-(鄰氯苯基)-4,5-二苯基咪唑二聚物3質量份、
作為(C)具有乙烯性雙鍵之化合物之於季戊四醇之4個末端加成平均15莫耳之環氧乙烷而成之四丙烯酸酯14質量份、以及
作為染料之鑽石綠0.05質量份及隱色結晶紫0.3質量份
溶解於溶劑中,而製備感光性樹脂組合物。
<Examples 1 to 3 and Comparative Example 1>
1. Preparation of photosensitive resin composition by using (A) alkali-soluble polymer methacrylic acid / benzyl methacrylate copolymer (polymerization ratio 20/80 (mass ratio), acid equivalent 430, weight average molecular weight 50,000) 47 parts by mass,
As the (B) photopolymerization initiator, 4,4'-bis (diethylamino) benzophenone 0.1 parts by mass and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer 3 parts by mass,
(C) 14 parts by mass of tetraacrylate obtained by adding an average of 15 moles of ethylene oxide to the four ends of pentaerythritol as a compound having an ethylenic double bond, and 0.05 parts by mass of diamond green as a dye and hidden 0.3 parts by mass of colored crystal violet was dissolved in a solvent to prepare a photosensitive resin composition.

2.支持膜之製作
製作聚對苯二甲酸乙二酯(PET)作為實施例1~3及比較例1之各支持膜。各支持膜中之光學異常區域之合計面積比率係如表1中所記載。支持膜中之微粒子之數量係藉由過濾器之網眼之粗細及使構成支持膜之材料通過過濾器之次數及添加微粒子之數量而加以調整。再者,光學異常區域(產生反射、散射等之部分)之面積之調整係藉由如下方法而進行:於PET膜之雙軸延伸後,適當地於180~250℃之條件下再次對膜進行熱壓接處理而使微粒子周圍之光學異常區域(即,空腔、或配向性或結晶性不同之區域等)消失。
2. Preparation of Support Film Polyethylene terephthalate (PET) was prepared as each support film of Examples 1 to 3 and Comparative Example 1. The total area ratio of the optically abnormal regions in each support film is as shown in Table 1. The number of fine particles in the support film is adjusted by the thickness of the mesh of the filter and the number of times the material constituting the support film passes through the filter and the number of added fine particles. Furthermore, the adjustment of the area of the optically abnormal region (the part where reflection, scattering, etc. occurs) is performed by the following method: after biaxial stretching of the PET film, the film is appropriately re-executed under the conditions of 180-250 ° C The thermocompression bonding process eliminates the optically abnormal regions around the particles (ie, cavities, regions with different alignment or crystallinity, etc.).

3.感光性樹脂積層體之製造
於聚對苯二甲酸乙二酯(PET)製之支持膜(厚度12 μm)之單面上,利用棒式塗佈機塗佈上述中所製備之感光性樹脂組合物,並於95℃之乾燥機中乾燥2.5分鐘而形成感光性樹脂組合物層,藉此獲得感光性樹脂積層體。感光性樹脂組合物層之乾燥厚度為20 μm。繼而,於感光性樹脂組合物層之未積層聚對苯二甲酸乙二酯膜之側之表面上,貼合19 μm厚之聚乙烯膜(Tamapoly股份有限公司製造,GF-818)作為保護層,而獲得感光性樹脂積層體。
3. The photosensitive resin laminate is manufactured on one side of a support film (thickness 12 μm) made of polyethylene terephthalate (PET), and the photosensitive prepared in the above is coated with a bar coater The resin composition was dried in a dryer at 95 ° C. for 2.5 minutes to form a photosensitive resin composition layer, thereby obtaining a photosensitive resin laminate. The dry thickness of the photosensitive resin composition layer is 20 μm. Next, a 19 μm thick polyethylene film (manufactured by Tamapoly Co., Ltd., GF-818) was laminated as a protective layer on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film was not laminated. To obtain a photosensitive resin laminate.

<基板整面>
利用軟蝕刻劑(菱江化學股份有限公司製造,CPE-900)對作為圖像性之評價基板之積層有18 μm壓延銅箔之0.4 mm厚之銅箔積層板進行處理,並利用10質量%H2 SO4 洗淨基板表面。
<Full surface of substrate>
Use a soft etchant (manufactured by Lingjiang Chemical Co., Ltd., CPE-900) to process a 0.4 mm thick copper foil laminate with 18 μm rolled copper foil as the evaluation substrate of the image, and use 10% by mass H 2 SO 4 cleans the substrate surface.

<層壓>
一面剝離感光性樹脂積層體之聚乙烯膜(保護層),一面於預熱至60℃之銅箔積層板,利用加熱輥貼合機(旭化成股份有限公司製造,AL-700),於輥溫度105℃下層壓感光性樹脂積層體。空氣壓係設為0.35 MPa,層壓速度係設為1.5 m/min。
<Lamination>
The polyethylene film (protective layer) of the photosensitive resin laminate was peeled off on one side, and the copper foil laminate preheated to 60 ° C on the other side was heated at a roller temperature using a heated roller bonding machine (manufactured by Asahi Kasei Co., Ltd., AL-700). The photosensitive resin laminate was laminated at 105 ° C. The air pressure system was set at 0.35 MPa, and the lamination speed was set at 1.5 m / min.

<曝光>
利用直接繪圖曝光機(ORC MANUFACTURING製造之FDi-3、主波長405±5 nm),使用斯圖費(Stouffer)41級階段式曝光表或特定之直接成像(DI)曝光用之遮罩圖案,進行曝光。曝光係以將上述斯圖費(Stouffer)41級階段式曝光表作為遮罩進行曝光、顯影時之最高殘膜級數成為14級之曝光量進行。
<Exposure>
Use a direct drawing exposure machine (FDi-3 manufactured by ORC MANUFACTURING, main wavelength 405 ± 5 nm), use a Stouffer 41-stage stage exposure meter or a specific direct imaging (DI) exposure mask pattern, Make an exposure. The exposure was performed with the exposure amount using the above-mentioned Stouffer 41-stage stepwise exposure meter as a mask, and the maximum number of remaining film stages during development was 14 stages.

<顯影>
於剝離聚對苯二甲酸乙二酯膜(支持膜)後,使用鹼性顯影機(FUJI KIKO製造,幹膜用顯影機),歷時特定時間噴霧30℃之1質量%Na2 CO3 水溶液,以最小顯影時間之2倍之時間溶解去除感光性樹脂組合物層之未曝光部分。此時,將未曝光部分之感光性樹脂組合物層完全溶解所需之最少之時間設為最小顯影時間。
<Development>
After peeling off the polyethylene terephthalate film (support film), using an alkaline developing machine (manufactured by FUJI KIKO, developing machine for dry film), spraying a 1 mass% Na 2 CO 3 aqueous solution at 30 ° C for a specific time, The unexposed portion of the photosensitive resin composition layer was dissolved and removed in a time twice as long as the minimum development time. At this time, the minimum time required to completely dissolve the photosensitive resin composition layer in the unexposed portion is set as the minimum development time.

<光學異常區域之合計面積之測定>
於落射型雷射顯微鏡(Olympus製造之OLS-4100)之物鏡之上部插入偏光濾光器(OLS4000-QWP)。其次於雷射顯微鏡之載置台上使用多孔質吸附板(Universal Giken製造之65F-HG)及真空泵而水平地吸引固定切斷為30 mm×30 mm之支持膜樣品。利用物鏡50倍之雷射光量60(雷射波長為405 nm)觀測進行了吸引固定之支持膜。此時,將支持膜之厚度方向之中心2 μm之區域規定為測定區域,並於測定區域259 μm×260 μm中以測定部位數200點進行測量(因此,測定區域合計成為0.259 mm×0.26 mm×200=13.5 mm2 )。
<Measurement of the total area of the optical abnormal area>
A polarizing filter (OLS4000-QWP) was inserted above the objective lens of an epi-laser microscope (OLS-4100 manufactured by Olympus). Secondly, a porous adsorption plate (65F-HG manufactured by Universal Giken) and a vacuum pump were used on the mounting table of the laser microscope to horizontally attract and fix the support membrane sample cut to 30 mm × 30 mm. The support film was attracted and fixed by observation with an objective lens 50 times the laser light amount 60 (laser wavelength is 405 nm). At this time, the area of 2 μm in the center of the thickness direction of the supporting film was defined as the measurement area, and the measurement area was measured at 200 points in the measurement area 259 μm × 260 μm (therefore, the total measurement area becomes 0.259 mm × 0.26 mm × 200 = 13.5 mm 2 ).

將所測量之圖像內之最大光量之像素與最小光量之像素之光量差分成4096等級(最大光量之值為4095,最小光量之值成為0)。製作將圖像內之像素之光量分佈圖表化而成之直方圖(橫軸:光量之等級(最小值0、最大值4095)、縱軸:像素之個數)。將自所製作之直方圖之存在2個之下擺部之值較大之下擺部之值加上400等級所得之等級設為閾值,將所測量之圖像二值化,對光量大於閾值之像素之面積進行合計,並將該合計面積設為光學異常區域之合計面積。算出光學異常區域部分之合計面積相對於測量面積之比率。The difference between the light quantity of the maximum light quantity pixel and the minimum light quantity pixel in the measured image is 4096 levels (the maximum light quantity value is 4095, and the minimum light quantity value is 0). Create a histogram that graphs the light intensity distribution of pixels in the image (horizontal axis: light intensity level (minimum value 0, maximum value 4095), vertical axis: number of pixels). Set the value obtained from the existence of the two hem parts of the histogram to be greater than the value of the hem part plus 400 levels as the threshold value, binarize the measured image, and count the pixels whose light intensity is greater than the threshold value The total area is calculated as the total area of the optically abnormal area. Calculate the ratio of the total area of the optically abnormal area to the measurement area.

<與光學異常區域相接之直徑0.5 μm以上之微粒子、直徑1.0 μm以上之微粒子、直徑2.0 μm以上之微粒子之數量>
於測定光學異常區域部分之合計面積後,將落射型雷射顯微鏡(Olympus製造之OLS-4100)切換為光學顯微鏡模式。其後,於測定區域259 μm×260 μm中測定與和藉由目測利用雷射顯微鏡模式確認之光學異常區域中之微粒子之位置相對應之光學異常區域相接之微粒子之數量及其直徑。
以測定部位數200點實施(即,於0.259 mm×0.26 mm×200=13.5 mm2 之面積內實施)同樣之測定,並對微粒子之每一直徑算出其合計數。
<Number of fine particles with a diameter of 0.5 μm or more, fine particles with a diameter of 1.0 μm or more, and fine particles with a diameter of 2.0 μm or more that are in contact with the optical anomaly area>
After measuring the total area of the optically abnormal region, the epi-laser microscope (OLS-4100 manufactured by Olympus) was switched to the optical microscope mode. After that, the number and diameter of the microparticles that are in contact with the optically abnormal region corresponding to the position of the particles in the optically abnormal region confirmed by the laser microscope mode are measured in the measurement region 259 μm × 260 μm.
The measurement was performed at 200 points (ie, within an area of 0.259 mm × 0.26 mm × 200 = 13.5 mm 2 ), and the total number of particles was calculated for each diameter.

<抗蝕劑突起之評價>
以成為L(線)/S(間隙)=8 μm/8 μm之方式使300 mm見方之評價用基板整個面曝光。此時,使曝光時之焦點之位置對準聚對苯二甲酸乙二酯膜表面。其次,於剝離聚對苯二甲酸乙二酯膜(支持膜)後,以最小顯影時間之2倍之顯影時間進行顯影。並且,利用光學顯微鏡使焦點對準抗蝕劑表面而觀察抗蝕圖案,並對2 μm以上之尺寸之突起進行計數。再者,觀察區域係設為3 mm見方(9 mm2 )。
將結果示於表1。
<Evaluation of resist protrusions>
The entire surface of the evaluation substrate of 300 mm square was exposed so that L (line) / S (gap) = 8 μm / 8 μm. At this time, the position of the focal point during exposure is aligned with the surface of the polyethylene terephthalate film. Secondly, after peeling the polyethylene terephthalate film (support film), development is performed with a development time that is twice the minimum development time. Then, the optical microscope was used to focus on the surface of the resist to observe the resist pattern, and projections with a size of 2 μm or more were counted. Furthermore, the observation area is set to 3 mm square (9 mm 2 ).
The results are shown in Table 1.

<線寬變粗之評價>
以成為L(線)/S(間隙)=8 μm/8 μm之方式使300 mm見方之評價用基板整個面曝光。此時,使曝光時之焦點之位置對準聚對苯二甲酸乙二酯膜之感光層樹脂側之表面。其次,於剝離聚對苯二甲酸乙二酯膜(支持膜)後,以最小顯影時間之2倍之顯影時間進行顯影。測定線寬,並測定寬度最粗之部分之線寬(無焦點偏移)。測定係對30根線對各3 mm之範圍進行,對各線中寬度最粗之部分之線寬進行測定,並將其設為平均值。其次,使曝光時之焦點之位置自聚對苯二甲酸乙二酯膜之感光層樹脂側之表面向400 μm基板內側偏移,除此以外,於與上述同樣之條件下進行測定,對30根線測定寬度最粗之部分之線寬,而獲得其平均值。
<Evaluation of thicker line width>
The entire surface of the evaluation substrate of 300 mm square was exposed so that L (line) / S (gap) = 8 μm / 8 μm. At this time, the position of the focal point during exposure is aligned with the surface of the polyethylene terephthalate film on the resin side of the photosensitive layer. Secondly, after peeling the polyethylene terephthalate film (support film), development is performed with a development time that is twice the minimum development time. Measure the line width, and measure the line width of the thickest part (without focus shift). The measurement is carried out on 30 lines with a range of 3 mm each, and the line width of the thickest part of each line is measured and set as the average value. Next, the position of the focal point at the time of exposure was shifted from the surface of the photosensitive layer resin side of the polyethylene terephthalate film toward the inside of the 400 μm substrate, except that the measurement was performed under the same conditions as above. The root line measures the width of the thickest part of the line and obtains its average value.

<實施例4~6及比較例2>
製作聚對苯二甲酸乙二酯(PET)作為實施例4~6及比較例2之各支持膜。各支持膜中之微粒子之數量係如表2中所記載。支持膜中之微粒子之數量係藉由過濾器之網眼之粗細及使構成支持膜之材料通過過濾器之次數及添加微粒子之數量而加以調整。
此時,藉由在PET膜之雙軸延伸後再次對膜於180~250℃之條件下進行熱壓接處理,而使微粒子周圍之光學異常區域(即,空腔、或配向性或結晶性不同之區域等)消失。又,支持膜之主區域與微粒子之折射率差係藉由改變微粒子之折射率而加以調整。
使用藉由上述方法製作者作為支持膜,除此以外,以與實施例1同樣之順序,進行感光性樹脂積層體之製作及抗蝕劑突起之測定。
<Examples 4 to 6 and Comparative Example 2>
Polyethylene terephthalate (PET) was produced as each support film of Examples 4 to 6 and Comparative Example 2. The number of fine particles in each support film is as shown in Table 2. The number of fine particles in the support film is adjusted by the thickness of the mesh of the filter and the number of times the material constituting the support film passes through the filter and the number of added fine particles.
At this time, by biaxially stretching the PET film, the film is again subjected to thermocompression bonding at 180 to 250 ° C to cause an optically abnormal region around the particles (ie, cavity, or alignment or crystallinity The different areas, etc.) disappear. In addition, the refractive index difference between the main region of the supporting film and the fine particles is adjusted by changing the refractive index of the fine particles.
Except that the fabricator produced by the above method was used as a support film, in the same manner as in Example 1, the production of the photosensitive resin laminate and the measurement of the resist protrusion were performed.

[表1]


表1
[Table 1]


Table 1

[表2]
表2
[Table 2]
Table 2

由表1及2所示之結果可知,於光學異常區域之合計面積減少之實施例1~3中,與光學異常區域之合計面積較大之比較例1相比,抗蝕劑突起減少,於與作為微粒子以外之光學異常區域之異常折射率區域相接之微粒子之數量減少之實施例4~6中,與和異常折射率區域相接之微粒子較多之比較例2相比,抗蝕劑突起減少。
[產業上之可利用性]
From the results shown in Tables 1 and 2, it can be seen that in Examples 1 to 3 in which the total area of the optically abnormal regions is reduced, the resist protrusions are reduced compared to Comparative Example 1 in which the total area of the optically abnormal regions is large. In Examples 4 to 6 in which the number of fine particles contacting the abnormal refractive index region which is an optical abnormal region other than fine particles is reduced, compared to Comparative Example 2 where there are many fine particles contacting the abnormal refractive index region, the resist Protrusion is reduced.
[Industry availability]

本發明之感光性樹脂積層體由於避免由支持膜之異物所引起之抗蝕圖案缺陷(突起),形成良好之抗蝕圖案形狀,故而可適宜地用於印刷配線板、可撓性基板、引線框架基板、COF(薄膜覆晶)用基板、半導體封裝用基板、液晶用透明電極、液晶用TFT用配線、PDP(電漿顯示器面板)用電極等之導體圖案之製造。Since the photosensitive resin laminate of the present invention avoids defects (protrusions) of the resist pattern caused by foreign substances in the support film and forms a good resist pattern shape, it can be suitably used for printed wiring boards, flexible substrates, and leads Manufacture of conductor patterns such as frame substrates, substrates for COF (film on chip), substrates for semiconductor packages, transparent electrodes for liquid crystals, wiring for TFTs for liquid crystals, and electrodes for PDP (plasma display panels).

圖1係對光學異常區域之合計面積之測定方法進行說明之圖。FIG. 1 is a diagram illustrating a method of measuring the total area of optically abnormal regions.

圖2係對微粒子數之利用雷射顯微鏡模式之測定進行說明之圖。 FIG. 2 is a diagram explaining the measurement of the number of fine particles using a laser microscope mode.

圖3係對微粒子數之利用光學顯微鏡模式之測定進行說明之圖。 FIG. 3 is a diagram for explaining the measurement of the number of fine particles using an optical microscope mode.

Claims (31)

一種感光性樹脂積層體,其係具備支持膜、與形成於上述支持膜上之感光性樹脂組合物層者,且 上述支持膜包含微粒子,包含利用落射型雷射顯微鏡於13.5 mm2 之面積中觀測上述支持膜時之光學異常區域之合計面積比率為300 ppm以下之區域。A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film, and the support film contains fine particles, including an area of 13.5 mm 2 using an epi-laser laser microscope The area where the total area ratio of the optically abnormal areas when the above support film is observed is 300 ppm or less. 如請求項1之感光性樹脂積層體,其中上述支持膜包含利用落射型雷射顯微鏡於13.5 mm2 之面積中觀測上述支持膜時之光學異常區域之合計面積比率為200 ppm以下之區域。The photosensitive resin laminate according to claim 1, wherein the support film includes a region where the total area ratio of the optically abnormal regions when the support film is observed in an area of 13.5 mm 2 using an epi-laser microscope is 200 ppm or less. 如請求項1之感光性樹脂積層體,其中上述支持膜包含利用落射型雷射顯微鏡於13.5 mm2 之面積中觀測上述支持膜時之光學異常區域之合計面積比率為100 ppm以下之區域。The photosensitive resin laminate according to claim 1, wherein the support film includes a region where the total area ratio of the optically abnormal regions when the support film is observed in an area of 13.5 mm 2 using an epi-laser microscope is 100 ppm or less. 如請求項1之感光性樹脂積層體,其中上述支持膜包含利用落射型雷射顯微鏡於13.5 mm2 之面積中觀測上述支持膜時之光學異常區域之合計面積比率為50 ppm以下之區域。The photosensitive resin laminate according to claim 1, wherein the support film includes a region where the total area ratio of the optically abnormal regions when the support film is observed in an area of 13.5 mm 2 using an epi-laser microscope is 50 ppm or less. 如請求項1至4中任一項之感光性樹脂積層體,其中上述支持膜以質量基準計,包含微粒子10 ppm以上。The photosensitive resin laminate according to any one of claims 1 to 4, wherein the support film contains 10 ppm or more of fine particles on a mass basis. 一種感光性樹脂積層體,其係具備支持膜、與形成於上述支持膜上之感光性樹脂組合物層者,且 上述支持膜包含微粒子, 上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑0.5 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量以數量平均計成為1200個以下之區域。A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film, and the support film contains fine particles, and the support film has an area of 13.5 mm 2 of the support film Among the above-mentioned fine particles with a diameter of 0.5 μm or more, the number of fine particles in contact with the area other than the fine particles in the optically abnormal area becomes an area of 1200 or less on average. 如請求項6之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑0.5 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量以數量平均計成為1000個以下之區域。The photosensitive resin laminate according to claim 6, wherein the support film has a diameter of 0.5 μm or more included in the area of 13.5 mm 2 of the support film, which is different from a region other than the particles of the optically abnormal region The number of connected microparticles becomes an area of less than 1000 on average. 如請求項6之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑0.5 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為900個以下之區域。The photosensitive resin laminate according to claim 6, wherein the support film has a diameter of 0.5 μm or more included in the area of 13.5 mm 2 of the support film, which is different from a region other than the particles of the optically abnormal region The number of connected microparticles becomes an area below 900. 如請求項6之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑0.5 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為500個以下之區域。The photosensitive resin laminate according to claim 6, wherein the support film has a diameter of 0.5 μm or more included in the area of 13.5 mm 2 of the support film, which is different from a region other than the particles of the optically abnormal region The number of connected microparticles becomes less than 500 areas. 如請求項6之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑0.5 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為200個以下之區域。The photosensitive resin laminate according to claim 6, wherein the support film has a diameter of 0.5 μm or more included in the area of 13.5 mm 2 of the support film, which is different from a region other than the particles of the optically abnormal region The number of connected microparticles becomes an area of less than 200. 如請求項6至10中任一項之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑1.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為500個以下之區域。The photosensitive resin laminate according to any one of claims 6 to 10, wherein the support film has an optical abnormality area among the fine particles having a diameter of 1.0 μm or more contained in an area of 13.5 mm 2 of the support film The number of particles in the area other than the particles is 500 or less. 如請求項11之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑1.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為300個以下之區域。The photosensitive resin laminate according to claim 11, wherein the support film has a diameter of 1.0 μm or more included in the area of 13.5 mm 2 of the support film, which is different from a region other than the particles of the optically abnormal region The number of connected microparticles becomes an area of less than 300. 如請求項11之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑1.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為100個以下之區域。The photosensitive resin laminate according to claim 11, wherein the support film has a diameter of 1.0 μm or more included in the area of 13.5 mm 2 of the support film, which is different from a region other than the particles of the optically abnormal region The number of connected microparticles becomes an area of less than 100. 如請求項11之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑1.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為50個以下之區域。The photosensitive resin laminate according to claim 11, wherein the support film has a diameter of 1.0 μm or more included in the area of 13.5 mm 2 of the support film, which is different from a region other than the particles of the optically abnormal region The number of connected microparticles becomes an area of less than 50. 如請求項6至14中任一項之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑2.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為200個以下之區域。The photosensitive resin laminate according to any one of claims 6 to 14, wherein the support film has the above-mentioned fine particles having a diameter of 2.0 μm or more contained in an area of 13.5 mm 2 of the support film and the optical abnormality region The number of particles in the area other than the particles is 200 or less. 如請求項15之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑2.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為100個以下之區域。The photosensitive resin laminate according to claim 15, wherein the support film has a diameter of 2.0 μm or more included in the area of 13.5 mm 2 of the support film, which is different from a region other than the particles of the optically abnormal region The number of connected microparticles becomes an area of less than 100. 如請求項15之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑2.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為50個以下之區域。The photosensitive resin laminate according to claim 15, wherein the support film has a diameter of 2.0 μm or more included in the area of 13.5 mm 2 of the support film, which is different from a region other than the particles of the optically abnormal region The number of connected microparticles becomes an area of less than 50. 如請求項15之感光性樹脂積層體,其中上述支持膜具有上述支持膜之13.5 mm2 之面積中所含之直徑2.0 μm以上之上述微粒子之中,與上述光學異常區域之微粒子以外之區域相接之微粒子之數量成為10個以下之區域。The photosensitive resin laminate according to claim 15, wherein the support film has a diameter of 2.0 μm or more included in the area of 13.5 mm 2 of the support film, which is different from a region other than the particles of the optically abnormal region The number of connected microparticles becomes a region of 10 or less. 如請求項1至18中任一項之感光性樹脂積層體,其中上述微粒子之折射率與上述支持膜之主區域之折射率的折射率差為0.2以下。The photosensitive resin laminate according to any one of claims 1 to 18, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.2 or less. 如請求項19之感光性樹脂積層體,其中上述微粒子之折射率與上述支持膜之主區域之折射率的折射率差為0.1以下。The photosensitive resin laminate according to claim 19, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.1 or less. 如請求項19之感光性樹脂積層體,其中上述微粒子之折射率與上述支持膜之主區域之折射率的折射率差為0.05以下。The photosensitive resin laminate according to claim 19, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.05 or less. 如請求項19之感光性樹脂積層體,其中上述微粒子之折射率與上述支持膜之主區域之折射率的折射率差為0.02以下。The photosensitive resin laminate according to claim 19, wherein the refractive index difference between the refractive index of the fine particles and the refractive index of the main region of the support film is 0.02 or less. 如請求項1至22中任一項之感光性樹脂積層體,其中上述光學異常區域包含空腔。The photosensitive resin laminate according to any one of claims 1 to 22, wherein the above-mentioned optical abnormal region includes a cavity. 如請求項1至23中任一項之感光性樹脂積層體,其中上述光學異常區域包含與上述支持膜之主區域配向性不同之區域。The photosensitive resin laminate according to any one of claims 1 to 23, wherein the optically abnormal region includes a region having a different orientation from the main region of the support film. 如請求項1至24中任一項之感光性樹脂積層體,其中上述光學異常區域包含與上述支持膜之主區域結晶性不同之區域。The photosensitive resin laminate according to any one of claims 1 to 24, wherein the optical abnormal region includes a region having a crystallinity different from the main region of the support film. 如請求項1至25中任一項之感光性樹脂積層體,其係線寬/間隙寬為20/20(μm)以下之配線形成用。The photosensitive resin laminate according to any one of claims 1 to 25, which is used for wiring formation having a line width / gap width of 20/20 (μm) or less. 如請求項26之感光性樹脂積層體,其係線寬/間隙寬未達10/10(μm)之配線形成用。The photosensitive resin laminate as claimed in claim 26, which is used for wiring formation where the line width / gap width is less than 10/10 (μm). 一種印刷配線板中之抗蝕圖案之製造方法,其使用如請求項1至27中任一項之感光性樹脂積層體。A method for manufacturing a resist pattern in a printed wiring board, which uses the photosensitive resin laminate according to any one of claims 1 to 27. 如請求項28之方法,其係利用半加成法進行。As in the method of claim 28, it is performed using a semi-additive method. 如請求項28或29之方法,其中上述抗蝕圖案之線寬/間隙寬未達10/10(μm)。The method according to claim 28 or 29, wherein the line width / gap width of the above resist pattern is less than 10/10 (μm). 一種感光性樹脂積層體,其係具備支持膜、與形成於上述支持膜上之感光性樹脂組合物層者,且 於直接使用繪圖曝光機於基板上形成線寬/間隙寬為8/8(μm)之抗蝕圖案之情形時,於支持膜之感光性樹脂組合物層側之表面對焦時之線寬、與自該表面沿厚度方向朝400 μm基板內側偏移時之線寬之差為1.8 μm以下。A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film, and In the case of directly forming a resist pattern with a line width / gap width of 8/8 (μm) on the substrate using a drawing exposure machine, the line width when the surface of the support film on the photosensitive resin composition layer side is focused, and The difference in line width when shifted from the surface in the thickness direction toward the inside of the 400 μm substrate is 1.8 μm or less.
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