TW201940334A - Dry film, hardened object, and electronic part provides a dry film with good adhesion between the resin layer and the protective film - Google Patents

Abstract

The present invention provides a dry film with good adhesion between the resin layer and the protective film, a dry film with less sedimentation of inorganic filler contained in the resin layer, and a hardened object of the resin layer of the dry film, and an electronic part with the hardened object. The present invention is provided with a carrier film, a resin layer, and a protective film. The protective film is a 2-axis extended polypropylene film. The resin layer comprises inorganic filler, polymer resin having a glass transition temperature of 20 DEG C or less and an average molecular weight of more than 30000, and an epoxy resin, wherein the resin layer comprises at least one of a semi-solid epoxy resin and a crystalline epoxy resin as the epoxy resin.

Description

乾膜、硬化物及電子零件Dry film, hardened material and electronic parts

本發明係有關乾膜、硬化物及電子零件。The present invention relates to dry films, hardened materials and electronic parts.

以往，設置於電子機器等所使用之印刷配線板之阻焊劑或層間絕緣層等之保護膜或絕緣層之形成手段之一為利用乾膜(積層薄膜)(例如專利文獻1)。乾膜係具有將具有所期望之特性的樹脂組成物塗佈於載體薄膜上後，經由乾燥步驟所得的樹脂層，一般而言，以再積層有保護與載體薄膜相反側之面用的保護薄膜的狀態，流通於市場上。將乾膜之樹脂層貼黏(以下也稱為「積層」)於基板後，藉由實施圖型化或硬化處理，可製造具有如上述之保護膜或絕緣層的印刷配線板。

[先前技術文獻]
[專利文獻]Conventionally, one of the means for forming a protective film or an insulating layer such as a solder resist or an interlayer insulating layer on a printed wiring board used in an electronic device or the like is to use a dry film (laminated film) (for example, Patent Document 1). A dry film is a resin layer obtained by applying a resin composition having desired characteristics to a carrier film and then drying the resin layer. Generally, a protective film for protecting the surface opposite to the carrier film is laminated on the resin film. State of circulation in the market. After the resin layer of the dry film is adhered (hereinafter also referred to as "lamination") to the substrate, a patterning or hardening process can be performed to produce a printed wiring board having the above-mentioned protective film or insulating layer.

[Prior technical literature]
[Patent Literature]

[專利文獻1] 日本特開2015-010179號公報[Patent Document 1] Japanese Patent Laid-Open No. 2015-010179

[發明所欲解決之課題][Problems to be Solved by the Invention]

乾膜之製造步驟中，積層保護薄膜時，例如樹脂層所含有之無機填料之調配量較多時等，樹脂層表面之黏性降低時，具有與此保護薄膜之密著性變差的問題。In the manufacturing process of the dry film, when the protective film is laminated, for example, when the amount of the inorganic filler contained in the resin layer is large, when the viscosity of the surface of the resin layer is reduced, there is a problem that the adhesion of the protective film is deteriorated. .

又，樹脂層所含有之無機填料之調配量較多時，形成樹脂層時，以溶劑等稀釋樹脂組成物，使塗佈容易來調整黏度時，樹脂組成物所含有之無機填料變得容易沉降，而有乾膜之品質變成不安定等的問題。In addition, when the amount of the inorganic filler contained in the resin layer is large, when the resin layer is formed, the resin composition is diluted with a solvent or the like to facilitate application and the viscosity is adjusted, the inorganic filler contained in the resin composition is liable to settle. However, there is a problem that the quality of the dry film becomes unstable.

因此，本發明之目的係提供樹脂層與保護薄膜之密著性佳，且樹脂層所含有之無機填料之沉降少的乾膜及該乾膜之樹脂層之硬化物及具有該硬化物之電子零件。

[用以解決課題之手段]Therefore, the object of the present invention is to provide a dry film with good adhesion between the resin layer and the protective film, and less sedimentation of the inorganic filler contained in the resin layer, a hardened product of the resin layer of the dry film, and an electron having the hardened product. Components.

[Means to solve the problem]

本發明人等，為了實現上述目的，首先，藉由將玻璃轉移溫度低的聚乙烯(PE)薄膜作為保護薄膜使用，考慮改善樹脂層與保護薄膜之密著性。雖改善密著性，但是發現保護薄膜積層後之冷卻時，在樹脂層表面產生收縮皺紋等新的問題。
此外，如聚對苯二甲酸乙二酯(PET)之玻璃轉移溫度高，且柔軟性低的保護薄膜，難以密著性佳進行積層。
因此，本發明人等，著眼於冷卻收縮少，亦即，相較於聚乙烯(PE)，玻璃轉移溫度較高，柔軟性良好之2軸延伸聚丙烯薄膜(OPP)，以此2軸延伸聚丙烯薄膜(OPP)作為保護薄膜使用，再檢討。
此檢討之中，2軸延伸聚丙烯薄膜(OPP)，即使施予壓紋加工或電暈處理，依然與樹脂層之密著性不足。而且，形成樹脂層時，成為問題的無機填料沉降，即使在塗佈前經常攪拌，仍未能消除。In order to achieve the above-mentioned object, the present inventors first considered improving the adhesion between the resin layer and the protective film by using a polyethylene (PE) film having a low glass transition temperature as a protective film. Although the adhesion was improved, new problems such as shrinkage wrinkles on the surface of the resin layer were found during cooling after the protective film was laminated.
In addition, a protective film such as polyethylene terephthalate (PET) has a high glass transition temperature and low flexibility, and is difficult to laminate with good adhesion.
Therefore, the present inventors focused on a biaxially-stretched polypropylene film (OPP) having a higher glass transition temperature and better flexibility than polyethylene (PE), and focused on less biaxial shrinkage than polyethylene (PE). Polypropylene film (OPP) is used as a protective film, and then reviewed.
In this review, the biaxially stretched polypropylene film (OPP) has insufficient adhesion to the resin layer even when embossed or corona treated. In addition, when the resin layer is formed, the inorganic filler that is a problem is settled and cannot be eliminated even if it is often stirred before coating.

因此，本發明人等有鑑於上述，為了開發樹脂層與2軸延伸聚丙烯薄膜(OPP)之密著性良好，且樹脂層所含有之無機填料之沉降少的乾膜，而精心檢討構成樹脂層的樹脂組成物。
結果，藉由將玻璃轉移溫度為20℃以下，且重量平均分子量為3萬以上的高分子樹脂與、半固形環氧樹脂及結晶性環氧樹脂之至少1種，調配於形成樹脂層用之樹脂組成物中，發現可解決上述課題，而完成本發明。Therefore, in view of the foregoing, in order to develop a dry film having good adhesion between the resin layer and the biaxially-stretched polypropylene film (OPP) and less sedimentation of the inorganic filler contained in the resin layer, the present inventors carefully reviewed the constituent resins. Resin composition of layers.
As a result, at least one of a polymer resin having a glass transition temperature of 20 ° C. or lower and a weight average molecular weight of 30,000 or more, and a semi-solid epoxy resin and a crystalline epoxy resin was formulated for forming a resin layer. The resin composition was found to solve the above-mentioned problems, and completed the present invention.

亦即，本發明之乾膜，其係具備載體薄膜、樹脂層及保護膜的乾膜，前述保護膜為2軸延伸聚丙烯薄膜，前述樹脂層包含無機填料、玻璃轉移溫度為20℃以下，且重量平均分子量為3萬以上的高分子樹脂及環氧樹脂，前述樹脂層包含作為前述環氧樹脂之半固形環氧樹脂及結晶性環氧樹脂其中之至少1種。That is, the dry film of the present invention is a dry film including a carrier film, a resin layer, and a protective film. The protective film is a biaxially stretched polypropylene film. The resin layer contains an inorganic filler and the glass transition temperature is 20 ° C or lower. The polymer resin and epoxy resin having a weight average molecular weight of 30,000 or more, and the resin layer includes at least one of a semi-solid epoxy resin and a crystalline epoxy resin as the epoxy resin.

本發明之乾膜，其中前述樹脂層包含作為硬化劑之具有酚性羥基之化合物、具有活性酯基之化合物、具有氰酸酯基之化合物及具有馬來醯亞胺基之化合物其中之至少任一種為佳。The dry film of the present invention, wherein the resin layer contains at least any one of a compound having a phenolic hydroxyl group as a hardener, a compound having an active ester group, a compound having a cyanate group, and a compound having a maleimide group. One is better.

本發明之乾膜，其中前述樹脂層包含作為前述無機填料之平均粒徑為0.1~10μm之無機填料與平均粒徑為0.01~5μm之無機填料的混合物，且前述平均粒徑為0.1~10μm之無機填料與前述平均粒徑為0.01~5μm之無機填料之粒徑分布測量時之峰間之差為0.05μm以上為佳。In the dry film of the present invention, the resin layer includes a mixture of the inorganic filler having an average particle diameter of 0.1 to 10 μm and the inorganic filler having an average particle diameter of 0.01 to 5 μm as the inorganic filler, and the average particle diameter of the inorganic filler It is preferable that the difference between the peaks in the particle size distribution measurement of the inorganic filler and the aforementioned inorganic filler having an average particle diameter of 0.01 to 5 μm is 0.05 μm or more.

本發明之乾膜，其中以前述樹脂層之固體成分全量基準，前述無機填料含有50質量%以上為佳。In the dry film of the present invention, it is preferable that the inorganic filler contains 50% by mass or more of the solid content of the resin layer.

本發明之硬化物，其係使前述乾膜的樹脂層硬化所得者。The cured product of the present invention is obtained by curing the resin layer of the dry film.

本發明之電子零件，其係具有前述硬化物者。

[發明效果]The electronic component of the present invention includes the hardened material.

[Inventive effect]

依據本發明時，可提供樹脂層與保護薄膜之密著性佳，且樹脂層所含有之無機填料之沉降少的乾膜及該乾膜之樹脂層之硬化物及具有該硬化物之電子零件。According to the present invention, it is possible to provide a dry film with excellent adhesion between the resin layer and the protective film, and less sedimentation of the inorganic filler contained in the resin layer, a hardened material of the resin layer of the dry film, and an electronic part having the hardened material. .

＜乾膜＞
本發明之乾膜，其特徵係具備載體薄膜、樹脂層及保護膜的乾膜，前述保護膜為2軸延伸聚丙烯薄膜，前述樹脂層包含無機填料、玻璃轉移溫度為20℃以下，且重量平均分子量為3萬以上的高分子樹脂及環氧樹脂，前述樹脂層包含作為前述環氧樹脂之半固形環氧樹脂及結晶性環氧樹脂其中之至少1種。＜ Dry film ＞
The dry film of the present invention is characterized by a dry film including a carrier film, a resin layer, and a protective film. The protective film is a biaxially stretched polypropylene film. The resin layer includes an inorganic filler, a glass transition temperature of 20 ° C or less, and a weight. A polymer resin and an epoxy resin having an average molecular weight of 30,000 or more, and the resin layer includes at least one of a semi-solid epoxy resin and a crystalline epoxy resin as the epoxy resin.

本發明中，特別是即使將對黏性低的樹脂層之密著力弱的2軸延伸聚丙烯薄膜作為保護薄膜使用時，藉由將玻璃轉移溫度為20℃以下，且重量平均分子量為3萬以上的高分子樹脂與固形環氧樹脂及結晶性環氧樹脂之至少任一種調配於樹脂層，可使樹脂層與保護薄膜之密著性變得良好。詳細的機構雖不明確，但是藉由調配如上述的高分子樹脂，因樹脂層之表面為霧面，而使密著力安定，又，作為環氧樹脂使用半固形環氧樹脂或結晶性環氧樹脂，以保護薄膜之密著溫度軟化或到達熔點，結果保護薄膜之密著安定。又，詳細的機構雖不明確，但是藉由將如上述的高分子樹脂調配於形成樹脂層用之樹脂組成物，而減少無機填料之沉降。In the present invention, even when a biaxially stretched polypropylene film having weak adhesion to a resin layer with low viscosity is used as a protective film, the glass transition temperature is 20 ° C or lower, and the weight average molecular weight is 3 At least one of a polymer resin of at least 10,000, a solid epoxy resin, and a crystalline epoxy resin is blended in the resin layer, so that the adhesion between the resin layer and the protective film can be improved. Although the detailed mechanism is not clear, by blending the polymer resin as described above, the surface of the resin layer is a matte surface, so that the adhesion is stable, and a semi-solid epoxy resin or a crystalline epoxy resin is used as the epoxy resin. The resin softens or reaches the melting point at the adhesion temperature of the protective film. As a result, the adhesion of the protective film is stable. Although the detailed mechanism is not clear, the above-mentioned polymer resin is formulated into a resin composition for forming a resin layer to reduce sedimentation of the inorganic filler.

樹脂層與保護薄膜之密著性及無機填料之沉降的課題，特別是無機填料之含量高的情形，較顯著，但是依據本發明時，即使無機填料之含量高的情形，也可製造樹脂層與保護薄膜之密著性佳，且樹脂層所含有之無機填料之沉降少的乾膜。The problems of the adhesion of the resin layer and the protective film and the sedimentation of the inorganic filler, especially when the content of the inorganic filler is high, are significant, but according to the present invention, the resin layer can be produced even when the content of the inorganic filler is high. Dry film with good adhesion to the protective film and less sedimentation of the inorganic filler contained in the resin layer.

又，無機填料之含量高的情形，作為保護薄膜使用OPP時，切割( slit)加工時容易產生OPP之剝離或龜裂、掉粉，但是依據本發明之乾膜時，可抑制加工時之剝離或龜裂、掉粉。In addition, when the content of the inorganic filler is high, when OPP is used as a protective film, the peeling, cracking, and powdering of OPP are likely to occur during slit processing. However, when the dry film according to the present invention is used, peeling during processing can be suppressed. Or cracked or powdered.

本發明之乾膜之樹脂層的硬化物，當貼合對象物有凹凸時，例如電路等之零件被埋入時，硬化物表面之平坦性也優異。因此，在硬化物之表面再形成電路等時，可形成微細的圖型，因此，適合作為層間絕緣材使用。The hardened product of the resin layer of the dry film of the present invention has excellent flatness on the surface of the hardened product when the bonding target has unevenness, such as when parts such as a circuit are buried. Therefore, when a circuit is formed on the surface of the hardened object, a fine pattern can be formed. Therefore, it is suitable for use as an interlayer insulating material.

此外，本發明之乾膜之樹脂層的硬化物，與貼合對象物之密著性優異，對於低粗度配線基板、蝕刻( etched out)基板、半導體，也可良好密著。Further, a dry film of the cured resin layer of the present invention, the bonding adhesion is excellent in the object, for low thickness of the wiring substrate, etching (etched out) substrate, a semiconductor, it may also be good adhesion.

本發明之乾膜之樹脂層的硬化物，其耐翹曲性也優異。The cured product of the resin layer of the dry film of the present invention is also excellent in warpage resistance.

圖1係表示本發明之乾膜之一實施形態的概略剖面圖。樹脂層12形成於載體薄膜13上，積層有保護薄膜14之三層構造的乾膜11。必要時，可在薄膜與樹脂層之間設置其他的樹脂層。又，本發明之乾膜的樹脂層，可為1層，也可為2層以上。FIG. 1 is a schematic cross-sectional view showing an embodiment of a dry film of the present invention. The resin layer 12 is formed on a carrier film 13, and a dry film 11 having a three-layer structure of a protective film 14 is laminated. If necessary, another resin layer may be provided between the film and the resin layer. The resin layer of the dry film of the present invention may be one layer or two or more layers.

[樹脂層]
本發明之乾膜的樹脂層，一般為被稱為B階段狀態的狀態，由硬化性樹脂組成物所得者。具體而言，乾膜的樹脂層係將硬化性樹脂組成物塗佈於薄膜後，經過乾燥步驟所得者。前述硬化性樹脂組成物，只要包含上述成分時，其他成分的種類或調配量無特別限定。樹脂層之厚度，無特別限定，例如厚度為1~200μm即可。本發明中，厚度較大時，平坦性優異，例如，厚度為30μm以上，50μm以上，進一步為100μm以上，也可適用。又，將本發明之乾膜的樹脂層多層重疊，也可形成厚度超過200μm的樹脂層。此時，使用輥積層機或真空積層機即可。[Resin layer]
The resin layer of the dry film of the present invention is generally a state called a B-stage state, and is obtained from a curable resin composition. Specifically, the resin layer of the dry film is obtained by applying a curable resin composition to a film and then subjecting it to a drying step. As long as the said curable resin composition contains the said component, there is no restriction | limiting in particular in the kind or compounding quantity of another component. The thickness of the resin layer is not particularly limited, and for example, the thickness may be 1 to 200 μm. In the present invention, when the thickness is large, the flatness is excellent. For example, the thickness is 30 μm or more, 50 μm or more, and more preferably 100 μm or more. Moreover, the resin layer of the dry film of the present invention can be laminated in multiple layers to form a resin layer having a thickness of more than 200 μm. In this case, a roll laminator or a vacuum laminator may be used.

[玻璃轉移溫度為20℃以下，且重量平均分子量為3萬以上的高分子樹脂]
前述樹脂層係含有玻璃轉移溫度為20℃以下，且重量平均分子量為3萬以上的高分子樹脂。前述高分子樹脂之玻璃轉移溫度，較佳為-40~20℃，更佳為-15~15℃，特佳為-5~15℃。在-5~15℃時，可良好抑制硬化物之翹曲。
又，前述高分子樹脂之重量平均分子量越高時，無機填料之沉降防止效果越大，故10萬以上為佳，更佳為20萬以上。上限值例如100萬以下。[Polymer resin with a glass transition temperature of 20 ° C or lower and a weight average molecular weight of 30,000 or more]
The resin layer contains a polymer resin having a glass transition temperature of 20 ° C. or lower and a weight average molecular weight of 30,000 or more. The glass transition temperature of the aforementioned polymer resin is preferably -40 to 20 ° C, more preferably -15 to 15 ° C, and particularly preferably -5 to 15 ° C. At -5 ~ 15 ℃, it can well suppress the warpage of hardened material.
In addition, as the weight average molecular weight of the polymer resin is higher, the sedimentation prevention effect of the inorganic filler is greater, so it is preferably 100,000 or more, more preferably 200,000 or more. The upper limit value is, for example, 1 million or less.

高分子樹脂，可列舉具有選自丁二烯骨架、醯胺骨架、醯亞胺骨架、縮醛骨架、碳酸酯骨架、酯骨架、胺基甲酸酯骨架、丙烯酸骨架及矽氧烷骨架之1種以上之骨架的高分子樹脂等。例如，具有丁二烯骨架的高分子樹脂(日本曹達公司製「G-1000」、「G-3000」、「GI-1000」、「GI-3000」、出光石油化學公司製「R-45EPI」、DAICEL化學工業公司製「PB3600」、「Epofriend AT501」、cray valley公司製「Ricon130」、「Ricon142」、「Ricon150」、「Ricon657」、「Ricon130MA」)、具有丁二烯骨架與聚醯亞胺骨架的高分子樹脂(日本特開2006-37083號公報記載者)、具有丙烯酸骨架之高分子樹脂(nagase chemtex公司製「SG-P3」、「SG-600LB」、「SG-280」、「SG-790」、「SG-K2」、根上工業公司製「SN-50」、「AS-3000E」、「ME-2000」)等。The polymer resin includes one selected from the group consisting of butadiene skeleton, amidine skeleton, amidine skeleton, acetal skeleton, carbonate skeleton, ester skeleton, urethane skeleton, acrylic skeleton, and siloxane skeleton. More than one kind of skeleton polymer resin. For example, polymer resins with a butadiene skeleton ("G-1000", "G-3000", "GI-1000", "GI-3000", "GI-3000", manufactured by Idemitsu Petrochemical Co., Ltd., and "R-45EPI" manufactured by Idemitsu Petrochemical Co., Ltd. , "PB3600", "Epofriend AT501" by DAICEL Chemical Industries, "Ricon130", "Ricon142", "Ricon150", "Ricon657", "Ricon130MA") manufactured by Cray Valley, Inc., butadiene skeleton and polyimide Polymer resin with a skeleton (as described in Japanese Patent Application Laid-Open No. 2006-37083), polymer resin with an acrylic skeleton ("SG-P3", "SG-600LB", "SG-280", "SG" manufactured by Nagase Chemtex Corporation) -790 "," SG-K2 "," SN-50 "," AS-3000E "," ME-2000 "made by Negami Industries, Ltd.).

前述高分子樹脂，就硬化物之平坦性的觀點，較佳為玻璃轉移溫度為20℃以下，且重量平均分子量為20萬以上的丙烯酸共聚物。又，就與2軸延伸聚丙烯薄膜(OPP)之接著性及低粗度基材或與電路之接著性的觀點，較佳為玻璃轉移溫度為-5~15℃，且重量平均分子量為20萬~50萬的丙烯酸共聚物。The polymer resin is preferably an acrylic copolymer having a glass transition temperature of 20 ° C or lower and a weight average molecular weight of 200,000 or more from the viewpoint of the flatness of the cured product. From the standpoint of adhesion to a biaxially-stretched polypropylene film (OPP) and a substrate having a low roughness or adhesion to a circuit, the glass transition temperature is preferably -5 to 15 ° C, and the weight average molecular weight is 20 500,000 to 500,000 acrylic copolymers.

前述丙烯酸酯共聚物也可具有官能基，官能基可列舉例如，羧基、羥基、環氧基、醯胺基等。The acrylate copolymer may have a functional group, and examples of the functional group include a carboxyl group, a hydroxyl group, an epoxy group, and a fluorenyl group.

前述丙烯酸酯共聚物係具有環氧基者為佳，具有環氧基及醯胺基者更佳。因具有環氧基，可抑制硬化物之翹曲。The acrylate copolymer is preferably one having an epoxy group, and more preferably one having an epoxy group and an amido group. Since it has an epoxy group, it can suppress the warpage of hardened materials.

前述丙烯酸酯共聚物，可列舉nagase chemtex公司製之teisanresin SG-70L、SG-708-6、WS-023 EK30、SG-P3、SG-80H、SG-280 EK23、SG-600TEA、SG-790。前述丙烯酸酯共聚物也可合成得到，合成方法可列舉例如，日本特開2016-102200號公報記載之合成方法。Examples of the acrylate copolymer include teisanresin SG-70L, SG-708-6, WS-023 EK30, SG-P3, SG-80H, SG-280 EK23, SG-600TEA, and SG-790 manufactured by Nagase Chemtex. The said acrylate copolymer can also be synthesize | combined, The synthesis method is mentioned, for example, the synthesis method described in Unexamined-Japanese-Patent No. 2016-102200.

前述高分子樹脂，可1種單獨使用或組合2種類以上使用。前述高分子之調配量係以組成物之固體成分全量基準，較佳為0.5~10質量%，更佳為1.0~7.0質量%，又更佳為2.0~7.0質量%，特佳為4.0~7.0質量%。The polymer resin may be used singly or in combination of two or more kinds. The compounding amount of the aforementioned polymer is based on the total solid content of the composition, preferably 0.5 to 10% by mass, more preferably 1.0 to 7.0% by mass, still more preferably 2.0 to 7.0% by mass, and particularly preferably 4.0 to 7.0. quality%.

又，本說明書中，重量平均分子量(Mw)之值，可藉由凝膠滲透層析法(GPC)法(聚苯乙烯標準)，以下述測量裝置、測量條件測量。
測量裝置：Waters製「Waters 2695」
檢測器：Waters製「Waters2414」、RI(示差折射率計)
管柱：Waters製「HSPgel Column，HR MB-L，3μm，6mm×150mm」×2+Waters製「HSPgel Column，HR1，3μm，6mm×150mm」×2
測量條件：
管柱溫度：40℃
RI檢測器設定溫度：35℃
展開溶劑：四氫呋喃
流速：0.5ml/分鐘
樣品量：10μl
樣品濃度：0.7wt%In addition, in this specification, the value of weight average molecular weight (Mw) can be measured by the gel permeation chromatography (GPC) method (polystyrene standard) using the following measuring apparatus and measurement conditions.
Measuring device: "Waters 2695" by Waters
Detector: "Waters2414" manufactured by Waters, RI (differential refractive index meter)
Column: "HSPgel Column, HR MB-L, 3μm, 6mm x 150mm" by Waters x 2+ "HSPgel Column, HR1, 3μm, 6mm x 150mm" by Waters x 2
Measurement conditions:
Column temperature: 40 ℃
RI detector set temperature: 35 ℃
Development solvent: tetrahydrofuran Flow rate: 0.5 ml / min Sample amount: 10 μl
Sample concentration: 0.7wt%

[環氧樹脂]
前述樹脂層包含環氧樹脂。環氧樹脂為具有環氧基的樹脂，以往公知者皆可使用。可列舉分子中具有2個環氧基之2官能性環氧樹脂、分子中具有3個以上之環氧基的多官能環氧樹脂等。又，也可為氫化的環氧樹脂。前述樹脂層係包含作為前述環氧樹脂之半固形環氧樹脂及結晶性環氧樹脂之至少任一種。半固形環氧樹脂及結晶性環氧樹脂，各自可1種單獨使用或組合2種類以上使用。又，前述樹脂層也可含有固形環氧樹脂或液狀環氧樹脂。本說明書中，固形環氧樹脂係指40℃下固體狀的環氧樹脂，而半固形環氧樹脂係指20℃下固體狀，40℃下液狀的環氧樹脂，液狀環氧樹脂係指20℃下液狀的環氧樹脂。液狀的判定係依據有關危險物之試驗及性狀之省令(平成元年自治省令第1號)之附件第2之「液狀的確認方法」來進行。例如以日本特開2016-079384之段落23~25所記載的方法進行。又，結晶性環氧樹脂係指結晶性強的環氧樹脂，熔點以下的溫度，高分子鏈正確規則性排列，雖為固形樹脂，但是熔融時，成為一般液狀樹脂之低黏度之熱硬化性的環氧樹脂。[Epoxy resin]
The resin layer contains epoxy resin. The epoxy resin is a resin having an epoxy group, and any conventionally known one can be used. Examples thereof include a bifunctional epoxy resin having two epoxy groups in a molecule, and a polyfunctional epoxy resin having three or more epoxy groups in a molecule. It may also be a hydrogenated epoxy resin. The resin layer includes at least one of a semi-solid epoxy resin and a crystalline epoxy resin as the epoxy resin. Each of the semi-solid epoxy resin and the crystalline epoxy resin may be used alone or in combination of two or more kinds. The resin layer may contain a solid epoxy resin or a liquid epoxy resin. In this specification, solid epoxy resin means solid epoxy resin at 40 ° C, and semi-solid epoxy resin means solid epoxy resin at 20 ° C, liquid epoxy resin at 40 ° C, and liquid epoxy resin. Refers to liquid epoxy resin at 20 ° C. The determination of the liquid state is based on the "Confirmation Method of Liquid State" in Annex 2 of the Provincial Decree (Provincial Decree No. 1 of the Heisei Year of the Autonomous Province) concerning the test of dangerous substances and properties. For example, the method is described in paragraphs 23 to 25 of Japanese Patent Application Laid-Open No. 2016-079384. In addition, crystalline epoxy resin refers to a highly crystalline epoxy resin. At a temperature below the melting point, the polymer chains are correctly and regularly arranged. Although it is a solid resin, when melted, it becomes a low-viscosity thermal curing of general liquid resins. Sexual epoxy.

半固形環氧樹脂，可列舉DIC公司製EPICLON 860、EPICLON 900-IM、EPICLON EXA-4816、EPICLON EXA-4822、旭ciba公司製araldite AER280、東都化成公司製EPOTOHTO YD-134、Mitsubishi Chemical公司製jER834、jER872、住友化學工業公司製ELA-134等之雙酚A型環氧樹脂；DIC公司製EPICLON HP-4032等之萘型環氧樹脂；DIC公司製EPICLON N-740等之苯酚酚醛清漆型環氧樹脂等。
作為半固形狀環氧樹脂，以包含選自由雙酚A型環氧樹脂、萘型環氧樹脂及苯酚酚醛清漆型環氧樹脂所組成之群組之至少1種為佳。因包含半固形狀環氧樹脂，故硬化物之玻璃轉移溫度(Tg)高，CTE降低，龜裂耐性優異。Semi-solid epoxy resins include EPICLON 860, EPICLON 900-IM, EPICLON EXA-4816, EPICLON EXA-4822 made by DIC, Araldite AER280 made by Asahi ciba, EPOTOH YD-134 made by Toto Kasei, and jER834 made by Mitsubishi Chemical. , JER872, Sumitomo Chemical Industries, Ltd. ELA-134 and other bisphenol A epoxy resin; DIC company EPICLON HP-4032 and other naphthalene epoxy resin; DIC company EPICLON N-740 and other phenol novolac type ring Oxygen resin and so on.
The semi-solid epoxy resin preferably contains at least one selected from the group consisting of a bisphenol A epoxy resin, a naphthalene epoxy resin, and a phenol novolac epoxy resin. Because it contains a semi-solid epoxy resin, the glass transition temperature (Tg) of the cured product is high, the CTE is reduced, and the crack resistance is excellent.

結晶性環氧樹脂，可使用例如具有聯苯結構、硫(sulfide)結構、伸苯基結構、萘結構等的結晶性環氧樹脂。聯苯型的環氧樹脂，例如可提供Mitsubishi Chemical公司製jER YX4000、jER YX4000H、jER YL6121H、jER YL6640、jER YL6677，二苯硫醚型環氧樹脂，例如可提供東都化成公司製EPOTOHTOYSLV-120TE，伸苯基型環氧樹脂，例如可提供東都化成公司製EPOTOHTOYDC-1312，萘型環氧樹脂，例如可提供DIC公司製EPICLON HP-4032、EPICLON HP-4032D、EPICLON HP-4700。又，結晶性環氧樹脂可使用東都化成公司製EPOTOHTOYSLV-90C、日產化成工業公司製TEPIC-S(三縮水甘油基異氰脲酸酯)。As the crystalline epoxy resin, for example, a crystalline epoxy resin having a biphenyl structure, a sulfur structure, a phenylene structure, a naphthalene structure, or the like can be used. Biphenyl type epoxy resins, such as jER YX4000, jER YX4000H, jER YL6121H, jER YL6640, and jER YL6677, manufactured by Mitsubishi Chemical, can be provided. For example, diphenyl sulfide type epoxy resins can be provided. For example, the phenylene type epoxy resin can be provided by Toto Kasei Co., Ltd. EPOTOHTOYDC-1312, and the naphthalene type epoxy resin can be provided by DIC Corporation, such as EPICLON HP-4032, EPICLON HP-4032D, and EPICLON HP-4700. As the crystalline epoxy resin, EPOTOHTOYSLV-90C manufactured by Tohto Kasei Co., Ltd. and TEPIC-S (triglycidyl isocyanurate) manufactured by Nissan Chemical Industry Co., Ltd. can be used.

固形環氧樹脂，可列舉DIC公司製HP-4700(萘型環氧樹脂)、DIC公司製EXA4700(4官能萘型環氧樹脂)、日本化藥公司製NC-7000(含有萘骨架之多官能固形環氧樹脂)等之萘型環氧樹脂；日本化藥公司製EPPN-502H(三苯酚環氧樹脂)等之酚類與具有酚性羥基之芳香族醛之縮合物的環氧化物(三苯酚型環氧樹脂)；DIC公司製EPICLONHP-7200H(含有二環戊二烯骨架之多官能固形環氧樹脂)等之二環戊二烯芳烷基型環氧樹脂；日本化藥公司製NC-3000H(含有聯苯骨架之多官能固形環氧樹脂)等之聯苯基芳烷基型環氧樹脂；日本化藥公司製NC-3000L等之聯苯基/苯酚酚醛清漆型環氧樹脂；DIC公司製EPICLONN660、EPICLONN690、N770、日本化藥公司製EOCN-104S等之酚醛清漆型環氧樹脂；新日鐵住金化學公司製TX0712等之含磷環氧樹脂；日產化學工業公司製TEPIC等之三(2,3-環氧基丙基)異氰脲酸酯等。藉由包含固形環氧樹脂，故硬化物之玻璃轉移溫度變高，耐熱性優異。Examples of the solid epoxy resin include HP-4700 (naphthalene-type epoxy resin) manufactured by DIC Corporation, EXA4700 (4-functional naphthalene-type epoxy resin) manufactured by DIC Corporation, and NC-7000 (naphthalene skeleton-containing polyfunctional resin) manufactured by DIC Corporation. Solid epoxy resin) and other naphthalene-type epoxy resins; epoxides (three condensates of phenols such as EPPN-502H (triphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd. and aromatic aldehydes having a phenolic hydroxyl group; Phenol-type epoxy resins); dicyclopentadiene aralkyl-type epoxy resins such as EPICLONHP-7200H (a difunctional solid epoxy resin containing a dicyclopentadiene skeleton) manufactured by DIC; NC manufactured by Nippon Kayaku Co., Ltd. -3000H (bifunctional solid epoxy resin containing biphenyl skeleton) biphenyl aralkyl type epoxy resin, etc .; biphenyl / phenol novolac type epoxy resin such as NC-3000L manufactured by Nippon Kayaku Co., Ltd .; Novolac epoxy resins such as EPICLONN660, EPICLONN690, N770 manufactured by DIC, EOCN-104S manufactured by Nippon Kayaku Co., Ltd .; phosphorus-containing epoxy resins manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. TX0712; Tris (2,3-epoxypropyl) isocyanurate and the like. By including a solid epoxy resin, the glass transition temperature of a hardened | cured material becomes high, and heat resistance is excellent.

液狀環氧樹脂，可列舉雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚AF型環氧樹脂、苯酚酚醛清漆型環氧樹脂、tert-丁基-兒茶酚型環氧樹脂、縮水甘油基胺型環氧樹脂、胺基苯酚型環氧樹脂、脂環式環氧樹脂等。因包含液狀環氧樹脂，故乾膜之可撓性優異。Examples of the liquid epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, phenol novolac epoxy resin, and tert-butyl-catechol ring. Oxygen resin, glycidylamine epoxy resin, aminophenol epoxy resin, alicyclic epoxy resin, etc. Since the liquid epoxy resin is contained, the dry film has excellent flexibility.

半固形環氧樹脂及結晶性環氧樹脂之調配量以合計，以環氧樹脂全量基準，較佳為5~40質量%，更佳為10~30質量%。在上述範圍內時，乾膜之樹脂層之黏性與柔軟性優異。The total amount of the semi-solid epoxy resin and the crystalline epoxy resin is based on the total amount of the epoxy resin, preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. When it is within the above range, the resin layer of the dry film is excellent in tackiness and flexibility.

本發明之熱硬化性樹脂組成物，在不損及本發明之效果的範圍內，也可含有(A)環氧樹脂以外的熱硬化性樹脂，例如可使用異氰酸酯化合物、嵌段異氰酸酯化合物、胺基樹脂、苯并噁嗪樹脂、碳二亞胺樹脂、環碳酸酯化合物、多官能氧雜環丁烷化合物、環硫化物樹脂等之公知慣用的熱硬化性樹脂。The thermosetting resin composition of the present invention may contain a thermosetting resin other than (A) an epoxy resin within a range that does not impair the effects of the present invention. For example, an isocyanate compound, a block isocyanate compound, and an amine may be used. Known and commonly used thermosetting resins such as base resins, benzoxazine resins, carbodiimide resins, cyclic carbonate compounds, polyfunctional oxetane compounds, episulfide resins, and the like.

[無機填料]
前述樹脂層含有無機填料。藉由調配無機填料，而抑制所得之硬化物的硬化收縮，且可提高密著性、硬度、配合位於絕緣層周圍之銅等之導體層與熱強度所致之龜裂耐性等的熱特性。無機填料可使用以往公知的無機填料，不限定於特定者，可列舉例如硫酸鋇、鈦酸鋇、無定形二氧化矽、結晶性二氧化矽、熔融二氧化矽、球狀二氧化矽等之二氧化矽、滑石、黏土、二氧化矽(Neuburger Kieselerde)粒子、水鋁石、碳酸鎂、碳酸鈣、氧化鈦、氧化鋁、氫氧化鋁、氮化矽、氮化鋁、鋯酸鈣等之體質顏料或、銅、錫、鋅、鎳、銀、鈀、鋁、鐵、鈷、金、鉑等之金屬粉體。無機填料以球狀粒子為佳。其中，較佳為二氧化矽，抑制硬化性組成物之硬化物的硬化收縮，成為更低CTE，提高密著性、硬度等之特性。又，如氧化鋁，比重較大的無機填料，一般沉降速度變快，但是本發明可抑制沉降，故可適用。無機填料之平均粒徑(中值粒徑、D50)係以0.01~10μm為佳。無機填料，就切割加工性的觀點，以平均粒徑為0.01~3μm的二氧化矽為佳。又，本說明書中，無機填料之平均粒徑，不僅一次粒子的粒徑，也包含二次粒子(凝聚物)之粒徑的平均粒徑。平均粒徑可藉由雷射繞射式粒徑分布測量裝置求得。以雷射繞射法之測量裝置，可列舉日機裝公司製Nanotrac wave等。[Inorganic filler]
The resin layer contains an inorganic filler. By blending an inorganic filler, the hardened shrinkage of the obtained hardened material is suppressed, and thermal properties such as adhesion, hardness, and the resistance to cracks due to the thermal conductivity of a conductive layer such as copper located around the insulating layer and thermal strength can be improved. As the inorganic filler, a conventionally known inorganic filler can be used and is not limited to a specific one, and examples thereof include barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, and spherical silica. Silicon dioxide, talc, clay, particles of Neuburger Kieselerde, gibbsite, magnesium carbonate, calcium carbonate, titanium oxide, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, calcium zirconate, etc. Constitution pigment or metal powder of copper, tin, zinc, nickel, silver, palladium, aluminum, iron, cobalt, gold, platinum, etc. The inorganic filler is preferably spherical particles. Among them, silicon dioxide is preferred to suppress the hardening shrinkage of the hardened material of the hardening composition, to lower the CTE, and to improve properties such as adhesion and hardness. In addition, as for alumina, an inorganic filler having a larger specific gravity generally has a faster sedimentation rate, but the present invention is applicable because it can suppress sedimentation. The average particle diameter (median diameter, D50) of the inorganic filler is preferably 0.01 to 10 μm. In terms of cutting processability, the inorganic filler is preferably silicon dioxide having an average particle diameter of 0.01 to 3 μm. In this specification, the average particle diameter of the inorganic filler includes not only the particle diameter of the primary particles, but also the average particle diameter of the secondary particles (agglomerates). The average particle diameter can be obtained by a laser diffraction type particle size distribution measuring device. Examples of the measurement device using the laser diffraction method include the Nanotrac wave manufactured by Nikkiso Co., Ltd. and the like.

前述無機填料可經表面處理。可經作為表面處理之以偶合劑的表面處理或、氧化鋁處理等之未導入有機基之表面處理。無機填料之表面處理方法，無特別限定，使用公知慣用的方法即可，具有硬化性反應基之表面處理劑，例如以具有硬化性反應基作為有機基之偶合劑等處理無機填料的表面即可。The aforementioned inorganic filler may be surface-treated. It may be subjected to a surface treatment using a coupling agent as a surface treatment or a surface treatment without introducing an organic group, such as alumina treatment. The surface treatment method of the inorganic filler is not particularly limited, and a known and commonly used method may be used. A surface treatment agent having a hardening reactive group, for example, a surface of the inorganic filler may be treated with a coupling agent having a hardening reactive group as an organic group. .

無機填料之表面處理係藉由偶合劑之表面處理為佳。偶合劑可使用矽烷系、鈦酸酯系、鋁酸鹽系及鋁鋯(zircoaluminate)系等之偶合劑。其中，以矽烷系偶合劑為佳。此矽烷系偶合劑之例，可列舉乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、N-(2-胺基甲基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-苯胺基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷等，此等可單獨使用或併用使用。此等之矽烷系偶合劑，預先藉由在無機填料表面吸附或反應被固定化為佳。在此，相對於無機填料100質量份，偶合劑的處理量，例如為0.5~10質量份。The surface treatment of the inorganic filler is preferably a surface treatment by a coupling agent. As the coupling agent, coupling agents such as a silane-based, titanate-based, aluminate-based, and zirconaluminate-based coupling agent can be used. Among them, a silane-based coupling agent is preferred. Examples of the silane-based coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinepropyltrimethoxysilane, 3-glycidyloxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacrylic acid Oxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. can be used alone or in combination. These silane-based coupling agents are preferably immobilized in advance by adsorption or reaction on the surface of the inorganic filler. Here, the processing amount of the coupling agent is, for example, 0.5 to 10 parts by mass with respect to 100 parts by mass of the inorganic filler.

硬化性反應基係以熱硬化性反應基為佳。熱硬化性反應基，可列舉羥基、羧基、異氰酸酯基、胺基、亞胺基、環氧基、氧雜環丁烷基、巰基、甲氧基甲基、甲氧基乙基、乙氧基甲基、乙氧基乙基、噁唑啉基等。其中，以胺基及環氧基之至少任一種為佳。又，經表面處理的無機填料，除熱硬化性反應基外，也可具有光硬化性反應基。The hardening reaction group is preferably a thermosetting reaction group. Examples of the thermosetting reactive group include a hydroxyl group, a carboxyl group, an isocyanate group, an amine group, an imino group, an epoxy group, an oxetanyl group, a mercapto group, a methoxymethyl group, a methoxyethyl group, and an ethoxy group. Methyl, ethoxyethyl, oxazoline and the like. Among them, at least any one of an amine group and an epoxy group is preferred. The surface-treated inorganic filler may have a photo-curable reactive group in addition to the thermo-curable reactive group.

又，經表面處理的無機填料，可以經表面處理的狀態包含於前述樹脂層中，形成前述樹脂層之硬化性樹脂組成物中，可各自調配無機填料與表面處理劑，在組成物中，無機填料可經表面處理，但是調配預先進行表面處理的無機填料為佳。藉由調配預先進行表面處理的無機填料，可防止各自調配時，可殘存未被表面處理消耗之表面處理劑所致之龜裂耐性等之降低。預先進行表面處理時，在溶劑或硬化性樹脂中混合預備分散了無機填料的預備分散液為佳，將進行了表面處理的無機填料預備分散於溶劑，將該預備分散液混合於組成物中，或將表面未處理之無機填料預備分散於溶劑時，充分地進行表面處理後，將該預備分散液混合於組成物中更佳。In addition, the surface-treated inorganic filler may be contained in the resin layer in a surface-treated state, and the curable resin composition forming the resin layer may be formulated with an inorganic filler and a surface-treating agent. The filler can be surface-treated, but it is better to prepare an inorganic filler that has been surface-treated in advance. By blending the inorganic filler that has been subjected to surface treatment in advance, it is possible to prevent a reduction in cracking resistance and the like caused by a surface treatment agent that is not consumed by the surface treatment during the respective formulation. When the surface treatment is performed in advance, it is preferable to mix a preliminary dispersion liquid prepared by dispersing an inorganic filler in a solvent or a hardening resin. The inorganic filler subjected to surface treatment is pre-dispersed in a solvent, and the preliminary dispersion liquid is mixed into the composition. Alternatively, when the inorganic filler having no surface treatment is preliminarily dispersed in a solvent, it is more preferable that the predispersion is mixed with the composition after the surface treatment is sufficiently performed.

無機填料可以粉體或固體狀態與環氧樹脂等混合，也可與溶劑或分散劑混合作為漿料後，與環氧樹脂等混合。The inorganic filler may be mixed with an epoxy resin or the like in a powder or solid state, or may be mixed with a solvent or a dispersant as a slurry and then mixed with the epoxy resin or the like.

無機填料可1種單獨使用，也可作為2種以上的混合物使用。無機填料之調配量係以乾膜之樹脂層的固體成分全量基準，較佳為10~90質量%，更佳為50~90質量%，又更佳為60~90質量%。無機填料之調配量為10質量%以上時，可抑制熱膨脹，提高耐熱性，而90質量%以下時，可抑制龜裂之發生。The inorganic filler may be used alone or as a mixture of two or more. The compounding amount of the inorganic filler is based on the total solid content of the resin layer of the dry film, preferably 10 to 90% by mass, more preferably 50 to 90% by mass, and even more preferably 60 to 90% by mass. When the blending amount of the inorganic filler is 10% by mass or more, thermal expansion can be suppressed and heat resistance can be improved, and when 90% by mass or less, cracks can be suppressed.

又，如上述，樹脂層與保護薄膜之密著性及無機填料之沉降的課題，特別是無機填料之含量高時較顯著。本發明中，無機填料之調配量多時，例如，以乾膜之樹脂層的固體成分全量基準，50質量%以上時，可得到特別優異的效果。此外，70質量%以上時，特別是無機填料之沉降顯著，但是依據本發明時，無機填料之沉降抑制優異。As described above, the problems of adhesion between the resin layer and the protective film and sedimentation of the inorganic filler are particularly significant when the content of the inorganic filler is high. In the present invention, when the blending amount of the inorganic filler is large, for example, when the solid content of the resin layer of the dry film is 50% by mass or more based on the total solid content, a particularly excellent effect can be obtained. In addition, when the content is 70% by mass or more, sedimentation of the inorganic filler is significant, but when the present invention is used, sedimentation suppression of the inorganic filler is excellent.

此外，就無機填料之沉降抑制的觀點，前述樹脂層包含平均粒徑為0.1~10μm之無機填料(以下也稱為「大徑無機填料」)與、平均粒徑為0.01~5μm之無機填料(以下也稱為「小徑無機填料」)的混合物，且前述平均粒徑為0.1~10μm之無機填料與前述平均粒徑為0.01~5μm之無機填料之粒徑分布測量時之粒徑的峰間之差為0.05μm以上為佳。調配這種平均粒徑不同的無機填料，藉由與玻璃轉移溫度為20℃以下，且重量平均分子量為3萬以上的高分子樹脂組合，更能防止無機填料之沉降，可抑制塗佈時之沉降。又，樹脂層之硬化物表面之平滑性也優異，零件埋入後也可維持樹脂層之厚度。此外，無機填料高填充容易，藉由高填充可得到彈性模數高的硬化物。粒徑之波峰值可藉由雷射繞射式粒徑分布測量裝置求得。以雷射繞射法之測量裝置，可列舉日機裝公司製Nanotrac wave等。又，包含3種以上的無機填料時，平均粒徑為0.01~5μm之範圍內之最小徑的無機填料作為前述小徑無機填料，其他以外的無機填料，平均粒徑為0.1~10μm之範圍內，前述最小徑之無機填料之粒徑分布測量時之峰間之差為0.05μm以上者，相當於全部前述大徑無機填料者。In addition, from the viewpoint of sedimentation suppression of the inorganic filler, the resin layer includes an inorganic filler having an average particle diameter of 0.1 to 10 μm (hereinafter also referred to as “large-diameter inorganic filler”) and an inorganic filler having an average particle diameter of 0.01 to 5 μm ( Hereinafter also referred to as a "small-diameter inorganic filler"), and the peak-to-peak value of the particle diameter distribution of the inorganic filler having an average particle diameter of 0.1 to 10 μm and the particle diameter distribution of the inorganic filler having an average particle diameter of 0.01 to 5 μm The difference is preferably 0.05 μm or more. By blending such inorganic fillers with different average particle diameters, by combining with a polymer resin with a glass transition temperature of 20 ° C or lower and a weight average molecular weight of 30,000 or more, it is possible to prevent the sedimentation of the inorganic fillers more effectively and to suppress the settlement. In addition, the smoothness of the surface of the hardened material of the resin layer is also excellent, and the thickness of the resin layer can be maintained even after the parts are embedded. In addition, the inorganic filler is easy to be filled with a high degree, and a hardened product having a high elastic modulus can be obtained by the high filling. The peak value of the particle size can be obtained by a laser diffraction type particle size distribution measuring device. Examples of the measurement device using the laser diffraction method include the Nanotrac wave manufactured by Nikkiso Co., Ltd. and the like. When three or more types of inorganic fillers are included, the inorganic filler having the smallest diameter in the range of 0.01 to 5 μm as the aforementioned small-diameter inorganic filler is used as the inorganic filler, and the other inorganic fillers have the average particle diameter in the range of 0.1 to 10 μm. The difference between the peaks in the particle size distribution measurement of the aforementioned inorganic filler with the smallest diameter is 0.05 μm or more, which corresponds to all the aforementioned inorganic fillers with the larger diameter.

前述平均粒徑為0.1~10μm的無機填料係以平均粒徑為0.1~8μm為佳。前述平均粒徑越小時，除膠渣後之硬化物表面之低粗面化越優異，越能抑制二氧化矽之沉降或凝聚。The inorganic filler having an average particle diameter of 0.1 to 10 μm preferably has an average particle diameter of 0.1 to 8 μm. The smaller the average particle size is, the better the roughened surface of the hardened surface after the rubber slag is removed, and the more the sedimentation or aggregation of silicon dioxide can be suppressed.

前述平均粒徑為0.01~5μm的無機填料係以平均粒徑為0.03~3μm為佳。前述平均粒徑越小時，除膠渣後之硬化物表面之低粗面化越優異，越能抑制二氧化矽之沉降或凝聚。The inorganic filler having an average particle diameter of 0.01 to 5 μm preferably has an average particle diameter of 0.03 to 3 μm. The smaller the average particle size is, the better the roughened surface of the hardened surface after the rubber slag is removed, and the more the sedimentation or aggregation of silicon dioxide can be suppressed.

前述平均粒徑為0.1~10μm的無機填料與前述平均粒徑為0.01~5μm之無機填料之粒徑分布測量時之峰間之差的最大值，例如為5μm。The maximum value of the difference between the peaks in the particle size distribution measurement of the inorganic filler having an average particle diameter of 0.1 to 10 μm and the inorganic filler having an average particle diameter of 0.01 to 5 μm is, for example, 5 μm.

前述平均粒徑為0.1~10μm之無機填料之調配量係以組成物的固體成分全量基準，較佳為5~80質量%。The compounding quantity of the said inorganic filler whose average particle diameter is 0.1-10 micrometers is based on the total solid content of a composition, Preferably it is 5-80 mass%.

前述平均粒徑為0.01~5μm之無機填料之調配量係以組成物的固體成分全量基準，較佳為5~15質量%。The compounding amount of the inorganic filler having an average particle diameter of 0.01 to 5 μm is based on the solid content of the composition, and is preferably 5 to 15% by mass.

[硬化劑]
前述樹脂層係含有硬化劑為佳。硬化劑可列舉，具有酚性羥基之化合物、聚羧酸及其酸酐、具有氰酸酯基之化合物、具有活性酯基之化合物、具有馬來醯亞胺基之化合物、脂環式烯烴聚合物等。硬化劑可1種單獨使用或組合2種以上使用。[hardener]
The resin layer preferably contains a hardener. Examples of the curing agent include compounds having a phenolic hydroxyl group, polycarboxylic acids and their anhydrides, compounds having a cyanate group, compounds having an active ester group, compounds having a maleimide group, and alicyclic olefin polymers. Wait. The hardener can be used alone or in combination of two or more.

本發明中，前述樹脂層，包含具有酚性羥基之化合物、具有活性酯基之化合物、具有氰酸酯基之化合物及具有馬來醯亞胺基之化合物之至少任一種為佳。藉由使用具有酚性羥基之化合物及具有活性酯基之化合物，可得到低粗度基材或與電路之接著性優異的硬化物。又，藉由使用氰酸酯，硬化物之Tg變高，提高耐熱性，藉由使用具有馬來醯亞胺基之化合物，硬化物之Tg變高，提高耐熱性，同時可降低CTE。In the present invention, the resin layer preferably contains at least any one of a compound having a phenolic hydroxyl group, a compound having an active ester group, a compound having a cyanate group, and a compound having a maleimide group. By using a compound having a phenolic hydroxyl group and a compound having an active ester group, a hardened product having a low-roughness substrate or excellent adhesion to a circuit can be obtained. In addition, by using a cyanate ester, the Tg of the cured product is increased to improve heat resistance, and by using a compound having a maleimide group, the Tg of the cured product is increased, heat resistance is improved, and CTE can be reduced.

前述具有酚性羥基之化合物，可使用苯酚酚醛清漆樹脂、烷基酚醛清漆樹脂、雙酚A酚醛清漆樹脂、二環戊二烯型酚樹脂、Xylok型酚樹脂、萜烯改質酚樹脂、甲酚/萘酚樹脂、聚乙烯基酚類、苯酚/萘酚樹脂、含有α-萘酚骨架之酚樹脂、含有三嗪骨架之甲酚醛清漆樹脂、聯苯基芳烷基型酚樹脂、Zilog型苯酚酚醛清漆樹脂等之以往公知者。
前述具有酚性羥基之化合物中，較佳為羥基當量為100g/eq.以上者。羥基當量為100g/eq.以上之具有酚性羥基之化合物，可列舉例如二環戊二烯骨架苯酚酚醛清漆樹脂(GDP系列、群榮化學公司製)、Zilog型苯酚酚醛清漆樹脂(MEH-7800、明和化成公司製)、聯苯基芳烷基型酚醛清漆樹脂(MEH-7851、明和化成公司製)、萘酚芳烷基型硬化劑(SN系列、新日鐵住金公司製)、含有三嗪骨架之甲酚醛清漆樹脂(LA-3018-50P、DIC公司製)、含有三嗪骨架之苯酚酚醛清漆樹脂(LA-705N、DIC公司製)等。As the compound having a phenolic hydroxyl group, a phenol novolac resin, an alkyl novolac resin, a bisphenol A novolac resin, a dicyclopentadiene type phenol resin, a Xylok type phenol resin, a terpene modified phenol resin, Phenol / naphthol resin, polyvinyl phenols, phenol / naphthol resin, phenol resin containing α-naphthol skeleton, cresol novolac resin containing triazine skeleton, biphenylaralkyl type phenol resin, Zilog type Conventionally known phenol novolac resins and the like.
Among the compounds having a phenolic hydroxyl group, a hydroxyl equivalent of 100 g / eq. Or more is preferred. Examples of the compound having a phenolic hydroxyl group with a hydroxyl equivalent of 100 g / eq. Or more include, for example, a dicyclopentadiene skeleton phenol novolac resin (GDP series, manufactured by Qunei Chemical Co., Ltd.), a Zilog type phenol novolac resin (MEH-7800) , Manufactured by Meiwa Chemical Co., Ltd.), biphenyl aralkyl type novolac resin (MEH-87851, manufactured by Meiwa Chemical Co., Ltd.), naphthol aralkyl type hardener (SN series, manufactured by Nippon Steel & Sumikin Co., Ltd.), containing three Azine skeleton cresol novolac resin (LA-3018-50P, manufactured by DIC Corporation), triazine skeleton phenol novolac resin (LA-705N, manufactured by DIC Corporation), and the like.

前述具有氰酸酯基之化合物係以一分子中具有2個以上之氰酸酯基(-OCN)的化合物為佳。具有氰酸酯基之化合物，可使用以往公知者。具有氰酸酯基之化合物，可列舉例如苯酚酚醛清漆型氰酸酯樹脂、烷基苯酚酚醛清漆型氰酸酯樹脂、二環戊二烯型氰酸酯樹脂、雙酚A型氰酸酯樹脂、雙酚F型氰酸酯樹脂、雙酚S型氰酸酯樹脂。又，也可為局部進行三嗪化的預聚物。The compound having a cyanate group is preferably a compound having two or more cyanate groups (-OCN) in one molecule. As the compound having a cyanate group, a conventionally known one can be used. Examples of the compound having a cyanate group include a phenol novolac type cyanate resin, an alkylphenol novolac type cyanate resin, a dicyclopentadiene type cyanate resin, and a bisphenol A type cyanate resin. , Bisphenol F-type cyanate resin, bisphenol S-type cyanate resin. It may also be a prepolymer that is partially triazinated.

市售之具有氰酸酯基的化合物，可列舉苯酚酚醛清漆型多官能氰酸酯樹脂(Lonza Japan公司製、PT30S)、雙酚A二氰酸酯之一部分或全部經三嗪化之三聚物的預聚物(Lonza Japan公司製、BA230S75)、含有二環戊二烯結構之氰酸酯樹脂(Lonza Japan公司製、DT-4000、DT-7000)等。Commercially available compounds having a cyanate group include phenol novolac-type polyfunctional cyanate resin (Lonza Japan Co., PT30S), and a part or all of the triazinated trimerization of bisphenol A dicyanate Prepolymer (manufactured by Lonza Japan, BA230S75), cyanate resin containing a dicyclopentadiene structure (manufactured by Lonza Japan, DT-4000, DT-7000), and the like.

前述具有活性酯基之化合物係以一分子中具有2個以上之活性酯基的化合物為佳。具有活性酯基之化合物，一般可藉由羧酸化合物與羥基化合物之縮合反應而得到。其中，使用作為羥基化合物之苯酚化合物或萘酚化合物所得之具有活性酯基的化合物為佳。苯酚化合物或萘酚化合物，可列舉氫醌、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、苯酚、o-甲酚、m-甲酚、p-甲酚、兒茶酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、間苯三酚、苯三醇、二環戊二烯基二酚、苯酚酚醛清漆等。又，具有活性酯基之化合物，可為萘二酚烷基/苯甲酸型。The compound having an active ester group is preferably a compound having two or more active ester groups in one molecule. The compound having an active ester group is generally obtained by a condensation reaction between a carboxylic acid compound and a hydroxy compound. Among them, a compound having an active ester group obtained by using a phenol compound or a naphthol compound as a hydroxy compound is preferred. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methylated bisphenol. S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 , 6-Dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol, pyroglycerol, dicyclopentadienyl diphenol, phenol novolac, etc. . In addition, the compound having an active ester group may be a naphthodiol alkyl / benzoic acid type.

市售之具有活性酯基之化合物，可列舉二環戊二烯型之二酚化合物，例如HPC8000-65T(DIC公司製)、HPC8100 -65T(DIC公司製)、HPC8150-65T(DIC公司製)。Commercially available compounds having an active ester group include dicyclopentadiene-type diphenol compounds such as HPC8000-65T (manufactured by DIC), HPC8100 -65T (manufactured by DIC), and HPC8150-65T (manufactured by DIC) .

前述具有馬來醯亞胺基之化合物為具有馬來醯亞胺骨架之化合物，以往公知者皆可使用。具有馬來醯亞胺基之化合物係以具有2以上之馬來醯亞胺骨架為佳，更佳為N,N’-1,3-伸苯基二馬來醯亞胺、N,N’-1,4-伸苯基二馬來醯亞胺、N,N’-4,4-二苯基甲烷雙馬來醯亞胺、1,2-雙(馬來醯亞胺)乙烷、1,6-雙馬來醯亞胺己烷、1,6-雙馬來醯亞胺-(2,2,4-三甲基)己烷、2,2’-雙-[4-(4-馬來醯亞胺苯氧基)苯基]丙烷、3,3’-二甲基-5,5’-二乙基-4,4’-二苯基甲烷雙馬來醯亞胺、4-甲基-1,3-伸苯基雙馬來醯亞胺、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷、雙酚A二苯醚雙馬來醯亞胺、聚苯基甲烷馬來醯亞胺、及此等之寡聚物、及具有馬來醯亞胺骨架之二胺縮合物之中之至少任一種。前述寡聚物係藉由使上述具有馬來醯亞胺基之化合物中之單體之具有馬來醯亞胺基的化合物進行縮合所得之寡聚物。The aforementioned compound having a maleimide group is a compound having a maleimide group, and any of the conventionally known ones can be used. The compound having a maleimide group is preferably a maleimide frame having 2 or more, more preferably N, N'-1,3-phenylene dimaleimide, N, N ' -1,4-phenylene dimaleimide, N, N'-4,4-diphenylmethane bismaleimide, 1,2-bis (maleimide) ethane, 1,6-bismaleimide hexane, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, 2,2'-bis- [4- (4 -Maleimide phenoxy) phenyl] propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4 -Methyl-1,3-phenylene bismaleimide, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, bisphenol A diphenyl ether bis horse At least one of lyme imine, polyphenylmethane maleimide, and oligomers thereof, and a diamine condensate having a maleimide skeleton. The oligomer is an oligomer obtained by condensing a compound having a maleimidine group among the monomers in the compound having a maleimide group.

市售之具有馬來醯亞胺基的化合物，可列舉BMI-1000(4,4’-二苯基甲烷雙馬來醯亞胺、大和化成工業公司製)、BMI-2300(苯基甲烷雙馬來醯亞胺、大和化成工業公司製)、BMI-3000(m-伸苯基雙馬來醯亞胺、大和化成工業公司製)、BMI-5100(3,3’-二甲基-5,5’-二甲基-4,4’-二苯基甲烷雙馬來醯亞胺、大和化成工業公司製)、BMI-7000(4-甲基-1,3,-伸苯基雙馬來醯亞胺、大和化成工業公司製)、BMI-TMH((1,6-雙馬來醯亞胺-2,2,4-三甲基)己烷、大和化成工業公司製)等。Commercially available compounds having a maleimidine group include BMI-1000 (4,4'-diphenylmethanebismaleimide, manufactured by Daiwa Chemical Industry Co., Ltd.), and BMI-2300 (phenylmethanebisimide Maleimide, manufactured by Yamato Chemical Industry Co., Ltd.), BMI-3000 (m-phenylene bismaleimide, manufactured by Daiwa Chemical Industry Co., Ltd.), BMI-5100 (3,3'-dimethyl-5 , 5'-dimethyl-4,4'-diphenylmethane bismaleimide, manufactured by Daiwa Chemical Industry Co., Ltd.), BMI-7000 (4-methyl-1,3, -phenylene bismaline Laimide, manufactured by Yamato Chemical Industry Co., Ltd.), BMI-TMH ((1,6-bismaleimide-2,2,4-trimethyl) hexane, manufactured by Daiwa Chemical Industry Co., Ltd.), and the like.

硬化劑之調配量係相對於環氧樹脂100質量份，較佳為20~100質量份，更佳為25~90質量份。The compounding amount of the hardener is preferably 100 to 100 parts by mass, and more preferably 25 to 90 parts by mass based on 100 parts by mass of the epoxy resin.

形成前述樹脂層之硬化性樹脂組成物之具體例，可列舉熱硬化性樹脂組成物、光硬化性熱硬化性樹脂組成物、含有光聚合起始劑之光硬化性熱硬化性樹脂組成物、含有光鹼發生劑之光硬化性熱硬化性樹脂組成物、含有光酸產生劑之光硬化性熱硬化性樹脂組成物、負型光硬化性熱硬化性樹脂組成物及正型感光性熱硬化性樹脂組成物、鹼顯影型光硬化性熱硬化性樹脂組成物、溶劑顯影型光硬化性熱硬化性樹脂組成物、膨潤剝離型熱硬化性樹脂組成物、溶解剝離型熱硬化性樹脂組成物，但是不限定於此等者。Specific examples of the curable resin composition forming the resin layer include a thermosetting resin composition, a photocurable thermosetting resin composition, a photocurable thermosetting resin composition containing a photopolymerization initiator, Photocurable thermosetting resin composition containing photobase generator, photocurable thermosetting resin composition containing photoacid generator, negative photocurable thermosetting resin composition, and positive photosensitive thermosetting Thermosetting resin composition, alkali developing type photocurable thermosetting resin composition, solvent developing type photocurable thermosetting resin composition, swelling and peeling type thermosetting resin composition, dissolution and peeling type thermosetting resin composition , But not limited to those.

以下，舉一例，關於以不含光硬化性成分之熱硬化性樹脂組成物形成樹脂層的情形，說明上述成分以外，可含有的成分。Hereinafter, as an example, regarding a case where the resin layer is formed of a thermosetting resin composition containing no photocurable component, components that can be contained in addition to the above components will be described.

前述樹脂層，也可含有環氧樹脂以外的熱硬化性樹脂，例如可使用異氰酸酯化合物、嵌段異氰酸酯化合物、胺基樹脂、苯并噁嗪樹脂、碳二亞胺樹脂、環碳酸酯化合物、多官能氧雜環丁烷化合物、環硫化物樹脂等之公知慣用的熱硬化性樹脂。The resin layer may contain a thermosetting resin other than an epoxy resin. For example, an isocyanate compound, a block isocyanate compound, an amine-based resin, a benzoxazine resin, a carbodiimide resin, a cyclic carbonate compound, or the like Known and commonly used thermosetting resins such as functional oxetane compounds and episulfide resins.

前述樹脂層為了提高所得之硬化膜的機械強度，可進一步含有熱塑性樹脂。熱塑性樹脂係以可溶於溶劑者為佳。可溶於溶劑時，可提高乾膜之柔軟性，可抑制龜裂之發生或掉粉。熱塑性樹脂，可列舉熱可塑性聚羥基聚醚樹脂或、環氧氯丙烷與各種2官能苯酚化合物之縮合物的苯氧基樹脂或存在於其骨架之羥醚部的羥基使用各種酸酐或酸氯化物，進行酯化的苯氧基樹脂、聚乙烯醇縮乙醛樹脂、聚醯胺樹脂、聚醯胺醯亞胺樹脂、嵌段共聚物等。熱塑性樹脂可1種單獨使用或組合2種以上使用。The resin layer may further contain a thermoplastic resin in order to improve the mechanical strength of the obtained cured film. The thermoplastic resin is preferably one which is soluble in a solvent. When soluble in solvents, it can improve the softness of the dry film, and can suppress the occurrence of cracks or powder loss. Examples of the thermoplastic resin include thermoplastic polyhydroxy polyether resins, phenoxy resins which are condensates of epichlorohydrin and various bifunctional phenol compounds, and various types of acid anhydrides or acid chlorides for the hydroxyl groups present in the hydroxyl ether portion of the skeleton. , Esterified phenoxy resin, polyvinyl acetal resin, polyamidoamine resin, polyamidoamine imine resin, block copolymer and the like. The thermoplastic resin may be used singly or in combination of two or more kinds.

熱塑性樹脂之調配量係以樹脂層之固體成分全量基準，較佳為0.5~20質量%，更佳為0.5~10質量%。熱塑性樹脂之調配量在上述範圍內時，容易得到均勻的粗化面狀態。The blending amount of the thermoplastic resin is based on the solid content of the resin layer, and is preferably 0.5 to 20% by mass, and more preferably 0.5 to 10% by mass. When the blending amount of the thermoplastic resin is within the above range, it is easy to obtain a uniform roughened surface state.

此外，前述樹脂層，必要時，可含有橡膠狀粒子。這種橡膠狀粒子，可列舉聚丁二烯橡膠、聚異丙烯橡膠、胺基甲酸酯改質聚丁二烯橡膠、環氧基改質聚丁二烯橡膠、丙烯腈改質聚丁二烯橡膠、羧基改質聚丁二烯橡膠、羧基或羥基改質的丙烯腈丁二烯橡膠、及彼等之交聯橡膠粒子、核殼型橡膠粒子等，可1種單獨使用或組合2種以上使用。此等之橡膠狀粒子，為了可提高所得之硬化膜之柔軟性，或提高龜裂耐性，可藉由氧化劑之表面粗化處理，提高與銅箔等之密著強度而添加。The resin layer may contain rubber-like particles if necessary. Examples of such rubbery particles include polybutadiene rubber, polyisopropylene rubber, urethane-modified polybutadiene rubber, epoxy-modified polybutadiene rubber, and acrylonitrile-modified polybutadiene. Ethylene rubber, carboxyl modified polybutadiene rubber, carboxyl or hydroxy modified acrylonitrile butadiene rubber, and their crosslinked rubber particles, core-shell rubber particles, etc., can be used alone or in combination of two Used above. These rubber-like particles can be added by roughening the surface of an oxidizing agent to increase the adhesion strength with copper foil, etc., in order to improve the flexibility of the obtained cured film or to improve the crack resistance.

橡膠狀粒子之平均粒徑係以0.005~1μm之範圍為佳，更佳為0.2~1μm之範圍。本發明中之橡膠狀粒子之平均粒徑係藉由雷射繞射式粒徑分布測量裝置而求得。例如，藉由超音波等橡膠狀粒子均勻地分散於適當的有機溶劑中，使用日機裝公司製Nanotrac wave，以橡膠狀粒子之粒度分布作為質量基準所製造，以其中值粒徑作為平均粒徑，進行測量。The average particle diameter of the rubber-like particles is preferably in the range of 0.005 to 1 μm, and more preferably in the range of 0.2 to 1 μm. The average particle diameter of the rubber-like particles in the present invention is obtained by a laser diffraction type particle size distribution measuring device. For example, it is produced by uniformly dispersing rubber-like particles such as ultrasonic waves in an appropriate organic solvent, using Nanotrac manufactured by Nikkiso Co., Ltd., using the particle size distribution of the rubber-like particles as a quality standard, and using the median particle diameter as the average particle. Diameter.

橡膠狀粒子之調配量係以樹脂層之固體成分全量基準，較佳為0.5~10質量%，更佳為1~5質量%。0.5質量%以上時，可得到龜裂耐性，可提高與導體圖型等之密著強度。10質量%以下時，熱膨脹係數(CTE)降低，玻璃轉移溫度(Tg)上昇，提高硬化特性。The compounding amount of the rubber-like particles is based on the solid content of the resin layer, and is preferably 0.5 to 10% by mass, and more preferably 1 to 5% by mass. When it is 0.5% by mass or more, crack resistance can be obtained, and adhesion strength with a conductor pattern and the like can be improved. When it is 10% by mass or less, the coefficient of thermal expansion (CTE) decreases, the glass transition temperature (Tg) increases, and the hardening characteristics are improved.

前述樹脂層可含有硬化促進劑。硬化促進劑係促進熱硬化反應者，為了更提高密著性、耐藥品性、耐熱性等之特性而使用。這種硬化促進劑之具體例，可列舉咪唑及其衍生物；乙醯胍胺、苯並胍胺等之胍胺類；二胺基二苯基甲烷、m-苯二胺、m-二甲苯二胺、二胺基二苯基碸、雙氰胺、脲、脲衍生物、三聚氰胺、多鹼肼等之多胺類；此等之有機酸鹽及/或環氧基加成物；三氟化硼之胺錯合物；乙基二胺基-S-三嗪、2,4-二胺基-S-三嗪、2,4-二胺基-6-二甲苯基-S-三嗪等之三嗪衍生物類；三甲基胺、三乙醇胺、N,N-二甲基辛基胺、N-苄基二甲基胺、吡啶、N-甲基嗎啉、六(N-甲基)三聚氰胺、2,4,6-三(二甲基胺基苯酚)、四甲基胍、m-胺基苯酚等之胺類；聚乙烯基苯酚、聚乙烯基苯酚溴化物、苯酚酚醛清漆、烷基苯酚酚醛清漆等之多酚類；三丁基膦、三苯基膦、三-2-氰基乙基膦等之有機膦類；三-n-丁基(2,5-二羥基苯基)鏻溴化物、十六烷基三丁基鏻氯化物等之鏻鹽類；苄基三甲基銨氯化物、苯基三丁基銨氯化物等之四級銨鹽類；前述多元酸酐；二苯基錪四氟硼酸酯、三苯基鋶六氟銻酸鹽、2,4,6-三苯硫基嘧啶鎓六氟磷酸酯等之光陽離子聚合觸媒；苯乙烯-馬來酸酐樹脂；苯基異氰酸酯與二甲基胺之等莫耳反應物或、甲伸苯基二異氰酸酯、異佛爾酮 二異氰酸酯等之有機聚異氰酸酯與二甲基胺之等莫耳反應物、金屬觸媒等之以往公知的硬化促進劑。硬化促進劑之中，就可得到BHAST耐性，較佳為鏻鹽類。The resin layer may contain a hardening accelerator. A hardening accelerator is used to promote a thermosetting reaction, and is used in order to further improve characteristics such as adhesion, chemical resistance, and heat resistance. Specific examples of such a hardening accelerator include imidazole and its derivatives; guanamines such as acetoguanamine and benzoguanamine; diaminodiphenylmethane, m-phenylenediamine, and m-xylene Polyamines such as diamine, diaminodiphenylphosphonium, dicyandiamide, urea, urea derivatives, melamine, polybasic hydrazine, etc .; these organic acid salts and / or epoxy adducts; trifluoro Boron amine complexes; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine And other triazine derivatives; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl Amines such as melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, m-aminophenol, etc .; polyvinylphenol, polyvinylphenol bromide, phenol novolac , Polyphenols such as alkylphenol novolac; organic phosphines such as tributylphosphine, triphenylphosphine, tri-2-cyanoethylphosphine; tri-n-butyl (2,5-dihydroxy Phenyl) phosphonium bromide, hexadecyltributylphosphonium chloride and other phosphonium salts; benzyltrimethylammonium chloride, benzene Quaternary ammonium salts such as tributylammonium chloride; the aforementioned polybasic acid anhydrides; diphenylphosphonium tetrafluoroborate, triphenylphosphonium hexafluoroantimonate, 2,4,6-triphenylthiopyrimidinium Photocationic polymerization catalysts such as hexafluorophosphate; styrene-maleic anhydride resin; Mol reactants such as phenyl isocyanate and dimethylamine; or methylphenyl diisocyanate; isophorone diisocyanate; etc. Mole reactants such as organic polyisocyanate and dimethylamine, metal catalysts and other conventionally known hardening accelerators. Among the hardening accelerators, BHAST resistance is obtained, and sulfonium salts are preferred.

硬化促進劑可1種單獨使用或混合2種以上使用。硬化促進劑之使用非必須，但是特別是欲促進硬化時，相對於環氧樹脂100質量份，較佳為在0.01~5質量份之範圍使用。金屬觸媒的情形，相對於具有氰酸酯基之化合物100質量份，以金屬換算，較佳為10~550ppm，更佳為25~200ppm。A hardening accelerator can be used individually by 1 type or in mixture of 2 or more types. The use of a hardening accelerator is not essential, but especially when it is intended to promote hardening, it is preferably used in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of the epoxy resin. In the case of a metal catalyst, it is preferably 10 to 550 ppm, and more preferably 25 to 200 ppm, based on 100 parts by mass of the compound having a cyanate group.

有機溶劑無特別限制，可列舉例如酮類、芳香族烴類、二醇醚類、乙二醇醚乙酸酯類、酯類、醇類、脂肪族烴、石油系溶劑等。具體而言，可列舉甲基乙基酮、環己酮、甲基丁基酮、甲基異丁基酮等之酮類；甲苯、二甲苯、四甲基苯等之芳香族烴類；溶纖劑、甲基溶纖劑、丁基溶纖劑、卡必醇、甲基卡必醇、丁基卡必醇、乙二醇單甲醚、乙二醇單***、乙二醇單丁醚、丙二醇單甲醚、二丙二醇單甲醚、二丙二醇二***、三乙二醇單***等之二醇醚類；乙酸乙酯、乙酸丁酯、乙酸異丁酯、乙二醇單***乙酸酯、二丙二醇甲醚乙酸酯、丙二醇甲醚乙酸酯、丙二醇***乙酸酯、丙二醇丁醚乙酸酯等之酯類；乙醇、丙醇、2-甲氧基丙醇、n-丁醇、異丁基醇、異戊醇、乙二醇、丙二醇等之醇類；辛烷、癸烷等之脂肪族烴；石油醚、石油腦、氫化石油腦、溶劑石油腦等之石油系溶劑等，及N,N-二甲基甲醯胺(DMF)、四氯乙烯、松節油等。又，可使用丸善石油化學公司製Swasol 1000、Swasol 1500、standard石油大阪發賣所公司製Solvesso 100、Solvesso 150、三共化學公司製solvent#100、solvent#150、Shell Chemicals Japan公司製shellsol A100、shellsol A150、出光興產公司製Ipsol 100號、Ipsol 150號等之有機溶劑。有機溶劑可1種單獨使用，也可作為2種以上的混合物使用。The organic solvent is not particularly limited, and examples thereof include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. Specific examples include ketones such as methyl ethyl ketone, cyclohexanone, methylbutyl ketone, and methyl isobutyl ketone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellulose, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol, butylcarbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol Glycol ethers such as monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, Dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ether acetate, propylene glycol butyl ether acetate and the like; ethanol, propanol, 2-methoxypropanol, n-butanol, Isobutyl alcohol, isoamyl alcohol, ethylene glycol, propylene glycol and other alcohols; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum brain, hydrogenated petroleum brain, solvent petroleum petroleum, etc. And N, N-dimethylformamide (DMF), tetrachloroethylene, turpentine, etc. In addition, Swasol 1000, Swasol 1500, manufactured by Maruzan Petrochemical Co., Ltd., Solvesso 100, Solvesso 150, manufactured by Standard Petroleum Osaka Distribution Co., Ltd., Solvent # 100, Solent # 150, manufactured by Sankyo Chemical Co., Ltd., Shellsol A100, manufactured by Shell Chemicals Japan A150, organic solvents such as Ipsol 100, Ipsol 150 made by Idemitsu Kosan. The organic solvents may be used singly or as a mixture of two or more kinds.

前述樹脂層中之殘留溶劑量係以0.5~7.0質量%為佳。殘留溶劑為7.0質量%以下時，抑制熱硬化時之突然沸騰，表面之平坦性更良好。又，可抑制熔融黏度過低，樹脂流動，且平坦性變得良好。殘留溶劑為0.5質量%以上時，積層時之流動性良好，且平坦性及埋入性變得更良好。The amount of the residual solvent in the resin layer is preferably 0.5 to 7.0% by mass. When the residual solvent is 7.0% by mass or less, sudden boiling during thermal curing is suppressed, and the surface flatness is more favorable. In addition, the melt viscosity can be suppressed from being too low, the resin can flow, and the flatness can be improved. When the residual solvent is 0.5% by mass or more, the fluidity at the time of lamination is good, and the flatness and embedding properties are further improved.

前述樹脂層，必要時，可使用酞菁藍、酞菁綠、碘綠、雙偶氮黃、水晶紫、氧化鈦、碳黑、萘黑等之以往公知的著色劑、石棉、Orben、Bentonite、微紛二氧化矽等之以往公知的增黏劑、聚矽氧系、氟系、高分子系等之消泡劑及/或平坦劑、噻唑系、***系、矽烷偶合劑等之密著性賦予劑、難燃劑、鈦酸酯系、鋁系之以往公知的添加劑類。As the resin layer, conventionally known coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, asbestos, Orben, Bentonite, and the like can be used. Adhesion of conventionally known thickeners such as micro-silicon dioxide, polysiloxane-based, fluorine-based, polymer-based defoamers and / or flatteners, thiazole-based, triazole-based, silane coupling agents, etc. Conventionally known additives such as property imparting agents, flame retardants, titanate-based, and aluminum-based.

使用本發明之乾膜之印刷配線板之製造方法，使用以往習知方法即可。例如，樹脂層為由熱硬化性樹脂組成物所成時，如圖1所示，在載體薄膜與保護薄膜之間挾著樹脂層之乾膜時，以如下述的方法可製造印刷配線板。由乾膜，剝離載體薄膜或保護薄膜之任一者，對形成有電路圖型之電路基板進行加熱積層後，使熱硬化。熱硬化可在烤箱中硬化，或以熱板壓製使硬化。將形成有電路的基材與本發明之乾膜進行積層或熱板壓製時，也可同時積層銅箔或電路形成之基材。在與形成有電路圖型之基材上之特定位置對應的位置，以雷射照射或鑽頭形成圖型或導孔，藉由使電路配線露出，可製造印刷配線板。此時，在圖型或導孔內之電路配線上存在無法完全除去而殘留的成分(殘渣)時，進行除膠渣處理。載體薄膜或保護薄膜之中殘留者，可在積層後、熱硬化後，雷射加工後或除膠渣處理後剝離即可。又，層間電路之連接方法，可藉由銅柱(Copper Pillar)之連接。The method for manufacturing a printed wiring board using the dry film of the present invention may be a conventionally known method. For example, when the resin layer is made of a thermosetting resin composition, as shown in FIG. 1, when a dry film of a resin layer is interposed between a carrier film and a protective film, a printed wiring board can be manufactured by the following method. Either the dry film, the carrier film or the protective film is peeled off, and the circuit board on which the circuit pattern is formed is heated and laminated, and then thermally cured. Heat hardening can be hardened in an oven or by hot plate pressing. When the substrate on which the circuit is formed and the dry film of the present invention are laminated or hot-plate pressed, a copper foil or a substrate on which the circuit is formed may also be laminated at the same time. A pattern or a guide hole is formed by laser irradiation or a drill at a position corresponding to a specific position on a substrate on which a circuit pattern is formed, and a printed wiring board can be manufactured by exposing the circuit wiring. At this time, if there is a component (residue) remaining on the circuit wiring in the pattern or the via hole that cannot be completely removed, the glue removal treatment is performed. Residuals in the carrier film or protective film can be peeled off after lamination, after thermal curing, after laser processing, or after removal of slag. In addition, the connection method of the inter-layer circuit can be connected by Copper Pillar.

[載體薄膜]
載體薄膜係指具有支撐乾膜之樹脂層之功能者，形成該樹脂層時，塗佈有硬化性樹脂組成物的薄膜。載體薄膜，例如可使用聚對苯二甲酸乙二酯或聚萘二甲酸乙二酯等之聚酯薄膜、聚醯亞胺薄膜、聚醯胺醯亞胺薄膜、聚乙烯薄膜、聚四氟乙烯薄膜、聚丙烯薄膜、聚苯乙烯薄膜等之由熱塑性樹脂所成的薄膜及進行表面處理的紙等。此等之中，就耐熱性、機械強度、使用性等的觀點，可適合使用聚酯薄膜。載體薄膜之厚度，無特別限定，但是大約在10~150μm之範圍配合用途適宜選擇。在設置載體薄膜之樹脂層的面，也可施予脫模處理。又，在設置載體薄膜之樹脂層的面，也可濺鍍或形成極薄銅箔。[Carrier film]
A carrier film is a film having a function of supporting a resin layer of a dry film, and when the resin layer is formed, the film is coated with a curable resin composition. As the carrier film, for example, a polyester film such as polyethylene terephthalate or polyethylene naphthalate, a polyimide film, a polyimide film, a polyethylene film, or a polytetrafluoroethylene can be used. Films made of thermoplastic resins such as films, polypropylene films, polystyrene films, and paper with surface treatment. Among these, a polyester film can be suitably used from a viewpoint of heat resistance, mechanical strength, usability, etc. The thickness of the carrier film is not particularly limited, but it is appropriately selected depending on the application in a range of about 10 to 150 μm. The surface on which the resin layer of the carrier film is provided may be subjected to a release treatment. In addition, the surface on which the resin layer of the carrier film is provided may be sputtered or formed into an extremely thin copper foil.

[保護薄膜]
保護薄膜係為了防止在乾膜之樹脂層的表面附著塵埃等，同時提高使用性為目的，被設置於與樹脂層之載體薄膜相反的面。本發明中，使用2軸延伸聚丙烯薄膜作為保護薄膜。因2軸延伸聚丙烯薄膜，故對樹脂層之積層後可減少冷卻收縮。保護薄膜之厚度，無特別限制，但是大約在10~100μm之範圍配合用途適宜選擇。在設置保護薄膜之樹脂層的面，施予壓紋加工或電暈處理、微黏著處理等之提高密著性的處理或脫模處理為佳。[Protective film]
The protective film is provided on the side opposite to the carrier film of the resin layer for the purpose of preventing dust and the like from adhering to the surface of the resin layer of the dry film and improving the usability. In the present invention, a biaxially stretched polypropylene film is used as a protective film. Due to the biaxially stretched polypropylene film, cooling shrinkage can be reduced after laminating the resin layer. The thickness of the protective film is not particularly limited, but it is appropriately selected according to the application in a range of about 10 to 100 μm. The surface of the resin layer on which the protective film is provided is preferably subjected to an embossing process, a corona treatment, a microadhesive treatment, or the like to improve adhesion or release treatment.

本發明之乾膜，較佳為用於形成電子零件，特別是印刷配線板之永久保護膜，其中，較佳為可用於形成阻焊劑層、層間絕緣層、可撓性的印刷配線板之被覆層。特別是本發明之乾膜，較佳為可用於形成無機填料含量多之硬化物的用途。藉由使用本發明之乾膜，貼合配線，也可形成配線板。又，也可作為半導體晶片用之封裝材料使用。

[實施例]The dry film of the present invention is preferably a permanent protective film for forming electronic parts, especially a printed wiring board. Among them, it is preferably a coating that can be used to form a solder resist layer, an interlayer insulation layer, and a flexible printed wiring board. Floor. In particular, the dry film of the present invention is preferably used for forming a hardened product having a large amount of inorganic filler. By using the dry film of the present invention, the wiring can be bonded to form a wiring board. It can also be used as a packaging material for semiconductor wafers.

[Example]

以下，舉本發明之實施例及比較例，具體說明本發明，但是本發明不限定於下述實施例者。又，以下，「份」及「%」無特別聲明時，皆為質量基準。Hereinafter, the present invention will be specifically described using examples and comparative examples of the present invention, but the present invention is not limited to the following examples. In addition, in the following, "part" and "%" are the basis of quality unless otherwise stated.

＜玻璃轉移溫度為20℃以下，且重量平均分子量為3萬以上之高分子化合物之製造例1＞〔高分子樹脂A、高分子樹脂B之製造〕
在反應容器中，混合2官能性羥基末端聚丁二烯G-3000(羥基當量=1800g/eq.、固體成分100wt%：日本曹達公司製)50g與、Ipsol 150(芳香族烴系混合溶劑：出光石油化學公司製)100g、二丁基錫月桂酸酯0.005g，使均勻地溶解。成為均勻時，昇溫至50℃，邊攪拌邊添加二異氰酸異佛爾酮 (IPDI、Mw=222、異氰酸酯基當量=111g/eq.) 3.08g，約3小時與、約12小時之兩種方式進行反應。將所得之反應液分別滴下至n-己烷溶液中，使白色沉澱物析出。然後，藉由過濾回收白色沉澱物，以100℃使乾燥2小時，得到比率約1：1之聚丁二烯與IPDI的聚合物。
對於所得之聚合物，進行GPC測量(Waters公司製、2695聚苯乙烯換算)與DSC測量((DSC-6100、Seiko Instruments公司製、昇溫速度5℃)，分別確認分子量Mw與玻璃轉移溫度Tg。結果反應時間較短者(以下稱為高分子樹脂A)，確認重量平均分子量Mw=50000、Tg=-10℃。另外，反應時間較長者(以下稱為高分子樹脂B)，確認重量平均分子量Mw=250000、Tg=-12℃。<Production Example 1 of a polymer compound having a glass transition temperature of 20 ° C. or lower and a weight average molecular weight of 30,000 or more> [Production of Polymer Resin A and Polymer Resin B]
In a reaction vessel, 50 g of bifunctional hydroxyl-terminated polybutadiene G-3000 (hydroxyl equivalent weight = 1800 g / eq., Solid content: 100% by weight: manufactured by Soda Co., Ltd.) and Ipsol 150 (aromatic hydrocarbon-based mixed solvent: 100 g of Idemitsu Petrochemical Co., Ltd. and 0.005 g of dibutyltin laurate were dissolved uniformly. When it becomes homogeneous, increase the temperature to 50 ° C, and add isophorone diisocyanate (IPDI, Mw = 222, isocyanate equivalent = 111g / eq.) 3.08g while stirring, for about 3 hours and about 12 hours Way to react. The obtained reaction solution was dropped into an n-hexane solution, and a white precipitate was deposited. Then, a white precipitate was recovered by filtration, and dried at 100 ° C. for 2 hours to obtain a polymer of polybutadiene and IPDI at a ratio of about 1: 1.
About the obtained polymer, GPC measurement (made by Waters Corporation, 2695 polystyrene conversion) and DSC measurement ((DSC-6100, manufactured by Seiko Instruments, heating rate 5 ° C)) were performed to confirm the molecular weight Mw and the glass transition temperature Tg, respectively. As a result, the shorter reaction time (hereinafter referred to as polymer resin A) was confirmed by weight average molecular weight Mw = 50,000 and Tg = -10 ° C. The longer reaction time (hereinafter referred to as polymer resin B) was confirmed by weight average molecular weight Mw = 250000, Tg = -12 ° C.

＜硬化性樹脂組成物之調製＞
將實施例及比較例所記載的溶劑置入容器中，加熱至50℃，邊攪拌，然後分別邊加入填料以外的各成分。確認彼等之成分溶解後，加入填料充分攪拌。然後，藉由三輥磨機進行混練，調製硬化性樹脂組成物。又，表中之數值表示質量份，又，溶劑以外表示固體成分量。<Preparation of curable resin composition>
The solvents described in the examples and comparative examples were placed in a container, heated to 50 ° C., and stirred, and then components other than the filler were added separately. After confirming that these ingredients are dissolved, the filler is added and stirred well. Then, the mixture was kneaded with a three-roll mill to prepare a curable resin composition. In addition, the numerical value in a table | surface shows a mass part, and other than a solvent shows the solid content amount.

＜攪拌靜置後之沉澱＞
將調製後之硬化性樹脂組成物置入透明的剝離螺桿管內，在設定為23℃之恆溫槽中，保管12小時進行熟成處理。投入硬化性樹脂組成物，自螺桿管之底部起50mm。熟成後，取出硬化性樹脂組成物，由側面目視觀察，確認硬化性樹脂組成物之沉降狀態。判斷基準如下述。
◎◎：未見沉降。
◎ ：自組成物之上部，確認未達1mm之透明的上澄液。
〇 ：自組成物之上部，確認1mm以上未達3mm之透明的上澄液。
△ ：自組成物之上部，確認3mm以上未達5mm之透明的上澄液。
× ：自組成物之上部，確認5mm以上之透明的上澄液。使用粒度測定器(grindmeter)確認沉降物時，確認凝聚粒。<Precipitation after stirring and standing>
The prepared curable resin composition was placed in a transparent peel-off screw tube, and stored in a constant temperature tank set at 23 ° C. for 12 hours for aging treatment. The hardening resin composition was put in and 50 mm from the bottom of the screw tube. After aging, the curable resin composition was taken out and visually observed from the side to confirm the sedimentation state of the curable resin composition. The judgment criteria are as follows.
◎: No settlement was observed.
: From the upper part of the composition, it was confirmed that the transparent liquid was less than 1 mm in size.
○: From the upper part of the composition, a transparent supernatant liquid of 1 mm or more and less than 3 mm was confirmed.
(Triangle | delta): From the upper part of the composition, it was confirmed that the transparent upper liquid was 3 mm or more and less than 5 mm.
×: From the upper part of the composition, a transparent upper liquid of 5 mm or more was confirmed. When sedimentation is confirmed using a particlemeter, aggregated particles are confirmed.

＜乾膜之製作與外觀之評價＞
將調製後之硬化性樹脂組成物調整溶劑的量，使成為黏度0.5~20dPa･s(轉動黏度計5rpm、25℃)，分別使用塗佈棒，塗佈於載體薄膜(PET薄膜；東麗公司製lumirror38R75，厚度38μm、大小30cm×30cm)，並使樹脂層之厚度在乾燥後成為40μm。接著，以熱風循環式乾燥爐，於70~120℃(平均100℃)下乾燥5~10分鐘，使樹脂層之殘留溶劑成為0.5~2.5質量%，在載體薄膜上形成樹脂層。樹脂層之表面狀態，在白色光源下，以目視區分為以下3種。
霧面(消光：matte)：即使在白色光源下，樹脂表面上未見光的反射。
半霧面：稍微看見白色光源之反射。
光澤：看見白色光源之反射。＜ Production of dry film and evaluation of appearance ＞
The prepared curable resin composition was adjusted to the amount of the solvent so as to have a viscosity of 0.5 to 20 dPa ･ s (rotational viscosity meter 5 rpm, 25 ° C.), and each was applied to a carrier film (PET film; Toray Co., Ltd.) using a coating rod. Made of lumirror 38R75, with a thickness of 38 μm and a size of 30 cm × 30 cm), and the thickness of the resin layer after drying is 40 μm. Next, it is dried in a hot-air circulation type drying furnace at 70 to 120 ° C. (average 100 ° C.) for 5 to 10 minutes, so that the residual solvent of the resin layer becomes 0.5 to 2.5 mass%, and a resin layer is formed on the carrier film. The surface state of the resin layer is visually divided into the following three types under a white light source.
Matte (matte): Even under a white light source, no reflection of light was seen on the resin surface.
Half matte: Slight reflection of white light source.
Gloss: See reflection from white light source.

＜與2軸延伸聚丙烯薄膜(OPP)之密著性＞
在製作後之乾膜之樹脂層表面，使用輥積層機，使OPP(AlphanFG-201、Fish Aires、王子f-tex)密著。輥積層機的條件為表面溫度80℃或110℃的2種，線壓力0.3MPa、輸送速度5cm/sec下進行。對於所得之3層構造之乾膜，製作寬1cm、長度10cm的短冊、OPP之剝離重量，依據、JIS-C-6481所記載之剝離強度之測量方法(90°方向、拉離速度(rate of pulling)50mm/min)進行測量。評價基準如下述。
◎：最大剝離強度3N/cm以上。
〇：最大剝離強度1N/cm以上未達3N/cm。
△：最大剝離強度未達1N/cm。
×：未密著。＜ Adhesion to biaxially stretched polypropylene film (OPP) ＞
On the surface of the resin layer of the produced dry film, an OPP (AlphanFG-201, Fish Aires, Oji f-tex) was adhered using a roll laminator. The conditions of the roll laminator are two types of surface temperature: 80 ° C or 110 ° C, linear pressure: 0.3 MPa, and conveying speed: 5 cm / sec. For the obtained 3-layer structured dry film, a short booklet with a width of 1 cm and a length of 10 cm, and the peeling weight of OPP were prepared according to the peeling strength measurement method (90 ° direction, pull-off speed (rate of) according to JIS-C-6481). pulling) 50mm / min). The evaluation criteria are as follows.
：: The maximum peeling strength is 3 N / cm or more.
○: The maximum peel strength is 1 N / cm or more and less than 3 N / cm.
△: The maximum peeling strength did not reach 1 N / cm.
×: Not adhered.

＜切割加工＞
對密著有OPP之尺寸30×30cm之3層構造的乾膜，使用切割刀將端部切斷成25×25cm尺寸，確認狀態。評價基準如下述。
◎：未發生OPP之浮起、樹脂之皺紋。
〇：切斷部，確認OPP之浮起(最大部分1mm未達)。
△：切斷部發生OPP之浮起與樹脂端部之龜裂(最大部分1mm以上未達5mm)。
×：切斷部發生OPP之浮起與樹脂端部之龜裂(最大部分5mm以上)。＜ Cutting Processing ＞
For a dry film with a three-layer structure of 30 × 30cm in close contact with OPP, the end was cut to a size of 25 × 25cm with a cutter to confirm the state. The evaluation criteria are as follows.
：: No floating of OPP and wrinkles of resin did not occur.
○: The cutting part confirms the floating of OPP (maximum part is less than 1mm).
(Triangle | delta): The floating part of OPP and the crack of the resin edge part generate | occur | produce in a cut | disconnected part (maximum part is 1 mm or more and less than 5 mm).
X: The OPP floats and the resin edge cracks occur in the cut part (maximum part 5mm or more).

＜玻璃轉移溫度(Tg)＞
將製作後之3層構造之乾膜的OPP剝離後，在電解銅箔之光澤面(GTS-MP-18、古河Circuit Foil)上，使用真空積層機MVLP-500(名機製作所製)貼合乾膜之樹脂層。條件為溫度80~110℃、壓力0.5MPa下進行。然後，剝離載體薄膜，使用熱風循環式乾燥爐使材料硬化。條件為100℃×30min+180℃×30min+200℃×60min下進行。接著，將所得之硬化物自銅箔剝離，得到硬化物。然後，將樣品切成測量尺寸(3mm×10mm之尺寸)，使用Seiko Instruments公司製之TMA6100進行測量。TMA測量係以試驗荷重5g，將樣品以10℃/分鐘的昇溫速度，自室溫昇溫至280℃後，空氣冷卻至室溫，連續測量2次。第2次之昇溫步驟的變極點作為Tg進行評價。評價基準如下述。
◎：Tg=190℃以上。
〇：Tg=未達190℃。<Glass transition temperature (Tg)>
After the OPP of the three-layer structure of the dried film was peeled off, it was laminated on the glossy surface of electrolytic copper foil (GTS-MP-18, Furukawa Circuit Foil) using a vacuum laminator MVLP-500 (manufactured by Meiki Seisakusho) Resin layer of dry film. The conditions were performed at a temperature of 80 to 110 ° C and a pressure of 0.5 MPa. Then, the carrier film was peeled off, and the material was hardened using a hot-air circulation drying oven. The conditions are 100 ° C × 30min + 180 ° C × 30min + 200 ° C × 60min. Then, the obtained hardened | cured material was peeled from the copper foil, and the hardened | cured material was obtained. Then, the sample was cut into a measurement size (a size of 3 mm × 10 mm) and measured using TMA6100 manufactured by Seiko Instruments. The TMA measurement was performed with a test load of 5 g, and the sample was heated from room temperature to 280 ° C. at a heating rate of 10 ° C./minute, and then air cooled to room temperature, and the measurement was performed twice. The pole change point of the second heating step was evaluated as Tg. The evaluation criteria are as follows.
：: Tg = 190 ° C or higher.
○: Tg = less than 190 ° C.

＜CTE＞
使用與Tg之測量方法同樣的方法實施TMA測量。第2次中自30℃至100℃為止之間的平均熱膨脹率作為CTE(單位為ppm)。＜ CTE ＞
The TMA measurement was performed using the same method as the Tg measurement method. The average thermal expansion coefficient from 30 ° C to 100 ° C in the second time was taken as the CTE (unit: ppm).

＜銅箔上之翹曲＞
對於製作後之乾膜，OPP剝離後，在電解銅箔(GTS-MP-18μm、古河Circuit Foil公司製、尺寸20×20cm)之光澤面上，使用真空積層機MVLP-500(名機製作所公司製)貼合乾膜。條件為溫度80~110℃、壓力0.5MPa下進行。然後，剝離載體薄膜，使用熱風循環式乾燥爐使材料硬化。條件為100℃×30min+180℃×30min+200℃×60min下進行。冷卻至室溫後，隨即使用游標尺(Vernier Caliper)計測銅箔之4角的翹曲狀態(翹曲形狀全部為向上翹曲(smiling)。評價基準如下述。
◎：無翹曲。
〇：4角之中，1號翹曲之大的部分之翹曲量未達3mm。
△：4角之中，1號翹曲之大的部分之翹曲量為3mm以上、未達10mm。
×：4角之中，1號翹曲之大的部分之翹曲量10mm以上。＜ Warpage on copper foil ＞
For the dry film after production, after peeling the OPP, a vacuum laminator MVLP-500 (Miki Seisakusho Co., Ltd.) was used on the glossy surface of electrolytic copper foil (GTS-MP-18 μm, Furukawa Circuit Foil, 20 × 20 cm). (Manufactured) Laminate dry film. The conditions were performed at a temperature of 80 to 110 ° C and a pressure of 0.5 MPa. Then, the carrier film was peeled off, and the material was hardened using a hot-air circulation drying oven. The conditions are 100 ° C × 30min + 180 ° C × 30min + 200 ° C × 60min. After cooling to room temperature, the warped state of the four corners of the copper foil was measured using a Vernier Caliper (all warped shapes are upwards. The evaluation criteria are as follows.
：: No warpage.
〇: Among the 4 corners, the warpage amount of the large part of No. 1 warp did not reach 3 mm.
Δ: Among the 4 corners, the warpage amount of the large warp portion No. 1 is 3 mm or more and less than 10 mm.
X: Among the four corners, the amount of warpage of the large warp portion No. 1 was 10 mm or more.

＜與基材之密著(低粗度電解銅)＞
將銅厚12μm、板厚0.2mm之銅箔基板(MCL-E-770G、日立化成工業製)進行電鍍銅(atotech公司製、鍍敷後之表面粗糙度100nm以下)，形成銅厚合計為20μm。接著，進行作為前處理之flat bond處理(處理後之表面粗糙度100nm以下、Merck公司製)。然後，將剝離OPP後之乾膜，使用2腔式真空積層機CVP-600(Nichigo-morton製)貼合於基板上之表裏。條件係分別以溫度80~110℃、壓力0.5MPa進行積層、壓製。接著，剝離載體薄膜後，使用熱風循環式乾燥爐使樹脂層硬化。條件為以100℃×30min+180℃×30min+200℃×60min進行。然後，在所得之硬化膜的表面使用切割刀製作尺寸1mm×1mm，100方格之棋盤格(JIS-K5400、依據棋盤格試驗)。然後，在切割後之硬化膜的表面黏貼聚酯膠帶((1)型號8422B：接著力5.1N/cm與、(2)型號879：接著力15N/cm、皆為3M公司製)，隨即持膠帶的端部，對硬化膜面保持垂直，瞬間將膠帶剝離。依據以下的基準判斷剝離後之塗膜的狀態。
◎◎：以膠帶(2)剝離的格數為0。
◎ ：以膠帶(2)剝離的格數1處以上未達5處。膠帶(1)之剝離的格數為0。
〇 ：以膠帶(1)剝離的格數1處以上未達5處。
△ ：以膠帶(1)剝離的格數5處以上未達20處。
× ：以膠帶(1)剝離的格數20處以上。＜ Adhesion to the substrate (low thickness electrolytic copper) ＞
A copper foil substrate (MCL-E-770G, manufactured by Hitachi Chemical Co., Ltd.) with a copper thickness of 12 μm and a thickness of 0.2 mm was plated with copper (manufactured by Atotech, the surface roughness after plating was 100 nm or less) to form a total copper thickness of 20 μm . Next, a flat bond treatment (a surface roughness after the treatment of 100 nm or less, manufactured by Merck) as a pre-treatment is performed. Then, the dry film after the OPP was peeled off was attached to a surface on a substrate using a two-chamber vacuum laminator CVP-600 (manufactured by Nichigo-morton). The conditions are laminated and pressed at a temperature of 80 to 110 ° C and a pressure of 0.5 MPa, respectively. Next, after peeling the carrier film, the resin layer was hardened using a hot-air circulation type drying oven. The conditions are 100 ° C × 30min + 180 ° C × 30min + 200 ° C × 60min. Then, on the surface of the obtained cured film, a checkerboard (JIS-K5400, based on a checkerboard test) having a size of 1 mm × 1 mm and a size of 100 squares was produced using a cutter. Then, a polyester tape was stuck on the surface of the cured film after cutting ((1) Model 8422B: Adhesive force 5.1N / cm and (2) Model 879: Adhesive force 15N / cm, both made by 3M Company), then held The end of the tape is kept perpendicular to the hardened film surface, and the tape is peeled off instantly. The state of the coating film after peeling was judged based on the following criteria.
◎: The number of cells peeled with the adhesive tape (2) was 0.
◎: The number of cells peeled off with the adhesive tape (2) is 1 or more and less than 5. The number of peeled cells of the tape (1) is 0.
○: The number of cells peeled off with the adhesive tape (1) is one or more and less than five.
△: The number of cells peeled off with the adhesive tape (1) was 5 or more and less than 20.
×: The number of cells peeled with the adhesive tape (1) was 20 or more.

＜平坦性＞
將黏晶(die bonding)薄片FH-900(厚度10μm、日立化成工業公司製)加熱至60℃貼合於厚度150μm、尺寸10×10mm之矽虛擬晶片(dummy chip)之裏面。然後，在鈉玻璃(厚度1.1mm、尺寸60×60mm、平岡特殊玻璃公司製)上，使用真空積層機MVLP-500(名機製作所公司製；條件為100℃、0.5MPa、時間1分鐘)以5mm間距貼合。然後，將剝離OPP後之乾膜，使用2腔式真空積層機CVP-600(Nichigo-morton製)使樹脂表面成為平坦的條件，並且樹脂層之厚度之合計成為200μm，來貼合於排列有虛擬晶片的玻璃基板上。各條件係分別以溫度80~110℃、壓力0.5MPa進行積層、壓製。接著，剝離載體薄膜後，使用熱風循環式乾燥爐使材料硬化。條件為100℃×30min+180℃×30min+200℃×60min下進行。所得之基板之虛擬晶片上之平坦性評價，使用表面粗糙度測量器SURFCORDER SE-600，評價晶片上與僅硬化物之部分之凹凸。判斷基準如下述。
◎：無凹凸。
〇：凹凸未達5μm。
△：凹凸5μm以上未達10μm。
×：凹凸10μm以上。<Flatness>
A die bonding sheet FH-900 (thickness: 10 μm, manufactured by Hitachi Chemical Co., Ltd.) was heated to 60 ° C. and bonded to a silicon dummy chip having a thickness of 150 μm and a size of 10 × 10 mm. Then, on a soda glass (thickness 1.1 mm, size 60 × 60 mm, manufactured by Hiraoka Special Glass Co., Ltd.), a vacuum laminator MVLP-500 (manufactured by Meiji Seisakusho; conditions: 100 ° C, 0.5 MPa, time 1 minute) was used 5mm pitch fit. Then, the dry film after the OPP was peeled off, the resin surface was flattened using a two-chamber vacuum laminator CVP-600 (manufactured by Nichigo-morton), and the total thickness of the resin layer was 200 μm, and it was attached to the array. Virtual wafer on glass substrate. Each condition is laminated and pressed at a temperature of 80 to 110 ° C and a pressure of 0.5 MPa. Next, after the carrier film is peeled off, the material is hardened using a hot-air circulation drying oven. The conditions are 100 ° C × 30min + 180 ° C × 30min + 200 ° C × 60min. For the flatness evaluation on the obtained virtual wafer of the substrate, the surface roughness measuring device SURFCORDER SE-600 was used to evaluate the unevenness on the wafer and only the hardened part. The judgment criteria are as follows.
：: No unevenness.
○: The unevenness is less than 5 μm.
Δ: The unevenness is 5 μm or more and less than 10 μm.
×: The unevenness is 10 μm or more.

*1：Mitsubishi Chemical公司製jER828、雙酚A型環氧樹脂、環氧當量189g/eq、液狀
*2：DIC公司製EPICLONN-740，苯酚酚醛清漆型環氧樹脂，環氧當量182g/eq、半固形
*3：Mitsubishi Chemical公司製EpikoteYX4000H、3,3’5,5’-四甲基-4,4-聯苯二酚二縮水甘油醚、環氧當量192g/eq、結晶性
*4：日本化藥公司製NC-3000H、聯苯基酚醛清漆型環氧化合物、環氧當量290g/eq、
*5：Lonza Japan公司製Primaset PT-30、酚醛清漆型氰酸酯樹脂、氰酸酯當量124g/eq、固形
*6：DIC公司製EPICLONHPC-8000、活性酯樹脂、活性當量223g/eq、固形
*7：DIC公司製LA-3018、含有ATN之甲酚醛清漆樹脂、羥基當量151g/eq、固形
*8：明和化成公司製HF-1M、苯酚酚醛清漆樹脂、羥基當量106g/eq、
*9：大和化成工業製BMI-2300、苯基甲烷雙馬來醯亞胺、馬來醯亞胺當量187g/eq、固形
*10：四國化成公司製2E4MZ、2-乙基-4-甲基咪唑
*11：東京化成工業公司製乙醯丙酮鈷(II)、粉末
*12：nagase chemtex公司製teisanresin SG-80H 不含MEK品、固體成分18質量%、丙烯酸酯共聚物(官能基：環氧基、醯胺基)
*13：nagase chemtex公司製teisanresin SG-P3 不含MEK品、固體成分15質量%、丙烯酸酯共聚物(官能基：環氧基)
*14：nagase chemtex公司製teisanresin SG-280 不含MEK品、固體成分23質量%、丙烯酸酯共聚物(官能基：羧基)
*15：nagase chemtex公司製teisanresin WS-023 不含MEK品、固體成分30質量%、丙烯酸酯共聚物(官能基：羧基、羥基)
*16：以上述合成的聚丁二烯與IPDI之聚合物(高分子樹脂A)
*17：以上述合成的聚丁二烯與IPDI之聚合物(高分子樹脂B)
*18：Mitsubishi Chemical公司製YX6954、苯氧基樹脂、Mw=38000、Tg=130℃
*19：admatechs公司製SO-C2、球狀二氧化矽、平均粒徑(D50)=0.5μm(與粒徑分布測量時之峰值相同。)
*20：admatechs公司製SO-C1、球狀二氧化矽、平均粒徑(D50)=200nm(與粒徑分布測量時之峰值相同。)
*21：使用admatechs公司製YA050SV2、乙烯基矽烷KBM-1003以1質量%處理後之球狀二氧化矽、平均粒徑(D50)=50nm(與粒徑分布測量時之峰值相同。)
*22：龍森公司製MUF-1BV、球狀二氧化矽、平均粒徑(D50)=3μm(與粒徑分布測量時之峰值相同。)
*23：龍森公司製MSS-T72、球狀二氧化矽、平均粒徑(D50)=5μm(與粒徑分布測量時之峰值相同。)
*24：admatechs公司製SO-C5、球狀二氧化矽、平均粒徑(D50)=1.5μm(與粒徑分布測量時之峰值相同。)
*25：Denka公司製ASFP-20、氧化鋁、平均粒徑(D50)=0.3μm(與粒徑分布測量時之峰值相同。)
*26：信越SILICONES公司製KBM-403、環氧基矽烷偶合劑
*27：甲基乙基酮* 1: jER828 manufactured by Mitsubishi Chemical, bisphenol A epoxy resin, epoxy equivalent 189 g / eq, liquid
* 2: EPICLONN-740 manufactured by DIC, phenol novolac epoxy resin, epoxy equivalent 182g / eq, semi-solid
* 3: Epikote YX4000H manufactured by Mitsubishi Chemical Co., 3,3'5,5'-tetramethyl-4,4-biphenylglycidyl ether, epoxy equivalent 192 g / eq, crystallinity
* 4: NC-3000H manufactured by Nippon Kayaku Co., biphenyl novolac epoxy compound, epoxy equivalent 290g / eq,
* 5: Primaset PT-30 manufactured by Lonza Japan, novolac type cyanate resin, 124g / eq cyanate equivalent, solid
* 6: EPICLONHPC-8000 manufactured by DIC, active ester resin, active equivalent 223g / eq, solid
* 7: LA-3018 manufactured by DIC, cresol novolac resin containing ATN, hydroxyl equivalent 151g / eq, solid
* 8: HF-1M manufactured by Meiwa Chemical Co., phenol novolac resin, hydroxyl equivalent 106g / eq,
* 9: BMI-2300 manufactured by Yamato Chemical Industries, phenylmethane bismaleimide, maleimide equivalent 187g / eq, solid
* 10: 2E4MZ, 2-ethyl-4-methylimidazole manufactured by Shikoku Chemical Co., Ltd.
* 11: Cobalt (II) acetoacetone, powder manufactured by Tokyo Chemical Industry Co., Ltd.
* 12: Teisanresin SG-80H manufactured by Nagase Chemtex Co., Ltd. does not contain MEK product, 18% by mass of solid content, acrylate copolymer (functional group: epoxy group, amido group)
* 13: Teisanresin SG-P3 manufactured by Nagase Chemtex Co., Ltd. does not contain MEK product, 15% by mass of solid content, acrylate copolymer (functional group: epoxy group)
* 14: Teisanresin SG-280 manufactured by Nagase Chemtex Co., Ltd. does not contain MEK product, 23% by mass of solid content, acrylate copolymer (functional group: carboxyl group)
* 15: Teisanresin WS-023 manufactured by Nagase Chemtex Co., Ltd. MEK-free product, 30% by mass of solid content, acrylate copolymer (functional group: carboxyl group, hydroxyl group)
* 16: Polymer of polybutadiene and IPDI synthesized above (Polymer Resin A)
* 17: Polymer (Polymer Resin B) of polybutadiene and IPDI synthesized as above
* 18: YX6954 manufactured by Mitsubishi Chemical, phenoxy resin, Mw = 38000, Tg = 130 ° C
* 19: SO-C2 manufactured by admatechs, spherical silica, average particle size (D50) = 0.5 μm (same as the peak value during particle size distribution measurement)
* 20: SO-C1 manufactured by admatechs, spherical silica, average particle size (D50) = 200nm (same as the peak value during particle size distribution measurement)
* 21: Using YA050SV2 manufactured by admatechs, vinyl silane KBM-1003 treated with 1% by mass of spherical silica, average particle size (D50) = 50nm (same as the peak value during particle size distribution measurement)
* 22: MUF-1BV manufactured by Longsen Corporation, spherical silica, average particle size (D50) = 3 μm (same as the peak value during particle size distribution measurement)
* 23: MSS-T72 manufactured by Longsen Corporation, spherical silica, average particle size (D50) = 5 μm (same as the peak value during particle size distribution measurement)
* 24: SO-C5 manufactured by admatechs, spherical silica, average particle size (D50) = 1.5 μm (same as the peak value during particle size distribution measurement)
* 25: ASFP-20 manufactured by Denka, alumina, average particle size (D50) = 0.3 μm (same as the peak value during particle size distribution measurement)
* 26: KBM-403, Epoxy Silane Coupling Agent, manufactured by Shin-Etsu Silicone Co., Ltd.
* 27: Methyl ethyl ketone

由上述表所示之結果，得知實施例之乾膜的情形，樹脂層與保護薄膜之密著性佳，且樹脂層所含有之無機填料之沉降少。又，得知實施例之乾膜的情形，加工時之剝離或龜裂、掉粉之抑制，耐翹曲性、與基底之密著性、硬化物表面之平坦性也優異。From the results shown in the above table, it was found that in the case of the dry film of the example, the adhesion between the resin layer and the protective film was good, and the sedimentation of the inorganic filler contained in the resin layer was small. In addition, it was found that the dry film of the example is excellent in peeling, cracking, and powder fall suppression during processing, and has excellent warpage resistance, adhesion to the substrate, and flatness of the surface of the cured product.

11‧‧‧三層構造之乾膜11‧‧‧Three-layer dry film

12‧‧‧樹脂層 12‧‧‧ resin layer

13‧‧‧載體薄膜 13‧‧‧ carrier film

14‧‧‧保護薄膜 14‧‧‧ protective film

[圖1] 以示意表示本發明之乾膜之一實施態樣的概略剖面圖。[Fig. 1] A schematic cross-sectional view schematically showing an embodiment of a dry film according to the present invention.

Claims (6)

一種乾膜，其係具備載體薄膜、樹脂層及保護膜的乾膜， 前述保護膜為2軸延伸聚丙烯薄膜， 前述樹脂層包含無機填料、玻璃轉移溫度為20℃以下，且重量平均分子量為3萬以上的高分子樹脂及環氧樹脂， 前述樹脂層包含作為前述環氧樹脂之半固形環氧樹脂及結晶性環氧樹脂其中之至少1種。A dry film comprising a carrier film, a resin layer and a protective film. The protective film is a biaxially stretched polypropylene film, The resin layer includes an inorganic filler, a polymer resin and an epoxy resin having a glass transition temperature of 20 ° C. or lower and a weight average molecular weight of 30,000 or more. The resin layer includes at least one of a semi-solid epoxy resin and a crystalline epoxy resin as the epoxy resin. 如請求項1之乾膜，其中前述樹脂層包含作為硬化劑之具有酚性羥基之化合物、具有活性酯基之化合物、具有氰酸酯基之化合物及具有馬來醯亞胺基之化合物其中之至少任一種。The dry film according to claim 1, wherein the resin layer contains a compound having a phenolic hydroxyl group as a hardener, a compound having an active ester group, a compound having a cyanate group, and a compound having a maleimide group. At least either. 如請求項1之乾膜，其中前述樹脂層包含平均粒徑為0.1~10μm之無機填料與平均粒徑為0.01~5μm之無機填料的混合物，且前述平均粒徑為0.1~10μm之無機填料與前述平均粒徑為0.01~5μm之無機填料之粒徑分布測量時之峰間之差為0.05μm以上。For example, the dry film of claim 1, wherein the resin layer includes a mixture of an inorganic filler having an average particle diameter of 0.1 to 10 μm and an inorganic filler having an average particle diameter of 0.01 to 5 μm, and the inorganic filler having the average particle diameter of 0.1 to 10 μm and The difference between the peaks in the particle size distribution measurement of the inorganic filler having an average particle diameter of 0.01 to 5 μm is 0.05 μm or more. 如請求項1~3中任一項之乾膜，其中以前述樹脂層之固體成分全量基準，前述無機填料含有50質量%以上。The dry film according to any one of claims 1 to 3, wherein the inorganic filler contains 50% by mass or more of the solid content of the resin layer. 一種硬化物，其係使如請求項1~4中任一項之乾膜的樹脂層硬化所得者。A hardened product obtained by hardening the resin layer of the dry film according to any one of claims 1 to 4. 一種電子零件，其係具有如請求項5之硬化物。An electronic component having a hardened body as claimed in claim 5.