TWI783931B - Use of energy ray curable film and use of protective film forming composite sheet - Google Patents
Use of energy ray curable film and use of protective film forming composite sheet Download PDFInfo
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- TWI783931B TWI783931B TW106113980A TW106113980A TWI783931B TW I783931 B TWI783931 B TW I783931B TW 106113980 A TW106113980 A TW 106113980A TW 106113980 A TW106113980 A TW 106113980A TW I783931 B TWI783931 B TW I783931B
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- Prior art keywords
- protective film
- film
- forming
- semiconductor wafer
- meth
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- ITHPEWAHFNDNIO-UHFFFAOYSA-N triphosphane Chemical compound PPP ITHPEWAHFNDNIO-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
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- Materials Engineering (AREA)
- Dicing (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
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Abstract
Description
本發明係關於一種保護膜形成用膜以及保護膜形成用複合片。 The present invention relates to a film for protective film formation and a composite sheet for protective film formation.
本申請案主張基於2016年4月28日在日本提出申請之日本專利特願2016-092101號之優先權，並將該申請案的內容引用至本文中。 This application claims priority based on Japanese Patent Application No. 2016-092101 filed in Japan on April 28, 2016, and the content of the application is incorporated herein.
近年來，業界使用稱為所謂倒裝(face down)方式之安裝方法製造半導體裝置。倒裝方式中，使用於電路面上具有凸塊等電極之半導體晶片，將前述電極與基板接合。因此，有時半導體晶片中的與電路面為相反側的背面裸露。 In recent years, semiconductor devices have been manufactured in the industry using a mounting method called a so-called face down method. In the flip-chip method, a semiconductor wafer having electrodes such as bumps on the circuit surface is used, and the electrodes are bonded to the substrate. Therefore, the back surface of the semiconductor wafer opposite to the circuit surface may be exposed.
有時於該裸露之半導體晶片的背面，形成含有有機材料之樹脂膜作為保護膜，從而以作為附有保護膜的半導體晶片組入至半導體裝置中。保護膜係用以防止在切割步驟或封裝之後半導體晶片產生龜裂。 In some cases, a resin film containing an organic material is formed as a protective film on the back surface of the bare semiconductor wafer, and the semiconductor wafer with the protective film is incorporated into a semiconductor device. The protective film is used to prevent cracking of the semiconductor wafer after the dicing step or packaging.
為了形成此種保護膜，例如使用於支持片上具備用以形成保護膜之保護膜形成用膜之保護膜形成用複合片。保護膜形成用複合片中，可使保護膜形成用膜藉由硬化而形成保護膜。另外，進而可利用支持片作為切割片，從而可製成保護膜形成用膜與切割片形成為一體之保護膜形成用複合片。 In order to form such a protective film, the composite sheet for protective film formation provided with the film for protective film formation for forming a protective film on a support sheet is used, for example. In the composite sheet for protective film formation, a protective film can be formed by hardening the film for protective film formation. Furthermore, the support sheet can be used as a dicing sheet, and a composite sheet for protective film formation in which the film for protective film formation and a dicing sheet are integrally formed can be obtained.
作為此種保護膜形成用複合片，例如此前主要利用具備熱硬化性之保護膜形成用膜之保護膜形成用複合片，前述熱硬化性之保護膜形成用膜藉由加熱而硬化，從而形成保護膜。該情形時，例如，於半導體晶圓的背面(與電極形成面為相反側的面)，藉由熱硬化性之保護膜形成用膜，貼附保護膜形成用複合片。然後，藉由加熱使保護膜形成用膜硬化而成為保護膜，藉由切割將半導體晶圓連同保護膜一起分割而製成半導體晶片(參照專利文獻1、專利文獻2)。 As such a composite sheet for forming a protective film, for example, a composite sheet for forming a protective film provided with a film for forming a thermosetting protective film, which is hardened by heating to form a composite sheet for forming a protective film, has been mainly used. protective film. In this case, for example, the protective film forming composite sheet is attached to the back surface (the surface opposite to the electrode forming surface) of the semiconductor wafer via a thermosetting protective film forming film. Then, the film for forming a protective film is cured by heating to form a protective film, and the semiconductor wafer is divided together with the protective film by dicing to form semiconductor wafers (see Patent Document 1 and Patent Document 2).
[先前技術文獻] [Prior Art Literature]
[專利文獻] [Patent Document]
專利文獻1：日本專利第5144433號公報。 Patent Document 1: Japanese Patent No. 5144433.
專利文獻2：日本專利特開2010-031183號公報。 Patent Document 2: Japanese Patent Laid-Open No. 2010-031183.
圖7係表示將先前之半導體晶片於壓紋載帶中封入捲
盤之狀態之概略剖面圖。將藉由切割半導體晶圓(省略圖示)而分割所得之附有保護膜的半導體晶片101逐個拾取。然後，收容於連續設置有多個凹陷部分(口袋102a)之包裝用膜(壓紋載帶102)的口袋102a，以於前述壓紋載帶102上貼附蓋帶103(封入捲盤)之狀態出貨而搬送至下一步驟。下一步驟中，將收容有附有保護膜的半導體晶片101之壓紋載帶102的蓋帶103剝離，並取出收容於口袋102a之附有保護膜的半導體晶片101，進而供於後續步驟。
Figure 7 is a representation of encapsulating the previous semiconductor wafer into a reel in an embossed carrier tape.
A schematic cross-sectional view of the state of the disk. The protective film-attached
且說，保護膜有時因於切割步驟中與半導體晶圓一起分割時的摩擦等而產生靜電，收容於壓紋載帶102之附有保護膜的半導體晶片101帶電。若附有保護膜的半導體晶片101帶電，則為了取出收容於壓紋載帶102的口袋102a中的附有保護膜的半導體晶片101而剝離壓紋載帶102的蓋帶103時，於所剝離之蓋帶103附著附有保護膜的半導體晶片101。因此，附有保護膜的半導體晶片101與所剝離之蓋帶103一起自壓紋載帶102移除。結果有產生以下不良情況之問題：無法順利地搬送至下一步驟，或者灰塵等異物因靜電而附著於半導體晶片等。
In other words, the protective film may generate static electricity due to friction when it is divided together with the semiconductor wafer in the dicing step, and the semiconductor wafer with the
本發明係為了解決上述問題而完成之發明。亦即，本發明之目的在於提供一種保護膜形成用膜以及保護膜形 成用複合片，前述保護膜形成用膜即便將切割並拾取之附有保護膜的半導體晶片收容於壓紋載帶而進行包裝(封入捲盤)，亦可防止收容於壓紋載帶中的附有保護膜的半導體晶片帶電。 The present invention is made to solve the above problems. That is, the object of the present invention is to provide a film for forming a protective film and a film in the form of a protective film. In the composite sheet for production, the film for forming the protective film can prevent the semiconductor wafer with the protective film that has been cut and picked up on the embossed carrier tape for packaging (encapsulation in a reel). A semiconductor wafer with a protective film is charged.
本發明者等人為了解決上述課題而反復進行銳意研究。結果發現，藉由將保護膜形成用膜或保護膜形成用複合片的表面電阻率設為1012Ω‧cm以下，可解決上述課題，從而完成本發明。 The inventors of the present invention have repeatedly conducted earnest research in order to solve the above-mentioned problems. As a result, they found that the above-mentioned problems can be solved by setting the surface resistivity of the film for forming a protective film or the composite sheet for forming a protective film to 10 12 Ω·cm or less, and completed the present invention.
亦即，本發明係一種保護膜形成用膜，為能量線硬化性之保護膜形成用膜，前述保護膜形成用膜被照射能量線而硬化時，表面電阻率為1012Ω‧cm以下。 That is, the present invention relates to a film for forming a protective film, which is an energy ray curable film for forming a protective film, wherein the film for forming a protective film has a surface resistivity of 10 12 Ω·cm or less when cured by irradiation with energy rays.
本發明之保護膜形成用膜中，較佳為前述保護膜形成用膜含有抗靜電劑。 In the film for protective film formation of this invention, it is preferable that the said film for protective film formation contains an antistatic agent.
另外，本發明之保護膜形成用膜中，較佳為前述抗靜電劑為選自由陰離子系界面活性劑系抗靜電劑、陽離子系界面活性劑系抗靜電劑、非離子系界面活性劑系抗靜電劑、及兩離子系界面活性劑系抗靜電劑所組成之群組中的至少1種。 In addition, in the protective film forming film of the present invention, it is preferable that the antistatic agent is selected from an anionic surfactant-based antistatic agent, a cationic surfactant-based antistatic agent, a nonionic surfactant-based antistatic agent, and a nonionic surfactant-based antistatic agent. The antistatic agent and the two ionic surfactants are at least one of the group consisting of antistatic agents.
進而，前述抗靜電劑較佳為鹼金屬鹽系。 Furthermore, the aforementioned antistatic agent is preferably an alkali metal salt.
前述抗靜電劑的含量較佳為相對於前述保護膜形成用膜中所含之樹脂成分之質量為6質量%至20質量%。 It is preferable that content of the said antistatic agent is 6 mass % - 20 mass % with respect to the mass of the resin component contained in the said film for protective film formation.
前述保護膜形成用膜較佳為進而含有能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)。 It is preferable that the said film for protective film formation further contains an energy ray curable component (a) and the polymer (b) which does not have an energy ray curable group.
前述保護膜形成用膜中，較佳為含有相對於前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計質量為6質量%至20質量%之前述抗靜電劑。 In the above-mentioned film for forming a protective film, it is preferable to contain the above-mentioned antistatic agent.
另外，本發明可為一種保護膜形成用複合片，於支持片上具備上述記載之保護膜形成用膜。 In addition, the present invention may be a composite sheet for protective film formation comprising the film for protective film formation described above on a support sheet.
根據本發明，提供一種保護膜形成用膜以及保護膜形成用複合片，前述保護膜形成用膜即便於收容於壓紋載帶之情形時，亦可防止附有保護膜的半導體晶片帶電。 According to the present invention, there are provided a film for forming a protective film capable of preventing electrification of a semiconductor wafer with a protective film even when stored in an embossed carrier tape, and a composite sheet for forming a protective film.
1A、1B、1C、1D、1E:保護膜形成用複合片 1A, 1B, 1C, 1D, 1E: composite sheet for protective film formation
1F:保護膜形成用膜片 1F: Membrane for protective film formation
10:支持片 10: Support sheet
10a:支持片的表面 10a: Surface of the support sheet
11:基材 11: Substrate
11a:基材的表面 11a: Surface of the substrate
12:黏著劑層 12: Adhesive layer
12a:黏著劑層的表面 12a: the surface of the adhesive layer
13、23:保護膜形成用膜 13, 23: Film for protective film formation
13a、23a:保護膜形成用膜的表面 13a, 23a: the surface of the film for protective film formation
15、15a、15b:剝離膜 15, 15a, 15b: Release film
16:治具用接著劑層 16: Adhesive layer for jig
16a:治具用接著劑層的表面 16a: The surface of the adhesive layer for jigs
101:附有保護膜的半導體晶片 101: Semiconductor wafer with protective film
102:壓紋載帶 102: Embossed carrier tape
102a:口袋 102a: pocket
103:蓋帶 103: cover tape
圖1係以示意方式表示本發明之保護膜形成用複合片的一實施形態之剖面圖。 Fig. 1 is a cross-sectional view schematically showing one embodiment of the protective film-forming composite sheet of the present invention.
圖2係以示意方式表示本發明之保護膜形成用複合片的另一實施形態之剖面圖。 Fig. 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention.
圖3係以示意方式表示本發明之保護膜形成用複合片的又一實施形態之剖面圖。 Fig. 3 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
圖4係以示意方式表示本發明之保護膜形成用複合片的又一實施形態之剖面圖。 Fig. 4 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
圖5係以示意方式表示本發明之保護膜形成用複合片的又一實施形態之剖面圖。 Fig. 5 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
圖6係以示意方式表示本發明之保護膜形成用膜的一實施形態之剖面圖。 Fig. 6 is a cross-sectional view schematically showing one embodiment of the film for forming a protective film of the present invention.
圖7係以示意方式表示將附有保護膜的半導體晶片收納於壓紋載帶的口袋，並貼附蓋帶而封蓋的狀態，以及剝離前述蓋帶後的狀態之剖面圖。 7 is a cross-sectional view schematically showing a state in which a semiconductor wafer with a protective film is stored in a pocket of an embossed carrier tape, and a cover tape is attached to cover it, and a state in which the cover tape is peeled off.
◇保護膜形成用膜 ◇Film for protective film formation
本發明之保護膜形成用膜為能量線硬化性之保護膜形成用膜，表面電阻率為1012Ω‧cm以下。 The film for forming a protective film of the present invention is an energy ray curable film for forming a protective film, and has a surface resistivity of 10 12 Ω‧cm or less.
本發明之保護膜形成用膜較佳為含有抗靜電劑。 It is preferable that the film for protective film formation of this invention contains an antistatic agent.
本發明之保護膜形成用膜中，較佳為前述抗靜電劑為選自由陰離子系界面活性劑系抗靜電劑、陽離子系界面活性劑系抗靜電劑、非離子系界面活性劑系抗靜電劑、及兩離子系界面活性劑系抗靜電劑所組成之群組中的至少1種。 In the film for forming a protective film of the present invention, the aforementioned antistatic agent is preferably selected from an anionic surfactant-based antistatic agent, a cationic surfactant-based antistatic agent, and a nonionic surfactant-based antistatic agent. , and at least one of the group consisting of two ionic surfactants and antistatic agents.
前述抗靜電劑較佳為鹼金屬鹽系。 The aforementioned antistatic agent is preferably an alkali metal salt.
前述保護膜形成用膜較佳為進而含有能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)。 It is preferable that the said film for protective film formation further contains an energy ray curable component (a) and the polymer (b) which does not have an energy ray curable group.
前述保護膜形成用膜中，較佳為含有相對於前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計質量為6質量%至20質量%之前述抗靜電劑。 In the above-mentioned film for forming a protective film, it is preferable to contain the above-mentioned antistatic agent.
本發明之保護膜形成用膜可於至少一表面具有第1剝離膜，亦可於另一表面進而具有第2剝離膜。本發明之保
護膜形成用膜可以捲繞成捲筒狀之長條狀膜之形式提供。圖6係以示意方式表示本發明之保護膜形成用膜的一實施形態之剖面圖。圖6中，依序積層有第1剝離膜15a、保護膜形成用膜13(23)及第2剝離膜15b。
The film for protective film formation of this invention may have a 1st release film on at least one surface, and may further have a 2nd release film on the other surface. Warranty of the invention
The film for pellicle formation can be provided in the form of a long film wound into a roll. Fig. 6 is a cross-sectional view schematically showing one embodiment of the film for forming a protective film of the present invention. In FIG. 6, the
◇保護膜形成用複合片 ◇Composite sheets for protective film formation
本發明之保護膜形成用複合片於支持片上具備能量線硬化性之保護膜形成用膜，且前述保護膜形成用膜的表面電阻率為1012Ω‧cm以下。 The composite sheet for forming a protective film of the present invention has an energy ray curable film for forming a protective film on a support sheet, and the surface resistivity of the film for forming a protective film is 10 12 Ω‧cm or less.
此處，所謂「表面電阻率為1012Ω‧cm以下之保護膜形成用膜」意指對前述保護膜形成用膜照射能量線而成為保護膜時，前述保護膜的表面電阻率為1012Ω‧cm以下之保護膜形成用膜。 Here, the "film for forming a protective film having a surface resistivity of 10 12 Ω·cm or less" means that when the film for forming a protective film is irradiated with energy rays to form a protective film, the protective film has a surface resistivity of 10 12 Films for forming protective films below Ω‧cm.
再者，本說明書中，所謂「保護膜形成用膜」意指硬化前之保護膜形成用膜，所謂「保護膜」意指保護膜形成用膜硬化後之膜。 In addition, in this specification, "the film for protective film formation" means the film for protective film formation before hardening, and "protective film" means the film of the film for protective film formation after hardening.
另外，相對於保護膜形成用膜之硬化前而言，硬化後，表面電阻率增大，抗靜電性降低。因此，為了使硬化後之保護膜的表面電阻率成為1012Ω‧cm以下，必須使硬化前之保護膜形成用膜的表面電阻率成為1011Ω‧cm以下。 Moreover, after curing, the surface resistivity increased and the antistatic property decreased compared to before curing of the film for forming a protective film. Therefore, in order to make the surface resistivity of the protective film after curing 10 12 Ω·cm or less, the surface resistivity of the film for forming a protective film before curing must be 10 11 Ω·cm or lower.
保護膜形成用膜的表面電阻率較佳為1011Ω‧cm以下，更佳為1010Ω‧cm以下，進而較佳為109Ω‧cm以下。保護膜形成用膜的表面電阻率的下限值並無特別限定。例如可設為108Ω‧cm。 The surface resistivity of the film for forming a protective film is preferably at most 10 11 Ω‧cm, more preferably at most 10 10 Ω‧cm, still more preferably at most 10 9 Ω‧cm. The lower limit of the surface resistivity of the film for protective film formation is not specifically limited. For example, it can be set to 10 8 Ω‧cm.
另外，保護膜的表面電阻率較佳為1012Ω‧cm以下， 更佳為1011Ω‧cm以下，進而較佳為1010Ω‧cm以下。保護膜的表面電阻率的下限值並無特別限定。例如可設為109Ω‧cm。 In addition, the surface resistivity of the protective film is preferably 10 12 Ω‧cm or less, more preferably 10 11 Ω‧cm or less, further preferably 10 10 Ω‧cm or less. The lower limit of the surface resistivity of a protective film is not specifically limited. For example, it can be set to 10 9 Ω‧cm.
前述保護膜形成用膜藉由照射能量線進行硬化而成為保護膜。該保護膜用以對半導體晶圓或半導體晶片的背面(與電極形成面為相反側的面)進行保護。保護膜形成用膜為軟質，可容易地貼附於貼附對象物。 The said film for protective film formation becomes a protective film by hardening by irradiating an energy ray. This protective film is used to protect the semiconductor wafer or the back surface (the surface opposite to the electrode formation surface) of the semiconductor wafer. The film for protective film formation is soft and can be easily attached to an object to be attached.
並且，藉由將保護膜形成用膜被照射能量線而硬化時的表面電阻率設為1012Ω‧cm以下，本發明之保護膜形成用複合片具有抗靜電性。例如，即便經由切割步驟，亦可防止半導體晶片帶電。另外，進而，封入捲盤而出貨，於下一步驟中剝離蓋帶時，可防止半導體晶片附著於蓋帶。 Furthermore, the composite sheet for protective film formation of the present invention has antistatic properties by setting the surface resistivity of the film for protective film formation to 10 12 Ω·cm or less when it is hardened by irradiation with energy rays. For example, even through the dicing step, the semiconductor wafer can be prevented from being charged. Furthermore, when the cover tape is peeled off in the next step, the semiconductor wafer can be prevented from adhering to the cover tape when it is packaged in a reel and shipped.
另外，由於可防止半導體晶片本身帶電，故而可防止灰塵或塵埃等因靜電而附著於半導體晶片。 In addition, since the semiconductor wafer itself can be prevented from being charged, it is possible to prevent dust or dust from adhering to the semiconductor wafer due to static electricity.
本發明中，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。 In the present invention, the so-called "energy line" means an electromagnetic wave or a beam of charged particles having energy quanta. Examples of the energy rays include ultraviolet rays, radiation, electron beams, and the like.
紫外線例如可藉由使用高壓水銀燈、融合(Fusion)H型燈、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。 Ultraviolet rays can be irradiated by using, for example, a high-pressure mercury lamp, a fusion (Fusion) H-type lamp, a xenon lamp, a black light lamp, or an LED (Light Emitting Diode; Light Emitting Diode) lamp as an ultraviolet source. The electron beam may be irradiated with an electron beam generated by an electron beam accelerator or the like.
本發明中，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 the present invention, the so-called "energy ray curability" means The property of curing by radiation, the so-called "non-energy radiation curing" means the property of not curing even when irradiated with energy radiation.
本發明之保護膜形成用複合片之使用對象亦即半導體晶圓或半導體晶片的厚度並無特別限定。但是，就獲得更顯著的本發明之效果而言，較佳為30μm至1000μm，更佳為100μm至300μm。 The object of use of the composite sheet for forming a protective film of the present invention, that is, the semiconductor wafer or the thickness of the semiconductor wafer is not particularly limited. However, in order to obtain a more remarkable effect of the present invention, it is preferably from 30 μm to 1000 μm, more preferably from 100 μm to 300 μm.
以下，對本發明之構成，詳細地進行說明。 Hereinafter, the configuration of the present invention will be described in detail.
◎支持片 ◎Support sheet
前述支持片可由1層(單層)構成，亦可由2層以上之多層構成。於支持片由多層構成之情形時，這些多層的構成材料及厚度相互可相同亦可不同，只要無損本發明之效果，則這些多層之組合併無特別限定。 The aforementioned support sheet may be composed of one layer (single layer), or may be composed of two or more layers. When the support sheet is composed of multiple layers, the constituent materials and thicknesses of these layers may be the same or different from each other, and the combination of these layers is not particularly limited as long as the effect of the present invention is not impaired.
再者，本說明書中，不限於支持片之情形，所謂「多層相互可相同亦可不同」意指「可全部層相同。進而，亦可全部層皆不相同，還可僅一部分層相同」。進而，所謂「多層相互不同」意指「各層的構成材料及厚度之至少一者相互不同」。 In addition, in this specification, not limited to the case of the support sheet, "multiple layers may be the same or different" means "all the layers may be the same. Furthermore, all the layers may be different, or only a part of the layers may be the same". Furthermore, "multiple layers are different from each other" means "at least one of constituent materials and thickness of each layer is different from each other".
作為較佳的支持片，例如可列舉：於基材上以直接接觸之方式積層黏著劑層而成之支持片、於基材上經由中間層積層黏著劑層而成之支持片、僅由基材構成之支持片等。 As a preferred support sheet, for example, a support sheet formed by laminating an adhesive layer on a base material in direct contact, a support sheet formed by laminating an adhesive layer on a base material through an intermediate layer, a support sheet formed by laminating an adhesive layer only on a base material, Supporting sheets made of materials, etc.
以下，按照上述支持片之每個種類，一面參照圖式一面說明本發明之保護膜形成用複合片之示例。再者，以下之說明中所使用之圖中，為了易於理解本發明之特徵，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。 Hereinafter, examples of the composite sheet for protective film formation of the present invention will be described for each type of the above-mentioned support sheet with reference to the drawings. In addition, in the drawings used in the following description, for the sake of easy understanding of the characteristics of the present invention, the main parts are sometimes enlarged and shown for convenience, and the dimensional ratio of each component is not limited to the same as the actual one. .
圖1係以示意方式表示本發明之保護膜形成用複合片的一實施形態之剖面圖。此處所示之保護膜形成用複合片1A於基材11上具備黏著劑層12，於黏著劑層12上具備保護膜形成用膜13。支持片10為基材11及黏著劑層12之積層體。換言之，保護膜形成用複合片1A具有於支持片10的一表面10a上積層有保護膜形成用膜13之構成。另外，保護膜形成用複合片1A進而於保護膜形成用膜13上具備剝離膜15。
Fig. 1 is a cross-sectional view schematically showing one embodiment of the protective film-forming composite sheet of the present invention. 1 A of composite sheets for protective film formation shown here are equipped with the
保護膜形成用複合片1A中，於基材11的一表面11a積層黏著劑層12。於黏著劑層12的表面12a的整個面積層保護膜形成用膜13，於保護膜形成用膜13的表面13a的一部分，亦即周緣部附近的區域積層治具用接著劑層16。於保護膜形成用膜13的表面13a中未積層治具用接著劑層16之面及治具用接著劑層16的表面16a(上表面及側面)積層有剝離膜15。
In the
保護膜形成用複合片1A中，硬化後之保護膜形成用膜13(亦即保護膜)與支持片10之間的黏著力，換言之保護膜與黏著劑層12之間的黏著力較佳為50mN/25mm至1500mN/25mm。
In the protective film forming
治具用接著劑層16例如可為含有接著劑成分之單層結構。另外，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之多層結構。
The
圖1所示之保護膜形成用複合片1A係以下述方式使用，亦即，在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a貼附半導體晶圓(省略圖示)的背面。進而，將治具用接著劑層16的表面16a中的上表面貼附於環狀框等治具。
The protective film forming
圖2係以示意方式表示本發明之保護膜形成用複合片的另一實施形態之剖面圖。再者，圖2以後之圖中，對於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，並省略該符號的詳細說明。 Fig. 2 is a cross-sectional view schematically showing another embodiment of the composite sheet for forming a protective film of the present invention. In addition, in FIG. 2 and subsequent figures, the same symbols as those shown in the already-described figures are attached to the same components as those shown in the already-described figures, and detailed explanations of the symbols are omitted.
關於此處所示之保護膜形成用複合片1B，除不具備治具用接著劑層16之方面以外，與圖1所示之保護膜形成用複合片1A相同。亦即，保護膜形成用複合片1B中，於基材11的一表面11a積層黏著劑層12。於黏著劑層12的表
面12a的整個面積層有保護膜形成用膜13，於保護膜形成用膜13的表面13a的整個面積層有剝離膜15。
The
圖2所示之保護膜形成用複合片1B係以下述方式使用，亦即，在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a中的中央側的一部分區域貼附半導體晶圓(省略圖示)的背面。進而，將保護膜形成用膜13的周緣部附近的區域貼附於環狀框等治具。
The
圖3係以示意方式表示本發明之保護膜形成用複合片的又一實施形態之剖面圖。 Fig. 3 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
關於此處所示之保護膜形成用複合片1C，除不具備黏著劑層12之方面以外，與圖1所示之保護膜形成用複合片1A相同。亦即，保護膜形成用複合片1C中，支持片10僅由基材11構成。並且，於基材11的一表面11a(支持片10的一表面10a)積層保護膜形成用膜13。於保護膜形成用膜13的表面13a的一部分，亦即周緣部附近的區域積層有治具用接著劑層16，於保護膜形成用膜13的表面13a中未積層治具用接著劑層16之面及治具用接著劑層16的表面16a(上表面及側面)積層有剝離膜15
1 C of composite sheets for protective film formation shown here are the same as 1 A of composite sheets for protective film formation shown in FIG. 1 except the point which does not have the
保護膜形成用複合片1C中，硬化後之保護膜形成用膜13(亦即保護膜)與支持片10之間的黏著力，換言之保護膜與基材11之間的黏著力較佳為50mN/25mm至
1500mN/25mm。
In the protective film forming composite sheet 1C, the adhesive force between the cured protective film forming film 13 (that is, the protective film) and the
圖3所示之保護膜形成用複合片1C係以下述方式使用，亦即，與圖1所示之保護膜形成用複合片1A同樣地，在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a貼附半導體晶圓(省略圖示)的背面。進而，將治具用接著劑層16的表面16a中的上表面貼附於環狀框等治具。
The composite sheet 1C for forming a protective film shown in FIG. 3 is used in the same manner as the
圖4係以示意方式表示本發明之保護膜形成用複合片的又一實施形態之剖面圖。 Fig. 4 is a cross-sectional view schematically showing still another embodiment of the composite sheet for forming a protective film of the present invention.
關於此處所示之保護膜形成用複合片1D，除不具備治具用接著劑層16之方面以外，與圖3所示之保護膜形成用複合片1C相同。亦即，保護膜形成用複合片1D中，於基材11的一表面11a積層保護膜形成用膜13。於保護膜形成用膜13的表面13a的整個面積層有剝離膜15。
The
圖4所示之保護膜形成用複合片1D係以下述方式使用，亦即，與圖2所示之保護膜形成用複合片1B同樣地，在移除剝離膜15之狀態下，於保護膜形成用膜13的表面13a中的中央側的一部分區域貼附半導體晶圓(省略圖示)的背面。進而，將保護膜形成用膜13的周緣部附近的區域貼附於環狀框等治具。
The protective film forming
圖5係以示意方式表示本發明之保護膜形成用複合片 的又一實施形態之剖面圖。 Fig. 5 schematically shows a composite sheet for forming a protective film of the present invention A cross-sectional view of yet another embodiment.
關於此處所示之保護膜形成用複合片1E，除保護膜形成用膜之形狀不同之方面以外，與圖1所示之保護膜形成用複合片1A相同。亦即，保護膜形成用複合片1E於基材11上具備黏著劑層12，於黏著劑層12上具備保護膜形成用膜23。支持片10為基材11及黏著劑層12之積層體。換言之，保護膜形成用複合片1E具有於支持片10的一表面10a上積層有保護膜形成用膜23之構成。另外，保護膜形成用複合片1E進而於保護膜形成用膜23上具備剝離膜15。
The
保護膜形成用複合片1E中，於基材11的一表面11a積層黏著劑層12。於黏著劑層12的表面12a的一部分，亦即中央側的區域積層有保護膜形成用膜23。並且，於黏著劑層12的表面12a中未積層保護膜形成用膜23之面及保護膜形成用膜23的表面23a(上表面及側面)上積層有剝離膜15。
In the
自上方往下俯視保護膜形成用複合片1E時，保護膜形成用膜23的表面積小於黏著劑層12。例如，具有圓形狀等形狀。
The surface area of the
保護膜形成用複合片1E中，硬化後之保護膜形成用膜23(亦即保護膜)與支持片10之間的黏著力，換言之保護膜與黏著劑層12之間的黏著力較佳為50mN/25mm至
1500mN/25mm。
In the protective film forming
圖5所示之保護膜形成用複合片1E係以下述方式使用，亦即，在移除剝離膜15之狀態下，於保護膜形成用膜23的表面23a貼附半導體晶圓(省略圖示)的背面。進而，將黏著劑層12的表面12a中未積層保護膜形成用膜23之面貼附於環狀框等治具。
The protective film forming
再者，圖5所示之保護膜形成用複合片1E中，亦可於黏著劑層12的表面12a中未積層保護膜形成用膜13之面，與圖1及圖3所示同樣地，積層治具用接著劑層(省略圖示)。具備此種治具用接著劑層之保護膜形成用複合片1E係與圖1及圖3所示之保護膜形成用複合片同樣地，將治具用接著劑層的表面貼附於環狀框等治具而使用。
Furthermore, in the
如此，關於本發明之保護膜形成用複合片，無論支持片及保護膜形成用膜為何種形態，均可具備治具用接著劑層。其中，通常，如圖1及圖3所示，作為具備治具用接著劑層之本發明之保護膜形成用複合片，較佳為於保護膜形成用膜上具備治具用接著劑層。 Thus, the composite sheet for protective film formation of this invention may be provided with the adhesive agent layer for jigs regardless of what form the support sheet and the film for protective film formation are. Among them, generally, as shown in FIGS. 1 and 3 , as the composite sheet for protective film formation of the present invention having an adhesive layer for jigs, it is preferable to have an adhesive layer for jigs on the film for protective film formation.
本發明之保護膜形成用複合片並不限定於圖1至圖5所示之保護膜形成用複合片。亦即，在無損本發明之效果之範圍內，亦可變更或刪除圖1至圖5所示之保護膜形成用 複合片的一部分構成，或者對前文所說明之保護膜形成用複合片進而追加其他構成。 The composite sheet for protective film formation of this invention is not limited to the composite sheet for protective film formation shown in FIGS. 1-5. That is, within the scope of not detracting from the effects of the present invention, the protective film formation shown in FIGS. 1 to 5 can also be changed or deleted. A part of the composite sheet, or adding other configurations to the composite sheet for protective film formation described above.
例如，圖3及圖4所示之保護膜形成用複合片中，亦可於基材11與保護膜形成用膜13之間設置中間層。作為中間層，可根據目的選擇任意中間層。
For example, in the composite sheet for protective film formation shown in FIG. 3 and FIG. 4, an intermediate layer may be provided between the
另外，圖1、圖2及圖5所示之保護膜形成用複合片中，亦可於基材11與黏著劑層12之間設置中間層。亦即，本發明之保護膜形成用複合片中，支持片亦可由基材、中間層及黏著劑層依序積層而成。此處，所謂中間層，與圖3及圖4所示之保護膜形成用複合片中可設置之中間層相同。
In addition, in the composite sheet for protective film formation shown in FIG. 1 , FIG. 2 and FIG. 5 , an intermediate layer may be provided between the
另外，圖1至圖5所示之保護膜形成用複合片中，可將前述中間層以外之層設置於任意部位。 In addition, in the composite sheet for protective film formation shown in FIGS. 1-5, the layer other than the said intermediate|middle layer can be provided in arbitrary places.
另外，本發明之保護膜形成用複合片中，亦可於剝離膜和與該剝離膜直接接觸之層之間產生一部分間隙。 Moreover, in the composite sheet for protective film formation of this invention, some gaps may be produced between the release film and the layer which directly contacts this release film.
另外，本發明之保護膜形成用複合片中，各層之大小或形狀可根據目的任意調節。 Moreover, in the composite sheet for protective film formation of this invention, the size and shape of each layer can be adjusted arbitrarily according to the purpose.
本發明之保護膜形成用複合片中，如後述般，較佳為黏著劑層等支持片中的與保護膜形成用膜直接接觸之層為非能量線硬化性。此種保護膜形成用複合片可使背面具備保護膜之半導體晶片更容易地拾取。 In the composite sheet for forming a protective film of the present invention, as described later, it is preferable that the layer in the support sheet such as the adhesive layer that is in direct contact with the film for forming a protective film is non-energy ray curable. Such a composite sheet for forming a protective film can more easily pick up a semiconductor wafer provided with a protective film on the back surface.
支持片可為透明，亦可為不透明，還可根據目的而著色。 The support sheet may be transparent or opaque, and may be colored according to the purpose.
其中，保護膜形成用膜具有能量線硬化性之本發明中，支持片較佳為使能量線透過之支持片。 Among them, in the present invention in which the film for forming a protective film has energy ray curability, the support sheet is preferably a support sheet that transmits energy rays.
例如，支持片中，波長375nm之光之透過率較佳為30%以上。更佳為50%以上，尤佳為70%以上。藉由前述光之透過率為此種範圍，經由支持片對保護膜形成用膜照射能量線(紫外線)時，保護膜形成用膜之硬化度進一步提高。 For example, in the support sheet, the transmittance of light with a wavelength of 375nm is preferably 30% or more. More preferably at least 50%, especially preferably at least 70%. When the transmittance of the said light is such a range, when the film for protective film formation is irradiated with an energy ray (ultraviolet ray) via a support sheet, the degree of hardening of the film for protective film formation improves further.
另一方面，支持片中，波長375nm之光之透過率的上限值並無特別限定。例如可設為95%。 On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 375 nm is not particularly limited. For example, it can be set to 95%.
另外，支持片中，波長532nm之光之透過率較佳為30%以上。更佳為50%以上，尤佳為70%以上。藉由前述光之透過率為此種範圍，經由支持片對保護膜形成用膜或保護膜照射雷射光而於這些進行印字時，可更清晰地進行印字。 In addition, in the support sheet, the transmittance of light with a wavelength of 532nm is preferably 30% or more. More preferably at least 50%, especially preferably at least 70%. When the transmittance of the said light is such a range, when printing is performed on these by irradiating laser light to the film for protective film formation or a protective film via a support sheet, it can print more clearly.
另一方面，支持片中，波長532nm之光之透過率的上限值並無特別限定。例如可設為95%。 On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 532 nm is not particularly limited. For example, it can be set to 95%.
另外，支持片中，波長1064nm之光之透過率較佳為30%以上。更佳為50%以上，尤佳為70%以上。藉由前述光之透過率為此種範圍，經由支持片對保護膜形成用膜或保護膜照射雷射光而於這些進行印字時，可更清晰地進行 印字。 In addition, in the support sheet, the transmittance of light with a wavelength of 1064nm is preferably 30% or more. More preferably at least 50%, especially preferably at least 70%. When the aforementioned light transmittance is in such a range, when printing is performed by irradiating laser light on the film for forming a protective film or the protective film through the support sheet, it is possible to perform more clearly. printing.
另一方面，支持片中，波長1064nm之光之透過率的上限值並無特別限定。例如可設為95%。 On the other hand, in the support sheet, the upper limit of the transmittance of light having a wavelength of 1064 nm is not particularly limited. For example, it can be set to 95%.
其次，對構成支持片之各層，進行更詳細的說明。 Next, each layer constituting the support sheet will be described in more detail.
○基材 ○Substrate
前述基材為片狀或膜狀，作為前述基材的構成材料，例如可列舉各種樹脂。 The aforementioned base material is in the form of a sheet or a film, and examples of the constituent material of the aforementioned base material include various resins.
作為前述樹脂，可列舉以下樹脂。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-萘二羧酸乙二酯、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；改質聚苯醚；聚苯硫醚；聚 碸；聚醚酮等。 As said resin, the following resin is mentioned. Examples include polyethylenes such as low-density polyethylene (LDPE; low density polyethylene), linear low-density polyethylene (LLDPE; linear low density polyethylene), and high-density polyethylene (HDPE; high density polyethylene); polypropylene, polypropylene Polyolefins other than polyethylene such as butene, polybutadiene, polymethylpentene, and norbornene resin; ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth) Ethylene-based copolymers such as acrylate copolymers and ethylene-norbornene copolymers (copolymers obtained using ethylene as a monomer); vinyl chloride-based resins such as polyvinyl chloride and vinyl chloride copolymers (using vinyl chloride as a monomer obtained resin); polystyrene; polycycloolefin; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene Polyesters such as ethylene 2,6-naphthalene dicarboxylate and wholly aromatic polyesters with aromatic ring groups in all structural units; copolymers of two or more of the aforementioned polyesters; poly(meth)acrylates; Polyurethane; polyacrylate urethane; polyimide; polyamide; polycarbonate; fluororesin; polyacetal; modified polyphenylene ether; polyphenylene sulfide; poly 碸; polyether ketone, etc.
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之量為相對較少量。 Moreover, as said resin, polymer alloys, such as a mixture of the said polyester and resin other than the said polyester, are also mentioned, for example. In the polymer alloy of the aforementioned polyester and a resin other than the aforementioned polyester, it is preferable that the amount of the resin other than the polyester is relatively small.
另外，作為前述樹脂，例如亦可列舉：前文所例示之前述樹脂之1種或2種以上交聯而成之交聯樹脂；使用前文所例示之前述樹脂之1種或2種以上之離子聚合物等改質樹脂。 In addition, examples of the aforementioned resins include: cross-linked resins obtained by cross-linking one or more types of the aforementioned resins exemplified above; modified resins.
再者，本說明書中，「(甲基)丙烯酸」的概念係包括「丙烯酸」及「甲基丙烯酸」兩者。關於與(甲基)丙烯酸類似之用語亦相同。 In addition, 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.
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，這些之組合及比率可任意選擇。 The resin which comprises a base material may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
基材可由1層(單層)構成，亦可由2層以上之多層構成。於由多層構成之情形時，這些多層相互可相同亦可不同，這些多層之組合並無特別限定。 The substrate may be composed of one layer (single layer), or may be composed of two or more layers. When composed of multiple layers, these layers may be the same as or different from each other, and the combination of these layers is not particularly limited.
基材的厚度較佳為50μm至300μm，更佳為60μm至100μm。藉由基材的厚度為此種範圍，前述保護膜形成用複合片的可撓性、及對半導體晶圓或半導體晶片之貼附性 進一步提高。 The thickness of the substrate is preferably from 50 μm to 300 μm, more preferably from 60 μm to 100 μm. When the thickness of the base material is within this range, the flexibility of the protective film forming composite sheet and the adhesion to the semiconductor wafer or the semiconductor wafer Further improve.
此處，所謂「基材的厚度」意指基材整體的厚度。例如，所謂由多層構成之基材的厚度意指構成基材之全部層的合計厚度。 Here, the "thickness of the substrate" means the thickness of the entire substrate. For example, the thickness of a substrate composed of multiple layers means the total thickness of all the layers constituting the substrate.
基材較佳為厚度精度高，亦即，任何部位的厚度不均均得到抑制。上述之構成材料中，作為可用於構成此種厚度精度高的基材之材料，可列舉以下之材料。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 preferably has high thickness accuracy, that is, suppresses uneven thickness at any location. Among the above-mentioned constituent materials, the following materials are exemplified as materials that can be used to constitute such a base material with high thickness accuracy. For example, polyethylene, polyolefins other than polyethylene, polyethylene terephthalate, ethylene-vinyl acetate copolymer, etc. are mentioned.
基材中，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 may contain various known additives such as fillers, colorants, antistatic agents, antioxidants, organic lubricants, catalysts, and softeners (plasticizers) in addition to the main constituent materials such as the aforementioned resins.
基材的光學特性滿足前文所說明之支持片的光學特性即可。亦即，基材可為透明，亦可為不透明。可根據目的而著色，亦可蒸鍍其他層。 It is sufficient that the optical properties of the substrate satisfy the optical properties of the support sheet described above. That is, the substrate may be transparent or opaque. It can be colored according to the purpose, and other layers can also be evaporated.
並且，保護膜形成用膜具有能量線硬化性之本發明中，基材較佳為使能量線透過之基材。 Furthermore, in the present invention in which the film for forming a protective film has energy ray curability, the substrate is preferably a substrate that transmits energy rays.
基材的表面亦可經實施以下處理以提高與設置於該基材上之黏著劑層等其他層之密接性：利用噴砂處理、溶劑處理等之凹凸化處理；或者電暈放電處理、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。 The surface of the base material can also be subjected to the following treatment to improve the adhesion with other layers such as the adhesive layer disposed on the base material: roughening treatment by sand blasting treatment, solvent treatment, etc.; or corona discharge treatment, electron beam treatment, etc. to irradiate Oxidation treatments such as plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, chromic acid treatment, hot air treatment, etc.
另外，基材的表面亦可經實施底塗處理。 In addition, the surface of the substrate may also be treated with a primer.
另外，基材亦可具有抗靜電塗層或以下用途之層等：將保護膜形成用複合片重疊保存時，防止基材接著於其他片或基材接著於吸附台。 In addition, the base material may have an antistatic coating layer or a layer for preventing the base material from sticking to other sheets or the base material from sticking to the suction table when the protective film forming composite sheets are stacked for storage.
這些之中，就抑制因切割時刀片摩擦而導致基材產生斷片之方面而言，基材尤佳為表面經實施電子束照射處理。 Among these, it is particularly preferable that the surface of the substrate is subjected to an electron beam irradiation treatment from the viewpoint of suppressing fragmentation of the substrate due to blade friction during dicing.
基材可利用公知的方法進行製造。例如，含有樹脂之基材可藉由使含有前述樹脂之樹脂組成物成形而進行製造。 The substrate can be produced by a known method. For example, a base material containing a resin can be produced by molding a resin composition containing the aforementioned resin.
○黏著劑層 ○Adhesive layer
前述黏著劑層為片狀或膜狀，含有黏著劑。 The aforementioned adhesive layer is sheet-like or film-like and contains an adhesive.
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。 Examples of the aforementioned adhesive include: acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, ester resins, etc. Resin, preferably acrylic resin.
再者，本發明中，「黏著性樹脂」的概念包括具有黏著性之樹脂及具有接著性之樹脂兩者。例如不僅包含本身具有黏著性之樹脂，亦包含藉由與添加劑等其他成分併用 而顯示黏著性之樹脂、或者藉由存在熱或水等觸發劑而顯示接著性之樹脂等。 Furthermore, in the present invention, the concept of "adhesive resin" includes both adhesive resin and adhesive resin. For example, it includes not only the adhesive resin itself, but also the combination of other ingredients such as additives. A resin that exhibits adhesiveness, or a resin that exhibits adhesiveness due to the presence of a trigger such as heat or water, etc.
黏著劑層可由1層(單層)構成，亦可由2層以上之多層構成。於由多層構成之情形時，這些多層相互可相同亦可不同，這些多層之組合並無特別限定。 The adhesive layer may be composed of one layer (single layer), or may be composed of two or more layers. When composed of multiple layers, these layers may be the same as or different from each other, and the combination of these layers is not particularly limited.
黏著劑層的厚度較佳為1μm至100μm。更佳為1μm至60μm，尤佳為1μm至30μm。 The thickness of the adhesive layer is preferably 1 μm to 100 μm. More preferably, it is 1 μm to 60 μm, and most preferably, it is 1 μm to 30 μm.
此處，所謂「黏著劑層的厚度」意指黏著劑層整體的厚度。例如，所謂由多層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厚度。 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 multiple layers means the total thickness of all the layers constituting the adhesive layer.
黏著劑層的光學特性滿足前文所說明之支持片的光學特性即可。亦即，黏著劑層可為透明，亦可為不透明。亦可根據目的而著色。 It is sufficient that the optical properties of the adhesive layer satisfy the optical properties of the support sheet described above. That is, the adhesive layer may be transparent or opaque. It can also be colored according to the purpose.
並且，保護膜形成用膜具有能量線硬化性之本發明中，黏著劑層較佳為使能量線透過之黏著劑層。 Furthermore, in the present invention in which the film for protective film formation has energy ray curability, the adhesive layer is preferably an adhesive layer that allows energy rays to pass through.
黏著劑層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。使用能量線硬化性之黏著劑所形成之黏著劑層可容易地調節硬化前及硬化後的物性。 The adhesive layer may be formed using an energy ray-curable adhesive or may be formed using a non-energy ray-curable adhesive. The adhesive layer formed by using the energy ray curable adhesive can easily adjust the physical properties before and after curing.
<<黏著劑組成物>> <<Adhesive composition>>
黏著劑層可使用含有黏著劑之黏著劑組成物而形成。例如，於黏著劑層之形成對象面塗敷黏著劑組成物，視需要使之乾燥，藉此可於目標部位形成黏著劑層。關於黏著劑層的更具體的形成方法，與其他層的形成方法一起，隨後詳細地進行說明。黏著劑組成物中的常溫下不會氣化的成分彼此的含量比率，通常與黏著劑層中的前述成分彼此的含量比率相同。再者，本說明書中，所謂「常溫」意指不特別冷或特別熱之溫度，亦即平常之溫度。例如可列舉15℃至25℃之溫度等。 The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, the adhesive layer can be formed on the target site by applying the adhesive composition on the surface to be formed of the adhesive layer and drying it if necessary. A more specific method of forming the adhesive layer will be described in detail later together with methods of forming other layers. The content ratio of the components that do not vaporize at normal temperature in the adhesive composition is usually the same as the content ratio of the aforementioned components in the adhesive layer. Furthermore, in this specification, the so-called "normal temperature" means a temperature that is neither particularly cold nor particularly hot, that is, an ordinary temperature. For example, the temperature etc. of 15 degreeC - 25 degreeC are mentioned.
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、繞線棒(Meyer bar)式塗佈機、接觸式塗佈機等。 The adhesive composition may be applied by a known method. For example, methods using the following various coaters: air knife coater, blade coater, rod coater, gravure coater, roll coater, roll knife coater, curtain coater, etc. Cloth machine, die coater, knife coater, screen coater, Meyer bar coater, contact coater, etc.
黏著劑組成物的乾燥條件並無特別限定。但是，於黏著劑組成物含有後述溶劑之情形時，較佳為進行加熱乾燥。該情形時，較佳為於例如70℃至130℃且10秒至5分鐘之條件下進行乾燥。 The drying conditions of the adhesive composition are not particularly limited. However, when the adhesive composition contains the solvent mentioned later, it is preferable to perform heat drying. In this case, it is preferable to dry under conditions of, for example, 70° C. to 130° C. and 10 seconds to 5 minutes.
於黏著劑層為能量線硬化性之情形時，作為含有能量線硬化性黏著劑之黏著劑組成物，亦即能量線硬化性之黏 著劑組成物，可列舉以下之黏著劑組成物。例如可列舉以下黏著劑組成物等：黏著劑組成物(I-1)，含有非能量線硬化性之黏著性樹脂(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)，含有能量線硬化性之黏著性樹脂(I-2a)(以下有時簡稱為「黏著性樹脂(I-2a)」)，該黏著性樹脂(I-2a)於非能量線硬化性之黏著性樹脂(I-1a)的側鏈導入有不飽和基；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。 When the adhesive layer is energy ray curable, as an adhesive composition containing an energy ray curable adhesive, that is, an energy ray curable adhesive The adhesive composition includes the following adhesive compositions. For example, the following adhesive composition can be mentioned: Adhesive composition (I-1), containing non-energy ray-curable adhesive resin (I-1a) (hereinafter sometimes referred to as "adhesive resin (I-1a) ”), and energy ray-curable compounds; adhesive composition (I-2), containing energy ray-curable adhesive resin (I-2a) (hereinafter sometimes referred to as “adhesive resin (I-2a)” ), the adhesive resin (I-2a) has an unsaturated group introduced into the side chain of the non-energy ray-curable adhesive resin (I-1a); the adhesive composition (I-3) contains the aforementioned adhesive resin (I-2a), and an energy ray-curable compound.
<黏著劑組成物(I-1)> <Adhesive composition (I-1)>
如上所述，前述黏著劑組成物(I-1)含有非能量線硬化性之黏著性樹脂(I-1a)、及能量線硬化性化合物。 As described above, the adhesive composition (I-1) contains a non-energy ray-curable adhesive resin (I-1a) and an energy ray-curable compound.
[黏著性樹脂(I-1a)] [Adhesive resin (I-1a)]
前述黏著性樹脂(I-1a)較佳為丙烯酸系樹脂。 The aforementioned adhesive resin (I-1a) is preferably an acrylic resin.
作為前述丙烯酸系樹脂，例如可列舉：至少具有源自(甲基)丙烯酸烷基酯之結構單元之丙烯酸系聚合物。 As said acrylic resin, the acrylic polymer which has the structural unit derived from an alkyl (meth)acrylate at least is mentioned, for example.
前述丙烯酸系樹脂所具有之結構單元可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The structural unit which the said acrylic resin has may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
作為前述(甲基)丙烯酸烷基酯，例如可列舉：構成烷基酯之烷基的碳數為1至20之(甲基)丙烯酸烷基酯。前述 烷基較佳為直鏈狀或支鏈狀。 As said alkyl (meth)acrylate, the alkyl (meth)acrylate whose carbon number of the alkyl group which comprises an alkyl ester is 1-20 is mentioned, for example. aforementioned The alkyl group is preferably linear or branched.
作為(甲基)丙烯酸烷基酯，更具體而言，可列舉以下之(甲基)丙烯酸烷基酯。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)、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等。 As an alkyl (meth)acrylate, the following alkyl (meth)acrylate is mentioned more specifically. Examples include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate ) isobutyl acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, (meth)acrylate base) decyl acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, (meth)acrylate base) myristyl acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmyl (meth)acrylate), Heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), nonadecyl (meth)acrylate, twenty-decyl (meth)acrylate Alkyl esters, etc.
就黏著劑層的黏著力提高之方面而言，前述丙烯酸系聚合物較佳為具有源自前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯之結構單元。並且，就黏著劑層的黏著力進一步提高之方面而言，前述烷基的碳數較佳為4至12，更佳為4至8。另外，前述烷基的碳數為4以上之(甲基)丙烯酸烷基酯較佳為丙烯酸烷基酯。 It is preferable that the said acrylic polymer has the structural unit derived from the said alkyl group and C4 or more alkyl (meth)acrylate from the point which the adhesive force of an adhesive agent layer improves. In addition, the carbon number of the alkyl group is preferably 4-12, more preferably 4-8, from the point of view of further improving the adhesive force of the adhesive layer. In addition, the alkyl (meth)acrylate having 4 or more carbon atoms in the alkyl group is preferably an alkyl acrylate.
前述丙烯酸系聚合物中，較佳為除源自(甲基)丙烯酸烷基酯之結構單元以外，進而具有源自含官能基之單體之結構單元。 In the aforementioned acrylic polymer, it is preferable to have a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate.
作為前述含官能基之單體，例如可列舉以下單體，該單體可藉由前述官能基與後述之交聯劑反應而成為交聯的起點，或者可藉由前述官能基與後述之含不飽和基之化合物中的不飽和基反應，而於丙烯酸系聚合物的側鏈導入不飽和基。 As the above-mentioned functional group-containing monomer, for example, the following monomers can be mentioned. The unsaturated group in the compound of the unsaturated group is reacted, and the unsaturated group is introduced into the side chain of the acrylic polymer.
作為含官能基之單體中的前述官能基，例如可列舉：羥基、羧基、胺基、環氧基等。 As said functional group in a functional group containing monomer, a hydroxyl group, a carboxyl group, an amino group, an epoxy group etc. are mentioned, for example.
亦即，作為含官能基之單體，例如可列舉：含羥基之單體、含羧基之單體、含胺基之單體、含環氧基之單體等。 That is, as a functional group containing monomer, a hydroxyl group containing monomer, a carboxyl group containing monomer, an amino group containing monomer, an epoxy group containing monomer etc. are mentioned, for example.
作為前述含羥基之單體，可列舉以下之單體。例如可列舉：(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(甲基)丙烯酸羥基烷基酯；乙烯醇、烯丙醇等非(甲基)丙烯酸系不飽和醇(不具有(甲基)丙烯醯基骨架之不飽和醇)等。 The following monomers are mentioned as said hydroxyl group containing monomer. For example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth) Hydroxyalkyl (meth)acrylates such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; non-(meth)acrylates such as vinyl alcohol and allyl alcohol ) acrylic unsaturated alcohol (unsaturated alcohol not having a (meth)acryl skeleton) and the like.
作為前述含羧基之單體，可列舉以下之單體。例如可 列舉：(甲基)丙烯酸、丁烯酸等乙烯性不飽和單羧酸(具有乙烯性不飽和鍵之單羧酸)；反丁烯二酸、衣康酸、順丁烯二酸、檸康酸等乙烯性不飽和二羧酸(具有乙烯性不飽和鍵之二羧酸)；前述乙烯性不飽和二羧酸之酐；2-羧基乙酯等(甲基)丙烯酸羧基烷基甲基丙烯酸酯等。 The following monomers are mentioned as said carboxyl group containing monomer. for example can List: (meth)acrylic acid, crotonic acid and other ethylenically unsaturated monocarboxylic acids (monocarboxylic acids with ethylenically unsaturated bonds); fumaric acid, itaconic acid, maleic acid, citron Ethylenically unsaturated dicarboxylic acids such as acids (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; (meth)acrylic acid carboxyalkylmethacrylic acid such as 2-carboxyethyl ester Esters etc.
含官能基之單體較佳為含羥基之單體、含羧基之單體，更佳為含羥基之單體。 The functional group-containing monomer is preferably a hydroxyl-containing monomer or a carboxyl-containing monomer, more preferably a hydroxyl-containing monomer.
構成前述丙烯酸系聚合物之含官能基之單體可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The functional group-containing monomer constituting the aforementioned acrylic polymer may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
前述丙烯酸系聚合物中，源自含官能基之單體之結構單元的含量相對於結構單元的總量，較佳為1質量%至35質量%。更佳為2質量%至32質量%，尤佳為3質量%至30質量%。 In the aforementioned acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1% by mass to 35% by mass relative to the total amount of the structural units. More preferably, it is 2 mass % to 32 mass %, Most preferably, it is 3 mass % to 30 mass %.
前述丙烯酸系聚合物中，亦可除源自(甲基)丙烯酸烷基酯之結構單元、及源自含官能基之單體之結構單元以外，進而具有源自其他單體之結構單元。 In addition to the structural unit derived from the alkyl (meth)acrylate and the structural unit derived from the functional group containing monomer, the said acrylic polymer may further have the structural unit derived from another monomer.
前述其他單體只要能夠與(甲基)丙烯酸烷基酯等共聚合，則並無特別限定。 The aforementioned other monomers are not particularly limited as long as they can be copolymerized with an alkyl (meth)acrylate or the like.
作為前述其他單體，例如可列舉：苯乙烯、α-甲基苯 乙烯、乙烯基甲苯、甲酸乙烯酯、乙酸乙烯酯、丙烯腈、丙烯醯胺等。 Examples of the aforementioned other monomers include: styrene, α-methylbenzene Ethylene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, acrylamide, etc.
構成前述丙烯酸系聚合物之前述其他單體可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The said other monomer which comprises the said acrylic polymer may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
前述丙烯酸系聚合物可用作上述之非能量線硬化性之黏著性樹脂(I-1a)。 The aforementioned acrylic polymer can be used as the aforementioned non-energy ray curable adhesive resin (I-1a).
另一方面，使前述丙烯酸系聚合物中的官能基與具有能量線聚合性不飽和基(能量線聚合性基)之含不飽和基之化合物反應而成之化合物可用作上述之能量線硬化性之黏著性樹脂(I-2a)。 On the other hand, a compound obtained by reacting a functional group in the aforementioned acrylic polymer with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group (energy ray polymerizable group) can be used for the aforementioned energy ray curing. Sexual adhesive resin (I-2a).
黏著劑組成物(I-1)所含有之黏著性樹脂(I-1a)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The adhesive resin (I-1a) contained in the adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-1)中，黏著性樹脂(I-1a)的含量較佳為5質量%至99質量%。更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 In the adhesive composition (I-1), the content of the adhesive resin (I-1a) is preferably 5% by mass to 99% by mass. More preferably, it is 10 mass % to 95 mass %, Most preferably, it is 15 mass % to 90 mass %.
[能量線硬化性化合物] [Energy Beam Curing Compound]
作為黏著劑組成物(I-1)所含有之前述能量線硬化性 化合物，可列舉具有能量線聚合性不飽和基且可藉由照射能量線而硬化之單體或低聚物。 The aforementioned energy ray hardening properties contained in the adhesive composition (I-1) Examples of the compound include monomers or oligomers that have an energy-ray-polymerizable unsaturated group and can be cured by irradiation with energy rays.
作為能量線硬化性化合物中的單體，可列舉以下之單體。例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇(甲基)丙烯酸酯、季戊四醇四(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(甲基)丙烯酸酯等多元(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯；聚酯(甲基)丙烯酸酯；聚醚(甲基)丙烯酸酯；環氧(甲基)丙烯酸酯等。 Examples of the monomer in the energy ray-curable compound include the following monomers. Examples include: trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediene Poly(meth)acrylates such as alcohol di(meth)acrylate, 1,6-hexanediol (meth)acrylate; (meth)urethane acrylate; polyester (meth)acrylate ; Polyether (meth) acrylate; Epoxy (meth) acrylate, etc.
能量線硬化性化合物中，作為低聚物，例如可列舉：上述所例示之單體進行聚合而成之低聚物等。 Among the energy ray-curable compounds, examples of the oligomer include oligomers obtained by polymerizing the monomers exemplified above, and the like.
就分子量相對較大，不易使黏著劑層的儲存彈性率降低之方面而言，能量線硬化性化合物較佳為(甲基)丙烯酸胺基甲酸酯、(甲基)丙烯酸胺基甲酸酯低聚物。 The energy ray-curable compound is preferably (meth)urethane acrylate, (meth)urethane Oligomer.
黏著劑組成物(I-1)所含有之前述能量線硬化性化合物可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The aforementioned energy ray-curable compound contained in the adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
前述黏著劑組成物(I-1)中，前述能量線硬化性化合物的含量較佳為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 aforementioned adhesive composition (I-1), the content of the aforementioned energy ray-curable compound is preferably 1% by mass to 95% by mass. More preferably, it is 5 mass % to 90 mass %, Most preferably, it is 10 mass % to 85 mass %.
[交聯劑] [Crosslinking agent]
作為黏著性樹脂(I-1a)，有時使用除源自(甲基)丙烯酸烷基酯之結構單元以外，進而具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物。該情形時，黏著劑組成物(I-1)較佳為進而含有交聯劑。 As the adhesive resin (I-1a), the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate may be used. In this case, it is preferable that the adhesive composition (I-1) further contains a crosslinking agent.
前述交聯劑例如與前述官能基反應而使黏著性樹脂(I-1a)彼此交聯。 The said crosslinking agent reacts with the said functional group, for example, and crosslinks adhesive resin (I-1a) mutually.
作為交聯劑，可列舉以下之化合物。例如可列舉：甲苯二異氰酸酯、六亞甲基二異氰酸酯、苯二甲基二異氰酸酯、這些二異氰酸酯之加合物等異氰酸酯系交聯劑(具有異氰酸酯基之交聯劑)；乙二醇縮水甘油醚等環氧系交聯劑(具有縮水甘油基之交聯劑)；六[1-(2-甲基)-氮丙啶基]三膦三嗪等氮丙啶系交聯劑(具有氮丙啶基之交聯劑)；鋁螯合物等金屬螯合物系交聯劑(具有金屬螯合物結構之交聯劑)；異氰脲酸酯系交聯劑(具有異氰脲酸骨架之交聯劑)等。 As a crosslinking agent, the following compounds are mentioned. Examples include isocyanate-based crosslinking agents (crosslinking agents having isocyanate groups) such as toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and adducts of these diisocyanates; ethylene glycol glycidol Epoxy-based cross-linking agents such as ethers (cross-linking agents with glycidyl groups); aziridine-based cross-linking agents such as hexa[1-(2-methyl)-aziridinyl]triphosphine triazine (with nitrogen propidyl-based cross-linking agent); aluminum chelate and other metal chelate-based cross-linking agents (cross-linking agents with metal chelate structures); isocyanurate-based cross-linking agents (with isocyanuric acid Skeleton cross-linking agent), etc.
就提高黏著劑的凝聚力而提高黏著劑層的黏著力之方面、及容易獲取等方面而言，交聯劑較佳為異氰酸酯系交聯劑。 The cross-linking agent is preferably an isocyanate-based cross-linking agent in terms of increasing the cohesive force of the adhesive to increase the adhesion of the adhesive layer, and in terms of ease of acquisition.
黏著劑組成物(I-1)所含有之交聯劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The crosslinking agent contained in the adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
前述黏著劑組成物(I-1)中，交聯劑的含量較佳為相對於黏著性樹脂(I-1a)的含量100質量份，為0.01質量份至50質量份。更佳為0.1質量份至20質量份，尤佳為0.3質量份至15質量份。 In the aforementioned adhesive composition (I-1), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the adhesive resin (I-1a). More preferably, it is 0.1 to 20 parts by mass, and most preferably, it is 0.3 to 15 parts by mass.
[光聚合起始劑] [Photopolymerization Initiator]
黏著劑組成物(I-1)亦可進而含有光聚合起始劑。對於含有光聚合起始劑之黏著劑組成物(I-1)，即便照射紫外線等相對較低能量之能量線，亦充分地進行硬化反應。 The adhesive composition (I-1) may further contain a photopolymerization initiator. Even if the adhesive composition (I-1) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.
作為前述光聚合起始劑，可列舉以下之化合物。例如可列舉：安息香、安息香甲醚、安息香乙醚、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；苄基苯基硫化物、一硫化四甲基秋蘭姆等硫化物化合物；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；2-氯蒽醌等。 The following compounds are mentioned as said photoinitiator. Examples include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal and other benzoin compounds; acetophenone, 2-hydroxy -Acetophenone compounds such as 2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one; bis(2,4 ,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and other acylphosphine oxide compounds; benzylphenyl sulfide, monosulfide Sulfide compounds such as tetramethylthiuram; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone, etc. Thioxanthone compounds; peroxide compounds; diketone compounds such as diacetyl; benzoyl; dibenzoyl; benzophenone; 2,4-diethylthioxanthone; 1,2-diphenyl Methane; 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone; 2-chloroanthraquinone, etc.
另外，作為前述光聚合起始劑，例如亦可使用1-氯蒽醌等醌化合物；胺等光增感劑等。 Moreover, as said photoinitiator, the quinone compounds, such as 1-chloroanthraquinone, the photosensitizers, such as an amine, etc. can also be used, for example.
黏著劑組成物(I-1)所含有之光聚合起始劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The photopolymerization initiator contained in the adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-1)中，光聚合起始劑的含量較佳為相對於前述能量線硬化性化合物的含量100質量份，為0.01質量份至20質量份。更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the adhesive composition (I-1), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the content of the energy ray-curable compound. More preferably, it is 0.03 parts by mass to 10 parts by mass, and most preferably, it is 0.05 parts by mass to 5 parts by mass.
[其他添加劑] [Other additives]
黏著劑組成物(I-1)中，在無損本發明之效果之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-1) may contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the effects of the present invention.
作為前述其他添加劑，例如可列舉：抗靜電劑、抗氧化劑、軟化劑(塑化劑)、填充材料(填料)、防鏽劑、著色劑(顏料、染料)、增感劑、黏著賦予劑、反應延遲劑、交聯促進劑(觸媒)等公知的添加劑。 Examples of the aforementioned other additives include antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, adhesion imparting agents, Known additives such as a reaction delayer and a crosslinking accelerator (catalyst).
再者，所謂反應延遲劑，例如抑制因混入至黏著劑組成物(I-1)中之觸媒之作用而導致保存中之黏著劑組成物(I-1)中進行目的外的交聯反應。作為反應延遲劑，例如可列舉藉由針對觸媒之螯合物而形成螯合物錯合物之化合物。更具體而言，可列舉1分子中具有2個以上之羰基 (-C(=O)-)之化合物。 Furthermore, the so-called reaction delaying agent, for example, inhibits the unintended crosslinking reaction in the adhesive composition (I-1) under storage due to the action of the catalyst mixed in the adhesive composition (I-1). . As a reaction retarder, the compound which forms a chelate complex by the chelate with respect to a catalyst is mentioned, for example. More specifically, those having two or more carbonyl groups in one molecule include (-C(=O)-) compounds.
黏著劑組成物(I-1)所含有之其他添加劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-1) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-1)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 In the adhesive composition (I-1), the content of other additives is not particularly limited, and may be appropriately selected according to the type of the other additives.
[溶劑] [solvent]
黏著劑組成物(I-1)亦可含有溶劑。黏著劑組成物(I-1)藉由含有溶劑，對塗敷對象面之塗敷適性提高。 The adhesive composition (I-1) may also contain a solvent. When the adhesive composition (I-1) contains a solvent, the applicability to the surface to be coated improves.
前述溶劑較佳為有機溶劑。作為前述有機溶劑，例如可列舉：甲基乙基酮、丙酮等酮；乙酸乙酯等酯(羧酸酯)；四氫呋喃、二噁烷等醚；環己烷、正己烷等脂肪族烴；甲苯、二甲苯等芳香族烴；1-丙醇、2-丙醇等醇等。 The aforementioned solvent is preferably an organic solvent. Examples of the organic solvent include: ketones such as methyl ethyl ketone and acetone; esters (carboxylates) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; aliphatic hydrocarbons such as cyclohexane and n-hexane; , xylene and other aromatic hydrocarbons; alcohols such as 1-propanol and 2-propanol, etc.
作為前述溶劑，例如可將製造黏著性樹脂(I-1a)時所使用之溶劑不自黏著性樹脂(I-1a)中去除，而直接於黏著劑組成物(I-1)中使用。進而，亦可於製造黏著劑組成物(I-1)時，另行添加與製造黏著性樹脂(I-1a)時所使用之溶劑相同種類或不同種類之溶劑。 As the aforementioned solvent, for example, the solvent used in the production of the adhesive resin (I-1a) can be directly used in the adhesive composition (I-1) without being removed from the adhesive resin (I-1a). Furthermore, when producing the adhesive composition (I-1), a solvent of the same type or a different type from the solvent used for producing the adhesive resin (I-1a) may be added separately.
黏著劑組成物(I-1)所含有之溶劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-1) may be only one kind, or may be two or more kinds. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-1)中，溶劑的含量並無特別限定，適宜調節即可。 In the adhesive composition (I-1), the content of the solvent is not particularly limited, and may be adjusted appropriately.
<黏著劑組成物(I-2)> <Adhesive composition (I-2)>
如上所述，前述黏著劑組成物(I-2)含有能量線硬化性之黏著性樹脂(I-2a)，該黏著性樹脂(I-2a)於非能量線硬化性之黏著性樹脂(I-1a)的側鏈導入有不飽和基。 As described above, the adhesive composition (I-2) contains the energy ray-curable adhesive resin (I-2a), and the adhesive resin (I-2a) is added to the non-energy ray-curable adhesive resin (I-2a). -1a) has an unsaturated group introduced into the side chain.
[黏著性樹脂(I-2a)] [Adhesive resin (I-2a)]
前述黏著性樹脂(I-2a)例如藉由使黏著性樹脂(I-1a)中的官能基與具有能量線聚合性不飽和基之含不飽和基之化合物反應而獲得。 The aforementioned adhesive resin (I-2a) is obtained, for example, by reacting a functional group in the adhesive resin (I-1a) with an unsaturated group-containing compound having an energy ray polymerizable unsaturated group.
前述含不飽和基之化合物除具有前述能量線聚合性不飽和基以外，進而具有以下基，該基藉由與黏著性樹脂(I-1a)中的官能基反應，可與黏著性樹脂(I-1a)鍵結。 The aforementioned unsaturated group-containing compound has, in addition to the aforementioned energy ray polymerizable unsaturated group, a group that reacts with a functional group in the adhesive resin (I-1a) to react with the adhesive resin (I-1a). - 1a) Bonding.
作為前述能量線聚合性不飽和基，例如可列舉：(甲基)丙烯醯基、乙烯基(Ethenyl group)、烯丙基(2-丙烯基)等。較佳為(甲基)丙烯醯基。 As said energy ray polymerizable unsaturated group, a (meth)acryl group, a vinyl group (Ethenyl group), an allyl group (2-propenyl group), etc. are mentioned, for example. A (meth)acryl group is preferred.
作為可與黏著性樹脂(I-1a)中的官能基鍵結之基，例 如可列舉：可與羥基或胺基鍵結之異氰酸酯基及縮水甘油基、以及可與羧基或環氧基鍵結之羥基及胺基等。 As the group that can be bonded to the functional group in the adhesive resin (I-1a), for example For example, an isocyanate group and a glycidyl group which can be bonded to a hydroxyl group or an amino group, a hydroxyl group and an amino group which can be bonded to a carboxyl group or an epoxy group, and the like can be mentioned.
作為前述含不飽和基之化合物，例如可列舉：異氰酸(甲基)丙烯醯氧基乙酯、(甲基)丙烯醯基異氰酸酯、(甲基)丙烯酸縮水甘油酯等。 Examples of the unsaturated group-containing compound include (meth)acryloxyethyl isocyanate, (meth)acryl isocyanate, and glycidyl (meth)acrylate.
黏著劑組成物(I-2)所含有之黏著性樹脂(I-2a)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-2)中，黏著性樹脂(I-2a)的含量較佳為5質量%至99質量%。更佳為10質量%至95質量%，尤佳為10質量%至90質量%。 In the adhesive composition (I-2), the content of the adhesive resin (I-2a) is preferably 5% by mass to 99% by mass. More preferably, it is 10 mass % to 95 mass %, Most preferably, it is 10 mass % to 90 mass %.
[交聯劑] [Crosslinking agent]
於使用例如與黏著性樹脂(I-1a)中相同的具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物作為黏著性樹脂(I-2a)之情形時，黏著劑組成物(I-2)亦可進而含有交聯劑。 In the case of using, for example, the aforementioned acrylic polymer having the same structural unit derived from a functional group-containing monomer as in the adhesive resin (I-1a) as the adhesive resin (I-2a), the adhesive composition (I-2) may further contain a crosslinking agent.
作為黏著劑組成物(I-2)中的前述交聯劑，可列舉與黏著劑組成物(I-1)中的交聯劑相同的化合物。 Examples of the crosslinking agent in the adhesive composition (I-2) include the same compounds as the crosslinking agent in the adhesive composition (I-1).
黏著劑組成物(I-2)所含有之交聯劑可僅為1種，亦可 為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The crosslinking agent contained in the adhesive composition (I-2) may be only one type, or There are two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
前述黏著劑組成物(I-2)中，交聯劑的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至50質量份。更佳為0.1質量份至20質量份，尤佳為0.3質量份至15質量份。 In the aforementioned adhesive composition (I-2), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). More preferably, it is 0.1 to 20 parts by mass, and most preferably, it is 0.3 to 15 parts by mass.
[光聚合起始劑] [Photopolymerization Initiator]
黏著劑組成物(I-2)亦可進而含有光聚合起始劑。對於含有光聚合起始劑之黏著劑組成物(I-2)，即便照射紫外線等相對較低能量之能量線，亦充分地進行硬化反應。 The adhesive composition (I-2) may further contain a photopolymerization initiator. Even if the adhesive composition (I-2) containing a photopolymerization initiator is irradiated with relatively low-energy energy rays such as ultraviolet rays, the hardening reaction proceeds sufficiently.
作為黏著劑組成物(I-2)中的前述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同的化合物。 Examples of the photopolymerization initiator in the adhesive composition (I-2) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1).
黏著劑組成物(I-2)所含有之光聚合起始劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The photoinitiator contained in the adhesive composition (I-2) may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-2)中，光聚合起始劑的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至20質量份。更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the adhesive composition (I-2), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-2a). More preferably, it is 0.03 parts by mass to 10 parts by mass, and most preferably, it is 0.05 parts by mass to 5 parts by mass.
[其他添加劑] [Other additives]
黏著劑組成物(I-2)中，在無損本發明之效果之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-2) may contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the effect of the present invention.
作為黏著劑組成物(I-2)中的前述其他添加劑，可列舉與黏著劑組成物(I-1)中的其他添加劑相同的化合物。 Examples of the other additives in the adhesive composition (I-2) include the same compounds as the other additives in the adhesive composition (I-1).
黏著劑組成物(I-2)所含有之其他添加劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-2)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 In the adhesive composition (I-2), the content of other additives is not particularly limited, and may be appropriately selected according to the type of the other additives.
[溶劑] [solvent]
以與黏著劑組成物(I-1)之情形相同之目的，黏著劑組成物(I-2)亦可含有溶劑。 The adhesive composition (I-2) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).
作為黏著劑組成物(I-2)中的前述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同的溶劑。 Examples of the solvent in the adhesive composition (I-2) include the same solvents as those in the adhesive composition (I-1).
黏著劑組成物(I-2)所含有之溶劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-2) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-2)中，溶劑的含量並無特別限定，適宜調節即可。 In the adhesive composition (I-2), the content of the solvent is not particularly limited, and may be adjusted appropriately.
<黏著劑組成物(I-3)> <Adhesive composition (I-3)>
如上所述，前述黏著劑組成物(I-3)含有前述黏著性樹脂(I-2a)、及能量線硬化性化合物。 As described above, the adhesive composition (I-3) contains the adhesive resin (I-2a) and an energy ray-curable compound.
黏著劑組成物(I-3)中，黏著性樹脂(I-2a)的含量較佳為5質量%至99質量%。更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 In the adhesive composition (I-3), the content of the adhesive resin (I-2a) is preferably 5% by mass to 99% by mass. More preferably, it is 10 mass % to 95 mass %, Most preferably, it is 15 mass % to 90 mass %.
[能量線硬化性化合物] [Energy Beam Curing Compound]
作為黏著劑組成物(I-3)所含有之前述能量線硬化性化合物，可列舉：具有能量線聚合性不飽和基，且可藉由照射能量線而硬化之單體及低聚物。亦即，可列舉與黏著劑組成物(I-1)所含有之能量線硬化性化合物相同的化合物。 Examples of the energy ray-curable compound contained in the adhesive composition (I-3) include monomers and oligomers that have an energy ray polymerizable unsaturated group and are curable by irradiation with energy ray. That is, the same compound as the energy ray-curable compound contained in the adhesive composition (I-1) can be mentioned.
黏著劑組成物(I-3)所含有之前述能量線硬化性化合物可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The aforementioned energy ray-curable compound contained in the adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
前述黏著劑組成物(I-3)中，前述能量線硬化性化合物的含量相對於黏著性樹脂(I-2a)的含量100質量份，較佳為0.01質量份至300質量份。更佳為0.03質量份至200質量份，尤佳為0.05質量份至100質量份。 In the adhesive composition (I-3), the content of the energy ray-curable compound is preferably 0.01 to 300 parts by mass relative to 100 parts by mass of the adhesive resin (I-2a). More preferably, it is 0.03 mass parts to 200 mass parts, and especially preferably it is 0.05 mass parts to 100 mass parts.
[光聚合起始劑] [Photopolymerization Initiator]
黏著劑組成物(I-3)亦可進而含有光聚合起始劑。對於 含有光聚合起始劑之黏著劑組成物(I-3)，即便照射紫外線等相對較低能量之能量線，亦充分地進行硬化反應。 The adhesive composition (I-3) may further contain a photopolymerization initiator. for The adhesive composition (I-3) containing a photopolymerization initiator sufficiently proceeds a hardening reaction even when irradiated with relatively low-energy energy rays such as ultraviolet rays.
作為黏著劑組成物(I-3)中的前述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同的化合物。 Examples of the photopolymerization initiator in the adhesive composition (I-3) include the same compounds as the photopolymerization initiator in the adhesive composition (I-1).
黏著劑組成物(I-3)所含有之光聚合起始劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The photoinitiator contained in the adhesive composition (I-3) may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-3)中，光聚合起始劑的含量相對於黏著性樹脂(I-2a)及前述能量線硬化性化合物的總含量100質量份，較佳為0.01質量份至20質量份。更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the adhesive composition (I-3), the content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total content of the adhesive resin (I-2a) and the aforementioned energy ray-curable compound. parts by mass. More preferably, it is 0.03 parts by mass to 10 parts by mass, and most preferably, it is 0.05 parts by mass to 5 parts by mass.
[其他添加劑] [Other additives]
黏著劑組成物(I-3)中，在無損本發明之效果之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-3) may contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the effect of the present invention.
作為前述其他添加劑，可列舉與黏著劑組成物(I-1)中的其他添加劑相同的化合物。 Examples of the above-mentioned other additives include the same compounds as the other additives in the adhesive composition (I-1).
黏著劑組成物(I-3)所含有之其他添加劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-3)中，其他添加劑的含量並無特別限 定，根據該其他添加劑的種類適宜選擇即可。 In the adhesive composition (I-3), the content of other additives is not particularly limited What is necessary is just to select appropriately according to the kind of this other additive.
[溶劑] [solvent]
以與黏著劑組成物(I-1)之情形相同之目的，黏著劑組成物(I-3)亦可含有溶劑。 The adhesive composition (I-3) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).
作為黏著劑組成物(I-3)中的前述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同的溶劑。 Examples of the solvent in the adhesive composition (I-3) include the same solvents as those in the adhesive composition (I-1).
黏著劑組成物(I-3)所含有之溶劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-3) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-3)中，溶劑的含量並無特別限定，適宜調節即可。 In the adhesive composition (I-3), the content of the solvent is not particularly limited, and may be adjusted appropriately.
<黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物> <Adhesive composition other than adhesive composition (I-1) to adhesive composition (I-3)>
前文主要對黏著劑組成物(I-1)、黏著劑組成物(I-2)及黏著劑組成物(I-3)進行了說明。對於這些3種黏著劑組成物以外之全部黏著劑組成物(本說明書中，稱為「黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物」)，亦可同樣地使用作為這些的含有成分所說明之成分。 The adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3) have been mainly described above. For all adhesive compositions other than these three adhesive compositions (in this specification, referred to as "adhesive compositions other than adhesive composition (I-1) to adhesive composition (I-3)") , The components described as these contained components can also be used in the same manner.
作為黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物，除能量線硬化性之黏著劑組成物以外，亦可列舉非能量線硬化性之黏著劑組成物。 Examples of adhesive compositions other than adhesive composition (I-1) to adhesive composition (I-3) include non-energy-ray-curable adhesives in addition to energy-ray-curable adhesive compositions. Composition.
作為非能量線硬化性之黏著劑組成物，可列舉以下之黏著劑組成物。例如可列舉：含有丙烯酸系樹脂、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、酯系樹脂等非能量線硬化性之黏著性樹脂(I-1a)之黏著劑組成物(I-4)，較佳為含有丙烯酸系樹脂之黏著劑組成物。 Examples of non-energy ray-curable adhesive compositions include the following adhesive compositions. For example, non-energy ray-curable materials containing acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, ester resin, etc. The adhesive composition (I-4) of the adhesive resin (I-1a) is preferably an adhesive composition containing an acrylic resin.
黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物較佳為含有1種或2種以上之交聯劑。前述交聯劑的含量可設為與上述之黏著劑組成物(I-1)等情形相同。 Adhesive compositions other than adhesive composition (I-1) to adhesive composition (I-3) preferably contain one or more crosslinking agents. The content of the aforementioned crosslinking agent can be set to be the same as that of the above-mentioned adhesive composition (I-1).
<黏著劑組成物(I-4)> <Adhesive composition (I-4)>
作為較佳的黏著劑組成物(I-4)，例如可列舉：含有前述黏著性樹脂(I-1a)及交聯劑之黏著劑組成物。 As a preferable adhesive composition (I-4), the adhesive composition containing the said adhesive resin (I-1a) and a crosslinking agent is mentioned, for example.
[黏著性樹脂(I-1a)] [Adhesive resin (I-1a)]
作為黏著劑組成物(I-4)中的黏著性樹脂(I-1a)，可列舉與黏著劑組成物(I-1)中的黏著性樹脂(I-1a)相同的黏著性樹脂。 Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) include the same adhesive resins as the adhesive resin (I-1a) in the adhesive composition (I-1).
黏著劑組成物(I-4)所含有之黏著性樹脂(I-1a)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-4)中，黏著性樹脂(I-1a)的含量較佳 為5質量%至99質量%。更佳為10質量%至95質量%，尤佳為15質量%至90質量%。 In the adhesive composition (I-4), the content of the adhesive resin (I-1a) is better 5% by mass to 99% by mass. More preferably, it is 10 mass % to 95 mass %, Most preferably, it is 15 mass % to 90 mass %.
[交聯劑] [Crosslinking agent]
作為黏著性樹脂(I-1a)，有時使用除源自(甲基)丙烯酸烷基酯之結構單元以外，進而具有源自含官能基之單體之結構單元之前述丙烯酸系聚合物。該情形時，黏著劑組成物(I-4)較佳為進而含有交聯劑。 As the adhesive resin (I-1a), the aforementioned acrylic polymer having a structural unit derived from a functional group-containing monomer in addition to a structural unit derived from an alkyl (meth)acrylate may be used. In this case, it is preferable that the adhesive composition (I-4) further contains a crosslinking agent.
作為黏著劑組成物(I-4)中的交聯劑，可列舉與黏著劑組成物(I-1)中的交聯劑相同的化合物。 Examples of the crosslinking agent in the adhesive composition (I-4) include the same compounds as the crosslinking agent in the adhesive composition (I-1).
黏著劑組成物(I-4)所含有之交聯劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The crosslinking agent contained in the adhesive composition (I-4) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
前述黏著劑組成物(I-4)中，交聯劑的含量相對於黏著性樹脂(I-1a)的含量100質量份，較佳為0.01質量份至50質量份。更佳為0.1質量份至20質量份，尤佳為0.3質量份至15質量份。 In the aforementioned adhesive composition (I-4), the content of the crosslinking agent is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the content of the adhesive resin (I-1a). More preferably, it is 0.1 to 20 parts by mass, and most preferably, it is 0.3 to 15 parts by mass.
[其他添加劑] [Other additives]
黏著劑組成物(I-4)中，在無損本發明之效果之範圍內，亦可含有不屬於上述之任一種成分之其他添加劑。 The adhesive composition (I-4) may contain other additives that do not belong to any of the above-mentioned components within the range that does not impair the effect of the present invention.
作為前述其他添加劑，可列舉與黏著劑組成物(I-1) 中的其他添加劑相同的化合物。 Examples of other additives mentioned above include the adhesive composition (I-1) The other additives in the same compound.
黏著劑組成物(I-4)所含有之其他添加劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The other additives contained in the adhesive composition (I-4) may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-4)中，其他添加劑的含量並無特別限定，根據該其他添加劑的種類適宜選擇即可。 In the adhesive composition (I-4), the content of other additives is not particularly limited, and may be appropriately selected according to the type of the other additives.
[溶劑] [solvent]
以與黏著劑組成物(I-1)之情形相同之目的，黏著劑組成物(I-4)亦可含有溶劑。 The adhesive composition (I-4) may also contain a solvent for the same purpose as in the case of the adhesive composition (I-1).
作為黏著劑組成物(I-4)中的前述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同的溶劑。 Examples of the solvent in the adhesive composition (I-4) include the same solvents as those in the adhesive composition (I-1).
黏著劑組成物(I-4)所含有之溶劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The solvent contained in the adhesive composition (I-4) may be only one kind, or may be two or more kinds. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
黏著劑組成物(I-4)中，溶劑的含量並無特別限定，適宜調節即可。 In the adhesive composition (I-4), the content of the solvent is not particularly limited, and may be adjusted appropriately.
本發明之保護膜形成用複合片中，黏著劑層較佳為非能量線硬化性。原因在於，若黏著劑層為能量線硬化性，則有時無法抑制於藉由照射能量線而使保護膜形成用膜硬化時，黏著劑層亦同時硬化。若黏著劑層與保護膜形成用膜同時硬化，則有時硬化後之保護膜形成用膜及黏著劑 層於這些之界面黏附至無法剝離之程度。該情形時，難以將背面具備硬化後之保護膜形成用膜，亦即保護膜之半導體晶片(本說明書中，有時稱為「附有保護膜的半導體晶片」)自具備硬化後之黏著劑層之支持片剝離，無法正常地拾取附有保護膜的半導體晶片。藉由將本發明中的支持片中的黏著劑層設為非能量線硬化性，可確實地避免此種不良情況。亦即，可更容易地拾取附有保護膜的半導體晶片。 In the composite sheet for forming a protective film of the present invention, the adhesive layer is preferably non-energy ray curable. The reason is that, if the adhesive layer is energy ray curable, it may not be possible to suppress the simultaneous curing of the adhesive layer when the film for protective film formation is cured by irradiation of energy rays. If the adhesive layer and the protective film forming film are cured at the same time, the cured protective film forming film and adhesive may be The layers adhere to these interfaces to such an extent that they cannot be peeled off. In this case, it is difficult to separate a semiconductor wafer (in this specification, sometimes referred to as a "semiconductor wafer with a protective film") with a cured protective film-forming film, that is, a protective film, from a cured adhesive. The support sheet of the first layer is peeled off, and the semiconductor wafer with the protective film cannot be picked up normally. Such disadvantages can be reliably avoided by making the adhesive layer in the support sheet in the present invention non-energy ray curable. That is, the semiconductor wafer with the protective film can be picked up more easily.
此處對黏著劑層為非能量線硬化性之情形之效果進行了說明。但是，即便支持片中的與保護膜形成用膜直接接觸之層為黏著劑層以外之層，只要該層為非能量線硬化性，則亦發揮相同的效果。 Here, the effect of the case where the adhesive layer is non-energy ray curable is described. However, even if the layer in direct contact with the film for protective film formation in a support sheet is a layer other than an adhesive layer, as long as this layer is non-energy ray curable, the same effect will be exhibited.
<<黏著劑組成物的製造方法>> <<Manufacturing method of adhesive composition>>
黏著劑組成物(I-1)至黏著劑組成物(I-3)、或黏著劑組成物(I-4)等黏著劑組成物(I-1)至黏著劑組成物(I-3)以外之黏著劑組成物藉由將前述黏著劑及視需要之前述黏著劑以外之成分等用以構成黏著劑組成物之各成分加以調配而獲得。 Adhesive composition (I-1) to adhesive composition (I-3), or adhesive composition (I-4), such as adhesive composition (I-1) to adhesive composition (I-3) The other adhesive composition is obtained by preparing the aforementioned adhesive and, if necessary, components other than the aforementioned adhesive, etc., which constitute the adhesive composition.
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。 The order of addition of each component is not particularly limited, and two or more components may be added at the same time.
於使用溶劑之情形時，可藉由下述方式使用，亦即，將溶劑與溶劑以外之任一種調配成分混合而將該調配成 分預先稀釋。進而，亦可藉由下述方式使用，亦即，不將溶劑以外之任一種調配成分預先稀釋，而將溶劑與這些調配成分混合。 In the case of using a solvent, it can be used by mixing the solvent with any one of the ingredients other than the solvent to prepare the compounded pre-diluted. Furthermore, it can also be used by mixing a solvent with these formulation components, without diluting any formulation components other than a solvent beforehand.
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；使用混合機而進行混合之方法；施加超音波而進行混合之方法等。 There is no particular limitation on the method of mixing the ingredients during preparation. What is necessary is just to select suitably from the following well-known methods: the method of rotating a stirring bar or stirring blade, etc. and mixing; the method of mixing using a mixer; the method of applying ultrasonic waves and mixing, etc.
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。但是，溫度較佳為15℃至30℃。 The temperature and time at the time of adding and mixing each component are not specifically limited as long as each compounding component is not deteriorated, What is necessary is just to adjust suitably. However, the temperature is preferably 15°C to 30°C.
◎保護膜形成用膜 ◎Film for protective film formation
本發明中，保護膜形成用膜硬化而獲得之保護膜與支持片之間的黏著力較佳為50mN/25mm至1500mN/25mm。更佳為52mN/25mm至1450mN/25mm，進而較佳為53mN/25mm至1430mN/25mm。藉由前述黏著力為前述下限值以上，拾取附有保護膜的半導體晶片時，目標外的附有保護膜的半導體晶片之拾取得到抑制。結果為，可高選擇性地拾取目標之附有保護膜的半導體晶片。另外，藉由前述黏著力為前述上限值以下，拾取附有保護膜的半導體晶片時，半導體晶片之破裂及缺損得到抑制。如此，藉由前述黏著力為特定範圍內，保護膜形成用複合片具有良好的拾取適性。 In the present invention, the adhesive force between the protective film obtained by curing the protective film-forming film and the support sheet is preferably 50 mN/25 mm to 1500 mN/25 mm. More preferably, it is 52mN/25mm to 1450mN/25mm, and still more preferably, it is 53mN/25mm to 1430mN/25mm. When the said adhesive force is more than the said lower limit value, when picking up the semiconductor wafer with a protective film, pick-up of the semiconductor wafer with a protective film outside the target is suppressed. As a result, a target semiconductor wafer with a protective film can be picked up with high selectivity. Moreover, when the said adhesive force is below the said upper limit, when picking up the semiconductor wafer with a protective film, cracking and chipping of a semiconductor wafer are suppressed. Thus, the composite sheet for protective film formation has favorable pick-up property by the said adhesive force being in a specific range.
再者，本發明中，即便為保護膜形成用膜硬化後，只要維持支持片及保護膜形成用膜之硬化物(換言之，支持片及保護膜)之積層結構，則亦將該積層結構體稱為「保護膜形成用複合片」。 Furthermore, in the present invention, even after the film for forming a protective film is cured, as long as the laminated structure of the hardened product of the support sheet and the film for forming a protective film (in other words, the support sheet and the protective film) is maintained, the laminated structure is also It is called "composite sheet for protective film formation".
保護膜與支持片之間的黏著力可利用以下之方法進行測定。 The adhesive force between the protective film and the support sheet can be measured by the following method.
亦即，將寬度為25mm且長度為任意之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜貼附於被接著體。 That is, the composite sheet for protective film formation with a width of 25 mm and arbitrary length was attached to the adherend through the film for protective film formation of the composite sheet for protective film formation.
繼而，照射能量線而使保護膜形成用膜硬化，形成保護膜。然後，自貼附於被接著體之該保護膜，使支持片以剝離速度300mm/min剝離。此時的剝離係設為以下所謂之180°剝離，亦即，以保護膜及支持片相互接觸之面彼此成為180°之角度之方式，將支持片沿該支持片的長度方向(保護膜形成用複合片的長度方向)剝離。然後，測定該180°剝離時的荷重(剝離力)，將該荷重(剝離力)的測定值設為前述黏著力(mN/25mm)。 Next, energy rays are irradiated to harden the film for forming a protective film to form a protective film. Then, the support sheet was peeled at a peeling speed of 300 mm/min from the protective film attached to the adherend. The peeling at this time is the following so-called 180° peeling, that is, the support sheet is placed along the longitudinal direction of the support sheet (protective film formation) in such a manner that the surfaces where the protective film and the support sheet are in contact with each other form an angle of 180°. Peel off in the longitudinal direction of the composite sheet. Then, the load (peeling force) at the time of this 180° peeling was measured, and the measured value of this load (peeling force) was made into the said adhesive force (mN/25mm).
供於測定之保護膜形成用複合片的長度只要為可穩定地檢測出黏著力之範圍，則並無特別限定。但是，較佳為100mm至300mm。另外，測定時，較佳為使保護膜形成用複合片成為貼附於被接著體之狀態，預先使保護膜形成用複合片之貼附狀態穩定化。 The length of the protective film-forming composite sheet used for the measurement is not particularly limited as long as it is within a range in which the adhesive force can be stably detected. However, it is preferably 100 mm to 300 mm. In addition, at the time of measurement, it is preferable to bring the composite sheet for protective film formation into a state attached to the adherend, and to stabilize the attached state of the composite sheet for protective film formation in advance.
本發明中，保護膜形成用膜與前述支持片之間的黏著力並無特別限定。例如，可為80mN/25mm以上等，較佳為100mN/25mm以上。更佳為150mN/25mm以上，尤佳為200mN/25mm以上。藉由前述黏著力為100mN/25mm以上，切割時，保護膜形成用膜與支持片之剝離得到抑制。例如，背面具備保護膜形成用膜之半導體晶片自支持片之飛散得到抑制。 In this invention, the adhesive force between the film for protective film formation and the said support sheet is not specifically limited. For example, it may be 80 mN/25mm or more, preferably 100 mN/25mm or more. More preferably, it is 150 mN/25mm or more, and most preferably, it is 200 mN/25mm or more. When the said adhesive force is 100 mN/25mm or more, peeling of the film for protective film formation and a support sheet is suppressed at the time of dicing. For example, the scattering of the semiconductor wafer provided with the film for protective film formation on the back surface from a support sheet is suppressed.
另一方面，保護膜形成用膜與前述支持片之間的黏著力的上限值並無特別限定。例如，可設為4000mN/25mm、3500mN/25mm、3000mN/25mm等之任一者。其中，這些為一例。 On the other hand, the upper limit of the adhesive force between the film for protective film formation and the said support sheet is not specifically limited. For example, any one of 4000mN/25mm, 3500mN/25mm, and 3000mN/25mm can be used. Among them, these are examples.
關於保護膜形成用膜與支持片之間的黏著力，除不藉由照射能量線使供於測定之保護膜形成用膜硬化之方面以外，可利用與上述之保護膜與支持片之間的黏著力相同的方法進行測定。 Regarding the adhesive force between the film for forming a protective film and the support sheet, except that the film for forming a protective film to be measured is not hardened by irradiation of energy rays, the adhesion between the above-mentioned protective film and the support sheet can be used. Adhesion was measured in the same way.
上述之保護膜與支持片之間的黏著力、及保護膜形成用膜與支持片之間的黏著力可適宜調節。例如，可藉由調節保護膜形成用膜的含有成分的種類及量、支持片中的設置保護膜形成用膜之層的構成材料、該層的表面狀態等而進行調節。 The above-mentioned adhesive force between the protective film and the support sheet, and the adhesive force between the film for forming a protective film and the support sheet can be appropriately adjusted. For example, it can be adjusted by adjusting the type and amount of components contained in the film for forming a protective film, the constituent material of the layer on which the film for forming a protective film is provided in the support sheet, the surface state of the layer, and the like.
例如，保護膜形成用膜的含有成分的種類及量可藉由後述之保護膜形成用組成物的含有成分的種類及量而進行調節。並且，藉由調節保護膜形成用組成物的含有成分中，例如不具有能量線硬化性基之聚合物(b)的種類及含量、填充材料(d)的含量、或交聯劑(f)的含量，可更容易地調節保護膜或保護膜形成用膜與支持片之間的黏著力。 For example, the types and amounts of components contained in the film for forming a protective film can be adjusted by the types and amounts of components contained in the composition for forming a protective film described later. Furthermore, by adjusting the type and content of the polymer (b) that does not have an energy ray curable group, the content of the filler (d), or the crosslinking agent (f) among the components contained in the protective film forming composition, content, the adhesive force between the protective film or the film for protective film formation and the support sheet can be adjusted more easily.
另外，例如，於支持片中的設置保護膜形成用膜之層為黏著劑層之情形時，該層的構成材料可藉由調節黏著劑層的含有成分的種類及量而適宜調節。並且，黏著劑層的含有成分的種類及量可藉由上述之黏著劑組成物的含有成分的種類及量而進行調節。 Moreover, for example, when the layer provided with the film for protective film formation in a support sheet is an adhesive layer, the constituent material of this layer can be adjusted suitably by adjusting the kind and quantity of the component contained in an adhesive layer. In addition, the types and amounts of the components contained in the adhesive layer can be adjusted by the types and amounts of the components contained in the above-mentioned adhesive composition.
另一方面，於支持片中的設置保護膜形成用膜之層為基材之情形時，關於保護膜或保護膜形成用膜與支持片之間的黏著力，除基材的構成材料以外，亦可藉由基材的表面狀態而進行調節。並且，基材的表面狀態例如可藉由下述方式而調節，亦即，實施前文作為提高基材與其他層之密接性之處理所列舉之表面處理。亦即，可藉由實施以下任一種處理而進行調節：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；底塗處理等。 On the other hand, when the layer on which the film for protective film formation is provided in the support sheet is the base material, regarding the adhesive force between the protective film or the film for protective film formation and the support sheet, in addition to the constituent materials of the base material, It can also be adjusted by the surface state of the substrate. In addition, the surface state of the substrate can be adjusted, for example, by performing the surface treatment mentioned above as the treatment for improving the adhesion between the substrate and other layers. That is, adjustment can be performed by performing any of the following treatments: roughening treatment by sandblasting, solvent treatment, etc.; corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone/ultraviolet irradiation treatment, flame treatment, Oxidation treatment such as chromic acid treatment and hot air treatment; primer treatment, etc.
保護膜形成用膜具有能量線硬化性。例如，可列舉含 有能量線硬化性成分(a)之膜，較佳為含有能量線硬化性成分(a)、不具有能量線硬化性基之聚合物(b)及抗靜電劑(j)之膜。 The film for protective film formation has energy ray curability. For example, include The film containing the energy ray curable component (a) is preferably a film containing the energy ray curable component (a), a polymer (b) without an energy ray curable group, and an antistatic agent (j).
能量線硬化性成分(a)較佳為未硬化。較佳為具有黏著性，更佳為未硬化且具有黏著性。 The energy ray curable component (a) is preferably uncured. It is preferably adhesive, more preferably uncured and adhesive.
保護膜形成用膜可僅為1層(單層)，亦可為2層以上之多層。於為多層之情形時，這些多層相互可相同亦可不同，這些多層之組合並無特別限定。 The film for protective film formation may be only 1 layer (single layer), and may be multilayer of 2 or more layers. In the case of multiple layers, these layers may be the same as or different from each other, and the combination of these layers is not particularly limited.
保護膜形成用膜的厚度較佳為1μm至100μm。更佳為5μm至75μm，尤佳為5μm至50μm。藉由保護膜形成用膜的厚度為前述下限值以上，可形成保護能力更高的保護膜。另外，藉由保護膜形成用膜的厚度為前述上限值以下，可抑制厚度過厚。 The thickness of the film for protective film formation is preferably 1 μm to 100 μm. More preferably, it is 5 μm to 75 μm, and most preferably, it is 5 μm to 50 μm. When the thickness of the film for protective film formation is more than the said lower limit, the protective film with higher protective ability can be formed. Moreover, when the thickness of the film for protective film formation is below the said upper limit, it can suppress that thickness is too thick.
此處，所謂「保護膜形成用膜的厚度」意指保護膜形成用膜整體的厚度。例如，所謂由多層構成之保護膜形成用膜的厚度意指構成保護膜形成用膜之全部層的合計厚度。 Here, "the thickness of the film for protective film formation" means the thickness of the whole film for protective film formation. For example, the thickness of the film for protective film formation which consists of multiple layers means the total thickness of all the layers which comprise the film for protective film formation.
關於使保護膜形成用膜硬化而形成保護膜時的硬化條件，只要使保護膜成為充分地發揮該保護膜之功能之程度的硬化度，則並無特別限定。根據保護膜形成用膜的種類適宜選擇即可。 The curing conditions for forming a protective film by curing the film for forming a protective film are not particularly limited as long as the protective film has a degree of curing sufficient to exhibit the function of the protective film. What is necessary is just to select suitably according to the kind of film for protective film formation.
例如，保護膜形成用膜之硬化時，能量線之照度較佳為4mW/cm2至280mW/cm2。並且，前述硬化時，能量線之光量較佳為3mJ/cm2至1000mJ/cm2。 For example, when curing the film for forming a protective film, the illuminance of energy rays is preferably 4 mW/cm 2 to 280 mW/cm 2 . In addition, during the aforementioned hardening, the light quantity of the energy ray is preferably 3 mJ/cm 2 to 1000 mJ/cm 2 .
<<保護膜形成用組成物>> <<Protective film forming composition>>
保護膜形成用膜可使用含有該保護膜形成用膜的構成材料之保護膜形成用組成物而形成。例如，於保護膜形成用膜之形成對象面塗敷保護膜形成用組成物，視需要使之乾燥，藉此可於目標部位形成保護膜形成用膜。保護膜形成用組成物中的常溫下不會氣化的成分彼此的含量比率，通常與保護膜形成用膜中的前述成分彼此的含量比率相同。此處，所謂「常溫」，如前文所說明。 The film for protective film formation can be formed using the composition for protective film formation containing the constituent material of this film for protective film formation. For example, a protective film-forming film can be formed on a target site by applying a protective film-forming composition to the surface to be formed of the protective film-forming film and drying it if necessary. The content ratio of the components that do not vaporize at normal temperature in the composition for forming a protective film is usually the same as the content ratio of the above-mentioned components in the film for forming a protective film. Here, the so-called "normal temperature" is as explained above.
利用公知的方法塗敷保護膜形成用組成物即可。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、繞線棒式塗佈機、接觸式塗佈機等。 What is necessary is just to apply|coat the composition for protective film formation by a well-known method. For example, methods using the following various coaters: air knife coater, blade coater, rod coater, gravure coater, roll coater, roll knife coater, curtain coater, etc. Cloth machine, die coater, knife coater, screen coater, wire rod coater, contact coater, etc.
保護膜形成用組成物的乾燥條件並無特別限定。但是，於保護膜形成用組成物含有後述溶劑之情形時，較佳為進行加熱乾燥。該情形時，較佳為於例如70℃至130℃且10秒至5分鐘之條件下進行乾燥。 The drying conditions of the protective film forming composition are not particularly limited. However, when the composition for protective film formation contains the solvent mentioned later, it is preferable to perform heat drying. In this case, it is preferable to dry under conditions of, for example, 70° C. to 130° C. and 10 seconds to 5 minutes.
<保護膜形成用組成物(IV-1)> <Protective film forming composition (IV-1)>
作為保護膜形成用組成物，例如可列舉含有前述能量線硬化性成分(a)之保護膜形成用組成物(IV-1)等。 As a composition for protective film formation, the composition for protective film formation (IV-1) etc. which contain the said energy-beam curable component (a) are mentioned, for example.
[能量線硬化性成分(a)] [energy ray hardening ingredient (a)]
能量線硬化性成分(a)係藉由照射能量線而硬化之成分，該成分用以對保護膜形成用膜賦予造膜性或可撓性等。 The energy ray curable component (a) is a component cured by irradiation of energy ray, and this component is used to impart film forming property, flexibility, etc. to the film for protective film formation.
作為能量線硬化性成分(a)，例如可列舉：具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)、及具有能量線硬化性基且分子量為100至80000之化合物(a2)。前述聚合物(a1)可至少一部分藉由後述之交聯劑(f)進行交聯，亦可不進行交聯。 Examples of the energy ray-curable component (a) include polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000, and compounds having an energy ray-curable group and having a molecular weight of 100 to 80,000 (a2). The aforementioned polymer (a1) may be at least partially crosslinked by a crosslinking agent (f) described later, or may not be crosslinked.
再者，本說明書中，所謂重量平均分子量，只要無特別說明，則意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。 In addition, in this specification, unless otherwise specified, weight average molecular weight means the polystyrene conversion value measured by the gel permeation chromatography (GPC; Gel Permeation Chromatography) method.
(具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)) (Polymer (a1) having an energy ray curable group and having a weight average molecular weight of 80,000 to 2,000,000)
作為具有能量線硬化性基且重量平均分子量為80000至2000000之聚合物(a1)，例如可列舉丙烯酸系樹脂(a1-1)，該丙烯酸系樹脂(a1-1)係丙烯酸系聚合物(a11)與能量線硬化性化合物(a12)聚合而成，前述丙烯酸系聚合物(a11)具有可與其他化合物所具有之基反應之官能基，前述能量 線硬化性化合物(a12)具有與前述官能基反應之基及能量線硬化性雙鍵等能量線硬化性基。 Examples of the polymer (a1) having an energy ray-curable group and having a weight average molecular weight of 80,000 to 2,000,000 include an acrylic resin (a1-1), which is an acrylic polymer (a11 ) and an energy ray-curable compound (a12), the aforementioned acrylic polymer (a11) has a functional group that can react with groups of other compounds, and the aforementioned energy The ray-curable compound (a12) has an energy ray-curable group such as a group reactive with the aforementioned functional group and an energy ray-curable double bond.
作為可與其他化合物所具有之基反應之前述官能基，例如可列舉：羥基、羧基、胺基、取代胺基(胺基的1個或2個氫原子被氫原子以外的基取代而成之基)、環氧基等。其中，就防止半導體晶圓或半導體晶片等的電路腐蝕之方面而言，前述官能基較佳為羧基以外的基。 Examples of the functional groups that can react with groups of other compounds include hydroxyl, carboxyl, amino, and substituted amino groups (one or two hydrogen atoms of the amino group are replaced by groups other than hydrogen atoms) group), epoxy group, etc. Among them, the aforementioned functional group is preferably a group other than a carboxyl group from the viewpoint of preventing corrosion of a semiconductor wafer or a circuit of a semiconductor wafer or the like.
這些之中，前述官能基較佳為羥基。 Among these, the aforementioned functional group is preferably a hydroxyl group.
‧具有官能基之丙烯酸系聚合物(a11) ‧Acrylic polymer with functional groups (a11)
作為具有前述官能基之丙烯酸系聚合物(a11)，例如可列舉：具有前述官能基之丙烯酸系單體、與不具有前述官能基之丙烯酸系單體進行共聚合而成。亦可為除這些單體以外，進而使丙烯酸系單體以外的單體(非丙烯酸系單體)進行共聚合而成之聚合物。 As an acrylic-type polymer (a11) which has the said functional group, what copolymerizes the acrylic-type monomer which has the said functional group, and the acrylic-type monomer which does not have the said functional group is mentioned, for example. In addition to these monomers, a polymer obtained by further copolymerizing a monomer (non-acrylic monomer) other than an acrylic monomer may be used.
另外，前述丙烯酸系聚合物(a11)可為無規共聚物，亦可為嵌段共聚物。 In addition, the aforementioned acrylic polymer (a11) may be a random copolymer or a block copolymer.
作為前述具有官能基之丙烯酸系單體，例如可列舉：含羥基之單體、含羧基之單體、含胺基之單體、含取代胺基之單體、含環氧基之單體等。 Examples of the aforementioned acrylic monomers having functional groups include: hydroxyl-containing monomers, carboxyl-containing monomers, amine-containing monomers, substituted amino-containing monomers, epoxy-containing monomers, etc. .
作為前述含羥基之單體，可列舉以下之單體。例如可 列舉：(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(甲基)丙烯酸羥基烷基酯；乙烯醇、烯丙醇等非(甲基)丙烯酸系不飽和醇(不具有(甲基)丙烯醯基骨架之不飽和醇)等。 The following monomers are mentioned as said hydroxyl group containing monomer. for example can Examples: hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate -Hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; non-(meth)acrylic acid such as vinyl alcohol and allyl alcohol It is an unsaturated alcohol (unsaturated alcohol not having a (meth)acryl skeleton) and the like.
作為前述含羧基之單體，可列舉以下之單體。例如可列舉：(甲基)丙烯酸、丁烯酸等乙烯性不飽和單羧酸(具有乙烯性不飽和鍵之單羧酸)；反丁烯二酸、衣康酸、順丁烯二酸、檸康酸等乙烯性不飽和二羧酸(具有乙烯性不飽和鍵之二羧酸)；前述乙烯性不飽和二羧酸之酐；2-羧基乙酯等(甲基)丙烯酸羧基烷基甲基丙烯酸酯等。 The following monomers are mentioned as said carboxyl group containing monomer. For example, ethylenically unsaturated monocarboxylic acids (monocarboxylic acids having an ethylenically unsaturated bond) such as (meth)acrylic acid and crotonic acid; fumaric acid, itaconic acid, maleic acid, Ethylenically unsaturated dicarboxylic acids such as citraconic acid (dicarboxylic acids having ethylenically unsaturated bonds); anhydrides of the aforementioned ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl esters, etc. acrylates, etc.
前述具有官能基之丙烯酸系單體較佳為含羥基之單體、或含羧基之單體，更佳為含羥基之單體。 The aforementioned acrylic monomers having functional groups are preferably hydroxyl-containing monomers or carboxyl-containing monomers, more preferably hydroxyl-containing monomers.
構成前述丙烯酸系聚合物(a11)且具有前述官能基之丙烯酸系單體可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The acrylic monomer which comprises the said acrylic polymer (a11) and has the said functional group may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
作為不具有前述官能基之丙烯酸系單體，可列舉以下之單體。例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基 )丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(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)丙烯酸烷基酯等。 As an acrylic monomer which does not have the said functional group, the following monomer is mentioned. Examples include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate ) n-butyl acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate , (meth) heptyl acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, (meth) base) isononyl acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), (meth) Tridecyl acrylate, Myristyl (meth)acrylate (myristyl (meth)acrylate), Pentadecyl (meth)acrylate, Hexadecyl (meth)acrylate ( (meth)acrylic palmityl ester), (meth)acrylic acid heptadecyl ester, (meth)acrylic acid octadecyl ester ((meth)acrylic acid stearyl) etc. Alkyl (meth)acrylate with a chain structure whose number is 1 to 18, etc.
另外，作為不具有前述官能基之丙烯酸系單體，可列舉以下之單體。例如亦可列舉：(甲基)丙烯酸甲氧基甲酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基甲酯、(甲基)丙烯酸乙氧基乙酯等含烷氧基烷基之(甲基)丙烯酸酯；包含(甲基)丙烯酸苯酯等(甲基)丙烯酸芳基酯等之具有芳香族基之(甲基)丙烯酸酯；非交聯性的(甲基)丙烯醯胺及其衍生物；(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸N,N-二甲胺基丙酯等非交聯性的具有三級胺基之(甲基)丙烯酸酯等。 Moreover, the following monomers are mentioned as an acrylic monomer which does not have the said functional group. For example, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, ethoxyethyl (meth)acrylate, etc. Alkoxyalkyl (meth)acrylates; (meth)acrylates with aromatic groups including aryl (meth)acrylates such as phenyl (meth)acrylates; non-crosslinking ( Meth)acrylamide and its derivatives; N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, etc. Grade amine (meth)acrylate, etc.
構成前述丙烯酸系聚合物(a11)且不具有前述官能基 之丙烯酸系單體可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 Constituting the aforementioned acrylic polymer (a11) and not having the aforementioned functional group The acrylic monomer may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
作為前述非丙烯酸系單體，例如可列舉：乙烯、降冰片烯等烯烴；乙酸乙烯酯；苯乙烯等。 Examples of the non-acrylic monomers include olefins such as ethylene and norbornene; vinyl acetate; and styrene.
構成前述丙烯酸系聚合物(a11)之前述非丙烯酸系單體可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The said non-acrylic monomer which comprises the said acrylic polymer (a11) may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
前述丙烯酸系聚合物(a11)中，由具有前述官能基之丙烯酸系單體衍生之結構單元的量相對於構成該丙烯酸系聚合物(a11)之結構單元的總量之比例(含量)較佳為0.1質量%至50質量%。更佳為1質量%至40質量%，尤佳為3質量%至30質量%。藉由前述比例為此種範圍，可將由前述丙烯酸系聚合物(a11)與前述能量線硬化性化合物(a12)之共聚合所獲得之前述丙烯酸系樹脂(a1-1)中能量線硬化性基的含量容易地調節為使第1保護膜的硬化程度較佳之範圍。 In the aforementioned acrylic polymer (a11), the ratio (content) of the amount of structural units derived from the acrylic monomer having the aforementioned functional group to the total amount of structural units constituting the aforementioned acrylic polymer (a11) is preferable 0.1% by mass to 50% by mass. More preferably, it is 1 mass % to 40 mass %, Most preferably, it is 3 mass % to 30 mass %. With the aforementioned ratio in such a range, the energy ray-curable group in the aforementioned acrylic resin (a1-1) obtained by copolymerization of the aforementioned acrylic polymer (a11) and the aforementioned energy ray-curable compound (a12) can be The content of is easily adjusted to a range in which the degree of hardening of the first protective film is better.
構成前述丙烯酸系樹脂(a1-1)之前述丙烯酸系聚合物(a11)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The said acrylic polymer (a11) which comprises the said acrylic resin (a1-1) may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
保護膜形成用組成物(IV-1)中，丙烯酸系樹脂(a1-1) 的含量較佳為1質量%至40質量%。更佳為2質量%至30質量%，尤佳為3質量%至20質量%。 In the protective film forming composition (IV-1), the acrylic resin (a1-1) The content of is preferably 1% by mass to 40% by mass. More preferably, it is 2 mass % to 30 mass %, Most preferably, it is 3 mass % to 20 mass %.
‧能量線硬化性化合物(a12) ‧Energy ray hardening compound (a12)
前述能量線硬化性化合物(a12)較佳為具有選自由異氰酸酯基、環氧基及羧基所組成之群組中的1種或2種以上作為可與前述丙烯酸系聚合物(a11)所具有之官能基反應之基，更佳為具有異氰酸酯基作為前述基。於前述能量線硬化性化合物(a12)例如具有異氰酸酯基作為前述基之情形時，該異氰酸酯基與前述具有羥基作為官能基之丙烯酸系聚合物(a11)的該羥基容易反應。 The energy ray-curable compound (a12) preferably has one or more kinds selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group as a compound that can be combined with the acrylic polymer (a11) The functional group-reactive group preferably has an isocyanate group as the aforementioned group. For example, when the energy ray-curable compound (a12) has an isocyanate group as the group, the isocyanate group reacts easily with the hydroxyl group of the acrylic polymer (a11) having a hydroxyl group as a functional group.
前述能量線硬化性化合物(a12)較佳為於1分子中具有1個至5個前述能量線硬化性基，更佳為具有1個至3個。 The aforementioned energy ray curable compound (a12) preferably has 1 to 5 aforementioned energy ray curable groups in 1 molecule, more preferably has 1 to 3 groups.
作為前述能量線硬化性化合物(a12)，可列舉以下化合物。例如可列舉：2-甲基丙烯醯氧基乙基異氰酸酯、間-異丙烯基-α,α-二甲基苄基異氰酸酯、甲基丙烯醯基異氰酸酯、異氰酸烯丙酯、異氰酸1,1-(雙丙烯醯氧基甲基)乙酯；藉由二異氰酸酯化合物或多異氰酸酯化合物與(甲基)丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物；藉由二異氰酸酯化合物或多異氰酸酯化合物、多元醇 化合物及(甲基)丙烯酸羥基乙酯之反應而獲得之丙烯醯基單異氰酸酯化合物等。 The following compounds are mentioned as said energy ray curable compound (a12). Examples include: 2-methacryloxyethyl isocyanate, m-isopropenyl-α,α-dimethylbenzyl isocyanate, methacryl isocyanate, allyl isocyanate, isocyanic acid 1,1-(Bisacryloxymethyl)ethyl ester; acryl monoisocyanate compounds obtained by reacting diisocyanate compounds or polyisocyanate compounds with hydroxyethyl (meth)acrylate; by diisocyanate compound or polyisocyanate compound, polyol Acryl monoisocyanate compound obtained by reaction of compound and hydroxyethyl (meth)acrylate, etc.
這些之中，前述能量線硬化性化合物(a12)較佳為2-甲基丙烯醯氧基乙基異氰酸酯。 Among these, the aforementioned energy ray-curable compound (a12) is preferably 2-methacryloxyethyl isocyanate.
構成前述丙烯酸系樹脂(a1-1)之前述能量線硬化性化合物(a12)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The said energy ray curable compound (a12) which comprises the said acrylic resin (a1-1) may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
前述丙烯酸系樹脂(a1-1)中，源自前述能量線硬化性化合物(a12)之能量線硬化性基的含量相對於源自前述丙烯酸系聚合物(a11)之前述官能基的含量之比例較佳為20莫耳%至120莫耳%。更佳為35莫耳%至100莫耳%，尤佳為50莫耳%至100莫耳%。藉由前述含量比例為此種範圍，藉由硬化所形成之保護膜之接著力變得更大。再者，於前述能量線硬化性化合物(a12)為一官能(1分子中具有1個前述基)之化合物之情形時，前述含量比例的上限值成為100莫耳%。但是，於前述能量線硬化性化合物(a12)為多官能(1分子中具有2個以上之前述基)之化合物之情形時，前述含量比例的上限值有時超過100莫耳%。 Ratio of the content of the energy ray-curable group derived from the energy ray-curable compound (a12) to the content of the functional group derived from the acrylic polymer (a11) in the acrylic resin (a1-1) Preferably it is 20 mol% to 120 mol%. More preferably 35 mol% to 100 mol%, especially preferably 50 mol% to 100 mol%. When the aforementioned content ratio is in such a range, the adhesive force of the protective film formed by curing becomes greater. In addition, when the said energy ray curable compound (a12) is a monofunctional (having 1 said group in 1 molecule) compound, the upper limit of the said content ratio becomes 100 mol%. However, when the energy ray-curable compound (a12) is a polyfunctional (having two or more groups in one molecule) compound, the upper limit of the content may exceed 100 mol%.
前述聚合物(a1)的重量平均分子量(Mw)較佳為100000至2000000，更佳為300000至1500000。 The weight average molecular weight (Mw) of the aforementioned polymer (a1) is preferably from 100,000 to 2,000,000, more preferably from 300,000 to 1,500,000.
於前述聚合物(a1)的至少一部分藉由交聯劑(f)進行交聯之情形時，前述聚合物(a1)可使不屬於上述說明之構成前述丙烯酸系聚合物(a11)之任一單體且具有與交聯劑(f)反應之基之單體進行聚合，在前述與交聯劑(f)反應之基中進行交聯。進而，亦可在源自前述能量線硬化性化合物(a12)之與前述官能基反應之基中進行交聯。 When at least a part of the aforementioned polymer (a1) is cross-linked by the cross-linking agent (f), the aforementioned polymer (a1) may be any one of the constituents of the aforementioned acrylic polymer (a11) that is not described above. The monomer and the monomer having a group reactive with the crosslinking agent (f) are polymerized, and crosslinking is performed in the group reactive with the crosslinking agent (f). Furthermore, crosslinking can also be performed in the group derived from the said energy ray curable compound (a12) which reacts with the said functional group.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之前述聚合物(a1)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The said polymer (a1) contained in the protective film forming composition (IV-1) and the protective film forming film may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
(具有能量線硬化性基且分子量為100至80000之化合物(a2)) (Compound (a2) having an energy ray curable group and having a molecular weight of 100 to 80000)
作為具有能量線硬化性基且分子量為100至80000之化合物(a2)所具有之能量線硬化性基，可列舉包含能量線硬化性雙鍵之基。作為較佳的該基，可列舉(甲基)丙烯醯基、乙烯基等。 Examples of the energy ray curable group contained in the compound (a2) having an energy ray curable group and having a molecular weight of 100 to 80,000 include a group containing an energy ray curable double bond. As this preferable group, a (meth)acryloyl group, a vinyl group, etc. are mentioned.
前述化合物(a2)只要滿足上述條件，則並無特別限定。但是，可列舉：具有能量線硬化性基之低分子量化合物、具有能量線硬化性基之環氧樹脂、具有能量線硬化性基之酚樹脂等。 The aforementioned compound (a2) is not particularly limited as long as it satisfies the aforementioned conditions. However, low molecular weight compounds having an energy ray curable group, epoxy resins having an energy ray curable group, phenol resins having an energy ray curable group, and the like are exemplified.
作為前述化合物(a2)中具有能量線硬化性基之低分 子量化合物，例如可列舉多官能之單體或低聚物等。較佳為具有(甲基)丙烯醯基之丙烯酸酯系化合物。 As a low score having an energy ray hardening group in the aforementioned compound (a2) Quantum compounds include, for example, polyfunctional monomers or oligomers. An acrylate compound having a (meth)acryl group is preferred.
作為前述丙烯酸酯系化合物，可列舉以下之化合物。例如可列舉：2-羥基-3-(甲基)丙烯醯氧基丙基甲基丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙氧基化乙氧基化雙酚A二(甲基)丙烯酸酯、2,2-雙[4-((甲基)丙烯醯氧基聚乙氧基)苯基]丙烷、乙氧基化雙酚A二(甲基)丙烯酸酯、2,2-雙[4-((甲基)丙烯醯氧基二乙氧基)苯基]丙烷、9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]茀、2,2-雙[4-((甲基)丙烯醯氧基聚丙氧基)苯基]丙烷、三環癸烷二甲醇二(甲基)丙烯酸酯(三環癸烷二羥甲基二(甲基)丙烯酸酯)、1,10-癸二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚丁二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、2,2-雙[4-((甲基)丙烯醯氧基乙氧基)苯基]丙烷、新戊二醇二(甲基)丙烯酸酯、乙氧基化聚丙二醇二(甲基)丙烯酸酯、2-羥基-1,3-二(甲基)丙烯醯氧基丙烷等2官能(甲基)丙烯酸酯；異氰脲酸三(2-(甲基)丙烯醯氧基乙基)酯、ε-己內酯改性異氰脲酸三-(2-(甲基)丙烯醯氧基乙基)酯、乙氧基化甘油三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯 酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇聚(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯；(甲基)丙烯酸胺基甲酸酯低聚物等多官能(甲基)丙烯酸酯低聚物等。 The following compounds are mentioned as said acrylate type compound. Examples include: 2-hydroxy-3-(meth)acryloxypropyl methacrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di( Meth)acrylate, 2,2-bis[4-((meth)acryloxypolyethoxy)phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, 2, 2-bis[4-((meth)acryloxydiethoxy)phenyl]propane, 9,9-bis[4-(2-(meth)acryloxyethoxy)phenyl ] flume, 2,2-bis[4-((meth)acryloxypolypropoxy)phenyl]propane, tricyclodecane dimethanol di(meth)acrylate (tricyclodecane dimethylol di(meth)acrylate), 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate base) acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, ethylene glycol Di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 2,2-bis[4-((meth)acryloxyethyl oxy)phenyl]propane, neopentyl glycol di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, 2-hydroxy-1,3-di(meth)acryloxy 2-functional (meth)acrylates such as propane; tris(2-(meth)acryloxyethyl)isocyanurate, ε-caprolactone modified tris-(2-( Meth)acryloxyethyl) ester, ethoxylated glyceryl tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, di-tris(meth)acrylate Methylolpropane Tetra(meth)acrylate, Ethoxylated Pentaerythritol Tetra(meth)propylene Polyfunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, dipentaerythritol hexa(meth)acrylate; (meth)acrylic acid urethane Polyfunctional (meth)acrylate oligomers such as ester oligomers, etc.
前述化合物(a2)中，作為具有能量線硬化性基之環氧樹脂、具有能量線硬化性基之酚樹脂，例如可使用「日本專利特開2013-194102號公報」中的段落0043等中所記載之樹脂。此種樹脂亦符合構成後述之熱硬化性成分(h)之樹脂，但本發明中視作前述化合物(a2)。 In the aforementioned compound (a2), as the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group, for example, those described in paragraph 0043 of "Japanese Patent Application Laid-Open No. 2013-194102" and the like can be used. Recorded resin. Such a resin also corresponds to the resin constituting the thermosetting component (h) described later, but is regarded as the aforementioned compound (a2) in the present invention.
前述化合物(a2)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 aforementioned compound (a2) is preferably from 100 to 30,000, more preferably from 300 to 10,000.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之前述化合物(a2)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The aforementioned compound (a2) contained in the composition (IV-1) for protective film formation and the film for protective film formation may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
[不具有能量線硬化性基之聚合物(b)] [Polymer (b) not having an energy ray curable group]
於保護膜形成用組成物(IV-1)及保護膜形成用膜含有前述化合物(a2)作為前述能量線硬化性成分(a)之情形時，較佳為進而亦含有不具有能量線硬化性基之聚合物(b)。 When the composition for forming a protective film (IV-1) and the film for forming a protective film contain the aforementioned compound (a2) as the aforementioned energy ray curable component (a), it is preferable to further contain The base polymer (b).
前述聚合物(b)可至少一部分藉由交聯劑(f)進行交聯 ，亦可不進行交聯。 The aforementioned polymer (b) may be at least partially crosslinked by a crosslinking agent (f) , and may not be cross-linked.
作為不具有能量線硬化性基之聚合物(b)，例如可列舉：丙烯酸系聚合物、苯氧基樹脂、胺基甲酸酯樹脂、聚酯、橡膠系樹脂、丙烯酸胺基甲酸酯樹脂、聚乙烯醇(polyvinyl alcohol；PVA)、丁醛樹脂、聚酯胺基甲酸酯樹脂等。 Examples of the polymer (b) not having an energy ray curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber-based resins, and acrylic urethane resins. , polyvinyl alcohol (polyvinyl alcohol; PVA), butyral resin, polyester urethane resin, etc.
這些之中，前述聚合物(b)較佳為丙烯酸系聚合物(以下有時簡稱為「丙烯酸系聚合物(b-1)」)。 Among these, the aforementioned polymer (b) is preferably an acrylic polymer (hereinafter sometimes simply referred to as "acrylic polymer (b-1)").
丙烯酸系聚合物(b-1)可為公知的聚合物。例如可為1種丙烯酸系單體的均聚物，亦可為2種以上丙烯酸系單體的共聚物，還可為1種或2種以上丙烯酸系單體與1種或2種以上除丙烯酸系單體以外的單體(非丙烯酸系單體)之共聚物。 The acrylic polymer (b-1) may be a known polymer. For example, it can be a homopolymer of one acrylic monomer, or a copolymer of two or more acrylic monomers, or one or two or more acrylic monomers and one or two or more acrylic monomers. Copolymers of monomers other than monomers (non-acrylic monomers).
作為構成丙烯酸系聚合物(b-1)之前述丙烯酸系單體，可列舉以下之單體。例如可列舉：(甲基)丙烯酸烷基酯、具有環狀骨架之(甲基)丙烯酸酯、含縮水甘油基之(甲基)丙烯酸酯、含羥基之(甲基)丙烯酸酯、含取代胺基之(甲基)丙烯酸酯等。此處，所謂「取代胺基」，如上文所說明。 The following monomers are mentioned as said acrylic-type monomer which comprises an acrylic-type polymer (b-1). Examples include: alkyl (meth)acrylates, (meth)acrylates having a cyclic skeleton, glycidyl-containing (meth)acrylates, hydroxyl-containing (meth)acrylates, substituted amine-containing Base (meth)acrylate, etc. Here, the "substituted amino group" is as described above.
作為前述(甲基)丙烯酸烷基酯，可列舉以下之(甲基) 丙烯酸烷基酯。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)丙烯酸烷基酯等。 Examples of the aforementioned alkyl (meth)acrylates include the following (methyl) Alkyl acrylate. Examples include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate ) isobutyl acrylate, second butyl (meth)acrylate, third butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, (meth)acrylate base) decyl acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), tridecyl (meth)acrylate, (meth)acrylate base) myristyl acrylate (myristyl (meth)acrylate), pentadecyl (meth)acrylate, cetyl (meth)acrylate (palmyl (meth)acrylate), Heptadecyl (meth)acrylate, octadecyl (meth)acrylate (stearyl (meth)acrylate), etc. The alkyl group constituting the alkyl ester is a chain structure with 1 to 18 carbon atoms Alkyl (meth)acrylate, etc.
作為具有前述環狀骨架之(甲基)丙烯酸酯，可列舉以下之(甲基)丙烯酸酯。例如可列舉：(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等。 As (meth)acrylate which has the said cyclic skeleton, the following (meth)acrylate is mentioned. Examples include cycloalkyl (meth)acrylates such as isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate. Cycloalkenyl (meth)acrylates such as dicyclopentenyl (meth)acrylate; Cycloalkenyloxyalkyl (meth)acrylates such as dicyclopentenyloxyethyl (meth)acrylate, etc.
作為前述含縮水甘油基之(甲基)丙烯酸酯，例如可列舉(甲基)丙烯酸縮水甘油酯等。 As said glycidyl group containing (meth)acrylate, glycidyl (meth)acrylate etc. are mentioned, for example.
作為前述含羥基之(甲基)丙烯酸酯，可列舉以下之(甲基)丙烯酸酯。例如可列舉：(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。 The following (meth)acrylates are mentioned as said hydroxyl group-containing (meth)acrylate. For example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth) 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and the like.
作為前述含取代胺基之(甲基)丙烯酸酯，例如可列舉(甲基)丙烯酸N-甲基胺基乙酯等。 As said substituted amino group containing (meth)acrylate, N-methylamino ethyl (meth)acrylate etc. are mentioned, for example.
作為構成丙烯酸系聚合物(b-1)之前述非丙烯酸系單體，例如可列舉：乙烯、降冰片烯等烯烴；乙酸乙烯酯；苯乙烯等。 Examples of the non-acrylic monomer constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; and styrene.
作為至少一部分藉由交聯劑(f)進行交聯且不具有前述能量線硬化性基之聚合物(b)，例如可列舉：前述聚合物(b)中的反應性官能基與交聯劑(f)反應之聚合物。 Examples of the polymer (b) that is at least partly crosslinked by the crosslinking agent (f) and does not have the aforementioned energy ray-curable group include: the reactive functional group and the crosslinking agent in the aforementioned polymer (b) (f) Reactive polymers.
前述反應性官能基根據交聯劑(f)之種類等適宜選擇即可，並無特別限定。例如，於交聯劑(f)為多異氰酸酯化合物之情形時，作為前述反應性官能基，可列舉羥基、羧基、胺基等，這些之中，較佳為與異氰酸酯基之反應性高之羥基。另外，於交聯劑(f)為環氧系化合物之情形時，作為前述反應性官能基，可列舉羧基、胺基、醯胺基等。這些之中，較佳為與環氧基之反應性高之羧基。其中，就防止半導體晶圓或半導體晶片的電路腐蝕之方面而言，前述反應性官能基較佳為羧基以外的基。 The said reactive functional group should just be suitably selected according to the kind of crosslinking agent (f), etc., and it does not specifically limit. For example, when the crosslinking agent (f) is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxyl group, an amino group, and the like, and among these, a hydroxyl group having high reactivity with an isocyanate group is preferable. . Moreover, when a crosslinking agent (f) is an epoxy compound, a carboxyl group, an amino group, an amide group etc. are mentioned as said reactive functional group. Among these, a carboxyl group having high reactivity with an epoxy group is preferable. Among them, the aforementioned reactive functional group is preferably a group other than a carboxyl group in terms of preventing corrosion of a semiconductor wafer or a circuit of a semiconductor wafer.
作為具有前述反應性官能基且不具有能量線硬化性基之聚合物(b)，例如可列舉：至少使具有前述反應性官能基之單體進行聚合而獲得之聚合物。於丙烯酸系聚合物(b-1)之情形時，作為構成該丙烯酸系聚合物(b-1)之單體所列舉之前述丙烯酸系單體及非丙烯酸系單體的任一者或兩者，使用具有前述反應性官能基之單體即可。例如，作為具有羥基作為反應性官能基之前述聚合物(b)，例如可列舉：使含羥基之(甲基)丙烯酸酯進行聚合所得之聚合物。除此以外，亦可列舉使上文所列舉之前述丙烯酸系單體或非丙烯酸系單體中1個或2個以上氫原子被前述反應性官能基取代而成之單體進行聚合而獲得之聚合物。 As a polymer (b) which has the said reactive functional group and does not have an energy-ray curable group, the polymer obtained by polymerizing at least the monomer which has the said reactive functional group is mentioned, for example. In the case of the acrylic polymer (b-1), any one or both of the aforementioned acrylic monomers and non-acrylic monomers listed as monomers constituting the acrylic polymer (b-1) , the monomers having the aforementioned reactive functional groups can be used. For example, as said polymer (b) which has a hydroxyl group as a reactive functional group, the polymer obtained by polymerizing the (meth)acrylate containing a hydroxyl group is mentioned, for example. In addition, ones obtained by polymerizing monomers in which one or more hydrogen atoms of the above-mentioned acrylic monomers or non-acrylic monomers are replaced by the above-mentioned reactive functional groups are also mentioned. polymer.
具有反應性官能基之前述聚合物(b)中，由具有反應性官能基之單體衍生之結構單元的量相對於構成該聚合物(b)之結構單元的全部量之比例(含量)較佳為1質量%至25質量%，更佳為2質量%至20質量%。藉由前述比例為此種範圍，前述聚合物(b)中，交聯程度成為更佳的範圍。 In the aforementioned polymer (b) having a reactive functional group, the ratio (content) of the amount of structural units derived from a monomer having a reactive functional group relative to the total amount of structural units constituting the polymer (b) is relatively small. Preferably, it is 1 mass % to 25 mass %, More preferably, it is 2 mass % to 20 mass %. When the ratio is in such a range, the degree of crosslinking in the polymer (b) is in a more preferable range.
就保護膜形成用組成物(IV-1)的造膜性更良好之方面而言，不具有能量線硬化性基之聚合物(b)的重量平均分子量(Mw)較佳為10000至2000000，更佳為100000至1500000。 The weight average molecular weight (Mw) of the polymer (b) not having an energy ray curable group is preferably 10,000 to 2,000,000 in terms of better film-forming properties of the protective film-forming composition (IV-1), More preferably, it is 100,000 to 1,500,000.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之不具有能量線硬化性基之聚合物(b)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The composition (IV-1) for protective film formation and the polymer (b) which does not have an energy ray curable group contained in the film for protective film formation may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
作為保護膜形成用組成物(IV-1)，可列舉含有前述聚合物(a1)及前述化合物(a2)的任一者或兩者之組成物。並且，於保護膜形成用組成物(IV-1)含有前述化合物(a2)之情形時，較佳為進而亦含有不具有能量線硬化性基之聚合物(b)。該情形時，亦較佳為進而含有前述(a1)。另外，保護膜形成用組成物(IV-1)亦可不含有前述化合物(a2)，且一併含有前述聚合物(a1)及不具有能量線硬化性基之聚合物(b)。 Examples of the composition (IV-1) for forming a protective film include a composition containing either or both of the aforementioned polymer (a1) and the aforementioned compound (a2). Moreover, when the composition (IV-1) for protective film formation contains the said compound (a2), it is preferable to further contain the polymer (b) which does not have an energy-ray curable group. In this case, it is also preferable to further include the above-mentioned (a1). In addition, the protective film forming composition (IV-1) may not contain the aforementioned compound (a2), and may also contain the aforementioned polymer (a1) and the polymer (b) not having an energy ray curable group.
於保護膜形成用組成物(IV-1)含有前述聚合物(a1)、前述化合物(a2)及不具有能量線硬化性基之聚合物(b)之情形時，保護膜形成用組成物(IV-1)中，前述化合物(a2)的含量相對於前述聚合物(a1)及不具有能量線硬化性基之聚合物(b)的總含量100質量份，較佳為10質量份至400質量份，更佳為30質量份至350質量份。 When the protective film forming composition (IV-1) contains the aforementioned polymer (a1), the aforementioned compound (a2) and the polymer (b) having no energy ray curable group, the protective film forming composition ( In IV-1), the content of the aforementioned compound (a2) is preferably 10 to 400 parts by mass relative to 100 parts by mass of the total content of the polymer (a1) and the polymer (b) not having an energy-ray-curable group. parts by mass, more preferably 30 to 350 parts by mass.
保護膜形成用組成物(IV-1)中，前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計含量相對於溶劑以外的成分的總含量之比例(亦即，保護膜形成 用膜中的前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計含量)較佳為5質量%至90質量%。更佳為10質量%至80質量%，尤佳為15質量%至70質量%。藉由前述合計含量之比例為此種範圍，保護膜形成用膜的能量線硬化性變得更良好。 Ratio of the total content of the aforementioned energy ray curable component (a) and polymer (b) having no energy ray curable group to the total content of components other than the solvent in the protective film forming composition (IV-1) (i.e., protective film formation The total content of the energy ray curable component (a) and the polymer (b) not having an energy ray curable group) in the film is preferably 5% by mass to 90% by mass. More preferably, it is 10 mass % to 80 mass %, Most preferably, it is 15 mass % to 70 mass %. When the ratio of the said total content is such a range, the energy ray curability of the film for protective film formation becomes more favorable.
於保護膜形成用組成物(IV-1)含有前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，前述聚合物(b)的含量相對於能量線硬化性成分(a)的含量100質量份，較佳為3質量份至160質量份，更佳為6質量份至130質量份。藉由前述聚合物(b)的前述含量為此種範圍，保護膜形成用膜的能量線硬化性變得更良好。 When the protective film-forming composition (IV-1) contains the aforementioned energy ray-curable component (a) and the polymer (b) having no energy-ray-curable group, the protective film-forming composition (IV-1 ) and the film for forming a protective film, the content of the aforementioned polymer (b) is preferably 3 to 160 parts by mass, more preferably 6 parts by mass, based on 100 parts by mass of the content of the energy ray-curable component (a). to 130 parts by mass. When the said content of the said polymer (b) is such a range, the energy ray curability of the film for protective film formation becomes more favorable.
保護膜形成用組成物(IV-1)中，除能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)以外，亦可含有以下之化合物。亦即，亦可根據目的而含有選自由光聚合起始劑(c)、填充材料(d)、偶合劑(e)、交聯劑(f)、著色劑(g)、熱硬化性成分(h)、及通用添加劑(z)所組成之群組中的1種或2種以上。例如，藉由使用含有前述能量線硬化性成分(a)及熱硬化性成分(h)之保護膜形成用組成物(IV-1)，所形成之保護膜形成用膜藉由加熱而對被接著體之接著力提高。進而，由該保護膜形成用膜所形成之保護膜的強度亦提高。 The protective film forming composition (IV-1) may contain the following compounds in addition to the energy ray curable component (a) and the polymer (b) not having an energy ray curable group. That is, according to the purpose, it may also contain a photopolymerization initiator (c), a filler (d), a coupling agent (e), a crosslinking agent (f), a colorant (g), a thermosetting component ( One or more of the group consisting of h), and the general-purpose additive (z). For example, by using the protective film-forming composition (IV-1) containing the aforementioned energy ray-curable component (a) and thermosetting component (h), the formed protective film-forming film is heated against the The bonding strength of the bonding body is improved. Furthermore, the intensity|strength of the protective film formed from this film for protective film formation also improves.
[光聚合起始劑(c)] [Photopolymerization initiator (c)]
作為光聚合起始劑(c)，可列舉以下之化合物。例如可列舉：安息香、安息香甲醚、安息香乙醚、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；苄基苯基硫化物、一硫化四甲基秋蘭姆等硫化物化合物；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；二苯甲酮、2-(二甲基胺基)-1-(4-嗎啉基苯基)-2-苄基-1-丁酮、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)等二苯甲酮化合物；過氧化物化合物；二乙醯等二酮化合物；苯偶醯；二苯偶醯；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；2-氯蒽醌等。 As a photoinitiator (c), the following compounds are mentioned. Examples include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal and other benzoin compounds; acetophenone, 2-hydroxy -Acetophenone compounds such as 2-methyl-1-phenyl-propan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one; bis(2,4 ,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and other acylphosphine oxide compounds; benzylphenyl sulfide, monosulfide Sulfide compounds such as tetramethylthiuram; α-ketol compounds such as 1-hydroxycyclohexyl phenyl ketone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; thioxanthone, etc. Thioxanthone compounds; benzophenone, 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, ethyl ketone, 1-[9- Benzophenone compounds such as ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime); peroxide compounds; di Diketone compounds such as acetylene; benzoyl; dibenzoyl; 2,4-diethylthioxanthone; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1-[4- (1-methylvinyl)phenyl]acetone; 2-chloroanthraquinone, etc.
另外，作為光聚合起始劑(c)，例如亦可使用1-氯蒽醌等醌化合物；胺等光增感劑等。 Moreover, as a photoinitiator (c), for example, quinone compounds, such as 1-chloroanthraquinone; Photosensitizers, such as an amine, etc. can also be used, for example.
保護膜形成用組成物(IV-1)所含有之光聚合起始劑(c)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The photopolymerization initiator (c) contained in the composition (IV-1) for protective film formation may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
於使用光聚合起始劑(c)之情形時，保護膜形成用組成物(IV-1)中，光聚合起始劑(c)的含量相對於能量線硬化性化合物(a)的含量100質量份，較佳為0.01質量份至20質量份。更佳為0.03質量份至10質量份，尤佳為0.05質量份至5質量份。 In the case of using the photopolymerization initiator (c), in the protective film forming composition (IV-1), the content of the photopolymerization initiator (c) relative to the content of the energy ray-curable compound (a) is 100 Parts by mass, preferably 0.01 to 20 parts by mass. More preferably, it is 0.03 parts by mass to 10 parts by mass, and most preferably, it is 0.05 parts by mass to 5 parts by mass.
[填充材料(d)] [Filler (d)]
藉由保護膜形成用膜含有填充材料(d)，保護膜形成用膜硬化所獲得之保護膜容易調整熱膨脹係數。結果為，使該熱膨脹係數對於保護膜之形成對象物而言最佳化，藉此使用保護膜形成用複合片所獲得之封裝的可靠性進一步提高。另外，藉由保護膜形成用膜含有填充材料(d)，可降低保護膜的吸濕率，或提高散熱性。 When the film for protective film formation contains the filler (d), the thermal expansion coefficient of the protective film obtained by curing the film for protective film formation becomes easy. As a result, the reliability of the package obtained by using the composite sheet for protective film formation improves further by optimizing this thermal expansion coefficient for the object to which a protective film is formed. Moreover, when the film for protective film formation contains a filler (d), the moisture absorption rate of a protective film can be reduced, and heat dissipation can be improved.
作為填充材料(d)，例如可列舉由導熱性材料構成之材料。 As a filler (d), what consists of a thermally conductive material is mentioned, for example.
填充材料(d)可為有機填充材料及無機填充材料之任一者，較佳為無機填充材料。 The filler (d) may be any one of an organic filler and an inorganic filler, and is preferably an inorganic filler.
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。 As preferred inorganic filler materials, for example, powders of silicon dioxide, alumina, talc, calcium carbonate, titanium dioxide, iron oxide, silicon carbide, boron nitride, etc. can be listed; these inorganic filler materials are spheroidized. Beads; surface-modified products of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers, etc.
這些之中，無機填充材料較佳為二氧化矽或氧化鋁。 Among these, the inorganic filler is preferably silica or alumina.
填充材料(d)的平均粒徑並無特別限定。但是，較佳為0.01μm至15μm。更佳為0.03μm至10μm，尤佳為0.05μm至8μm。 The average particle size of the filler (d) is not particularly limited. However, it is preferably 0.01 μm to 15 μm. More preferably, it is 0.03 μm to 10 μm, and most preferably, it is 0.05 μm to 8 μm.
藉由填充材料(d)的平均粒徑為此種範圍，可維持對保護膜之形成對象物之接著性，並且可抑制保護膜之光之透過率之降低。 When the average particle diameter of the filler (d) is in such a range, the adhesiveness to the formation object of a protective film can be maintained, and the fall of the light transmittance of the protective film can be suppressed.
再者，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累計值50%下的粒徑(D50)之值。 In addition, in this specification, unless otherwise specified, the "average particle diameter" means the particle diameter (D 50 ) at 50% of the cumulative value in the particle size distribution curve obtained by the laser diffraction scattering method. value.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之填充材料(d)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The filler (d) contained in the composition for forming a protective film (IV-1) and the film for forming a protective film may be only one type, or may be two or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
於使用填充材料(d)之情形時，保護膜形成用組成物(IV-1)中，填充材料(d)的含量相對於溶劑以外的全部成分的總含量之比例(亦即，保護膜形成用膜中的填充材料(d)的含量)較佳為5質量%至83質量%，更佳為7質量%至78質量%。藉由填充材料(d)的含量為此種範圍，更容易調整上述之熱膨脹係數。 In the case of using the filler (d), in the composition for forming a protective film (IV-1), the ratio of the content of the filler (d) to the total content of all components other than the solvent (that is, the protective film forming The content of the filler (d) in the film) is preferably from 5% by mass to 83% by mass, more preferably from 7% by mass to 78% by mass. When the content of the filler (d) falls within such a range, it becomes easier to adjust the above-mentioned coefficient of thermal expansion.
[偶合劑(e)] [Coupling agent (e)]
藉由使用具有可與無機化合物或有機化合物反應之官能基之偶合劑作為偶合劑(e)，可提高保護膜形成用膜對被接著體之接著性及密接性。另外，藉由使用偶合劑(e)，保護膜形成用膜硬化而獲得之保護膜無損耐熱性而耐水性提高。 By using a coupling agent having a functional group reactive with an inorganic compound or an organic compound as the coupling agent (e), the adhesiveness and adhesion of the film for protective film formation to an adherend can be improved. Moreover, by using a coupling agent (e), the protective film obtained by hardening the film for protective film formation improves water resistance, without impairing heat resistance.
偶合劑(e)較佳為具有可與能量線硬化性成分(a)、不具有能量線硬化性基之聚合物(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。 The coupling agent (e) is preferably a compound having a functional group capable of reacting with a functional group of the energy ray curable component (a), the polymer (b) having no energy ray curable group, and the like. More preferably, it is a silane coupling agent.
作為較佳的前述矽烷偶合劑，可列舉以下之化合物。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、咪唑矽烷等。 The following compounds are mentioned as preferable said silane coupling agent. Examples include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, Glyceryloxymethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-( Phenylamino)propyltrimethoxysilane, 3-anilinopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Methyldimethoxysilane, bis(3-triethoxysilylpropyl)tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyl trimethoxysilane Acetyloxysilane, imidazole silane, etc.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有 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，這些之組合及比率可任意選擇。 Contained in the composition for forming a protective film (IV-1) and the film for forming a protective film The coupling agent (e) may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
於使用偶合劑(e)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，偶合劑(e)的含量相對於能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(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，可獲得更顯著的以下由使用偶合劑(e)所帶來之效果：填充材料(d)於樹脂中的分散性提高，或保護膜形成用膜與被接著體之接著性提高等。另外，藉由偶合劑(e)的前述含量為前述上限值以下，可進一步抑制產生逸氣。 In the case of using the coupling agent (e), in the protective film forming composition (IV-1) and the protective film forming film, the content of the coupling agent (e) is relative to the energy ray curable component (a) and does not contain The total content of the energy ray-curable polymer (b) is 100 parts by mass, preferably 0.03 to 20 parts by mass. More preferably, it is 0.05 to 10 parts by mass, and most preferably, it is 0.1 to 5 parts by mass. When the aforementioned content of the coupling agent (e) is more than the aforementioned lower limit value, the following effect brought by the use of the coupling agent (e) can be obtained more significantly: the dispersibility of the filler (d) in the resin is improved, or Improvement of the adhesion between the film for protective film formation and the adherend, etc. Moreover, when the said content of a coupling agent (e) is below the said upper limit, generation|occurrence|production of outgassing can be suppressed further.
[交聯劑(f)] [Crosslinking agent (f)]
藉由使用交聯劑(F)，使上述之能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)進行交聯，可調節保護膜形成用膜的初期接著力及凝聚力。 The initial adhesive force of the film for protective film formation can be adjusted by crosslinking the above-mentioned energy ray curable component (a) or the polymer (b) not having an energy ray curable group by using a crosslinking agent (F). and cohesion.
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。 Examples of the crosslinking agent (f) include: organic polyvalent isocyanate compounds, organic polyvalent imine compounds, metal chelate crosslinking agents (crosslinking agents having a metal chelate structure), aziridine crosslinking agents, etc. agent (crosslinking agent with aziridine group), etc.
作為前述有機多元異氰酸酯化合物，可列舉以下之化合物。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之化合物之反應物，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，並且於分子末端部具有異氰酸酯基之預聚物。 The following compounds are mentioned as said organic polyvalent isocyanate compound. Examples 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; terminal isocyanate urethane prepolymers obtained by reacting the aforementioned aromatic polyvalent isocyanate compounds, etc., with polyol compounds, etc. The aforementioned "adduct" means that the aforementioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanate compound is mixed with ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil, etc. Examples of the reactant of the low-molecular-weight active hydrogen compound include xylylene diisocyanate adduct of trimethylolpropane, which will be described later, as examples of the aforementioned adduct. In addition, the "isocyanate-terminated urethane prepolymer" means a prepolymer having a urethane bond and an isocyanate group at a molecular terminal.
作為前述有機多元異氰酸酯化合物，更具體而言，可列舉以下之化合物。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；1,4-二甲苯二異氰酸酯；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；對三羥甲基丙烷等多元醇的全部或一部分羥基，加成甲苯二異 氰酸酯、六亞甲基二異氰酸酯及苯二甲基二異氰酸酯的任1種或2種以上而成之化合物；離胺酸二異氰酸酯等。 As said organic polyvalent isocyanate compound, the following compounds are mentioned more specifically. Examples include: 2,4-toluene diisocyanate; 2,6-toluene diisocyanate; 1,3-xylylene diisocyanate; 1,4-xylene diisocyanate; Diisocyanate; Diphenylmethane-2,4'-diisocyanate; 3-Methyldiphenylmethane diisocyanate; Hexamethylene diisocyanate; Isophorone diisocyanate; Dicyclohexylmethane-4,4' -diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; toluene diisocyanate added to all or part of the hydroxyl groups of polyols such as trimethylolpropane Any one or two or more of cyanate, hexamethylene diisocyanate and xylylene diisocyanate; lysine diisocyanate, etc.
作為前述有機多元亞胺化合物，可列舉以下之化合物。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。 The following compounds are mentioned as said organic polyvalent imine compound. For example, N,N'-diphenylmethane-4,4'-bis(1-aziridine formamide), trimethylolpropane-tri-β-aziridinyl propionate, tetra Methylolmethane-tri-β-aziridinyl propionate, N,N'-toluene-2,4-bis(1-aziridinecarboxamide) triethylene melamine, etc.
於使用有機多元異氰酸酯化合物作為交聯劑(f)之情形時，作為能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)，較佳為使用含羥基之聚合物。於交聯劑(f)具有異氰酸酯基，能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)具有羥基之情形時，藉由交聯劑(f)與能量線硬化性成分(a)或不具有能量線硬化性基之聚合物(b)之反應，可將交聯結構簡便地導入至保護膜形成用膜中。 In the case of using an organic polyvalent isocyanate compound as the crosslinking agent (f), it is preferable to use a hydroxyl group-containing polymer as the energy ray curable component (a) or the polymer (b) having no energy ray curable group . When the crosslinking agent (f) has an isocyanate group and the energy ray-curable component (a) or the polymer (b) without energy ray-curable groups has a hydroxyl group, the crosslinking agent (f) and the energy ray The reaction of the curable component (a) or the polymer (b) not having an energy ray curable group can easily introduce a crosslinked structure into the film for forming a protective film.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之交聯劑(f)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The composition (IV-1) for protective film formation and the crosslinking agent (f) contained in the film for protective film formation may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
於使用交聯劑(f)之情形時，保護膜形成用組成物(IV-1)中，交聯劑(f)的含量相對於能量線硬化性成分(a) 及不具有能量線硬化性基之聚合物(b)的總含量100質量份，較佳為0.01質量份至20質量份。更佳為0.1質量份至10質量份，尤佳為0.5質量份至5質量份。藉由交聯劑(f)的前述含量為前述下限值以上，可獲得更顯著的由使用交聯劑(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，可抑制交聯劑(f)之過量使用。 When the crosslinking agent (f) is used, the content of the crosslinking agent (f) relative to the energy ray curable component (a) in the protective film forming composition (IV-1) The total content of the polymer (b) without energy ray curable groups is 100 parts by mass, preferably 0.01 to 20 parts by mass. More preferably, it is 0.1 to 10 parts by mass, and most preferably, it is 0.5 to 5 parts by mass. When the said content of a crosslinking agent (f) is more than the said lower limit, the more remarkable effect by using a crosslinking agent (f) can be acquired. Moreover, the excessive use of a crosslinking agent (f) can be suppressed by the said content of a crosslinking agent (f) being below the said upper limit.
[著色劑(g)] [coloring agent (g)]
作為著色劑(g)，例如可列舉：無機系顏料、有機系顏料、有機系染料等公知的著色劑。 As a coloring agent (g), well-known coloring agents, such as an inorganic pigment, an organic pigment, and an organic dye, are mentioned, for example.
作為前述有機系顏料及有機系染料，可列舉以下之化合物。例如可列舉：銨系色素、花青系色素、部花青系色素、克酮鎓(croconium)系色素、方酸鎓(squalilium)系色素、薁鎓系色素、聚次甲基系色素、萘醌系色素、吡喃鎓系色素、酞菁系色素、萘酞菁系色素、萘內醯胺系色素、偶氮系色素、縮合偶氮系色素、靛藍系色素、紫環酮(perinone)系色素、苝系色素、二噁烷系色素、喹吖啶酮系色素、異吲哚啉酮系色素、喹啉黃(quinophthalone)系色素、吡咯系色素、硫代靛藍系色素、金屬錯合物系色素(金屬錯鹽染料)、二硫醇金屬錯合物系色素、吲哚酚系色素、三烯丙基甲烷系色素、蒽醌系色素、萘酚系色素、次甲基偶氮系色素、苯并咪唑酮系色素、皮蒽酮系色素及士林(threne)系色素等。 As said organic type pigment and organic type dye, the following compounds are mentioned. Examples include ammonium-based dyes, cyanine-based dyes, merocyanine-based dyes, croconium-based dyes, squalilium-based dyes, azulenium-based dyes, polymethine-based dyes, and naphthalene-based dyes. Quinone dyes, pyrylium dyes, phthalocyanine dyes, naphthalocyanine dyes, naphtholactamide dyes, azo dyes, condensed azo dyes, indigo dyes, perinone dyes Pigments, perylene dyes, dioxane dyes, quinacridone dyes, isoindolinone dyes, quinophthalone dyes, pyrrole dyes, thioindigo dyes, metal complexes Pigments (metal complex salt dyes), dithiol metal complex pigments, indoxyl pigments, triallyl methane pigments, anthraquinone pigments, naphthol pigments, methine azo pigments , benzimidazolone-based pigments, pyranthrone-based pigments, and threne-based pigments.
作為前述無機系顏料，例如可列舉：碳黑、鈷系色素、鐵系色素、鉻系色素、鈦系色素、釩系色素、鋯系色素、鉬系色素、釕系色素、鉑系色素、ITO(Indium Tin Oxide；氧化銦錫)系色素、ATO(Antimony Tin Oxide；氧化銻錫)系色素等。 Examples of the inorganic pigments include carbon black, cobalt-based pigments, iron-based pigments, chromium-based pigments, titanium-based pigments, vanadium-based pigments, zirconium-based pigments, molybdenum-based pigments, ruthenium-based pigments, platinum-based pigments, ITO (Indium Tin Oxide; Indium Tin Oxide) pigments, ATO (Antimony Tin Oxide; Antimony Tin Oxide) pigments, etc.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之著色劑(g)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The coloring agent (g) contained in the protective film forming composition (IV-1) and the protective film forming film may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
於使用著色劑(g)之情形時，保護膜形成用膜中的著色劑(g)的含量根據目的適宜調節即可。例如，有時藉由雷射照射對保護膜實施印字，藉由調節保護膜形成用膜中的著色劑(g)的含量，調節保護膜的透光性，可調節印字視認性。該情形時，保護膜形成用組成物(IV-1)中，著色劑(g)的含量相對於溶劑以外的全部成分的總含量之比例(亦即，保護膜形成用膜中的著色劑(g)的含量)較佳為0.1質量%至10質量%。更佳為0.4質量%至7.5質量%，尤佳為0.8質量%至5質量%。藉由著色劑(g)的前述含量為前述下限值以上，可獲得更顯著的由使用著色劑(g)所帶來之效果。另外，藉由著色劑(g)的前述含量為前述上限值以下，可抑制著色劑(g)之過量使用。 When using a coloring agent (g), what is necessary is just to adjust content of the coloring agent (g) in the film for protective film formation suitably according to the objective. For example, sometimes printing is performed on a protective film by laser irradiation, and by adjusting the content of the coloring agent (g) in the film for protective film formation, the light transmittance of the protective film can be adjusted to adjust the visibility of printed characters. In this case, in the protective film forming composition (IV-1), the ratio of the content of the coloring agent (g) to the total content of all components other than the solvent (that is, the coloring agent (g) in the protective film forming film The content of g)) is preferably 0.1% by mass to 10% by mass. More preferably, it is 0.4 mass % to 7.5 mass %, Most preferably, it is 0.8 mass % to 5 mass %. When the said content of a coloring agent (g) is more than the said lower limit, the more remarkable effect by using a coloring agent (g) can be acquired. Moreover, the excessive use of a coloring agent (g) can be suppressed by the said content of a coloring agent (g) being below the said upper limit.
[熱硬化性成分(h)] [Thermosetting component (h)]
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之熱硬化性成分(h)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The thermosetting component (h) contained in the protective film forming composition (IV-1) and the protective film forming film may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
作為熱硬化性成分(h)，例如可列舉：環氧系熱硬化性樹脂、熱硬化性聚醯亞胺、聚胺基甲酸酯、不飽和聚酯、聚矽氧樹脂等，較佳為環氧系熱硬化性樹脂。 Examples of the thermosetting component (h) include: epoxy-based thermosetting resins, thermosetting polyimides, polyurethanes, unsaturated polyesters, silicone resins, etc., preferably Epoxy based thermosetting resin.
(環氧系熱硬化性樹脂) (Epoxy Thermosetting Resin)
環氧系熱硬化性樹脂係由環氧樹脂(h1)及熱硬化劑(h2)構成。保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之環氧系熱硬化性樹脂可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The epoxy-based thermosetting resin is composed of an epoxy resin (h1) and a thermosetting agent (h2). The epoxy-based thermosetting resin contained in the composition (IV-1) for protective film formation and the film for protective film formation may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
‧環氧樹脂(h1) ‧Epoxy resin (h1)
作為環氧樹脂(h1)，可列舉公知的樹脂。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等2官能以上之環氧化合物。 Known resins are mentioned as an epoxy resin (h1). Examples include polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrogenated products thereof, o-cresol novolak epoxy resins, dicyclopentadiene epoxy resins, biphenyl cyclo Oxygen resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenylene skeleton type epoxy resin and other epoxy compounds with more than two functions.
作為環氧樹脂(h1)，亦可使用具有不飽和烴基之環氧樹脂。具有不飽和烴基之環氧樹脂相較於不具有不飽和烴基之環氧樹脂而言，與丙烯酸系樹脂之相容性較高。因此，藉由使用具有不飽和烴基之環氧樹脂，使用保護膜形成用複合片所獲得之封裝的可靠性提高。 An epoxy resin having an unsaturated hydrocarbon group can also be used as the epoxy resin (h1). Epoxy resins with unsaturated hydrocarbon groups are more compatible with acrylic resins than epoxy resins without unsaturated hydrocarbon groups. Therefore, by using the epoxy resin which has an unsaturated hydrocarbon group, the reliability of the package obtained using the composite sheet for protective film formation improves.
作為具有不飽和烴基之環氧樹脂，例如可列舉：多官能系環氧樹脂的一部分環氧基更換為具有不飽和烴基之基而成之化合物。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 resin which has an unsaturated hydrocarbon group, the compound which replaced some epoxy groups of a polyfunctional epoxy resin with the group which has an unsaturated hydrocarbon group is mentioned, for example. Such a compound is obtained, for example, by adding (meth)acrylic acid or a derivative thereof to an epoxy group.
另外，作為具有不飽和烴基之環氧樹脂，例如可列舉：於構成環氧樹脂之芳香環等上直接鍵結有具有不飽和烴基之基之化合物等。不飽和烴基為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：乙烯基(Ethenyl group)、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 resin which has an unsaturated hydrocarbon group, the compound etc. which have the group which has an unsaturated hydrocarbon group directly bonded to the aromatic ring etc. which comprise an epoxy resin are mentioned, for example. The unsaturated hydrocarbon group is a polymerizable unsaturated group, and specific examples of the unsaturated hydrocarbon group include vinyl (Ethenyl group), 2-propenyl (allyl), (meth)acryl, ( Meth)acrylamide group, etc., preferably acrylyl group.
環氧樹脂(h1)的數量平均分子量並無特別限定。但是，就保護膜形成用膜的硬化性、以及保護膜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。 The number average molecular weight of the epoxy resin (h1) is not particularly limited. However, it is preferably from 300 to 30000 in terms of the curability of the film for protective film formation, and the strength and heat resistance of the protective film. More preferably, it is 400 to 10,000, and most preferably, it is 500 to 3,000.
環氧樹脂(h1)的環氧當量較佳為100g/eq至1000g/eq，更佳為150g/eq至800g/eq。 The epoxy equivalent of the epoxy resin (h1) is preferably from 100 g/eq to 1000 g/eq, more preferably from 150 g/eq to 800 g/eq.
環氧樹脂(h1)可單獨使用1種，亦可併用2種以上。於併用2種以上之情形時，這些之組合及比率可任意選擇。 An epoxy resin (h1) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, the combination and ratio of these can be chosen arbitrarily.
‧熱硬化劑(h2) ‧Heat curing agent (h2)
熱硬化劑(h2)發揮作為針對環氧樹脂(h1)之硬化劑的功能。 The thermosetting agent (h2) functions as a curing agent for the epoxy resin (h1).
作為熱硬化劑(h2)，例如可列舉：1分子中具有2個以上可與環氧基反應之官能基之化合物。作為前述官能基，例如可列舉：酚性羥基、醇性羥基、胺基、羧基、酸基酐化而成之基等。較佳為酚性羥基、胺基、或酸基經酐化而成之基，更佳為酚性羥基或胺基。 As a thermosetting agent (h2), the compound which has 2 or more functional groups which can react with an epoxy group in 1 molecule is mentioned, for example. As said functional group, a phenolic hydroxyl group, an alcoholic hydroxyl group, an amino group, a carboxyl group, a group obtained by acid anhydride etc. are mentioned, for example. It is preferably a phenolic hydroxyl group, an amino group, or an anhydrided acid group, more preferably a phenolic hydroxyl group or an amino group.
熱硬化劑(h2)中，作為具有酚性羥基之酚系硬化劑，例如可列舉：多官能酚樹脂、聯苯酚、酚醛清漆型酚樹脂、二環戊二烯系酚樹脂、芳烷基酚樹脂等。 Among the thermosetting agents (h2), examples of phenolic curing agents having phenolic hydroxyl groups include polyfunctional phenolic resins, biphenols, novolak-type phenolic resins, dicyclopentadiene-based phenolic resins, and aralkylphenolic resins. resin etc.
熱硬化劑(h2)中，作為具有胺基之胺系硬化劑，例如可列舉：二氰二胺(以下有時簡稱為「Dicyanodiamide；DICY」)等。 Among the thermosetting agents (h2), examples of the amine-based curing agent having an amino group include dicyanodiamine (hereinafter sometimes abbreviated as "Dicyanodiamide; DICY") and the like.
熱硬化劑(h2)亦可具有不飽和烴基。 The thermosetting agent (h2) may have an unsaturated hydrocarbon group.
作為具有不飽和烴基之熱硬化劑(h2)，例如可列舉：酚樹脂的一部分羥基被具有不飽和烴基之基取代而成之化合物、酚樹脂的芳香環上直接鍵結具有不飽和烴基之基而成之化合物等。 Examples of the thermosetting agent (h2) having an unsaturated hydrocarbon group include: a compound in which a part of the hydroxyl groups of a phenol resin is substituted by a group having an unsaturated hydrocarbon group; a group having an unsaturated hydrocarbon group directly bonded to the aromatic ring of the phenol resin; Compounds etc.
熱硬化劑(h2)中的前述不飽和烴基與上述之具有不飽和烴基之環氧樹脂中的不飽和烴基相同。 The aforementioned unsaturated hydrocarbon group in the thermosetting agent (h2) is the same as the unsaturated hydrocarbon group in the above-mentioned epoxy resin having an unsaturated hydrocarbon group.
於使用酚系硬化劑作為熱硬化劑(h2)之情形時，就保護膜自支持片之剝離性提高之方面而言，熱硬化劑(h2)較佳為軟化點或玻璃轉移溫度高的酚系硬化劑。 In the case of using a phenolic hardener as the thermosetting agent (h2), the thermosetting agent (h2) is preferably a phenol with a high softening point or glass transition temperature in terms of improving the peelability of the protective film from the support sheet. Department of hardening agent.
熱硬化劑(h2)中，例如多官能酚樹脂、酚醛清漆型酚樹脂、二環戊二烯系酚樹脂、芳烷基酚樹脂等樹脂成分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。 In the thermosetting agent (h2), the number average molecular weight of resin components such as polyfunctional phenol resins, novolac phenol resins, dicyclopentadiene-based phenol resins, and aralkylphenol resins is preferably from 300 to 30,000. More preferably, it is 400 to 10,000, and most preferably, it is 500 to 3,000.
熱硬化劑(h2)中，例如，聯苯酚、二氰二胺等非樹脂成分的分子量並無特別限定，例如較佳為60至500。 In the thermosetting agent (h2), for example, the molecular weight of non-resin components such as biphenol and dicyandiamide is not particularly limited, and is preferably 60 to 500, for example.
熱硬化劑(h2)可單獨使用1種，亦可併用2種以上。於併用2種以上之情形時，這些之組合及比率可任意選擇。 A thermosetting agent (h2) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, the combination and ratio of these can be chosen arbitrarily.
於使用熱硬化性成分(h)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，熱硬化劑(h2)的含量相對於環氧樹脂(h1)的含量100質量份，較佳為0.01質量份至20質量份。 When the thermosetting component (h) is used, the content of the thermosetting agent (h2) relative to the content of the epoxy resin (h1) in the composition for forming a protective film (IV-1) and the film for forming a protective film 100 parts by mass, preferably 0.01 to 20 parts by mass.
於使用熱硬化性成分(h)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中，熱硬化性成分(h)的含量 (例如，環氧樹脂(h1)及熱硬化劑(h2)的總含量)相對於不具有能量線硬化性基之聚合物(b)的含量100質量份，較佳為1質量份至500質量份。 When the thermosetting component (h) is used, the content of the thermosetting component (h) in the protective film forming composition (IV-1) and the protective film forming film (For example, the total content of the epoxy resin (h1) and the thermosetting agent (h2)) is preferably 1 to 500 parts by mass relative to 100 parts by mass of the polymer (b) having no energy-ray-curable group share.
[抗靜電劑(j)] [Antistatic agent (j)]
關於本發明中所使用之抗靜電劑(j)，只要可將保護膜形成膜的表面電阻率調節為所期望之值即可，並無特別限定。 The antistatic agent (j) used in the present invention is not particularly limited as long as the surface resistivity of the protective film forming film can be adjusted to a desired value.
例如可列舉選自由陰離子系界面活性劑系抗靜電劑、陽離子系界面活性劑系抗靜電劑、非離子系界面活性劑系抗靜電劑、及兩離子系界面活性劑系抗靜電劑所組成之群組中的至少1種等。 For example, one selected from anionic surfactant-based antistatic agents, cationic surfactant-based antistatic agents, nonionic surfactant-based antistatic agents, and two-ionic surfactant-based antistatic agents. At least 1 species etc. in the group.
另外，亦可使用高分子型抗靜電劑。例如，可使用聚醚酯醯胺系、環氧乙烷-表氯醇系、及聚醚酯系等非離子系高分子型抗靜電劑、聚苯乙烯碸系等陰離子系高分子型抗靜電劑、含四級銨鹽基之丙烯酸酯聚合物系等陽離子系高分子型抗靜電劑。 In addition, polymer antistatic agents can also be used. For example, non-ionic polymer antistatic agents such as polyether ester amide, ethylene oxide-epichlorohydrin, and polyether ester, and anionic polymer antistatic agents such as polystyrene-based antistatic agents can be used. Cationic polymer antistatic agents such as acrylate polymers containing quaternary ammonium bases.
進而，亦可使用：山梨糖醇酐單月桂酸酯、聚氧乙烯山梨糖醇酐單月桂酸酯等單月桂酸酯系抗靜電劑；甘油脂肪酸酯單甘油酯、甘油脂肪酸酯乙醯化單甘油酯、甘油脂肪酸酯有機酸單甘油酯、及甘油脂肪酸酯中鏈脂肪酸三甘油酯等甘油酯系抗靜電劑；聚甘油脂肪酸酯、山梨糖醇酐脂肪酸酯、丙二醇脂肪酸酯、特殊脂肪酸酯、及高級醇脂肪酸酯等酯型抗靜電劑 。 Further, monolaurate-based antistatic agents such as sorbitan monolaurate and polyoxyethylene sorbitan monolaurate; glycerin fatty acid ester monoglyceride, glycerin fatty acid ester acetyl Glyceride-based antistatic agents such as monoglycerides, glycerin fatty acid esters, organic acid monoglycerides, and glycerin fatty acid esters, medium-chain fatty acid triglycerides; polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fats Ester-type antistatic agents such as acid esters, special fatty acid esters, and higher alcohol fatty acid esters .
以上之抗靜電劑(j)中，較佳為鹼金屬鹽系抗靜電劑，進而較佳為Li鹽系抗靜電劑。 Among the above antistatic agents (j), an alkali metal salt-based antistatic agent is preferred, and a Li salt-based antistatic agent is further preferred.
本發明中，前述抗靜電劑(j)的含量較佳為相對於前述保護膜形成用膜中所含之樹脂成分的質量含有1質量%至20質量%，進而較佳為3質量%至10質量%。亦即，於前述保護膜形成用膜進而含有能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)之情形時，前述保護膜形成用膜中，較佳為含有相對於前述能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計質量為1質量%至20質量%之前述抗靜電劑，進而較佳為3質量%至10質量%。 In the present invention, the content of the antistatic agent (j) is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 10% by mass, based on the mass of the resin component contained in the film for forming a protective film. quality%. That is, when the film for forming a protective film further contains an energy ray curable component (a) and a polymer (b) not having an energy ray curable group, it is preferable that the film for forming a protective film contains The amount of the aforementioned antistatic agent is 1% by mass to 20% by mass, more preferably 3% by mass to 10% by mass.
若抗靜電劑(j)的含量低於前述下限值，則存在無法獲得充分的導電性，抗靜電性提高之問題。另一方面，若抗靜電劑的含量超過前述上限值，則存在滲出至保護層與Si之界面，可靠性降低之問題。 When content of an antistatic agent (j) is less than the said lower limit, sufficient electroconductivity cannot be acquired, and there exists a problem that antistatic property improves. On the other hand, when the content of the antistatic agent exceeds the above-mentioned upper limit, there is a problem of bleeding to the interface between the protective layer and Si and lowering the reliability.
[應用方法] [application method]
本發明中，作為應用抗靜電劑(j)之方法，並無特別限定。可藉由於保護膜形成用組成物中添加抗靜電劑(j)進行混合而混練，亦可於保護膜形成用組成物或保護膜形成用膜的表面塗佈抗靜電劑(j)。進而，亦可於保護膜形成用組成物或保護膜形成用膜的表面呈膜狀地塗佈含有抗靜電 劑(j)之層。進而，亦可藉由對貼附於保護膜形成用膜表面之剝離片的剝離層(表面)賦予抗靜電劑(j)而實現保護膜形成用膜之抗靜電。 In the present invention, the method of applying the antistatic agent (j) is not particularly limited. The antistatic agent (j) may be added and kneaded by adding the antistatic agent (j) to the protective film forming composition, or the antistatic agent (j) may be coated on the surface of the protective film forming composition or protective film forming film. Furthermore, the surface of the composition for protective film formation or the film for protective film formation may be coated with antistatic A layer of agent (j). Furthermore, antistatic of the film for protective film formation can also be achieved by providing an antistatic agent (j) to the release layer (surface) of the release sheet stuck on the surface of the film for protective film formation.
[通用添加劑(z)] [General Additives (z)]
通用添加劑(z)可為公知的添加劑，可根據目的任意選擇，並無特別限定。但是，作為較佳的通用添加劑(z)，例如可列舉：塑化劑、抗靜電劑、抗氧化劑、吸氣劑等。 The general-purpose additive (z) may be a known additive and may be arbitrarily selected according to the purpose, and is not particularly limited. However, examples of preferred general-purpose additives (z) include plasticizers, antistatic agents, antioxidants, getters, and the like.
保護膜形成用組成物(IV-1)及保護膜形成用膜所含有之通用添加劑(z)可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The general-purpose additive (z) contained in the protective film forming composition (IV-1) and the protective film forming film may be only 1 type, or may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
於使用通用添加劑(z)之情形時，保護膜形成用組成物(IV-1)及保護膜形成用膜中的通用添加劑(z)的含量並無特別限定，根據目的適宜選擇即可。 When using the general additive (z), the content of the general additive (z) in the protective film forming composition (IV-1) and the protective film forming film is not particularly limited, and may be appropriately selected according to the purpose.
[溶劑] [solvent]
保護膜形成用組成物(IV-1)較佳為進而含有溶劑。含有溶劑之保護膜形成用組成物(IV-1)的操作性良好。 It is preferable that the composition (IV-1) for protective film formation further contains a solvent. The composition (IV-1) for forming a protective film containing a solvent has good handleability.
前述溶劑並無特別限定。但是，作為較佳的前述溶劑，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。 The aforementioned solvent is not particularly limited. However, as a preferable solvent, for example: hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, 2-propanol, isobutanol (2-methylpropan-1-ol), and 1-butanol; ; Ethyl acetate and other esters; Acetone, methyl ethyl ketone and other ketones; Tetrahydrofuran and other ethers; Dimethylformamide , Amides (compounds having an amide bond) such as N-methylpyrrolidone, etc.
保護膜形成用組成物(IV-1)所含有之溶劑可僅為1種，亦可為2種以上。於為2種以上之情形時，這些之組合及比率可任意選擇。 The solvent contained in the composition (IV-1) for protective film formation may be only 1 type, and may be 2 or more types. In the case of two or more, the combination and ratio of these can be selected arbitrarily.
就可將保護膜形成用組成物(IV-1)中的含有成分更均勻地混合之方面而言，保護膜形成用組成物(IV-1)所含有之溶劑較佳為甲基乙基酮、甲苯或乙酸乙酯等。 The solvent contained in the protective film-forming composition (IV-1) is preferably methyl ethyl ketone from the viewpoint that the components contained in the protective film-forming composition (IV-1) can be more uniformly mixed , toluene or ethyl acetate, etc.
<<保護膜形成用組成物的製造方法>> <<Manufacturing Method of Protective Film Forming Composition>>
保護膜形成用組成物(IV-1)等保護膜形成用組成物係藉由將用以構成該保護膜形成用組成物之各成分加以調配而獲得。 The composition for protective film formation, such as the composition for protective film formation (IV-1), is obtained by preparing each component which comprises this composition for protective film formation.
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。 The order of addition of each component is not particularly limited, and two or more components may be added at the same time.
於使用溶劑之情形時，可藉由下述方式使用，亦即，將溶劑與溶劑以外之任一種調配成分混合而將該調配成分預先稀釋。另外，亦可藉由下述方式使用，亦即，不將溶劑以外之任一種調配成分預先稀釋，而將溶劑與這些調配成分混合。 In the case of using a solvent, it can be used by mixing the solvent with any one of the formulated components other than the solvent and diluting the formulated component in advance. Moreover, it can also be used by mixing a solvent with these formulation components, without diluting any formulation components other than a solvent beforehand.
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；使用混合機而進行混合之方法；施加超音波而進行混合之方法等。 There is no particular limitation on the method of mixing the ingredients during preparation. What is necessary is just to select suitably from the following well-known methods: the method of rotating a stirring bar or stirring blade, etc. and mixing; the method of mixing using a mixer; the method of applying ultrasonic waves and mixing, etc.
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 temperature and time for adding and mixing the components are not particularly limited as long as the components are not degraded, and may be appropriately adjusted. The temperature is preferably 15°C to 30°C.
與本發明之保護膜形成用複合片同樣地，作為貼附於半導體晶圓或半導體晶片中的與電路面為相反側的背面且於支持片上具備顯示接著性之層之複合片，有切晶黏晶片。 Like the composite sheet for forming a protective film of the present invention, as a composite sheet attached to a semiconductor wafer or the back surface of a semiconductor wafer opposite to the circuit surface and provided with a layer showing adhesion on a support sheet, there is a cut crystal sticky chips.
但是，切晶黏晶片所具備之接著劑層發揮以下功能，亦即，與半導體晶片一起自支持片拾取後，將該半導體晶片安裝於基板、引線框架、或其他半導體晶片等時，作為接著劑之功能。另一方面，關於本發明之保護膜形成用複合片中的保護膜形成用膜，就與半導體晶片一起自支持片拾取之方面而言，與前述接著劑層相同，但最終藉由硬化而成為保護膜，具有保護所貼附之半導體晶片的背面之功能。如此，本發明中的保護膜形成用膜的用途與切晶黏晶片中的接著劑層不同，當然所要求之性能亦不同。並且，反映該用途之差異，通常，若與切晶黏晶片中的接著劑層進行比較，則保護膜形成用膜通常存在較硬，難以拾取之傾向。因此，通常難以將切晶黏晶片中的接著劑層直接轉用作保護膜形成用複合片中的保護膜形成用膜。作為本發明之具備能量線硬化性之保護膜形成用膜之保護膜形成用複合片，附有保護膜的半導體晶片的拾取適性空前之極其優異。 However, the adhesive layer included in the die-bonding wafer functions as an adhesive when the semiconductor wafer is picked up from the support sheet together with the semiconductor wafer and then mounted on a substrate, lead frame, or other semiconductor wafer, etc. function. On the other hand, the protective film forming film in the protective film forming composite sheet of the present invention is the same as the above-mentioned adhesive layer in terms of picking up from the support sheet together with the semiconductor wafer, but finally becomes The protective film has the function of protecting the back side of the attached semiconductor chip. Thus, the use of the film for forming a protective film in the present invention is different from that of the adhesive layer in die-bonding wafers, and of course the required performance is also different. In addition, reflecting the difference in the application, generally, the film for forming a protective film tends to be relatively hard and difficult to pick up when compared with the adhesive layer in a die-bonding wafer. Therefore, it is generally difficult to directly transfer the adhesive layer in the die-bonding wafer to the film for protective film formation in the composite sheet for protective film formation. As the protective film forming composite sheet of the protective film forming film having energy ray curability of the present invention, the pick-up property of a semiconductor wafer with a protective film is extremely excellent as never before.
◇保護膜形成用複合片的製造方法 ◇Manufacturing method of composite sheet for protective film formation
本發明之保護膜形成用複合片可藉由將上述各層以成為對應的位置關係之方式依序積層而製造。各層之形成方法如前文所說明。 The composite sheet for protective film formation of this invention can be manufactured by laminating|stacking each said layer sequentially so that it may become a corresponding positional relationship. The formation method of each layer is as described above.
例如，製造支持片時，於基材上積層黏著劑層之情形時，於基材上塗敷上述之黏著劑組成物，視需要使之乾燥即可。 For example, in the case of laminating an adhesive layer on a substrate when producing a support sheet, the above-mentioned adhesive composition may be applied on the substrate and dried if necessary.
另一方面，例如，於已積層於基材上之黏著劑層上進而積層保護膜形成用膜之情形時，可於黏著劑層上塗敷保護膜形成用組成物，直接形成保護膜形成用膜。保護膜形成用膜以外之層亦可使用用以形成該層之組成物，利用同樣的方法，於黏著劑層上積層該層。如此，於使用任一種組成物，形成連續之2層之積層結構之情形時，可於由前述組成物形成之層上，進而塗敷組成物而新形成層。其中，較佳為藉由下述方式而形成連續之2層之積層結構，亦即，於另一剝離膜上，使用前述組成物，預先形成這些2層中後積層之層，將該已形成之層中的與和前述剝離膜接觸之側為相反側的露出面，與既已形成之其餘層的露出面貼合。此時，前述組成物較佳為塗敷於剝離膜的剝離處理面。形成積層結構後，視需要移除剝離膜即可。 On the other hand, for example, when a film for forming a protective film is laminated on an adhesive layer already laminated on a base material, the composition for forming a protective film may be coated on the adhesive layer to directly form a film for forming a protective film. . The layer other than the film for protective film formation can also use the composition for forming this layer, and this layer is laminated|stacked on an adhesive agent layer by the same method. In this way, when using any one of the compositions to form a continuous two-layer laminated structure, the composition can be further coated on the layer formed of the aforementioned composition to form a new layer. Among them, it is preferable to form a continuous two-layer laminated structure by using the above-mentioned composition on another release film, forming the layer of the last layer in these two layers in advance, and forming the layer that has been formed Among the layers, the exposed surface on the opposite side to the side in contact with the release film is bonded to the exposed surface of the other layers already formed. In this case, the aforementioned composition is preferably applied to the release-treated surface of the release film. After the laminated structure is formed, the release film may be removed if necessary.
例如，有時製造於基材上積層黏著劑層，於前述黏著 劑層上積層保護膜形成用膜之保護膜形成用複合片(支持片為基材及黏著劑層之積層物之保護膜形成用複合片)。該情形時，於基材上塗敷黏著劑組成物，視需要使之乾燥，藉此於基材上積層黏著劑層，另行於剝離膜上塗敷保護膜形成用組成物，視需要使之乾燥。如此，於剝離膜上形成保護膜形成用膜。然後，將該保護膜形成用膜的露出面與已積層於基材上之黏著劑層的露出面貼合，於黏著劑層上積層保護膜形成用膜，藉此獲得保護膜形成用複合片。 For example, sometimes an adhesive layer is laminated on a base material, and in the aforementioned adhesive Composite sheet for forming a protective film in which a film for forming a protective film is laminated on the agent layer (composite sheet for forming a protective film in which the support sheet is a laminate of a substrate and an adhesive layer). In this case, the adhesive composition is applied on the base material, dried if necessary, and the adhesive layer is laminated on the base material, and the composition for forming a protective film is separately applied on the release film, and dried if necessary. In this way, the film for protective film formation was formed on the peeling film. Then, the exposed surface of the film for forming a protective film is bonded to the exposed surface of the adhesive layer laminated on the substrate, and the film for forming a protective film is laminated on the adhesive layer to obtain a composite sheet for forming a protective film. .
再者，於基材上積層黏著劑層之情形時，如上所述，亦可代替於基材上塗敷黏著劑組成物之方法，於剝離膜上塗敷黏著劑組成物，視需要使之乾燥，藉此於剝離膜上預先形成黏著劑層，將該層的露出面與基材的一表面貼合，藉此於基材上積層黏著劑層。 Furthermore, in the case of laminating an adhesive layer on a substrate, as described above, instead of applying the adhesive composition on the substrate, the adhesive composition may be applied on a release film and dried if necessary. In this way, an adhesive layer is preliminarily formed on the release film, and the exposed surface of the layer is bonded to one surface of the substrate, whereby the adhesive layer is laminated on the substrate.
任一種方法中，均於形成目標積層結構後的任意時間點移除剝離膜即可。 In either method, it is sufficient to remove the peeling film at any time point after forming the target laminated structure.
如此，構成保護膜形成用複合片之基材以外之層均可利用下述方法積層，亦即，預先形成於剝離膜上，貼合於目標層的表面。因此，視需要適宜選擇採用此種步驟之層，製造保護膜形成用複合片即可。 In this way, layers other than the base material constituting the protective film-forming composite sheet can be laminated by a method in which they are formed in advance on a release film and bonded to the surface of the target layer. Therefore, what is necessary is just to select suitably the layer which adopts such a process as needed, and to manufacture the composite sheet for protective film formation.
再者，保護膜形成用複合片通常以如下狀態保管，亦即，於該保護膜形成用複合片中的與支持片為相反側的最 表層(例如，保護膜形成用膜)的表面貼合有剝離膜之狀態。因此，亦可藉由下述方式而獲得保護膜形成用複合片，亦即，於該剝離膜(較佳為該剝離膜的剝離處理面)上，塗敷保護膜形成用組成物等用以形成構成最表層之層之組成物，視需要使之乾燥，藉此於剝離膜上預先形成構成最表層之層，於該層中的與和剝離膜接觸之側為相反側的露出面上，利用上述任一種方法積層其餘各層，不移除剝離膜而保持貼合狀態不變。 In addition, the composite sheet for protective film formation is normally stored in the state which is the most opposite side to the support sheet in this composite sheet for protective film formation. The surface layer (for example, the film for protective film formation) is the state which bonded the release film to the surface. Therefore, a composite sheet for forming a protective film can also be obtained by coating the composition for forming a protective film or the like on the release film (preferably the release-treated surface of the release film) for The composition forming the layer constituting the outermost layer is dried as necessary, whereby the layer constituting the outermost layer is preliminarily formed on the release film, and on the exposed surface of the layer opposite to the side in contact with the release film, Use any of the above methods to laminate the remaining layers without removing the release film and keep the bonded state unchanged.
◇保護膜形成用複合片的使用方法 ◇How to use the composite sheet for protective film formation
本發明之保護膜形成用複合片例如可利用以下所示之方法使用。 The composite sheet for protective film formation of this invention can be used by the method shown below, for example.
亦即，將保護膜形成用複合片藉由該保護膜形成用複合片之保護膜形成用膜貼附於半導體晶圓的背面(與電極形成面為相反側的面)。繼而，對保護膜形成用膜照射能量線，使保護膜形成用膜硬化而成為保護膜。繼而，藉由切割，將半導體晶圓連同保護膜一起分割而製成半導體晶片。然後，將半導體晶片，保持貼附有該保護膜之狀態(亦即，以附有保護膜的半導體晶片之形式)自支持片拉離而進行拾取。 That is, the composite sheet for protective film formation is attached to the back surface (surface opposite to the electrode formation surface) of a semiconductor wafer via the film for protective film formation of this composite sheet for protective film formation. Next, energy rays are irradiated to the film for protective film formation, and the film for protective film formation is hardened, and it becomes a protective film. Then, by dicing, the semiconductor wafer is divided together with the protective film to produce semiconductor wafers. Then, the semiconductor wafer is pulled away from the support sheet while the protective film is attached (that is, in the form of the semiconductor wafer with the protective film) and picked up.
以下，利用與先前法相同的方法，將所獲得之附有保護膜的半導體晶片的半導體晶片倒裝晶片連接於基板的電路面後，將整體藉由樹脂進行密封，藉此製成半導體封裝。然後，使用該半導體封裝，製作目標半導體裝置即可 。 Next, the obtained protective film-attached semiconductor wafer was flip-chip connected to the circuit surface of the substrate by the same method as the previous method, and the whole was sealed with resin to produce a semiconductor package. Then, use this semiconductor package to fabricate the target semiconductor device .
再者，此處對使保護膜形成用膜硬化而成為保護膜後進行切割之情形進行了說明，但於使用本發明之保護膜形成用複合片之情形時，進行這些步驟之順序亦可相反。亦即，於半導體晶圓的背面貼附保護膜形成用複合片後，藉由切割，將半導體晶圓連同保護膜形成用膜一起分割而製成半導體晶片。繼而，對已分割之保護膜形成用膜照射能量線，使保護膜形成用膜硬化而成為保護膜。以下，與上述同樣地，將附有保護膜的半導體晶片自支持片拉離而進行拾取，製作目標半導體裝置即可。 Furthermore, the case where the film for forming a protective film is cured to form a protective film and then cut is described here, but when the composite sheet for forming a protective film of the present invention is used, the order of these steps may be reversed. . That is, after affixing the composite sheet for protective film formation to the back surface of a semiconductor wafer, the semiconductor wafer is divided together with the film for protective film formation by dicing, and semiconductor wafers are produced. Next, the divided film for forming a protective film is irradiated with energy rays to harden the film for forming a protective film to form a protective film. Thereafter, in the same manner as above, the semiconductor wafer with the protective film may be pulled away from the support sheet and picked up to produce a target semiconductor device.
◇捲筒型 ◇Roll type
圖6係以示意方式表示本發明之又一實施形態之保護膜形成用膜之剖面圖。 Fig. 6 is a cross-sectional view schematically showing a film for forming a protective film according to still another embodiment of the present invention.
如圖6所示，本實施形態之保護膜形成用膜1F被稱為「捲筒型」。該保護膜形成用膜1F由以下結構構成，亦即，於剝離膜15a(以下有時稱為「第1剝離膜」)與剝離膜15b(以下有時稱為「第2剝離膜」)之間應用層狀的保護膜形成用組成物13之結構。
As shown in FIG. 6, the
該保護膜形成用膜1F中所使用之保護膜形成用組成物13係依照既存之保護膜形成用組成物。
The
該保護膜形成用膜1F例如可藉由下述方式而形成，亦即，於第1剝離膜15a的剝離面上應用保護膜形成用組成物
13，進而於該保護膜形成用組成物13上，以使剝離面側朝向保護膜形成用組成物13側之方式應用第2剝離膜15b，並進行按壓。保護膜形成用組成物的應用方法依照上述之保護膜形成用組成物的應用方法。
The
◇保護膜形成用膜的使用方法 ◇How to use the protective film forming film
本發明之保護膜形成用膜例如可利用以下所示之方法而使用。 The film for protective film formation of this invention can be used by the method shown below, for example.
亦即，於半導體晶圓的背面(與電極形成面為相反側的面)，貼附保護膜形成用膜。繼而，對保護膜形成用膜照射能量線，使保護膜形成用膜硬化而成為保護膜。繼而，藉由切割，將半導體晶圓連同保護膜一起分割而製成半導體晶片。並且，將半導體晶片，保持貼附有該保護膜之狀態(亦即，以附有保護膜的半導體晶片之形式)自支持片拉離而進行拾取。 That is, the film for protective film formation is affixed to the back surface (surface opposite to the electrode formation surface) of a semiconductor wafer. Next, energy rays are irradiated to the film for protective film formation, and the film for protective film formation is hardened, and it becomes a protective film. Then, by dicing, the semiconductor wafer is divided together with the protective film to produce semiconductor wafers. Then, the semiconductor wafer is pulled away from the support sheet while the protective film is attached (that is, in the form of the semiconductor wafer with the protective film) and picked up.
所拾取之附有保護膜的半導體晶片101收納於如圖7所示之壓紋載帶102的口袋102a，於口袋102a的開口部貼附蓋帶103。藉此，將前述開口部封閉而進行包裝。然後，將壓紋載帶102以捲繞於捲盤之狀態進行保管、搬送、或商業交易，於下一步驟亦即將附有保護膜的半導體晶片101的半導體晶片倒裝晶片連接於基板的電路面之步驟中使用。
The picked up
本說明書中，所謂「壓紋載帶」係指於聚苯乙烯、聚 對苯二甲酸乙二酯或聚丙烯等樹脂製之長條狀片形成有以固定間隔成列設置之多個凹部(有時稱為口袋)之包裝材料，前述多個各口袋中，可收納例如本發明之附有保護膜的半導體晶片。前述多個各口袋通常藉由下述方式而封閉遮蓋，亦即，於收納有本發明之附有保護膜的半導體晶片等被收納物之狀態下，將該開口部貼附長條狀之蓋帶。包裝有附有保護膜的半導體晶片之壓紋載帶可以捲繞於捲盤之狀態使用。例如，可將前述捲盤設置於貼片機，於基板安裝附有保護膜的半導體晶片。壓紋載帶的口袋可根據被收納物的大小進行設計、加工。本說明書中的壓紋載帶的各口袋例如可列舉縱向尺寸0.5mm至30mm、橫向尺寸0.5mm至30mm及深度0.1mm至10mm之口袋。前述長條狀的蓋帶的厚度為10μm至100μm，由PET(polyethylene terephthalate；聚對苯二甲酸乙二酯)、聚乙烯等素材形成。 In this manual, the so-called "embossed carrier tape" refers to polystyrene, poly A packaging material in which a long strip of resin such as ethylene terephthalate or polypropylene is formed with a plurality of recesses (sometimes called pockets) arranged in a row at fixed intervals. Each of the aforementioned pockets can accommodate For example, the semiconductor wafer with protective film of the present invention. The above-mentioned plurality of pockets are usually closed and covered by attaching a strip-shaped cover to the opening in a state where the object to be stored, such as a semiconductor chip with a protective film of the present invention, is stored. bring. The embossed carrier tape packaged with a semiconductor wafer with a protective film can be used in the state of being wound on a reel. For example, the aforementioned reel may be set in a mounter to mount a semiconductor wafer with a protective film on a substrate. The pockets of the embossed carrier tape can be designed and processed according to the size of the stored objects. The pockets of the embossed carrier tape in this specification include, for example, pockets with a longitudinal dimension of 0.5 mm to 30 mm, a transverse dimension of 0.5 mm to 30 mm, and a depth of 0.1 mm to 10 mm. The aforementioned elongated cover tape has a thickness of 10 μm to 100 μm, and is formed of materials such as PET (polyethylene terephthalate; polyethylene terephthalate), polyethylene, and the like.
以下，利用與先前法相同的方法，將所獲得之附有保護膜的半導體晶片的半導體晶片倒裝晶片連接於基板的電路面後，將整體藉由樹脂進行密封，藉此製成半導體封裝。然後，使用該半導體封裝，製作目標半導體裝置即可。 Next, the obtained protective film-attached semiconductor wafer was flip-chip connected to the circuit surface of the substrate by the same method as the previous method, and the whole was sealed with resin to produce a semiconductor package. Then, using this semiconductor package, it is only necessary to fabricate a target semiconductor device.
再者，此處對使保護膜形成用膜硬化而成為保護膜後進行切割之情形進行了說明，但於使用本發明之保護膜形 成用膜之情形時，進行這些步驟之順序亦可相反。亦即，於半導體晶圓的背面貼附保護膜形成用膜後，藉由切割，將半導體晶圓連同保護膜形成用膜一起分割而製成半導體晶片。繼而，對已分割之保護膜形成用膜照射能量線，使保護膜形成用膜硬化而成為保護膜。以下，與上述同樣地，將附有保護膜的半導體晶片自支持片拉離而進行拾取，製作目標半導體裝置即可。 Furthermore, the case where the film for forming a protective film is hardened to form a protective film and then diced has been described here, but when using the protective film of the present invention to form In the case of forming a film, the order of these steps can also be reversed. That is, after affixing the film for protective film formation on the back surface of a semiconductor wafer, the semiconductor wafer is divided together with the film for protective film formation by dicing, and semiconductor wafers are produced. Next, the divided film for forming a protective film is irradiated with energy rays to harden the film for forming a protective film to form a protective film. Thereafter, in the same manner as above, the semiconductor wafer with the protective film may be pulled away from the support sheet and picked up to produce a target semiconductor device.
[實施例] [Example]
以下，藉由具體的實施例對本發明進行更詳細的說明。但是，本發明並不受以下所示之實施例之任何限定。 Hereinafter, the present invention will be described in more detail by specific examples. However, this invention is not limited at all by the Example shown below.
以下表示用於製造保護膜形成用組成物之成分。 The components used to manufacture the composition for protective film formation are shown below.
‧能量線硬化性成分 ‧Energy ray hardening ingredients
(a2)-1：三環癸烷二羥甲基二丙烯酸酯(日本化藥公司製造之「KAYARAD R-684」，2官能紫外線硬化性化合物，分子量304)。 (a2)-1: tricyclodecane dimethylol diacrylate ("KAYARAD R-684" manufactured by Nippon Kayaku Co., Ltd., bifunctional ultraviolet curable compound, molecular weight 304).
‧不具有能量線硬化性基之聚合物 ‧Polymers without energy ray hardening groups
(b)-1：使丙烯酸丁酯(以下簡稱為「BA」)(10質量份)、丙烯酸甲酯(以下簡稱為「MA」)(70質量份)、甲基丙烯酸縮水甘油酯(以下簡稱為「GMA」)(5質量份)及丙烯酸-2-羥基乙酯(以下簡稱為「HEA」)(15質量份)進行共聚合而成之丙烯酸系樹脂(重量平均分子量300000，玻璃轉移溫度-1℃)。 (b)-1: Butyl acrylate (hereinafter referred to as "BA") (10 parts by mass), methyl acrylate (hereinafter referred to as "MA") (70 parts by mass), glycidyl methacrylate (hereinafter referred to as Acrylic resin (weight average molecular weight: 300,000, glass transition temperature - 1°C).
‧光聚合起始劑 ‧Photopolymerization initiator
(c)-1：2-(二甲基胺基)-1-(4-嗎啉基苯基)-2-苄基-1-丁酮(BASF公司製造之「Irgacure(註冊商標)369」)。 (c)-1: 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone ("Irgacure (registered trademark) 369" manufactured by BASF Corporation) ).
(c)-2：乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)(BASF公司製造之「Irgacure(註冊商標)OXE02」)。 (c)-2: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime ) ("Irgacure (registered trademark) OXE02" manufactured by BASF Corporation).
‧填充材料 ‧Filler
(d)-1：二氧化矽填料(經乙烯基進行表面修飾，平均粒徑50nm)。 (d)-1: Silica filler (surface modified by vinyl, average particle diameter 50nm).
‧偶合劑 ‧Coupling agent
(e)-1：3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業公司製造之「KBM-503」，矽烷偶合劑)。 (e)-1: 3-methacryloxypropyltrimethoxysilane ("KBM-503" manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent).
‧著色劑 ‧Colorant
(g)-1：將酞菁系藍色色素(Pigment Blue 15：3)32質量份、異吲哚啉酮系黃色色素(Pigment Yellow 139)18質量份、及蒽醌系紅色色素(Pigment Red 177)50質量份進行混合，以前述3種色素的合計量/苯乙烯丙烯酸樹脂量=1/3(質量比)之方式進行顏料化而獲得之顏料。 (g)-1: 32 parts by mass of phthalocyanine-based blue pigment (Pigment Blue 15:3), 18 parts by mass of isoindolinone-based yellow pigment (Pigment Yellow 139), and anthraquinone-based red pigment (Pigment Red 177) A pigment obtained by mixing 50 parts by mass and performing pigmentation such that the total amount of the aforementioned three kinds of pigments/the amount of styrene acrylic resin=1/3 (mass ratio).
‧抗靜電劑： ‧Antistatic agent:
(j)-1：以四乙二醇二甲醚作為載體之醯亞胺鋰型之抗靜電劑(三光化學工業製造之「Sankonol TGR」)。 (j)-1: Lithium imide type antistatic agent using tetraethylene glycol dimethyl ether as a carrier ("Sankonol TGR" manufactured by Sanko Chemical Industry Co., Ltd.).
[實施例1] [Example 1]
<保護膜形成用複合片之製造> <Manufacture of composite sheet for protective film formation>
(保護膜形成用組成物(IV-1)之製造) (Manufacture of protective film forming composition (IV-1))
使能量線硬化性成分(a2)-1、聚合物(b)-1、光聚合起始劑(c)-1、光聚合起始劑(c)-2、填充材料(d)-1、偶合劑(e)-1、著色劑(g)-1及抗靜電劑(j)-1，以這些的含量(固形物成分量，質量份)成為表1所示之值之方式溶解或分散於甲基乙基酮，於23℃下進行攪拌，藉此製備固形物成分濃度為50質量%之保護膜形成用組成物(IV-1)。 Energy ray curable component (a2)-1, polymer (b)-1, photopolymerization initiator (c)-1, photopolymerization initiator (c)-2, filler (d)-1, The coupling agent (e)-1, the colorant (g)-1, and the antistatic agent (j)-1 were dissolved or dispersed so that the contents (solid content, parts by mass) of these became the values shown in Table 1 Stirring was carried out at 23° C. in methyl ethyl ketone to prepare a composition (IV-1) for forming a protective film having a solid content concentration of 50% by mass.
(黏著劑組成物(I-4)之製造) (Manufacture of Adhesive Composition (I-4))
製備固形物成分濃度為30質量%之非能量線硬化性之黏著劑組成物(I-4)，該黏著劑組成物(I-4)含有丙烯酸系聚合物(100質量份，固形物成分)、及3官能苯二甲基二異氰酸酯系交聯劑(三井武田化學公司製造之「Takenate D110N」)(10.7質量份，固形物成分)，進而含有作為溶劑之甲基乙基酮。前述丙烯酸系聚合物係使丙烯酸-2-乙基己酯(以下簡稱為「2EHA」)(36質量份)、BA(59質量份)、及HEA(5質量份)進行共聚合而成，且重量平均分子量為600000。 Preparation of a non-energy ray-curable adhesive composition (I-4) having a solid content concentration of 30% by mass, the adhesive composition (I-4) containing an acrylic polymer (100 parts by mass, solid content) , and a trifunctional xylylene diisocyanate crosslinking agent ("Takenate D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (10.7 parts by mass, solid content), and methyl ethyl ketone as a solvent. The aforementioned acrylic polymer is obtained by copolymerizing 2-ethylhexyl acrylate (hereinafter referred to as "2EHA") (36 parts by mass), BA (59 parts by mass), and HEA (5 parts by mass), and The weight average molecular weight was 600,000.
(支持片之製造) (Support the manufacture of the film)
於聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進行剝離處理之剝離膜(Lintec公司製造之「SP-PET381031」，厚度38μm。以下有時表示為「P1」)的前述剝離處理面，塗敷上述所獲得之黏著劑組成物(I-4)，於120℃下加 熱乾燥2分鐘，藉此形成厚度10μm之非能量線硬化性之黏著劑層。 The release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 μm. It may be referred to as "P1" hereinafter) is a release film made of polyethylene terephthalate film with silicone treatment on one side. Peel off the treated surface, apply the adhesive composition (I-4) obtained above, and heat at 120°C Heat drying for 2 minutes, thereby forming a non-energy ray curable adhesive layer with a thickness of 10 μm.
繼而，於該黏著劑層的露出面，貼合作為基材之聚丙烯系膜(楊氏率400MPa，厚度80μm，以下有時表示為「S1」)，藉此獲得於前述基材的一表面上具備前述黏著劑層之支持片(10)-1。 Then, on the exposed surface of the adhesive layer, a polypropylene-based film (Young's rate 400 MPa, thickness 80 μm, sometimes referred to as "S1" below) as a base material was pasted, thereby obtaining a The supporting sheet (10)-1 with the aforementioned adhesive layer on it.
(保護膜形成用複合片之製造) (Manufacture of composite sheets for protective film formation)
於聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進行剝離處理之剝離膜(Lintec公司製造之「SP-PET381031」，厚度38μm，P1)的前述剝離處理面，藉由刀式塗佈機塗敷上述所獲得之保護膜形成用組成物(IV-1)，於100℃下乾燥2分鐘，藉此製作厚度25μm之能量線硬化性之保護膜形成用膜(13)-1。 On the peeling-treated side of the peeling film ("SP-PET381031" manufactured by Lintec, thickness 38 μm, P1) which is peeled with silicone on one side of the polyethylene terephthalate film, the The protective film-forming composition (IV-1) obtained above was applied by a type coater, and dried at 100°C for 2 minutes to produce an energy-ray-curable protective film-forming film (13) with a thickness of 25 μm- 1.
繼而，自上述所獲得之支持片(10)-1之黏著劑層移除剝離膜，於該黏著劑層的露出面貼合上述所獲得之保護膜形成用膜(13)-1的露出面，製作保護膜形成用複合片，該保護膜形成用複合片係基材、黏著劑層、保護膜形成用膜(13)-1及剝離膜於這些的厚度方向上依序積層而成。所獲得之保護膜形成用複合片之構成示於表2。 Next, the release film was removed from the adhesive layer of the support sheet (10)-1 obtained above, and the exposed surface of the protective film forming film (13)-1 obtained above was attached to the exposed surface of the adhesive layer. , producing a composite sheet for protective film formation in which the base material, the adhesive layer, the film (13)-1 for protective film formation, and the release film are sequentially laminated in the thickness direction of these composite sheets. Table 2 shows the composition of the obtained composite sheet for forming a protective film.
<保護膜形成用膜之評價> <Evaluation of film for protective film formation>
(保護膜形成用膜的表面電阻率) (Surface resistivity of protective film forming film)
使用表面電阻率測定裝置ADVANTEST公司製造之DIGITAL ELECTRONMETER R8252，針對所獲得之保護膜形成用膜，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，對保護膜形成用複合片照射紫外線而使之硬化，測定此時的表面電阻率。 Using a surface resistivity measuring device, Digital Electronmeter R8252 manufactured by Advantest Co., Ltd., an ultraviolet irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.) was used for the obtained film for forming a protective film at an illumination intensity of 195mW/cm 2 and a light intensity of 170mJ/ The composite sheet for forming a protective film was irradiated with ultraviolet rays under the condition of 2 cm 2 to harden it, and the surface resistivity at that time was measured.
設為藉由進行照射而使保護膜形成用膜硬化時的保護膜。結果示於表2。 It was set as the protective film when the film for protective film formation was hardened by irradiation. The results are shown in Table 2.
再者，表2中的「抗靜電劑[質量%]」意指保護膜形成用膜中，相對於能量線硬化性成分(a)及不具有能量線硬化性基之聚合物(b)的合計質量之抗靜電劑的含量。 In addition, "antistatic agent [mass %]" in Table 2 means the amount of antistatic agent in the film for forming a protective film relative to the energy ray curable component (a) and the polymer (b) not having an energy ray curable group. Total mass of antistatic agent content.
(蓋帶附著性試驗) (Cover tape adhesion test)
將上述所獲得之保護膜形成用複合片，藉由該保護膜形成用複合片之保護膜形成用膜(13)-1，貼附於6吋矽晶圓(厚度100μm)之#2000研磨面，進而將該片固定於環狀框，靜置30分鐘。 Attach the protective film forming composite sheet obtained above to the #2000 polished surface of a 6-inch silicon wafer (thickness 100 μm) through the protective film forming film (13)-1 of the protective film forming composite sheet , and further fix the sheet to a ring frame, and let it stand for 30 minutes.
繼而，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，自支持片(10)-1側對保護膜形成用複合片照射紫外線，藉此使保護膜形成用膜(13)-1硬化，成為保護膜。 Then, using an ultraviolet irradiation device (“RAD2000m/8” manufactured by Lintec Corporation), under the conditions of illuminance 195mW/cm 2 and light intensity 170mJ/cm 2 , the composite sheet for protective film formation was applied from the support sheet (10)-1 side. By irradiating ultraviolet rays, the film (13)-1 for protective film formation is hardened|cured, and it becomes a protective film.
繼而，使用切割刀片，將矽晶圓連同保護膜一起切割而單片化，獲得縱3mm×橫3mm、保護層厚度25μm、Si層厚350μm之矽晶片。 Then, using a dicing blade, the silicon wafer together with the protective film was cut into individual pieces to obtain a silicon wafer with a length of 3mm x width of 3mm, a thickness of the protective layer of 25 μm, and a thickness of Si layer of 350 μm.
繼而，使用黏晶機(Canon Machinery公司製造之「BESTEM-D02」)，拾取20個附有保護膜之矽晶片。 Then, use a die bonder ("BESTEM-D02" manufactured by Canon Machinery Co., Ltd.) to pick up 20 silicon wafers with protective films.
於縱12cm×橫12cm、厚度5mm之鐵板上，將前述所獲得之附有保護膜之矽晶片16個，以相互間隔均等之方式，以分別縱4個×橫4個載置於正方形之格子狀之位置，於上述矽晶片上被覆縱12cm×橫3.8cm之蓋帶(Sumitomo Bakelite公司製造，CSL-Z7302)，載置於加熱至40℃之熱盤上，於該熱盤上載置金屬板，並以施加於附有保護膜之矽晶片之壓力成為350gf之方式進行設置，進行一分鐘過熱。然後，移除金屬板，剝離前述蓋帶，對附有保護膜之矽晶片是否附著於蓋帶進行試驗。結果示於表2。 On an iron plate with a length of 12 cm x a width of 12 cm and a thickness of 5 mm, 16 silicon wafers with a protective film obtained above were placed on a square in the form of 4 lengths x 4 widths at equal intervals. The above-mentioned silicon wafer is covered with a cover tape (manufactured by Sumitomo Bakelite Co., Ltd., CSL-Z7302) at a grid-shaped position of 12 cm x 3.8 cm, placed on a hot plate heated to 40 ° C, and placed on the hot plate. The plate was installed so that the pressure applied to the silicon wafer with the protective film became 350gf, and overheated for one minute. Then, remove the metal plate, peel off the aforementioned cover tape, and test whether the silicon wafer with the protective film is attached to the cover tape. The results are shown in Table 2.
作為判定方法，於16個附有保護膜之矽晶片中至少一個附著於蓋帶之情形時，判定為「有」，於16個附有保護膜之矽晶片中沒有一個附著於蓋帶之情形時，判定為「無」。 As a judgment method, when at least one of the 16 silicon wafers with a protective film is attached to the cover tape, it is judged as "yes", and when none of the 16 silicon wafers with a protective film is attached to the cover tape , the judgment is "none".
<保護膜形成用複合片之製造及保護膜形成用膜之評價> <Manufacture of protective film forming composite sheet and evaluation of protective film forming film>
[實施例2] [Example 2]
將抗靜電劑(h)-1的含量設為6質量份，除此以外，利用與實施例1相同的方法，製作保護膜形成用膜(13)-2。進而，使用該保護膜形成用膜(13)-2製造保護膜形成用複合片，對保護膜形成用膜之特性進行評價。結果示於表2。 Except having made content of the antistatic agent (h)-1 into 6 mass parts, the film (13)-2 for protective film formation was produced by the method similar to Example 1. Furthermore, the composite sheet for protective film formation was manufactured using this film (13)-2 for protective film formation, and the characteristic of the film for protective film formation was evaluated. The results are shown in Table 2.
[實施例3][捲筒型] [Example 3] [roll type]
<保護膜形成用膜之製造> <Manufacture of protective film forming film>
於剝離膜1(聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進行剝離處理之剝離膜(Lintec公司製造之「SP-PET381031」，厚度38μm。P1)的剝離面側的表面，藉由刀式塗佈機塗敷上述所獲得之保護膜形成用組成物(IV-1)，使之乾燥後，於該保護膜形成用組成物(IV-1)上貼合剝離膜2(聚對苯二甲酸乙二酯製膜的單面經聚矽氧處理進行剝離處理之剝離膜(Lintec公司製造之「SP-PET382150」，厚度38μm。以下有時表示為「P2」))，繼而，於100℃下乾燥2分鐘，藉此製作厚度25μm之能量線硬化性之保護膜形成用膜(13)-1。 On the release surface side of release film 1 (a release film ("SP-PET381031" manufactured by Lintec Co., Ltd., thickness 38 μm, P1) with one side of a polyethylene terephthalate film treated with silicone for release treatment) On the surface, the protective film-forming composition (IV-1) obtained above was coated with a knife coater, dried, and a release film was pasted on the protective film-forming composition (IV-1) 2 (Peeling film made of polyethylene terephthalate film, one side of which is treated with silicone and released ("SP-PET382150" manufactured by Lintec Co., Ltd., thickness 38μm. Hereinafter, it may be referred to as "P2")) , and then dried at 100° C. for 2 minutes to prepare an energy-ray-curable protective film-forming film (13)-1 having a thickness of 25 μm.
<保護膜形成用膜之評價> <Evaluation of film for protective film formation>
(表面電阻率) (surface resistivity)
使用表面電阻率測定裝置ADVANTEST公司製造之DIGITAL ELECTRONMETER R8252，針對所獲得之保護膜形成用膜，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，對保護膜形成用複合片照射紫外線而使之硬化，測定此時的表面電阻率。測定所獲得之保護膜形成用膜的表面電阻率。結果示於表2。 Using a surface resistivity measuring device, Digital Electronmeter R8252 manufactured by Advantest Co., Ltd., the film for forming a protective film obtained was subjected to an ultraviolet irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.) at an illumination intensity of 195mW/cm 2 and a light intensity of 170mJ/ The composite sheet for forming a protective film was irradiated with ultraviolet rays under the condition of 2 cm 2 to harden it, and the surface resistivity at that time was measured. The surface resistivity of the obtained film for protective film formation was measured. The results are shown in Table 2.
(蓋帶附著性試驗) (Cover tape adhesion test)
於6吋矽晶圓(厚度100μm)之#2000研磨面，貼附上述所獲得之保護膜形成用膜，靜置30分鐘。 On the #2000 polished surface of a 6-inch silicon wafer (thickness 100 μm), stick the protective film formation film obtained above and let it stand for 30 minutes.
繼而，使用紫外線照射裝置(Lintec公司製造之「RAD2000m/8」)，於照度195mW/cm2、光量170mJ/cm2之條件下，自保護膜形成用膜側照射紫外線，藉此使保護膜形成用膜(14)-1硬化，成為保護膜。繼而，使用切割刀片，將矽晶圓連同保護膜一起切割而單片化，獲得縱3mm×橫3mm、保護層厚度25μm、Si層厚350μm之矽晶片。 Next, using an ultraviolet irradiation device ("RAD2000m/8" manufactured by Lintec Co., Ltd.), under the conditions of illuminance 195mW/cm 2 and light intensity 170mJ/cm 2 , ultraviolet rays were irradiated from the protective film forming film side to form a protective film. The film (14)-1 is hardened to become a protective film. Then, using a dicing blade, the silicon wafer together with the protective film was cut into individual pieces to obtain a silicon wafer with a length of 3 mm x width of 3 mm, a thickness of the protective layer of 25 μm, and a thickness of Si layer of 350 μm.
繼而，使用黏晶機(Canon Machinery公司製造之「BESTEM-D02」)，拾取20個附有保護膜之矽晶片。 Then, use a die bonder ("BESTEM-D02" manufactured by Canon Machinery Co., Ltd.) to pick up 20 silicon wafers with protective films.
於縱12cm×橫12cm、厚度5mm之鐵板上，將前述所獲得之附有保護膜之矽晶片16個，以相互間隔均等之方式，以分別4個×4個合計16個載置於正方形之格子狀之位置，於上述矽晶片上被覆縱12cm×橫3.8cm之蓋帶(Sumitomo Bakelite公司製造，CSL-Z7302)，載置於加熱至40℃之熱盤上，於該熱盤上載置金屬板，並以施加於附有保護膜之矽晶片之壓力成為350gf之方式進行設置，進行一分鐘過熱。然後，移除金屬板，剝離前述蓋帶，對附有保護膜之矽晶片是否附著於蓋帶進行試驗。結果示於表2。 On an iron plate with a length of 12 cm x a width of 12 cm and a thickness of 5 mm, 16 silicon wafers with a protective film obtained above were placed on a square in the form of 4 x 4 total of 16 wafers at equal intervals. The above-mentioned silicon wafer is covered with a cover tape (manufactured by Sumitomo Bakelite Co., Ltd., CSL-Z7302) on the grid-shaped position of 12 cm in length and 3.8 cm in width, placed on a hot plate heated to 40 ° C, and placed on the hot plate The metal plate was installed so that the pressure applied to the silicon wafer with the protective film became 350gf, and overheated for one minute. Then, remove the metal plate, peel off the aforementioned cover tape, and test whether the silicon wafer with the protective film is attached to the cover tape. The results are shown in Table 2.
[實施例4][捲筒型] [Example 4] [roll type]
<保護膜形成用複合片之製造> <Manufacture of composite sheet for protective film formation>
(保護膜形成用組成物(IV-1)之製造) (Manufacture of protective film forming composition (IV-1))
如表1所示，將抗靜電劑的含量(調配量)設為6質量份 代替3質量份，除此方面以外，利用與實施例3相同的方法，製備保護膜形成用組成物(IV-1)，製作保護膜形成用膜，對特性進行評價。結果示於表2。 As shown in Table 1, the content (preparation amount) of the antistatic agent is set to 6 parts by mass Instead of 3 parts by mass, except this point, the composition (IV-1) for protective film formation was prepared by the method similar to Example 3, the film for protective film formation was produced, and the characteristic was evaluated. The results are shown in Table 2.
[比較例1][一體型] [comparative example 1] [integrated type]
將抗靜電劑之調配量設為0重量份，除此方面以外，以與實施例1相同的方式，製作保護膜形成用複合片，對保護膜形成用膜之特性進行評價。結果示於表2。 Except having made the compounding quantity of an antistatic agent into 0 weight part, it carried out similarly to Example 1, the composite sheet for protective film formation was produced, and the characteristic of the film for protective film formation was evaluated. The results are shown in Table 2.
[比較例2][捲筒型] [comparative example 2] [roll type]
將抗靜電劑之調配量設為0重量份，除此以外，以與實施例3相同的方式，製作保護膜形成用膜，對該保護膜形成用膜之特性進行評價。結果示於表2。 Except having made the compounding quantity of an antistatic agent into 0 weight part, it carried out similarly to Example 3, the film for protective film formation was produced, and the characteristic of the film for protective film formation was evaluated. The results are shown in Table 2.
<保護膜形成用複合片之製造及保護膜形成用膜之評價> <Manufacture of protective film forming composite sheet and evaluation of protective film forming film>
針對上述所獲得之保護膜形成用膜，利用與實施例1相同的方法進行評價。結果示於表2。 The film for protective film formation obtained above was evaluated by the method similar to Example 1. The results are shown in Table 2.
根據上述結果可明確，於使用實施例1、實施例2之保護膜形成用複合片、實施例3、實施例4之保護膜形成用膜之情形時，保護膜形成用膜的表面電阻率成為1.0×1012Ω‧cm以下，封入捲盤後剝離蓋帶之蓋帶附著試驗中，收容於壓紋載帶之附有保護膜之矽晶片亦未附著於蓋帶。 From the above results, it is clear that in the case of using the composite sheet for protective film formation of Example 1 and Example 2, and the film for protective film formation of Example 3 and Example 4, the surface resistivity of the film for protective film formation becomes Below 1.0×10 12 Ω‧cm, in the cover tape adhesion test in which the cover tape was peeled off after sealing in a reel, the silicon wafer with a protective film accommodated on the embossed carrier tape did not adhere to the cover tape.
相對於此，於使用未調配抗靜電劑之比較例1之保護膜形成用複合片、比較例2之保護膜之情形時，保護膜的表面電阻率大於1.0×1012Ω‧cm，封入捲盤後剝離蓋帶之蓋帶附著試驗中，收容於壓紋載帶之附有保護膜之矽晶片亦附著於蓋帶。 On the other hand, when using the protective film-forming composite sheet of Comparative Example 1 and the protective film of Comparative Example 2 that did not contain an antistatic agent, the surface resistivity of the protective film was greater than 1.0×10 12 Ω‧cm, and it was enclosed in a roll In the cover tape adhesion test in which the cover tape was peeled off after reeling, the silicon wafer with a protective film accommodated on the embossed carrier tape also adhered to the cover tape.
(產業可利用性) (industry availability)
本發明可用於製造半導體裝置。 The present invention can be used in the manufacture of semiconductor devices.
1A:保護膜形成用複合片 1A: Composite sheet for protective film formation
10:支持片 10: Support piece
10a:支持片的表面 10a: Surface of the support sheet
11:基材 11: Substrate
11a:基材的表面 11a: Surface of the substrate
12:黏著劑層 12: Adhesive layer
12a:黏著劑層的表面 12a: the surface of the adhesive layer
13:保護膜形成用膜 13: Film for protective film formation
13a:保護膜形成用膜的表面 13a: The surface of the film for protective film formation
15:剝離膜 15: Peel off film
16:治具用接著劑層 16: Adhesive layer for jig
16a:治具用接著劑層的表面 16a: The surface of the adhesive layer for jigs
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| JPWO2020116284A1 (en) * | 2018-12-05 | 2021-10-21 | リンテック株式会社 | Manufacturing method of composite sheet for forming protective film and semiconductor chip |
| CN113169124A (en) * | 2018-12-05 | 2021-07-23 | 琳得科株式会社 | Composite sheet for forming protective film and method for manufacturing semiconductor chip |
| CN113016066A (en) * | 2018-12-05 | 2021-06-22 | 琳得科株式会社 | Composite sheet for forming protective film and method for manufacturing semiconductor chip |
| KR20210098950A (en) * | 2018-12-05 | 2021-08-11 | 린텍 가부시키가이샤 | Composite sheet for forming a protective film, and manufacturing method of a semiconductor chip |
| WO2020116278A1 (en) * | 2018-12-05 | 2020-06-11 | リンテック株式会社 | Protective-coat-forming composite sheet, and semiconductor chip production method |
| KR20210098975A (en) * | 2018-12-05 | 2021-08-11 | 린텍 가부시키가이샤 | Composite sheet for forming a protective film, and manufacturing method of a semiconductor chip |
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| CN101818032A (en) * | 2009-02-16 | 2010-09-01 | 琳得科株式会社 | Adhesive composition and adhesive sheet |
| CN103153810A (en) * | 2010-09-30 | 2013-06-12 | 住友电木株式会社 | Cover tape for packaging electronic component |
| CN103980845A (en) * | 2013-02-13 | 2014-08-13 | 琳得科株式会社 | Pressure sensitive adhesion composition, pressure sensitive adhesive and pressure sensitive adhesion sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2017188216A1 (en) | 2019-03-07 |
| TW201808606A (en) | 2018-03-16 |
| JP6847929B2 (en) | 2021-03-24 |
| KR20220018615A (en) | 2022-02-15 |
| KR102581057B1 (en) | 2023-09-20 |
| KR20230079498A (en) | 2023-06-07 |
| KR20190003470A (en) | 2019-01-09 |
| CN108884244B (en) | 2022-01-11 |
| CN108884244A (en) | 2018-11-23 |
| WO2017188216A1 (en) | 2017-11-02 |
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