TW202039749A

TW202039749A - Film adhesive, laminated sheet, composite sheet, and manufacturing method of laminate

Info

Publication number: TW202039749A
Application number: TW108147333A
Authority: TW
Inventors: 佐藤陽輔
Original assignee: 日商琳得科股份有限公司
Priority date: 2018-12-28
Filing date: 2019-12-24
Publication date: 2020-11-01
Also published as: CN113165350A; JP7421497B2; KR20210110291A; JPWO2020137934A1; WO2020137934A1

Abstract

A film adhesive of the present embodiment contains an acrylic-based resin(a), an epoxy compound(b1), and a phosphorus-based antioxidant(z), wherein the linear transmissivity of light having a wavelength of 400 to 800nm of the film adhesive before heating at 260 °C is 90% or more, and the linear transmissivity of light having a wavelength of 400 to 800nm of the film adhesive after heating at 260 °C for ten minutes is 85% or more, and the thickness of the film adhesive is 10 to 40 μm.

Description

膜狀接著劑、積層片、複合片、以及積層體之製造方法Film adhesive, laminated sheet, composite sheet, and method for manufacturing laminated body

本發明係關於一種膜狀接著劑、積層片、複合片、以及積層體之製造方法。本申請案基於2018年12月28日在日本提出申請之日本專利特願2018-246837號主張優先權，且將該申請案的內容引用至本文中。The present invention relates to a method for manufacturing a film adhesive, a laminated sheet, a composite sheet, and a laminated body. This application claims priority based on Japanese Patent Application No. 2018-246837 filed in Japan on December 28, 2018, and the content of the application is cited herein.

於製造或加工構成電子機器之各種零件時，根據目的使用各種膜狀接著劑。例如，於將半導體晶片安裝於基板的電路形成面之情形時，於半導體晶片的背面預先貼附膜狀接著劑，經由該膜狀接著劑，將半導體晶片接著(黏晶)於基板的電路形成面。另外，於保護感測器等晶片的電路形成面之情形時，經由具有透光性之膜狀接著劑，將前述電路形成面由透光性罩(cover)被覆。When manufacturing or processing various parts of electronic equipment, various film adhesives are used according to the purpose. For example, when a semiconductor chip is mounted on the circuit formation surface of a substrate, a film-like adhesive is attached to the back of the semiconductor chip in advance, and the semiconductor chip is bonded (bonded) to the circuit formation of the substrate through the film-like adhesive. surface. In addition, when protecting the circuit formation surface of a chip such as a sensor, the circuit formation surface is covered with a translucent cover via a film-like adhesive having translucency.

另一方面，具備此種膜狀接著劑之零件有時會因回焊步驟等加熱步驟而暴露於高溫下。該情形時，有時因熱的影響而導致膜狀接著劑變質成為問題。例如，若具有透光性之膜狀接著劑變色，則難以經由該膜狀接著劑而讀取資訊。對於膜狀接著劑，為了表現接著性而含有樹脂成分，根據情況，為了賦予熱硬化性而含有熱硬化性成分，但這些成分有的對熱不穩定。亦即，先前的膜狀接著劑容易因加熱而變色。On the other hand, parts provided with such a film-like adhesive are sometimes exposed to high temperatures due to heating steps such as reflow steps. In this case, deterioration of the film-like adhesive may be a problem due to the influence of heat. For example, if a translucent film-like adhesive changes color, it is difficult to read information through the film-like adhesive. The film-like adhesive contains a resin component in order to express adhesiveness and, depending on the situation, a thermosetting component in order to impart thermosetting properties, but some of these components are unstable to heat. That is, the conventional film-like adhesive is easily discolored by heating.

作為具有透光性之膜狀接著劑，例如揭示有一種黏晶膜，係半導體晶片之黏晶用，波長1065nm之光線透過率為80%以上(參照專利文獻1)。 [先前技術文獻] [專利文獻]As a light-transmitting film adhesive, for example, a die-attach film is disclosed, which is used for die-bonding of semiconductor chips, and has a light transmittance of 80% or more at a wavelength of 1065 nm (refer to Patent Document 1). [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本特許第6310748號公報。[Patent Document 1] Japanese Patent No. 6310748.

[發明所欲解決之課題][The problem to be solved by the invention]

然而，專利文獻1中，關於黏晶膜之加熱後的顏色等加熱後的物性並未揭示。However, Patent Document 1 does not disclose the physical properties of the mucosal film after heating, such as the color after heating.

本發明的目的在於提供一種於加熱前後具有透光性且加熱後的著色得到抑制之膜狀接著劑、使用前述膜狀接著劑之積層片及複合片、以及使用前述膜狀接著劑之積層體之製造方法。 [用以解決課題之手段]The object of the present invention is to provide a film-like adhesive that has translucency before and after heating and suppresses coloration after heating, a laminated sheet and a composite sheet using the aforementioned film-like adhesive, and a laminated body using the aforementioned film-like adhesive The manufacturing method. [Means to solve the problem]

本發明提供一種膜狀接著劑，含有丙烯酸系樹脂(a)、環氧化合物(b1)、及磷系抗氧化劑(z)，且於260℃加熱前的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為90%以上，於260℃加熱10分鐘後的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為85%以上，前述膜狀接著劑的厚度為10μm至40μm。本發明的膜狀接著劑中，前述環氧化合物(b1)亦可為脂肪族系化合物。本發明的膜狀接著劑中，亦可係前述膜狀接著劑進而含有酚樹脂(b2)，且前述膜狀接著劑中的前述酚樹脂(b2)的含量相對於前述膜狀接著劑的總質量之比例為10質量%以下。The present invention provides a film-like adhesive containing acrylic resin (a), epoxy compound (b1), and phosphorus antioxidant (z), and the aforementioned film-like adhesive before heating at 260°C has a wavelength of 400 nm to The linear transmittance of light at 800nm is 90% or more, and the linear transmittance of the film adhesive after heating at 260°C for 10 minutes at a wavelength of 400nm to 800nm is over 85%. The thickness of the film adhesive is 10μm to 40μm. In the film adhesive of the present invention, the epoxy compound (b1) may be an aliphatic compound. In the film adhesive of the present invention, the film adhesive may further contain a phenol resin (b2), and the content of the phenol resin (b2) in the film adhesive is relative to the total amount of the film adhesive The mass ratio is 10 mass% or less.

本發明的膜狀接著劑中，前述磷系抗氧化劑(z)亦可為脂肪族系亞磷酸酯。本發明的膜狀接著劑中，亦可係前述膜狀接著劑進而含有脂肪族系多元異氰酸酯交聯劑，且前述丙烯酸系樹脂(a)具有能夠與前述交聯劑鍵結之官能基。本發明提供一種積層片，具備前述膜狀接著劑、及設置於前述膜狀接著劑的一面上之樹脂膜。本發明提供一種複合片，具備前述膜狀接著劑、及設置於前述膜狀接著劑的一面上之切割片，前述切割片具備基材、及設置於前述基材的一面上之黏著劑層，前述黏著劑層配置於前述基材與前述膜狀接著劑之間。本發明提供一種積層體之製造方法，係於前述膜狀接著劑的一面貼合晶片的電路形成面，於前述膜狀接著劑的另一面貼合透光性罩，藉此獲得依序積層前述晶片、前述膜狀接著劑、及前述透光性罩而構成之積層體。 [發明功效]In the film-like adhesive of the present invention, the phosphorus antioxidant (z) may be an aliphatic phosphite. In the film adhesive of the present invention, the film adhesive may further contain an aliphatic polyvalent isocyanate crosslinking agent, and the acrylic resin (a) may have a functional group capable of bonding with the crosslinking agent. The present invention provides a laminated sheet including the film-like adhesive and a resin film provided on one side of the film-like adhesive. The present invention provides a composite sheet comprising the film adhesive and a dicing sheet provided on one side of the film adhesive. The dicing sheet includes a substrate and an adhesive layer provided on one side of the substrate, The adhesive layer is disposed between the substrate and the film adhesive. The present invention provides a method of manufacturing a laminated body, which is to bond the circuit forming surface of a chip on one side of the film-like adhesive, and bond a light-transmitting cover to the other side of the film-like adhesive, thereby obtaining the sequential lamination A laminate composed of a wafer, the aforementioned film-like adhesive, and the aforementioned translucent cover. [Invention Effect]

本發明的膜狀接著劑於加熱前後具有透光性，且加熱後的著色得到抑制。藉由使用具備本發明的膜狀接著劑之本發明的積層片或複合片，能夠將前述膜狀接著劑設置於作為前述膜狀接著劑之應用對象之零件。藉由本發明的積層體之製造方法，能夠製造依序積層晶片、膜狀接著劑、及透光性罩而構成之積層體。The film-like adhesive of the present invention has translucency before and after heating, and the coloration after heating is suppressed. By using the laminated sheet or composite sheet of the present invention provided with the film-like adhesive of the present invention, the film-like adhesive can be placed on a part that is an application target of the film-like adhesive. According to the manufacturing method of the laminated body of this invention, the laminated body which laminated|stacked the wafer, the film adhesive, and the translucent cover in order can be manufactured.

◇膜狀接著劑本發明的一實施形態的膜狀接著劑含有丙烯酸系樹脂(a)、環氧化合物(b1)、及磷系抗氧化劑(z)，且於260℃加熱前的前述膜狀接著劑在波長為400nm至800nm之光(本說明書中，有時簡稱為「光(400nm至800nm)」)之直線透過率(本說明書中，有時簡稱為「加熱前直線透過率」)為90%以上，於260℃加熱10分鐘後的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率(本說明書中，有時簡稱為「加熱後直線透過率」)為85%以上，前述膜狀接著劑的厚度為10μm至40μm。本實施形態的膜狀接著劑於在260℃等加熱前後，渾濁及著色得到抑制，光(400nm至800nm)之直線透過率高。◇Film adhesive The film adhesive of one embodiment of the present invention contains acrylic resin (a), epoxy compound (b1), and phosphorus antioxidant (z), and the film adhesive before heating at 260°C has a wavelength of 400nm to 800nm light (in this manual, sometimes referred to as "light (400nm to 800nm)") linear transmittance (in this manual, sometimes referred to as "before heating linear transmittance") is 90% or more, After heating at 260°C for 10 minutes, the film-like adhesive has a linear transmittance of light with a wavelength of 400nm to 800nm (in this specification, sometimes referred to as "linear transmittance after heating") of 85% or more. The thickness of the agent is 10 μm to 40 μm. The film-like adhesive of this embodiment suppresses turbidity and coloration before and after heating at 260°C or the like, and has a high linear transmittance of light (400 nm to 800 nm).

本實施形態的膜狀接著劑可於製造或加工構成電子機器之各種零件時，用於目標物之接著用。例如，可將感測器等晶片的電路形成面經由前述膜狀接著劑由透光性罩(保護罩)被覆。亦即，前述膜狀接著劑可用作用以對晶片的電路形成面將罩接著之膜。該情形時，由於膜狀接著劑如上所述於加熱前後透光性高且著色得到抑制，故而隔著透光性罩及膜狀接著劑，能夠穩定且高精度地視認存在於晶片的電路形成面之視覺資訊。The film-like adhesive of this embodiment can be used for adhesion of target objects when manufacturing or processing various parts constituting electronic equipment. For example, the circuit formation surface of a wafer such as a sensor may be covered with a translucent cover (protective cover) via the film-like adhesive. That is, the aforementioned film-like adhesive can be used to bond the film to the circuit forming surface of the chip. In this case, since the film-like adhesive has high translucency before and after heating and the coloring is suppressed as described above, it is possible to stably and accurately visualize the circuit formation existing on the wafer through the translucent cover and the film-like adhesive. Visual information of the face.

作為前述透光性罩(保護罩)之被覆對象之感測器，例如可列舉指紋感測器。但，此係感測器的一例。As the sensor to be covered by the translucent cover (protective cover), for example, a fingerprint sensor can be cited. However, this is an example of a sensor.

本說明書中，將基板及晶片中之形成有電路之面稱為「電路形成面」。此外，本說明書中，僅記載為「晶片」時，並非僅指半導體晶片，亦包括半導體晶片以外的晶片。In this specification, the surface on which the circuit is formed in the substrate and the chip is referred to as the "circuit forming surface". In addition, in this specification, when only described as "wafer", it does not refer to only semiconductor wafers, but also includes wafers other than semiconductor wafers.

本實施形態的膜狀接著劑較佳為具有熱硬化性，進而具有感壓接著性。兼具有熱硬化性及感壓接著性之膜狀接著劑於未硬化狀態下能夠藉由輕輕地按壓而貼附於各種被接著體。另外，膜狀接著劑亦可為能夠藉由進行加熱使之軟化而貼附於各種被接著體。膜狀接著劑藉由硬化而最終成為耐衝擊性高之硬化物，該硬化物於嚴酷的高溫、高濕度條件下亦能夠保持充分的接著特性。The film-like adhesive of this embodiment preferably has thermosetting properties and further has pressure-sensitive adhesive properties. The film-like adhesive with both thermosetting and pressure-sensitive adhesive properties can be attached to various adherends by lightly pressing in the uncured state. In addition, the film-like adhesive may be softened by heating and attached to various adherends. The film-like adhesive finally becomes a cured product with high impact resistance by curing, and the cured product can maintain sufficient adhesive properties even under severe high temperature and high humidity conditions.

本實施形態的膜狀接著劑藉由含有磷系抗氧化劑(z)，加熱前後的著色得到抑制。The film-like adhesive of this embodiment contains the phosphorus antioxidant (z), so that coloration before and after heating is suppressed.

於260℃加熱前的本實施形態的膜狀接著劑的光(400nm至800nm)之直線透過率(亦即前述加熱前直線透過率)為90%以上，較佳為92%以上，更佳為94%以上，進而較佳為95%以上。藉由前述加熱前直線透過率為前述下限值以上，加熱前的前述膜狀接著劑於隔著該膜狀接著劑觀察圖像時，能夠正確地識別圖像之性質(本說明書中，有時簡稱為「圖像識別性」)高。The linear transmittance of light (400nm to 800nm) of the film-like adhesive of this embodiment before heating at 260°C (that is, the linear transmittance before heating) is 90% or more, preferably 92% or more, more preferably 94% or more, more preferably 95% or more. Since the linear transmittance before heating is higher than the lower limit, the film adhesive before heating can accurately recognize the nature of the image when the image is observed through the film adhesive (in this specification, there is Sometimes referred to as "image recognition") is high.

光(400nm至800nm)之前述加熱前直線透過率的上限值並無特別限定，亦可為100%。例如，前述加熱前直線透過率為99.8%以下之膜狀接著劑更容易製造。The upper limit of the linear transmittance before heating of light (400 nm to 800 nm) is not particularly limited, and may be 100%. For example, the aforementioned film-like adhesive with a linear transmittance of 99.8% or less before heating is easier to manufacture.

光(400nm至800nm)之前述加熱前直線透過率可適宜調節為將上述之任一下限值與上限值任意組合而設定之範圍內。例如，一實施形態中，前述加熱前直線透過率較佳為90%至99.8%，更佳為92%至99.8%，進而較佳為94%至99.8%，尤佳為95%至99.8%。但，這些係前述加熱前直線透過率的一例。The aforementioned linear transmittance of light (400nm to 800nm) before heating can be appropriately adjusted to a range set by any combination of any of the above-mentioned lower limit and upper limit. For example, in one embodiment, the linear transmittance before heating is preferably 90% to 99.8%, more preferably 92% to 99.8%, further preferably 94% to 99.8%, and particularly preferably 95% to 99.8%. However, these are examples of the aforementioned linear transmittance before heating.

於260℃加熱10分鐘後的本實施形態的膜狀接著劑的光(400nm至800nm)之直線透過率(亦即前述加熱後直線透過率)為85%以上，較佳為86%以上，更佳為87%以上，進而較佳為88%以上，例如可為89%以上、91%以上及93%以上之任一者。藉由前述加熱後直線透過率為前述下限值以上，加熱後的前述膜狀接著劑的圖像識別性高。The linear transmittance of light (400nm to 800nm) of the film adhesive of this embodiment after heating at 260°C for 10 minutes (that is, the linear transmittance after heating) is 85% or more, preferably 86% or more, more It is preferably 87% or more, and more preferably 88% or more, for example, it may be any of 89% or more, 91% or more, and 93% or more. Since the linear transmittance after heating is equal to or higher than the lower limit, the film-like adhesive after heating has high image recognition.

光(400nm至800nm)之前述加熱後直線透過率的上限值並無特別限定，亦可為100%。例如，前述加熱後直線透過率為99.8%以下之膜狀接著劑更容易製造。The upper limit of the linear transmittance of light (400 nm to 800 nm) after heating is not particularly limited, and it may be 100%. For example, the aforementioned film-like adhesive with a linear transmittance of 99.8% or less after heating is easier to manufacture.

光(400nm至800nm)之前述加熱後直線透過率可適宜調節為將上述之任一下限值與上限值任意組合而設定之範圍內。例如，一實施形態中，前述加熱後直線透過率較佳為85%至99.8%，更佳為86%至99.8%，進而較佳為87%至99.8%，尤佳為88%至99.8%，例如可為89%至99.8%、91%至99.8%、及93%至99.8%之任一者。但，這些係前述加熱後直線透過率的一例。The linear transmittance of light (400nm to 800nm) after heating can be appropriately adjusted to be within the range set by any combination of the above-mentioned lower limit and upper limit. For example, in one embodiment, the linear transmittance after heating is preferably 85% to 99.8%, more preferably 86% to 99.8%, still more preferably 87% to 99.8%, particularly preferably 88% to 99.8%, For example, it can be any of 89% to 99.8%, 91% to 99.8%, and 93% to 99.8%. However, these are examples of the aforementioned linear transmittance after heating.

光(400nm至800nm)之前述加熱前直線透過率及加熱後直線透過率可使用分光光度計，利用公知的方法進行測定。The linear transmittance before heating and the linear transmittance after heating of light (400 nm to 800 nm) can be measured by a known method using a spectrophotometer.

規定前述加熱後直線透過率時的260℃、10分鐘之前述膜狀接著劑的加熱條件係考慮回焊步驟等加熱步驟中的條件而設定。The heating conditions for the film adhesive at 260°C for 10 minutes when the linear transmittance after heating is defined are set in consideration of the conditions in the heating step such as the reflow step.

本實施形態的膜狀接著劑的剪切強度並無特別限定，較佳為20N/2mm□以上，更佳為50N/2mm□以上，例如可為60N/2mm□以上。藉由膜狀接著劑的剪切強度為前述下限值以上，該膜狀接著劑對貼附對象物之接著力變得更強。此外，本說明書中，單位「N/2mm□」與「N/(2mm×2mm)」同義。The shear strength of the film-like adhesive of the present embodiment is not particularly limited, but is preferably 20N/2mm□ or more, more preferably 50N/2mm□ or more, for example, 60N/2mm□ or more. When the shear strength of the film-like adhesive is greater than or equal to the aforementioned lower limit, the adhesive force of the film-like adhesive to the sticking object becomes stronger. In addition, in this manual, the unit "N/2mm□" is synonymous with "N/(2mm×2mm)".

前述膜狀接著劑的剪切強度的上限值亦無特別限定。例如，剪切強度為300N/2mm□以下之膜狀接著劑更容易製造。The upper limit of the shear strength of the aforementioned film adhesive is also not particularly limited. For example, a film adhesive with a shear strength of 300N/2mm□ or less is easier to manufacture.

前述膜狀接著劑的剪切強度可適宜調節為將上述之任一下限值與上限值任意組合而設定之範圍內。例如，一實施形態中，前述剪切強度較佳為20N/2mm□至300N/2mm□，更佳為50N/2mm□至300N/2mm□，例如可為60N/2mm□至300N/2mm□。但，這些係前述剪切強度的一例。The shear strength of the aforementioned film-like adhesive can be appropriately adjusted to be within a range set by any combination of the above-mentioned lower limit and upper limit. For example, in one embodiment, the aforementioned shear strength is preferably 20N/2mm□ to 300N/2mm□, more preferably 50N/2mm□ to 300N/2mm□, for example, 60N/2mm□ to 300N/2mm□. However, these are examples of the aforementioned shear strength.

本實施形態中的前述膜狀接著劑的剪切強度係利用以下所示之方法測定。 (膜狀接著劑的剪切強度之測定方法) 使用大小為2mm×2mm且厚度為20μm之膜狀接著劑、大小為30mm×30mm且厚度為300μm之銅板、及矽晶片，製作前述膜狀接著劑的一面整面貼附於前述矽晶片的表面，另一面整面貼附於前述銅板的表面而構成之試片。於該試片中至少一側面，進行前述膜狀接著劑與前述矽晶片之側面的對位。於23℃之溫度條件下，於前述試片中之進行前述對位之側面，對前述膜狀接著劑與前述矽晶片兩者，沿相對於前述膜狀接著劑的前述另一面呈平行的方向，以200μm/s之速度施加力，採用直至前述膜狀接著劑被破壞為止所施加之力的最大值作為前述膜狀接著劑的剪切強度(N/2mm□)。The shear strength of the film-like adhesive in this embodiment is measured by the method shown below. (Measurement method of shear strength of film adhesive) Using a film-like adhesive with a size of 2mm×2mm and a thickness of 20μm, a copper plate with a size of 30mm×30mm and a thickness of 300μm, and a silicon wafer, the entire surface of the film-like adhesive produced is attached to the surface of the silicon wafer , The other side of the whole surface is attached to the surface of the aforementioned copper plate to constitute a test piece. On at least one side surface of the test piece, alignment of the film adhesive and the side surface of the silicon wafer is performed. Under the temperature condition of 23℃, on the side of the test piece where the alignment is performed, both the film adhesive and the silicon wafer are parallel to the other surface of the film adhesive The force is applied at a speed of 200 μm/s, and the maximum value of the force applied until the film adhesive is broken is used as the shear strength (N/2mm□) of the film adhesive.

前述膜狀接著劑可由1層(單層)所構成，亦可由2層以上之複數層所構成，於由複數層所構成之情形時，這些複數層相互可相同亦可不同，這些複數層的組合並無特別限定。The aforementioned film-like adhesive may be composed of one layer (single layer), or may be composed of two or more layers. When composed of multiple layers, these plural layers may be the same or different from each other. The combination is not particularly limited.

此外，本說明書中，並不限於膜狀接著劑之情形，所謂「複數層相互可相同亦可不同」，意指「可全部層相同，亦可全部層皆不同，還可僅一部分層相同」，進而，所謂「複數層相互不同」，意指「各層的構成材料及厚度的至少一者相互不同」。In addition, in this specification, it is not limited to the case of the film-like adhesive. The so-called "a plurality of layers may be the same or different from each other" means "all the layers may be the same, or all the layers may be different, and only some of the layers may be the same." Furthermore, the phrase "a plurality of layers are different from each other" means that "at least one of the constituent materials and thickness of each layer is different from each other".

前述膜狀接著劑的厚度為10μm至40μm，例如可為10μm至35μm、10μm至30μm、及10μm至25μm之任一者，亦可為13μm至40μm、16μm至40μm、及19μm至40μm之任一者，還可為13μm至35μm、16μm至30μm、及19μm至25μm之任一者。藉由膜狀接著劑的厚度為前述下限值以上，膜狀接著劑對接著對象物之接著力變得更強。藉由膜狀接著劑的厚度為前述上限值以下，無論有無加熱，膜狀接著劑對於光(例如光(400nm至800nm))之直線透過率皆變高。此處，所謂「膜狀接著劑的厚度」，意指膜狀接著劑整體的厚度，例如所謂由複數層所構成之膜狀接著劑的厚度，意指構成膜狀接著劑之全部層的合計的厚度。The thickness of the aforementioned film-like adhesive is 10 μm to 40 μm, for example, it may be any of 10 μm to 35 μm, 10 μm to 30 μm, and 10 μm to 25 μm, or any of 13 μm to 40 μm, 16 μm to 40 μm, and 19 μm to 40 μm. It may also be any of 13 μm to 35 μm, 16 μm to 30 μm, and 19 μm to 25 μm. When the thickness of the film-like adhesive is greater than or equal to the aforementioned lower limit, the adhesive force of the film-like adhesive to the adherend becomes stronger. When the thickness of the film adhesive is below the aforementioned upper limit, the linear transmittance of the film adhesive with respect to light (for example, light (400 nm to 800 nm)) becomes higher regardless of heating. Here, the "thickness of the film adhesive" means the thickness of the entire film adhesive. For example, the thickness of the film adhesive composed of multiple layers means the total of all the layers constituting the film adhesive thickness of.

[接著劑組成物] 前述膜狀接著劑可使用含有該膜狀接著劑的構成材料(亦即，丙烯酸系樹脂(a)、環氧化合物(b1)、及磷系抗氧化劑(z))之接著劑組成物而形成。例如，於膜狀接著劑之形成對象面塗敷接著劑組成物，並根據需要使之乾燥，藉此能夠於目標部位形成膜狀接著劑。接著劑組成物中的常溫下不會氣化的成分彼此的含量之比率通常與膜狀接著劑中的前述成分彼此的含量之比率相同。此外，本說明書中，所謂「常溫」，意指不特別冷或特別熱的溫度，亦即平常的溫度，例如可列舉15℃至25℃之溫度等。[Adhesive composition] The aforementioned film-like adhesive can be formed using an adhesive composition containing the constituent material of the film-like adhesive (that is, acrylic resin (a), epoxy compound (b1), and phosphorus antioxidant (z)) . For example, the adhesive composition is applied to the surface to be formed of the film-like adhesive, and dried as necessary, whereby the film-like adhesive can be formed on the target site. The ratio of the contents of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the contents of the aforementioned components in the film adhesive. In addition, in this specification, the term "normal temperature" means a temperature that is not particularly cold or particularly hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C, etc.

利用公知的方法塗敷接著劑組成物即可，例如可列舉使用以下各種塗佈機之方法：氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模具塗佈機、刀式塗佈機、絲網塗佈機、Meyer棒式塗佈機、輕觸式塗佈機等。The adhesive composition can be applied by a known method. For example, methods using the following various coaters can be mentioned: air knife coater, knife coater, bar coater, gravure coater, roll coater Cloth machine, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, touch coater, etc.

接著劑組成物的乾燥條件並無特別限定，於接著劑組成物含有後述溶媒之情形時，較佳為進行加熱乾燥。含有溶媒之接著劑組成物例如較佳為於70℃至130℃且10秒至5分鐘之條件下進行乾燥。以下，對於膜狀接著劑及接著劑組成物的含有成分詳細地進行說明。The drying conditions of the adhesive composition are not particularly limited, but when the adhesive composition contains a solvent described later, it is preferable to perform heating and drying. The solvent-containing adhesive composition is preferably dried under the conditions of 70°C to 130°C and 10 seconds to 5 minutes, for example. Hereinafter, the film adhesive and the components contained in the adhesive composition will be described in detail.

[丙烯酸系樹脂(a)] 丙烯酸系樹脂(a)係可視為選自由(甲基)丙烯酸、(甲基)丙烯酸酯、及這些之衍生物所組成之群組中的1種或2種以上進行聚合反應而形成之成分。此外，本說明書中，所謂「衍生物」，只要無特別說明，則意指具有原本的化合物的1個以上之基由該基以外的基(取代基)取代而成之結構之化合物。此處，所謂「基」，不僅包括複數個原子鍵結而構成之原子團，亦包括1個原子。丙烯酸系樹脂(a)係用以對膜狀接著劑賦予造膜性及可撓性等，並且提高對前述晶片等接著對象之接著性(貼附性)之樹脂成分。[Acrylic resin (a)] The acrylic resin (a) can be regarded as a component selected from the group consisting of (meth)acrylic acid, (meth)acrylic acid ester, and these derivatives by polymerization reaction of one or more kinds. In addition, in this specification, the "derivative", unless otherwise specified, means a compound having a structure in which one or more groups of the original compound are substituted with groups (substituents) other than the group. Here, the so-called "radical" includes not only a group of atoms formed by bonding a plurality of atoms, but also one atom. The acrylic resin (a) is a resin component for imparting film-forming properties and flexibility to the film-like adhesive, and improving the adhesiveness (adhesiveness) to the bonding object such as the aforementioned wafer.

本說明書中，「(甲基)丙烯酸」的概念包括「丙烯酸」及「甲基丙烯酸」兩者。關於與(甲基)丙烯酸類似的用語亦相同。In this specification, the concept of "(meth)acrylic acid" includes both "acrylic acid" and "methacrylic acid". The same applies to terms similar to (meth)acrylic acid.

接著劑組成物及膜狀接著劑所含有之丙烯酸系樹脂(a)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The acrylic resin (a) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

作為丙烯酸系樹脂(a)，可列舉公知的丙烯酸系聚合物。丙烯酸系樹脂(a)的重量平均分子量(Mw)較佳為10000至2000000，更佳為100000至1500000。藉由丙烯酸系樹脂(a)的重量平均分子量為此種範圍內，容易將膜狀接著劑與被接著體之間的接著力調節為較佳的範圍。另一方面，藉由丙烯酸系樹脂(a)的重量平均分子量為前述下限值以上，膜狀接著劑的形狀穩定性(保管時的經時穩定性)提高。另外，藉由丙烯酸系樹脂(a)的重量平均分子量為前述上限值以下，膜狀接著劑變得容易追隨於被接著體的凹凸面，能進一步抑制於被接著體與膜狀接著劑之間產生空隙等。此外，本說明書中，所謂「重量平均分子量」，只要無特別說明，則係指藉由凝膠滲透層析(GPC；Gel Permeation Chromatography)法所測定之聚苯乙烯換算值。As acrylic resin (a), a well-known acrylic polymer can be mentioned. The weight average molecular weight (Mw) of the acrylic resin (a) is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin (a) is in such a range, it is easy to adjust the adhesive force between the film-like adhesive and the adherend to a preferable range. On the other hand, when the weight average molecular weight of the acrylic resin (a) is more than the aforementioned lower limit, the shape stability of the film adhesive (stability with time during storage) is improved. In addition, since the weight average molecular weight of the acrylic resin (a) is below the aforementioned upper limit, the film-like adhesive becomes easy to follow the uneven surface of the adherend, which can further suppress the difference between the adherend and the film-like adhesive. There are gaps between them. In addition, in this specification, the "weight average molecular weight" means a polystyrene conversion value measured by a gel permeation chromatography (GPC; Gel Permeation Chromatography) method unless otherwise specified.

丙烯酸系樹脂(a)的玻璃轉移溫度(Tg)較佳為-60℃至70℃，更佳為-30℃至50℃。藉由丙烯酸系樹脂(a)的Tg為前述下限值以上，膜狀接著劑與被接著體之間的接著力得到抑制，於拾取時更容易將具備膜狀接著劑之前述晶片自後述切割片扯離。藉由丙烯酸系樹脂(a)的Tg為前述上限值以下，膜狀接著劑與被接著體之間的接著力提高。The glass transition temperature (Tg) of the acrylic resin (a) is preferably -60°C to 70°C, more preferably -30°C to 50°C. When the Tg of the acrylic resin (a) is higher than the aforementioned lower limit, the adhesive force between the film-like adhesive and the adherend is suppressed, and the aforementioned wafer with the film-like adhesive is easier to cut from the following during pickup Pieces ripped off. When the Tg of the acrylic resin (a) is equal to or lower than the aforementioned upper limit, the adhesive force between the film-like adhesive and the adherend is improved.

作為構成丙烯酸系樹脂(a)之前述(甲基)丙烯酸酯，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)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯((甲基)丙烯酸月桂酯)、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸十四烷基酯((甲基)丙烯酸肉豆蔻酯)、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯((甲基)丙烯酸棕櫚酯)、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯((甲基)丙烯酸硬脂酯)等構成烷基酯之烷基為碳數為1至18之鏈狀結構之(甲基)丙烯酸烷基酯；(甲基)丙烯酸異冰片酯、(甲基)丙烯酸二環戊酯等(甲基)丙烯酸環烷基酯；(甲基)丙烯酸苄酯等(甲基)丙烯酸芳烷基酯；(甲基)丙烯酸二環戊烯酯等(甲基)丙烯酸環烯基酯；(甲基)丙烯酸二環戊烯氧基乙酯等(甲基)丙烯酸環烯氧基烷基酯；(甲基)丙烯醯亞胺；(甲基)丙烯酸縮水甘油酯等含縮水甘油基之(甲基)丙烯酸酯；(甲基)丙烯酸羥基甲酯、(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3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸3-羥基丁酯、(甲基)丙烯酸4-羥基丁酯等含羥基之(甲基)丙烯酸酯；(甲基)丙烯酸N-甲基胺基乙酯等含取代胺基之(甲基)丙烯酸酯等。此處，所謂「取代胺基」，意指具有胺基的1個或2個氫原子由氫原子以外的基取代而成之結構之基。Examples of the (meth)acrylate constituting the acrylic resin (a) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylate. Isopropyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate , Hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, (meth) )N-nonyl acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate ((meth)acrylic acid) Lauryl ester), tridecyl (meth)acrylate, tetradecyl (meth)acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, (meth) ) Cetyl acrylate (palmityl (meth)acrylate), heptadecyl (meth)acrylate, stearyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group of the alkyl ester is an alkyl (meth)acrylate with a chain structure of 1 to 18 carbon atoms; isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, etc. (meth) Cycloalkyl acrylate; aralkyl (meth)acrylate such as benzyl (meth)acrylate; cycloalkenyl (meth)acrylate such as dicyclopentenyl (meth)acrylate; (meth)acrylic acid Dicyclopentenyloxyethyl and other (meth)acrylic acid cycloalkenyloxyalkyl esters; (meth)acrylimines; (meth)acrylic acid glycidyl esters and other glycidyl-containing (meth)acrylic acid Esters; hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylic acid 2 -Hydroxybutyl, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyl-containing (meth)acrylates; N-methylaminoethyl (meth)acrylate Etc. (meth)acrylates containing substituted amino groups. Here, the "substituted amino group" means a group having a structure in which one or two hydrogen atoms having an amino group are substituted with groups other than hydrogen atoms.

丙烯酸系樹脂(a)例如亦可為除前述(甲基)丙烯酸酯以外，使選自(甲基)丙烯酸、衣康酸、乙酸乙烯酯、丙烯腈、苯乙烯及N-羥甲基丙烯醯胺等中的1種或2種以上之單體共聚而獲得之樹脂。The acrylic resin (a) may be selected from (meth)acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-methylolacrylic acid in addition to the aforementioned (meth)acrylate. A resin obtained by copolymerizing one or more monomers among amines.

構成丙烯酸系樹脂(a)之單體可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The monomer constituting the acrylic resin (a) may be only one type or two or more types, and when it is two or more types, the combination and ratio of these can be arbitrarily selected.

丙烯酸系樹脂(a)中，除上述之羥基以外，亦可具有乙烯基、(甲基)丙烯醯基、胺基、羧基、異氰酸酯基等能夠與其他化合物鍵結之官能基。丙烯酸系樹脂(a)中的以羥基為代表之這些官能基可經由後述之交聯劑(f)而與其他化合物鍵結，亦可不經由交聯劑(f)而與其他化合物直接鍵結。藉由丙烯酸系樹脂(a)利用前述官能基與其他化合物鍵結，有使用膜狀接著劑所獲得之封裝體的可靠性提高之傾向。In addition to the above-mentioned hydroxyl groups, the acrylic resin (a) may also have functional groups capable of bonding with other compounds, such as vinyl groups, (meth)acrylic groups, amino groups, carboxyl groups, and isocyanate groups. The functional groups represented by the hydroxyl group in the acrylic resin (a) may be bonded to other compounds via the crosslinking agent (f) described later, or may be directly bonded to other compounds without the crosslinking agent (f). When the acrylic resin (a) utilizes the aforementioned functional group to bond with other compounds, the reliability of the package obtained by using the film-like adhesive tends to be improved.

作為較佳的丙烯酸系樹脂(a)，例如可列舉具有能夠與後述之交聯劑(f)鍵結之官能基之樹脂。As a preferable acrylic resin (a), the resin which has the functional group which can bond with the crosslinking agent (f) mentioned later is mentioned, for example.

接著劑組成物中，丙烯酸系樹脂(a)的含量相對於溶媒以外的全部成分的總含量之比例(亦即，膜狀接著劑中的丙烯酸系樹脂(a)的含量相對於膜狀接著劑的總質量之比例)較佳為10質量%至90質量%，更佳為15質量%至70質量%，進而較佳為20質量%至65質量%，例如可為30質量%至65質量%。藉由前述比例為前述下限值以上，膜狀接著劑的結構進一步穩定化。藉由前述比例為前述上限值以下，容易增加環氧化合物(b1)及磷系抗氧化劑(z)等丙烯酸系樹脂(a)以外的成分的使用量，從而更容易獲得由使用丙烯酸系樹脂(a)以外的成分所帶來之效果。In the adhesive composition, the ratio of the content of the acrylic resin (a) to the total content of all components other than the solvent (that is, the content of the acrylic resin (a) in the film adhesive relative to the film adhesive The ratio of the total mass of) is preferably 10% by mass to 90% by mass, more preferably 15% by mass to 70% by mass, still more preferably 20% by mass to 65% by mass, for example, 30% by mass to 65% by mass . When the aforementioned ratio is equal to or higher than the aforementioned lower limit, the structure of the film-like adhesive is further stabilized. When the aforementioned ratio is less than the aforementioned upper limit, it is easy to increase the amount of epoxy compound (b1) and phosphorus antioxidant (z) other than acrylic resin (a), and it is easier to obtain (a) The effects brought by ingredients other than those.

[環氧化合物(b1)] 環氧化合物(b1)可為樹脂成分及非樹脂成分之任一種。作為環氧化合物(b1)，可列舉公知的環氧化合物，例如可列舉：多官能系環氧樹脂、聯苯化合物、雙酚A二縮水甘油醚及其氫化物、鄰甲酚酚醛清漆環氧樹脂、二環戊二烯型環氧樹脂、聯苯型環氧樹脂、雙酚A型環氧樹脂、雙酚F型環氧樹脂、伸苯基骨架型環氧樹脂、三嗪型脂環式環氧化合物等2官能以上之環氧化合物。[Epoxy Compound (b1)] The epoxy compound (b1) may be any of a resin component and a non-resin component. As the epoxy compound (b1), known epoxy compounds may be mentioned, for example, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and its hydrogenated products, ortho-cresol novolac epoxy Resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin, triazine type alicyclic type Epoxy compounds with more than two functions such as epoxy compounds.

作為環氧化合物(b1)，亦可使用具有不飽和烴基之環氧化合物。具有不飽和烴基之環氧化合物相較於不具有不飽和烴基之環氧化合物，與丙烯酸系樹脂(a)之相容性較高。因此，藉由使用具有不飽和烴基之環氧化合物(b1)，使用膜狀接著劑所獲得之封裝體的可靠性提高。As the epoxy compound (b1), an epoxy compound having an unsaturated hydrocarbon group can also be used. The epoxy compound having an unsaturated hydrocarbon group has higher compatibility with the acrylic resin (a) than the epoxy compound having no unsaturated hydrocarbon group. Therefore, by using the epoxy compound (b1) having an unsaturated hydrocarbon group, the reliability of the package obtained by using the film-like adhesive is improved.

作為具有不飽和烴基之環氧化合物(b1)，例如可列舉具有多官能系環氧化合物的環氧基的一部分變換為具有不飽和烴基之基之結構之化合物。此種化合物例如藉由使(甲基)丙烯酸或其衍生物與環氧基進行加成反應而獲得。As an epoxy compound (b1) which has an unsaturated hydrocarbon group, the compound which converted a part of the epoxy group which has a polyfunctional epoxy compound into the structure which has a group which has an unsaturated hydrocarbon group, for example is mentioned. Such a compound is obtained, for example, by performing an addition reaction of (meth)acrylic acid or a derivative thereof with an epoxy group.

另外，作為具有不飽和烴基之環氧化合物(b1)，例如可列舉於構成環氧化合物之芳香環等直接鍵結有具有不飽和烴基之基之化合物等。不飽和烴基係具有聚合性之不飽和基，作為該不飽和烴基的具體例，可列舉次乙基(乙烯基)、2-丙烯基(烯丙基)、(甲基)丙烯醯基、(甲基)丙烯醯胺基等，較佳為丙烯醯基。Moreover, as an epoxy compound (b1) which has an unsaturated hydrocarbon group, the compound etc. which are directly bonded to the group which has an unsaturated hydrocarbon group, such as an aromatic ring which comprises an epoxy compound, are mentioned, for example. The unsaturated hydrocarbon group is a polymerizable unsaturated group. Specific examples of the unsaturated hydrocarbon group include ethylene (vinyl), 2-propenyl (allyl), (meth)acryloyl, ( The meth)acrylamido group and the like are preferably acrylamido group.

作為樹脂成分之環氧化合物(b1)(換言之，環氧樹脂(b1))的數量平均分子量並無特別限定，就膜狀接著劑的硬化性、以及膜狀接著劑之硬化物的強度及耐熱性之方面而言，較佳為300至30000，更佳為400至10000，尤佳為500至3000。環氧化合物(b1)的環氧當量較佳為100g/eq至1000g/eq，更佳為120g/eq至600g/eq。The number average molecular weight of the epoxy compound (b1) (in other words, the epoxy resin (b1)) as the resin component is not particularly limited, as regards the curability of the film adhesive and the strength and heat resistance of the cured film of the film adhesive In terms of sex, it is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000. The epoxy equivalent of the epoxy compound (b1) is preferably 100 g/eq to 1000 g/eq, more preferably 120 g/eq to 600 g/eq.

接著劑組成物及膜狀接著劑所含有之環氧化合物(b1)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The epoxy compound (b1) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

環氧化合物(b1)較佳為脂肪族系化合物。本說明書中，所謂「脂肪族系化合物」，意指具有脂肪族基且不具有芳香族基之化合物。另外，「脂肪族基」包括鏈狀脂肪族基及脂肪族環式基(別名：脂環式基)。另外，「芳香族基」包括芳香族烴基及芳香族雜環式基。藉由接著劑組成物及膜狀接著劑含有脂肪族系化合物作為環氧化合物(b1)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有脂肪族系化合物(換言之，不含有芳香族系化合物)，上述之著色的抑制效果顯著變高。The epoxy compound (b1) is preferably an aliphatic compound. In this specification, the "aliphatic compound" means a compound having an aliphatic group and no aromatic group. In addition, "aliphatic group" includes chain aliphatic group and aliphatic cyclic group (alias: alicyclic group). In addition, the "aromatic group" includes an aromatic hydrocarbon group and an aromatic heterocyclic group. When the adhesive composition and the film-like adhesive contain an aliphatic compound as the epoxy compound (b1), the effect of suppressing the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes higher, and By containing only aliphatic compounds (in other words, not containing aromatic compounds), the above-mentioned coloring inhibitory effect is significantly increased.

環氧化合物(b1)較佳為不具有選自由碳原子間的三鍵(C≡C)、碳原子間的雙鍵(C=C)、氰基(-C≡N)及芳香族基所組成之群組中的1種或2種以上。藉由接著劑組成物及膜狀接著劑含有不具有這些鍵或基之化合物作為環氧化合物(b1)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有不具有這些鍵或基之化合物(換言之，不含有具有這些鍵或基之化合物)，上述之著色的抑制效果顯著變高。The epoxy compound (b1) preferably does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N) and an aromatic group. One or more types in the group. Since the adhesive composition and the film-like adhesive contain a compound that does not have these bonds or groups as the epoxy compound (b1), the effect of suppressing the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes Even higher, by containing only a compound that does not have these bonds or groups (in other words, does not contain a compound that has these bonds or groups), the aforementioned coloring inhibitory effect becomes significantly higher.

環氧化合物(b1)較佳為脂肪族系化合物，且不具有選自由碳原子間的三鍵(C≡C)、碳原子間的雙鍵(C=C)及氰基(-C≡N)所組成之群組中的1種或2種以上。藉由接著劑組成物及膜狀接著劑含有不具有這些鍵或基之脂肪族系化合物作為環氧化合物(b1)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有不具有這些鍵或基之脂肪族系化合物(換言之，不含有具有這些鍵或基之脂肪族系化合物)，上述之著色的抑制效果顯著變高。The epoxy compound (b1) is preferably an aliphatic compound, and does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), and a cyano group (-C≡N). ) One or more of the group consisting of. When the adhesive composition and the film adhesive contain an aliphatic compound that does not have these bonds or groups as the epoxy compound (b1), the coloration of the film adhesive after heating (for example, heating at 260°C) is suppressed The effect becomes higher, and by only containing the aliphatic compound not having these bonds or groups (in other words, not containing the aliphatic compound having these bonds or groups), the above-mentioned coloring inhibitory effect becomes significantly higher.

接著劑組成物及膜狀接著劑中，環氧化合物(b1)的含量相對於丙烯酸系樹脂(a)的含量100質量份，較佳為5質量份至500質量份，例如可為5質量份至200質量份、5質量份至150質量份、5質量份至110質量份、及5質量份至100質量份之任一者。藉由環氧化合物(b1)的前述含量為此種範圍，更容易調節膜狀接著劑與後述之樹脂膜或切割片之間的接著力。In the adhesive composition and the film-like adhesive, the content of the epoxy compound (b1) relative to 100 parts by mass of the acrylic resin (a), preferably 5 parts by mass to 500 parts by mass, for example, 5 parts by mass To any one of 200 parts by mass, 5 parts by mass to 150 parts by mass, 5 parts by mass to 110 parts by mass, and 5 parts by mass to 100 parts by mass. When the aforementioned content of the epoxy compound (b1) is in such a range, it is easier to adjust the adhesive force between the film-like adhesive and the resin film or dicing sheet described later.

[磷系抗氧化劑(z)] 磷系抗氧化劑(z)只要為具有磷原子作為構成原子，且具有抗氧化作用之化合物，則並無特別限定。作為磷系抗氧化劑(z)，例如可列舉磷的氧化數為3之化合物。[Phosphorus antioxidant (z)] The phosphorus antioxidant (z) is not particularly limited as long as it has a phosphorus atom as a constituent atom and has an antioxidant effect. As the phosphorus antioxidant (z), for example, a compound having a phosphorus oxidation number of 3 can be cited.

接著劑組成物及膜狀接著劑所含有之磷系抗氧化劑(z)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The phosphorous antioxidant (z) contained in the adhesive composition and the film-like adhesive may be only one type, or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

磷系抗氧化劑(z)較佳為脂肪族系化合物。藉由接著劑組成物及膜狀接著劑含有脂肪族系化合物作為磷系抗氧化劑(z)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有脂肪族系化合物(換言之，不含有芳香族系化合物)，上述之著色的抑制效果顯著變高。The phosphorus antioxidant (z) is preferably an aliphatic compound. When the adhesive composition and the film adhesive contain an aliphatic compound as the phosphorus antioxidant (z), the effect of inhibiting the coloration of the film adhesive after heating (for example, heating at 260°C) becomes higher. By containing only aliphatic compounds (in other words, not containing aromatic compounds), the above-mentioned coloring inhibitory effect is significantly increased.

磷系抗氧化劑(z)較佳為不具有選自由碳原子間的三鍵(C≡C)、碳原子間的雙鍵(C=C)、氰基(-C≡N)及芳香族基所組成之群組中的1種或2種以上。藉由接著劑組成物及膜狀接著劑含有不具有這些鍵或基之化合物作為磷系抗氧化劑(z)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有不具有這些鍵或基之化合物(換言之，不含有具有這些鍵或基之化合物)，上述之著色的抑制效果顯著變高。The phosphorus antioxidant (z) preferably does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N) and an aromatic group One or more types in the group. When the adhesive composition and the film-like adhesive contain compounds that do not have these bonds or groups as the phosphorus antioxidant (z), the effect of inhibiting the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes Even higher, by containing only a compound that does not have these bonds or groups (in other words, does not contain a compound that has these bonds or groups), the aforementioned coloring inhibitory effect becomes significantly higher.

磷系抗氧化劑(z)較佳為脂肪族系化合物，且不具有選自由碳原子間的三鍵(C≡C)、碳原子間的雙鍵(C=C)及氰基(-C≡N)所組成之群組中的1種或2種以上。藉由接著劑組成物及膜狀接著劑含有不具有這些鍵或基之脂肪族系化合物作為磷系抗氧化劑(z)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有不具有這些鍵或基之脂肪族系化合物(換言之，不含有具有這些鍵或基之脂肪族系化合物)，上述之著色的抑制效果顯著變高。The phosphorus antioxidant (z) is preferably an aliphatic compound, and does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), and a cyano group (-C≡) N) One or more of the group consisting of. When the adhesive composition and the film-like adhesive contain aliphatic compounds that do not have these bonds or groups as the phosphorus antioxidant (z), the film-like adhesive is colored after heating (for example, heating at 260°C) The inhibitory effect becomes higher, and by only containing aliphatic compounds that do not have these bonds or groups (in other words, does not contain aliphatic compounds that have these bonds or groups), the above-mentioned coloring inhibitory effect is significantly increased.

就穩定地顯示抗氧化作用之方面而言，磷系抗氧化劑(z)較佳為亞磷酸酯。其中，磷系抗氧化劑(z)更佳為脂肪族系亞磷酸酯，進而較佳為脂肪族系亞磷酸三烷基酯。In terms of stably exhibiting an antioxidant effect, the phosphorus antioxidant (z) is preferably a phosphite. Among them, the phosphorus antioxidant (z) is more preferably an aliphatic phosphite, and still more preferably an aliphatic trialkyl phosphite.

作為脂肪族系亞磷酸三烷基酯，例如可列舉：亞磷酸三乙酯((C₂ H₅ O)₃ P)、亞磷酸三(2-乙基己基)酯((CH₃ CH₂ CH₂ CH₂ CH(CH₂ CH₃ )CH₂ O)₃ P)、亞磷酸三癸酯((C₁₀ H₂₁ O)₃ P)、亞磷酸三月桂酯((C₁₂ H₂₅ O)₃ P)、亞磷酸三(十三烷基)酯((C₁₃ H₂₇ O)₃ P)、亞磷酸三硬脂酯((C₁₈ H₃₇ O)₃ P)、雙(癸基)季戊四醇二亞磷酸酯(C₁₀ H₂₁ OP(OCH₂ )₂ C(CH₂ O)₂ POC₁₀ H₂₁ )、雙(十三烷基)季戊四醇二亞磷酸酯(C₁₃ H₂₇ OP(OCH₂ )₂ C(CH₂ O)₂ POC₁₃ H₂₇ )、二硬脂基季戊四醇二亞磷酸酯(C₁₈ H₃₇ OP(OCH₂ )₂ C(CH₂ O)₂ POC₁₈ H₃₇ )、氫化雙酚A-季戊四醇亞磷酸酯聚合物(具有式「-(OC₆ H₁₂ C(CH₃ )₂ C₆ H₁₂ OP(OCH₂ )₂ C(CH₂ O)₂ P)-」所表示之重複單元之聚合物)等。As aliphatic trialkyl phosphites, for example, triethyl phosphite ((C ₂ H ₅ O) ₃ P), tris(2-ethylhexyl) phosphite ((CH ₃ CH ₂ CH ₂ CH ₂ CH(CH ₂ CH ₃ )CH ₂ O) ₃ P), tridecyl phosphite ((C ₁₀ H ₂₁ O) ₃ P), trilauryl phosphite ((C ₁₂ H ₂₅ O) ₃ P ), tris(tridecyl) phosphite ((C ₁₃ H ₂₇ O) ₃ P), tristearyl phosphite ((C ₁₈ H ₃₇ O) ₃ P), bis(decyl) pentaerythritol Phosphate (C ₁₀ H ₂₁ OP(OCH ₂ ) ₂ C(CH ₂ O) ₂ POC ₁₀ H ₂₁ ), bis(tridecyl) pentaerythritol diphosphite (C ₁₃ H ₂₇ OP(OCH ₂ ) ₂ C (CH ₂ O) ₂ POC ₁₃ H ₂₇ ), distearyl pentaerythritol diphosphite (C ₁₈ H ₃₇ OP(OCH ₂ ) ₂ C(CH ₂ O) ₂ POC ₁₈ H ₃₇ ), hydrogenated bisphenol A- Pentaerythritol phosphite polymer (polymerization of repeating units represented by the formula "-(OC ₆ H ₁₂ C(CH ₃ ) ₂ C ₆ H ₁₂ OP(OCH ₂ ) ₂ C(CH ₂ O) ₂ P)-"物) etc.

接著劑組成物中，磷系抗氧化劑(z)的含量相對於溶媒以外的全部成分的總含量之比例(亦即，膜狀接著劑中的磷系抗氧化劑(z)的含量相對於膜狀接著劑的總質量之比例)較佳為0.1質量%至5質量%，更佳為0.2質量%至3質量%，進而較佳為0.3質量%至1.5質量%，例如可為0.3質量%至1質量%。藉由前述比例為前述下限值以上，能更顯著地獲得由使用磷系抗氧化劑(z)所帶來之效果。藉由前述比例為前述上限值以下，磷系抗氧化劑(z)的過量使用得到抑制。In the adhesive composition, the ratio of the content of the phosphorus antioxidant (z) to the total content of all components other than the solvent (that is, the content of the phosphorus antioxidant (z) in the film adhesive relative to the film The ratio of the total mass of the adhesive) is preferably 0.1% by mass to 5% by mass, more preferably 0.2% by mass to 3% by mass, still more preferably 0.3% by mass to 1.5% by mass, for example, 0.3% by mass to 1 quality%. When the aforementioned ratio is greater than or equal to the aforementioned lower limit, the effect of using the phosphorus antioxidant (z) can be more remarkably obtained. When the aforementioned ratio is below the aforementioned upper limit, excessive use of the phosphorus-based antioxidant (z) is suppressed.

前述膜狀接著劑中，為了改良該膜狀接著劑的各種物性，除丙烯酸系樹脂(a)、環氧化合物(b1)、及磷系抗氧化劑(z)以外，亦可進而根據需要含有不符合這些任一種成分之其他成分。作為前述膜狀接著劑所含有之其他成分，例如可列舉：酚樹脂(b2)、硬化促進劑(c)、填充材料(d)、偶合劑(e)、交聯劑(f)、能量線硬化性樹脂(g)、光聚合起始劑(h)、磷系抗氧化劑(z)以外的抗氧化劑(y)(本說明書中，有時簡稱為「其他抗氧化劑(y)」)、丙烯酸系樹脂(a)以外的熱塑性樹脂(x)(本說明書中，有時簡稱為「熱塑性樹脂(x)」)、通用添加劑(i)等。Among the aforementioned film adhesives, in order to improve various physical properties of the film adhesive, in addition to acrylic resin (a), epoxy compound (b1), and phosphorus antioxidant (z), it may further contain Other ingredients that meet any of these ingredients. Examples of other components contained in the film adhesive include: phenol resin (b2), curing accelerator (c), filler (d), coupling agent (e), crosslinking agent (f), energy ray Curable resin (g), photopolymerization initiator (h), antioxidant (y) other than phosphorous antioxidant (z) (in this specification, sometimes referred to as "other antioxidant (y)"), acrylic Thermoplastic resin (x) other than the resin (a) (in this specification, sometimes referred to as "thermoplastic resin (x)"), general additives (i), and the like.

[酚樹脂(b2)] 酚樹脂(b2)作為針對環氧化合物(b1)之熱硬化劑發揮功能。本實施形態中，於併用環氧化合物(b1)及酚樹脂(b2)之情形時，這些的組合作為環氧系熱硬化性樹脂發揮功能。本實施形態中，有時將此種環氧系熱硬化性樹脂稱為「環氧系熱硬化性樹脂(b)」。[Phenolic resin (b2)] The phenol resin (b2) functions as a thermosetting agent for the epoxy compound (b1). In this embodiment, when the epoxy compound (b1) and the phenol resin (b2) are used together, the combination of these functions as an epoxy-based thermosetting resin. In the present embodiment, such epoxy-based thermosetting resin may be referred to as "epoxy-based thermosetting resin (b)".

酚樹脂(b2)只要於1分子中具有2個以上之酚性羥基作為能夠與環氧基反應之官能基即可。The phenol resin (b2) only needs to have two or more phenolic hydroxyl groups as functional groups that can react with epoxy groups in one molecule.

作為酚樹脂(b2)，例如可列舉：多官能酚樹脂、酚醛清漆型酚樹脂、二環戊二烯型酚樹脂、芳烷基型酚樹脂等。As a phenol resin (b2), a polyfunctional phenol resin, a novolak type phenol resin, a dicyclopentadiene type phenol resin, an aralkyl type phenol resin, etc. are mentioned, for example.

酚樹脂(b2)亦可具有不飽和烴基。作為具有不飽和烴基之其他酚樹脂(b2)，例如可列舉：具有酚樹脂的羥基的一部分由具有不飽和烴基之基取代而成之結構之化合物、具有於酚樹脂的芳香環直接鍵結有具有不飽和烴基之基之結構之化合物等。酚樹脂(b2)中的前述不飽和烴基與上述之具有不飽和烴基之環氧化合物中的不飽和烴基相同。The phenol resin (b2) may have an unsaturated hydrocarbon group. As another phenol resin (b2) having an unsaturated hydrocarbon group, for example, a compound having a structure in which a part of the hydroxyl group of the phenol resin is substituted with a group having an unsaturated hydrocarbon group, and a compound having a structure directly bonded to the aromatic ring of the phenol resin Compounds with the structure of an unsaturated hydrocarbon group, etc. The aforementioned unsaturated hydrocarbon group in the phenol resin (b2) is the same as the unsaturated hydrocarbon group in the aforementioned epoxy compound having an unsaturated hydrocarbon group.

就容易調節膜狀接著劑的接著力之方面而言，酚樹脂(b2)較佳為軟化點或玻璃轉移溫度高。In terms of easy adjustment of the adhesive force of the film adhesive, the phenol resin (b2) preferably has a high softening point or glass transition temperature.

酚樹脂(b2)的數量平均分子量較佳為300至30000，更佳為400至10000，尤佳為500至3000。The number average molecular weight of the phenol resin (b2) is preferably 300 to 30,000, more preferably 400 to 10,000, and particularly preferably 500 to 3,000.

接著劑組成物及膜狀接著劑所含有之酚樹脂(b2)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The phenol resin (b2) contained in the adhesive composition and the film-like adhesive may be only one type, or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

於使用酚樹脂(b2)之情形時，接著劑組成物中，酚樹脂(b2)的含量相對於溶媒以外的全部成分的總含量之比例(亦即，膜狀接著劑中的酚樹脂(b2)的含量相對於膜狀接著劑的總質量之比例)並無特別限定，較佳為10質量%以下，更佳為7.5質量%以下，進而較佳為5質量%以下。藉由前述比例為前述上限值以下，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高。When the phenol resin (b2) is used, the ratio of the content of the phenol resin (b2) to the total content of all components other than the solvent in the adhesive composition (that is, the phenol resin (b2) in the film adhesive The ratio of the content of) to the total mass of the film-like adhesive) is not particularly limited, but is preferably 10% by mass or less, more preferably 7.5% by mass or less, and still more preferably 5% by mass or less. When the aforementioned ratio is below the aforementioned upper limit, the effect of suppressing coloration after heating (for example, heating at 260°C) of the film adhesive becomes higher.

於使用酚樹脂(b2)之情形時，接著劑組成物中，酚樹脂(b2)的含量相對於溶媒以外的全部成分的總含量之比例(亦即，膜狀接著劑中的酚樹脂(b2)的含量相對於膜狀接著劑的總質量之比例)的下限值並無特別限定。例如，就更顯著地獲得由使用酚樹脂(b2)所帶來之效果之方面而言，前述比例較佳為0.5質量%以上。When the phenol resin (b2) is used, the ratio of the content of the phenol resin (b2) to the total content of all components other than the solvent in the adhesive composition (that is, the phenol resin (b2) in the film adhesive The lower limit of the ratio of the content of) to the total mass of the film-like adhesive) is not particularly limited. For example, in terms of obtaining the effect of using the phenol resin (b2) more significantly, the aforementioned ratio is preferably 0.5% by mass or more.

於使用酚樹脂(b2)之情形時，前述比例可適宜調節為將上述之下限值與任一上限值任意組合而設定之範圍內。例如，一實施形態中，前述比例較佳為0.5質量%至10質量%，更佳為0.5質量%至7.5質量%，進而較佳為0.5質量%至5質量%。In the case of using the phenol resin (b2), the aforementioned ratio can be appropriately adjusted to be within a range set by arbitrarily combining the above-mentioned lower limit and any upper limit. For example, in one embodiment, the aforementioned ratio is preferably 0.5% by mass to 10% by mass, more preferably 0.5% by mass to 7.5% by mass, and still more preferably 0.5% by mass to 5% by mass.

於使用酚樹脂(b2)之情形時，接著劑組成物及膜狀接著劑中，酚樹脂(b2)的含量相對於環氧化合物(b1)的含量100質量份，例如可為3質量份至30質量份、3質量份至25質量份、及3質量份至20質量份之任一者，亦可為5質量份至30質量份、10質量份至30質量份、及15質量份至30質量份之任一者，還可為5質量份至25質量份、及10質量份至20質量份之任一者。In the case of using the phenol resin (b2), in the adhesive composition and the film-like adhesive, the content of the phenol resin (b2) relative to 100 parts by mass of the epoxy compound (b1) can be, for example, 3 parts by mass to Any one of 30 parts by mass, 3 parts by mass to 25 parts by mass, and 3 parts by mass to 20 parts by mass, may also be 5 parts by mass to 30 parts by mass, 10 parts by mass to 30 parts by mass, and 15 parts by mass to 30 Any one of parts by mass may also be any one of 5 parts by mass to 25 parts by mass, and 10 parts by mass to 20 parts by mass.

[硬化促進劑(c)] 硬化促進劑(c)係用以調節接著劑組成物及膜狀接著劑的硬化速度之成分。作為較佳的硬化促進劑(c)，例如可列舉：三乙二胺、苄基二甲胺、三乙醇胺、二甲胺基乙醇、三(二甲胺基甲基)苯酚等三級胺；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5-羥基甲基咪唑等咪唑類(1個以上之氫原子由氫原子以外的基取代而成之咪唑)；三丁基膦、二苯基膦、三苯基膦等有機膦類(1個以上之氫原子由有機基取代而成之膦)；四苯基硼酸四苯基鏻、四苯基硼酸三苯基膦等四苯基硼鹽；以前述咪唑類作為客體化合物之包接化合物等。[Hardening accelerator (c)] The curing accelerator (c) is a component used to adjust the curing speed of the adhesive composition and the film-like adhesive. As a preferable hardening accelerator (c), for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol can be cited; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazoles in which one or more hydrogen atoms are replaced by groups other than hydrogen atoms); organic phosphines such as tributylphosphine, diphenylphosphine, and triphenylphosphine (one or more Phosphine in which hydrogen atoms are substituted by organic groups); tetraphenyl boron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate; inclusion compounds with the aforementioned imidazoles as guest compounds, etc.

接著劑組成物及膜狀接著劑所含有之硬化促進劑(c)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The hardening accelerator (c) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

於使用硬化促進劑(c)之情形時，接著劑組成物及膜狀接著劑中，硬化促進劑(c)的含量相對於環氧化合物(b1)及酚樹脂(b2)的總含量100質量份，較佳為0.01質量份至7質量份，更佳為0.1質量份至4質量份。藉由硬化促進劑(c)的前述含量為前述下限值以上，能更顯著地獲得由使用硬化促進劑(c)所帶來之效果。藉由硬化促進劑(c)的含量為前述上限值以下，例如抑制高極性的硬化促進劑(c)於高溫、高濕度條件下在膜狀接著劑中向與被接著體之接著界面側移動而偏析之效果變高，從而使用膜狀接著劑所獲得之封裝體的可靠性進一步提高。此外，於不使用酚樹脂(b2)之情形時，環氧化合物(b1)及酚樹脂(b2)的總含量意指環氧化合物(b1)的含量。In the case of using the hardening accelerator (c), the content of the hardening accelerator (c) in the adhesive composition and the film adhesive is relative to the total content of the epoxy compound (b1) and phenol resin (b2) 100 mass Parts, preferably 0.01 parts by mass to 7 parts by mass, more preferably 0.1 parts by mass to 4 parts by mass. When the aforementioned content of the hardening accelerator (c) is more than the aforementioned lower limit, the effect of using the hardening accelerator (c) can be more remarkably obtained. Since the content of the hardening accelerator (c) is below the aforementioned upper limit, for example, the hardening accelerator (c) with high polarity is suppressed to the adhesive interface side with the adherend in the film-like adhesive under high temperature and high humidity conditions The effect of migration and segregation becomes higher, and the reliability of the package obtained by using the film-like adhesive is further improved. In addition, when the phenol resin (b2) is not used, the total content of the epoxy compound (b1) and the phenol resin (b2) means the content of the epoxy compound (b1).

[填充材料(d)] 膜狀接著劑藉由含有填充材料(d)，容易調整該膜狀接著劑的熱膨脹係數，使該熱膨脹係數對於膜狀接著劑之貼附對象物而言最佳化，藉此使用膜狀接著劑所獲得之封裝體的可靠性進一步提高。另外，藉由膜狀接著劑含有填充材料(d)，亦能夠降低膜狀接著劑之硬化物的吸濕率，或提高散熱性。[Filling material (d)] By containing the filler (d), the film adhesive can easily adjust the thermal expansion coefficient of the film adhesive, and optimize the thermal expansion coefficient for the object to be attached to the film adhesive, thereby using film adhesive The reliability of the package obtained by the agent is further improved. In addition, when the film adhesive contains the filler (d), the moisture absorption rate of the cured product of the film adhesive can also be reduced, or heat dissipation can be improved.

填充材料(d)可為有機填充材料及無機填充材料之任一種，較佳為無機填充材料。作為較佳的無機填充材料，例如可列舉：二氧化矽、氧化鋁、滑石、碳酸鈣、鈦白、鐵丹、碳化矽、氮化硼等的粉末；將這些無機填充材料球形化而成之珠粒；這些無機填充材料的表面改質品；這些無機填充材料的單晶纖維；玻璃纖維等。這些之中，無機填充材料較佳為二氧化矽或二氧化矽的表面改質品。The filling material (d) may be any one of an organic filling material and an inorganic filling material, preferably an inorganic filling material. As a preferable inorganic filler, for example, powders such as silica, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be cited; these inorganic fillers are made by sphericalization Beads; surface modification products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc. Among these, the inorganic filler material is preferably silicon dioxide or a surface modified product of silicon dioxide.

填充材料(d)的平均粒徑並無特別限定，較佳為10nm至100nm，更佳為10nm至80nm，進而較佳為10nm至60nm。藉由填充材料(d)的平均粒徑為前述上限值以下，前述膜狀接著劑的渾濁得到高度抑制，前述膜狀接著劑的光(400nm至800nm)之前述加熱前直線透過率及加熱後直線透過率提高，結果加熱前及加熱後的前述膜狀接著劑的圖像識別性變得更高。藉由填充材料(d)的平均粒徑為前述下限值以上，能更顯著地獲得由使用填充材料(d)所帶來之效果。此外，本說明書中，所謂「平均粒徑」，只要無特別說明，則意指藉由雷射繞射散射法所求出之粒度分佈曲線中的累計值50%時的粒徑(D₅₀ )的值。The average particle diameter of the filler (d) is not particularly limited, and is preferably 10 nm to 100 nm, more preferably 10 nm to 80 nm, and still more preferably 10 nm to 60 nm. Since the average particle size of the filler (d) is below the above upper limit, the turbidity of the film adhesive is highly suppressed, and the linear transmittance and heating of the light (400nm to 800nm) of the film adhesive before heating The rear linear transmittance increases, and as a result, the image recognition of the film-like adhesive before and after heating becomes higher. When the average particle size of the filler (d) is more than the aforementioned lower limit, the effect of using the filler (d) can be more remarkably obtained. In addition, in this specification, the "average particle size" means the particle size (D ₅₀ ) at 50% of the cumulative value in the particle size distribution curve obtained by the laser diffraction scattering method, unless otherwise specified. Value.

接著劑組成物及膜狀接著劑所含有之填充材料(d)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The filler (d) contained in the adhesive composition and the film-like adhesive may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these can be arbitrarily selected.

於使用填充材料(d)之情形時，接著劑組成物中，填充材料(d)的含量相對於溶媒以外的全部成分的總含量之比例(亦即，膜狀接著劑中的填充材料(d)的含量相對於膜狀接著劑的總質量之比例)較佳為7.5質量%至50質量%，更佳為10質量%至45質量%，尤佳為12.5質量%至40質量%。藉由填充材料(d)的含量為此種範圍，更容易調整上述熱膨脹係數。In the case of using the filler (d), the ratio of the content of the filler (d) to the total content of all components other than the solvent in the adhesive composition (that is, the filler (d) in the film adhesive The content of) relative to the total mass of the film adhesive) is preferably 7.5% to 50% by mass, more preferably 10% to 45% by mass, and particularly preferably 12.5% to 40% by mass. When the content of the filler (d) is in this range, it is easier to adjust the thermal expansion coefficient.

[偶合劑(e)] 膜狀接著劑藉由含有偶合劑(e)，對被接著體之接著性及密接性提高。另外，藉由膜狀接著劑含有偶合劑(e)，該膜狀接著劑之硬化物不損害耐熱性而耐水性提高。偶合劑(e)具有能夠與無機化合物或有機化合物反應之官能基。[Coupling agent (e)] By containing the coupling agent (e), the film-like adhesive improves the adhesion and adhesion to the adherend. In addition, when the film adhesive contains the coupling agent (e), the cured product of the film adhesive does not impair heat resistance and improves water resistance. The coupling agent (e) has a functional group capable of reacting with an inorganic compound or an organic compound.

偶合劑(e)較佳為具有能夠與丙烯酸系樹脂(a)、環氧系熱硬化性樹脂(b)等所具有之官能基反應之官能基之化合物，更佳為矽烷偶合劑。作為較佳的前述矽烷偶合劑，例如可列舉：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乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基甲基二乙氧基矽烷、2-(3,4-環氧環己基)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-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基甲基二乙氧基矽烷、3-(苯基胺基)丙基三甲氧基矽烷、3-苯胺基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽烷基丙基)四硫化物、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、咪唑矽烷、低聚物型或聚合物型有機矽氧烷等。The coupling agent (e) is preferably a compound having a functional group capable of reacting with a functional group possessed by the acrylic resin (a), epoxy-based thermosetting resin (b), etc., and more preferably a silane coupling agent. As a preferred silane coupling agent, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyl Triethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethyl Oxyoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyl Diethoxysilane, 3-(phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethyl Oxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, vinyl triacetoxysilane, imidazole silane, oligomer type or polymer type organosiloxane, etc.

偶合劑(e)較佳為脂肪族系化合物。藉由接著劑組成物及膜狀接著劑含有脂肪族系化合物作為偶合劑(e)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有脂肪族系化合物(換言之，不含有芳香族系化合物)，上述之著色的抑制效果顯著變高。The coupling agent (e) is preferably an aliphatic compound. When the adhesive composition and the film-like adhesive contain an aliphatic compound as the coupling agent (e), the effect of inhibiting the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes higher. When only aliphatic compounds are contained (in other words, no aromatic compounds are contained), the aforementioned coloring inhibitory effect is significantly increased.

偶合劑(e)較佳為不具有選自由碳原子間的三鍵(C≡C)、碳原子間的雙鍵(C=C)、氰基(-C≡N)及芳香族基所組成之群組中的1種或2種以上。藉由接著劑組成物及膜狀接著劑含有不具有這些鍵或基之化合物作為偶合劑(e)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有不具有這些鍵或基之化合物(換言之，不含有具有這些鍵或基之化合物)，上述之著色的抑制效果顯著變高。The coupling agent (e) preferably does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N) and an aromatic group. One or more types in the group. Since the adhesive composition and the film-like adhesive contain compounds that do not have these bonds or groups as the coupling agent (e), the effect of inhibiting the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes more High, by containing only a compound that does not have these bonds or groups (in other words, does not contain a compound that has these bonds or groups), the aforementioned coloring inhibitory effect becomes significantly higher.

偶合劑(e)較佳為脂肪族系化合物，且不具有選自由碳原子間的三鍵(C≡C)、碳原子間的雙鍵(C=C)及氰基(-C≡N)所組成之群組中的1種或2種以上。藉由接著劑組成物及膜狀接著劑含有不具有這些鍵或基之脂肪族系化合物作為偶合劑(e)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有不具有這些鍵或基之脂肪族系化合物(換言之，不含有具有這些鍵或基之脂肪族系化合物)，上述之著色的抑制效果顯著變高。The coupling agent (e) is preferably an aliphatic compound and does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C) and a cyano group (-C≡N) One or more types in the group. When the adhesive composition and the film-like adhesive contain an aliphatic compound that does not have these bonds or groups as the coupling agent (e), the film-like adhesive is heated (for example, heated at 260°C) to suppress the coloration effect To be higher, by only containing aliphatic compounds that do not have these bonds or groups (in other words, do not contain aliphatic compounds that have these bonds or groups), the above-mentioned coloring inhibitory effect becomes significantly higher.

偶合劑(e)中，作為脂肪族系化合物(脂肪族系偶合劑)，更具體而言，例如可列舉：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乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基甲基二乙氧基矽烷、2-(3,4-環氧環己基)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-胺基丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基三甲氧基矽烷、3-(2-胺基乙基胺基)丙基甲基二乙氧基矽烷、3-脲基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽烷基丙基)四硫化物、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、低聚物型或聚合物型有機矽氧烷等。In the coupling agent (e), as an aliphatic compound (aliphatic coupling agent), more specifically, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl Trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-Aminoethylamino)propylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Dimethoxysilane, bis(3-triethoxysilylpropyl) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethyl Acetoxysilane, oligomer type or polymer type organosiloxane, etc.

接著劑組成物及膜狀接著劑所含有之偶合劑(e)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The coupling agent (e) contained in the adhesive composition and the film-like adhesive may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these can be arbitrarily selected.

於使用偶合劑(e)之情形時，接著劑組成物及膜狀接著劑中，偶合劑(e)的含量相對於丙烯酸系樹脂(a)及環氧系熱硬化性樹脂(b)的總含量100質量份，較佳為0.03質量份至20質量份，更佳為0.05質量份至10質量份，尤佳為0.1質量份至5質量份。藉由偶合劑(e)的前述含量為前述下限值以上，能更顯著地獲得如下由使用偶合劑(e)所帶來之效果：填充材料(d)向樹脂中的分散性提高、以及膜狀接著劑與被接著體之接著性提高等。藉由偶合劑(e)的前述含量為前述上限值以下，能進一步抑制產生逸氣。When the coupling agent (e) is used, the content of the coupling agent (e) in the adhesive composition and the film-like adhesive is relative to the total of the acrylic resin (a) and epoxy-based thermosetting resin (b) The content is 100 parts by mass, preferably 0.03 parts by mass to 20 parts by mass, more preferably 0.05 parts by mass to 10 parts by mass, and particularly preferably 0.1 parts by mass to 5 parts by mass. When the aforementioned content of the coupling agent (e) is above the aforementioned lower limit, the following effects brought about by the use of the coupling agent (e) can be obtained more remarkably: the dispersibility of the filler (d) into the resin is improved, and The adhesiveness of the film adhesive and the adherend is improved. When the aforementioned content of the coupling agent (e) is below the aforementioned upper limit, the generation of outgassing can be further suppressed.

[交聯劑(f)] 於使用具有能夠與上述其他化合物鍵結之官能基，例如乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等之樹脂等作為丙烯酸系樹脂(a)之情形時，接著劑組成物及膜狀接著劑亦可含有交聯劑(f)，該交聯劑(f)用以使前述官能基與其他化合物鍵結而進行交聯。藉由使用交聯劑(f)進行交聯，能夠調節膜狀接著劑的初始接著力及凝聚力。[Crosslinker (f)] When using a resin having a functional group capable of bonding with the above-mentioned other compounds, such as a vinyl group, a (meth)acryl group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, etc., as the acrylic resin (a), The adhesive composition and the film-like adhesive may also contain a crosslinking agent (f) for bonding the aforementioned functional group to another compound to perform crosslinking. By using the crosslinking agent (f) for crosslinking, the initial adhesive force and cohesive force of the film-like adhesive can be adjusted.

作為交聯劑(f)，例如可列舉：有機多元異氰酸酯化合物、有機多元亞胺化合物、金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)、氮丙啶系交聯劑(具有氮丙啶基之交聯劑)等。As the crosslinking agent (f), for example, organic polyisocyanate compounds, organic polyimine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking Agent (crosslinking agent with aziridinyl group) and the like.

作為前述有機多元異氰酸酯化合物，例如可列舉：芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物及脂環族多元異氰酸酯化合物(以下，有時將這些化合物統一簡稱為「芳香族多元異氰酸酯化合物等」)；前述芳香族多元異氰酸酯化合物等的三聚物、異氰脲酸酯體及加合物；使前述芳香族多元異氰酸酯化合物等與多元醇化合物反應而獲得之末端異氰酸酯胺基甲酸酯預聚物等。前述「加合物」意指前述芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物或脂環族多元異氰酸酯化合物，與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷或蓖麻油等含低分子活性氫化合物而成之反應物。作為前述加合物的示例，可列舉：如後述之三羥甲基丙烷之苯二甲基二異氰酸酯加成物、三羥甲基丙烷之異佛爾酮二異氰酸酯加成物、三羥甲基丙烷之甲苯二異氰酸酯加成物、三羥甲基丙烷之六亞甲基二異氰酸酯加成物等。另外，所謂「末端異氰酸酯胺基甲酸酯預聚物」，意指具有胺基甲酸酯鍵，並且於分子的末端部具有異氰酸酯基之預聚物。Examples of the aforementioned organic polyvalent isocyanate compound include: aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, and alicyclic polyvalent isocyanate compounds (hereinafter, these compounds may be collectively referred to as "aromatic polyvalent isocyanate compounds, etc."); Trimers, isocyanurate bodies, and adducts of the aforementioned aromatic polyvalent isocyanate compounds, etc.; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc. with polyol compounds, etc. . The aforementioned "adduct" means the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound, or alicyclic polyisocyanate compound, which contains ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. Reactant made of low molecular active hydrogen compounds. Examples of the aforementioned adduct include: xylylene diisocyanate adduct of trimethylolpropane, isophorone diisocyanate adduct of trimethylolpropane, and trimethylol Toluene diisocyanate adduct of propane, hexamethylene diisocyanate adduct of trimethylolpropane, etc. In addition, the term "terminal isocyanate urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at the end of the molecule.

作為前述有機多元異氰酸酯化合物，更具體而言，例如可列舉：2,4-甲苯二異氰酸酯；2,6-甲苯二異氰酸酯；1,3-苯二甲基二異氰酸酯；1,4-苯二甲基二異氰酸酯；二苯基甲烷-4,4'-二異氰酸酯；二苯基甲烷-2,4'-二異氰酸酯；3-甲基二苯基甲烷二異氰酸酯；六亞甲基二異氰酸酯；異佛爾酮二異氰酸酯；二環己基甲烷-4,4'-二異氰酸酯；二環己基甲烷-2,4'-二異氰酸酯；對於三羥甲基丙烷等多元醇的全部或一部分羥基加成有甲苯二異氰酸酯、異佛爾酮二異氰酸酯、六亞甲基二異氰酸酯及苯二甲基二異氰酸酯中的任1種或2種以上而成之化合物；離胺酸二異氰酸酯等。As the aforementioned organic polyvalent isocyanate compound, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylylene diisocyanate Diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophor Ketone diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; toluene diisocyanate is added to all or part of the hydroxyl groups of polyols such as trimethylolpropane Compounds of any one or more of isocyanate, isophorone diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.

作為前述有機多元亞胺化合物，例如可列舉：N,N'-二苯基甲烷-4,4'-雙(1-氮丙啶甲醯胺)、三羥甲基丙烷-三-β-氮丙啶基丙酸酯、四羥甲基甲烷-三-β-氮丙啶基丙酸酯、N,N'-甲苯-2,4-雙(1-氮丙啶甲醯胺)三伸乙基三聚氰胺等。As the aforementioned organic polyimine compound, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridine methamide), trimethylolpropane-tri-β-nitrogen Propidinyl propionate, tetramethylolmethane-tris-β-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinylmethamine) triethylene Based on melamine and so on.

於使用有機多元異氰酸酯化合物作為交聯劑(f)之情形時，作為丙烯酸系樹脂(a)，較佳為使用含羥基之聚合物。於交聯劑(f)具有異氰酸酯基，丙烯酸系樹脂(a)具有羥基之情形時，藉由交聯劑(f)與丙烯酸系樹脂(a)之反應，能夠將交聯結構簡便地導入至膜狀接著劑。When an organic polyvalent isocyanate compound is used as the crosslinking agent (f), as the acrylic resin (a), it is preferable to use a hydroxyl group-containing polymer. When the crosslinking agent (f) has an isocyanate group and the acrylic resin (a) has a hydroxyl group, the crosslinking structure can be easily introduced into the Film adhesive.

交聯劑(f)較佳為脂肪族系化合物。藉由接著劑組成物及膜狀接著劑含有脂肪族系化合物作為交聯劑(f)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有脂肪族系化合物(換言之，不含有芳香族系化合物)，上述之著色的抑制效果顯著變高。The crosslinking agent (f) is preferably an aliphatic compound. Since the adhesive composition and the film-like adhesive contain an aliphatic compound as the crosslinking agent (f), the effect of inhibiting the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes higher. By containing only aliphatic compounds (in other words, not containing aromatic compounds), the above-mentioned coloring inhibitory effect is significantly increased.

交聯劑(f)較佳為不具有選自由碳原子間的三鍵(C≡C)、碳原子間的雙鍵(C=C)、氰基(-C≡N)及芳香族基所組成之群組中的1種或2種以上。藉由接著劑組成物及膜狀接著劑含有不具有這些鍵或基之化合物作為交聯劑(f)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有不具有這些鍵或基之化合物(換言之，不含有具有這些鍵或基之化合物)，上述之著色的抑制效果顯著變高。The crosslinking agent (f) preferably does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), a cyano group (-C≡N) and an aromatic group. One or more types in the group. When the adhesive composition and the film-like adhesive contain a compound that does not have these bonds or groups as the crosslinking agent (f), the effect of suppressing the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes Even higher, by containing only a compound that does not have these bonds or groups (in other words, does not contain a compound that has these bonds or groups), the aforementioned coloring inhibitory effect becomes significantly higher.

交聯劑(f)較佳為脂肪族系化合物，且不具有選自由碳原子間的三鍵(C≡C)、碳原子間的雙鍵(C=C)及氰基(-C≡N)所組成之群組中的1種或2種以上。藉由接著劑組成物及膜狀接著劑含有不具有這些鍵或基之脂肪族系化合物作為交聯劑(f)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有不具有這些鍵或基之脂肪族系化合物(換言之，不含有具有這些鍵或基之脂肪族系化合物)，上述之著色的抑制效果顯著變高。The crosslinking agent (f) is preferably an aliphatic compound, and does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), and a cyano group (-C≡N). ) One or more of the group consisting of. When the adhesive composition and the film-like adhesive contain an aliphatic compound that does not have these bonds or groups as the crosslinking agent (f), the coloration of the film-like adhesive after heating (for example, heating at 260°C) is suppressed The effect becomes higher, and by only containing the aliphatic compound not having these bonds or groups (in other words, not containing the aliphatic compound having these bonds or groups), the above-mentioned coloring inhibitory effect becomes significantly higher.

就上述之著色的抑制效果特別高，且具有作為交聯劑優異的特性之方面而言，交聯劑(f)較佳為脂肪族系有機多元異氰酸酯化合物(脂肪族系多元異氰酸酯交聯劑)。作為前述脂肪族系多元異氰酸酯交聯劑，更具體而言，例如可列舉：2,4-甲苯二異氰酸酯；2,6-甲苯二異氰酸酯；六亞甲基二異氰酸酯；異佛爾酮二異氰酸酯；二環己基甲烷-4,4'-二異氰酸酯；二環己基甲烷-2,4'-二異氰酸酯；對於三羥甲基丙烷等多元醇的全部或一部分羥基加成有甲苯二異氰酸酯、異佛爾酮二異氰酸酯及六亞甲基二異氰酸酯中的任1種或2種以上而成之化合物；離胺酸二異氰酸酯等。In terms of the above-mentioned coloring inhibitory effect being particularly high and having excellent characteristics as a crosslinking agent, the crosslinking agent (f) is preferably an aliphatic organic polyisocyanate compound (aliphatic polyisocyanate crosslinking agent) . As the aforementioned aliphatic polyvalent isocyanate crosslinking agent, more specifically, for example, 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; hexamethylene diisocyanate; isophorone diisocyanate; Dicyclohexylmethane-4,4'-diisocyanate; Dicyclohexylmethane-2,4'-diisocyanate; toluene diisocyanate and isophor are added to all or part of the hydroxyl groups of polyols such as trimethylolpropane A compound composed of any one or more of ketone diisocyanate and hexamethylene diisocyanate; lysine diisocyanate, etc.

關於前述膜狀接著劑，於著眼於丙烯酸系樹脂(a)及交聯劑(f)之情形時，就上述之著色的抑制效果特別高，且具有優異的特性之方面而言，較佳為含有前述脂肪族系多元異氰酸酯交聯劑作為交聯劑(f)，且含有具有能夠與前述脂肪族系多元異氰酸酯交聯劑鍵結之官能基之化合物作為丙烯酸系樹脂(a)。Regarding the aforementioned film-like adhesive, when focusing on the acrylic resin (a) and the crosslinking agent (f), the above-mentioned coloring inhibitory effect is particularly high and has excellent characteristics, preferably The aliphatic polyvalent isocyanate crosslinking agent is contained as the crosslinking agent (f), and a compound having a functional group capable of bonding with the aliphatic polyvalent isocyanate crosslinking agent is contained as the acrylic resin (a).

接著劑組成物及膜狀接著劑所含有之交聯劑(f)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The crosslinking agent (f) contained in the adhesive composition and the film-like adhesive may be only one type, or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

於使用交聯劑(f)之情形時，接著劑組成物及膜狀接著劑中，交聯劑(f)的含量相對於丙烯酸系樹脂(a)的含量100質量份，較佳為0.3質量份至12質量份，更佳為0.3質量份至3.5質量份，進而較佳為0.3質量份至2質量份。藉由交聯劑(f)的前述含量為前述下限值以上，能更顯著地獲得由使用交聯劑(f)所帶來之效果。另外，藉由交聯劑(f)的前述含量為前述上限值以下，交聯劑(f)的過量使用得到抑制。In the case of using a crosslinking agent (f), the content of the crosslinking agent (f) in the adhesive composition and the film-like adhesive is preferably 0.3 parts by mass relative to 100 parts by mass of the acrylic resin (a) Parts to 12 parts by mass, more preferably 0.3 parts by mass to 3.5 parts by mass, and still more preferably 0.3 parts by mass to 2 parts by mass. When the aforementioned content of the cross-linking agent (f) is more than the aforementioned lower limit, the effect of using the cross-linking agent (f) can be obtained more significantly. In addition, when the aforementioned content of the crosslinking agent (f) is below the aforementioned upper limit, excessive use of the crosslinking agent (f) is suppressed.

[能量線硬化性樹脂(g)] 接著劑組成物及膜狀接著劑亦可含有能量線硬化性樹脂(g)。膜狀接著劑藉由含有能量線硬化性樹脂(g)，能夠藉由照射能量線而改變特性。[Energy ray curable resin (g)] The adhesive composition and the film-like adhesive may contain energy ray-curable resin (g). By containing the energy-ray curable resin (g), the film-like adhesive can change its characteristics by irradiating energy rays.

本說明書中，所謂「能量線」，意指具有能量量子之電磁波或帶電粒子束，作為該能量線的示例，可列舉紫外線、放射線、電子束等。紫外線例如可藉由使用高壓水銀燈、熔合燈、氙氣燈、黑光燈或LED(Light Emitting Diode；發光二極體)燈等作為紫外線源而進行照射。電子束可照射藉由電子束加速器等產生之電子束。本說明書中，所謂「能量線硬化性」，意指藉由照射能量線而硬化之性質，所謂「非能量線硬化性」，意指即便照射能量線亦不硬化之性質。In this specification, the term "energy rays" means electromagnetic waves or charged particle beams having energy quantum, and examples of the energy rays include ultraviolet rays, radiation rays, electron beams, and the like. The ultraviolet light can be irradiated by using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode) lamp as an ultraviolet source. The electron beam can be irradiated with an electron beam generated by an electron beam accelerator or the like. In this specification, the "energy ray curability" means the property of being hardened by irradiation with energy rays, and the "non-energy ray hardening property" means the property of not being hardened even if energy rays are irradiated.

能量線硬化性樹脂(g)係使能量線硬化性化合物聚合(硬化)而獲得。作為前述能量線硬化性化合物，例如可列舉於分子內具有至少1個聚合性雙鍵之化合物，較佳為具有(甲基)丙烯醯基之丙烯酸酯系化合物。The energy ray curable resin (g) is obtained by polymerizing (curing) an energy ray curable compound. Examples of the aforementioned energy-beam curable compound include compounds having at least one polymerizable double bond in the molecule, and acrylate-based compounds having a (meth)acryloyl group are preferred.

作為前述丙烯酸酯系化合物，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯等含鏈狀脂肪族骨架之(甲基)丙烯酸酯；二(甲基)丙烯酸二環戊酯等含環狀脂肪族骨架之(甲基)丙烯酸酯；聚乙二醇二(甲基)丙烯酸酯等聚伸烷基二醇(甲基)丙烯酸酯；寡酯(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯低聚物；環氧改性(甲基)丙烯酸酯；前述聚伸烷基二醇(甲基)丙烯酸酯以外的聚醚(甲基)丙烯酸酯；衣康酸低聚物等。Examples of the acrylate-based compounds include: trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate Base) acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol two(meth)acrylate, 1,6-hexanediol two (Meth)acrylates and other (meth)acrylates containing chain aliphatic skeletons; (meth)acrylates such as dicyclopentyl di(meth)acrylates containing cyclic aliphatic skeletons; polyethylene glycol Di(meth)acrylate and other polyalkylene glycol (meth)acrylate; oligoester (meth)acrylate; (meth)acrylate urethane oligomer; epoxy modified (former Base) acrylate; polyether (meth)acrylate other than the aforementioned polyalkylene glycol (meth)acrylate; itaconic acid oligomer, etc.

能量線硬化性樹脂(g)的重量平均分子量較佳為100至30000，更佳為300至10000。The weight average molecular weight of the energy ray curable resin (g) is preferably 100 to 30,000, more preferably 300 to 10,000.

接著劑組成物所含有之能量線硬化性樹脂(g)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The energy ray curable resin (g) contained in the adhesive composition may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

於使用能量線硬化性樹脂(g)之情形時，接著劑組成物中，能量線硬化性樹脂(g)的含量相對於接著劑組成物的總質量之比例較佳為1質量%至95質量%，更佳為5質量%至90質量%，尤佳為10質量%至85質量%。In the case of using energy ray curable resin (g), the ratio of the content of energy ray curable resin (g) in the adhesive composition to the total mass of the adhesive composition is preferably 1% to 95% by mass %, more preferably 5 mass% to 90 mass%, particularly preferably 10 mass% to 85% by mass.

[光聚合起始劑(h)] 於接著劑組成物及膜狀接著劑含有能量線硬化性樹脂(g)之情形時，為了使能量線硬化性樹脂(g)高效率地進行聚合反應，亦可含有光聚合起始劑(h)。[Photopolymerization initiator (h)] When the adhesive composition and the film-like adhesive contain energy ray curable resin (g), in order to efficiently polymerize the energy ray curable resin (g), a photopolymerization initiator (h ).

作為前述光聚合起始劑(h)，例如可列舉：安息香、安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚、安息香苯甲酸、安息香苯甲酸甲酯、安息香二甲基縮酮等安息香化合物；苯乙酮、2-羥基-2-甲基-1-苯基-丙烷-1-酮、2,2-二甲氧基-1,2-二苯基乙烷-1-酮等苯乙酮化合物；雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦等醯基氧化膦化合物；苄基苯基硫醚、一硫化四甲基秋蘭姆等硫醚化合物；1-羥基環己基苯基酮等α-酮醇化合物；偶氮雙異丁腈等偶氮化合物；二茂鈦等二茂鈦化合物；噻噸酮等噻噸酮化合物；過氧化物化合物；二乙醯等二酮化合物；苯偶醯；二苯偶醯；二苯甲酮；2,4-二乙基噻噸酮；1,2-二苯基甲烷；2-羥基-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；1-氯蒽醌、2-氯蒽醌等醌化合物等。另外，作為光聚合起始劑(h)，例如亦可列舉胺等光增感劑等。Examples of the aforementioned photopolymerization initiator (h) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, and benzoin dimethyl ketal Benzoin compounds; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one Acetophenone compounds; bis(2,4,6-trimethylbenzyl) phenyl phosphine oxide, 2,4,6-trimethylbenzyl diphenyl phosphine oxide, etc. Compounds; sulfide compounds such as benzyl phenyl sulfide and tetramethylthiuram monosulfide; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; dicene Titanocene compounds such as titanium; thioxanthone compounds such as thioxanthone; peroxide compounds; diacetone compounds such as diacetin; benzil; benzil; benzophenone; 2,4-diethyl Thioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 1-chloroanthraquinone, 2-chloroanthracene Quinone and other quinone compounds. In addition, as the photopolymerization initiator (h), for example, photosensitizers such as amines can also be cited.

光聚合起始劑(h)較佳為脂肪族系化合物。藉由接著劑組成物及膜狀接著劑含有脂肪族系化合物作為光聚合起始劑(h)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有脂肪族系化合物(換言之，不含有芳香族系化合物)，上述之著色的抑制效果顯著變高。The photopolymerization initiator (h) is preferably an aliphatic compound. By the adhesive composition and the film-like adhesive containing aliphatic compounds as the photopolymerization initiator (h), the effect of inhibiting the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes higher , By containing only aliphatic compounds (in other words, not containing aromatic compounds), the above-mentioned coloring inhibitory effect is significantly increased.

光聚合起始劑(h)較佳為不具有選自由碳原子間的三鍵(C≡C)、碳原子間的雙鍵(C=C)、氰基(-C≡N)及芳香族基所組成之群組中的1種或2種以上。藉由接著劑組成物及膜狀接著劑含有不具有這些鍵或基之化合物作為光聚合起始劑(h)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有不具有這些鍵或基之化合物(換言之，不含有具有這些鍵或基之化合物)，上述之著色的抑制效果顯著變高。The photopolymerization initiator (h) preferably does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), cyano group (-C≡N) and aromatic One or more of the group consisting of the base. Since the adhesive composition and the film-like adhesive contain a compound that does not have these bonds or groups as the photopolymerization initiator (h), the film-like adhesive is heated (for example, heated at 260°C) to suppress the coloration effect It becomes higher, and by only containing a compound that does not have these bonds or groups (in other words, does not contain a compound that has these bonds or groups), the aforementioned coloring inhibitory effect becomes significantly higher.

光聚合起始劑(h)較佳為脂肪族系化合物，且不具有選自由碳原子間的三鍵(C≡C)、碳原子間的雙鍵(C=C)及氰基(-C≡N)所組成之群組中的1種或2種以上。藉由接著劑組成物及膜狀接著劑含有不具有這些鍵或基之脂肪族系化合物作為光聚合起始劑(h)，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有不具有這些鍵或基之脂肪族系化合物(換言之，不含有具有這些鍵或基之脂肪族系化合物)，上述之著色的抑制效果顯著變高。The photopolymerization initiator (h) is preferably an aliphatic compound, and does not have a triple bond between carbon atoms (C≡C), a double bond between carbon atoms (C=C), and a cyano group (-C). ≡N) One or more of the group consisting of. When the adhesive composition and the film-like adhesive contain an aliphatic compound that does not have these bonds or groups as the photopolymerization initiator (h), the film-like adhesive is colored after heating (for example, heating at 260°C) The inhibitory effect of chromophore becomes higher, and by containing only aliphatic compounds without these bonds or groups (in other words, without aliphatic compounds having these bonds or groups), the above-mentioned coloring inhibitory effect becomes significantly higher.

光聚合起始劑(h)中，作為脂肪族系化合物(脂肪族系光聚合起始劑)，更具體而言，例如可列舉：醯基氧化膦化合物；一硫化四甲基秋蘭姆等硫醚化合物；偶氮雙異丁腈等偶氮化合物；過氧化物化合物；二乙醯等二酮化合物；胺等光增感劑等。此處所例示之化合物中，作為脂肪族系化合物且不具有選自由碳原子間的三鍵(C≡C)、碳原子間的雙鍵(C=C)及氰基(-C≡N)所組成之群組中的1種或2種以上之光聚合起始劑(h)，例如可列舉偶氮雙異丁腈以外的化合物。In the photopolymerization initiator (h), as an aliphatic compound (aliphatic photopolymerization initiator), more specifically, for example, an acylphosphine oxide compound; tetramethylthiuram monosulfide, etc. Sulfide compounds; azo compounds such as azobisisobutyronitrile; peroxide compounds; diketone compounds such as diacetyl; photosensitizers such as amines, etc. Among the compounds exemplified here, they are aliphatic compounds and do not have triple bonds between carbon atoms (C≡C), double bonds between carbon atoms (C=C), and cyano groups (-C≡N). One or two or more types of photopolymerization initiators (h) in the composition group include, for example, compounds other than azobisisobutyronitrile.

接著劑組成物及膜狀接著劑所含有之光聚合起始劑(h)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The photopolymerization initiator (h) contained in the adhesive composition and the film-like adhesive may be only one type, or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected .

於使用光聚合起始劑(h)之情形時，接著劑組成物中，光聚合起始劑(h)的含量相對於能量線硬化性樹脂(g)的含量100質量份，較佳為0.1質量份至20質量份，更佳為1質量份至10質量份，尤佳為2質量份至5質量份。In the case of using the photopolymerization initiator (h), the content of the photopolymerization initiator (h) in the adhesive composition relative to 100 parts by mass of the energy ray curable resin (g) is preferably 0.1 Parts by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass, particularly preferably 2 parts by mass to 5 parts by mass.

[其他抗氧化劑(y)] 前述接著劑組成物及膜狀接著劑亦可在無損本發明的效果之範圍內含有前述其他抗氧化劑(y)。其他抗氧化劑(y)只要為磷系抗氧化劑(z)以外的抗氧化劑，則並無特別限定，可為有機化合物及無機化合物之任一種。[Other antioxidants (y)] The aforementioned adhesive composition and film-like adhesive may contain the aforementioned other antioxidant (y) within a range that does not impair the effects of the present invention. The other antioxidant (y) is not particularly limited as long as it is an antioxidant other than the phosphorus antioxidant (z), and may be either an organic compound or an inorganic compound.

接著劑組成物及膜狀接著劑所含有之其他抗氧化劑(y)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The other antioxidants (y) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected.

於使用其他抗氧化劑(y)之情形時，接著劑組成物及膜狀接著劑中，其他抗氧化劑(y)的含量相對於磷系抗氧化劑(z)的含量100質量份，較佳為10質量份以下，更佳為5質量份以下，進而較佳為1質量份以下。藉由其他抗氧化劑(y)的前述含量為前述上限值以下，前述膜狀接著劑之加熱前後的著色更得到抑制。In the case of using other antioxidants (y), the content of other antioxidants (y) in the adhesive composition and the film-like adhesive is preferably 10 parts by mass relative to 100 parts by mass of the phosphorus antioxidant (z) Parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 1 part by mass or less. When the aforementioned content of the other antioxidant (y) is below the aforementioned upper limit value, the coloration of the aforementioned film adhesive before and after heating is further suppressed.

前述接著劑組成物及膜狀接著劑較佳為不含有其他抗氧化劑(y)。The aforementioned adhesive composition and film-like adhesive preferably do not contain other antioxidants (y).

[熱塑性樹脂(x)] 前述接著劑組成物及膜狀接著劑亦可在無損本發明的效果之範圍內含有前述熱塑性樹脂(x)。藉由使用熱塑性樹脂(x)，例如有時於拾取時更容易將具備膜狀接著劑之前述晶片自後述切割片扯離，或膜狀接著劑變得容易追隨於被接著體的凹凸面，能進一步抑制於被接著體與膜狀接著劑之間產生空隙等。[Thermoplastic resin (x)] The aforementioned adhesive composition and film-like adhesive may contain the aforementioned thermoplastic resin (x) within a range that does not impair the effects of the present invention. By using the thermoplastic resin (x), for example, it may be easier to pull the aforementioned wafer with the film-like adhesive from the dicing sheet described later during pickup, or the film-like adhesive may easily follow the uneven surface of the adherend. The generation of voids and the like between the adherend and the film-like adhesive can be further suppressed.

熱塑性樹脂(x)只要為丙烯酸系樹脂(a)以外的熱塑性樹脂，則並無特別限定。作為前述熱塑性樹脂，例如可列舉：聚酯、聚胺基甲酸酯、苯氧基樹脂、聚丁烯、聚丁二烯、聚苯乙烯等。The thermoplastic resin (x) is not particularly limited as long as it is a thermoplastic resin other than the acrylic resin (a). As said thermoplastic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, polystyrene, etc. are mentioned, for example.

熱塑性樹脂(x)的重量平均分子量較佳為1000至100000，更佳為3000至80000。The weight average molecular weight of the thermoplastic resin (x) is preferably 1,000 to 100,000, more preferably 3,000 to 80,000.

熱塑性樹脂(x)的玻璃轉移溫度(Tg)較佳為-30℃至150℃，更佳為-20℃至120℃。The glass transition temperature (Tg) of the thermoplastic resin (x) is preferably -30°C to 150°C, more preferably -20°C to 120°C.

接著劑組成物及膜狀接著劑所含有之熱塑性樹脂(x)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The thermoplastic resin (x) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types, and when there are two or more types, the combination and ratio of these can be arbitrarily selected.

於使用熱塑性樹脂(x)之情形時，接著劑組成物及膜狀接著劑中，熱塑性樹脂(x)的含量相對於丙烯酸系樹脂(a)的含量100質量份，較佳為10質量份以下，更佳為5質量份以下，進而較佳為1質量份以下。藉由熱塑性樹脂(x)的前述含量為前述上限值以下，能更顯著地獲得由使用丙烯酸系樹脂(a)所帶來之效果。When using the thermoplastic resin (x), in the adhesive composition and the film-like adhesive, the content of the thermoplastic resin (x) is 100 parts by mass relative to the content of the acrylic resin (a), preferably 10 parts by mass or less , More preferably 5 parts by mass or less, and still more preferably 1 part by mass or less. When the aforementioned content of the thermoplastic resin (x) is equal to or less than the aforementioned upper limit value, the effect of using the acrylic resin (a) can be more remarkably obtained.

前述接著劑組成物及膜狀接著劑較佳為不含有熱塑性樹脂(x)。The aforementioned adhesive composition and film-like adhesive preferably do not contain the thermoplastic resin (x).

[通用添加劑(i)] 通用添加劑(i)可為公知的添加劑，可根據目的任意選擇，並無特別限定。作為較佳的通用添加劑(i)，例如可列舉：塑化劑、抗靜電劑、著色劑(染料、顏料)、吸氣劑(gettering agent)等。[General additives (i)] The general-purpose additive (i) may be a well-known additive, and can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred general additives (i) include, for example, plasticizers, antistatic agents, colorants (dyes, pigments), gettering agents, and the like.

於通用添加劑(i)為有機化合物之情形時，此種通用添加劑(i)(本說明書中，簡稱為「有機通用添加劑」)較佳為脂肪族系化合物。藉由接著劑組成物及膜狀接著劑含有脂肪族系化合物作為有機通用添加劑，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有脂肪族系化合物(換言之，不含有芳香族系化合物)，上述之著色的抑制效果顯著變高。When the general-purpose additive (i) is an organic compound, such general-purpose additive (i) (referred to as "organic general-purpose additive" in this specification) is preferably an aliphatic compound. By the adhesive composition and the film-like adhesive containing aliphatic compounds as general-purpose organic additives, the effect of suppressing the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes higher. By only containing The aliphatic compound (in other words, does not contain an aromatic compound), the above-mentioned coloring inhibitory effect is significantly increased.

有機通用添加劑較佳為不具有選自由碳原子間的三鍵(C≡C)、碳原子間的雙鍵(C=C)、氰基(-C≡N)及芳香族基所組成之群組中的1種或2種以上。藉由接著劑組成物及膜狀接著劑含有不具有這些鍵或基之化合物作為有機通用添加劑，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有不具有這些鍵或基之化合物(換言之，不含有具有這些鍵或基之化合物)，上述之著色的抑制效果顯著變高。Organic general-purpose additives are preferably not selected from the group consisting of triple bonds between carbon atoms (C≡C), double bonds between carbon atoms (C=C), cyano groups (-C≡N) and aromatic groups One or more types in the group. Since the adhesive composition and the film-like adhesive contain compounds that do not have these bonds or groups as general-purpose organic additives, the effect of inhibiting the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes higher. By only containing a compound that does not have these bonds or groups (in other words, does not contain a compound that has these bonds or groups), the above-mentioned coloring inhibitory effect is significantly increased.

有機通用添加劑較佳為脂肪族系化合物，且不具有選自由碳原子間的三鍵(C≡C)、碳原子間的雙鍵(C=C)及氰基(-C≡N)所組成之群組中的1種或2種以上。藉由接著劑組成物及膜狀接著劑含有不具有這些鍵或基之脂肪族系化合物作為有機通用添加劑，膜狀接著劑之加熱(例如於260℃之加熱)後的著色的抑制效果變得更高，藉由僅含有不具有這些鍵或基之脂肪族系化合物(換言之，不含有具有這些鍵或基之脂肪族系化合物)，上述之著色的抑制效果顯著變高。The general-purpose organic additives are preferably aliphatic compounds and do not have three bonds between carbon atoms (C≡C), double bonds between carbon atoms (C=C) and cyano groups (-C≡N). One or more types in the group. When the adhesive composition and the film-like adhesive contain aliphatic compounds that do not have these bonds or groups as general-purpose organic additives, the effect of inhibiting the coloration of the film-like adhesive after heating (for example, heating at 260°C) becomes Even higher, by only containing aliphatic compounds that do not have these bonds or groups (in other words, not containing aliphatic compounds that have these bonds or groups), the above-mentioned coloring inhibitory effect becomes significantly higher.

接著劑組成物及膜狀接著劑所含有之通用添加劑(i)可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。接著劑組成物及膜狀接著劑中的通用添加劑(i)的含量並無特別限定，根據目的適宜選擇即可。The general additives (i) contained in the adhesive composition and the film-like adhesive may be only one type or two or more types. When there are two or more types, the combination and ratio of these can be arbitrarily selected. The content of the general-purpose additive (i) in the adhesive composition and the film-like adhesive is not particularly limited, and may be appropriately selected according to the purpose.

[溶媒] 接著劑組成物較佳為進而含有溶媒。含有溶媒之接著劑組成物的操作性變得良好。前述溶媒並無特別限定，作為較佳的前述溶媒，例如可列舉：甲苯、二甲苯等烴；甲醇、乙醇、2-丙醇、異丁醇(2-甲基丙烷-1-醇)、1-丁醇等醇；乙酸乙酯等酯；丙酮、甲基乙基酮等酮；四氫呋喃等醚；二甲基甲醯胺、N-甲基吡咯啶酮等醯胺(具有醯胺鍵之化合物)等。接著劑組成物所含有之溶媒可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。[Solvent] The adhesive composition preferably further contains a solvent. The workability of the solvent-containing adhesive composition becomes better. The aforementioned solvent is not particularly limited. As preferred aforementioned solvents, for example, hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutanol (2-methylpropane-1-ol), 1 -Alcohols such as butanol; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran; amides such as dimethylformamide and N-methylpyrrolidone (compounds with amide bonds )Wait. The solvent contained in the adhesive composition may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these can be arbitrarily selected.

就能夠使接著劑組成物中的含有成分更均勻地混合之方面而言，接著劑組成物所含有之溶媒較佳為甲基乙基酮等。The solvent contained in the adhesive composition is preferably methyl ethyl ketone or the like in terms of enabling the components contained in the adhesive composition to be mixed more uniformly.

[接著劑組成物之製造方法] 接著劑組成物係藉由調配用以構成該接著劑組成物之各成分而獲得。調配各成分時的添加順序並無特別限定，亦可同時添加2種以上之成分。於使用溶媒之情形時，可藉由下述方式使用：將溶媒與溶媒以外的任一種調配成分混合而將該調配成分預先稀釋；或是，不將溶媒以外的任一種調配成分預先稀釋而是將溶媒與這些調配成分混合。[Method of manufacturing adhesive composition] The adhesive composition is obtained by formulating the components used to form the adhesive composition. The order of addition when formulating each component is not particularly limited, and two or more components may be added at the same time. When a solvent is used, it can be used in the following manner: mixing the solvent with any compounding component other than the solvent and diluting the compounding component in advance; or, not diluting any compounding component other than the solvent in advance. The solvent is mixed with these formulation ingredients.

調配時混合各成分之方法並無特別限定，自以下公知的方法中適宜選擇即可：使攪拌子或攪拌翼等旋轉而進行混合之方法；使用混合機進行混合之方法；施加超音波進行混合之方法等。關於添加及混合各成分時的溫度及時間，只要不使各調配成分劣化，則並無特別限定，適宜調節即可，溫度較佳為15℃至30℃。The method of mixing the ingredients during the preparation is not particularly limited, and can be appropriately selected from the following known methods: a method of rotating a stirrer or a stirring blade, etc. for mixing; a method of mixing using a mixer; applying ultrasonic waves for mixing The method and so on. Regarding the temperature and time when each component is added and mixed, as long as it does not deteriorate each compounding component, it is not particularly limited and may be adjusted appropriately. The temperature is preferably 15°C to 30°C.

圖1係以示意方式表示本發明的一實施形態的膜狀接著劑之剖視圖。此外，以下的說明中所使用之圖中，為了易於理解本發明的特徵，方便起見，有時將成為主要部分之部分放大表示，而並不限於各構成要素的尺寸比率等與實際相同。Fig. 1 is a cross-sectional view schematically showing a film adhesive according to an embodiment of the present invention. In addition, in the drawings used in the following description, in order to make it easier to understand the features of the present invention and for convenience, the main parts may be enlarged and shown, and the dimensional ratios of the constituent elements are not limited to the actual size.

此處所示之膜狀接著劑13於該膜狀接著劑13的一面(本說明書中，有時稱為「第1面」)13a上具備第1剝離膜151，於與前述第1面13a為相反側的另一面(本說明書中，有時稱為「第2面」)13b上具備第2剝離膜152。此處，對如此般第1剝離膜151、膜狀接著劑13及第2剝離膜152依序於這些層的厚度方向上積層而構成之積層片標附符號109。此種膜狀接著劑13(積層片109)例如適於以捲筒狀保存。The film-like adhesive 13 shown here is provided with a first release film 151 on one side of the film-like adhesive 13 (in this specification, sometimes referred to as "first side") 13a. The other surface on the opposite side (in this specification, sometimes referred to as the "second surface") 13b is provided with a second release film 152. Here, the laminated sheet formed by laminating the first peeling film 151, the film-like adhesive 13 and the second peeling film 152 in the thickness direction of these layers in this manner is denoted by reference numeral 109. Such a film-like adhesive 13 (laminated sheet 109) is suitable for storage in a roll shape, for example.

膜狀接著劑13具有上述之透光性。膜狀接著劑13的厚度為10μm至40μm。膜狀接著劑13可使用上述之接著劑組成物而形成。The film adhesive 13 has the above-mentioned translucency. The film adhesive 13 has a thickness of 10 μm to 40 μm. The film-like adhesive 13 can be formed using the above-mentioned adhesive composition.

第1剝離膜151及第2剝離膜152均可為公知的剝離膜。第1剝離膜151及第2剝離膜152可相互相同，例如亦可自膜狀接著劑13剝離時所需之剝離力相互不同等相互不同的剝離膜。Both the first release film 151 and the second release film 152 may be known release films. The first peeling film 151 and the second peeling film 152 may be the same as each other, and for example, the peeling force required when peeling from the film-like adhesive 13 is different from each other may be different from each other.

圖1所示之膜狀接著劑13係移除第1剝離膜151及第2剝離膜152中的任一剝離膜，所產生之露出面成為該膜狀接著劑13向貼附對象物之貼附面。此處，作為貼附對象物，例如可列舉前述晶片等。於前述晶片之情形時，膜狀接著劑13的貼附面成為該晶片的電路形成面。The film adhesive 13 shown in FIG. 1 removes any one of the first release film 151 and the second release film 152, and the resulting exposed surface becomes the sticking of the film adhesive 13 to the object to be attached. Attached. Here, as the sticking object, for example, the aforementioned wafer or the like can be cited. In the case of the aforementioned wafer, the attachment surface of the film-like adhesive 13 becomes the circuit formation surface of the wafer.

作為較佳的前述膜狀接著劑的一實施形態，例如可列舉以下之膜狀接著劑：含有丙烯酸系樹脂(a)、環氧化合物(b1)、及磷系抗氧化劑(z)；且於260℃加熱前的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為90%以上，於260℃加熱10分鐘後的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為85%以上，前述膜狀接著劑的厚度為10μm至40μm；使用大小為2mm×2mm且厚度為20μm之前述膜狀接著劑、大小為30mm×30mm且厚度為300μm之銅板、及矽晶片，製作前述膜狀接著劑的一面整面貼附於前述矽晶片的表面，另一面整面貼附於前述銅板的表面而構成，且前述膜狀接著劑與前述矽晶片之側面經對位之試片，於23℃之溫度條件下，於前述試片中之前述經對位之側面，對前述膜狀接著劑與前述矽晶片兩者，沿相對於前述膜狀接著劑的前述另一面平行的方向，以200μm/s之速度施加力，將直至前述膜狀接著劑受到破壞為止所施加之力的最大值設為前述膜狀接著劑的剪切強度(N/2mm□)時，前述剪切強度為20N/2mm□以上。As a preferred embodiment of the aforementioned film-like adhesive, for example, the following film-like adhesive: containing acrylic resin (a), epoxy compound (b1), and phosphorus antioxidant (z); and The film adhesive before heating at 260°C has a linear transmittance of more than 90% for light with a wavelength of 400nm to 800nm, and the film adhesive after heating at 260°C for 10 minutes has a linear transmittance of light with a wavelength of 400nm to 800nm The transmittance is 85% or more. The thickness of the film adhesive is 10μm to 40μm; the film adhesive with a size of 2mm×2mm and a thickness of 20μm, a copper plate with a size of 30mm×30mm and a thickness of 300μm, and silicon For the wafer, one side of the film-like adhesive is attached to the surface of the silicon wafer, and the other side is attached to the surface of the copper plate. The film-like adhesive is aligned with the side of the silicon wafer The test piece, at a temperature of 23℃, on the aligned side of the test piece, for both the film adhesive and the silicon wafer, along the other surface opposite to the film adhesive A force is applied at a speed of 200μm/s in parallel directions, and the maximum value of the force applied until the film adhesive is broken is set to the shear strength (N/2mm□) of the film adhesive, The shear strength is above 20N/2mm□.

作為較佳的前述膜狀接著劑的一實施形態，例如可列舉以下之膜狀接著劑：含有丙烯酸系樹脂(a)、環氧化合物(b1)、及磷系抗氧化劑(z)，且於260℃加熱前的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為90%以上，於260℃加熱10分鐘後的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為85%以上，前述膜狀接著劑的厚度為10μm至40μm；前述磷系抗氧化劑(z)為脂肪族系化合物，且不具有選自由碳原子間的三鍵、碳原子間的雙鍵、及氰基所組成之群組中的1種或2種以上；前述膜狀接著劑中的前述磷系抗氧化劑(z)的含量相對於前述膜狀接著劑的總質量之比例為0.1質量%至5質量%。As a preferred embodiment of the aforementioned film-like adhesive, for example, the following film-like adhesives include acrylic resin (a), epoxy compound (b1), and phosphorus antioxidant (z), and The film adhesive before heating at 260°C has a linear transmittance of more than 90% for light with a wavelength of 400nm to 800nm, and the film adhesive after heating at 260°C for 10 minutes has a linear transmittance of light with a wavelength of 400nm to 800nm The transmittance is 85% or more, the thickness of the film-like adhesive is 10 μm to 40 μm; the phosphorus antioxidant (z) is an aliphatic compound and does not have a triple bond between carbon atoms and a double bond between carbon atoms One or more of the group consisting of a bond and a cyano group; the ratio of the content of the phosphorus antioxidant (z) in the film adhesive to the total mass of the film adhesive is 0.1 Mass% to 5 mass%.

作為較佳的前述膜狀接著劑的一實施形態，例如可列舉以下之膜狀接著劑：含有丙烯酸系樹脂(a)、環氧化合物(b1)、及磷系抗氧化劑(z)，且於260℃加熱前的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為90%以上，於260℃加熱10分鐘後的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為85%以上，前述膜狀接著劑的厚度為10μm至40μm；前述環氧化合物(b1)及磷系抗氧化劑(z)均為脂肪族系化合物，且不具有選自由碳原子間的三鍵、碳原子間的雙鍵、及氰基所組成之群組中的1種或2種以上。As a preferred embodiment of the aforementioned film-like adhesive, for example, the following film-like adhesives include acrylic resin (a), epoxy compound (b1), and phosphorus antioxidant (z), and The film adhesive before heating at 260°C has a linear transmittance of more than 90% for light with a wavelength of 400nm to 800nm, and the film adhesive after heating at 260°C for 10 minutes has a linear transmittance of light with a wavelength of 400nm to 800nm The transmittance is more than 85%, the thickness of the film-like adhesive is 10μm to 40μm; the epoxy compound (b1) and the phosphorus antioxidant (z) are aliphatic compounds, and do not have carbon atoms One or more of the group consisting of triple bonds, double bonds between carbon atoms, and cyano groups.

作為較佳的前述膜狀接著劑的一實施形態，例如可列舉以下之膜狀接著劑：含有丙烯酸系樹脂(a)、環氧化合物(b1)、交聯劑(f)、及磷系抗氧化劑(z)，且於260℃加熱前的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為90%以上，於260℃加熱10分鐘後的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為85%以上，前述膜狀接著劑的厚度為10μm至40μm；前述磷系抗氧化劑(z)及交聯劑(f)均為脂肪族系化合物，且不具有選自由碳原子間的三鍵、碳原子間的雙鍵、及氰基所組成之群組中的1種或2種以上。As a preferred embodiment of the aforementioned film-like adhesive, for example, the following film-like adhesives: containing acrylic resin (a), epoxy compound (b1), crosslinking agent (f), and phosphorus-based Oxidizing agent (z), and the film adhesive before heating at 260°C has a linear transmittance of more than 90% for light with a wavelength of 400nm to 800nm. The film adhesive after heating at 260°C for 10 minutes has a wavelength of The linear transmittance of light from 400nm to 800nm is more than 85%, the thickness of the aforementioned film-like adhesive is 10μm to 40μm; the aforementioned phosphorus antioxidant (z) and crosslinking agent (f) are both aliphatic compounds and not It has one or more types selected from the group consisting of triple bonds between carbon atoms, double bonds between carbon atoms, and cyano groups.

作為較佳的前述膜狀接著劑的一實施形態，例如可列舉以下之膜狀接著劑：含有丙烯酸系樹脂(a)、環氧化合物(b1)、填充材料(d)、及磷系抗氧化劑(z)，且於260℃加熱前的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為90%以上，於260℃加熱10分鐘後的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為85%以上，前述膜狀接著劑的厚度為10μm至40μm；前述填充材料(d)的平均粒徑為10nm至100nm。As a preferred embodiment of the aforementioned film-like adhesive, for example, the following film-like adhesives include acrylic resin (a), epoxy compound (b1), filler (d), and phosphorus antioxidant (z) The film adhesive before heating at 260°C has a linear transmittance of more than 90% for light with a wavelength of 400nm to 800nm, and the film adhesive after heating at 260°C for 10 minutes has a wavelength of 400nm The linear transmittance of light to 800 nm is over 85%, the thickness of the film adhesive is 10 μm to 40 μm; the average particle size of the filler (d) is 10 nm to 100 nm.

◇積層片及複合片本發明的一實施形態的積層片係具備前述膜狀接著劑、及設置於前述膜狀接著劑的一面上之樹脂膜而構成。另外，本發明的一實施形態的複合片具備前述膜狀接著劑、及設置於前述膜狀接著劑的一面上之切割片，前述切割片具備基材、及設置於前述基材的一面上之黏著劑層，前述黏著劑層配置於前述基材與前述膜狀接著劑之間。◇Laminated sheet and composite sheet The laminated sheet according to one embodiment of the present invention includes the film-like adhesive and a resin film provided on one surface of the film-like adhesive. In addition, a composite sheet according to an embodiment of the present invention includes the film adhesive and a dicing sheet provided on one side of the film adhesive, and the dicing sheet includes a substrate and a dicing sheet provided on one side of the substrate. The adhesive layer, the adhesive layer is disposed between the substrate and the film adhesive.

前述積層片只要於前述膜狀接著劑的至少一面上設置有樹脂膜即可，亦可僅於單面上設置有樹脂膜，還可於雙面上(亦即，前述一面上、及與前述一面為相反側的另一面上)設置有樹脂膜。The laminated sheet may be provided with a resin film on at least one side of the film-like adhesive, or may be provided with a resin film on one side only, or on both sides (that is, the above-mentioned one side, and the above-mentioned A resin film is provided on the other side on the opposite side.

於前述積層片中，於前述膜狀接著劑的雙面上設置有前述樹脂膜之情形時，這些樹脂膜相互可相同亦可不同，這些樹脂膜的組合並無特別限定。In the laminated sheet, when the resin film is provided on both sides of the film-like adhesive, these resin films may be the same or different from each other, and the combination of these resin films is not particularly limited.

前述樹脂膜可由1層(單層)所構成，亦可由2層以上之複數層所構成，於由複數層所構成之情形時，這些複數層相互可相同亦可不同，這些複數層的組合並無特別限定。The aforementioned resin film may be composed of one layer (single layer), or may be composed of two or more layers. When composed of multiple layers, these plural layers may be the same or different from each other. The combination of these plural layers There is no particular limitation.

前述樹脂膜可為僅以樹脂作為構成材料之片，亦可為以樹脂及樹脂以外的成分作為構成材料，且以樹脂作為主要構成材料之片。The aforementioned resin film may be a sheet containing only resin as a constituent material, or a sheet containing resin and components other than resin as a constituent material and resin as a main constituent material.

作為前述樹脂膜的構成材料之前述樹脂，例如可列舉：低密度聚乙烯(LDPE；Low Density Polyethylene)、直鏈低密度聚乙烯(LLDPE；Linear Low Density Polyethylene)、高密度聚乙烯(HDPE；High Density Polyethylene)等聚乙烯；聚丙烯、聚丁烯、聚丁二烯、聚甲基戊烯、降冰片烯樹脂等聚乙烯以外的聚烯烴；乙烯-乙酸乙烯酯共聚物、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、乙烯-降冰片烯共聚物等乙烯系共聚物(使用乙烯作為單體而獲得之共聚物)；聚氯乙烯、氯乙烯共聚物等氯乙烯系樹脂(使用氯乙烯作為單體而獲得之樹脂)；聚苯乙烯；聚環烯烴；聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯、聚間苯二甲酸乙二酯、聚-2,6-萘二甲酸乙二酯、全部結構單元具有芳香族環式基之全芳香族聚酯等聚酯；2種以上之前述聚酯之共聚物；聚(甲基)丙烯酸酯；聚胺基甲酸酯；聚丙烯酸胺基甲酸酯；聚醯亞胺；聚醯胺；聚碳酸酯；氟樹脂；聚縮醛；改性聚苯醚；聚苯硫醚；聚碸；聚醚酮等。另外，作為前述樹脂，例如亦可列舉前述聚酯與前述聚酯以外的樹脂之混合物等聚合物合金。前述聚酯與前述聚酯以外的樹脂之聚合物合金較佳為聚酯以外的樹脂的量為相對較少量。另外，作為前述樹脂，例如亦可列舉：前文例示之前述樹脂中的1種或2種以上交聯而成之交聯樹脂；使用前文例示之前述樹脂中的1種或2種以上之離子聚合物等改性樹脂。Examples of the resin as the constituent material of the resin film include low density polyethylene (LDPE; Low Density Polyethylene), linear low density polyethylene (LLDPE; Linear Low Density Polyethylene), and high density polyethylene (HDPE; High Density Polyethylene) and other polyethylene; polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin and other polyolefins other than polyethylene; ethylene-vinyl acetate copolymer, ethylene-(methyl) ) Vinyl copolymers such as acrylic copolymers, ethylene-(meth)acrylate copolymers, and ethylene-norbornene copolymers (copolymers obtained by using ethylene as a monomer); polyvinyl chloride, vinyl chloride copolymers, etc. Vinyl chloride resin (resin obtained by using vinyl chloride as a monomer); polystyrene; polycyclic olefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate , Polyethylene isophthalate, polyethylene-2,6-naphthalate, fully aromatic polyesters with aromatic cyclic groups in all structural units; among two or more of the aforementioned polyesters Copolymer; Poly(meth)acrylate; Polyurethane; Polyacrylate urethane; Polyimide; Polyamide; Polycarbonate; Fluorine resin; Polyacetal; Modified polyphenylene Ether; polyphenylene sulfide; polysulfide; polyetherketone, etc. Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and resin other than the said polyester, can also be mentioned, for example. The polymer alloy of the polyester and the resin other than the polyester preferably has a relatively small amount of the resin other than the polyester. In addition, as the aforementioned resin, for example, a cross-linked resin obtained by cross-linking one or more of the aforementioned resins exemplified above; ionic polymerization using one or more of the aforementioned resins exemplified above Modified resin such as material.

前述樹脂膜可為剝離膜，亦可為後述之基材。關於基材，另行詳細地進行說明。The aforementioned resin film may be a release film or a substrate described later. The base material will be described in detail separately.

作為前述剝離膜，例如可列舉具備樹脂層及設置於前述樹脂層的一面上之剝離處理層而構成之由複數層所構成之膜。Examples of the release film include a film composed of a plurality of layers provided with a resin layer and a release treatment layer provided on one surface of the resin layer.

前述剝離膜可藉由將前述樹脂層的一面進行剝離處理而製造。前述樹脂層可藉由將含有樹脂之樹脂組成物進行成形或塗敷，並根據需要使之乾燥而製作。The release film can be produced by subjecting one side of the resin layer to a release treatment. The aforementioned resin layer can be produced by molding or coating a resin composition containing a resin, and drying it if necessary.

作為前述樹脂層的構成材料之樹脂與作為前述樹脂膜的構成材料之前述樹脂相同。前述樹脂層的剝離處理例如可藉由醇酸系、聚矽氧系、氟系、不飽和聚酯系、聚烯烴系或蠟系等公知的各種剝離劑進行。就具有耐熱性之方面而言，前述剝離劑較佳為醇酸系、聚矽氧系或氟系之剝離劑。The resin as the constituent material of the resin layer is the same as the resin as the constituent material of the resin film. The peeling treatment of the aforementioned resin layer can be performed by various known peeling agents such as alkyd, silicone, fluorine, unsaturated polyester, polyolefin, or wax. In terms of heat resistance, the aforementioned release agent is preferably an alkyd, silicone, or fluorine release agent.

前述樹脂層可由1層(單層)所構成，亦可由2層以上之複數層所構成，於由複數層所構成之情形時，這些複數層相互可相同亦可不同，這些複數層的組合並無特別限定。The aforementioned resin layer may be composed of one layer (single layer), or may be composed of two or more layers. When composed of multiple layers, these plural layers may be the same or different from each other. The combination of these plural layers There is no particular limitation.

作為於前述膜狀接著劑的雙面上設置前述剝離膜作為樹脂膜而構成之積層片，例如可列舉圖1所示之積層片109。As a laminated sheet comprised by providing the said release film as a resin film on both sides of the said film-like adhesive agent, the laminated sheet 109 shown in FIG. 1 is mentioned, for example.

作為於前述膜狀接著劑的僅單面上設置樹脂膜而構成之積層片，例如可列舉圖2所示之積層片108。此外，於圖2以後的圖中，對與既已說明之圖所示相同的構成要素，標附與該已說明之圖之情形相同的符號，並省略該構成要素之詳細說明。As a laminated sheet constituted by providing a resin film on only one side of the aforementioned film-like adhesive agent, for example, a laminated sheet 108 shown in FIG. 2 can be cited. In addition, in the drawings after FIG. 2, the same components as those shown in the previously described diagrams are assigned the same reference numerals as in the previously described diagrams, and detailed descriptions of the components are omitted.

此處所示之積層片108係於膜狀接著劑13的第1面13a上具備樹脂膜19而構成。樹脂膜19如上所述，可為剝離膜(例如圖1中的第1剝離膜151或第2剝離膜152)，亦可為後述之基材。The laminated sheet 108 shown here is provided with the resin film 19 on the 1st surface 13a of the film-shaped adhesive agent 13, and is comprised. As described above, the resin film 19 may be a release film (for example, the first release film 151 or the second release film 152 in FIG. 1), or may be a substrate described later.

前述樹脂膜的厚度可根據目的任意設定，並無特別限定。前述樹脂膜的厚度例如可為10μm至200μm。The thickness of the aforementioned resin film can be arbitrarily set according to the purpose and is not particularly limited. The thickness of the aforementioned resin film may be, for example, 10 μm to 200 μm.

本實施形態的積層片並不限定於圖2所示之積層片，亦可在無損本發明的效果之範圍內，將圖2所示之積層片的一部分構成變更或刪除，或者對前文說明之積層片進一步追加其他構成。更具體而言，如下所述。The laminated sheet of this embodiment is not limited to the laminated sheet shown in FIG. 2, and a part of the structure of the laminated sheet shown in FIG. 2 may be changed or deleted within a range that does not impair the effect of the present invention, or the foregoing description The laminated sheet further adds other structures. More specifically, it is as follows.

例如，本實施形態的積層片可於膜狀接著劑的第2面不具備任何層，亦可於膜狀接著劑的第2面中周緣部附近的區域，具備用以將積層片固定於環狀框架等治具之治具用接著劑層。治具用接著劑層例如可為含有接著劑成分之單層結構，亦可為於成為芯材之片的雙面積層有含有接著劑成分之層而成之複數層結構。For example, the laminated sheet of this embodiment may not have any layer on the second surface of the film-like adhesive, or it may be provided in the area near the peripheral edge of the second surface of the film-like adhesive for fixing the laminated sheet to the ring. Adhesive layer for fixtures such as shaped frames. The adhesive layer for a jig may have, for example, a single-layer structure containing an adhesive component, or a multiple-layer structure in which a double-area layer of a sheet used as a core material has a layer containing an adhesive component.

例如，自積層片之膜狀接著劑側或樹脂膜側的上方往下俯視積層片時，膜狀接著劑及樹脂膜的表面積可為同等或大致同等，於本實施形態的積層片中，亦可係膜狀接著劑的表面積小於樹脂膜的表面積，樹脂膜的一部分區域露出。該情形時，例如亦可係至少樹脂膜的寬度方向的周緣部未由膜狀接著劑被覆而露出。此種積層片亦可於該樹脂膜的露出面具備上述之治具用接著劑層。For example, when the laminate sheet is viewed from above the film adhesive side or the resin film side of the laminate sheet, the surface area of the film adhesive and the resin film may be the same or approximately the same. In the laminate sheet of this embodiment, The surface area of the film-like adhesive may be smaller than that of the resin film, and a part of the resin film is exposed. In this case, for example, at least the peripheral portion in the width direction of the resin film may be exposed without being covered with the film-like adhesive. Such a laminated sheet may be provided with the adhesive layer for jigs mentioned above on the exposed surface of this resin film.

圖3係以示意方式表示本發明的一實施形態的複合片的一例之剖視圖。此處所示之複合片101係具備膜狀接著劑13、及設置於膜狀接著劑13的第2面13b上之切割片10，切割片10具備基材11、及設置於基材11的一面(本說明書中，有時稱為「第1面」)11a上之黏著劑層12，黏著劑層12配置於基材11與膜狀接著劑13之間而構成。換言之，複合片101係基材11、黏著劑層12及膜狀接著劑13依序於這些層的厚度方向上積層而構成。切割片10之膜狀接著劑13側的面(本說明書中，有時稱為「第1面」)10a與黏著劑層12中之與基材11側為相反側的面(本說明書中，有時稱為「第1面」)12a相同。Fig. 3 is a cross-sectional view schematically showing an example of a composite sheet according to an embodiment of the present invention. The composite sheet 101 shown here includes a film adhesive 13 and a dicing sheet 10 provided on the second surface 13b of the film adhesive 13. The dicing sheet 10 includes a substrate 11 and a dicing sheet 10 provided on the substrate 11 The adhesive layer 12 on one side (in this specification, sometimes referred to as the "first side") 11a is formed by disposing the adhesive layer 12 between the base material 11 and the film-like adhesive 13. In other words, the composite sheet 101 is formed by stacking the base material 11, the adhesive layer 12, and the film-like adhesive 13 in order in the thickness direction of these layers. The surface of the dicing sheet 10 on the side of the film-like adhesive 13 (in this specification, sometimes referred to as the "first surface") 10a and the surface of the adhesive layer 12 opposite to the substrate 11 side (in this specification, Sometimes referred to as "the first side") 12a is the same.

複合片101進而於膜狀接著劑13上具備剝離膜15。於複合片101中，於基材11的第1面11a積層有黏著劑層12，於黏著劑層12的第1面12a的整面或大致整面積層有膜狀接著劑13，於膜狀接著劑13的第1面13a的整面或大致整面積層有剝離膜15。The composite sheet 101 further includes a release film 15 on the film-like adhesive 13. In the composite sheet 101, an adhesive layer 12 is laminated on the first surface 11a of the base material 11, and a film-like adhesive 13 is layered on the entire surface or substantially the entire area of the first surface 12a of the adhesive layer 12. The release film 15 is layered on the entire surface or substantially the entire area of the first surface 13a of the adhesive 13.

切割片10亦可為公知的切割片。對於切割片10中的基材11及黏著劑層12依序進行說明。The cutting piece 10 may also be a well-known cutting piece. The base material 11 and the adhesive layer 12 in the dicing sheet 10 will be described in order.

切割片10中的基材11為片狀或膜狀，作為該切割片10的構成材料，例如可列舉各種樹脂。作為切割片10的構成材料之前述樹脂，可列舉與作為前述積層片中的前述樹脂膜的構成材料之樹脂相同的樹脂。The base material 11 in the dicing sheet 10 has a sheet shape or a film shape, and as a constituent material of the dicing sheet 10, various resins can be cited, for example. The resin as the constituent material of the dicing sheet 10 includes the same resin as the resin as the constituent material of the resin film in the laminated sheet.

構成基材之樹脂可僅為1種，亦可為2種以上，於為2種以上之情形時，這些的組合及比率可任意選擇。The resin constituting the base material may be only one type, or two or more types. In the case of two or more types, the combination and ratio of these can be arbitrarily selected.

基材可由1層(單層)所構成，亦可由2層以上之複數層所構成，於由複數層所構成之情形時，這些複數層相互可相同亦可不同，這些複數層的組合並無特別限定。The base material can be composed of one layer (single layer) or two or more layers. In the case of multiple layers, these multiple layers may be the same or different from each other. There is no combination of these multiple layers. Specially limited.

基材11的厚度較佳為50μm至300μm，更佳為60μm至150μm。藉由基材11的厚度為此種範圍，複合片101的可撓性、及對貼附對象物之貼附性進一步提高。此處，所謂「基材的厚度」，意指基材整體的厚度，例如所謂由複數層所構成之基材的厚度，意指構成基材之全部層的合計的厚度。The thickness of the substrate 11 is preferably 50 μm to 300 μm, more preferably 60 μm to 150 μm. When the thickness of the base material 11 is in such a range, the flexibility of the composite sheet 101 and the adhesion to the adhesion target are further improved. Here, the "thickness of the substrate" means the thickness of the entire substrate. For example, the thickness of the substrate composed of a plurality of layers means the total thickness of all the layers constituting the substrate.

基材11較佳為厚度精度高，亦即較佳為無論部位如何厚度不均皆得到抑制。作為上述之構成材料中可用於構成此種厚度精度高之基材之材料，例如可列舉：聚乙烯、聚乙烯以外的聚烯烴、聚對苯二甲酸乙二酯、乙烯-乙酸乙烯酯共聚物等。The base material 11 preferably has high thickness accuracy, that is, it is preferable that the thickness unevenness is suppressed regardless of the location. Among the above-mentioned constituent materials, materials that can be used to form such a substrate with high thickness accuracy include, for example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, and ethylene-vinyl acetate copolymers. Wait.

基材11中，除前述樹脂等主要構成材料以外，亦可含有填充材料、著色劑、抗靜電劑、抗氧化劑、有機潤滑劑、觸媒、軟化劑(塑化劑)等公知的各種添加劑。The base material 11 may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the aforementioned main constituent materials such as resins.

基材11可為透明，亦可為不透明，還可根據目的而著色，還可被其他層所蒸鍍。The substrate 11 may be transparent or opaque, may be colored according to the purpose, and may be vapor-deposited by other layers.

為了提高基材11與設置於該基材11上之其他層(此處為黏著劑層12)等之密接性，亦可對基材11的表面實施如下處理：利用噴砂處理、溶劑處理等之凹凸化處理；電暈放電處理、電子束照射處理、電漿處理、臭氧／紫外線照射處理、火焰處理、鉻酸處理、熱風處理等氧化處理等。另外，基材11的表面亦可經實施底塗處理。另外，基材11亦可具有抗靜電塗層、於將複合片重疊保存時防止基材11接著於其他片或基材11接著於吸附台之層等。In order to improve the adhesion between the substrate 11 and other layers (here, the adhesive layer 12) provided on the substrate 11, the surface of the substrate 11 can also be treated as follows: sandblasting, solvent treatment, etc. Concave-convex treatment; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment and other oxidation treatments. In addition, the surface of the substrate 11 may be subjected to primer treatment. In addition, the substrate 11 may also have an antistatic coating to prevent the substrate 11 from adhering to other sheets or the substrate 11 from adhering to the layer of the suction table when the composite sheet is stacked and stored.

基材11可利用公知的方法製造。例如，含有樹脂之基材11可藉由將含有前述樹脂之樹脂組成物進行成形而製造。The base material 11 can be manufactured by a well-known method. For example, the resin-containing substrate 11 can be manufactured by molding a resin composition containing the aforementioned resin.

切割片10中的黏著劑層12為片狀或膜狀，含有黏著劑。作為前述黏著劑，例如可列舉：丙烯酸系樹脂、胺基甲酸酯系樹脂、橡膠系樹脂、聚矽氧系樹脂、環氧系樹脂、聚乙烯醚、聚碳酸酯、酯系樹脂等黏著性樹脂，較佳為丙烯酸系樹脂。The adhesive layer 12 in the dicing sheet 10 has a sheet or film shape and contains an adhesive. Examples of the aforementioned adhesives include: acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ether, polycarbonate, ester resins, etc. The resin is preferably an acrylic resin.

此外，本說明書中，「黏著性樹脂」包括具有黏著性之樹脂及具有接著性之樹脂兩者。例如，前述黏著性樹脂不僅包括樹脂本身具有黏著性之樹脂，亦包括藉由與添加劑等其他成分併用而顯示黏著性之樹脂、及藉由存在熱或水等觸發(trigger)而顯示接著性之樹脂等。In addition, in this specification, "adhesive resin" includes both adhesive resin and adhesive resin. For example, the aforementioned adhesive resins include not only resins with adhesive properties, but also resins that exhibit adhesiveness when used in combination with other ingredients such as additives, and those that exhibit adhesiveness by the presence of heat or water as a trigger. Resin etc.

黏著劑層12可由1層(單層)所構成，亦可由2層以上之複數層所構成，於由複數層所構成之情形時，這些複數層相互可相同亦可不同，這些複數層的組合並無特別限定。The adhesive layer 12 may be composed of one layer (single layer), or may be composed of two or more layers. When composed of multiple layers, these multiple layers may be the same or different from each other. The combination of these multiple layers It is not particularly limited.

黏著劑層12的厚度並無特別限定，較佳為1μm至100μm，更佳為1μm至60μm，尤佳為1μm至30μm。此處，所謂「黏著劑層的厚度」，意指黏著劑層整體的厚度，例如所謂由複數層所構成之黏著劑層的厚度，意指構成黏著劑層之全部層的合計的厚度。The thickness of the adhesive layer 12 is not particularly limited, and is preferably 1 μm to 100 μm, more preferably 1 μm to 60 μm, and particularly preferably 1 μm to 30 μm. Here, the "thickness of the adhesive layer" means the thickness of the entire adhesive layer. For example, the thickness of an adhesive layer composed of a plurality of layers means the total thickness of all layers constituting the adhesive layer.

黏著劑層12可使用能量線硬化性黏著劑而形成，亦可使用非能量線硬化性黏著劑而形成。亦即，黏著劑層12可為能量線硬化性及非能量線硬化性之任一種。能量線硬化性的黏著劑層12能夠容易地調節於硬化前及硬化後的物性。例如，藉由使能量線硬化性的黏著劑層12硬化，能夠容易地調節該黏著劑層12對貼附對象物之黏著力。The adhesive layer 12 may be formed using an energy ray curable adhesive, or may be formed using a non-energy ray curable adhesive. That is, the adhesive layer 12 may be either energy ray curable or non-energy ray curable. The energy-ray-curable adhesive layer 12 can easily adjust the physical properties before and after curing. For example, by curing the energy-ray-curable adhesive layer 12, the adhesive force of the adhesive layer 12 to the object to be attached can be easily adjusted.

黏著劑層12可使用含有黏著劑之黏著劑組成物而形成。例如，於黏著劑層12之形成對象面塗敷黏著劑組成物，並根據需要使之乾燥，藉此能夠於目標部位形成黏著劑層12。黏著劑組成物中的常溫下不會氣化的成分彼此的含量之比率通常與黏著劑層12中的前述成分彼此的含量之比率相同。本說明書中，所謂「常溫」，意指不特別冷或特別熱的溫度，亦即平常的溫度，例如可列舉15℃至25℃之溫度等。The adhesive layer 12 can be formed using an adhesive composition containing an adhesive. For example, the adhesive composition is applied to the surface to be formed of the adhesive layer 12, and dried as necessary, whereby the adhesive layer 12 can be formed on the target site. The ratio of the contents of the components that do not vaporize at room temperature in the adhesive composition is usually the same as the ratio of the contents of the aforementioned components in the adhesive layer 12. In this specification, the term "normal temperature" means a temperature that is not particularly cold or particularly hot, that is, a normal temperature, for example, a temperature of 15°C to 25°C.

利用公知的方法塗敷黏著劑組成物即可，例如可列舉使用以下各種塗佈機之方法：氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥刀塗佈機、簾幕式塗佈機、模具塗佈機、刀式塗佈機、絲網塗佈機、Meyer棒式塗佈機、接觸式塗佈機等。The adhesive composition can be applied by a known method. For example, the following methods can be cited: air knife coater, knife coater, bar coater, gravure coater, roll coater Cloth machine, roll knife coater, curtain coater, die coater, knife coater, screen coater, Meyer bar coater, contact coater, etc.

於基材11上設置黏著劑層12之情形時，例如於基材11上塗敷黏著劑組成物，並根據需要使之乾燥，藉此於基材11上積層黏著劑層12即可。另外，於基材11上設置黏著劑層12之情形時，例如亦可藉由下述方式於基材11上積層黏著劑層12：於剝離膜上塗敷黏著劑組成物，並根據需要使之乾燥，藉此於剝離膜上預先形成黏著劑層12，使該黏著劑層12的露出面與基材11的一表面(此處為第1面11a)貼合。該情形時的剝離膜於複合片101的製造過程或使用過程中的任一時間點移除即可。When the adhesive layer 12 is provided on the substrate 11, for example, an adhesive composition is coated on the substrate 11 and dried as required, thereby laminating the adhesive layer 12 on the substrate 11. In addition, when the adhesive layer 12 is provided on the substrate 11, for example, the adhesive layer 12 can also be laminated on the substrate 11 by applying the adhesive composition on the release film and making it as needed By drying, an adhesive layer 12 is formed in advance on the release film, and the exposed surface of the adhesive layer 12 is bonded to one surface of the substrate 11 (here, the first surface 11a). In this case, the release film may be removed at any point in the manufacturing process or use process of the composite sheet 101.

於黏著劑層12為能量線硬化性之情形時，作為能量線硬化性的黏著劑組成物，例如可列舉以下之黏著劑組成物等：黏著劑組成物(I-1)，含有非能量線硬化性的黏著性樹脂(I-1a)(以下，有時簡稱為「黏著性樹脂(I-1a)」)及能量線硬化性化合物；黏著劑組成物(I-2)，含有於前述黏著性樹脂(I-1a)的側鏈導入有不飽和基之能量線硬化性的黏著性樹脂(I-2a)(以下，有時簡稱為「黏著性樹脂(I-2a)」)；黏著劑組成物(I-3)，含有前述黏著性樹脂(I-2a)及能量線硬化性化合物。In the case where the adhesive layer 12 is energy ray curable, as an energy ray curable adhesive composition, for example, the following adhesive composition etc. can be cited: the adhesive composition (I-1) contains non-energy rays Curable adhesive resin (I-1a) (hereinafter sometimes referred to as "adhesive resin (I-1a)") and energy ray curable compound; adhesive composition (I-2), contained in the aforementioned adhesive Adhesive resin (I-2a) (hereinafter, sometimes referred to as "adhesive resin (I-2a)") with energy ray curable resin with unsaturated groups introduced into the side chain of the adhesive resin (I-1a); The composition (I-3) contains the aforementioned adhesive resin (I-2a) and an energy ray curable compound.

於黏著劑層12為非能量線硬化性之情形時，作為非能量線硬化性的黏著劑組成物，例如可列舉含有前述黏著性樹脂(I-1a)之黏著劑組成物(I-4)等。When the adhesive layer 12 is non-energy-ray-curable, as the non-energy-ray-curable adhesive composition, for example, an adhesive composition (I-4) containing the aforementioned adhesive resin (I-1a) Wait.

剝離膜15與圖1所示之第1剝離膜151或第2剝離膜152相同。The release film 15 is the same as the first release film 151 or the second release film 152 shown in FIG. 1.

並不限於複合片101之情形，於本實施形態的複合片中，剝離膜(例如圖3所示之剝離膜15)為任意的構成，本實施形態的複合片可具備亦可不具備剝離膜。It is not limited to the case of the composite sheet 101. In the composite sheet of this embodiment, the release film (for example, the release film 15 shown in FIG. 3) has an arbitrary structure, and the composite sheet of this embodiment may or may not have a release film.

複合片101係以經移除剝離膜15之狀態，於膜狀接著劑13的第1面13a貼附對象物(例如晶片的電路形成面)而使用。The composite sheet 101 is used by attaching an object (for example, the circuit formation surface of a wafer) to the first surface 13a of the film-like adhesive 13 in a state where the release film 15 has been removed.

本實施形態的複合片不限定於圖3所示之複合片，亦可在無損本發明的效果之範圍內，將圖3所示之複合片的一部分構成變更或刪除，或者對前文說明之複合片進而追加其他構成。更具體而言，如下所述。The composite sheet of this embodiment is not limited to the composite sheet shown in FIG. 3, and a part of the composite sheet shown in FIG. 3 may be changed or deleted within a range that does not impair the effect of the present invention, or the composite sheet described above The sheet further adds other components. More specifically, it is as follows.

前文對具備由基材及黏著劑層積層而構成之切割片之複合片進行了說明，但本實施形態的複合片亦可具備僅由基材所構成之切割片。亦即，前述複合片亦可具備基材、及設置於前述基材的一面上之膜狀接著劑，於前述基材與前述膜狀接著劑之間不配置黏著劑層而構成。作為此種複合片，可列舉於圖2所示之積層片108中，樹脂膜19為基材(例如圖3所示之基材11)之複合片。In the foregoing, the composite sheet including the dicing sheet formed by laminating the base material and the adhesive has been described, but the composite sheet of the present embodiment may include the dicing sheet formed only of the base material. That is, the composite sheet may include a base material and a film-like adhesive provided on one surface of the base material, and the adhesive layer may not be arranged between the base material and the film-like adhesive. As such a composite sheet, in the laminated sheet 108 shown in FIG. 2, a composite sheet in which the resin film 19 is a base material (for example, the base material 11 shown in FIG. 3) can be cited.

前文對具備由基材及黏著劑層積層而構成之切割片之複合片進行了說明，但本實施形態的複合片亦可具備除基材及黏著劑層以外進而具備中間層而構成之切割片。作為此種切割片，例如可列舉：具備基材、設置於前述基材的一面上之黏著劑層、及設置於前述黏著劑層中之與前述基材側為相反側的面上之中間層之切割片。於使用此種切割片之情形時，複合片中，於前述黏著劑層與前述膜狀接著劑之間配置中間層。In the foregoing, the composite sheet including the dicing sheet composed of the base material and the adhesive layer is described, but the composite sheet of this embodiment may be provided with the dicing sheet composed of the intermediate layer in addition to the base material and the adhesive layer. . Examples of such a dicing sheet include: a base material, an adhesive layer provided on one surface of the base material, and an intermediate layer provided on the surface of the adhesive layer opposite to the base material side The cutting piece. When using such a dicing sheet, in the composite sheet, an intermediate layer is arranged between the adhesive layer and the film-like adhesive.

例如，本實施形態的複合片可於膜狀接著劑的第1面僅具備前述剝離膜，亦可於膜狀接著劑的第1面中周緣部附近的區域，具備用以將複合片固定於環狀框架等治具之治具用接著劑層。該情形時的治具用接著劑層與上文說明之治具用接著劑層相同。For example, the composite sheet of this embodiment may be provided with only the aforementioned release film on the first surface of the film-like adhesive, or may be provided in the area near the peripheral edge of the first surface of the film-like adhesive for fixing the composite sheet to Adhesive layer for jigs such as ring frames. The adhesive layer for the jig in this case is the same as the adhesive layer for the jig described above.

例如，於自複合片之膜狀接著劑側或切割片側的上方往下俯視複合片時，膜狀接著劑及切割片的表面積可為同等或大致同等，於本實施形態的複合片中，亦可係膜狀接著劑的表面積小於切割片的表面積，切割片(例如黏著劑層)的一部分區域露出。該情形時，例如亦可係至少切割片的寬度方向的周緣部未由膜狀接著劑被覆而露出。此種複合片亦可於該切割片的露出面具備上述之治具用接著劑層。For example, when looking down on the composite sheet from above the film adhesive side or the dicing sheet side of the composite sheet, the surface area of the film adhesive and the dicing sheet may be the same or approximately the same. In the composite sheet of this embodiment, The surface area of the film-like adhesive is smaller than the surface area of the dicing sheet, and a part of the dicing sheet (for example, the adhesive layer) is exposed. In this case, for example, at least the peripheral edge part in the width direction of the dicing piece may be exposed without being covered with a film-like adhesive. Such a composite sheet may be provided with the aforementioned adhesive layer for jigs on the exposed surface of the dicing sheet.

前文中，作為構成複合片之層，表示了基材、黏著劑層、中間層、膜狀接著劑、治具用接著劑層及剝離膜，但本實施形態的複合片亦可具備不符合這些任一層之其他層。於前述複合片具備前述其他層之情形時，前述其他層的配置位置並無特別限定。In the foregoing, as the layers constituting the composite sheet, the base material, the adhesive layer, the intermediate layer, the film-like adhesive, the jig adhesive layer, and the release film are shown. However, the composite sheet of this embodiment may have non-compliance with these Any other layer. When the said composite sheet is equipped with the said other layer, the arrangement position of the said other layer is not specifically limited.

本實施形態的複合片中，各層的大小及形狀可根據目的任意選擇。In the composite sheet of this embodiment, the size and shape of each layer can be arbitrarily selected according to the purpose.

◇積層片(膜狀接著劑)之使用方法 [積層體及其製造方法] 本實施形態的積層片中的膜狀接著劑例如可用作用以對感測器等晶片的電路形成面接著透光性罩之膜。更具體而言，藉由使用前述膜狀接著劑，能夠製造如下之積層體：具備晶片、設置於前述晶片的電路形成面上之膜狀接著劑、及設置於前述膜狀接著劑中之與前述晶片側為相反側的面上之透光性罩而構成。◇How to use laminated sheet (film adhesive) [Laminate and its manufacturing method] The film-like adhesive in the laminated sheet of this embodiment can be used, for example, to act as a film for bonding a light-transmitting cover to the circuit forming surface of a chip such as a sensor. More specifically, by using the aforementioned film-like adhesive, it is possible to manufacture a laminate including a chip, a film-like adhesive provided on the circuit forming surface of the aforementioned chip, and a film-like adhesive provided in the aforementioned film-like adhesive. The aforementioned wafer side is constituted by a translucent cover on the opposite surface.

圖4係以示意方式表示前述積層體的一例之剖視圖。此處所示之積層體801係具備晶片8、設置於晶片8的電路形成面8a上之膜狀接著劑13、及設置於膜狀接著劑13中之與晶片8側為相反側的面(第1面)13a上之透光性罩7而構成。Fig. 4 is a cross-sectional view schematically showing an example of the aforementioned laminate. The laminated body 801 shown here includes a wafer 8, a film adhesive 13 provided on the circuit forming surface 8a of the wafer 8, and a surface provided on the film adhesive 13 on the opposite side to the wafer 8 side ( The first surface) 13a is constituted by a translucent cover 7.

積層體801中，晶片8與膜狀接著劑13之各自對向的面，亦即晶片8的電路形成面8a與膜狀接著劑13之晶片8側的面(第2面)13b直接接觸。另外，膜狀接著劑13與透光性罩7之各自對向的面，亦即膜狀接著劑13的第1面13a與透光性罩7之膜狀接著劑13側的面(本說明書中，有時稱為「第2面」)7b直接接觸。如此，積層體801係晶片8、膜狀接著劑13、及透光性罩7依序於這些層的厚度方向上積層，晶片8的電路形成面8a配置於膜狀接著劑13側而構成。In the layered body 801, the respective facing surfaces of the wafer 8 and the film adhesive 13, that is, the circuit forming surface 8a of the wafer 8 and the surface (second surface) 13b on the wafer 8 side of the film adhesive 13 are in direct contact. In addition, the respective opposing surfaces of the film adhesive 13 and the translucent cover 7, that is, the first surface 13a of the film adhesive 13 and the surface on the film adhesive 13 side of the translucent cover 7 (this specification , Sometimes referred to as "the second surface") 7b is in direct contact. In this way, the laminated body 801 is composed of the wafer 8, the film-like adhesive 13, and the translucent cover 7 sequentially stacked in the thickness direction of these layers, and the circuit forming surface 8a of the wafer 8 is arranged on the film-like adhesive 13 side.

積層體801中的膜狀接著劑13例如係於圖1所示之積層片109中經移除第1剝離膜151及第2剝離膜152所得，或者於圖2所示之積層片108中經移除樹脂膜19所得。The film-like adhesive 13 in the laminate 801 is, for example, obtained by removing the first release film 151 and the second release film 152 in the laminate sheet 109 shown in FIG. 1, or may be obtained in the laminate sheet 108 shown in FIG. The resin film 19 is removed.

此外，圖4中省略圖示晶片8的電路。另外，符號7a表示透光性罩7中之與前述第2面7b為相反側的面(本說明書中，有時稱為「第1面」)。In addition, the circuit of the wafer 8 is omitted in FIG. 4. In addition, the symbol 7a indicates the surface of the translucent cover 7 on the opposite side to the aforementioned second surface 7b (in this specification, it may be referred to as the "first surface").

透光性罩7能夠保護晶片8的電路形成面8a，並且能夠自透光性罩7的第1面7a側的外部視認透光性罩7的第2面7b側的外部。另一方面，膜狀接著劑13具有上述之透光性。因此，積層體801中，經由透光性罩7及膜狀接著劑13(隔著透光性罩7及膜狀接著劑13)，能夠視認存在於晶片8的電路形成面8a之視覺資訊。進而，如上所述，膜狀接著劑13於加熱前後透光性高，且著色得到抑制。因此，積層體801能夠穩定且高精度地視認晶片8上的視覺資訊。The translucent cover 7 can protect the circuit forming surface 8a of the wafer 8 and can view the outside on the second surface 7b side of the translucent cover 7 from the outside on the first surface 7a side of the translucent cover 7. On the other hand, the film adhesive 13 has the above-mentioned translucency. Therefore, in the laminated body 801, the visual information existing on the circuit forming surface 8a of the chip 8 can be visually recognized through the translucent cover 7 and the film-like adhesive 13 (through the translucent cover 7 and the film-like adhesive 13). Furthermore, as described above, the film-like adhesive 13 has high translucency before and after heating, and coloring is suppressed. Therefore, the laminated body 801 can visually recognize the visual information on the chip 8 stably and accurately.

作為晶片8，例如可使用指紋感測器，該情形時，積層體801可用作指紋感測器模組。As the chip 8, for example, a fingerprint sensor can be used. In this case, the laminated body 801 can be used as a fingerprint sensor module.

使用前述膜狀接著劑之前述積層體並不限定於圖4所示之積層體，亦可在無損本發明的效果之範圍內，將圖4所示之積層體的一部分構成變更或刪除，或者對前文說明之積層體進而追加其他構成。The laminated body using the film-like adhesive is not limited to the laminated body shown in FIG. 4, and a part of the laminated body shown in FIG. 4 may be changed or deleted within a range that does not impair the effects of the present invention, or Other structures are added to the laminate described above.

前述積層體例如可藉由於前述膜狀接著劑的一面(第2面)貼合晶片的電路形成面，於前述膜狀接著劑的另一面(第1面)貼合透光性罩而製造。The laminated body can be manufactured by, for example, bonding one surface (second surface) of the film-like adhesive to the circuit forming surface of the chip, and bonding a translucent cover to the other surface (first surface) of the film-like adhesive.

◇複合片之使用方法 [積層體及其製造方法] 本實施形態的複合片可利用與公知的切晶黏晶片之情形相同的方法使用。圖5係用於以示意方式說明本實施形態的複合片之使用方法的一例之剖視圖。此處對使用圖3所示之複合片101之情形進行表示。◇How to use composite sheet [Laminate and its manufacturing method] The composite sheet of this embodiment can be used in the same way as in the case of a known die-cut wafer. Fig. 5 is a cross-sectional view for schematically explaining an example of the method of using the composite sheet of the present embodiment. Here, the case where the composite sheet 101 shown in FIG. 3 is used is shown.

如此處所示，複合片101係於經移除剝離膜15後，將膜狀接著劑13的第1面13a貼附於晶片8的電路形成面8a而使用。As shown here, the composite sheet 101 is used after the release film 15 is removed, and the first surface 13a of the film-like adhesive 13 is attached to the circuit forming surface 8a of the wafer 8.

於將複合片101貼附於晶片8之後，例如將晶片8進行切割而單片化，將膜狀接著劑13沿著經單片化的晶片8的外周切斷。此時，晶片8之單片化及膜狀接著劑13之切斷可利用公知的方法進行，例如可同時進行這些操作，亦可將晶片8單片化後，另行將膜狀接著劑13切斷。After the composite sheet 101 is attached to the wafer 8, for example, the wafer 8 is diced and singulated, and the film-like adhesive 13 is cut along the outer periphery of the singulated wafer 8. At this time, the singulation of the wafer 8 and the cutting of the film-like adhesive 13 can be performed by a known method. For example, these operations can be performed simultaneously, or after the wafer 8 is singulated, the film-like adhesive 13 can be cut separately. Off.

繼而，將單片化後的晶片8連同切斷後的膜狀接著劑13一起自切割片10扯離而進行拾取。於黏著劑層12為能量線硬化性之情形時，使黏著劑層12進行能量線硬化，使對膜狀接著劑13之黏著力降低後，進行拾取，藉此能夠更容易地進行拾取。Then, the singulated wafer 8 is pulled away from the dicing sheet 10 together with the cut film-like adhesive 13 and picked up. In the case where the adhesive layer 12 is energy ray curable, the adhesive layer 12 is energy ray hardened to reduce the adhesive force to the film-like adhesive 13 and then picked up, thereby making it easier to pick up.

繼而，於切斷及拾取後的膜狀接著劑13的第2面貼合透光性罩，藉此能夠製造前述積層體(例如圖4所示之積層體801)。Then, a translucent cover is attached to the second surface of the film-like adhesive 13 after cutting and pickup, thereby making it possible to manufacture the aforementioned laminate (for example, the laminate 801 shown in FIG. 4).

此處對如此般將複合片中的膜狀接著劑貼合於晶片，於晶片之單片化後及膜狀接著劑之切斷後，對於該切斷後的膜狀接著劑貼合透光性罩之情形進行了說明，但晶片及透光性罩對膜狀接著劑之貼合的順序亦可相反。亦即，亦可藉由下述方式製造前述積層體(例如圖4所示之積層體801)：將膜狀接著劑的第1面貼附於透光性罩的第2面後，將透光性罩進行切割而單片化，切斷膜狀接著劑，根據需要使黏著劑層進行能量線硬化後，將單片化後的透光性罩連同切斷後的膜狀接著劑一起自切割片扯離而進行拾取，繼而於該切斷及拾取後的膜狀接著劑的第1面貼合晶片。 [實施例]Here, the film-like adhesive in the composite sheet is bonded to the wafer in this way, and after the singulation of the wafer and the cutting of the film-like adhesive, a translucent cover is attached to the cut film-like adhesive The situation has been described, but the order of bonding the wafer and the translucent cover to the film adhesive may be reversed. That is, the aforementioned laminated body (for example, the laminated body 801 shown in FIG. 4) can also be manufactured by the following method: after the first surface of the film-like adhesive is attached to the second surface of the translucent cover, the transparent cover The optical cover is cut into individual pieces, the film-like adhesive is cut, and the adhesive layer is cured by energy ray if necessary, and then the singulated light-transmitting cover is self-cut with the cut film-like adhesive. The sheet is pulled apart and picked up, and then the wafer is bonded to the first surface of the film-like adhesive after the cutting and pickup. [Example]

以下，藉由具體的實施例對本發明更詳細地進行說明。但，本發明並不受以下所示之實施例的任何限定。Hereinafter, the present invention will be described in more detail with specific examples. However, the present invention is not limited at all by the examples shown below.

[接著劑組成物的製造原料] 以下表示本實施例及比較例中用於製造接著劑組成物之原料。[Materials for manufacturing adhesive composition] The raw materials used in the production of the adhesive composition in the present examples and comparative examples are shown below.

[丙烯酸系樹脂(a)] (a)-1：使丙烯酸甲酯(85質量份)及丙烯酸2-羥基乙酯(15質量份)共聚而獲得之丙烯酸系樹脂(重量平均分子量800000、玻璃轉移溫度6℃)。 (a)-2：使丙烯酸甲酯(95質量份)及丙烯酸2-羥基乙酯(5質量份)共聚而獲得之丙烯酸系樹脂(重量平均分子量800000、玻璃轉移溫度9℃)。 (a)-3：具有環氧基之丙烯酸酯共聚物(重量平均分子量850000、玻璃轉移溫度12℃)。 [環氧化合物(b1)] (b1)-1：加成有丙烯醯基之甲酚酚醛清漆型環氧樹脂(日本化藥公司製造的「CNA147」，環氧當量518g/eq、數量平均分子量2100、不飽和基的含量與環氧基的含量為等量) (b1)-2：氫化雙酚A型環氧樹脂(共榮社化學公司製造的「Epolight 4000」，環氧當量310g/eq至340g/eq) [酚樹脂(b2)] (b2)-1：芳烷基型酚樹脂(Air Water Chemical公司製造的「HE100C-10」) [硬化促進劑(c)] (c)-1：三苯基膦(北興化學工業公司製造) [填充材料(d)] (d)-1：經甲基丙烯醯基修飾之球狀二氧化矽(Admatechs公司製造的「YA050C-MJE」，平均粒徑50nm) (d)-2：經環氧基修飾之球狀二氧化矽(Admatechs公司製造的「YA050C-MKK」，平均粒徑50nm) (d)-3：經環氧基修飾之二氧化矽填料(Admatechs公司製造的「SC2050MA」，平均粒徑500nm) [交聯劑(f)] (f)-1：三羥甲基丙烷之甲苯二異氰酸酯三聚物加成物(東曹公司製造的「Coronate L」) (f)-2：三羥甲基丙烷之異佛爾酮二異氰酸酯三聚物加成物(三井化學公司製造的「D-140N」) [磷系抗氧化劑(z)] (z)-1：雙(癸基)季戊四醇二亞磷酸酯(城北化學工業公司製造的「JPE-10」，脂肪族系亞磷酸酯) (z)-2：亞磷酸三(2-乙基己基)酯(城北化學工業公司製造的「JP-308E」，脂肪族系亞磷酸酯) [其他抗氧化劑(y)] (y)-1：1,3,5-三(3,5-二第三丁基-4-羥基苄基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮(ADEKA公司製造的「AO-20」，受阻酚)[Acrylic resin (a)] (a)-1: Acrylic resin obtained by copolymerizing methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass) (weight average molecular weight 800000, glass transition temperature 6°C). (a)-2: Acrylic resin obtained by copolymerizing methyl acrylate (95 parts by mass) and 2-hydroxyethyl acrylate (5 parts by mass) (weight average molecular weight 800000, glass transition temperature 9°C). (a)-3: Acrylate copolymer with epoxy group (weight average molecular weight 850,000, glass transition temperature 12°C). [Epoxy Compound (b1)] (b1)-1: Cresol novolac type epoxy resin ("CNA147" manufactured by Nippon Kayaku Co., Ltd.) with addition of acrylic groups, epoxy equivalent 518g/eq, number average molecular weight 2100, unsaturated group content and The content of epoxy groups is equal) (b1)-2: Hydrogenated bisphenol A epoxy resin ("Epolight 4000" manufactured by Kyoeisha Chemical Company, epoxy equivalent 310g/eq to 340g/eq) [Phenolic resin (b2)] (b2)-1: Aralkyl phenol resin ("HE100C-10" manufactured by Air Water Chemical) [Hardening accelerator (c)] (c)-1: Triphenylphosphine (manufactured by Beixing Chemical Industry Co., Ltd.) [Filling material (d)] (d)-1: Spherical silica modified with methacrylic acid group ("YA050C-MJE" manufactured by Admatechs, with an average particle size of 50nm) (d)-2: Spherical silica modified with epoxy group ("YA050C-MKK" manufactured by Admatechs, with an average particle size of 50nm) (d)-3: Silica filler modified with epoxy group ("SC2050MA" manufactured by Admatechs, average particle size 500nm) [Crosslinker (f)] (f)-1: Toluene diisocyanate trimer adduct of trimethylolpropane ("Coronate L" manufactured by Tosoh Corporation) (f)-2: Trimethylolpropane isophorone diisocyanate trimer adduct ("D-140N" manufactured by Mitsui Chemicals) [Phosphorus antioxidant (z)] (z)-1: Bis(decyl)pentaerythritol diphosphite ("JPE-10" manufactured by Johoku Chemical Industry Co., Ltd., aliphatic phosphite) (z)-2: Tris(2-ethylhexyl) phosphite ("JP-308E" manufactured by Johoku Chemical Industry Co., Ltd., aliphatic phosphite) [Other antioxidants (y)] (y)-1: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H, 5H)-Triketone ("AO-20" manufactured by ADEKA, hindered phenol)

[實施例1] [膜狀接著劑之製造] [接著劑組成物之製造] 使丙烯酸系樹脂(a)-1(58質量份)、環氧化合物(b1)-1(18質量份)、酚樹脂(b2)-1(3質量份)、填充材料(d)-1(20質量份)、交聯劑(f)-1(0.5質量份)及磷系抗氧化劑(z)-1(0.5質量份)溶解或分散於甲基乙基酮，於23℃進行攪拌，藉此獲得甲基乙基酮以外的全部成分的合計濃度為32質量%之接著劑組成物。此外，此處所示之甲基乙基酮以外的成分的調配量全部為不包含溶媒成分之目標物的調配量。[Example 1] [Manufacture of film adhesive] [Manufacture of Adhesive Composition] Acrylic resin (a)-1 (58 parts by mass), epoxy compound (b1)-1 (18 parts by mass), phenol resin (b2)-1 (3 parts by mass), filler (d)-1 ( 20 parts by mass), crosslinking agent (f)-1 (0.5 parts by mass), and phosphorus antioxidant (z)-1 (0.5 parts by mass) are dissolved or dispersed in methyl ethyl ketone, and stirred at 23°C. This obtained an adhesive composition in which the total concentration of all components other than methyl ethyl ketone was 32% by mass. In addition, all the compounding amounts of components other than methyl ethyl ketone shown here are the compounding amounts of the target substance which does not contain a solvent component.

[膜狀接著劑之製造] 使用聚對苯二甲酸乙二酯(PET；polyethylene terephthalate)製膜的單面藉由聚矽氧處理進行了剝離處理之剝離膜(琳得科公司製造的「SP-PET381031」，厚度38μm)，於該剝離膜的前述剝離處理面塗敷上述所獲得之接著劑組成物，於100℃加熱乾燥2分鐘，藉此形成厚度20μm之膜狀接著劑，獲得前述剝離膜及膜狀接著劑於這些層的厚度方向上積層而構成之接著片。[Manufacture of film adhesive] Use a polyethylene terephthalate (PET; polyethylene terephthalate) film made of a peel-off film ("SP-PET381031" made by Lindeco, thickness 38μm) that has been peeled off by silicone treatment on one side, The adhesive composition obtained above was applied to the release-treated surface of the release film, and heated and dried at 100°C for 2 minutes to form a film-like adhesive with a thickness of 20 μm. The release film and the film-like adhesive were obtained on these The layer is laminated in the thickness direction to form an adhesive sheet.

[膜狀接著劑之評價] [剪切強度之測定] 使用貼片機(琳得科公司製造的「Adwill RAD2500 m/12」)，於貼附溫度23℃、貼附速度20mm/s之條件下，將切割片(琳得科公司製造的「Adwill D-678」)貼附於6吋矽晶圓(厚度350μm)，將該切割片及矽晶圓之積層物固定於環狀框架。繼而，使用切割裝置(DISCO公司製造的「DFD6362」)，藉由切割刀片(DISCO公司製造的「NBC-ZH2050-SE27HECC」)，於刀片轉速30000rpm、切斷速度40mm/s之條件下，進行切割，獲得大小為2mm×2mm之複數個矽晶片(以下，有時稱為「矽晶片群」)。上述之切割片係基材及黏著劑層積層而構成，於切割時，藉由切割刀片切入至該切割片中的基材中的深度20μm之區域。[Evaluation of Film Adhesive] [Determination of Shear Strength] Using a placement machine ("Adwill RAD2500 m/12" manufactured by Lindeco), under the conditions of attaching temperature of 23℃ and attaching speed of 20mm/s, cut the slices ("Adwill D -678") is attached to a 6-inch silicon wafer (thickness 350μm), and the laminate of the dicing sheet and silicon wafer is fixed to the ring frame. Then, using a cutting device ("DFD6362" manufactured by DISCO), a cutting blade ("NBC-ZH2050-SE27HECC" manufactured by DISCO) was used to cut under the conditions of a blade rotation speed of 30,000 rpm and a cutting speed of 40 mm/s. , Obtain a plurality of silicon chips (hereinafter, sometimes referred to as "silicon chip group") with a size of 2mm×2mm. The above-mentioned dicing sheet is formed by laminating a base material and an adhesive. When cutting, the cutting blade is used to cut into the 20 μm depth region of the base material in the dicing sheet.

繼而，將上述所獲得之接著片一邊加熱至60℃，一邊藉由該接著片中的膜狀接著劑貼附於上述所獲得之矽晶片群。此時，接著片係貼附於矽晶片群中的矽晶片中與貼附有切割片之側為相反側的面(露出面)。然後，沿著矽晶片的外周，切斷該貼附後的接著片。藉由以上之步驟，獲得切割片、矽晶片及接著片依序於這些層的厚度方向上積層而構成且大小為2mm×2mm之積層物。Then, while heating the adhesive sheet obtained above to 60° C., the film-like adhesive in the adhesive sheet was attached to the silicon wafer group obtained above. At this time, the adhesive sheet is attached to the surface (exposed surface) on the side opposite to the side on which the dicing sheet is attached among the silicon wafers in the silicon wafer group. Then, the attached adhesive sheet is cut along the outer periphery of the silicon wafer. Through the above steps, a dicing wafer, a silicon wafer, and an adhesive wafer are sequentially stacked in the thickness direction of these layers to form a laminate with a size of 2mm×2mm.

繼而，自該積層物中的膜狀接著劑移除前述剝離膜，使用手動黏晶機，將新產生之膜狀接著劑的露出面貼附於大小為30mm×30mm且厚度為300μm之銅板的表面。此時，膜狀接著劑係藉由一邊加熱至125℃，一邊施加2.45N(250gf)之力壓抵於銅板而貼附。進而，將這些貼合而成之積層體於175℃加熱5小時，藉此獲得試片。Then, the release film was removed from the film-like adhesive in the laminate, and the exposed surface of the newly-produced film-like adhesive was attached to the copper plate with a size of 30mm×30mm and a thickness of 300μm using a manual die bonder. surface. At this time, the film-like adhesive was applied by pressing against the copper plate while heating to 125°C while applying a force of 2.45N (250gf). Furthermore, the laminated body formed by these bonding was heated at 175 degreeC for 5 hours, and the test piece was obtained.

繼而，使用萬能型黏結強度試驗機(Nordson Advanced Technology公司製造的「DAGE4000」)，於23℃之溫度條件下，藉由剪切工具(shear tool)，以200μm/s之速度，於前述試片的側面，對膜狀接著劑及矽晶片兩者，沿相對於膜狀接著劑對銅板之貼附面平行的方向施加力。然後，確認直至膜狀接著劑受到破壞為止所施加之力的最大值，採用該最大值作為膜狀接著劑的剪切強度(N/2mm□)。結果示於表1。Then, using a universal bonding strength tester ("DAGE4000" manufactured by Nordson Advanced Technology), at a temperature of 23°C, with a shear tool at a speed of 200μm/s, On the side surface of the film adhesive and silicon wafer, force is applied in a direction parallel to the attaching surface of the film adhesive to the copper plate. Then, the maximum value of the force applied until the film-like adhesive is broken is confirmed, and this maximum value is adopted as the shear strength (N/2mm□) of the film-like adhesive. The results are shown in Table 1.

[在光(400nm至800nm)之加熱前直線透過率之測定] 將上述所獲得之膜狀接著劑一邊於40℃加熱一邊貼附於玻璃製標本(厚度0.9mm)的一面。膜狀接著劑於剛製造後至該貼附之期間未進行加熱處理。繼而，將貼附後的膜狀接著劑中自玻璃製標本伸出之部分切斷，獲得相同大小的膜狀接著劑及玻璃製標本以這些層的周緣部的位置一致之狀態於這些層的厚度方向上積層而構成之試片(以下，稱為「加熱前試片」)。[Measurement of linear transmittance before heating of light (400nm to 800nm)] The film-like adhesive obtained above was applied to one side of a glass specimen (thickness 0.9 mm) while heating at 40°C. The film-like adhesive was not heat-treated during the period from immediately after manufacture to the application. Then, the part of the film-like adhesive that protruded from the glass specimen was cut to obtain the film-like adhesive of the same size and the glass specimen. The positions of the peripheral edges of these layers were aligned with those of these layers. A test piece (hereinafter referred to as a "test piece before heating") formed by layering in the thickness direction.

針對用於製作前述加熱前試片之玻璃製標本，於製作加熱前試片之前，預先使用分光光度計(Shimadzu公司製造的「UV-3101PC」)，測定光(400nm至800nm)之直線透過率(以下，稱為「基準直線透過率」)。針對上述所獲得之加熱前試片，亦利用相同的方法，測定光(400nm至800nm)之直線透過率。自加熱前試片在各波長下之光(400nm至800nm)之直線透過率的測定值減去在相同波長下之前述基準直線透過率的測定值，採用相減所獲得之值作為加熱前的膜狀接著劑在光(400nm至800nm)之直線透過率(亦即，前述加熱前直線透過率)。結果示於表1。For the glass specimen used to make the pre-heating test piece, before making the pre-heating test piece, use a spectrophotometer (“UV-3101PC” manufactured by Shimadzu Corporation) to measure the linear transmittance of light (400nm to 800nm) (Hereinafter referred to as "reference linear transmittance"). For the pre-heating test piece obtained above, the same method was used to measure the linear transmittance of light (400nm to 800nm). Subtract the measured value of the aforementioned reference linear transmittance at the same wavelength from the measured value of the linear transmittance of the test piece at each wavelength (400nm to 800nm) before heating, and use the value obtained by subtraction as the value before heating The linear transmittance of the film adhesive at light (400nm to 800nm) (that is, the linear transmittance before heating). The results are shown in Table 1.

[在光(400nm至800nm)之加熱後直線透過率之測定] 使用電爐，將測定上述在光(400nm至800nm)之加熱前直線透過率後的試片於260℃加熱10分鐘。繼而，將該加熱後的試片放置冷卻至與室溫相同的溫度。繼而，對於該加熱及放置冷卻後的試片(以下，稱為「加熱後試片」)，利用與上述之加熱前試片之情形相同的方法，測定在光(400nm至800nm)之直線透過率。自加熱後試片在各波長下之光(400nm至800nm)之直線透過率的測定值減去在相同波長下之前述基準直線透過率的測定值，採用相減所獲得之值作為加熱後的膜狀接著劑在光(400nm至800nm)之直線透過率(亦即，前述加熱後直線透過率)。結果示於表1。[Measurement of linear transmittance after heating with light (400nm to 800nm)] Using an electric furnace, the test piece after measuring the linear transmittance before heating with light (400 nm to 800 nm) was heated at 260° C. for 10 minutes. Then, the heated test piece was left to cool to the same temperature as room temperature. Then, for the test piece after heating and cooling (hereinafter referred to as "test piece after heating"), the linear transmission of light (400nm to 800nm) was measured using the same method as that of the test piece before heating. rate. After heating, the measured value of the linear transmittance of the light at each wavelength (400nm to 800nm) of the test piece is subtracted from the measured value of the aforementioned reference linear transmittance at the same wavelength, and the value obtained by subtraction is used as the value after heating The linear transmittance of the film adhesive at light (400nm to 800nm) (that is, the linear transmittance after heating). The results are shown in Table 1.

[基於RGB(Red Green Blue；紅綠藍)之加熱前的指紋識別性之評價] 於左手食指腹之前，配置數位相機(Canon公司製造的「IXY650」)，將左手食指腹的表面與相機透鏡的表面之間的距離調節為50mm，於該狀態以微距模式獲取左手食指的指紋的攝像資料(以下，稱為「基準攝像資料」)。維持該左手食指與數位相機之配置關係不變，於左手食指腹與數位相機之間進而配置前述加熱前試片。此時，以連結左手食指腹與數位相機之直線相對於前述加熱前試片中的玻璃製標本的露出面(亦即，和膜狀接著劑之貼附面為相反側的面)正交，且前述露出面成為數位相機側之方式，配置前述加熱前試片。於該條件下，利用與獲取前述基準攝像資料時相同的方法，以微距模式獲取左手食指的指紋的攝像資料(以下，稱為「加熱前透過攝像資料」)。[Based on the evaluation of RGB (Red Green Blue) fingerprint recognition before heating] Place a digital camera ("IXY650" manufactured by Canon) in front of the left index finger and adjust the distance between the surface of the left index finger and the surface of the camera lens to 50mm. In this state, the fingerprint of the left index finger is obtained in macro mode Camera data (hereinafter referred to as "reference camera data"). Maintaining the configuration relationship between the index finger of the left hand and the digital camera unchanged, the pre-heating test piece is further arranged between the pad of the index finger of the left hand and the digital camera. At this time, the straight line connecting the pad of the index finger of the left hand and the digital camera is orthogonal to the exposed surface of the glass specimen in the pre-heating test piece (that is, the surface opposite to the application surface of the film-like adhesive), In addition, the exposed surface becomes the digital camera side, and the pre-heating test piece is arranged. Under this condition, the same method as when acquiring the aforementioned reference imaging data is used to acquire the imaging data of the fingerprint of the left index finger in the macro mode (hereinafter referred to as "pre-heating imaging data").

使用繪圖軟體(Microsoft公司製造的「Paint」)，將上述所獲得之基準攝像資料及加熱前透過攝像資料展開，自各自的資料擷取指紋的山部與谷部的顏色，並以RGB數值化。自由加熱前透過攝像資料獲取之指紋的山部的R值減去由基準攝像資料獲取之指紋的山部的R值，採用相減所獲得之值作為加熱前評價時的指紋的山部的R值。利用與上述相同的方法，求出加熱前評價時的指紋的山部的G值及B值。利用與上述相同的方法，自由加熱前透過攝像資料獲取之指紋的谷部的R值減去由基準攝像資料獲取之指紋的谷部的R值，採用相減所獲得之值作為加熱前評價時的指紋的谷部的R值。利用與上述相同的方法，求出加熱前評價時的指紋的谷部的G值及B值。進而，算出前述山部的R值與前述谷部的R值之差的絕對值(以下，有時記載為「絕對值ΔR」)，算出前述山部的G值與前述谷部的G值之差的絕對值(以下，有時記載為「絕對值ΔG」)，算出前述山部的B值與前述谷部的B值之差的絕對值(以下，有時記載為「絕對值ΔB」)。Use drawing software ("Paint" made by Microsoft Corporation) to expand the above-obtained reference camera data and pre-heated camera data, extract the colors of the mountains and valleys of the fingerprint from the respective data, and digitize them with RGB . The R value of the mountain of the fingerprint obtained through the imaging data before free heating minus the R value of the fingerprint of the fingerprint acquired from the reference imaging data, and the value obtained by subtraction is used as the R value of the fingerprint of the fingerprint during the evaluation before heating value. Using the same method as described above, the G value and the B value of the peak of the fingerprint during the pre-heating evaluation were obtained. Using the same method as above, the R value of the valley of the fingerprint acquired through the imaging data before free heating minus the R value of the valley of the fingerprint acquired from the reference imaging data, and the value obtained by subtraction is used as the pre-heating evaluation The R value of the valley of the fingerprint. Using the same method as described above, the G value and B value of the valley portion of the fingerprint during the evaluation before heating were obtained. Furthermore, the absolute value of the difference between the R value of the mountain and the R value of the valley is calculated (hereinafter sometimes referred to as "absolute value ΔR"), and the difference between the G value of the mountain and the G value of the valley is calculated The absolute value of the difference (hereinafter sometimes referred to as "absolute value ΔG"), calculate the absolute value of the difference between the B value of the aforementioned mountain part and the aforementioned valley B value (hereinafter, sometimes referred to as "absolute value ΔB") .

基於這些算出值，依據下述基準，評價基於RGB之加熱前的膜狀接著劑的指紋識別性。結果示於表1。 (評價基準) A：絕對值ΔR、絕對值ΔG及絕對值ΔB中至少1種為10以上。 B：絕對值ΔR、絕對值ΔG及絕對值ΔB全部未達10，且絕對值ΔR、絕對值ΔG及絕對值ΔB中至少1種為5以上。 C：絕對值ΔR、絕對值ΔG及絕對值ΔB全部未達5。Based on these calculated values, the fingerprint recognition property of the film-like adhesive before heating based on RGB was evaluated based on the following criteria. The results are shown in Table 1. (Evaluation criteria) A: At least one of absolute value ΔR, absolute value ΔG, and absolute value ΔB is 10 or more. B: Absolute value ΔR, absolute value ΔG, and absolute value ΔB are all less than 10, and at least one of absolute value ΔR, absolute value ΔG, and absolute value ΔB is 5 or more. C: Absolute value ΔR, absolute value ΔG, and absolute value ΔB are all less than 5.

[基於RGB之加熱後的指紋識別性之評價] 除了使用前述加熱後試片代替前述加熱前試片之方面以外，利用與上述之「加熱前的指紋識別性之評價」之情形相同的方法，評價基於RGB之加熱後的膜狀接著劑的指紋識別性。更具體而言，於本評價時，獲取「加熱後透過攝像資料」代替前述加熱前透過攝像資料。另外，使用該加熱後透過攝像資料，代替加熱前評價時的指紋的山部的R值、G值及B值，求出加熱後評價時的指紋的山部的R值、G值及B值，代替加熱前評價時的指紋的谷部的R值、G值及B值，求出加熱後評價時的指紋的谷部的R值、G值及B值。進而，自這些R值、G值及B值算出加熱後評價時的絕對值ΔR、絕對值ΔG及絕對值ΔB來代替加熱前評價時的前述絕對值ΔR、絕對值ΔG及絕對值ΔB。結果示於表1。[Evaluation of fingerprint recognition after heating based on RGB] Except for using the aforementioned heated test piece instead of the aforementioned pre-heated test piece, the same method as in the case of "evaluation of fingerprint recognition before heating" described above was used to evaluate the fingerprints of the film adhesive after heating based on RGB Recognizability. More specifically, in this evaluation, "post-heating transmission imaging data" was acquired instead of the aforementioned pre-heating transmission imaging data. In addition, using the transmitted imaging data after heating, instead of the R value, G value, and B value of the peak of the fingerprint during evaluation before heating, the R value, G value, and B value of the peak of the fingerprint during evaluation after heating were obtained. Instead of the R, G, and B values of the valleys of the fingerprint during the evaluation before heating, the R, G, and B values of the valleys of the fingerprint during the evaluation after heating are obtained. Furthermore, the absolute value ΔR, absolute value ΔG, and absolute value ΔB in the evaluation after heating are calculated from these R value, G value, and B value instead of the aforementioned absolute value ΔR, absolute value ΔG, and absolute value ΔB in the evaluation before heating. The results are shown in Table 1.

[基於目視之加熱前的指紋識別性之評價] 隨機選定5名觀察者，利用以下所示之方法，1名1名地目視觀察指紋。亦即，於左手食指腹之前，配置1名觀察者，將左手食指腹的表面與觀察者的眼睛之間的距離調節為150mm，於該狀態直接目視觀察左手食指的指紋。維持該左手食指與觀察者之配置關係不變，於左手食指腹與觀察者之間進而配置前述加熱前試片。此時的前述加熱前試片的配置形態設為與上述之「基於RGB之加熱前的指紋識別性之評價」時的加熱前試片之情形相同。於該條件下，與如上述般直接目視觀察之情形同樣地，隔著前述加熱前試片，目視觀察左手食指的指紋。[Based on visual evaluation of fingerprint recognition before heating] Five observers are randomly selected, and one by one visually observes the fingerprints using the method shown below. That is, in front of the left index finger, an observer is arranged, the distance between the surface of the left index finger and the observer's eyes is adjusted to 150 mm, and the fingerprint of the left index finger is directly observed in this state. Keeping the arrangement relationship between the left index finger and the observer unchanged, the aforementioned pre-heating test piece is further arranged between the left index finger and the observer. The arrangement form of the test piece before heating at this time is the same as that of the test piece before heating in the aforementioned "evaluation of fingerprint recognition before heating based on RGB". Under this condition, as in the case of direct visual observation as described above, the fingerprint of the index finger of the left hand was visually observed through the test piece before heating.

藉由該方法，讓5名觀察者全員直接及隔著加熱前試片目視觀察指紋，由隔著加熱前試片時的指紋的觀看結果、與直接目視時的指紋的觀看結果之比較，依據下述基準，評價基於目視之加熱前的膜狀接著劑的指紋識別性。結果示於表1。表1的「指紋識別性」一欄中的括號內的數值表示「判定為於指紋的觀看結果無差異之觀察者的人數(人)」。 A：觀察者5名全員判定為於指紋的觀看結果無差異。 B：觀察者5名中4名判定為於指紋的觀看結果無差異。 C：觀察者5名中2名以上判定為指紋的顏色相互不同，於觀看結果有差異。With this method, all five observers are allowed to directly and visually observe the fingerprints through the pre-heating test piece. The comparison of the fingerprint observation result through the pre-heating test piece and the fingerprint observation result under direct visual inspection is based on The following criteria evaluated the fingerprint recognition property of the film-like adhesive before heating based on visual observation. The results are shown in Table 1. The numerical value in parentheses in the column of "fingerprint recognition" in Table 1 indicates "the number of observers (persons) judged to be indistinguishable from the fingerprint viewing result". A: All 5 observers judged that there is no difference in the result of fingerprint viewing. B: 4 out of 5 observers judged that there is no difference in the result of fingerprint viewing. C: Two or more of the 5 observers judged that the colors of the fingerprints are different from each other, and there is a difference in the viewing result.

[基於目視之加熱後的指紋識別性之評價] 除了使用前述加熱後試片代替前述加熱前試片之方面以外，利用與上述之「基於目視之加熱前的指紋識別性之評價」之情形相同的方法，評價基於目視之加熱後的膜狀接著劑的指紋識別性。結果示於表1。[Based on visual evaluation of fingerprint recognition after heating] Except for using the aforementioned heated test piece instead of the aforementioned pre-heated test piece, the same method as in the case of "Evaluation of Fingerprint Recognition before Heating Based on Visual Inspection" was used to evaluate the film-like adhesive after heating based on visual inspection. The fingerprint identification of the agent. The results are shown in Table 1.

[膜狀接著劑之製造及評價] [實施例2至實施例4] 除了以接著劑組成物的含有成分的種類及含量成為如表1所示之方式，變更製造接著劑組成物時的調配成分的種類及調配量之任一者或兩者之方面以外，利用與實施例1之情形相同的方法，製造膜狀接著劑並進行評價。結果示於表1。[Manufacturing and Evaluation of Film Adhesive] [Example 2 to Example 4] In addition to changing any one or both of the type and the amount of the compounding components when the adhesive composition is manufactured, the types and contents of the components contained in the adhesive composition are as shown in Table 1. In the same manner as in Example 1, a film-like adhesive was produced and evaluated. The results are shown in Table 1.

[比較例1至比較例5] 除了以接著劑組成物的含有成分的種類及含量成為如表2所示之方式，變更製造接著劑組成物時的調配成分的種類及調配量之任一者或兩者之方面以外，利用與實施例1之情形相同的方法，嘗試膜狀接著劑之製造及評價。結果示於表2。[Comparative Example 1 to Comparative Example 5] In addition to changing any one or both of the type and the amount of the compounding components when the adhesive composition is manufactured, the types and contents of the components contained in the adhesive composition are as shown in Table 2 In the same way as in Example 1, the production and evaluation of the film-like adhesive were tried. The results are shown in Table 2.

此外，表1及表2中的含有成分一欄記載為「-」時，表示接著劑組成物不含有該成分。In addition, when the column of contained components in Table 1 and Table 2 is described as "-", it means that the adhesive composition does not contain the component.

[表1] 實施例1 實施例2 實施例3 實施例4 接著劑組成物的含有成分(質量份) 丙烯酸系樹脂(a) (a)-1 58 44.3 - - (a)-2 - - 62.5 59 (a)-3 - - - - 環氧化合物(b1) (b1)-1 18 - 6 8.5 (b1)-2 - 40 - - 酚樹脂(b2) (b2)-1 3 - 1 1.5 硬化促進劑(c) (c)-1 - 0.2 - - 填充材料(d) (d)-1 20 - 30 30 (d)-2 - 15 - - (d)-3 - - - - 交聯劑(f) (f)-1 0.5 - - - (f)-2 - - - 0.5 磷系抗氧化劑(z) (z)-1 0.5 - 0.5 - (z)-2 - 0.5 - 0.5 其他抗氧化劑(y) (y)-1 - - - - 評價結果剪切強度(N/2mm□) 63 53 51 52 加熱前直線透過率(%) 97 96 98 97 加熱後直線透過率(%) 92 89 95 90 基於RGB之加熱前的指紋識別性山部 R 220 225 215 181 G 158 164 150 112 B 161 163 156 115 谷部 R 216 219 208 177 G 143 143 130 104 B 152 153 143 111 絕對值ΔR 4 6 7 4 絕對值ΔG 15 21 20 8 絕對值ΔB 9 10 13 4 指紋識別性 A A A B 基於目視之加熱前的指紋識別性之評價 A(5) A(5) A(5) A(5) 基於RGB之加熱後的指紋識別性山部 R 189 149 192 205 G 128 90 127 135 B 133 92 129 137 谷部 R 183 147 183 209 G 112 83 109 133 B 120 84 117 143 絕對值ΔR 6 2 9 4 絕對值ΔG 16 7 18 2 絕對值ΔB 13 8 12 6 指紋識別性 A B A B 基於目視之加熱後的指紋識別性之評價 A(5) A(5) A(5) A(5) [Table 1] Example 1 Example 2 Example 3 Example 4 Ingredients (parts by mass) of the adhesive composition Acrylic resin (a) (a)-1 58 44.3 - - (a)-2 - - 62.5 59 (a)-3 - - - - Epoxy compound (b1) (b1)-1 18 - 6 8.5 (b1)-2 - 40 - - Phenolic resin (b2) (b2)-1 3 - 1 1.5 Hardening accelerator (c) (c)-1 - 0.2 - - Filling material (d) (d)-1 20 - 30 30 (d)-2 - 15 - - (d)-3 - - - - Crosslinking agent (f) (f)-1 0.5 - - - (f)-2 - - - 0.5 Phosphorus antioxidants (z) (z)-1 0.5 - 0.5 - (z)-2 - 0.5 - 0.5 Other antioxidants (y) (y)-1 - - - - Evaluation results Shear strength (N/2mm□) 63 53 51 52 Linear transmittance before heating (%) 97 96 98 97 Linear transmittance after heating (%) 92 89 95 90 Fingerprint recognition before heating based on RGB Yamabe R 220 225 215 181 G 158 164 150 112 B 161 163 156 115 Yabe R 216 219 208 177 G 143 143 130 104 B 152 153 143 111 Absolute value ΔR 4 6 7 4 Absolute value ΔG 15 twenty one 20 8 Absolute value ΔB 9 10 13 4 Fingerprint identification A A A B Evaluation of fingerprint recognition before heating based on visual inspection A(5) A(5) A(5) A(5) Fingerprint recognition after heating based on RGB Yamabe R 189 149 192 205 G 128 90 127 135 B 133 92 129 137 Yabe R 183 147 183 209 G 112 83 109 133 B 120 84 117 143 Absolute value ΔR 6 2 9 4 Absolute value ΔG 16 7 18 2 Absolute value ΔB 13 8 12 6 Fingerprint identification A B A B Evaluation of fingerprint recognition after heating based on visual inspection A(5) A(5) A(5) A(5)

[表2] 比較例1 比較例2 比較例3 比較例4 比較例5 接著劑組成物的含有成分(質量份) 丙烯酸系樹脂(a) (a)-1 40 - 39.5 - 58 (a)-2 - - - - - (a)-3 - 68.5 - - - 環氧化合物(b1) (b1)-1 - - - - 18 (b1)-2 40 - 40 60 - 酚樹脂(b2) (b2)-1 - 11 - - 3 硬化促進劑(c) (c)-1 - - - - - 填充材料(d) (d)-1 - 20 - - - (d)-2 20 - 20 39.5 - (d)-3 - - - - 20 交聯劑(f) (f)-1 - 0.5 - - 0.5 (f)-2 - - - - - 磷系抗氧化劑(z) (z)-1 - - - - 0.5 (z)-2 - - - 0.5 - 其他抗氧化劑(y) (y)-1 - - 0.5 - - 評價結果剪切強度(N/2mm□) 44 - 52 - 50 加熱前直線透過率(%) 96 91 95 - 35 加熱後直線透過率(%) 77 42 64 - 28 基於RGB之加熱前的指紋識別性山部 R 198 217 220 - 192 G 125 151 158 - 127 B 132 155 159 - 123 谷部 R 183 210 220 - 192 G 108 150 144 - 131 B 112 153 157 - 126 絕對值ΔR 15 7 0 - 0 絕對值ΔG 17 1 14 - 4 絕對值ΔB 20 2 2 - 3 指紋識別性 A B A - C 基於目視之加熱前的指紋識別性之評價 A(5) A(5) A(5) - C(0) 基於RGB之加熱後的指紋識別性山部 R 154 152 142 - 164 G 94 99 85 - 110 B 96 93 78 - 87 谷部 R 153 148 139 - 166 G 90 95 84 - 106 B 92 91 81 - 84 絕對值ΔR 1 4 3 - 2 絕對值ΔG 4 4 1 - 4 絕對值ΔB 4 2 3 - 3 指紋識別性 C C C - C 基於目視之加熱後的指紋識別性之評價 C(2) C(0) C(0) - C(0) [Table 2] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Ingredients (parts by mass) of the adhesive composition Acrylic resin (a) (a)-1 40 - 39.5 - 58 (a)-2 - - - - - (a)-3 - 68.5 - - - Epoxy compound (b1) (b1)-1 - - - - 18 (b1)-2 40 - 40 60 - Phenolic resin (b2) (b2)-1 - 11 - - 3 Hardening accelerator (c) (c)-1 - - - - - Filling material (d) (d)-1 - 20 - - - (d)-2 20 - 20 39.5 - (d)-3 - - - - 20 Crosslinking agent (f) (f)-1 - 0.5 - - 0.5 (f)-2 - - - - - Phosphorus antioxidants (z) (z)-1 - - - - 0.5 (z)-2 - - - 0.5 - Other antioxidants (y) (y)-1 - - 0.5 - - Evaluation results Shear strength (N/2mm□) 44 - 52 - 50 Linear transmittance before heating (%) 96 91 95 - 35 Linear transmittance after heating (%) 77 42 64 - 28 Fingerprint recognition before heating based on RGB Yamabe R 198 217 220 - 192 G 125 151 158 - 127 B 132 155 159 - 123 Yabe R 183 210 220 - 192 G 108 150 144 - 131 B 112 153 157 - 126 Absolute value ΔR 15 7 0 - 0 Absolute value ΔG 17 1 14 - 4 Absolute value ΔB 20 2 2 - 3 Fingerprint identification A B A - C Evaluation of fingerprint recognition before heating based on visual inspection A(5) A(5) A(5) - C(0) Fingerprint recognition after heating based on RGB Yamabe R 154 152 142 - 164 G 94 99 85 - 110 B 96 93 78 - 87 Yabe R 153 148 139 - 166 G 90 95 84 - 106 B 92 91 81 - 84 Absolute value ΔR 1 4 3 - 2 Absolute value ΔG 4 4 1 - 4 Absolute value ΔB 4 2 3 - 3 Fingerprint identification C C C - C Evaluation of fingerprint recognition after heating based on visual inspection C(2) C(0) C(0) - C(0)

由上述結果可明顯看出，於實施例1至實施例4中，於260℃加熱前後的膜狀接著劑均透光性高，著色得到抑制，指紋識別性高。於實施例1至實施例4中，於260℃加熱前的膜狀接著劑在光(400nm至800nm)之直線透過率為96%以上(96%至98%)，於260℃加熱後的膜狀接著劑在光(400nm至800nm)之直線透過率為89%以上(89%至95%)。It can be clearly seen from the above results that in Examples 1 to 4, the film adhesives before and after heating at 260° C. have high light transmittance, coloration is suppressed, and fingerprint recognition is high. In Examples 1 to 4, the film-like adhesive before heating at 260°C has a linear transmittance of light (400nm to 800nm) of more than 96% (96% to 98%), and the film after heating at 260°C The linear transmittance of the adhesive in light (400nm to 800nm) is above 89% (89% to 95%).

於實施例1至實施例4中，膜狀接著劑的剪切強度為51N/2mm□以上(51N/2mm□至63N/2mm□)，膜狀接著劑的接著力足夠強。In Examples 1 to 4, the shear strength of the film adhesive is 51N/2mm□ or more (51N/2mm□ to 63N/2mm□), and the adhesive force of the film adhesive is sufficiently strong.

相對於此，於比較例1至比較例3中，雖然於260℃加熱前的膜狀接著劑均透光性高，著色得到抑制，但於260℃加熱後的膜狀接著劑的透光性低，著色未得到抑制，指紋識別性低。於比較例1至比較例3中，於260℃加熱後的膜狀接著劑的光(400nm至800nm)之直線透過率為77%以下。於比較例1至比較例2中，推測由於膜狀接著劑不含有抗氧化劑，故而因加熱所致之著色未得到抑制。於比較例3中，推測雖然膜狀接著劑含有抗氧化劑，但由於抗氧化劑並非磷系抗氧化劑(z)，故而因加熱所致之著色未得到抑制。In contrast, in Comparative Examples 1 to 3, although the film adhesives before heating at 260°C have high light transmittance and coloring is suppressed, the film adhesives after heating at 260°C have light transmittance Low, coloring is not suppressed, and fingerprint recognition is low. In Comparative Examples 1 to 3, the linear transmittance of light (400 nm to 800 nm) of the film-like adhesive after heating at 260° C. is 77% or less. In Comparative Example 1 to Comparative Example 2, it is presumed that since the film-like adhesive does not contain an antioxidant, the coloration caused by heating is not suppressed. In Comparative Example 3, it is presumed that although the film-like adhesive contains an antioxidant, since the antioxidant is not a phosphorus-based antioxidant (z), the coloration due to heating is not suppressed.

於比較例5中，於260℃加熱前的階段的膜狀接著劑已經透光性低，發生白濁，指紋識別性低。因此，於260℃下加熱後的膜狀接著劑亦為白濁之狀態，指紋識別性低。於比較例5中，推測由於使用平均粒徑大之填充材料(d)-3，故而膜狀接著劑發生白濁。該情況亦由僅所使用之填充材料(d)的種類不同之實施例1的膜狀接著劑與比較例5的膜狀接著劑之比較而明確。In Comparative Example 5, the film-like adhesive at the stage before heating at 260°C had low light transmittance, became cloudy, and had low fingerprint recognition. Therefore, the film-like adhesive after heating at 260°C is also in a cloudy state and has low fingerprint recognition. In Comparative Example 5, it is presumed that the film-like adhesive is cloudy due to the use of the filler (d)-3 having a large average particle diameter. This situation is also clear from the comparison between the film adhesive of Example 1 and the film adhesive of Comparative Example 5, which differ only in the type of filler (d) used.

於比較例4中，無法形成膜狀接著劑。原因在於，接著劑組成物不含有丙烯酸系樹脂(a)等造膜成分。於比較例4中，無法進行膜狀接著劑之評價。In Comparative Example 4, the film-like adhesive could not be formed. The reason is that the adhesive composition does not contain film-forming components such as acrylic resin (a). In Comparative Example 4, evaluation of the film adhesive could not be performed.

進而，於比較例1中，膜狀接著劑的剪切強度為44N/2mm□，膜狀接著劑的接著力較實施例1至實施例4之情形弱。於比較例2中，膜狀接著劑的接著力過弱，無法測定膜狀接著劑的剪切強度。原因在於，接著劑組成物不含有環氧化合物(b1)等環氧化合物。 [產業可利用性]Furthermore, in Comparative Example 1, the shear strength of the film-like adhesive was 44N/2 mm□, and the adhesive force of the film-like adhesive was weaker than that of Examples 1 to 4. In Comparative Example 2, the adhesive force of the film adhesive was too weak, and the shear strength of the film adhesive could not be measured. The reason is that the adhesive composition does not contain epoxy compounds such as epoxy compound (b1). [Industry Availability]

本發明可於製造或加工構成電子機器之各種零件時，用作接著劑。The present invention can be used as an adhesive when manufacturing or processing various parts constituting electronic equipment.

7:透光性罩 7a:透光性罩的第1面 7b:透光性罩的第2面 8:晶片 8a:晶片的電路形成面 10:切割片 10a:切割片的第1面 11:基材 11a:基材的第1面 12:黏著劑層 12a:黏著劑層的第1面 13:膜狀接著劑 13a:膜狀接著劑的第1面 13b:膜狀接著劑的第2面 15:剝離膜 19:樹脂膜 101:複合片 108,109:積層片 151:第1剝離膜 152:第2剝離膜 801:積層體7: Translucent cover 7a: The first side of the translucent cover 7b: The second side of the translucent cover 8: chip 8a: The circuit formation surface of the chip 10: Cutting sheet 10a: The first side of the cutting disc 11: Substrate 11a: The first side of the substrate 12: Adhesive layer 12a: The first side of the adhesive layer 13: Film adhesive 13a: The first side of the film adhesive 13b: The second side of the film adhesive 15: peeling film 19: Resin film 101: composite sheet 108,109: Multilayer tablets 151: The first release film 152: The second release film 801: layered body

[圖1]係以示意方式表示本發明的一實施形態的膜狀接著劑及積層片的一例之剖視圖。 [圖2]係以示意方式表示本發明的一實施形態的積層片的另一例之剖視圖。 [圖3]係以示意方式表示本發明的一實施形態的複合片的一例之剖視圖。 [圖4]係以示意方式表示使用本發明的一實施形態的膜狀接著劑而製造之積層體的一例之剖視圖。 [圖5]係用於以示意方式說明本發明的一實施形態的複合片之使用方法的一例之剖視圖。Fig. 1 is a cross-sectional view schematically showing an example of a film-like adhesive and a laminated sheet according to an embodiment of the present invention. Fig. 2 is a cross-sectional view schematically showing another example of the laminated sheet according to an embodiment of the present invention. Fig. 3 is a cross-sectional view schematically showing an example of a composite sheet according to an embodiment of the present invention. [Fig. 4] Fig. 4 is a cross-sectional view schematically showing an example of a laminate manufactured using the film-like adhesive according to an embodiment of the present invention. Fig. 5 is a cross-sectional view for schematically explaining an example of the method of using the composite sheet according to one embodiment of the present invention.

13:膜狀接著劑 13: Film adhesive

13a:膜狀接著劑的第1面 13a: The first side of the film adhesive

13b:膜狀接著劑的第2面 13b: The second side of the film adhesive

109:積層片 109: Multilayer

151:第1剝離膜 151: The first release film

152:第2剝離膜 152: The second release film

Claims

一種膜狀接著劑，含有丙烯酸系樹脂(a)、環氧化合物(b1)、及磷系抗氧化劑(z)；於260℃加熱前的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為90%以上；於260℃加熱10分鐘後的前述膜狀接著劑在波長為400nm至800nm之光之直線透過率為85%以上；前述膜狀接著劑的厚度為10μm至40μm。A film-like adhesive containing acrylic resin (a), epoxy compound (b1), and phosphorus antioxidant (z); The linear transmittance of the aforementioned film adhesive before heating at 260°C for light with a wavelength of 400nm to 800nm is above 90%; After heating at 260°C for 10 minutes, the linear transmittance of the aforementioned film-like adhesive for light with a wavelength of 400nm to 800nm is over 85%; The thickness of the aforementioned film-like adhesive is 10 μm to 40 μm.

如請求項1所記載之膜狀接著劑，其中前述環氧化合物(b1)為脂肪族系化合物。The film-like adhesive according to claim 1, wherein the epoxy compound (b1) is an aliphatic compound.

如請求項1或2所記載之膜狀接著劑，其中前述膜狀接著劑進而含有酚樹脂(b2)；前述膜狀接著劑中的前述酚樹脂(b2)的含量相對於前述膜狀接著劑的總質量之比例為10質量%以下。The film adhesive according to claim 1 or 2, wherein the film adhesive further contains a phenol resin (b2); The ratio of the content of the phenol resin (b2) in the film adhesive to the total mass of the film adhesive is 10% by mass or less.

如請求項1至3中任一項所記載之膜狀接著劑，其中前述磷系抗氧化劑(z)為脂肪族系亞磷酸酯。The film-like adhesive according to any one of claims 1 to 3, wherein the phosphorous antioxidant (z) is an aliphatic phosphite.

如請求項1至4中任一項所記載之膜狀接著劑，其中前述膜狀接著劑進而含有脂肪族系多元異氰酸酯交聯劑；前述丙烯酸系樹脂(a)具有能夠與前述交聯劑鍵結之官能基。The film adhesive according to any one of claims 1 to 4, wherein the film adhesive further contains an aliphatic polyisocyanate crosslinking agent; The acrylic resin (a) has a functional group capable of bonding with the crosslinking agent.

一種積層片，具備如請求項1至5中任一項所記載之膜狀接著劑、及設置於前述膜狀接著劑的一面上之樹脂膜。A laminated sheet comprising the film-like adhesive described in any one of claims 1 to 5, and a resin film provided on one side of the film-like adhesive.

一種複合片，具備如請求項1至5中任一項所記載之膜狀接著劑、及設置於前述膜狀接著劑的一面上之切割片；前述切割片具備基材、及設置於前述基材的一面上之黏著劑層；前述黏著劑層配置於前述基材與前述膜狀接著劑之間。A composite sheet comprising the film-like adhesive described in any one of claims 1 to 5, and a cutting sheet provided on one side of the film-like adhesive; The aforementioned dicing sheet includes a substrate and an adhesive layer provided on one surface of the aforementioned substrate; The adhesive layer is disposed between the substrate and the film-like adhesive.

一種積層體之製造方法，係於如請求項1至5中任一項所記載之膜狀接著劑的一面貼合晶片的電路形成面，於前述膜狀接著劑的另一面貼合透光性罩，藉此獲得依序積層前述晶片、前述膜狀接著劑、及前述透光性罩而構成之積層體。A method for manufacturing a laminate, in which one side of the film adhesive described in any one of claims 1 to 5 is bonded to the circuit forming surface of the chip, and the other side of the film adhesive is bonded to the other surface of the film with light-transmitting properties The cover obtains a laminated body formed by sequentially laminating the wafer, the film-like adhesive, and the translucent cover.