TW201945488A - Supporting sheet and composite sheet for forming protective film - Google Patents
Supporting sheet and composite sheet for forming protective film Download PDFInfo
- Publication number
- TW201945488A TW201945488A TW108109743A TW108109743A TW201945488A TW 201945488 A TW201945488 A TW 201945488A TW 108109743 A TW108109743 A TW 108109743A TW 108109743 A TW108109743 A TW 108109743A TW 201945488 A TW201945488 A TW 201945488A
- Authority
- TW
- Taiwan
- Prior art keywords
- protective film
- forming
- film
- meth
- adhesive layer
- Prior art date
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- 230000001681 protective effect Effects 0.000 title claims abstract description 551
- 239000002131 composite material Substances 0.000 title claims abstract description 163
- 239000012790 adhesive layer Substances 0.000 claims abstract description 309
- 239000000758 substrate Substances 0.000 claims abstract description 165
- 238000012360 testing method Methods 0.000 claims abstract description 66
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- 235000010215 titanium dioxide Nutrition 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 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
- 229920006337 unsaturated polyester resin 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
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
-
- 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
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Dicing (AREA)
Abstract
Description
本發明係關於支撐片及保護膜形成用複合片。The present invention relates to a support sheet and a composite sheet for forming a protective film.
近年，採用通稱「倒置(face down)方式」安裝法進行半導體裝置製造。倒置方式係使用電路面上設有凸塊等電極的半導體晶片，由上述電極接合於基板。因而，半導體晶片雙面中設有電路面之一面的對向面便呈裸露狀態。In recent years, semiconductor devices have been manufactured using a so-called "face down" mounting method. The inversion method uses a semiconductor wafer provided with electrodes such as bumps on a circuit surface, and the electrodes are bonded to a substrate. Therefore, the opposite sides of one side of the semiconductor wafer provided with one of the circuit faces are exposed.
在該呈裸露的半導體晶片背面上形成當作保護膜用之含有機材料的樹脂膜，再依具保護膜之半導體晶片形式組裝於半導體裝置中。保護膜係為在切割步驟、封裝之後，能防止半導體晶片發生龜裂而使用。A resin film containing an organic material as a protective film is formed on the back of the exposed semiconductor wafer, and the semiconductor film is assembled in a semiconductor device in the form of a semiconductor wafer with a protective film. The protective film is used to prevent cracking of the semiconductor wafer after the dicing step and packaging.
此種保護膜係例如藉由使具硬化性保護膜形成用薄膜進行硬化而形成。又，經調節物性的非硬化性保護膜形成用薄膜亦可直接利用為保護膜。所以，保護膜形成用薄膜係使用於貼附在半導體晶圓的背面。保護膜形成用薄膜亦有在例如與半導體晶圓加工時所使用支撐片呈一體化的保護膜形成用複合片狀態下，貼附於半導體晶圓背面上，亦有在未與支撐片呈一體化狀態下貼附於半導體晶圓背面上。Such a protective film is formed, for example, by curing a thin film for forming a curable protective film. In addition, the non-curable protective film-forming film whose physical properties are adjusted can also be directly used as a protective film. Therefore, the thin film for forming a protective film is used for attaching to the back surface of a semiconductor wafer. The protective film-forming film may be attached to the back surface of the semiconductor wafer in a state where the protective film-forming composite sheet is integrated with the supporting sheet used in the processing of the semiconductor wafer, for example, or is not integrated with the supporting sheet. It is affixed to the back surface of a semiconductor wafer in a modified state.
保護膜形成用複合片係利用其中的保護膜形成用薄膜貼附於半導體晶片背面後，再依各自的合適時序施行例如:利用保護膜形成用薄膜的硬化形成保護膜、保護膜形成用薄膜或保護膜之切斷、半導體晶圓分割(切割)為半導體晶片、以及從支撐片上拾取背面具有經切斷後保護膜形成用薄膜或保護膜的半導體晶片(具保護膜形成用薄膜之半導體晶片或具保護膜之半導體晶片)等。而，在拾取具保護膜形成用薄膜之半導體晶片時，藉由保護膜形成用薄膜的硬化而成為具保護膜之半導體晶片，最終使用具保護膜之半導體晶片製造半導體裝置。依此，保護膜形成用複合片中的支撐片可利用為切割片。另外，當保護膜形成用薄膜係非硬化性的情況，在該等各項步驟中，保護膜形成用薄膜直接被使用為保護膜。The composite sheet for forming a protective film is formed by attaching the protective film-forming thin film to the back of the semiconductor wafer, and then performing it according to the appropriate timing. For example, the protective film is formed by curing the protective film, the protective film-forming film, or Cutting the protective film, dividing (cutting) the semiconductor wafer into semiconductor wafers, and picking up a semiconductor wafer with a protective film-forming film or protective film on the back from the support sheet (a semiconductor wafer with a protective film-forming film or Protective film for semiconductor wafers). On the other hand, when picking up a semiconductor wafer with a thin film for forming a protective film, a semiconductor wafer with a protective film is formed by curing the thin film for forming a protective film. Finally, a semiconductor device with a protective film is used to manufacture a semiconductor device. Accordingly, the support sheet in the composite sheet for forming a protective film can be used as a dicing sheet. In addition, when the thin film for protective film formation is non-hardenable, in each of these steps, the thin film for protective film formation is used as a protective film as it is.
另一方面，保護膜形成用薄膜在未與支撐片呈一體化狀態下，貼附於半導體晶圓背面之後，在該保護膜形成用薄膜雙面中，於臨半導體晶圓貼附面之對向的露出面上貼附著支撐片。其餘以後均依照與上述使用保護膜形成用複合片的情況為相同方法，獲得具保護膜之半導體晶片或具保護膜形成用薄膜之半導體晶片，並製造半導體裝置。此情況，保護膜形成用薄膜係依未與支撐片呈一體化狀態下，貼附於半導體晶圓背面，但藉由與貼附後的支撐片呈一體化，而構成保護膜形成用複合片。On the other hand, after the thin film for forming a protective film is attached to the back surface of the semiconductor wafer without being integrated with the supporting sheet, the double-sided film for forming the protective film is formed on the opposite side of the surface to be attached to the semiconductor wafer. A support sheet is attached to the exposed surface. In the rest, the semiconductor wafer with a protective film or a semiconductor wafer with a thin film for forming a protective film is obtained in the same manner as in the case of using the composite film for forming a protective film, and a semiconductor device is manufactured. In this case, the thin film for forming a protective film is attached to the back of the semiconductor wafer without being integrated with the support sheet, but is formed into a composite sheet for forming a protective film by being integrated with the support sheet after being attached. .
針對此種保護膜形成用複合片，例如有揭示切割膠帶一體型半導體背面保護用薄膜，係具備有:切割膠帶(支撐片)與半導體背面保護用薄膜(保護膜形成用薄膜)的切割膠帶一體型半導體背面保護用薄膜(保護膜形成用複合片)，而該切割膠帶(支撐片)係具有:具凹凸加工面之基材、與積層於該基材之上述凹凸加工面上的黏著劑層；該半導體背面保護用薄膜(保護膜形成用薄膜)係積層於該切割膠帶的黏著劑層上；其中，上述切割膠帶的霧度係45%以下(參照專利文獻1)。Regarding such a protective film forming composite sheet, for example, a dicing tape-integrated semiconductor back surface protection film is disclosed. The dicing tape includes a dicing tape (support sheet) and a semiconductor back surface protection film (protective film formation film). A thin film for protecting the back surface of a bulk semiconductor (composite sheet for forming a protective film), and the dicing tape (support sheet) has a substrate having a concave-convex processing surface and an adhesive layer laminated on the concave-convex processing surface of the substrate. The semiconductor back surface protection film (thin film for protective film formation) is laminated on the adhesive layer of the dicing tape; wherein the haze of the dicing tape is 45% or less (see Patent Document 1).
但是，專利文獻1所揭示的保護膜形成用複合片(切割膠帶一體型半導體背面保護用薄膜)，因為係在基材的凹凸加工面上積層黏著劑層，因而會有黏著劑無法充分追隨基材的凹凸，導致在基材與黏著劑間會有發生剝離。又，對保護膜或保護膜形成用薄膜的黏著劑層之一面，會有利用雷射照射而施行刻印的情形，但依照黏著劑層的凹凸形狀，會有導致隔著基材與黏著劑層的刻印檢視性降低之情況。
[先行技術文獻]
[專利文獻]However, the composite sheet for forming a protective film (a dicing tape-integrated semiconductor back surface protection film) disclosed in Patent Document 1 has an adhesive layer laminated on the embossed surface of the substrate, so that the adhesive cannot sufficiently follow the substrate. The unevenness of the material causes peeling between the substrate and the adhesive. In addition, on one side of the adhesive layer of the protective film or the film for forming a protective film, marking may be performed by laser irradiation. However, depending on the uneven shape of the adhesive layer, it may cause the substrate and the adhesive layer to pass through. The visibility of the marking is reduced.
[Advanced technical literature]
[Patent Literature]
[專利文獻1]日本專利第5432853號公報[Patent Document 1] Japanese Patent No. 5432853
[發明所欲解決之課題][Problems to be Solved by the Invention]
本發明目的在於提供 支撐片以及包括上述支撐片的保護膜形成用複合片，在基材的凹凸面側設有黏著劑層構成的支撐片，在其黏著劑層上設有保護膜形成用薄膜的保護膜形成用複合片中，可實現基材與黏著劑層間之良好密接性、以及保護膜或保護膜形成用薄膜隔著支撐片的良好刻印檢視性。
[解決課題之技術手段]An object of the present invention is to provide a support sheet and a composite sheet for forming a protective film including the above-mentioned support sheet. A support sheet composed of an adhesive layer is provided on the uneven surface side of the substrate, and a protective film-forming film is provided on the adhesive layer. In the composite sheet for forming a protective film, good adhesion between the substrate and the adhesive layer, and good marking visibility of the protective film or the film for forming a protective film with the support sheet interposed therebetween can be achieved.
[Technical means to solve the problem]
本發明所提供的支撐片，係包括基材，且在上述基材上設有黏著劑層的支撐片；其中，上述基材臨上述黏著劑層側的面係凹凸面；從上述支撐片的5個地方切取試驗片，在這5片試驗片，分別在黏著劑層臨上述基材側，求取相鄰凸部的頂點間之節距(pitch)時，上述節距的平均值係3μm以上且未滿15μm。The support sheet provided by the present invention is a support sheet including a substrate, and an adhesive layer is provided on the substrate; wherein the surface of the substrate facing the adhesive layer side is an uneven surface; The test pieces were cut out at five places, and the average of the above pitches was 3 μm when the pitch between adjacent vertices of the convex portions was obtained at the adhesive layer facing the substrate side. Above and less than 15 μm.
本發明的支撐片，亦可上述黏著劑層係直接接觸於上述基材的凹凸面。
再者，本發明所提供的保護膜形成用複合片，係在上述支撐片中的黏著劑層上設置保護膜形成用薄膜。
[發明效果]In the support sheet of the present invention, the adhesive layer may directly contact the uneven surface of the substrate.
Moreover, the composite sheet for forming a protective film provided by the present invention is provided with a thin film for forming a protective film on the adhesive layer in the support sheet.
[Inventive effect]
藉由使用本發明的支撐片構成保護膜形成用複合片，便可實現基材與黏著劑間之良好密接性、以及保護膜或保護膜形成用薄膜隔著支撐片的良好刻印檢視性。By using the support sheet of the present invention to form a composite sheet for forming a protective film, it is possible to achieve good adhesion between the substrate and the adhesive, and good marking visibility of the protective film or the film for forming a protective film through the support sheet.
◇支撐片及保護膜形成用複合片
本發明一實施形態的支撐片，係包括基材，且在上述基材上設有黏著劑層的支撐片；其中，上述基材臨上述黏著劑層側的面係凹凸面；從上述支撐片的5個地方切取試驗片，在這5片試驗片，分別在黏著劑層臨上述基材側，求取相鄰凸部的頂點間之節距時，上述節距的平均值(本說明書中，有時稱「P值」)係3μm以上且未滿15μm。另外，本說明書中，觀察黏著劑層截面時，若黏著劑層臨基材側之一面從下降轉為上升的凸部頂部、與黏著劑層臨基材側之一面從上升轉為下降的凹部最深部間之高度差達1μm以上，便視為此高度差有效，將具有此有效高度差的上述頂部，特定為凸部的有效頂點，並將相鄰上述頂點間的距離定義為上述「相鄰凸部頂點間之節距」。
再者，本發明一實施形態的保護膜形成用複合片，係在上述支撐片中的黏著劑層上設有保護膜形成用薄膜。◇ Support sheet and composite sheet for forming a protective film The support sheet according to an embodiment of the present invention is a support sheet including a substrate and an adhesive layer is provided on the substrate; wherein the substrate is near the adhesive layer side The surface is a concave-convex surface; a test piece is cut from five places of the support sheet, and the five test pieces are respectively located on the adhesive layer facing the substrate side, and the pitch between the vertices of adjacent convex parts is obtained, The average value of the pitches (in this specification, may be referred to as "P value") is 3 μm or more and less than 15 μm. In addition, in this specification, when observing the cross section of the adhesive layer, if the surface of the adhesive layer facing the substrate side changes from falling to rising top of the convex portion, and the surface of the adhesive layer facing the substrate side changing from rising to falling concave portion The height difference between the deepest parts is more than 1 μm, it is considered that the height difference is valid. The top with the effective height difference is specified as the effective vertex of the convex portion, and the distance between the adjacent vertices is defined as the "phase The pitch between the vertices of adjacent convex parts. "
Furthermore, a protective film-forming composite sheet according to an embodiment of the present invention includes a protective film-forming film provided on the adhesive layer in the support sheet.
上述支撐片係在基材的凹凸面側設有黏著劑層，包括此支撐片構成的保護膜形成用複合片，黏著劑層將充分追隨該基材的凹凸面，俾抑制基材與黏著劑層間的剝離情形。
更具體而言，當上述黏著劑層的P值未滿15μm時，因為黏著劑層會充分追隨基材的凹凸，因而基材與黏著劑層間不會發生剝離，使基材與黏著劑層間之密接性良好。
另一方面，當上述黏著劑層的P值達3μm以上時，保護膜或保護膜形成用薄膜隔著支撐片的刻印檢視性呈良好。The support sheet is provided with an adhesive layer on the uneven surface side of the substrate, and includes a composite sheet for forming a protective film composed of the support sheet. The adhesive layer will fully follow the uneven surface of the substrate, and inhibit the substrate and the adhesive. Peeling between layers.
More specifically, when the P value of the above-mentioned adhesive layer is less than 15 μm, since the adhesive layer will sufficiently follow the unevenness of the substrate, no peeling will occur between the substrate and the adhesive layer, so that the distance between the substrate and the adhesive layer will not occur. Good adhesion.
On the other hand, when the P value of the adhesive layer is 3 μm or more, the marking visibility of the protective film or the film for forming a protective film through the support sheet is good.
上述試驗片係從支撐片的5個地方切取，將支撐片在其厚度方向整個切斷而獲得。試驗片係包括構成支撐片所有層的小片。The above-mentioned test piece was cut from five places of the support sheet, and the support sheet was cut in its entire thickness direction to obtain the test piece. The test strips consist of small pieces that make up all the layers of the support sheet.
試驗片的大小並無特別的限定，較佳係構成試驗片各層(基材、黏著劑層等)的積層面或露出面1邊長度達2mm以上。藉由使用此種大小的試驗片，便可更高精度求得黏著劑層的S值與L值。
上述1邊長度的最大值並無特別的限定。例如就從試驗片製作更容易的觀點，上述1邊的長度較佳係在10mm以下。The size of the test piece is not particularly limited, and it is preferable that the length of one side of the build-up layer or the exposed surface of each layer (substrate, adhesive layer, etc.) of the test piece is 2 mm or more. By using a test piece of this size, the S value and L value of the adhesive layer can be obtained with higher accuracy.
The maximum value of the length of one side is not particularly limited. For example, from the viewpoint of making test pieces easier, the length of one side is preferably 10 mm or less.
試驗片的平面形狀─即，構成試驗片各層(基材、黏著劑層等)的積層面或露出面之形狀，較佳係多邊形狀，就從試驗片切取更容易的觀點，更佳係四邊形狀。The planar shape of the test piece, that is, the shape of the build-up layer or exposed surface of each layer (substrate, adhesive layer, etc.) of the test piece, is preferably a polygonal shape, and it is easier to cut from the test piece, and more preferably a quadrangle. shape.
試驗片較佳係可舉例如構成試驗片各層(基材、黏著劑層等)的積層面或露出面大小呈3mm×3mm四邊形狀。但，此僅為較佳試驗片一例而已。The test piece is preferably, for example, a laminated layer or an exposed surface of each layer (substrate, adhesive layer, etc.) constituting the test piece having a size of 3 mm × 3 mm in a quadrangular shape. However, this is just one example of a better test piece.
支撐片在試驗片的5個地方切取位置並無特別的限定，為能更高精度求取黏著劑層的P值，可經考慮後述保護膜形成用薄膜的積層預定位置才再行選擇。
例如支撐片在1片保護膜形成用薄膜的積層預定位置中，選擇屬於配置預定的保護膜形成用薄膜中心(重心)部之1個地方，以及靠近保護膜形成用薄膜周緣部位處、且相對於此中心(重心)部幾乎成點對稱位置配置預定的4個地方等5個地方。The cutting positions of the support sheet at the five places of the test sheet are not particularly limited. In order to obtain the P value of the adhesive layer with higher accuracy, it may be selected after taking into account the predetermined position of the laminated layer of the protective film-forming film described later.
For example, the support sheet is located at a predetermined position of the laminated layer of the protective film forming film, and is selected as one of the center (center of gravity) part of the predetermined protective film forming film, and near the peripheral edge of the protective film forming film. Five predetermined places, such as four places, are arranged at point-symmetrical positions in the center (center of gravity).
支撐片中，試驗片切取位置的中心(重心)間距離較佳係50~200mm。藉由依此設定，便可以更高精度求得黏著劑層的S值與L值。In the supporting piece, the distance between the centers (centers of gravity) of the cutting positions of the test pieces is preferably 50 to 200 mm. By setting in this way, the S value and L value of the adhesive layer can be obtained with higher accuracy.
為能從試驗片求取黏著劑層的P值，便針對試驗片重新形成截面，再針對此形成的截面，便在各個試驗片逐一測定黏著劑層臨基材側相鄰凸部頂點間的節距，並計算出節距的平均值。
重新形成的截面係針對1片試驗片可僅有1面、亦可達2面以上，但通常僅1面便足夠。
所以，只要從這些至少5個節距計算P值便可。In order to obtain the P value of the adhesive layer from the test piece, the cross-section is re-formed for the test piece, and the cross-section formed for this is then measured one by one between each vertex of the adjacent convex portion of the adhesive layer adjacent to the substrate side. Pitch and calculate the average of the pitch.
The re-formed cross section may have only one side or more than two sides for one test piece, but usually only one side is sufficient.
So, just calculate the P value from these at least 5 pitches.
上述截面中，若黏著劑層臨基材側之一面從下降轉為上升的凸部頂部與黏著劑層臨基材側之一面從上升轉為下降的凹部最深部間之高度差達1μm以上，便視為此高度差有效，將具有此有效高度差的上述凹部，特定為凹部的有效最深點，並將相鄰上述最深點間的距離定義為上述「相鄰凹部最深點間之節距」。
本發明中，亦可非上述凸部頂點間的節距，而是上述凹部最深點間的節距平均值成為如同上述P值。此種黏著劑層亦是達成與規定凸部頂點間之節距平均值的黏著劑層同樣效果。In the above-mentioned cross section, if the height difference between the top of the surface of the adhesive layer facing the substrate from falling to rising and the depth of the concave portion of the surface of the adhesive layer facing from the substrate to rising from falling to 1 μm or more, It is considered that the height difference is valid. The above-mentioned recess having the effective height difference is specified as the effective deepest point of the recess, and the distance between the adjacent deepest points is defined as the "pitch between the deepest points of adjacent recesses". .
In the present invention, instead of the pitch between the vertexes of the convex portions, the average pitch between the deepest points of the concave portions may be the same as the P value. This type of adhesive layer is also an adhesive layer that achieves the same effect as the average value of the pitch between the vertices of the convex portions.
試驗片係可依照公知方法形成截面。例如藉由使用公知截面試料製作裝置(截面拋光機)，便可以抑制變動、高重現性，在試驗片中形成截面。The test piece can be formed into a cross section in accordance with a known method. For example, by using a known cross-section sample preparation device (cross-section polishing machine), it is possible to suppress variations and achieve high reproducibility, and to form a cross-section in a test piece.
黏著劑層的凸部頂點間之節距係例如使用掃描式電子顯微鏡(SEM)，觀察試驗片的上述截面便可測定。The pitch between the apexes of the convex portions of the adhesive layer can be measured by observing the above-mentioned cross section of the test piece using, for example, a scanning electron microscope (SEM).
各試驗片的上述截面中，測定黏著劑層凸部頂點間節距的區域，以在構成試驗片各層(基材、黏著劑層等)積層方向的正交方向(大致相對於各層積層面或露出面的平行方向)的50~1500μm的區域為佳。藉由依此設定，便可以高效率且高精度測定黏著劑層凸部頂點間之節距。In the above-mentioned cross section of each test piece, the area of the pitch between the apexes of the convex portions of the adhesive layer is measured so as to be in an orthogonal direction (approximately relative to each layer or A region of 50 to 1500 μm in the direction parallel to the exposed surface is preferred. With this setting, the pitch between the vertices of the convex portions of the adhesive layer can be measured with high efficiency and high accuracy.
針對尚未構成保護膜形成用複合片階段的支撐片、與已構成保護膜形成用複合片的支撐片間，比較黏著劑層凸部頂點間之節距平均值時，這些節距平均值係相互相同、或已構成保護膜形成用複合片的支撐片之上述節距平均值略小，其差值在這麼小的情況仍屬於可忽視的程度。
所以，不使用支撐片而使用從保護膜形成用複合片切取的試驗片，依照與使用從支撐片所切取試驗片情況的相同方法亦可求取層黏著劑層的P值。依此使用從保護膜形成用複合片所切取的試驗片時，若黏著劑層的P值係3μm以上且未滿15μm時，此保護膜形成用複合片便反映出上述本發明的效果。When comparing the average of the pitches between the support sheet that has not yet formed the protective sheet forming composite sheet stage and the support sheet that has formed the protective sheet forming composite sheet, the average values of the pitches between the vertexes of the adhesive layer are relative to each other. The average value of the above-mentioned pitches of the support sheet which is the same or has formed the composite sheet for forming a protective film is slightly smaller, and the difference is still a negligible degree in such a small case.
Therefore, instead of using a support sheet, a test piece cut from a composite sheet for forming a protective film can be used, and the P value of the adhesive layer can also be determined by the same method as in the case where the test piece cut from the support sheet is used. When a test piece cut out from the composite sheet for forming a protective film is used in this way, if the P value of the adhesive layer is 3 μm or more and less than 15 μm, the composite film for forming a protective film reflects the effects of the present invention described above.
即，本發明一實施形態的保護膜形成用複合片，係在上述支撐片中的黏著劑層上，設有保護膜形成用薄膜的保護膜形成用複合片；其中，從上述保護膜形成用複合片的5個地方切取試驗片，再針對這5片試驗片分別求取黏著劑層凸部頂點間之節距而求取上述P值時，上述P值係3μm以上且未滿15μm。That is, the composite sheet for forming a protective film according to an embodiment of the present invention is a composite sheet for forming a protective film, which is provided on the adhesive layer in the support sheet, and is a film for forming a protective film; When the test piece was cut out at five places of the composite sheet, and the pitch between the vertices of the convex portions of the adhesive layer was obtained for the five test pieces, the P value was obtained. The P value was 3 μm or more and less than 15 μm.
另外，從保護膜形成用複合片切取的試驗片，係將保護膜形成用複合片在厚度方向整個切斷而獲得，包括構成保護膜形成用複合片之所有層的小片。In addition, the test piece cut out from the composite sheet for protective film formation was obtained by cutting the composite sheet for protective film formation in its entirety in the thickness direction, and includes small pieces of all layers constituting the composite sheet for protective film formation.
以下，參照圖式，針對本發明保護膜形成用複合片的全體構成進行說明。另外，以下說明所使用的圖，為能容易瞭解本發明特徵，為了方便有將重要部位予以部分放大圖示的情況，各構成要件的尺寸比率等不一定同實際尺寸。Hereinafter, the overall configuration of the protective film-forming composite sheet of the present invention will be described with reference to the drawings. In addition, the drawings used in the following description are for easy understanding of the features of the present invention. For convenience, some important parts may be partially enlarged and illustrated. The dimensional ratios and the like of the constituent elements are not necessarily the same as the actual dimensions.
圖1所示係本發明一實施形態的支撐片與保護膜形成用複合片之示意剖視圖。
此處所示保護膜形成用複合片1A係包括基材11，在基材11上設有黏著劑層12，在黏著劑層12上設有保護膜形成用薄膜13。支撐片10係基材11與黏著劑層12的積層體，保護膜形成用複合片1A，換言之係具有在支撐片10其中一面(本說明書中亦稱「第1面」)10a上，積層保護膜形成用薄膜13的構成。又，保護膜形成用複合片1A係更進一步在保護膜形成用薄膜13上設有剝離薄膜15。FIG. 1 is a schematic cross-sectional view of a support sheet and a composite sheet for forming a protective film according to an embodiment of the present invention.
The protective film-forming composite sheet 1A shown here includes a substrate 11, an adhesive layer 12 is provided on the substrate 11, and a protective film-forming film 13 is provided on the adhesive layer 12. The support sheet 10 is a laminated body of the base material 11 and the adhesive layer 12, and a protective film-forming composite sheet 1A. In other words, it is provided on one side of the support sheet 10 (also referred to as the “first side” in this specification) 10 a to be laminated and protected. The structure of the thin film 13 for film formation. Further, the protective film-forming composite sheet 1A is further provided with a release film 15 on the protective film-forming film 13.
保護膜形成用複合片1A中，在基材11其中一面(本說明書中亦稱「第1面」)11a積層黏著劑層12，在黏著劑層12臨基材11側的相反側的面(本說明書中亦稱「第1面」)12a的全面，積層保護膜形成用薄膜13，在保護膜形成用薄膜13雙面中臨黏著劑層12側的相反側的面(本說明書中亦稱「第1面」)13a其中一部分(即周緣部附近的區域)，積層夾具用接著劑層16，在保護膜形成用薄膜13的第1面13a中未積層著夾具用接著劑層16之一面、與夾具用接著劑層16未接觸到保護膜形成用薄膜13之一面16a(上面與側面)，積層剝離薄膜15。
另外，圖1中，元件符號13b係表示保護膜形成用薄膜13臨黏著劑層12側的面(本說明書中亦稱「第2面」)。In the protective film-forming composite sheet 1A, an adhesive layer 12 is laminated on one surface of the substrate 11 (also referred to as "first surface" in the present specification) 11a, and the surface of the adhesive layer 12 opposite to the substrate 11 side ( In the present specification, it is also referred to as "the first side") 12a. The protective film-forming film 13 is laminated, and the protective film-forming film 13 is on the opposite side of the adhesive layer 12 side on both sides (also referred to in the present specification as "First surface") A part of 13a (that is, a region near the peripheral edge portion) is laminated with the adhesive layer 16 for a jig, and one surface of the protective film forming film 13 is not laminated with one of the adhesive layer 16 for a jig 1. One side 16 a (upper and side surfaces) of the protective film forming film 13 is not contacted with the adhesive layer 16 for a jig, and the release film 15 is laminated.
In addition, in FIG. 1, the element symbol 13 b indicates a surface (also referred to as a “second surface” in this specification) on the side of the protective film-forming film 13 on the side of the adhesive layer 12.
夾具用接著劑層16亦可例如含有接著劑成分的單層構造，亦可在成為芯材的片材雙面上積層著含接著劑成分之層而構成複數層構造。The jig adhesive layer 16 may have, for example, a single-layer structure including an adhesive component, or a layer including an adhesive component may be laminated on both sides of a sheet to be a core material to form a multiple-layer structure.
保護膜形成用複合片1A中，基材11的第1面11a係凹凸面。
再者，黏著劑層12係直接接觸到基材11的第1面(凹凸面)11a狀態而設置。所以，黏著劑層12臨基材11側的面(本說明書中亦稱「第2面」)12b係凹凸面。In the protective film-forming composite sheet 1A, the first surface 11a of the base material 11 is an uneven surface.
The adhesive layer 12 is provided in a state in which it is in direct contact with the first surface (uneven surface) 11 a of the substrate 11. Therefore, the surface of the adhesive layer 12 on the side of the substrate 11 (also referred to as "second surface" in this specification) 12b is an uneven surface.
保護膜形成用複合片1A中，基材11臨黏著劑層12側的相反側的面(本說明書中亦稱「第2面」)11b係可為凹凸面或平滑面(非凹凸面、亮澤面)中之任一者，但以平滑面為佳。基材11的第2面11b亦可謂為支撐片10臨保護膜形成用薄膜13側的相反側的面(本說明書中亦稱「第2面」)10b。
關於「凹凸面」、「平滑面」，容後詳述。In the protective film-forming composite sheet 1A, the surface on the opposite side of the base material 11 from the side of the adhesive layer 12 (also referred to as the "second surface" in this specification) 11b may be a concave-convex surface or a smooth surface (non-convex surface, bright It is preferably smooth surface. The second surface 11b of the base material 11 may also be referred to as a surface (also referred to as a "second surface" in this specification) 10b on the opposite side of the support sheet 10 from the side of the protective film-forming film 13 side.
The "convex surface" and "smooth surface" will be described in detail later.
圖1所示保護膜形成用複合片1A係在已去除剝離薄膜15的狀態下，在保護膜形成用薄膜13的第1面13a貼附半導體晶圓(未圖示)的背面，更在夾具用接著劑層16的面16a中，於上面貼附著環形框架等夾具而使用。The protective sheet-forming composite sheet 1A shown in FIG. 1 is a state where the release film 15 has been removed, and the back surface of the semiconductor wafer (not shown) is attached to the first surface 13 a of the protective film-forming film 13, and further on the jig. On the surface 16a of the adhesive layer 16, a jig such as a ring frame is attached to the upper surface and used.
圖2係一起顯示本發明另一實施形態的保護膜形成用複合片與支撐片之示意剖視圖。
另外，在圖2以後的圖中，針對已說明過的圖式所示相同構成要件，便賦予與該說明過圖式相同的元件符號，並省略詳細說明。FIG. 2 is a schematic cross-sectional view showing a protective film-forming composite sheet and a support sheet together according to another embodiment of the present invention.
In addition, in the drawings after FIG. 2, the same constituent elements as those shown in the drawings are assigned the same reference numerals as those described in the drawings, and detailed descriptions are omitted.
此處所示保護膜形成用複合片1B係未設置夾具用接著劑層16之外，與圖1所示保護膜形成用複合片1A相同。即，保護膜形成用複合片1B中，在基材11的第1面11a積層黏著劑層12，並在黏著劑層12的第1面12a全面積層保護膜形成用薄膜13，更於保護膜形成用薄膜13的第1面13a全面積層剝離薄膜15。The protective sheet-forming composite sheet 1B shown here is the same as the protective film-forming composite sheet 1A shown in FIG. 1 except that the jig adhesive layer 16 is not provided. That is, in the composite sheet 1B for forming a protective film, the adhesive layer 12 is laminated on the first surface 11a of the base material 11 and the protective film-forming film 13 is formed on the first surface 12a of the adhesive layer 12 over the entire area. The first surface 13 a of the forming film 13 is a full-area layer release film 15.
保護膜形成用複合片1B中，亦是基材11的第1面11a屬於凹凸面。
再者，黏著劑層12係呈直接接觸到基材11的第1面(凹凸面)11a狀態而設置。所以，黏著劑層12臨基材11側的面(第2面)12b係凹凸面。
保護膜形成用複合片1B中，亦是基材11的第2面11b(換言之，支撐片10的第2面10b)可為凹凸面或平滑面(非凹凸面)中之任一者，但以平滑面為佳。In the protective film-forming composite sheet 1B, the first surface 11a of the base material 11 also belongs to an uneven surface.
The adhesive layer 12 is provided in a state of being in direct contact with the first surface (uneven surface) 11 a of the substrate 11. Therefore, the surface (second surface) 12b of the adhesive layer 12 on the substrate 11 side is an uneven surface.
In the protective sheet-forming composite sheet 1B, the second surface 11b of the base material 11 (in other words, the second surface 10b of the support sheet 10) may be either an uneven surface or a smooth surface (non-concave surface), but A smooth surface is preferred.
圖2所示保護膜形成用複合片1B係在已去除剝離薄膜15的狀態下，於保護膜形成用薄膜13的第1面13a中，在中央側其中一部分區域處貼附半導體晶圓(未圖示)，更在周緣附近區域處貼附著環形框架等夾具而使用。The protective film-forming composite sheet 1B shown in FIG. 2 is a state where a semiconductor wafer (not shown) is attached to a part of the central side of the first surface 13a of the protective film-forming film 13 with the release film 15 removed. (Shown), and a jig such as a ring frame is attached to the area near the periphery and used.
圖3所示係本發明再另一實施形態的保護膜形成用複合片與支撐片之示意剖視圖。
此處所示保護膜形成用複合片1C係除保護膜形成用薄膜的形狀不同之外，其餘均與圖2所示保護膜形成用複合片1B相同。即，保護膜形成用複合片1C係包括基材11，在基材11上包括黏著劑層12，更在黏著劑層12上設有保護膜形成用薄膜23。支撐片10係基材11與黏著劑層12的積層體，保護膜形成用複合片1C，換言之係具有在支撐片10的第1面(臨保護膜形成用薄膜23側的面)10a上，積層著保護膜形成用薄膜23的構成。又，保護膜形成用複合片1C係更進一步在保護膜形成用薄膜23上包括剝離薄膜15。FIG. 3 is a schematic cross-sectional view of a protective sheet-forming composite sheet and a support sheet according to still another embodiment of the present invention.
The protective sheet forming composite sheet 1C shown here is the same as the protective film forming composite sheet 1B shown in FIG. 2 except that the shape of the protective film forming film is different. That is, the protective film-forming composite sheet 1C includes a base material 11, an adhesive layer 12 on the base material 11, and a protective film-forming film 23 is further provided on the adhesive layer 12. The support sheet 10 is a laminated body of the base material 11 and the adhesive layer 12 and the protective film forming composite sheet 1C, in other words, is provided on the first surface (the surface facing the protective film-forming film 23 side) 10a of the support sheet 10, The thin film 23 for forming a protective film is laminated. Furthermore, the protective film-forming composite sheet 1C further includes a release film 15 on the protective film-forming film 23.
保護膜形成用複合片1C中，在基材11的第1面11a積層著黏著劑層12，並在黏著劑層12的第1面12a其中一部分(即，中央區域)積層著保護膜形成用薄膜23。而且，在黏著劑層12的第1面12a中未積層保護膜形成用薄膜23的區域、與保護膜形成用薄膜23未接觸到黏著劑層12之一面23a(上面與側面)上，積層著剝離薄膜15。
另外，圖3中，元件符號23b係表示保護膜形成用薄膜23臨黏著劑層12側的面(本說明書中亦稱「第2面」)。In the protective film-forming composite sheet 1C, the adhesive layer 12 is laminated on the first surface 11a of the base material 11, and a part of the first surface 12a of the adhesive layer 12 (that is, the central region) is laminated on the protective film forming layer. Film 23. In the first surface 12a of the adhesive layer 12, a region where the protective film-forming film 23 is not laminated, and the protective film-forming film 23 is not in contact with one surface 23a (upper and side surfaces) of the adhesive layer 12, and is laminated. Peeling film 15.
In addition, in FIG. 3, the element symbol 23b shows the surface (it is also called "second surface" in this specification) on the side of the protective film formation film 23 by the side of the adhesive layer 12.
當從上方朝下俯視保護膜形成用複合片1C時，保護膜形成用薄膜23的表面積較小於黏著劑層12的表面積，且具有例如圓形狀等形狀。When the protective film forming composite sheet 1C is viewed from above, the protective film forming film 23 has a smaller surface area than that of the adhesive layer 12 and has a shape such as a circular shape.
保護膜形成用複合片1C中，亦是基材11的第1面11a呈凹凸面。
再者，黏著劑層12係設計呈直接接觸到基材11的第1面(凹凸面)11a狀態。所以，黏著劑層12臨基材11側的面(第2面)12b係凹凸面。
保護膜形成用複合片1C中，亦是基材11的第2面11b(換言之，支撐片10的第2面10b)係可為凹凸面或平滑面(非凹凸面)中之任一者，但以平滑面為佳。In the protective film-forming composite sheet 1C, the first surface 11a of the base material 11 also has an uneven surface.
In addition, the adhesive layer 12 is designed to be in a state of directly contacting the first surface (uneven surface) 11 a of the base material 11. Therefore, the surface (second surface) 12b of the adhesive layer 12 on the substrate 11 side is an uneven surface.
In the protective film-forming composite sheet 1C, the second surface 11b of the base material 11 (in other words, the second surface 10b of the support sheet 10) may be any of an uneven surface and a smooth surface (non-convex surface). But smooth surface is better.
圖3所示保護膜形成用複合片1C係在已去除剝離薄膜15狀態下，於保護膜形成用薄膜23之面23a貼附半導體晶圓(未圖示)的背面，更在黏著劑層12的第1面12a中未積層保護膜形成用薄膜23的區域處，貼附環形框架等夾具而使用。The protective film-forming composite sheet 1C shown in FIG. 3 is attached to the back surface of the semiconductor wafer (not shown) on the surface 23 a of the protective film-forming film 23 with the release film 15 removed, and further on the adhesive layer 12. In a region of the first surface 12a where the protective film-forming film 23 is not laminated, a jig such as a ring frame is attached and used.
另外，圖3所示保護膜形成用複合片1C，亦可在黏著劑層12的第1面12a中未積層保護膜形成用薄膜23的區域處，同圖1所示積層著夾具用接著劑層(未圖示)。此種包括夾具用接著劑層的保護膜形成用複合片1C，係與圖1所示保護膜形成用複合片同樣，在夾具用接著劑層的上面貼附著環形框架等夾具而使用。In addition, the composite sheet 1C for forming a protective film shown in FIG. 3 may be laminated on the first surface 12 a of the adhesive layer 12 in a region where the thin film 23 for forming a protective film is not laminated, as shown in FIG. 1. Layer (not shown). Such a protective film-forming composite sheet 1C including an adhesive layer for a jig is used in the same manner as a composite film for forming a protective film shown in FIG. 1 by attaching a jig such as a ring frame to the upper surface of the adhesive layer for a jig.
依此，保護膜形成用複合片係不管支撐片及保護膜形成用薄膜採何種形態，均可包括夾具用接著劑層。但，通常如圖1所示，包括夾具用接著劑層的保護膜形成用複合片，以在保護膜形成用薄膜上設有夾具用接著劑層為佳。Accordingly, the composite sheet for forming a protective film can include an adhesive layer for a jig regardless of the form of the supporting sheet and the thin film for forming a protective film. However, as shown in FIG. 1, a composite film for forming a protective film including an adhesive layer for a jig is generally preferably provided with an adhesive layer for a jig on a film for forming a protective film.
本發明一實施形態的保護膜形成用複合片並不僅侷限於圖1~圖3所示，在不致損及本發明效果之範圍內，亦可變更或刪除圖1~圖3所示的其中一部分構成，亦可在截至目前所說明的構成中更進一步追加其他構成等等。The composite sheet for forming a protective film according to an embodiment of the present invention is not limited to those shown in FIG. 1 to FIG. 3, and a part of FIG. 1 to FIG. 3 may be changed or deleted as long as the effect of the present invention is not impaired. For the configuration, other configurations may be further added to the configuration described so far.
例如圖1~圖3所示保護膜形成用複合片，亦可在基材11與黏著劑層12之間設置中間層。即，本發明的保護膜形成用複合片，支撐片亦可依照基材、中間層及黏著劑層的順序，在其厚度方向上積層構成。中間層係可配合目的任意選擇。
再者，圖1~圖3所示保護膜形成用複合片亦可在任意地方設置上述中間層以外的層。
再者，保護膜形成用複合片中，亦可在剝離薄膜、與此剝離薄膜直接接觸的層之間，局部產生間隙。
再者，保護膜形成用複合片的各層大小、形狀等係可配合目的任意調整。For example, in the composite sheet for forming a protective film shown in FIGS. 1 to 3, an intermediate layer may be provided between the substrate 11 and the adhesive layer 12. That is, in the composite sheet for forming a protective film of the present invention, the support sheet may be formed by laminating layers in the thickness direction in the order of the substrate, the intermediate layer, and the adhesive layer. The middle layer can be arbitrarily selected according to the purpose.
The composite sheet for forming a protective film shown in FIGS. 1 to 3 may be provided with a layer other than the above-mentioned intermediate layer at any place.
Furthermore, in the composite sheet for forming a protective film, a gap may be locally generated between the release film and a layer directly contacting the release film.
The size, shape, and the like of each layer of the protective film-forming composite sheet can be arbitrarily adjusted according to the purpose.
但，如圖1~圖3所示，保護膜形成用複合片中，較好係黏著劑層直接接觸於基材的凹凸面(第1面)，換言之，在基材與黏著劑層之間並未設置中間層，而是在基材上直接接觸而積層著黏著劑層。
再者，保護膜形成用複合片中，較好係保護膜形成用薄膜直接接觸於黏著劑層的第1面，換言之，在黏著劑層與保護膜形成用薄膜之間並沒有設置其他層，而是在黏著劑層上直接接觸而積層著保護膜形成用薄膜。
再者，保護膜形成用複合片，更佳係這些條件均能滿足，即依照基材、黏著劑層及保護膜形成用薄膜的順序，在其厚度方向上相互直接接觸積層而構成。However, as shown in FIG. 1 to FIG. 3, in the composite sheet for forming a protective film, it is preferable that the adhesive layer directly contacts the uneven surface (first surface) of the substrate, in other words, between the substrate and the adhesive layer. No intermediate layer is provided, but an adhesive layer is laminated directly on the substrate.
Furthermore, in the composite sheet for forming a protective film, it is preferable that the thin film for forming a protective film directly contacts the first surface of the adhesive layer. In other words, no other layer is provided between the adhesive layer and the thin film for forming a protective film. Instead, a thin film for protective film formation is laminated directly on the adhesive layer.
Furthermore, the composite film for forming a protective film preferably satisfies these conditions, that is, it is constituted by directly contacting the layers in the thickness direction in accordance with the order of the substrate, the adhesive layer, and the film for forming the protective film.
上述支撐片較佳係透明。
支撐片配合目的亦可被著色、亦可蒸鍍有其他層。
例如當保護膜形成用薄膜係能量線硬化性的情況，支撐片以使能量線穿透為佳。The support sheet is preferably transparent.
The supporting sheet may be colored according to the purpose, or may be vapor-deposited with other layers.
For example, when the thin film for protective film formation is energy ray curable, it is preferable to support the sheet so as to penetrate the energy ray.
本說明書中，所謂「能量線」係指電磁波或帶電粒子束中具有能量量子，可舉例如:紫外線、放射線、電子束等。紫外線係可使用例如紫外線源之高壓水銀燈、熔絲燈(fusion lamp)、氙燈、黑光燈(black-light)或LED燈等進行照射。電子束係可照射由電子束加速器等所生成者。
本說明書中，所謂「能量線硬化性」係指藉由能量線的照射而硬化的性質；所謂「非能量線硬化性」係即便照射能量線但仍不會硬化的性質。In this specification, the "energy ray" refers to an energy quantum in an electromagnetic wave or a charged particle beam, and examples thereof include ultraviolet rays, radiation, and electron beams. The ultraviolet rays can be irradiated using, for example, a high-pressure mercury lamp, a fusion lamp, a xenon lamp, a black-light, or an LED lamp. The electron beam system can irradiate a generator generated by an electron beam accelerator or the like.
In the present specification, the "energy ray hardenability" refers to a property that is hardened by irradiation with energy rays; the "non-energy ray hardenability" refers to a property that does not harden even when energy rays are irradiated.
支撐片的波長375nm光穿透率較佳係達30%以上、更佳係達50%以上、特佳係達70%以上。藉由上述光的穿透率在此種範圍內，當隔著支撐片對保護膜形成用薄膜照射能量線(紫外線)時，便更加提升保護膜形成用薄膜的硬化度。
支撐片的波長375nm光之穿透率上限值並無特別的限定。例如上述光的穿透率以在95%以下為佳。The light transmittance of the support sheet at a wavelength of 375 nm is preferably more than 30%, more preferably more than 50%, and particularly good 70%. When the light transmittance is within this range, when the protective film-forming film is irradiated with energy rays (ultraviolet rays) through the support sheet, the hardening degree of the protective film-forming film is further enhanced.
The upper limit of the transmittance of the support sheet with a wavelength of 375 nm is not particularly limited. For example, the light transmittance is preferably 95% or less.
支撐片的波長532nm光穿透率較佳係30%以上、更佳係50%以上、特佳係70%以上。藉由上述光的穿透率在此種範圍內，當隔著支撐片對保護膜形成用薄膜或保護膜照射雷射光而在其上刻印時，可更清晰地刻印。
支撐片的波長532nm光之穿透率上限值並無特別的限定。例如上述光穿透率以在95%以下為佳。The light transmittance of the support sheet at a wavelength of 532 nm is preferably 30% or more, more preferably 50% or more, and 70% or more particularly. When the above-mentioned light transmittance is within such a range, when the protective film-forming film or the protective film is irradiated with laser light through the support sheet to be engraved thereon, it can be more clearly marked.
The upper limit of the transmittance of the support sheet with a wavelength of 532 nm is not particularly limited. For example, the light transmittance is preferably 95% or less.
支撐片的波長1064nm光穿透率較佳係達30%以上、更佳係達50%以上、特佳係達70%以上。藉由上述光的穿透率在此種範圍內，當隔著支撐片對保護膜形成用薄膜或保護膜照射雷射光而在其上刻印時，可更清晰地刻印。
支撐片的波長1064nm光之穿透率上限值並無特別的限定。例如上述光的穿透率以在95%以下為佳。The light transmittance of the support sheet at a wavelength of 1064 nm is preferably more than 30%, more preferably more than 50%, and particularly good 70%. When the above-mentioned light transmittance is within such a range, when the protective film-forming film or the protective film is irradiated with laser light through the support sheet to be engraved thereon, it can be more clearly marked.
The upper limit of the transmittance of the support sheet with a wavelength of 1064 nm is not particularly limited. For example, the light transmittance is preferably 95% or less.
支撐片的穿透清晰度較佳係達30以上、更佳係達100以上、特佳係達200以上。藉由上述穿透清晰度在此種範圍內，可更加輕易隔著支撐片確認保護膜形成用薄膜的浮起脫落、刻印不良情況、及缺損等。
支撐片的穿透清晰度並無特別的限定。例如上述穿透清晰度可在430以下。
支撐片的穿透清晰度係可根據JIS K 7374-2007進行測定。The penetration clarity of the support sheet is preferably 30 or more, more preferably 100 or more, and more preferably 200 or more. When the above-mentioned penetration clarity is within such a range, it is possible to more easily confirm the rise and fall of the protective film-forming film through the support sheet, defective marking, and defects.
The penetration definition of the support sheet is not particularly limited. For example, the above-mentioned penetration clarity may be below 430.
The transparency of the support sheet can be measured in accordance with JIS K 7374-2007.
其次，針對構成支撐片與保護膜形成用複合片的各層進行詳細說明。Next, each layer which comprises a support sheet and a protective film formation composite sheet is demonstrated in detail.
○基材
上述基材係片狀或薄膜狀，且具有凹凸面。○ Base material The base material is in the form of a sheet or a film, and has an uneven surface.
本說明書中，所謂「凹凸面」係指根據JIS B 0601:2013所規定的最大高度粗糙度Rz達0.01μm以上之面。
再者，所謂「平滑面」係指非為凹凸面，而是高平滑度的面，亦稱「非凹凸面」或「亮澤面」。例如平滑面包含具有不屬於上述凹凸面程度的極小凹凸度之面。In the present specification, the "uneven surface" refers to a surface having a maximum height roughness Rz of 0.01 μm or more in accordance with JIS B 0601: 2013.
In addition, the "smooth surface" refers to a surface that is not a concave-convex surface but has a high smoothness, and is also referred to as a "non-concave surface" or a "glossy surface". For example, the smooth surface includes a surface having an extremely small degree of unevenness that does not belong to the degree of the uneven surface.
基材係可僅其中一面為凹凸面，亦可雙面均為凹凸面，以僅其中一面為凹凸面為佳。換言之，上述基材中，以僅其中一面為平滑面為佳。支撐片中，基材的凹凸面成為設置黏著劑層之一面。The base material may have a concave-convex surface only on one side, or both sides may be a concave-convex surface, and it is preferable that only one side is a concave-convex surface. In other words, it is preferable that only one of the substrates is a smooth surface. In the support sheet, the uneven surface of the substrate becomes one surface on which the adhesive layer is provided.
基材係可僅由1層(單層)構成，亦可由2層以上的複數層構成，當由複數層構成的情況，這些複數層係相互可為相同、亦可為不同，這些複數層的組合並無特別的限定。
當基材係由複數層構成的情況，這些複數層中，最外層之一面(最靠近黏著劑層之一面、或最靠近黏著劑層之一面與最遠離之一面的雙面)係成為上述凹凸面。The base material system may be composed of only one layer (single layer), or may be composed of a plurality of layers. When composed of a plurality of layers, these plural layers may be the same as or different from each other. The combination is not particularly limited.
When the substrate is composed of a plurality of layers, one of the outermost layers (one surface closest to the adhesive layer, or one surface closest to the adhesive layer and two surfaces furthest from the adhesive layer) of the plurality of layers becomes the aforementioned unevenness. surface.
本說明書不僅侷限於基材的情況，所謂「複數層係相互可為相同、亦可為不同」係指「所有層可為相同、亦可所有層均不同、亦可僅其中一部分的層相同」；又，所謂「複數層相互不同」係指「各層的構成材料與厚度中之至少其中一者係相互不同」。This specification is not limited to the case of a substrate. The so-called "multiple layers may be the same or different from each other" means "all layers may be the same, all layers may be different, or only some of the layers may be the same." ; "Plural layers are different from each other" means "at least one of the constituent materials and the thickness of each layer is different from each other".
基材設有黏著劑層之一側的凹凸面(第1面)中，根據JIS B 0601:2013所測定的最大高度粗糙度(Rz)，較佳係0.01~8μm、更佳係0.1~7μm、特佳係0.5~6μm。藉由基材的上述Rz達上述下限值以上，抑制單獨將基材捲取為捲筒狀、解捲時發生不良情況。又，在支撐片或保護膜形成用複合片的製造過程中，關於含基材的積層物亦同樣地抑制捲取、解捲時發生不良情況。另一方面，藉由基材的上述Rz在上述上限值以下，便可使黏著劑層與保護膜形成用薄膜的積層性、以及保護膜或保護膜形成用薄膜隔著支撐片的刻印檢視性均更良好。The maximum height roughness (Rz) measured in accordance with JIS B 0601: 2013 of the uneven surface (first surface) on one side of the base material provided with an adhesive layer, preferably 0.01 to 8 μm, and more preferably 0.1 to 7 μm , Extra good line 0.5 ~ 6μm. When the Rz of the base material is equal to or higher than the lower limit value described above, it is possible to prevent the base material from being rolled into a roll shape alone, and the occurrence of defects during unwinding can be suppressed. In the manufacturing process of the support sheet or the composite sheet for forming a protective film, the substrate-containing laminate is also similarly suppressed from being defective during winding and unwinding. On the other hand, when the above-mentioned Rz of the base material is below the above-mentioned upper limit value, the lamination property of the adhesive layer and the film for forming a protective film, and the marking inspection of the protective film or the film for forming a protective film through the support sheet can be inspected. Sex is better.
當基材的雙面均為凹凸面的情況，此雙面的凹凸度係相互可為相同、亦可為不同。When both sides of the substrate are uneven surfaces, the unevenness of the two sides may be the same or different from each other.
上述基材的構成材料係可舉例如各種樹脂。
上述樹脂係可舉例如:低密度聚乙烯(LDPE)、直鏈低密度聚乙烯(LLDPE)、高密度聚乙烯(HDPE)等聚乙烯；聚丙烯、聚丁烯、聚丁二烯、聚甲基戊烯、降莰烯樹脂等聚乙烯以外的聚烯烴；乙烯-醋酸乙烯酯共聚物、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯共聚物、乙烯-降莰烯共聚物等乙烯系共聚物(單體係使用乙烯所獲得的共聚物)；聚氯乙烯、氯乙烯共聚物等氯乙烯系樹脂(單體係使用氯乙烯所獲得的樹脂)；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、所有構成單元均具有芳香族環式基的全芳香族聚酯等聚酯；上述聚酯2種以上的共聚物；聚(甲基)丙烯酸酯；聚氨酯；聚氨酯丙烯酸酯；聚醯亞胺；聚醯胺；聚碳酸酯；氟樹脂；聚縮醛；改質聚伸苯醚；聚苯硫醚；聚碸；聚醚酮等。
再者，上述樹脂亦可舉例如由上述聚酯與其外的樹脂的混合物等聚合物摻合物(polymer alloy)。上述聚酯與其外的樹脂的聚合物摻合物，較佳係聚酯以外的樹脂量屬於較少量。
再者，上述樹脂亦可舉例如:由截至目前為止所例示上述樹脂中之1種或2種以上交聯後的交聯樹脂；使用截至目前為止所例示上述樹脂中之1種或2種以上的離子聚合物等改質樹脂。Examples of the constituent material of the substrate include various resins.
Examples of the above resins include polyethylenes such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE); polypropylene, polybutene, polybutadiene, and polymethylmethacrylate. Polyolefins other than polyethylene such as pentene and norbornene resin; ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylate copolymer, ethylene-norbornene Copolymers such as vinyl copolymers (copolymers obtained by using ethylene in a single system); vinyl chloride resins such as polyvinyl chloride and vinyl chloride copolymers (resins obtained by using vinyl chloride in a single system); polystyrene; Polycycloolefins; polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene isophthalate, polyethylene 2,6-naphthalene dicarboxylate Esters, polyesters such as wholly aromatic polyesters having an aromatic cyclic group in all constituent units; copolymers of two or more of the above-mentioned polyesters; poly (meth) acrylates; polyurethanes; polyurethane acrylates; polyimide Polyamide; Polycarbonate; Fluororesin; Polyacetal; Modified Polyphenylene Ether; Polyphenylene Sulfide; Polyfluorene Polyether ketone.
The resin may also be a polymer alloy such as a mixture of the polyester and a resin other than the polyester. The polymer blend of the above-mentioned polyester and a resin other than the above is preferably a relatively small amount of resin other than the polyester.
In addition, the resin may be, for example, one or two or more of the resins exemplified so far after being crosslinked, and one or two or more of the resins exemplified so far. Modified resins such as ionic polymers.
本說明書中，所謂「(甲基)丙烯酸」係包含「丙烯酸」與「甲基丙烯酸」雙方的概念。關於(甲基)丙烯酸的類似用詞亦同，例如所謂「(甲基)丙烯醯基」係包含「丙烯醯基」與「甲基丙烯醯基」雙方的概念；所謂「(甲基)丙烯酸酯」係包含「丙烯酸酯」與「甲基丙烯酸酯」雙方的概念。In the present specification, the term "(meth) acrylic acid" includes both the concepts of "acrylic acid" and "methacrylic acid". Similar terms are also used for (meth) acrylic acid. For example, the so-called "(meth) acrylfluorenyl" includes both the concept of "acrylfluorenyl" and "methacrylfluorenyl"; the so-called "(meth) acrylic acid" "Ester" includes both the concepts of "acrylate" and "methacrylate".
構成基材的樹脂係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The resin system constituting the base material may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
基材的厚度較佳係在50~300μm範圍內、更佳係在60~150μm範圍內。藉由基材的厚度在此種範圍內，便可更加提升上述保護膜形成用複合片的可撓性、對半導體晶圓或半導體晶片的貼附性。
如上述，因為基材具有凹凸面，因而厚度係依照基材的部位會有變動。所以，基材厚度的最小值可達上述下限值以上，且基材厚度的最大值可在上述上限值以下。
另外，所謂「基材厚度」係指基材全體的厚度，例如由複數層構成的基材厚度，係指構成基材的所有層之合計厚度。The thickness of the substrate is preferably in the range of 50 to 300 μm, and more preferably in the range of 60 to 150 μm. When the thickness of the substrate is within this range, the flexibility of the composite sheet for forming a protective film and the adhesion to a semiconductor wafer or a semiconductor wafer can be further improved.
As described above, since the substrate has uneven surfaces, the thickness varies depending on the location of the substrate. Therefore, the minimum value of the substrate thickness can be above the lower limit value, and the maximum value of the substrate thickness can be below the upper limit value.
The "substrate thickness" refers to the thickness of the entire substrate, for example, the thickness of the substrate composed of a plurality of layers, and the total thickness of all the layers constituting the substrate.
基材的厚度係例如使用掃描式電子顯微鏡(SEM)，觀察基材的側面或截面便可測定。
基材的截面係例如依照與上述支撐片及保護膜形成用複合片的試驗片截面情況之同樣方法便可形成。The thickness of the substrate can be measured by, for example, using a scanning electron microscope (SEM) and observing the side surface or the cross section of the substrate.
The cross section of the base material can be formed, for example, in the same manner as in the case of the cross section of the test piece of the support sheet and the composite sheet for forming a protective film.
例如與前所說明方法同樣，從支撐片或保護膜形成用複合片的複數個地方(例如5個地方)切取試驗片，針對此試驗片求取基材厚度的最小值與最大值，再從這些數值進一步求取這些最小值平均值與最大值平均值時，上述最小值平均值可在上述基材厚度的下限值以上，上述最大值平均值亦可在上述基材厚度的上限值以下。For example, in the same manner as described above, a test piece is cut from a plurality of places (for example, five places) of a support sheet or a composite sheet for forming a protective film, and the minimum and maximum thicknesses of the substrate are obtained for this test piece. When these values are further used to find the minimum average value and the maximum average value, the minimum average value may be above the lower limit value of the substrate thickness, and the maximum average value may also be the upper limit value of the substrate thickness. the following.
基材臨黏著劑層側的面的相鄰凸部頂點間的節距、或基材臨黏著劑層側的面的相鄰凹部最深部間的節距(以下亦將基材臨黏著劑層側的面的相鄰凸部頂點間的節距、與基材臨黏著劑層側的面的相鄰凹部最深點間的節距，統稱為「基材節距」)，以3μm以上且未滿15μm為佳、較佳係3.5μm以上且未滿14μm、更佳係4μm以上且未滿13μm、特佳係4.5μm以上且未滿12μm。藉由基材節距設在此種範圍內，可使基材與黏著劑層間之密接性更良好。The pitch between the vertices of adjacent convex portions on the surface of the substrate adjacent to the adhesive layer side, or the pitch between the deepest portions of adjacent concave portions on the surface of the substrate adjacent to the adhesive layer side (hereinafter, the substrate adjacent to the adhesive layer is also referred to). The pitch between the vertices of adjacent convex portions on the side surface and the deepest point between adjacent recesses on the surface of the substrate adjacent to the adhesive layer side are collectively referred to as the "substrate pitch"). It is preferably at least 15 μm, more preferably at least 3.5 μm and less than 14 μm, more preferably at least 4 μm and less than 13 μm, and particularly preferably at least 4.5 μm and less than 12 μm. By setting the substrate pitch within such a range, the adhesion between the substrate and the adhesive layer can be made better.
基材節距係例如使用掃描式電子顯微鏡(SEM)，觀察基材的側面或截面便可測定。
基材的截面係例如依照與上述支撐片及保護膜形成用複合片的試驗片截面的情況之同樣方法便可形成。The substrate pitch is measured by, for example, using a scanning electron microscope (SEM) and observing the side or cross section of the substrate.
The cross-section of the base material can be formed in the same manner as in the case of the cross-section of the test piece of the support sheet and the composite sheet for forming a protective film, for example.
例如與前所說明方法同樣，從支撐片或保護膜形成用複合片的複數個地方(例如5個地方)切取試驗片，在此試驗片，分別在各基材臨上述黏著劑層側的面，求取相鄰凸部頂點間之節距、或相鄰凹部部最深點間之節距時，上述節距的平均值較佳係3μm以上且未滿15μm。另外，本說明書中，觀察基材截面時，若基材臨黏著劑層側的面從上升轉為下降的凸部頂部與基材臨黏著劑層側的面從下降轉為上升的凹部最深部間之高度差達1μm以上，便視為此高度差有效，將具有此有效高度差的上述頂部，特定為凸部的有效頂點，並將相鄰上述頂點間的距離定義為上述「相鄰凸部頂點間之節距」，且將具上述有效高度差的上述最深部，特定為凹部的有效最深點，並將相鄰上述最深點間的距離定義為上述「相鄰凹部最深點間之節距」。For example, in the same manner as described above, test pieces are cut out from a plurality of places (for example, five places) of a support sheet or a composite sheet for forming a protective film, and the test pieces are respectively provided on the surface of each substrate facing the side of the adhesive layer. When obtaining the pitch between the apexes of adjacent convex parts or the pitch between the deepest points of adjacent concave parts, the average value of the above pitches is preferably 3 μm or more and less than 15 μm. In addition, in this specification, when observing the cross section of the substrate, if the surface of the substrate facing the adhesive layer side changes from rising to falling, the top of the convex portion and the surface of the substrate facing the adhesive layer side changes from falling to the deepest portion of the concave portion. If the height difference between them is more than 1 μm, the height difference is considered to be valid. The top with the effective height difference is specified as the effective vertex of the convex portion, and the distance between the adjacent vertices is defined as the “adjacent convex The distance between the vertices of the two adjacent vertices ", and the deepest part with the effective height difference is specified as the effective deepest point of the recess, and the distance between the adjacent deepest points is defined as the" knot between the deepest points of adjacent recesses " distance".
基材係除上述樹脂等主要的構成材料之外，亦可含有例如:填充材、著色劑、抗靜電劑、抗氧化劑、有機滑劑、觸媒、軟化劑(可塑劑)等公知各種添加劑。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 resin described above.
基材較佳係透明。
基材係配合目的可被著色、亦可蒸鍍其他的層。
例如保護膜形成用薄膜為能量線硬化性的情況，基材以使能量線穿透為佳。The substrate is preferably transparent.
The base material may be colored for other purposes, or other layers may be deposited.
For example, in the case where the protective film-forming film is energy ray-curable, it is preferable that the base material penetrates the energy ray.
基材係為了提升與在其上面所設置黏著劑層等直接接觸的層之密接性，亦可對表面施行例如: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等。
再者，基材的表面亦可施行底漆處理。
再者，基材係可具有:抗靜電塗層；在重疊保護膜形成用複合片並保存時，可具有防止基材接著於其他片材、基材接著於吸附平台等的層等。The base material is used to improve the adhesiveness of the layer in direct contact with a layer such as an adhesive layer provided thereon, and the surface may be subjected to, for example, corona discharge treatment, electron beam irradiation treatment, plasma treatment, ozone / ultraviolet irradiation treatment, Oxidation treatment such as flame treatment, chromic acid treatment, hot air treatment, etc.
Furthermore, the surface of the substrate may be treated with a primer.
Furthermore, the base material may include an antistatic coating, and when a composite sheet for forming a protective film is stacked and stored, it may have a layer that prevents the base material from adhering to another sheet, the base material to an adsorption platform, and the like.
基材係可利用公知方法製造。例如含有樹脂的基材係藉由將含有上述樹脂的樹脂組成物施行成形便可製造。The base material can be produced by a known method. For example, a resin-containing substrate can be produced by molding a resin composition containing the resin.
當使用未具凹凸面的基材(換言之，雙面均為平滑面的基材)時，只要對基材的平滑面施行凹凸化處理便可。
凹凸化處理係可依照公知方法實施。例如使用具凹凸面的金屬輥或金屬板，藉由將其上述的凹凸面按壓於基材的平滑面，便可對基材的平滑面施行凹凸化處理。此時，以將經加熱狀態的金屬輥或金屬板按壓於基材的平滑面為佳。又，基材的平滑面亦可利用噴砂處理、或溶劑處理等施行凹凸化處理。When a base material having no uneven surface is used (in other words, a substrate having both sides having a smooth surface), the smooth surface of the substrate need only be subjected to an unevenness treatment.
The unevenness treatment can be performed in accordance with a known method. For example, by using a metal roller or a metal plate having a concave-convex surface, the smooth surface of the base material can be subjected to a concave-convex treatment by pressing the concave-convex surface described above against the smooth surface of the base material. In this case, it is preferable to press the heated metal roll or metal plate against the smooth surface of the substrate. The smooth surface of the substrate may be subjected to a roughening treatment by a sandblasting treatment, a solvent treatment, or the like.
○黏著劑層
上述黏著劑層係片狀或薄膜狀。
黏著劑層中，通常無論在基材與黏著劑層間有無設置中間層，均會受基材的上述凹凸面影響，導致至少臨基材側的面會成為凹凸面。○ Adhesive layer The above-mentioned adhesive layer is sheet-like or film-like.
In the adhesive layer, whether or not an intermediate layer is provided between the substrate and the adhesive layer is generally affected by the uneven surface of the substrate, and the surface at least on the substrate side becomes an uneven surface.
黏著劑層係可由1層(單層)構成，亦可由2層以上的複數層構成，當由複數層構成的情況，這些複數層係相互可為相同、亦可為不同，且這些複數層的組合並無特別的限定。
當黏著劑層係由複數層構成的情況，這些複數層中的最外層之一面(最接近基材之一面)將成為上述凹凸面。The adhesive layer system may be composed of one layer (single layer) or plural layers of two or more layers. When composed of plural layers, these plural layers may be the same or different from each other. The combination is not particularly limited.
When the adhesive layer is composed of a plurality of layers, one of the outermost layers (the surface closest to the substrate) of the plurality of layers will become the above-mentioned uneven surface.
此處，參照圖式，針對基材與黏著劑層進行更詳細說明。
圖4所示係本發明一實施形態的保護膜形成用複合片之示意放大剖視圖。在此，舉圖1所示保護膜形成用複合片1A為例進行說明。另外，圖4中省略圖示剝離薄膜。Here, the substrate and the adhesive layer will be described in more detail with reference to the drawings.
FIG. 4 is a schematic enlarged cross-sectional view of a composite sheet for forming a protective film according to an embodiment of the present invention. Here, the composite sheet 1A for protective film formation shown in FIG. 1 is demonstrated as an example. Note that the release film is omitted in FIG. 4.
如前所說明，基材11的第1面11a係凹凸面。而，黏著劑層12係設置成直接接觸於基材11的第1面(凹凸面)11a，黏著劑層12的第2面12b可輕易追隨基材11的第1面11a。所以，黏著劑層12的第2面12b亦呈凹凸面。As described above, the first surface 11a of the base material 11 is an uneven surface. In addition, the adhesive layer 12 is provided in direct contact with the first surface (concavo-convex surface) 11 a of the substrate 11, and the second surface 12 b of the adhesive layer 12 can easily follow the first surface 11 a of the substrate 11. Therefore, the second surface 12b of the adhesive layer 12 also has an uneven surface.
黏著劑層12臨基材側相鄰凸部頂點間的節距並非固定，依照黏著劑層12的部位會有變動。此處，將黏著劑層12的的節距依元件符號Pa1 、Pa2 及Pa3 表示。The pitch between the apexes of the adjacent convex portions adjacent to the base material side of the adhesive layer 12 is not fixed, and may vary according to the location of the adhesive layer 12. Here, the pitch of the adhesive layer 12 is represented by element symbols P a1 , P a2, and P a3 .
保護膜形成用複合片1A中，從其5個地方切取試驗片，再在這5片試驗片形成截面，再在此新形成的截面分別求取黏著劑層的的節距值(上述Pa1 、Pa2 及Pa3 值)。然後，計算出上述節距的平均值Pa (上述Pa1 、Pa2 及Pa3 的平均值)，再從至少5個Pa 值求取平均值(上述P值)，結果係3μm以上且未滿15μm。In the protective film-forming composite sheet 1A, test pieces were cut out from five places, and sections were formed on these five test pieces. Then, the pitch value of the adhesive layer was obtained from the newly formed sections (the above P a1). , P a2 and P a3 values). Then, calculate the average value P a of the pitch (the average value of the P a1 , P a2, and P a3 ), and then calculate the average value (the P value) from at least 5 P a values. The result is 3 μm or more and It is less than 15 μm.
從保護膜形成用複合片1A切取試驗片、試驗片的截面形成、上述截面的黏著劑層節距測定，係如前所說明，可依照與從尚未構成保護膜形成用複合片的支撐片切取試驗片之情況同樣地實行。The test piece, the cross-section formation of the test piece, and the measurement of the adhesive layer pitch of the above-mentioned cross-section were cut from the composite sheet for protective film formation 1A, as described above. The same applies to the test piece.
黏著劑層12的厚度Ta 並非固定，依照黏著劑層12的部位會有變動。此處，黏著劑層12的厚度最小值以符號Ta1 表示，黏著劑層12的厚度最大值以符號Ta2 表示。The thickness T a of the adhesive layer 12 is not fixed, and varies depending on the location of the adhesive layer 12. Here, the minimum thickness of the adhesive layer 12 is represented by the symbol T a1 , and the maximum thickness of the adhesive layer 12 is represented by the symbol T a2 .
保護膜形成用複合片1A中，從其5個地方切取試驗片， 在這5片試驗片形成截面，並就此新形成的截面分別求取黏著劑層的厚度最小值Ta1 與最大值Ta2 。然後，從至少5個Ta1 值求取其平均值(上述S值)，結果為1.5μm以上，且從至少5個Ta2 值求取其平均值(上述L值)，結果係9μm以下。In the protective film forming composite sheet 1A, test pieces were cut out from five places, and the five test pieces were formed into cross sections. The newly formed cross sections were used to obtain the minimum thickness T a1 and the maximum value T a2 of the adhesive layer. . Then, an average value (the above-mentioned S value) was obtained from at least five T a1 values, and the result was 1.5 μm or more, and an average value (the above-mentioned L value) was obtained from at least five T a2 values, and the result was 9 μm or less.
從保護膜形成用切取複合片1A的試驗片、試驗片的截面形成、上述截面的黏著劑層厚度最小值Ta1 與最大值Ta2 測定，係如前所說明，可依照與從尚未構成保護膜形成用複合片的支撐片切取試驗片之情況同樣地實行。The test piece of the composite film 1A cut out for the formation of the protective film, the cross-section formation of the test piece, and the minimum thickness T a1 and the maximum value T a2 of the adhesive layer thickness of the above-mentioned cross section were measured as described above. The same applies to the case where a test piece is cut out from the support sheet of the film-forming composite sheet.
另外，尚未構成保護膜形成用複合片的支撐片之放大剖視圖，係與圖4中省略圖示保護膜形成用薄膜13的情況相同。In addition, an enlarged cross-sectional view of a supporting sheet that has not yet constituted a protective film-forming composite sheet is the same as the case where the protective film-forming film 13 is omitted in FIG. 4.
作為保護膜形成用複合片1A，此處顯示在基材11與黏著劑層12之間，存在有其未貼合的區域(本說明書中亦稱「未貼合區域」)91。但，即便保護膜形成用複合片1A具有此種未貼合區域91，在保護膜形成用複合片1A厚度方向上的未貼合區域91大小例如為0.5μm以下的保護膜形成用複合片1A，其基材11與黏著劑層12間之積層性仍良好，可謂具有良好特性。As the protective film-forming composite sheet 1A, it is shown here that there is an unattached region (also referred to as "unattached region" in this specification) 91 between the substrate 11 and the adhesive layer 12. However, even if the composite sheet 1A for protective film formation has such an unbonded region 91, the size of the non-bonded region 91 in the thickness direction of the composite film 1A for protective film formation is, for example, a composite sheet 1A for protective film formation having a size of, for example, 0.5 μm or less. The stackability between the substrate 11 and the adhesive layer 12 is still good, which can be said to have good characteristics.
另外，本說明書中，所謂「在保護膜形成用複合片厚度方向的未貼合區域大小」，係指「保護膜形成用複合片中，相鄰2層在上述片的厚度方向之層間距離」，有時簡稱「層間距離」。例如上述「在保護膜形成用複合片1A的厚度方向之未貼合區域91大小」，係指「在上述片1A的厚度方向之基材11與黏著劑層12間的層間距離」。
當1個地方的未貼合區域大小(層間距離)有變動時，便將最大值採用為未貼合區域的大小(層間距離)。In addition, in this specification, "the size of the non-bonded area in the thickness direction of the protective film-forming composite sheet" means "the distance between two adjacent layers in the thickness direction of the said sheet in the protective film-forming composite sheet" , Sometimes referred to as "the distance between layers". For example, the above-mentioned "the size of the non-bonded area 91 in the thickness direction of the protective film-forming composite sheet 1A" means "the interlayer distance between the substrate 11 and the adhesive layer 12 in the thickness direction of the sheet 1A".
When the size (distance between layers) of the non-adhesion area at one place changes, the maximum value is adopted as the size (distance between layers) of the non-adhesion area.
未貼合區域的大小(層間距離)係可依照與例如上述黏著劑層P值的情況同樣方法進行測定。即，依照與求取黏著劑層之P值時的相同方法，在保護膜形成用複合片的試驗片中形成截面，再在此截面便可求取未貼合區域的大小。或者，亦可在未製作試驗片情況下，以保護膜形成用複合片自體形成截面，再在此截面求取未貼合區域的大小。The size (distance between layers) of the non-adhered regions can be measured in the same manner as in the case of the P-value of the adhesive layer described above. That is, in the same manner as when the P value of the adhesive layer is obtained, a cross section is formed in a test piece of the protective film-forming composite sheet, and the size of the non-bonded area can be obtained from this cross section. Alternatively, when a test piece is not produced, a cross section may be formed by the protective sheet-forming composite sheet itself, and the size of the non-adhered region may be determined on this cross section.
未貼合區域91的大小(上述層間距離)係例如可為0.4μm以下、0.3μm以下、0.2μm以下及0.1μm以下中之任一者。The size (the interlayer distance) of the non-adhered region 91 may be any one of, for example, 0.4 μm or less, 0.3 μm or less, 0.2 μm or less, and 0.1 μm or less.
保護膜形成用複合片1A亦有完全沒有存在未貼合區域91的情形。In the protective film-forming composite sheet 1A, the non-adhered region 91 may not be present at all.
此處舉保護膜形成用複合片1A為例，針對基材與黏著劑層進行說明，但關於保護膜形成用複合片1B、保護膜形成用複合片1C等之其他實施形態的保護膜形成用複合片的情況，亦是同樣的基材與黏著劑層。Here, the protective film forming composite sheet 1A is taken as an example to describe the substrate and the adhesive layer. However, the protective film forming composite sheet 1B, the protective film forming composite sheet 1C, and other embodiments of the protective film formation are described. In the case of a composite sheet, the same substrate and adhesive layer are also used.
黏著劑層的P值係在3μm以上、且未滿15μm之前提下，則無特別的限定。
黏著劑層的P值以未滿14μm為佳、較佳係未滿13μm、更佳係未滿12μm、特佳係未滿11μm，例如可為未滿8.5μm及未滿6μm中之任一者。藉由上述P值未滿上述上限值，使基材與黏著劑層間之密接性良好。The P value of the adhesive layer is not particularly limited as long as it is lower than 3 μm and less than 15 μm.
The P value of the adhesive layer is preferably less than 14 μm, preferably less than 13 μm, more preferably less than 12 μm, and particularly preferably less than 11 μm. For example, it may be any of less than 8.5 μm and less than 6 μm. . When the P value is less than the upper limit value, the adhesion between the substrate and the adhesive layer is made good.
另一方面，黏著劑層的P值係3μm以上、以3.5μm以上為佳、較佳係4μm以上、更佳係4.5μm以上、特佳係5μm以上，例如可為5.5μm以上及8μm以上中之任一者。藉由上述P值達上述下限值以上，使保護膜或保護膜形成用薄膜隔著支撐片的刻印檢視性呈良好。On the other hand, the P value of the adhesive layer is 3 μm or more, preferably 3.5 μm or more, more preferably 4 μm or more, more preferably 4.5 μm or more, and particularly preferably 5 μm or more. For example, it may be 5.5 μm or more and 8 μm or more. Either. When the P value is equal to or more than the lower limit value, the marking visibility of the protective film or the film for forming a protective film through the supporting sheet is improved.
黏著劑層的P值係可在上述較佳下限值與上限值任意組合設定的範圍內適當調整。例如黏著劑層的P值以3.5μm以上且未滿14μm為佳、較佳係4μm以上且未滿13μm、更佳係4.5μm以上且未滿12μm、特佳係5μm以上且未滿11μm。但，這些僅為黏著劑層的P值的一例。The P value of the adhesive layer can be appropriately adjusted within a range set by any combination of the above-mentioned preferred lower limit value and upper limit value. For example, the P value of the adhesive layer is preferably 3.5 μm or more and less than 14 μm, more preferably 4 μm or more and less than 13 μm, more preferably 4.5 μm or more and less than 12 μm, and particularly preferably 5 μm or more and less than 11 μm. However, these are only examples of the P value of the adhesive layer.
黏著劑層的厚度係與前所說明的方法同樣，從上述支撐片的5個地方切取試驗片，再在這5片試驗片分別求取黏著劑層的厚度最小值與最大值時，較佳係上述最小值的平均值(本說明書中亦稱「S值」)達1.5μm以上，且最大值的平均值(本說明書中亦稱「L值」)在9μm以下。The thickness of the adhesive layer is the same as the method described above. It is preferable to cut out test pieces from five places of the support sheet, and then determine the minimum and maximum thicknesses of the adhesive layer on the five test pieces. The average value of the minimum value (also referred to as “S value” in this specification) is 1.5 μm or more, and the average value of the maximum value (also referred to as “L value” in this specification) is 9 μm or less.
藉由上述黏著劑層的S值達1.5μm以上，便輕易使黏著劑層與保護膜形成用薄膜間之積層性良好。本說明書中所謂「積層性」在無特別聲明前提下，係指對象2層的積層狀態的正常度。所謂「積層性良好」係指例如對象的相鄰2層間完全沒有未貼合區域(空隙部)、或未貼合區域數量少且未貼合區域的層間距離小。
另一方面，藉由上述黏著劑層的L值在9μm以下，便輕易使保護膜或保護膜形成用薄膜隔著支撐片的刻印檢視性呈良好。When the S value of the above-mentioned adhesive layer reaches 1.5 μm or more, the build-up property between the adhesive layer and the film for forming a protective film is easily made good. The so-called "layering property" in this specification refers to the normality of the layering state of the target two layers unless otherwise specified. The term “good stackability” means that, for example, there are no unbonded areas (voids) between two adjacent layers of the object, or the number of unbonded areas is small and the interlayer distance between the unbonded areas is small.
On the other hand, when the L value of the above-mentioned adhesive layer is 9 μm or less, the marking visibility of the protective film or the film for forming a protective film through the supporting sheet is easily improved.
黏著劑層的S值較佳係1.5μm以上且未滿9μm、更佳係1.7μm以上、特佳係1.9μm以上，例如可為2.3μm以上、2.7μm以上、3.1μm以上及3.5μm以上中之任一者。藉由上述S值達上述下限值以上，便使黏著劑層與保護膜形成用薄膜的積層性更良好。The S value of the adhesive layer is preferably 1.5 μm or more and less than 9 μm, more preferably 1.7 μm or more, and particularly preferably 1.9 μm or more. For example, it may be 2.3 μm or more, 2.7 μm or more, 3.1 μm or more, and 3.5 μm or more. Either. When the S value is equal to or more than the lower limit value described above, the build-up property of the adhesive layer and the protective film-forming film is further improved.
另一方面，黏著劑層的S值係可例如8μm以下。此種黏著劑層係可更輕易形成。On the other hand, the S value of the adhesive layer may be, for example, 8 μm or less. Such an adhesive layer system can be formed more easily.
黏著劑層的S值係可在上述較佳下限值與上限值任意組合設定的範圍內適當調整。例如黏著劑層的S值較佳係1.5~8μm、更佳係1.7~8μm、特佳係1.9~8μm，例如亦可為2.3~8μm、2.7~8μm、3.1~8μm及3.5~8μm中之任一者。但，這些僅為黏著劑層的S值的一例。The S value of the adhesive layer can be appropriately adjusted within a range set by any combination of the above-mentioned preferred lower limit value and upper limit value. For example, the S value of the adhesive layer is preferably 1.5 to 8 μm, more preferably 1.7 to 8 μm, and particularly preferably 1.9 to 8 μm. For example, it may be any of 2.3 to 8 μm, 2.7 to 8 μm, 3.1 to 8 μm, and 3.5 to 8 μm. One. However, these are only examples of the S value of the adhesive layer.
黏著劑層的S值係可在上述較佳下限值與上限值任意組合設定的範圍內適當調整。例如黏著劑層的S值較佳係1.5~8μm、更佳係1.7~8μm、特佳係1.9~8μm，例如亦可為2.3~8μm、2.7~8μm、3.1~8μm及3.5~8μm中之任一者。但，這些僅為黏著劑層的S值的一例。The S value of the adhesive layer can be appropriately adjusted within a range set by any combination of the above-mentioned preferred lower limit value and upper limit value. For example, the S value of the adhesive layer is preferably 1.5 to 8 μm, more preferably 1.7 to 8 μm, and particularly preferably 1.9 to 8 μm. For example, it may be any of 2.3 to 8 μm, 2.7 to 8 μm, 3.1 to 8 μm, and 3.5 to 8 μm. One. However, these are only examples of the S value of the adhesive layer.
黏著劑層的L值較佳係9μm以下且大於1.5μm、更佳係8.6μm以下、特佳係8.3μm以下，例如可為7.7μm以下、7.3μm以下、6.9μm以下及6.5μm以下中之任一者。藉由上述L值在上述上限值以下，便使保護膜或保護膜形成用薄膜隔著支撐片的刻印檢視性更良好。The L value of the adhesive layer is preferably 9 μm or less and greater than 1.5 μm, more preferably 8.6 μm or less, and particularly preferably 8.3 μm or less. For example, it may be 7.7 μm or less, 7.3 μm or less, 6.9 μm or less, and 6.5 μm or less. Either. When the L value is equal to or less than the upper limit value, the marking visibility of the protective film or the film for forming a protective film through the supporting sheet is better.
另一方面，黏著劑層的L值亦可例如2.5μm以上。此種黏著劑層係可更輕易形成。On the other hand, the L value of the adhesive layer may be, for example, 2.5 μm or more. Such an adhesive layer system can be formed more easily.
黏著劑層的L值係可在上述較佳下限值與上限值任意組合設定的範圍內適當調整。例如黏著劑層的L值較佳係2.5~9μm、更佳係2.5~8.6μm、特佳係2.5~8.3μm，例如可為2.5~7.7μm、2.5~7.3μm、2.5~6.9μm及2.5~6.5μm中之任一者。The L value of the adhesive layer can be appropriately adjusted within a range set by any combination of the above-mentioned preferred lower limit value and upper limit value. For example, the L value of the adhesive layer is preferably 2.5 to 9 μm, more preferably 2.5 to 8.6 μm, and particularly good 2.5 to 8.3 μm. For example, it may be 2.5 to 7.7 μm, 2.5 to 7.3 μm, 2.5 to 6.9 μm, and 2.5 to Any of 6.5 μm.
黏著劑層的厚度(例如Ta
)係在不致損及本發明效果之前提下，並無特別的限定，以滿足上述S值與L值的條件為佳。
例如黏著劑層的厚度亦可為1.5~9μm。The thickness (for example, T a ) of the adhesive layer is set before it does not impair the effect of the present invention, and is not particularly limited, and it is better to satisfy the conditions of the above-mentioned S value and L value.
For example, the thickness of the adhesive layer may be 1.5 to 9 μm.
另外，所謂「黏著劑層的厚度」係指黏著劑層全體的厚度，例如由複數層構成的黏著劑層的厚度，便指構成黏著劑層的所有層之合計厚度。依照此種觀點規定上述黏著劑層的厚度最小值與最大值。The "thickness of the adhesive layer" refers to the thickness of the entire adhesive layer. For example, the thickness of an adhesive layer composed of a plurality of layers means the total thickness of all the layers constituting the adhesive layer. According to such a viewpoint, the minimum and maximum thicknesses of the adhesive layer are specified.
黏著劑層係含有黏著劑。
上述黏著劑係可舉例如:丙烯酸系樹脂、胺甲酸乙酯系樹脂、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，較佳係丙烯酸系樹脂。The adhesive layer contains an adhesive.
Examples of the adhesives include acrylic resins, urethane resins, rubber resins, silicone resins, epoxy resins, polyvinyl ethers, polycarbonates, and ester resins. It is preferably an acrylic resin.
本說明書中，所謂「黏著性樹脂」係包含具黏著性樹脂、與具接著性樹脂雙方的概念，例如不僅樹脂自體具有黏著性者，亦包含藉由併用添加劑等其他成分而呈現黏著性的樹脂、藉由熱或水等觸發物(trigger)存在而呈現接著性的樹脂等。In this specification, the term "adhesive resin" includes both the concept of an adhesive resin and an adhesive resin. For example, not only the resin itself has adhesiveness, but also those that exhibit adhesiveness by using other components such as additives in combination. Resin, resin that exhibits adhesiveness when a trigger such as heat or water is present.
黏著劑層較佳係呈透明。
黏著劑層亦可配合目的被著色。
例如當保護膜形成用薄膜為能量線硬化性的情況，黏著劑層以使能量線穿透為佳。The adhesive layer is preferably transparent.
The adhesive layer can also be colored according to the purpose.
For example, when the protective film-forming film is energy ray-curable, the adhesive layer is preferably made to penetrate the energy ray.
黏著劑層亦可使用能量線硬化性黏著劑形成，亦可使用非能量線硬化性黏著劑形成。使用能量線硬化性黏著劑形成的黏著劑層，可輕易調整硬化前與硬化後的物性。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 using the energy ray hardening adhesive can easily adjust the physical properties before and after hardening.
＜＜黏著劑組成物＞＞
黏著劑層可使用含有黏著劑的黏著劑組成物來形成。例如在黏著劑層形成標的面塗佈黏著劑組成物，視需要施行乾燥，便可在目標部位處形成黏著劑層。關於黏著劑層的更具體形成方法，會與其外之層的形成方法一併在後詳述。黏著劑組成物中常溫下不會氣化之成分間的含有量比率，通常同黏著劑層的上述成分間之含有量比率。＜＜ Adhesive composition ＞＞
The adhesive layer can be formed using an adhesive composition containing an adhesive. For example, an adhesive composition is coated on the surface of the adhesive layer forming target, and if necessary, drying is performed to form an adhesive layer at a target portion. A more specific method of forming the adhesive layer will be described in detail later along with the method of forming the outer layer. The content ratio between the components in the adhesive composition that does not vaporize at normal temperature is usually the same as the content ratio between the above components of the adhesive layer.
本說明書中，所謂「常溫」係指不會特別冷、或特別熱的溫度，即平常的溫度，例如15~25℃的溫度等。In this specification, the "normal temperature" refers to a temperature that is not particularly cold or extremely hot, that is, a normal temperature, such as a temperature of 15 to 25 ° C.
黏著劑組成物的塗佈係可利用公知方法實施，例如使用氣刀塗佈機（Air-knife-coater）、刮刀塗佈機（Blade-coater）、棒式塗佈機（Bar-coater）、凹版塗佈機（Gravure-coater）、輥式塗佈機（Roll-coater）、輥式刀塗機（Roll-knife-coater）、淋幕塗佈機（Curtain-coater）、模塗機（Die-Coater）、刀塗機（Knife-coater）、網版塗佈機（Screen-coater）、麥勒棒塗機（Meyer-bar-coater）、吻合式塗佈機（Kiss-coater）等各種塗佈機的方法。The application of the adhesive composition can be performed by a known method, for example, using an air-knife-coater, a blade-coater, a bar-coater, Gravure-coater, Roll-coater, Roll-knife-coater, Curtain-coater, Die coater -Coater, Knife-coater, Screen-coater, Meyer-bar-coater, Kiss-coater, etc. Method of cloth deployment.
黏著劑組成物的乾燥條件並無特別的限定，當黏著劑組成物係含有後述溶劑的情況，以施行加熱乾燥為佳。含有溶劑的黏著劑組成物是以以例如70~130℃、10秒~5分鐘的條件施行乾燥為佳。The drying conditions of the adhesive composition are not particularly limited. When the adhesive composition contains a solvent described later, it is preferable to perform heat drying. The solvent-containing adhesive composition is preferably dried under conditions of, for example, 70 to 130 ° C. for 10 seconds to 5 minutes.
當黏著劑層為能量線硬化性的情況，含有能量線硬化性黏著劑的黏著劑組成物(即，能量線硬化性黏著劑組成物)，係可舉例如:含有非能量線硬化性黏著性樹脂(I-1a)(以下簡稱「黏著性樹脂(I-1a)」)、與能量線硬化性化合物的黏著劑組成物(I-1)；含有經在非能量線硬化性黏著性樹脂(I-1a)的側鏈，導入不飽和基的能量線硬化性黏著性樹脂(I-2a)(以下簡稱「黏著性樹脂(I-2a)」)之黏著劑組成物(I-2)；含有上述黏著性樹脂(I-2a)、與能量線硬化性化合物的黏著劑組成物(I-3)等。When the adhesive layer is energy-ray-curable, the adhesive composition containing the energy-ray-curable adhesive (ie, the energy-ray-curable adhesive composition) may include, for example, non-energy-ray-curable adhesive. Resin (I-1a) (hereinafter referred to as "adhesive resin (I-1a)"), and an adhesive composition (I-1) with an energy ray-curable compound; it contains a non-energy ray-curable adhesive resin ( The side chain of I-1a) is an adhesive composition (I-2) of an energy ray-curable adhesive resin (I-2a) (hereinafter referred to as "adhesive resin (I-2a)") having an unsaturated group introduced therein; An adhesive composition (I-3) containing the above-mentioned adhesive resin (I-2a) and an energy ray-curable compound, and the like.
＜黏著劑組成物(I-1)＞
上述黏著劑組成物(I-1)係如上述，含有非能量線硬化性黏著性樹脂(I-1a)、與能量線硬化性化合物。＜ Adhesive composition (I-1) ＞
The said adhesive composition (I-1) is a non-energy-ray-curable adhesive resin (I-1a) and an energy-ray-curable compound as mentioned above.
[黏著性樹脂(I-1a)]
上述黏著性樹脂(I-1a)較佳係丙烯酸系樹脂。
上述丙烯酸系樹脂係可舉例如至少具有由(甲基)丙烯酸烷基酯所衍生構成單元的丙烯酸系聚合體。
上述丙烯酸系樹脂所具有的構成單元係可僅為1種、亦可為2種以上，當2種以上的情況，其組合與比率係可任意選擇。[Adhesive resin (I-1a)]
The adhesive resin (I-1a) is preferably an acrylic resin.
Examples of the acrylic resin system include an acrylic polymer having at least a structural unit derived from an alkyl (meth) acrylate.
The constituent units of the acrylic resin may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be arbitrarily selected.
上述(甲基)丙烯酸烷基酯係可例如構成烷基酯的烷基碳數為1~20者，而上述烷基較佳係直鏈狀或分支鏈狀。
(甲基)丙烯酸烷基酯更具體係可舉例如:(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)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(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)丙烯酸肉荳蔻酯)、(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)丙烯酸廿烷基酯等。The (meth) acrylic acid alkyl ester may be, for example, one having an alkyl carbon number of 1 to 20, and the alkyl group is preferably linear or branched.
More examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( N-butyl methacrylate, isobutyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, amyl (meth) acrylate, (meth) acrylic acid Hexyl ester, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate , Isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), ( Tridecyl (meth) acrylate, Tetradecyl (meth) acrylate (Myristyl (meth) acrylate), Pentadecyl (meth) acrylate, Hexadecyl (meth) acrylate Base ester (palm (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), decyl (meth) acrylate Nine alkyl esters, alkyl alkyl (meth) acrylates, etc. .
就從提升黏著劑層的黏著力的觀點，上述丙烯酸系聚合體較佳係具有由上述烷基碳數4以上之(甲基)丙烯酸烷基酯所衍生的構成單元。而，就從更加提升黏著劑層黏著力的觀點，上述烷基的碳數較佳係4~12、更佳係4~8。又，上述烷基碳數達4以上的(甲基)丙烯酸烷基酯較佳係丙烯酸烷基酯。From the viewpoint of improving the adhesive force of the adhesive layer, the acrylic polymer preferably has a structural unit derived from the (meth) acrylic acid alkyl ester having an alkyl carbon number of 4 or more. However, from the viewpoint of further improving the adhesive force of the adhesive layer, the carbon number of the alkyl group is preferably 4-12, and more preferably 4-8. The (meth) acrylic acid alkyl ester having an alkyl carbon number of 4 or more is preferably an alkyl acrylate.
上述丙烯酸系聚合體由(甲基)丙烯酸烷基酯所衍生構成單元之外，以還具有由含官能基之單體所衍生的構成單元為佳。
上述含官能基單體，可列舉藉由上述官能基與後述交聯劑進行反應而成為交聯起點、藉由上述官能基與後述含不飽和基化合物中的不飽和基進行反應等，便可在丙烯酸系聚合體的側鏈中導入不飽和基者。The acrylic polymer preferably has a structural unit derived from a functional group-containing monomer in addition to the structural unit derived from an alkyl (meth) acrylate.
Examples of the functional group-containing monomer include a reaction starting point of the crosslinking reaction between the functional group and a crosslinking agent described later, and a reaction of the functional group with an unsaturated group in the unsaturated group-containing compound described later. An unsaturated group is introduced into the side chain of the acrylic polymer.
含官能基單體中的上述官能基係可舉例如:羥基、羧基、胺基、環氧基等。
即，含官能基單體係可舉例如:含羥基單體、含羧基單體、含胺基單體、含環氧基單體等。Examples of the functional group in the functional group-containing monomer include a hydroxyl group, a carboxyl group, an amine group, and an epoxy group.
That is, the functional group-containing monosystem may include, for example, a hydroxyl-containing monomer, a carboxyl-containing monomer, an amine-containing monomer, an epoxy-containing monomer, and the like.
上述含羥基單體係可舉例如:(甲基)丙烯酸羥甲酯、(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸-3-羥丙酯、(甲基)丙烯酸-2-羥丁酯、(甲基)丙烯酸-3-羥丁酯、(甲基)丙烯酸-4-羥丁酯等(甲基)丙烯酸羥烷基酯；乙烯醇、烯丙醇等非(甲基)丙烯酸系不飽和醇(未具(甲基)丙烯醯基骨架的不飽和醇)等。Examples of the above-mentioned hydroxyl-containing monosystem include: hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and -3 (meth) acrylate -Hydroxyalkyl (meth) acrylates such as hydroxypropyl ester, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. ; Non- (meth) acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols without a (meth) acrylfluorenyl skeleton) and the like.
上述含羧基單體係可舉例如:(甲基)丙烯酸、巴豆酸等乙烯性不飽和單羧酸(具乙烯性不飽和鍵的單羧酸)；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(具乙烯性不飽和鍵的二羧酸)；上述乙烯性不飽和二羧酸的酸酐；甲基丙烯酸-2-羧乙酯等(甲基)丙烯酸羧烷基酯等等。Examples of the carboxyl-containing monosystem include: (meth) acrylic acid, crotonic acid and other ethylenically unsaturated monocarboxylic acids (monocarboxylic acids with ethylenically unsaturated bonds); fumaric acid, itaconic acid, cis Ethylene unsaturated dicarboxylic acids such as butenedioic acid and citraconic acid (dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the above ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. Carboxyalkyl (meth) acrylates and the like.
含官能基單體較佳係含羥基單體、含羧基單體，更佳係含羥基單體。The functional group-containing monomer is preferably a hydroxyl-containing monomer or a carboxyl-containing monomer, and more preferably a hydroxyl-containing monomer.
構成上述丙烯酸系聚合體的含官能基單體係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The functional group-containing single system constituting the acrylic polymer may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be arbitrarily selected.
上述丙烯酸系聚合體中，由含官能基單體所衍生構成單元的含有量，相對於構成單元總量，較佳係1~35質量%、更佳係2~30質量%、特佳係3~27質量%。In the above-mentioned acrylic polymer, the content of the structural unit derived from the functional group-containing monomer is preferably 1 to 35% by mass, more preferably 2 to 30% by mass, and particularly good to 3 based on the total amount of the structural unit. ~ 27% by mass.
上述丙烯酸系聚合體係由(甲基)丙烯酸烷基酯所衍生構成單元、及由含官能基單體所衍生構成單元之外，尚亦可更進一步具有由其他單體所衍生的構成單元。
上述其他單體係在能與(甲基)丙烯酸烷基酯等進行共聚之前提下，其餘並無特別的限定。
上述其他單體係可舉例如:苯乙烯、α-甲基苯乙烯、乙烯基甲苯、甲酸乙烯酯、醋酸乙烯酯、丙烯腈、丙烯醯胺等。The acrylic polymerization system described above may further include a structural unit derived from an alkyl (meth) acrylate and a structural unit derived from a functional group-containing monomer, and may further include a structural unit derived from another monomer.
The other single systems mentioned above are extracted before being copolymerized with alkyl (meth) acrylate and the like, and the rest are not particularly limited.
Examples of the other single systems include styrene, α-methylstyrene, vinyl toluene, vinyl formate, vinyl acetate, acrylonitrile, and acrylamide.
構成上述丙烯酸系聚合體的上述其他單體係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The above-mentioned other single systems constituting the acrylic polymer may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
上述丙烯酸系聚合體係可使用為上述非能量線硬化性黏著性樹脂(I-1a)。
另一方面，使上述丙烯酸系聚合體中的官能基，與具能量線聚合性不飽和基(能量線聚合性基)的不飽和基含有化合物產生者，可使用上述能量線硬化性黏著性樹脂(I-2a)。The acrylic polymerization system may be the non-energy-ray-curable adhesive resin (I-1a).
On the other hand, if the functional group in the acrylic polymer and a compound containing an energy ray polymerizable unsaturated group (energy ray polymerizable group) contains a compound generator, the energy ray-curable adhesive resin may be used. (I-2a).
黏著劑組成物(I-1)所含有的黏著性樹脂(I-1a)係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。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 types, the combination and ratio thereof may be arbitrarily selected.
黏著劑組成物(I-1)中，黏著性樹脂(I-1a)的含有量較佳係5~99質量%、更佳係10~95質量%、特佳係15~90質量%。The content of the adhesive resin (I-1a) in the adhesive composition (I-1) is preferably 5 to 99% by mass, more preferably 10 to 95% by mass, and particularly good 15 to 90% by mass.
[能量線硬化性化合物]
黏著劑組成物(I-1)所含有的上述能量線硬化性化合物，係可舉例如具有能量線聚合性不飽和基，利用能量線照射便可硬化的單體或寡聚物。
能量線硬化性化合物中，單體係可舉例如:三羥甲基丙烷三[(甲基)丙烯酸酯]、新戊四醇(甲基)丙烯酸酯、新戊四醇四[(甲基)丙烯酸酯]、二新戊四醇六[(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；胺甲酸乙酯(甲基)丙烯酸酯；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。
能量線硬化性化合物中，寡聚物可列舉由上述所例示單體進行聚合而成的寡聚物等。
能量線硬化性化合物係就從分子量較大、不易使黏著劑層之儲存彈性模數降低的觀點，較佳係胺甲酸乙酯(甲基)丙烯酸酯、胺甲酸乙酯(甲基)丙烯酸酯寡聚物。[Energy ray hardening compound]
Examples of the energy ray-curable compound contained in the adhesive composition (I-1) include monomers or oligomers that have an energy ray polymerizable unsaturated group and can be hardened by energy ray irradiation.
Among the energy ray-curable compounds, a single system may be, for example, trimethylolpropane tri [(meth) acrylate], neopentyl tetraol (meth) acrylate, neopentyl tetraki [(methyl) Acrylate], dipentaerythritol hexa [(meth) acrylate], 1,4-butanediol di [(meth) acrylate], 1,6-hexanediol (meth) acrylate, etc. Poly (meth) acrylates; urethane (meth) acrylates; polyester (meth) acrylates; polyether (meth) acrylates; epoxy (meth) acrylates and the like.
Examples of the energy ray-curable compound include oligomers obtained by polymerizing the monomers exemplified above.
The energy ray-curable compound is preferably a urethane (meth) acrylate or a urethane (meth) acrylate from the viewpoint that the molecular weight is large and the storage elastic modulus of the adhesive layer is not easily reduced. Oligomer.
黏著劑組成物(I-1)所含有的上述能量線硬化性化合物係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The energy ray-curable compound contained in the adhesive composition (I-1) may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
上述黏著劑組成物(I-1)中，上述能量線硬化性化合物的含有量較佳係1~95質量%、更佳係5~90質量%、特佳係10~85質量%。The content of the energy ray-curable compound in the adhesive composition (I-1) is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, and particularly preferably 10 to 85% by mass.
[交聯劑]
黏著性樹脂(I-1a)係由(甲基)丙烯酸烷基酯所衍生構成單元之外，更進一步使用具有由含官能基單體所衍生構成單元的上述丙烯酸系聚合體時，黏著劑組成物(I-1)較佳係更進一步含有交聯劑。[Crosslinking agent]
The adhesive resin (I-1a) is composed of an adhesive in addition to the structural unit derived from an alkyl (meth) acrylate, and when the above-mentioned acrylic polymer having a structural unit derived from a functional group-containing monomer is used. The substance (I-1) preferably further contains a crosslinking agent.
上述交聯劑係例如與上述官能基產生反應，而使黏著性樹脂(I-1a)彼此間進行交聯者。
交聯劑係可舉例如:二異氰酸甲苯酯、六亞甲基二異氰酸酯、二異氰酸伸苯二甲酯、這些二異氰酸酯的加成體等異氰酸酯系交聯劑(具異氰酸酯基之交聯劑)；乙二醇環氧丙醚等環氧系交聯劑(具環氧丙基之交聯劑)；六[1-(2-甲基)-吖丙啶基]三磷酸三嗪等氮丙啶系交聯劑(具吖丙啶基之交聯劑)；鋁螯合等金屬螯合系交聯劑(具金屬螯合構造之交聯劑)；異三聚氰酸酯系交聯劑(具異三聚氰酸骨架之交聯劑)等。
就從提升黏著劑凝聚力，俾提升黏著劑層黏著力的觀點，以及可輕易取得等觀點，交聯劑較佳係異氰酸酯系交聯劑。The crosslinking agent is, for example, one that reacts with the functional group and crosslinks the adhesive resin (I-1a) with each other.
Examples of the crosslinking agent include isocyanate-based crosslinking agents such as toluene diisocyanate, hexamethylene diisocyanate, phenylene diisocyanate, and adducts of these diisocyanates (such as those having isocyanate groups). Cross-linking agent); Epoxy-based cross-linking agents such as ethylene glycol propylene ether (cross-linking agent with epoxy propyl group); hexa [1- (2-methyl) -aziridinyl] triphosphate triphosphate Azine and other aziridine-based crosslinkers (crosslinkers with aziridinyl); metal chelate crosslinkers such as aluminum chelate (crosslinkers with metal chelate structure); isocyanurates Cross-linking agent (cross-linking agent with isocyanuric acid skeleton) and the like.
From the viewpoints of improving the cohesive force of the adhesive, increasing the adhesive force of the adhesive layer, and easily obtaining, the crosslinking agent is preferably an isocyanate crosslinking agent.
黏著劑組成物(I-1)所含有的交聯劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The crosslinking agent system contained in the adhesive composition (I-1) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
上述黏著劑組成物(I-1)中，交聯劑的含有量，相對於黏著性樹脂(I-1a)含有量100質量份，較佳係0.01~50質量份、更佳係0.1~20質量份、特佳係0.3~15質量份。The content of the crosslinking agent in the adhesive composition (I-1) is 100 parts by mass relative to the content of the adhesive resin (I-1a), preferably 0.01 to 50 parts by mass, and more preferably 0.1 to 20 Mass parts, particularly good 0.3 to 15 mass parts.
[光聚合起始劑]
黏著劑組成物(I-1)亦可更進一步含有光聚合起始劑。含有光聚合起始劑的黏著劑組成物(I-1)即便照射紫外線等較低能量的能量線，仍充分進行硬化反應。[Photopolymerization initiator]
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 low energy energy rays such as ultraviolet rays, the curing reaction proceeds sufficiently.
上述光聚合起始劑係可舉例如:苯偶姻、苯偶姻甲醚、苯偶姻乙醚、苯偶姻異丙醚、苯偶姻異丁醚、苯偶姻安息香酸、苯偶姻安息香酸甲酯、苯偶姻二甲縮酮等苯偶姻化合物；苯乙酮、2-羥-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化氧化膦化合物；苄基苯硫醚、單硫化四甲胺硫甲醯等硫醚化合物；1-羥環己基苯酮等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；氧硫等氧硫化合物；過氧化合物；二乙醯等二酮化合物；苄基；二苄基；二苯基酮；2,4-二乙基氧硫；1,2-二苯甲烷；2-羥-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等。
再者，上述光聚合起始劑亦可使用例如:1-氯蒽醌等醌化合物；胺等光增感劑等。Examples of the photopolymerization initiator system include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, and benzoin benzoin. Benzoin compounds such as methyl ester, benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 2,2-dimethoxy- Acetophenone compounds such as 1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzylidene) phenylphosphine oxide, 2,4,6-trimethylbenzene Halogenated phosphine oxide compounds such as methylphenyl diphenylphosphine oxide; thioether compounds such as benzyl phenyl sulfide and tetramethylamine thioformamidine monosulfide; α-keto alcohol compounds such as 1-hydroxycyclohexyl phenone; azo Azo compounds such as bisisobutyronitrile; titanocene compounds such as titanocene; oxygen and sulfur Isosulfur Compounds; peroxy compounds; dione compounds such as diethylfluorene; benzyl; dibenzyl; diphenyl ketone; 2,4-diethyloxosulfide ; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] acetone; 2-chloroanthraquinone and the like.
In addition, as the photopolymerization initiator, for example, a quinone compound such as 1-chloroanthraquinone; a photosensitizer such as amine or the like can be used.
黏著劑組成物(I-1)所含有的光聚合起始劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The photopolymerization initiator system 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 types, the combination and ratio thereof may be arbitrarily selected.
黏著劑組成物(I-1)中，光聚合起始劑的含有量，相對於上述能量線硬化性化合物含有量100質量份，較佳係0.01~20質量份、更佳係0.03~10質量份、特佳係0.05~5質量份。The content of the photopolymerization initiator in the adhesive composition (I-1) is 100 parts by mass relative to the content of the energy ray-curable compound, preferably 0.01 to 20 parts by mass, and more preferably 0.03 to 10 parts by mass. Parts, particularly good quality, 0.05 to 5 parts by mass.
[其他添加劑]
黏著劑組成物(I-1)係在不致損及本發明效果之範圍內，亦可含有不隸屬上述任一成分的其他添加劑。
上述其他添加劑係可舉例如:抗靜電劑、抗氧化劑、軟化劑(可塑劑)、填充材(填料)、防銹劑、著色劑(顏料、染料)、增感劑、賦黏劑、反應阻滯劑、交聯促進劑(觸媒)等公知添加劑。
另外，所謂「反應阻滯劑」係抑制例如因在黏著劑組成物(I-1)中混入的觸媒作用，造成保存中的黏著劑組成物(I-1)進行非為目的之交聯反應。反應阻滯劑可列舉利用螯合對觸媒形成螯合錯合物者，更具體可列舉1分子中具有2個以上羰基(-C(=O)-)者。[Other additives]
The adhesive composition (I-1) is within a range that does not impair the effects of the present invention, and may contain other additives that are not affiliated with any of the above-mentioned components.
Examples of the other additives mentioned above include: antistatic agents, antioxidants, softeners (plasticizers), fillers (fillers), rust inhibitors, colorants (pigments, dyes), sensitizers, tackifiers, and reaction resistance Well-known additives such as retarders and crosslinking accelerators (catalysts).
In addition, the so-called "reaction blocker" suppresses, for example, a non-intended cross-linking of the adhesive composition (I-1) during storage due to a catalyst action mixed in the adhesive composition (I-1). reaction. Examples of the reaction blocker include those that form a chelate complex by a chelating catalyst, and more specifically, those having two or more carbonyl groups (-C (= O)-) in one molecule.
黏著劑組成物(I-1)所含有的其他添加劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The other additives contained in the adhesive composition (I-1) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
黏著劑組成物(I-1)中的其他添加劑含有量並無特別的限定，只要配合種類再行適當選擇便可。The content of other additives in the adhesive composition (I-1) is not particularly limited, as long as it is appropriately selected according to the type of blending.
[溶劑]
黏著劑組成物(I-1)亦可含有溶劑。黏著劑組成物(I-1)係藉由含有溶劑，而提升對塗佈標的面的塗佈適性。[Solvent]
The adhesive composition (I-1) may contain a solvent. The adhesive composition (I-1) improves the coating suitability to the surface of the coating target by containing a solvent.
上述溶劑較佳係有機溶劑，而上述有機溶劑係可舉例如:甲乙酮、丙酮等酮；醋酸乙酯等酯(羧酸酯)；四氫呋喃、二㗁烷等醚；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-丙醇等醇等等。The above solvents are preferably organic solvents, and the above organic solvents are, for example, ketones such as methyl ethyl ketone and acetone; esters (carboxylic acid esters) such as ethyl acetate; ethers such as tetrahydrofuran and dioxane; fats such as cyclohexane and n-hexane; Group hydrocarbons; aromatic hydrocarbons such as toluene and xylene; alcohols such as 1-propanol and 2-propanol; and the like.
上述溶劑係例如可在黏著性樹脂(I-1a)製造時所使用者未從黏著性樹脂(I-1a)去除情況下，直接使用於黏著劑組成物(I-1)，亦可在黏著劑組成物(I-1)製造時，另行添加與黏著性樹脂(I-1a)製造時所使用者相同或不同種類的溶劑。The above-mentioned solvent can be used directly in the adhesive composition (I-1), for example, when the user does not remove the adhesive resin (I-1a) during the production of the adhesive resin (I-1a). When the agent composition (I-1) is produced, a solvent which is the same as or different from that used by the user of the adhesive resin (I-1a) is separately added.
黏著劑組成物(I-1)所含有的溶劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The solvent contained in the adhesive composition (I-1) may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
黏著劑組成物(I-1)中的溶劑含有量並無特別的限定，只要適當調整便可。The solvent content in the adhesive composition (I-1) is not particularly limited, as long as it is appropriately adjusted.
＜黏著劑組成物(I-2)＞
上述黏著劑組成物(I-2)係如上述，含有在非能量線硬化性黏著性樹脂(I-1a)的側鏈，導入不飽和基後的能量線硬化性黏著性樹脂(I-2a)。＜ Adhesive composition (I-2) ＞
The said adhesive composition (I-2) is the energy-ray-curable adhesive resin (I-2a) which contains the side chain of a non-energy-ray-curable adhesive resin (I-1a) and introduce | transduced an unsaturated group as mentioned above. ).
[黏著性樹脂(I-2a)]
上述黏著性樹脂(I-2a)係例如藉由使黏著性樹脂(I-1a)中的官能基，與具能量線聚合性不飽和基的含不飽和基化合物進行反應便可獲得。[Adhesive resin (I-2a)]
The adhesive resin (I-2a) can be 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.
上述含不飽和基化合物係上述能量線聚合性不飽和基之外，更進一步具有藉由與黏著性樹脂(I-1a)中的官能基進行反應，便能與黏著性樹脂(I-1a)鍵結之基的化合物。
上述能量線聚合性不飽和基係可舉例如:(甲基)丙烯醯基、乙烯基(ethenyl group)、烯丙基(2-丙烯基)等，較佳係(甲基)丙烯醯基。
能與黏著性樹脂(I-1a)中之官能基鍵結的基，係可舉例如:能與羥基或胺基鍵結的異氰酸酯基及環氧丙基、以及能與羧基或環氧基鍵結的羥基及胺基等。The unsaturated group-containing compound is in addition to the energy ray polymerizable unsaturated group described above, and further has the ability to react with the adhesive resin (I-1a) by reacting with a functional group in the adhesive resin (I-1a). Bonded compounds.
Examples of the energy ray polymerizable unsaturated group include (meth) acrylfluorenyl, ethylene (ethenyl group), allyl (2-propenyl), and the like, and preferably (meth) acrylfluorenyl.
Examples of the group capable of bonding to a functional group in the adhesive resin (I-1a) include, for example, an isocyanate group and an epoxy group capable of bonding to a hydroxyl group or an amino group, and a bond to a carboxyl group or an epoxy group. Hydroxyl and amine groups.
上述含不飽和基化合物係可舉例如:異氰酸(甲基)丙烯醯氧基乙酯、(甲基)丙烯醯基異氰酸酯、(甲基)丙烯酸環氧丙酯等。Examples of the unsaturated group-containing compound system include (meth) acrylic fluorenyl ethyl isocyanate, (meth) acryl fluorenyl isocyanate, and glycidyl (meth) acrylate.
黏著劑組成物(I-2)所含有的黏著性樹脂(I-2a)係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The adhesive resin (I-2a) contained in the adhesive composition (I-2) may be only one type, or two or more types. In the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
黏著劑組成物(I-2)中的黏著性樹脂(I-2a)含有量，相對於黏著劑組成物(I-2)總質量，較佳係5~99質量%、更佳係10~95質量%、特佳係10~90質量%。The content of the adhesive resin (I-2a) in the adhesive composition (I-2) is preferably 5 to 99% by mass and more preferably 10 to the total mass of the adhesive composition (I-2). 95% by mass, 10 ~ 90% by mass.
[交聯劑]
黏著性樹脂(I-2a)係使用例如與黏著性樹脂(I-1a)中同樣之具有由含官能基單體所衍生構成單元的上述丙烯酸系聚合體時，黏著劑組成物(I-2)亦可更進一步含有交聯劑。[Crosslinking agent]
For the adhesive resin (I-2a), for example, when the above-mentioned acrylic polymer having a structural unit derived from a functional group-containing monomer is used as in the adhesive resin (I-1a), the adhesive composition (I-2 ) May further contain a crosslinking agent.
黏著劑組成物(I-2)中的上述交聯劑，可列舉與黏著劑組成物(I-1)中的交聯劑相同者。
黏著劑組成物(I-2)所含有的交聯劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。Examples of the crosslinking agent in the adhesive composition (I-2) include the same as the crosslinking agent in the adhesive composition (I-1).
The crosslinking agent system contained in the adhesive composition (I-2) may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
上述黏著劑組成物(I-2)中的交聯劑含有量，相對於黏著性樹脂(I-2a)含有量100質量份，較佳係0.01~50質量份、更佳係0.1~20質量份、特佳係0.3~15質量份。The content of the crosslinking agent in the adhesive composition (I-2) is 100 parts by mass relative to the content of the adhesive resin (I-2a), preferably 0.01 to 50 parts by mass, and more preferably 0.1 to 20 parts by mass. And 0.3 to 15 parts by mass.
[光聚合起始劑]
黏著劑組成物(I-2)亦可更進一步含有光聚合起始劑。含有光聚合起始劑的黏著劑組成物(I-2)係即便照射紫外線等較低能量的能量線，仍充分進行硬化反應。[Photopolymerization initiator]
The adhesive composition (I-2) may further contain a photopolymerization initiator. The adhesive composition (I-2) containing a photopolymerization initiator is sufficiently hardened even when it is irradiated with low energy energy rays such as ultraviolet rays.
黏著劑組成物(I-2)中的上述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同者。
黏著劑組成物(I-2)所含有的光聚合起始劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。Examples of the photopolymerization initiator in the adhesive composition (I-2) include the same as the photopolymerization initiator in the adhesive composition (I-1).
The photopolymerization initiator system 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 types, the combination and ratio thereof may be arbitrarily selected.
黏著劑組成物(I-2)中的光聚合起始劑含有量，相對於黏著性樹脂(I-2a)含有量100質量份，較佳係0.01~20質量份、更佳係0.03~10質量份、特佳係0.05~5質量份。The photopolymerization initiator content in the adhesive composition (I-2) is 100 parts by mass relative to the content of the adhesive resin (I-2a), preferably 0.01 to 20 parts by mass, and more preferably 0.03 to 10 Mass parts, especially good, 0.05-5 mass parts.
[其他添加劑]
黏著劑組成物(I-2)係在不致損及本發明效果之範圍內，亦可含有不隸屬上述任一成分的其他添加劑。
黏著劑組成物(I-2)中的上述其他添加劑，可列舉與黏著劑組成物(I-1)中的其他添加劑相同者。
黏著劑組成物(I-2)所含有的其他添加劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。[Other additives]
The adhesive composition (I-2) is within a range that does not impair the effects of the present invention, and may contain other additives that are not affiliated with any of the above-mentioned components.
Examples of the other additives in the adhesive composition (I-2) include the same as the other additives in the adhesive composition (I-1).
The other additives contained in the adhesive composition (I-2) may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
黏著劑組成物(I-2)中的其他添加劑含有量並無特別的限定，只要配合種類再行適當選擇便可。The content of other additives in the adhesive composition (I-2) is not particularly limited, as long as it is appropriately selected according to the type of blending.
[溶劑]
黏著劑組成物(I-2)係在與黏著劑組成物(I-1)情況的同樣目的下，亦可含有溶劑。
黏著劑組成物(I-2)中的上述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同者。
黏著劑組成物(I-2)所含有的溶劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。
黏著劑組成物(I-2)中的溶劑含有量並無特別的限定，只要適當調整便可。[Solvent]
The adhesive composition (I-2) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1).
Examples of the solvent in the adhesive composition (I-2) include the same solvents as those in the adhesive composition (I-1).
The solvent system contained in the adhesive composition (I-2) may be only one type, or two or more types. In the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
The solvent content in the adhesive composition (I-2) is not particularly limited, as long as it is appropriately adjusted.
＜黏著劑組成物(I-3)＞
上述黏著劑組成物(I-3)係如上述，含有上述黏著性樹脂(I-2a)、與能量線硬化性化合物。＜ Adhesive composition (I-3) ＞
The adhesive composition (I-3) is as described above, and contains the adhesive resin (I-2a) and an energy ray-curable compound.
黏著劑組成物(I-3)中的黏著性樹脂(I-2a)含有量，相對於黏著劑組成物(I-3)總質量，較佳係5~99質量%、更佳係10~95質量%、特佳係15~90質量%。The content of the adhesive resin (I-2a) in the adhesive composition (I-3) is preferably 5 to 99% by mass, and more preferably 10 to the total mass of the adhesive composition (I-3). 95% by mass, 15 ~ 90% by mass.
[能量線硬化性化合物]
黏著劑組成物(I-3)所含有的上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、且利用能量線照射便可硬化的單體及寡聚物，可列舉與黏著劑組成物(I-1)所含有能量線硬化性化合物相同者。
黏著劑組成物(I-3)所含有的上述能量線硬化性化合物，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。[Energy ray hardening compound]
Examples of the energy ray-curable compound contained in the adhesive composition (I-3) include monomers and oligomers which have an energy ray polymerizable unsaturated group and which can be hardened by energy ray irradiation, and examples include adhesion and adhesion. The agent composition (I-1) contains the same energy ray-curable compound.
The energy ray-curable compound contained in the adhesive composition (I-3) may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio thereof can be arbitrarily selected.
上述黏著劑組成物(I-3)中的上述能量線硬化性化合物含有量，相對於黏著性樹脂(I-2a)含有量100質量份，較佳係0.01~300質量份、更佳係0.03~200質量份、特佳係0.05~100質量份。The content of the energy ray-curable compound in the adhesive composition (I-3) is 100 parts by mass with respect to the content of the adhesive resin (I-2a), preferably 0.01 to 300 parts by mass, and more preferably 0.03 ~ 200 parts by mass, 0.05 ~ 100 parts by mass.
[光聚合起始劑]
黏著劑組成物(I-3)亦可更進一步含有光聚合起始劑。含有光聚合起始劑的黏著劑組成物(I-3)係即便照射紫外線等較低能量的能量線，仍充分進行硬化反應。[Photopolymerization initiator]
The adhesive composition (I-3) may further contain a photopolymerization initiator. The adhesive composition (I-3) containing a photopolymerization initiator is sufficiently hardened even when irradiated with a low energy energy beam such as ultraviolet rays.
黏著劑組成物(I-3)中的上述光聚合起始劑，可列舉與黏著劑組成物(I-1)中的光聚合起始劑相同者。
黏著劑組成物(I-3)所含有的光聚合起始劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。Examples of the photopolymerization initiator in the adhesive composition (I-3) include the same as the photopolymerization initiator in the adhesive composition (I-1).
The photopolymerization initiator system 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 types, the combination and ratio thereof may be arbitrarily selected.
黏著劑組成物(I-3)中的光聚合起始劑含有量，相對於黏著性樹脂(I-2a)與上述能量線硬化性化合物的總含有量100質量份，較佳係0.01~20質量份、更佳係0.03~10質量份、特佳係0.05~5質量份。The photopolymerization initiator content in the adhesive composition (I-3) is preferably 0.01 to 20 parts by mass with respect to 100 mass parts of the total content of the adhesive resin (I-2a) and the energy ray-curable compound. Mass parts, more preferably 0.03 to 10 parts by mass, and extra best parts 0.05 to 5 parts by mass.
[其他添加劑]
黏著劑組成物(I-3)係在不致損及本發明效果之範圍內，亦可含有不隸屬上述任一成分的其他添加劑。
上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者。
黏著劑組成物(I-3)所含有的其他添加劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。[Other additives]
The adhesive composition (I-3) is within a range that does not impair the effect of the present invention, and may contain other additives that are not affiliated with any of the above-mentioned components.
Examples of the other additives include the same as the other additives in the adhesive composition (I-1).
The other additives contained in the adhesive composition (I-3) may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
黏著劑組成物(I-3)中的其他添加劑含有量並無特別的限定，只要配合種類再行適當選擇便可。The content of other additives in the adhesive composition (I-3) is not particularly limited, as long as it is appropriately selected according to the type of blending.
[溶劑]
黏著劑組成物(I-3)係在與黏著劑組成物(I-1)情況的同樣目的下，亦可含有溶劑。
黏著劑組成物(I-3)中的上述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同者。
黏著劑組成物(I-3)所含有的溶劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。
黏著劑組成物(I-3)中的溶劑含有量並無特別的限定，只要適當調整便可。[Solvent]
The adhesive composition (I-3) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1).
Examples of the solvent in the adhesive composition (I-3) include the same solvents as those in the adhesive composition (I-1).
The solvent composition contained in the adhesive composition (I-3) may be only one type, or two or more types. In the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
The solvent content in the adhesive composition (I-3) is not particularly limited, as long as it is appropriately adjusted.
＜黏著劑組成物(I-1)~(I-3)以外的黏著劑組成物＞
截至目前主要針對黏著劑組成物(I-1)、黏著劑組成物(I-2)及黏著劑組成物(I-3)進行說明，惟已說明的這些組成物的含有成分，仍同樣可使用在這3種黏著劑組成物以外的所有黏著劑組成物(本說明書中亦稱「黏著劑組成物(I-1)~(I-3)以外的黏著劑組成物」)。<Adhesive composition other than adhesive composition (I-1) to (I-3)>
So far, the adhesive composition (I-1), the adhesive composition (I-2), and the adhesive composition (I-3) have mainly been described. However, the components contained in these compositions have been described. All the adhesive compositions (other than the "adhesive composition (I-1) to (I-3) except the adhesive composition (I-1) to (I-3)" in this specification)) were used except for these three adhesive compositions.
黏著劑組成物(I-1)~(I-3)以外的黏著劑組成物係除能量線硬化性黏著劑組成物之外，亦可列舉非能量線硬化性黏著劑組成物。
非能量線硬化性黏著劑組成物係可舉例如含有:丙烯酸系樹脂、胺甲酸乙酯系樹脂、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黏著性樹脂(I-1a)的黏著劑組成物(I-4)，較佳係含有丙烯酸系樹脂。Adhesive compositions other than the adhesive composition (I-1) to (I-3) include energy-ray-curable adhesive compositions, and non-energy-ray-curable adhesive compositions.
Examples of the non-energy ray-curable adhesive composition system include acrylic resin, urethane resin, rubber resin, silicone resin, epoxy resin, polyvinyl ether, polycarbonate, and ester. The adhesive composition (I-4) of the non-energy-ray-curable adhesive resin (I-1a), such as a resin, preferably contains an acrylic resin.
黏著劑組成物(I-1)~(I-3)以外的黏著劑組成物，較佳係含有1種或2種以上的交聯劑，且含有量係可設為與上述黏著劑組成物(I-1)等的情況相同。The adhesive composition other than the adhesive composition (I-1) to (I-3) preferably contains one or two or more kinds of cross-linking agents, and the content can be set to be the same as the above-mentioned adhesive composition. The same applies to (I-1).
＜黏著劑組成物(I-4)＞
黏著劑組成物(I-4)較佳可列舉含有上述黏著性樹脂(I-1a)、與交聯劑者。＜ Adhesive composition (I-4) ＞
Preferred examples of the adhesive composition (I-4) include those containing the above-mentioned adhesive resin (I-1a) and a crosslinking agent.
[黏著性樹脂(I-1a)]
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)相同者。
黏著劑組成物(I-4)所含有的黏著性樹脂(I-1a)係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。[Adhesive resin (I-1a)]
Examples of the adhesive resin (I-1a) in the adhesive composition (I-4) are the same as the adhesive resin (I-1a) in the adhesive composition (I-1).
The adhesive resin (I-1a) contained in the adhesive composition (I-4) may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
黏著劑組成物(I-4)中的黏著性樹脂(I-1a)含有量，相對於黏著劑組成物(I-4)的總質量，較佳係5~99質量%、更佳係10~95質量%、特佳係15~90質量%。The content of the adhesive resin (I-1a) in the adhesive composition (I-4) is preferably 5 to 99% by mass and more preferably 10 to the total mass of the adhesive composition (I-4). ~ 95% by mass and 15 ~ 90% by mass of the special line.
黏著劑組成物(I-4)中，黏著性樹脂(I-1a)含有量相對於溶劑以外所有成分總含有量的比例(即，黏著劑層的黏著性樹脂(I-1a)含有量)，較佳係30~90質量%、更佳係40~85質量%、特佳係50~80質量%。The ratio of the content of the adhesive resin (I-1a) to the total content of all components except the solvent in the adhesive composition (I-4) (that is, the content of the adhesive resin (I-1a) in the adhesive layer) 30% to 90% by mass, 40% to 85% by mass, and 50% to 80% by mass.
[交聯劑]
黏著性樹脂(I-1a)係由(甲基)丙烯酸烷基酯所衍生構成單元之外，更進一步使用具有由含官能基單體所衍生構成單元的上述丙烯酸系聚合體時，黏著劑組成物(I-4)較佳係更進一步含有交聯劑。[Crosslinking agent]
The adhesive resin (I-1a) is composed of an adhesive in addition to the structural unit derived from an alkyl (meth) acrylate, and when the above-mentioned acrylic polymer having a structural unit derived from a functional group-containing monomer is used. The substance (I-4) preferably further contains a crosslinking agent.
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)的交聯劑相同者。
黏著劑組成物(I-4)所含有的交聯劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。Examples of the cross-linking agent in the adhesive composition (I-4) include the same as the cross-linking agent in the adhesive composition (I-1).
The crosslinking agent system contained in the adhesive composition (I-4) may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
上述黏著劑組成物(I-4)中的交聯劑含有量，相對於黏著性樹脂(I-1a)含有量100質量份，較佳係0.01~50質量份、更佳係0.3~50質量份、特佳係1~50質量份，例如可為10~50質量份、15~50質量份、及20~50質量份等中之任一者。The content of the crosslinking agent in the adhesive composition (I-4) is 100 parts by mass relative to the content of the adhesive resin (I-1a), preferably 0.01 to 50 parts by mass, and more preferably 0.3 to 50 parts by mass. 1-50 parts by mass, particularly preferably, any one of 10-50 parts by mass, 15-50 parts by mass, and 20-50 parts by mass.
[其他添加劑]
黏著劑組成物(I-4)係在不致損及本發明效果之範圍內，亦可含有不隸屬上述任一成分的其他添加劑。
上述其他添加劑，可列舉與黏著劑組成物(I-1)中的其他添加劑相同者。
黏著劑組成物(I-4)所含有的其他添加劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。[Other additives]
The adhesive composition (I-4) is within a range that does not impair the effect of the present invention, and may contain other additives that are not affiliated with any of the above-mentioned components.
Examples of the other additives mentioned above are the same as the other additives in the adhesive composition (I-1).
The other additives contained in the adhesive composition (I-4) may be only one kind or two or more kinds. In the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
黏著劑組成物(I-4)中的其他添加劑含有量並無特別的限定，只要配合種類再行適當選擇便可。The content of the other additives in the adhesive composition (I-4) is not particularly limited, as long as it is appropriately selected according to the type of blending.
[溶劑]
黏著劑組成物(I-4)係在與黏著劑組成物(I-1)情況的同樣目的下，亦可含有溶劑。
黏著劑組成物(I-4)中的上述溶劑，可列舉與黏著劑組成物(I-1)中的溶劑相同者。
黏著劑組成物(I-4)所含有的溶劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。
黏著劑組成物(I-4)中的溶劑含有量並無特別的限定，只要適當調整便可。[Solvent]
The adhesive composition (I-4) may contain a solvent for the same purpose as in the case of the adhesive composition (I-1).
Examples of the solvent in the adhesive composition (I-4) include the same solvents as those in the adhesive composition (I-1).
The solvent contained in the adhesive composition (I-4) may be only one type, or two or more types. In the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
The solvent content in the adhesive composition (I-4) is not particularly limited, as long as it is appropriately adjusted.
上述保護膜形成用複合片中，黏著劑層較佳係非能量線硬化性。理由係若黏著劑層為能量線硬化性，則當利用能量線照射而使保護膜形成用薄膜硬化時，有無法抑制黏著劑層亦同時硬化的情形。若黏著劑層會與保護膜形成用薄膜同時硬化，則硬化後的保護膜形成用薄膜(即保護膜)與黏著劑層會在其界面出現無法剝離程度的貼附。此情況，較難將背面設有經硬化後保護膜形成用薄膜(即保護膜)的半導體晶片(具保護膜之半導體晶片)，從包括硬化後黏著劑層的支撐片上剝離，導致具保護膜之半導體晶片無法正常拾取。上述支撐片中，將黏著劑層設為非能量線硬化性，便可確實迴避此種不良情況，俾能更輕易地拾取具保護膜之半導體晶片。In the protective sheet-forming composite sheet, the adhesive layer is preferably non-energy ray-curable. The reason is that if the adhesive layer is energy ray-curable, when the protective film-forming film is cured by energy ray irradiation, the adhesive layer may not be suppressed from being cured at the same time. If the adhesive layer and the protective film-forming film are cured at the same time, the hardened protective film-forming film (that is, the protective film) and the adhesive layer will adhere to the interface at a level that cannot be peeled off. In this case, it is difficult to peel a semiconductor wafer (a semiconductor wafer with a protective film) provided with a cured protective film (i.e., a protective film) on the back surface from a support sheet including a cured adhesive layer, resulting in a protective film. The semiconductor wafer cannot be picked up normally. In the above-mentioned support sheet, by setting the adhesive layer to be non-energy ray hardenable, such a disadvantage can be reliably avoided, and a semiconductor wafer with a protective film can be more easily picked up.
此處雖針對黏著劑層係非能量線硬化性時的效果進行說明，但即便與支撐片之保護膜形成用薄膜直接接觸的層係黏著劑層以外的層，只要此層係非能量線硬化性，仍可達同樣效果。Although the effect when the adhesive layer is non-energy ray-curable is described here, even if the layer is other than the layer-based adhesive layer that is in direct contact with the protective film forming film of the support sheet, as long as the layer is non-energy-ray-curable And still achieve the same effect.
＜＜黏著劑組成物之製造方法＞＞
黏著劑組成物(I-1)~(I-3)、黏著劑組成物(I-4)等除黏著劑組成物(I-1)~(I-3)以外的黏著劑組成物，係藉由將上述黏著劑、與視需要的上述黏著劑以外的成分等構成黏著劑組成物的各成分，予以摻合便可獲得。
各成分摻合時的添加順序並無特別的限定，亦可2種以上的成分同時添加。
使用溶劑時，可將溶劑與溶劑以外的任一摻合成分進行混合，再將此摻合成分施行預稀釋後才使用，亦可在未將溶劑以外的任一摻合成分施行預稀釋，便將溶劑與這些摻合成分混合來使用。
摻合時，將各成分混合的方法並無特別的限定，可從例如:使攪拌子或攪拌葉片等旋轉而進行混合的方法；使用混合機進行混合的方法；施加超音波進行混合的方法等公知方法中適當選擇。
各成分的添加、及混合時的溫度與時間係在各摻合成分不會劣化前提下，並無特別的限定，只要適當調整便可，溫度較佳係15~30℃。＜ Method for manufacturing adhesive composition ＞＞
Adhesive compositions other than the adhesive composition (I-1) to (I-3) such as the adhesive composition (I-1) to (I-3) and the adhesive composition (I-4) It can be obtained by blending each component constituting the adhesive composition, such as the above-mentioned adhesive, and components other than the above-mentioned adhesive, if necessary.
The order of addition of each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, the solvent can be mixed with any blending component other than the solvent, and then the blending component can be used after being pre-diluted. Alternatively, any blending component other than the solvent can be pre-diluted. A solvent is mixed with these blending components and used.
There is no particular limitation on the method of mixing the components during blending. For example, a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, a method of mixing by applying an ultrasonic wave, etc. It is appropriately selected from known methods.
The addition of each component, and the temperature and time during mixing are not particularly limited as long as each blending component does not deteriorate, as long as it is appropriately adjusted, the temperature is preferably 15 to 30 ° C.
◎保護膜形成用薄膜
上述保護膜形成用薄膜係藉由硬化、或未硬化而維持原狀態下形成保護膜。此保護膜係供保護半導體晶圓或半導體晶片的背面(臨電極形成面的相反側的面)用。保護膜形成用薄膜係軟質，可輕易貼附於貼附標的物上。◎ Film for forming protective film The above-mentioned film for forming protective film is formed into a protective film by curing or not curing. This protective film is used to protect the semiconductor wafer or the back surface of the semiconductor wafer (the surface opposite to the electrode formation surface). The thin film for forming the protective film is soft, and can be easily attached to the label.
上述保護膜形成用薄膜係可為硬化性、亦可為非硬化性。
硬化性保護膜形成用薄膜係可為熱硬化性及能量線硬化性中之任一者、亦可具有熱硬化性與能量線硬化性雙方特性。
保護膜形成用薄膜係使用含有其構成材料的保護膜形成用組成物便可形成。The protective film-forming film system may be curable or non-curable.
The thin film for forming a curable protective film may be either thermosetting or energy ray curable, or may have both thermosetting and energy ray curable properties.
The thin film for protective film formation can be formed using the composition for protective film formation containing the constituent material.
本說明書中，所謂「非硬化性」係指不管利用加熱、能量線照射等任何手段均不會硬化的性質。
本發明中，在即便將保護膜形成用薄膜硬化後，仍可維持支撐片與保護膜形成用薄膜之硬化物(換言之，支撐片與保護膜) 的積層構造前提下，將此積層體稱為「保護膜形成用複合片」。In the present specification, the "non-hardening property" refers to a property that does not harden by any means such as heating and energy ray irradiation.
In the present invention, this laminated body is referred to as a laminated body on the premise that the laminated structure of the support sheet and the protective film forming film (in other words, the supporting sheet and the protective film) can be maintained even after the protective film forming film is cured. "Composite sheet for protective film formation".
保護膜形成用薄膜係不管種類如何，均可由1層(單層)構成、亦可由2層以上的複數層構成。當保護膜形成用薄膜係由複數層構成的情況，這些複數層係相互可為相同、亦可為不同。Regardless of the type, the thin film for forming a protective film may be composed of one layer (single layer), or may be composed of two or more layers. When the thin film for forming a protective film is composed of a plurality of layers, these plural layer systems may be the same as or different from each other.
此處，再度參照圖4，針對黏著劑層與保護膜形成用薄膜更進一步詳細說明。
如前所說明，基材11的第1面11a係凹凸面。但，黏著劑層12中，若例如其S值達1.5μm以上，便抑制此凹凸面的影響，降低黏著劑層12的第1面12a之凹凸度。所以，黏著劑層12與保護膜形成用薄膜13間之積層性呈良好。例如即便在黏著劑層12與保護膜形成用薄膜13之間，存在有這些未貼合的區域(未貼合區域)92，但其數量在橫跨保護膜形成用複合片1A中的保護膜形成用薄膜13形成區域總域中，仍在3處以下等極少狀態。上述未貼合區域92係例如從基材11側觀察保護膜形成用複合片1A便可輕易確認。Here, referring to FIG. 4 again, the adhesive layer and the thin film for forming a protective film will be described in more detail.
As described above, the first surface 11a of the base material 11 is an uneven surface. However, if the S value of the adhesive layer 12 is 1.5 μm or more, the influence of the uneven surface is suppressed, and the unevenness of the first surface 12 a of the adhesive layer 12 is reduced. Therefore, the lamination property between the adhesive layer 12 and the protective film-forming film 13 is good. For example, even if these non-adhered regions (non-adhered regions) 92 exist between the adhesive layer 12 and the protective film-forming film 13, the number of the non-adhered regions (non-adhered regions) 92 is across the protective film in the protective film forming composite sheet 1A. In the total area of the formation region of the thin film 13 for formation, there are still few states such as three or less. The non-bonded region 92 is easily confirmed by observing the composite film forming protective sheet 1A from the base material 11 side, for example.
再者，保護膜形成用複合片1A係即便具有此種未貼合區域92，在保護膜形成用複合片1A厚度方向上的未貼合區域92大小(層間距離)為例如0.5μm以下之保護膜形成用複合片1A，其黏著劑層12與保護膜形成用薄膜13間之積層性更良好。此處所謂「未貼合區域92大小(層間距離)」，係指「在保護膜形成用複合片1A厚度方向，黏著劑層12與保護膜形成用薄膜13間之層間距離」。In addition, even if the composite sheet for protective film formation 1A has such an unbonded region 92, the size (interlayer distance) of the non-bonded region 92 in the thickness direction of the protective film forming composite sheet 1A is, for example, 0.5 μm or less The film-forming composite sheet 1A has a better lamination property between the adhesive layer 12 and the protective film-forming film 13. The "size of the non-bonded area 92 (interlayer distance)" herein means "the interlayer distance between the adhesive layer 12 and the protective film-forming film 13 in the thickness direction of the protective film-forming composite sheet 1A".
未貼合區域92的大小(上述層間距離)，係與上述未貼合區域91的上述層間距離最大值(大小)同樣，較佳係0.5μm以下，例如可為0.4μm以下、0.3μm以下、0.2μm以下及0.1μm以下中之任一者。The size (the inter-layer distance) of the non-bonded region 92 is the same as the maximum value (size) of the inter-layer distance of the non-bonded region 91, and is preferably 0.5 μm or less. For example, it may be 0.4 μm or less, 0.3 μm or less, Any one of 0.2 μm or less and 0.1 μm or less.
未貼合區域92的大小(層間距離)係例如成為對象的雙層組合不同之外，依照與上述未貼合區域91大小(層間距離)的情況相同方法，便可求取。The size (interlayer distance) of the non-adhered region 92 can be obtained by the same method as the case of the size (interlayer distance) of the non-adhesion region 91 except that the target combination of two layers is different.
保護膜形成用複合片1A亦有完全未存在未貼合區域92的情形。In the protective film forming composite sheet 1A, the non-adhesive region 92 may not exist at all.
另一方面，如上述，若降低黏著劑層12的第1面12a之凹凸度，保護膜形成用薄膜13的厚度Tp 並非固定，而是依照保護膜形成用薄膜13(黏著劑層12)的部位會有變動，但其變動幅度極小。On the other hand, as described above, if the unevenness of the first surface 12a of the adhesive layer 12 is reduced, the thickness T p of the protective film-forming film 13 is not fixed, but conforms to the protective film-forming film 13 (adhesive layer 12). There will be changes in the location, but the range of change is extremely small.
再者，如上述，若降低黏著劑層12的第1面12a之凹凸度，保護膜形成用薄膜13臨黏著劑層12側的面(第2面)13b便為平滑、或降低凹凸度。所以，不會損及保護膜形成用薄膜13的外觀。
所以，若由上述保護膜形成用薄膜13形成保護膜，則所形成的保護膜臨黏著劑層12側的面(第2面)仍可呈平滑、或降低凹凸度，不致損及保護膜外觀。
依此，保護膜形成用複合片1A中，保護膜形成用薄膜13與保護膜均可成為設計性優異。Further, as described above, if the unevenness of the first surface 12a of the adhesive layer 12 is reduced, the surface (second surface) 13b of the protective film-forming film 13 on the side of the adhesive layer 12 is smoothed or the unevenness is reduced. Therefore, the appearance of the protective film-forming film 13 is not impaired.
Therefore, if the protective film is formed from the protective film-forming film 13, the surface (second surface) of the protective film formed on the side of the adhesive layer 12 can still be smooth, or the degree of unevenness can be reduced without damaging the appearance of the protective film. .
Accordingly, in the composite sheet for forming a protective film 1A, both the thin film 13 for forming a protective film and the protective film are excellent in designability.
保護膜形成用薄膜13的第2面13b，凸部最高部位、與凹部最深部位間之最大高低差，較佳係在2μm以下，例如可為1.5μm以下、及1μm以下中之任一者。此種保護膜形成用薄膜13與保護膜的設計性特優。The maximum height difference between the second surface 13b of the protective film-forming film 13 and the highest portion of the convex portion and the deepest portion of the concave portion is preferably 2 μm or less, and may be, for example, any of 1.5 μm or less and 1 μm or less. Such a protective film-forming film 13 and the protective film are particularly excellent in designability.
保護膜形成用薄膜13的第2面13b之上述最大高低差，係例如利用前所說明的方法，由保護膜形成用複合片的試驗片或保護膜形成用複合片自體形成截面，再使用掃描式電子顯微鏡(SEM)，藉由觀察此截面便可求得。The above-mentioned maximum height difference of the second surface 13b of the protective film-forming film 13 is, for example, a cross-section of a test piece of a protective film-forming composite sheet or a protective film-forming composite sheet by itself forming a cross section by the method described above, and then reused. A scanning electron microscope (SEM) can be obtained by observing this cross section.
此處雖舉保護膜形成用複合片1A為例，針對黏著劑層與保護膜形成用薄膜進行說明，但關於保護膜形成用複合片1B、保護膜形成用複合片1C等其他實施形態的保護膜形成用複合片的情況，亦是同樣的黏著劑層及保護膜形成用薄膜。Here, the composite sheet for forming a protective film 1A is taken as an example to describe the adhesive layer and the thin film for forming a protective film. However, the protection of other embodiments such as the composite sheet for forming a protective film and the composite sheet for forming a protective film 1C In the case of a film-forming composite sheet, the same adhesive layer and protective film-forming film are also used.
本發明的保護膜形成用複合片中，保護膜形成用薄膜的厚度(例如Tp )較佳係1~100μm、更佳係3~75μm、特佳係5~50μm。藉由保護膜形成用薄膜的厚度達上述下限值以上，便可形成更高保護能力的保護膜。藉由保護膜形成用薄膜的厚度在上述上限值以下，抑制厚度過厚。In the protective sheet-forming composite sheet of the present invention, the thickness (for example, T p ) of the thin film for forming a protective film is preferably 1 to 100 μm, more preferably 3 to 75 μm, and particularly preferably 5 to 50 μm. When the thickness of the thin film for forming a protective film exceeds the above-mentioned lower limit value, a protective film having a higher protective ability can be formed. When the thickness of the protective film-forming film is equal to or less than the above-mentioned upper limit value, the excessive thickness is suppressed.
當保護膜形成用薄膜的厚度會依保護膜形成用薄膜的部位而有所變動的情況，則保護膜形成用薄膜的厚度最小值可在上述下限值以上，且保護膜形成用薄膜的厚度最大值可在上述上限值以下。When the thickness of the thin film for protective film formation varies depending on the location of the thin film for protective film formation, the minimum thickness of the thin film for protective film formation may be greater than the above-mentioned lower limit, and the thickness of the thin film for protective film formation The maximum value can be below the above upper limit.
另外，所謂「保護膜形成用薄膜的厚度」，係指保護膜形成用薄膜全體的厚度，例如由複數層構成的保護膜形成用薄膜的厚度，係指構成保護膜形成用薄膜的所有層之合計厚度。The "thickness of the film for forming a protective film" refers to the thickness of the entire film for forming a protective film. For example, the thickness of the film for forming a protective film composed of a plurality of layers means the thickness of all the layers constituting the film for forming a protective film. Total thickness.
保護膜形成用薄膜的厚度係例如使用掃描式電子顯微鏡(SEM)，觀察保護膜形成用薄膜的側面或截面便可測定。
保護膜形成用薄膜的截面係例如依照與上述支撐片及保護膜形成用複合片的試驗片截面的情況之同樣方法便可形成。The thickness of the thin film for protective film formation can be measured by observing the side surface or cross section of the thin film for protective film formation using a scanning electron microscope (SEM), for example.
The cross-section of the thin film for forming a protective film can be formed in the same manner as in the case of the cross-section of the test piece of the above-mentioned support sheet and the composite sheet for forming a protective film, for example.
例如利用前所說明的方法，從保護膜形成用複合片的複數個地方(例如5個地方)切取試驗片，針對此試驗片求取保護膜形成用薄膜的厚度最小值與最大值，再從這些數值求取這些最小值平均值與最大值平均值時，上述最小值平均值可達上述保護膜形成用薄膜的厚度下限值以上，且上述最大值平均值可在上述保護膜形成用薄膜的厚度上限值以下。For example, the test piece is cut from a plurality of places (for example, five places) of the composite sheet for forming a protective film by the method described above, and the minimum and maximum thicknesses of the thin film for forming a protective film are obtained for this test piece. When these numerical values are used to find the minimum average value and the maximum average value, the minimum average value can reach the thickness lower limit value of the film for forming the protective film, and the maximum value average value can be in the protective film forming film. The thickness is below the upper limit.
保護膜形成用薄膜係使用含有其構成材料的保護膜形成用組成物便可形成。例如在保護膜形成用薄膜的形成標的面上塗佈保護膜形成用組成物，視需要施行乾燥，便可在目標部位處形成保護膜形成用薄膜。保護膜形成用組成物中在常溫不會氣化的成分間之含有量比率，通常係同保護膜形成用薄膜的上述成分間之含有量比率。The thin film for protective film formation can be formed using the composition for protective film formation containing the constituent material. For example, the protective film-forming composition is coated on the surface of the formation target of the protective film-forming film, and if necessary, drying, the protective film-forming film can be formed at the target site. The content ratio between components that do not vaporize at room temperature in the composition for forming a protective film is usually the same as the content ratio between the components of the film for forming a protective film.
保護形成用組成物的塗佈係可利用公知方法實行，例如使用氣刀塗佈機、刮刀塗佈機、棒式塗佈機、凹版塗佈機、輥式塗佈機、輥式刀塗機、淋幕塗佈機、模塗機、刀塗機、網版塗佈機、麥勒棒塗機、吻合式塗佈機等各種塗佈機的方法。The coating system for protecting the composition for formation can be performed by a known method, for example, using an air knife coater, a knife coater, a bar coater, a gravure coater, a roll coater, or a roll knife coater. , Shower curtain coater, die coater, knife coater, screen coater, Mailer bar coater, anastomotic coater and other coaters.
保護膜形成用組成物的乾燥條件並無特別的限定，當保護膜形成用組成物含有後述溶劑的情況，以使其加熱乾燥為佳。而，含有溶劑的保護膜形成用組成物，是以以例如70~130℃、10秒~5分鐘的條件施行乾燥為佳。但，當保護膜形成用組成物係熱硬化性的情況，則以以所形成保護膜形成用薄膜不會熱硬化的方式，使保護膜形成用組成物乾燥為佳。The drying conditions of the composition for forming a protective film are not particularly limited. When the composition for forming a protective film contains a solvent described later, it is preferable to heat and dry it. The composition for forming a protective film containing a solvent is preferably dried under conditions of, for example, 70 to 130 ° C. for 10 seconds to 5 minutes. However, when the composition for forming a protective film is thermosetting, it is preferable to dry the composition for forming a protective film so that the formed thin film for forming a protective film does not thermally harden.
以下，針對保護膜形成用薄膜與保護膜形成用組成物，依照種類別進行詳細說明。Hereinafter, the thin film for forming a protective film and the composition for forming a protective film will be described in detail according to various types.
○熱硬化性保護膜形成用薄膜
較佳熱硬化性保護膜形成用薄膜，可列舉含有聚合體成分(A)與熱硬化性成分(B)者。
聚合體成分(A)係可視為由聚合性化合物進行聚合反應而形成的成分。
熱硬化性成分(B)係能以熱為反應的觸發，進行硬化(聚合)反應的成分。另外，本發明的聚合反應亦包括縮聚反應。○ The film for forming a thermosetting protective film is preferably a film for forming a thermosetting protective film, and examples thereof include a polymer component (A) and a thermosetting component (B).
The polymer component (A) can be regarded as a component formed by a polymerization reaction of a polymerizable compound.
The thermosetting component (B) is a component capable of performing a curing (polymerization) reaction by using heat as a trigger of a reaction. The polymerization reaction of the present invention also includes a polycondensation reaction.
將熱硬化性保護膜形成用薄膜貼附於半導體晶圓的背面之後，使熱硬化時的硬化條件，在硬化物成為充分發揮其機能程度的硬化度前提下，並無特別的限定，可配合熱硬化性保護膜形成用薄膜的種類再行適當選擇。
例如熱硬化性保護膜形成用薄膜的熱硬化時的加熱溫度，較佳係100~200℃、更佳係110~180℃、特佳係120~170℃。而，上述硬化時的加熱時間較佳係0.5~5小時、更佳係0.5~3小時、特佳係1~2小時。After the thin film for forming a thermosetting protective film is attached to the back surface of a semiconductor wafer, the hardening conditions at the time of thermal hardening are not particularly limited as long as the hardened material has a degree of hardening that fully exerts its functions. The type of the thin film for forming a thermosetting protective film is appropriately selected.
For example, the heating temperature during thermal curing of the film for forming a thermosetting protective film is preferably 100 to 200 ° C, more preferably 110 to 180 ° C, and particularly preferably 120 to 170 ° C. The heating time during the hardening is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and particularly preferably 1 to 2 hours.
＜熱硬化性保護膜形成用組成物(III-1)＞
較佳熱硬化性保護膜形成用組成物，可列舉例如:含有聚合體成分(A)與熱硬化性成分(B)的熱硬化性保護膜形成用組成物(III-1)(本說明書中亦簡稱「組成物(III-1)」)等。<Composition (III-1) for forming a thermosetting protective film>
A preferable composition for forming a thermosetting protective film includes, for example, a composition (III-1) for forming a thermosetting protective film containing a polymer component (A) and a thermosetting component (B) (in this specification) Also referred to as "composition (III-1)").
[聚合體成分(A)]
聚合體成分(A)係供對熱硬化性保護膜形成用薄膜賦予造膜性、可撓性等的成分。
組成物(III-1)與熱硬化性保護膜形成用薄膜所含有的聚合體成分(A)，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。[Polymer component (A)]
The polymer component (A) is a component for providing film-forming properties, flexibility, and the like to a film for forming a thermosetting protective film.
The polymer component (A) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and The ratio system can be arbitrarily selected.
聚合體成分(A)係可舉例如:丙烯酸系樹脂、聚酯、胺甲酸乙酯系樹脂、丙烯酸胺甲酸乙酯樹脂、聚矽氧系樹脂、橡膠系樹脂、苯氧樹脂、熱硬化性聚醯亞胺等，較佳係丙烯酸系樹脂。Examples of the polymer component (A) include: acrylic resin, polyester, urethane resin, acrylic urethane resin, silicone resin, rubber resin, phenoxy resin, and thermosetting polymer. Acrylimide and the like are preferably acrylic resins.
聚合體成分(A)中的上述丙烯酸系樹脂，可列舉公知的丙烯酸聚合體。
丙烯酸系樹脂的重量平均分子量(Mw)較佳係10000~2000000、更佳係100000~1500000。藉由丙烯酸系樹脂的重量平均分子量達上述下限值以上，則提升熱硬化性保護膜形成用薄膜的形狀安定性(保管時的經時安定性)。又，藉由丙烯酸系樹脂的重量平均分子量在上述上限值以下，則熱硬化性保護膜形成用薄膜會輕易追隨被黏物的凹凸面，更加抑制被黏物與熱硬化性保護膜形成用薄膜間發生孔隙等。Examples of the acrylic resin in the polymer component (A) include known acrylic polymers.
The weight average molecular weight (Mw) of the acrylic resin is preferably 10,000 to 2,000,000, and more preferably 100,000 to 1,500,000. When the weight average molecular weight of the acrylic resin reaches the above-mentioned lower limit value or more, the shape stability (time-lapse stability during storage) of the film for forming a thermosetting protective film is improved. In addition, when the weight average molecular weight of the acrylic resin is below the above-mentioned upper limit value, the film for forming a thermosetting protective film will easily follow the uneven surface of the adherend, and the formation of the adherend and the thermosetting protective film will be further suppressed Pores and the like occur between the films.
本說明書中，所謂「重量平均分子量」在無特別聲明前提下，係指利用凝膠滲透色層分析儀(GPC)法所測定的聚苯乙烯換算值。In this specification, the "weight average molecular weight" refers to a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
丙烯酸系樹脂的玻璃轉移溫度(Tg)較佳係-60~70℃、更佳係-30~50℃。藉由丙烯酸系樹脂的Tg達上述下限值以上，抑制例如保護膜形成用薄膜之硬化物(即保護膜)與支撐片間之接著力，俾適度提升支撐片的剝離性。又，藉由丙烯酸系樹脂的Tg在上述上限值以下，則提升熱硬化性保護膜形成用薄膜與保護膜的被黏物間之接著力。
另外，不僅侷限於丙烯酸系樹，本說明書中的樹脂Tg係例如使用微分掃描熱量計(DSC)，將升溫速度或降溫速度設為10℃/min，使測定標的物溫度在-70℃至150℃間變化，藉由確認反曲點便可求得。The glass transition temperature (Tg) of the acrylic resin is preferably -60 to 70 ° C, and more preferably -30 to 50 ° C. When the Tg of the acrylic resin is equal to or higher than the above-mentioned lower limit value, for example, the adhesion between the hardened body of the protective film-forming film (that is, the protective film) and the supporting sheet is suppressed, and the peelability of the supporting sheet is appropriately increased. In addition, when the Tg of the acrylic resin is equal to or less than the above-mentioned upper limit value, the adhesion between the film for forming a thermosetting protective film and the adherend of the protective film is increased.
In addition, the resin Tg is not limited to acrylic trees. For example, a differential scanning calorimeter (DSC) is used for the resin Tg in this specification, and the heating rate or cooling rate is set to 10 ° C / min, so that the temperature of the measurement target is -70 ° C to 150 ° C. Change between ℃, can be obtained by confirming the inflection point.
丙烯酸系樹脂係可舉例如:1種或2種以上(甲基)丙烯酸酯的聚合體；從(甲基)丙烯酸、衣康酸、醋酸乙烯酯、丙烯腈、苯乙烯及N-羥甲基丙烯醯胺等之中選擇2種以上單體的共聚物等。Examples of the acrylic resin are: a polymer of one or more (meth) acrylic acid esters; from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxymethyl Among acrylamide and the like, a copolymer of two or more monomers is selected.
構成丙烯酸系樹脂的上述(甲基)丙烯酸酯，係可舉例如:(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)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(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)丙烯酸肉荳蔻酯)、(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，構成烷基酯的烷基係碳數1~18的鏈狀構造(甲基)丙烯酸烷基酯；
(甲基)丙烯酸異莰酯、(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)丙烯酸芳烷酯；
(甲基)丙烯酸二環戊烯酯等(甲基)丙烯酸環烯基酯；
(甲基)丙烯酸二環戊烯氧基乙酯等(甲基)丙烯酸環烯氧基烷基酯；
(甲基)丙烯酸醯亞胺；
(甲基)丙烯酸環氧丙酯等含環氧丙基之(甲基)丙烯酸酯；
(甲基)丙烯酸羥甲酯、(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸-3-羥丙酯、(甲基)丙烯酸-2-羥丁酯、(甲基)丙烯酸-3-羥丁酯、(甲基)丙烯酸-4-羥丁酯等含羥基之(甲基)丙烯酸酯；
(甲基)丙烯酸-N-甲胺基乙酯等含取代胺基之(甲基)丙烯酸酯等。此處所謂「取代胺基」係指胺基的1個或2個氫原子，被氫原子以外之基取代而成的基。Examples of the (meth) acrylate constituting the acrylic resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. Ester, n-butyl (meth) acrylate, isobutyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, amyl (meth) acrylate, (formyl) (Hexyl) hexyl acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylic acid N-nonyl ester, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, lauryl (meth) acrylate (lauryl (meth) acrylate) ), Tridecyl (meth) acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, (meth) acrylic acid Cetyl ester (palmyl (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), and the like constitute the alkane 1 to 18 carbon chain (Meth) acrylic acid alkyl ester;
Cycloalkyl (meth) acrylates, such as isoamyl (meth) acrylate, dicyclopentyl (meth) acrylate;
Aryl (meth) acrylate, such as benzyl (meth) acrylate;
Cycloalkenyl (meth) acrylate such as dicyclopentenyl (meth) acrylate;
Cyclomethenyl (meth) acrylate, such as dicyclopentenyloxy (meth) acrylate;
(Meth) acrylic acid imine;
(Meth) acrylic acid-containing (meth) acrylic acid esters such as propylene glycol (meth) acrylate;
Hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid Hydroxy-containing (meth) acrylates such as 2-hydroxybutyl ester, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate;
Substituted amino groups such as (meth) acrylic acid-N-methylaminoethyl ester and the like. The "substituted amino group" herein refers to a group in which one or two hydrogen atoms of an amine group are substituted with a group other than a hydrogen atom.
丙烯酸系樹脂係例如除上述(甲基)丙烯酸酯之外，尚亦可由從(甲基)丙烯酸、衣康酸、醋酸乙烯酯、丙烯腈、苯乙烯及N-羥甲基丙烯醯胺等之中選擇1種或2種以上的單體，進行共聚合而成者。For example, in addition to the above (meth) acrylic acid esters, acrylic resins can also be made from (meth) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene, and N-hydroxymethacrylamide. Among them, one or more monomers are selected and copolymerized.
構成丙烯酸系樹脂的單體係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The single system constituting the acrylic resin may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be arbitrarily selected.
丙烯酸系樹脂亦可具有例如:乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等的能與其他化合物鍵結的官能基。丙烯酸系樹脂的上述官能基係可經由後述交聯劑(F)而與其他化合物鍵結，亦可在未經由交聯劑(F)情況下直接鍵結於其他化合物。藉由丙烯酸系樹脂利用上述官能基而與其他化合物鍵結，便具有提升使用保護膜形成用複合片所獲得封裝之可靠度的傾向。The acrylic resin may have, for example, a functional group capable of bonding to another compound such as a vinyl group, a (meth) acrylfluorenyl group, an amine group, a hydroxyl group, a carboxyl group, or an isocyanate group. The functional group of the acrylic resin may be bonded to another compound via a cross-linking agent (F) described later, or may be directly bonded to another compound without the cross-linking agent (F). By bonding the acrylic resin with other compounds by using the above-mentioned functional group, there is a tendency to improve the reliability of the package obtained by using the composite sheet for forming a protective film.
本發明中，聚合體成分(A)係可未使用丙烯酸系樹脂情況下，單獨使用丙烯酸系樹脂以外的熱可塑性樹脂(以下亦簡稱「熱可塑性樹脂」)，亦可併用丙烯酸系樹脂。藉由使用上述熱可塑性樹脂，則提升保護膜從支撐片的剝離性、使熱硬化性保護膜形成用薄膜可輕易追隨被黏物的凹凸面等，有時會更加抑制被黏物與熱硬化性保護膜形成用薄膜間發生孔隙等。In the present invention, when the polymer component (A) is not an acrylic resin, a thermoplastic resin other than the acrylic resin (hereinafter also simply referred to as "thermoplastic resin") may be used alone, or an acrylic resin may be used in combination. By using the above-mentioned thermoplastic resin, the peelability of the protective film from the support sheet is improved, the film for forming the thermosetting protective film can easily follow the uneven surface of the adherend, etc., and sometimes the adherend and the thermosetting can be further suppressed. Pores and the like occur between thin films for forming a protective film.
上述熱可塑性樹脂的重量平均分子量較佳係1000~100000、更佳係3000~80000。The weight average molecular weight of the thermoplastic resin is preferably 1,000 to 100,000, and more preferably 3,000 to 80,000.
上述熱可塑性樹脂的玻璃轉移溫度(Tg)較佳係-30~150℃、更佳係-20~120℃。The glass transition temperature (Tg) of the thermoplastic resin is preferably -30 to 150 ° C, and more preferably -20 to 120 ° C.
上述熱可塑性樹脂，可舉例如:聚酯、聚氨酯、苯氧樹脂、聚丁烯、聚丁二烯、聚苯乙烯等。Examples of the thermoplastic resin include polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene.
組成物(III-1)及熱硬化性保護膜形成用薄膜所含有的上述熱可塑性樹脂，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The thermoplastic resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio are Can be chosen arbitrarily.
組成物(III-1)中，聚合體成分(A)含有量相對於溶劑除外所有成分總含有量的比例(即，熱硬化性保護膜形成用薄膜的聚合體成分(A)含有量)，不管聚合體成分(A)的種類，均較佳係5~85質量%、更佳係5~75質量%，例如可為5~65質量%、5~50質量%、及10~35質量%等中之任一者。In the composition (III-1), the ratio of the content of the polymer component (A) to the total content of all components excluding the solvent (that is, the content of the polymer component (A) in the film for forming a thermosetting protective film), Regardless of the type of the polymer component (A), it is preferably 5 to 85% by mass, more preferably 5 to 75% by mass, and may be, for example, 5 to 65% by mass, 5 to 50% by mass, and 10 to 35% by mass. Either of them.
聚合體成分(A)會有亦屬於熱硬化性成分(B)的情況。本發明中，當組成物(III-1)係含有此種隸屬於聚合體成分(A)與熱硬化性成分(B)雙方的成分時，便視同組成物(III-1)係含有聚合體成分(A)與熱硬化性成分(B)。The polymer component (A) may also be a thermosetting component (B). In the present invention, when the composition (III-1) contains such a component belonging to both the polymer component (A) and the thermosetting component (B), it is deemed that the composition (III-1) contains polymerization Body component (A) and thermosetting component (B).
[熱硬化性成分(B)]
熱硬化性成分(B)係供使熱硬化性保護膜形成用薄膜硬化用的成分。
組成物(III-1)及熱硬化性保護膜形成用薄膜所含有的熱硬化性成分(B)，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。[Thermosetting component (B)]
The thermosetting component (B) is a component for curing a film for forming a thermosetting protective film.
The composition (III-1) and the thermosetting component (B) contained in the film for forming a thermosetting protective film may be only one type or two or more types, and in the case of two or more types, a combination thereof The ratio can be selected arbitrarily.
熱硬化性成分(B)係可舉例如:環氧系熱硬化性樹脂、熱硬化性聚醯亞胺、聚氨酯、不飽和聚酯、聚矽氧樹脂等，較佳係環氧系熱硬化性樹脂。Examples of the thermosetting component (B) include epoxy-based thermosetting resin, thermosetting polyimide, polyurethane, unsaturated polyester, and silicone resin, and epoxy-based thermosetting is preferred. Resin.
(環氧系熱硬化性樹脂)
環氧系熱硬化性樹脂係由環氧樹脂(B1)與熱硬化劑(B2)構成。
組成物(III-1)及熱硬化性保護膜形成用薄膜所含有的環氧系熱硬化性樹脂，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。(Epoxy-based thermosetting resin)
The epoxy-based thermosetting resin is composed of an epoxy resin (B1) and a thermosetting agent (B2).
The epoxy resin-based thermosetting resin contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or two or more types, and in the case of two or more types, a combination The ratio can be selected arbitrarily.
・環氧樹脂(B1)
環氧樹脂(B1)可列舉公知物，例如:多官能基系環氧樹脂、聯苯化合物、雙酚A二環氧丙醚及其氫化物、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、伸苯骨架型環氧樹脂等雙官能基以上的環氧化合物。・ Epoxy resin (B1)
Examples of the epoxy resin (B1) include known epoxy resins, polyfunctional epoxy resins, biphenyl compounds, bisphenol A diglycidyl ether and hydrides thereof, o-cresol novolac epoxy resin, and dicyclopentyl. Diene type epoxy resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenylene skeleton type epoxy resin.
環氧樹脂(B1)亦可使用具有不飽和烴基的環氧樹脂。具有不飽和烴基的環氧樹脂之與丙烯酸系樹脂間之相溶性，較高於與未具不飽和烴基的環氧樹脂間之相溶性。所以，藉由使用具有不飽和烴基的環氧樹脂，便可提升使用保護膜形成用複合片所獲得具保護膜之半導體晶片的可靠度。The epoxy resin (B1) may be an epoxy resin having an unsaturated hydrocarbon group. The compatibility between the epoxy resin having an unsaturated hydrocarbon group and the acrylic resin is higher than the compatibility with the epoxy resin having no unsaturated hydrocarbon group. Therefore, by using an epoxy resin having an unsaturated hydrocarbon group, the reliability of a semiconductor wafer having a protective film obtained by using the composite sheet for forming a protective film can be improved.
具不飽和烴基的環氧樹脂係可列舉例如多官能基系環氧樹脂的部分環氧基，被轉換為具不飽和烴基之基而形成的化合物。此種化合物係例如藉由使(甲基)丙烯酸或其衍生物，對環氧基進行加成反應便可獲得。
再者，具不飽和烴基的環氧樹脂係可列舉例如在構成環氧樹脂的芳香環等，直接鍵結著具不飽和烴基之基的化合物等。
不飽和烴基係具有聚合性的不飽和基，具體例係可舉例如: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，較佳係丙烯醯基。Examples of the epoxy resin system having an unsaturated hydrocarbon group include compounds in which a part of epoxy groups of a polyfunctional epoxy resin is converted into a group having an unsaturated hydrocarbon group. Such a compound can be obtained, for example, by adding (meth) acrylic acid or a derivative thereof to an epoxy group.
Examples of the epoxy resin having an unsaturated hydrocarbon group include a compound having an unsaturated hydrocarbon group directly bonded to an aromatic ring or the like constituting the epoxy resin.
The unsaturated hydrocarbon group has a polymerizable unsaturated group, and specific examples include an ethylenyl group, a 2-propenyl group, an allyl group, a (meth) acryl group, and a (meth) acryl group. An amino group and the like are preferably an acrylfluorenyl group.
環氧樹脂(B1)的數量平均分子量並無特別的限定，就從熱硬化性保護膜形成用薄膜的硬化性、以及硬化後的保護膜強度與耐熱性觀點，較佳係300~30000、更佳係300~10000、特佳係300~3000。The number average molecular weight of the epoxy resin (B1) is not particularly limited. From the viewpoint of the curability of the film for forming a thermosetting protective film, and the strength and heat resistance of the cured protective film, it is preferably 300 to 30,000, more The best line is 300 ~ 10000, the special line is 300 ~ 3000.
本說明書中，所謂「數量平均分子量」在無特別聲明前提下，係指利用凝膠滲透色層分析儀(GPC)法所測定的聚苯乙烯換算值。In this specification, the "quantity average molecular weight" refers to a polystyrene conversion value measured by a gel permeation chromatography (GPC) method unless otherwise specified.
環氧樹脂(B1)的環氧當量較佳係100~1000g/eq、更佳係150~950g/eq。The epoxy equivalent of the epoxy resin (B1) is preferably 100 to 1000 g / eq, and more preferably 150 to 950 g / eq.
環氧樹脂(B1)係可單獨使用1種、亦可併用2種以上，若倂用2種以上的情況，其組合與比率係可任意選擇。The epoxy resin (B1) can be used singly or in combination of two or more kinds. If two or more kinds are used, the combination and ratio can be arbitrarily selected.
・熱硬化劑(B2)
熱硬化劑(B2)係對環氧樹脂(B1)具有硬化劑的機能。
熱硬化劑(B2)可列舉1分子中具有2個以上能與環氧基產生反應之官能基的化合物。上述官能基係可舉例如:酚性羥基、醇性羥基、胺基、羧基、以及由酸基經酸酐化的基等，較佳係酚性羥基、胺基、或由酸基經酸酐化的基，更佳係酚性羥基或胺基。・ Heat hardener (B2)
The thermosetting agent (B2) has a function of a curing agent for the epoxy resin (B1).
Examples of the thermosetting agent (B2) include compounds having two or more functional groups capable of reacting with epoxy groups in one molecule. Examples of the functional group include a phenolic hydroxyl group, an alcoholic hydroxyl group, an amine group, a carboxyl group, and an acid-anhydrided group. An phenolic hydroxyl group, an amine group, or an acid-anhydride group is preferred. More preferably, it is a phenolic hydroxyl group or an amine group.
熱硬化劑(B2)中，具有酚性羥基的酚系硬化劑係可舉例如:多官能基酚樹脂、聯苯、酚醛清漆型酚樹脂、二環戊二烯型酚樹脂、芳烷基型酚樹脂等。
熱硬化劑(B2)中，具有胺基的胺系硬化劑可列舉例如:二氰二胺等。Examples of the thermal hardener (B2) include phenolic hardeners having a phenolic hydroxyl group: polyfunctional phenol resins, biphenyls, novolac-type phenol resins, dicyclopentadiene-type phenol resins, and aralkyl-type resins. Phenol resin and so on.
Examples of the thermal curing agent (B2) include an amine-based curing agent having an amine group, such as dicyandiamine.
熱硬化劑(B2)亦可具有不飽和烴基。
具不飽和烴基的熱硬化劑(B2)係可舉例如:酚樹脂的部分羥基被具不飽和烴基的基所取代之化合物，以及在酚樹脂的芳香環直接鍵結具不飽和烴基之基而形成的化合物等。
熱硬化劑(B2)中的上述不飽和烴基，係與上述具不飽和烴基之環氧樹脂中的不飽和烴基為同樣者。The thermosetting agent (B2) may have an unsaturated hydrocarbon group.
Examples of the thermosetting agent (B2) having an unsaturated hydrocarbon group include compounds in which a part of hydroxyl groups of a phenol resin is replaced with a group having an unsaturated hydrocarbon group, and a group having an unsaturated hydrocarbon group is directly bonded to the aromatic ring of the phenol resin. Formed compounds, etc.
The unsaturated hydrocarbon group in the thermosetting agent (B2) is the same as the unsaturated hydrocarbon group in the epoxy resin having an unsaturated hydrocarbon group.
當熱硬化劑(B2)係使用酚系硬化劑的情況，就從提升保護膜從支撐片的剝離性觀點，熱硬化劑(B2)較佳係軟化點或玻璃轉移溫度較高者。When the thermosetting agent (B2) is a phenol-based curing agent, the thermosetting agent (B2) is preferably one having a higher softening point or a higher glass transition temperature from the viewpoint of improving the peelability of the protective film from the support sheet.
熱硬化劑(B2)中，例如多官能基酚樹脂、酚醛清漆型酚樹脂、二環戊二烯型酚樹脂、芳烷基型酚樹脂等樹脂成分的數量平均分子量，較佳係300~30000、更佳係400~10000、特佳係500~3000。
熱硬化劑(B2)中，例如聯苯、二氰二胺等非樹脂成分的分子量並無特別的限定，較佳係例如60~500。The number average molecular weight of the resin components such as the polyfunctional phenol resin, novolac-type phenol resin, dicyclopentadiene-type phenol resin, and aralkyl-type phenol resin in the thermosetting agent (B2) is preferably 300 to 30,000 4, better line 400 ~ 10000, special line 500 ~ 3000.
In the thermosetting agent (B2), the molecular weight of non-resin components such as biphenyl and dicyandiamine is not particularly limited, but is preferably 60 to 500, for example.
熱硬化劑(B2)係可單獨使用1種、亦可併用2種以上，若倂用2種以上的情況，其組合與比率係可任意選擇。The thermosetting agent (B2) can be used singly or in combination of two or more kinds. If two or more kinds are used, the combination and ratio can be arbitrarily selected.
組成物(III-1)及熱硬化性保護膜形成用薄膜中，熱硬化劑(B2) 的含有量相對於環氧樹脂(B1) 的含有量100質量份，較佳係0.1~500質量份、更佳係1~200質量份，亦可例如1~100質量份、1~50質量份、1~25質量份、及1~10質量份等中之任一者。藉由熱硬化劑(B2)的上述含有量達上述下限值以上，使熱硬化性保護膜形成用薄膜的硬化更容易進行。又，藉由熱硬化劑(B2)的上述含有量在上述上限值以下，降低熱硬化性保護膜形成用薄膜的吸濕率，更加提升使用保護膜形成用複合片所獲得封裝的可靠度。In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting agent (B2) relative to the content of the epoxy resin (B1) is 100 parts by mass, and preferably 0.1 to 500 parts by mass More preferably, it is 1 to 200 parts by mass, or any one of 1 to 100 parts by mass, 1 to 50 parts by mass, 1 to 25 parts by mass, and 1 to 10 parts by mass. When the content of the thermosetting agent (B2) is equal to or higher than the above-mentioned lower limit value, curing of the film for forming a thermosetting protective film is more easily performed. In addition, as the content of the thermosetting agent (B2) is below the upper limit, the moisture absorption rate of the film for forming a thermosetting protective film is reduced, and the reliability of the package obtained by using the composite sheet for forming a protective film is further improved. .
組成物(III-1)及熱硬化性保護膜形成用薄膜中，熱硬化性成分(B)的含有量(例如環氧樹脂(B1)與熱硬化劑(B2)的總含有量)，相對於聚合體成分(A)含有量100質量份，較佳係20~500質量份、更佳係30~300質量份、特佳係40~150質量份，可例如45~100質量份、及50~80質量份等中之任一者。藉由熱硬化性成分(B)的上述含有量在此種範圍內，例如抑制保護膜形成用薄膜之硬化物與支撐片間之接著力，提升支撐片的剝離性。In the composition (III-1) and the film for forming a thermosetting protective film, the content of the thermosetting component (B) (for example, the total content of the epoxy resin (B1) and the thermosetting agent (B2)) is relatively The content of the polymer component (A) is 100 parts by mass, preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and particularly good 40 to 150 parts by mass, for example, 45 to 100 parts by mass, and 50 ~ 80 parts by mass. When the above-mentioned content of the thermosetting component (B) is within such a range, for example, the adhesion between the cured product of the protective film-forming film and the support sheet is suppressed, and the peelability of the support sheet is improved.
[硬化促進劑(C)]
組成物(III-1)及熱硬化性保護膜形成用薄膜亦可含有硬化促進劑(C)。硬化促進劑(C)係供調整組成物(III-1)之硬化速度的成分。
較佳硬化促進劑(C)係可舉例如:三伸乙二胺、苄基二甲胺、三乙醇胺、二甲胺基乙醇、參(二甲胺基甲基)酚等的三級胺；2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2-苯基-4,5-二羥甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑等咪唑類(1個以上氫原子被氫原子以外的基所取代之咪唑)；三丁膦、二苯膦、三苯膦等有機膦類(1個以上氫原子被有機基所取代的膦)；四苯鏻四苯基硼酸鹽、三苯膦四苯基硼酸鹽等四苯硼酸鹽等。[Hardening accelerator (C)]
The composition (III-1) and the film for forming a thermosetting protective film may contain a curing accelerator (C). The hardening accelerator (C) is a component for adjusting the hardening rate of the composition (III-1).
Preferred hardening accelerators (C) are, for example, tertiary amines such as triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, gins (dimethylaminomethyl) phenol, and the like; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4,5-dimethylol imidazole, 2-phenyl-4-methyl-5- Imidazoles such as hydroxymethylimidazole (imidazole with more than one hydrogen atom replaced by a group other than a hydrogen atom); organic phosphines such as tributylphosphine, diphenylphosphine, triphenylphosphine (more than one hydrogen atom is replaced by an organic group) Substituted phosphines); tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, and the like.
組成物(III-1)及熱硬化性保護膜形成用薄膜所含有的硬化促進劑(C)，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The composition (III-1) and the hardening accelerator (C) contained in the film for forming a thermosetting protective film may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and The ratio system can be arbitrarily selected.
當使用硬化促進劑(C)的情況，在組成物(III-1)及熱硬化性保護膜形成用薄膜中，硬化促進劑(C)含有量相對於熱硬化性成分(B)含有量100質量份，較佳係0.01~10質量份、更佳係0.1~7質量份。藉由硬化促進劑(C)的上述含有量達上述下限值以上，便可使由使用硬化促進劑(C)所造成的效果更加明顯。又，藉由硬化促進劑(C)的含有量在上述上限值以下，則例如可提高抑制高極性硬化促進劑(C)在高溫・高濕度條件下，於熱硬化性保護膜形成用薄膜中偏析朝與被黏物間之接著界面移動的效果，更加提升使用保護膜形成用複合片所獲得具保護膜之半導體晶片的可靠度。When a hardening accelerator (C) is used, the content of the hardening accelerator (C) in the composition (III-1) and the film for forming a thermosetting protective film is 100 relative to the content of the thermosetting component (B). It is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 7 parts by mass. When the content of the hardening accelerator (C) is at least the above-mentioned lower limit, the effect caused by using the hardening accelerator (C) can be made more pronounced. Further, when the content of the hardening accelerator (C) is below the above-mentioned upper limit value, for example, it is possible to increase the suppression of the high-polarity hardening accelerator (C) in a film for forming a thermosetting protective film under high temperature and high humidity conditions. The effect of the middle segregation moving toward the interface between the adherend and the substrate further increases the reliability of the semiconductor wafer with a protective film obtained by using the protective film-forming composite sheet.
[填充材(D)]
組成物(III-1)及熱硬化性保護膜形成用薄膜亦可含有填充材(D)。熱硬化性保護膜形成用薄膜藉由含有填充材(D)，可更輕易將上述吸水率與黏著力變化率調整於目標範圍內。又，熱硬化性保護膜形成用薄膜及保護膜係藉由含有填充材(D)，可更輕易地調節熱膨脹係數，藉由將此熱膨脹係數對熱硬化性保護膜形成用薄膜或保護膜的形成標的物呈最佳化，便可更加提升使用保護膜形成用複合片所獲得具保護膜之半導體晶片的可靠度。又，熱硬化性保護膜形成用薄膜藉由含有填充材(D)，亦可降低保護膜的吸濕率、提升散熱性等。[Filling material (D)]
The composition (III-1) and the film for forming a thermosetting protective film may contain a filler (D). By including the filler (D) in the film for forming a thermosetting protective film, it is possible to more easily adjust the above-mentioned water absorption rate and adhesive force change rate within a target range. In addition, the film for forming a thermosetting protective film and the protective film can more easily adjust the coefficient of thermal expansion by containing the filler (D), and the coefficient of thermal expansion can be applied to the film or film of the film for forming a thermosetting protective film. The formation of the target is optimized, which can further improve the reliability of the semiconductor wafer with a protective film obtained by using the protective film-forming composite sheet. In addition, by including the filler (D) in the film for forming a thermosetting protective film, the moisture absorption rate of the protective film can be reduced, and heat dissipation properties can be improved.
填充材(D)係有機填充材與無機填充材任一者均可，較佳係無機填充材。
較佳無機填充材係可舉例如:二氧化矽、氧化鋁、滑石、碳酸鈣、鈦白、氧化鐵紅、碳化矽、氮化硼等粉末；將這些無機填充材施行球形化後的球珠；這些無機填充材的表面改質物；這些無機填充材的單結晶纖維；玻璃纖維等。
這些之中，無機填充材較佳係二氧化矽或氧化鋁、更佳係二氧化矽。The filler (D) may be either an organic filler or an inorganic filler, and is preferably an inorganic filler.
Preferred inorganic filler materials include, for example, silicon dioxide, aluminum oxide, talc, calcium carbonate, titanium white, iron oxide red, silicon carbide, boron nitride, and other powders; spherical beads made of these inorganic fillers ; Surface modifiers of these inorganic fillers; single crystal fibers of these inorganic fillers; glass fibers and the like.
Among these, the inorganic filler is preferably silicon dioxide or aluminum oxide, and more preferably silicon dioxide.
組成物(III-1)及熱硬化性保護膜形成用薄膜所含有的填充材(D)，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The composition (III-1) and the filler (D) contained in the film for forming a thermosetting protective film may be only one type, or two or more types. In the case of two or more types, the combination and ratio thereof Department can be arbitrarily selected.
當使用填充材(D)的情況，組成物(III-1)中，填充材(D)含有量相對於溶劑以外所有成分總含有量的比例(即，熱硬化性保護膜形成用薄膜的填充材(D)含有量)，較佳係5~80質量%、更佳係10~70質量%，例如可為20~65質量%、30~65質量%及40~65質量%等中之任一者。藉由填充材(D)含有量在此種範圍內，便更輕易調整上述熱膨脹係數，且更加提升保護膜形成用薄膜與保護膜的強度。When the filler (D) is used, in the composition (III-1), the ratio of the content of the filler (D) to the total content of all components except the solvent (that is, the filling of the film for forming a thermosetting protective film) (D) content), preferably 5 to 80% by mass, more preferably 10 to 70% by mass, for example, any of 20 to 65% by mass, 30 to 65% by mass, and 40 to 65% by mass, etc. One. When the content of the filler (D) is within such a range, the above-mentioned thermal expansion coefficient can be adjusted more easily, and the strength of the protective film-forming film and the protective film can be further improved.
[偶合劑(E)]
組成物(III-1)及熱硬化性保護膜形成用薄膜亦可含有偶合劑(E)。偶合劑(E)係藉由使用具有能與無機化合物或有機化合物產生反應之官能基者，便可提升熱硬化性保護膜形成用薄膜對被黏物的接著性與密接性。又，藉由使用偶合劑(E)，熱硬化性保護膜形成用薄膜的硬化物(保護膜)便可在不會損及耐熱性情況下，提升耐水性。[Coupling agent (E)]
The composition (III-1) and the film for forming a thermosetting protective film may contain a coupling agent (E). The coupling agent (E) can improve the adhesion and adhesion of the film for forming a thermosetting protective film to an adherend by using a functional group capable of reacting with an inorganic compound or an organic compound. Moreover, by using a coupling agent (E), the hardened | cured material (protective film) of the film for thermosetting protective film formation can improve water resistance without impairing heat resistance.
偶合劑(E)較佳係具有能與聚合體成分(A)、熱硬化性成分(B)等所具有官能基產生反應之官能基的化合物，更佳係矽烷偶合劑。
較佳的上述矽烷偶合劑係可舉例如:3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙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-脲丙基三乙氧基矽烷、3-巰丙基三甲氧基矽烷、3-巰丙基甲基二甲氧基矽烷、雙(3-三乙氧基矽烷丙基)四磺胺、甲基三甲氧基矽烷、甲基三乙氧基矽烷、乙烯三甲氧基矽烷、乙烯三乙醯氧基矽烷、咪唑矽烷等。The coupling agent (E) is preferably a compound having a functional group capable of reacting with a functional group such as a polymer component (A), a thermosetting component (B), and more preferably a silane coupling agent.
Preferred examples of the above-mentioned silane coupling agent systems include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxy Propyltriethoxysilane, 3-glycidoxymethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyl Methylmethyldiethoxysilane, 3- (phenylamino) propyltrimethoxysilane, 3-anilinepropyltrimethoxysilane, 3-ureapropyltriethoxysilane, 3-mercaptopropane Trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfonamide, methyltrimethoxysilane, methyltriethoxysilane, ethylene Trimethoxysilane, ethylene triethoxysilane, imidazole silane, etc.
組成物(III-1)及熱硬化性保護膜形成用薄膜所含有的偶合劑(E)，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The composition (III-1) and the coupling agent (E) contained in the film for forming a thermosetting protective film may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio thereof Department can be arbitrarily selected.
使用偶合劑(E)的情況，組成物(III-1)及熱硬化性保護膜形成用薄膜中，偶合劑(E)的含有量，相對於聚合體成分(A)與熱硬化性成分(B)的總含有量100質量份，較佳係0.03~20質量份、更佳係0.05~10質量份、特佳係0.1~5質量份。藉由偶合劑(E)的上述含有量達上述下限值以上，便可提升填充材(D)對樹脂的分散性、提升熱硬化性保護膜形成用薄膜與被黏物間之接著性等，可使由使用偶合劑(E)造成的效果更加明顯。又，藉由偶合劑(E)的上述含有量在上述上限值以下，更加抑制發生逸氣情形。When a coupling agent (E) is used, the content of the coupling agent (E) in the composition (III-1) and the film for forming a thermosetting protective film is higher than that of the polymer component (A) and the thermosetting component ( B) The total content is 100 parts by mass, preferably from 0.03 to 20 parts by mass, more preferably from 0.05 to 10 parts by mass, and particularly preferably from 0.1 to 5 parts by mass. When the content of the coupling agent (E) reaches the above lower limit value, the dispersibility of the filler (D) to the resin can be improved, and the adhesion between the film for forming a thermosetting protective film and the adherend can be improved. , Can make the effect caused by using the coupling agent (E) more obvious. In addition, since the above-mentioned content of the coupling agent (E) is equal to or less than the above-mentioned upper limit value, occurrence of outgassing is further suppressed.
[交聯劑(F)]
當聚合體成分(A)係使用上述丙烯酸系樹脂等具有能與其他化合物鍵結之乙烯基、(甲基)丙烯醯基、胺基、羥基、羧基、異氰酸酯基等官能基者的情況，組成物(III-1)與熱硬化性保護膜形成用薄膜亦可含有交聯劑(F)。交聯劑(F)係供使聚合體成分(A)中的上述官能基與其他化合物鍵結進行交聯用的成分，藉由依此進行交聯，便可調節熱硬化性保護膜形成用薄膜的初期接著力與凝聚力。[Crosslinking agent (F)]
When the polymer component (A) is a functional group such as the above-mentioned acrylic resin having a functional group such as a vinyl group, a (meth) acryl group, an amino group, a hydroxyl group, a carboxyl group, or an isocyanate group, which can be bonded to other compounds, (III-1) and the film for forming a thermosetting protective film may contain a crosslinking agent (F). The cross-linking agent (F) is a component for cross-linking the above-mentioned functional group in the polymer component (A) with another compound. By performing cross-linking in this manner, the film for forming a thermosetting protective film can be adjusted. Initial cohesion and cohesion.
交聯劑(F)係可舉例如:有機多元異氰酸酯化合物、有機多元亞胺化合物、金屬螯合系交聯劑(具金屬螯合構造的交聯劑)、氮丙啶系交聯劑(具吖丙啶基的交聯劑)等。Examples of the crosslinking agent (F) include: organic polyisocyanate compounds, organic polyimide compounds, metal chelate crosslinking agents (crosslinking agents with metal chelate structures), and aziridine crosslinking agents (having Aziridinyl crosslinking agent) and the like.
上述有機多元異氰酸酯化合物係可舉例如: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(以下將這些化合物統稱為「芳香族多元異氰酸酯化合物等」)；上述芳香族多元異氰酸酯化合物等的三聚體、異三聚氰酸酯體及加成體；由上述芳香族多元異氰酸酯化合物等、與多元醇化合物進行反應獲得的末端異氰酸酯胺甲酸乙酯預聚物等。上述「加成體」係指由上述芳香族多元異氰酸酯化合物、脂肪族多元異氰酸酯化合物或脂環族多元異氰酸酯化合物，與乙二醇、丙二醇、新戊二醇、三羥甲基丙烷或蓖麻油等含低分子活性氫化合物的反應產物。上述加成體之例可列舉如後述的三羥甲基丙烷之二異氰酸伸苯二甲酯加成物等。又，所謂「末端異氰酸酯胺甲酸乙酯預聚物」係如前所說明。Examples of the organic polyisocyanate compounds include: aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds (hereinafter these compounds are collectively referred to as "aromatic polyisocyanate compounds"); the above-mentioned aromatic polyisocyanates; Trimers, isotricyanate bodies, and adducts of compounds, etc .; terminal isocyanate urethane prepolymers, etc., obtained by reacting the above-mentioned aromatic polyisocyanate compounds and the like with polyol compounds. The "adduct" refers to an aromatic polyisocyanate compound, an aliphatic polyisocyanate compound, or an alicyclic polyisocyanate compound, and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, or castor oil, etc. The reaction product of low-molecular active hydrogen compounds. Examples of the adduct include trimethylolpropane diisocyanate adduct and the like as described below. The "terminal isocyanate urethane prepolymer" is as described above.
上述有機多元異氰酸酯化合物更具體係可舉例如:2,4-二異氰酸甲苯酯；2,6-二異氰酸甲苯酯；1,3-二異氰酸伸苯二甲酯；1,4-二甲苯二異氰酸酯；二苯甲烷-4,4'-二異氰酸酯；二苯甲烷-2,4'-二異氰酸酯；3-甲基二苯甲烷二異氰酸酯；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；在三羥甲基丙烷等的多元醇之所有或部分羥基，加成二異氰酸甲苯酯、六亞甲基二異氰酸酯及二異氰酸伸苯二甲酯中之任1種或2種以上的化合物；離胺酸二異氰酸酯等。The above organic polyisocyanate compounds can be more systematic, for example: 2,4-diisocyanate toluene; 2,6-diisocyanate toluene; 1,3-diisocyanate phthalate; 1, 4-xylene diisocyanate; diphenylmethane-4,4'-diisocyanate; diphenylmethane-2,4'-diisocyanate; 3-methyldiphenylmethane diisocyanate; hexamethylene diisocyanate; isophor Diisocyanate; dicyclohexylmethane-4,4'-diisocyanate; dicyclohexylmethane-2,4'-diisocyanate; all or part of the hydroxyl groups in a polyhydric alcohol such as trimethylolpropane, and the addition of two Any one or two or more compounds of toluene isocyanate, hexamethylene diisocyanate, and phenylene diisocyanate; lysine diisocyanate, and the like.
上述有機多元亞胺化合物係可舉例如:N,N'-二苯甲烷-4,4'-雙(1-氮丙啶羧醯胺)、三羥甲基丙烷-三-β-吖丙啶基丙酸酯、四羥甲基甲烷-三-β-吖丙啶基丙酸酯、N,N'-甲苯-2,4-雙(1-氮丙啶羧醯胺)三伸乙基三聚氰胺等。Examples of the organic polyimide compound include: N, N'-diphenylmethane-4,4'-bis (1-aziridinecarboxamide), trimethylolpropane-tri-β-aziridine Propionate, tetramethylol methane-tri-β-aziridinyl propionate, N, N'-toluene-2,4-bis (1-aziridinecarboxamide) triethyl melamine Wait.
當交聯劑(F)係使用有機多元異氰酸酯化合物的情況，聚合體成分(A)較佳係使用含羥基聚合體。當交聯劑(F)具有異氰酸酯基，且聚合體成分(A)具有羥基的情況，藉由交聯劑(F)與聚合體成分(A)的反應，便可簡便地在熱硬化性保護膜形成用薄膜中導入交聯構造。When the cross-linking agent (F) is an organic polyisocyanate compound, the polymer component (A) is preferably a hydroxyl-containing polymer. When the cross-linking agent (F) has an isocyanate group and the polymer component (A) has a hydroxyl group, the reaction of the cross-linking agent (F) and the polymer component (A) can easily protect the thermosetting property. A cross-linked structure is introduced into the film for film formation.
組成物(III-1)及熱硬化性保護膜形成用薄膜所含有的交聯劑(F)，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The composition (III-1) and the cross-linking agent (F) contained in the film for forming a thermosetting protective film may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and The ratio system can be arbitrarily selected.
當使用交聯劑(F)的情況，組成物(III-1)中的交聯劑(F)含有量，相對於聚合體成分(A)含有量100質量份，較佳係0.01~20質量份、更佳係0.1~10質量份、特佳係0.5~5質量份。藉由交聯劑(F)的上述含有量達上述下限值以上，便可使由使用交聯劑(F)所造成效果更加明顯。又，藉由交聯劑(F)的上述含有量在上述上限值以下，便可抑制交聯劑(F)過度使用。When using a cross-linking agent (F), the content of the cross-linking agent (F) in the composition (III-1) is preferably 100 to 100 parts by mass with respect to the polymer component (A), preferably 0.01 to 20 parts by mass Parts, more preferably 0.1 to 10 parts by mass, and special parts 0.5 to 5 parts by mass. When the content of the cross-linking agent (F) is at least the above-mentioned lower limit, the effect caused by using the cross-linking agent (F) can be made more pronounced. Moreover, when the said content of a crosslinking agent (F) is below the said upper limit, an excessive use of a crosslinking agent (F) can be suppressed.
[能量線硬化性樹脂(G)]
組成物(III-1)亦可含有能量線硬化性樹脂(G)。藉由熱硬化性保護膜形成用薄膜含有能量線硬化性樹脂(G)，便可利用能量線照射使特性變化。[Energy ray hardening resin (G)]
The composition (III-1) may contain an energy ray-curable resin (G). When the film for forming a thermosetting protective film contains an energy ray-curable resin (G), the characteristics can be changed by energy ray irradiation.
能量線硬化性樹脂(G)係由能量線硬化性化合物進行聚合(硬化)而獲得。
上述能量線硬化性化合物可列舉1分子內具有至少1個聚合性雙鍵的化合物，較佳係具(甲基)丙烯醯基的丙烯酸酯系化合物。The energy ray-curable resin (G) is obtained by polymerizing (curing) an energy ray-curable compound.
Examples of the energy ray-curable compound include a compound having at least one polymerizable double bond in one molecule, and an acrylic compound having a (meth) acrylfluorenyl group is preferred.
上述丙烯酸酯系化合物係可舉例如:三羥甲基丙烷三[(甲基)丙烯酸酯]、四羥甲基甲烷四[(甲基)丙烯酸酯]、新戊四醇三[(甲基)丙烯酸酯]、新戊四醇四[(甲基)丙烯酸酯]、二新戊四醇單羥五[(甲基)丙烯酸酯]、二新戊四醇六[(甲基)丙烯酸酯]、1,4-丁二醇二[(甲基)丙烯酸酯]、1,6-己二醇二[(甲基)丙烯酸酯]等含鏈狀脂肪族骨架之(甲基)丙烯酸酯；二(甲基)丙烯酸二環戊酯等含環狀脂肪族骨架之(甲基)丙烯酸酯；聚乙二醇二[(甲基)丙烯酸酯]等聚烷二醇(甲基)丙烯酸酯；寡聚酯(甲基)丙烯酸酯；胺甲酸乙酯(甲基)丙烯酸酯寡聚物；環氧改質(甲基)丙烯酸酯；上述聚烷二醇(甲基)丙烯酸酯以外的聚醚(甲基)丙烯酸酯；衣康酸寡聚物等。Examples of the acrylate-based compound include: trimethylolpropane tri [(meth) acrylate], tetramethylolmethane tetra [(meth) acrylate], and neopentaerythritol tri [(methyl) Acrylate], neopentaerythritol tetra [(meth) acrylate], dipentaerythritol monohydroxypenta [(meth) acrylate], dipentaerythritol hexa [(meth) acrylate], 1,4-butanediol di [(meth) acrylate], 1,6-hexanediol di [(meth) acrylate] and other (meth) acrylates containing a chain-like aliphatic skeleton; di ( (Meth) acrylates containing cyclic aliphatic skeletons such as dicyclopentyl methacrylate; polyalkylene glycol (meth) acrylates such as polyethylene glycol di [(meth) acrylate]; oligomeric Esters (meth) acrylates; urethane (meth) acrylate oligomers; epoxy modified (meth) acrylates; polyethers other than the polyalkylene glycol (meth) acrylates described above Group) acrylates; itaconic acid oligomers and the like.
上述能量線硬化性化合物的重量平均分子量較佳係100~30000、更佳係300~10000。The weight-average molecular weight of the energy ray-curable compound is preferably 100 to 30,000, and more preferably 300 to 10,000.
聚合時所使用的上述能量線硬化性化合物，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The above-mentioned energy ray-curable compound used at the time of polymerization may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
組成物(III-1)所含有的能量線硬化性樹脂(G)係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The energy ray-curable resin (G) contained in the composition (III-1) may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio thereof may be arbitrarily selected.
當使用能量線硬化性樹脂(G)的情況，組成物(III-1)的能量線硬化性樹脂(G)含有量，較佳係1~95質量%、更佳係5~90質量%、特佳係10~85質量%。When the energy ray curable resin (G) is used, the content of the energy ray curable resin (G) of the composition (III-1) is preferably 1 to 95% by mass, more preferably 5 to 90% by mass, Extra high quality is 10 to 85% by mass.
[光聚合起始劑(H)]
當組成物(III-1)係含有能量線硬化性樹脂(G)的情況，為能有效率地進行能量線硬化性樹脂(G)的聚合反應，亦可含有光聚合起始劑(H)。[Photopolymerization initiator (H)]
When the composition (III-1) contains the energy ray-curable resin (G), in order to efficiently perform the polymerization reaction of the energy ray-curable resin (G), a photopolymerization initiator (H) may also be contained. .
組成物(III-1)中的光聚合起始劑(H)係可舉例如:苯偶姻、苯偶姻甲醚、苯偶姻乙醚、苯偶姻異丙醚、苯偶姻異丁醚、苯偶姻安息香酸、苯偶姻安息香酸甲酯、苯偶姻二甲縮酮等苯偶姻化合物；苯乙酮、2-羥-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化氧化膦化合物；苄基苯硫醚、單硫化四甲胺硫甲醯等硫醚化合物；1-羥環己基苯酮等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；氧硫等氧硫化合物；過氧化合物；二乙醯等二酮化合物；苄基；二苄基；二苯基酮；2,4-二乙基氧硫；1,2-二苯甲烷；2-羥-2-甲基-1-[4-(1-甲基乙烯基)苯基]丙酮；2-氯蒽醌等。
再者，上述光聚合起始劑尚可舉例如:1-氯蒽醌等醌化合物；胺等光增感劑等。Examples of the photopolymerization initiator (H) in the composition (III-1) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Benzoin compounds such as benzoin benzoic acid, methyl benzoin benzoate, benzoin dimethyl ketal; acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1- Acetophenone compounds such as ketones, 2,2-dimethoxy-1,2-diphenylethane-1-one; bis (2,4,6-trimethylbenzyl) phenylphosphine oxide And 2,4,6-trimethylbenzylidene diphenylphosphine oxide and other halogenated phosphine oxide compounds; benzyl phenyl sulfide, tetramethylamine sulfide and other sulfide compounds; 1-hydroxycyclohexyl Α-keto alcohol compounds such as benzophenone; azo compounds such as azobisisobutyronitrile; titanocene compounds such as titanocene; oxysulfur Isosulfur Compounds; peroxy compounds; dione compounds such as diethylfluorene; benzyl; dibenzyl; diphenyl ketone; 2,4-diethyloxosulfide ; 1,2-diphenylmethane; 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] acetone; 2-chloroanthraquinone and the like.
In addition, the photopolymerization initiator may include, for example, quinone compounds such as 1-chloroanthraquinone, and photosensitizers such as amines.
組成物(III-1)所含有的光聚合起始劑(H)係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The photopolymerization initiator (H) contained in the composition (III-1) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
當使用光聚合起始劑(H)的情況，組成物(III-1)中的光聚合起始劑(H)含有量，相對於能量線硬化性樹脂(G)含有量100質量份，較佳係0.1~20質量份、更佳係1~10質量份、特佳係2~5質量份。When the photopolymerization initiator (H) is used, the content of the photopolymerization initiator (H) in the composition (III-1) is 100 parts by mass relative to the content of the energy ray-curable resin (G). 0.1 to 20 parts by mass, 1 to 10 parts by mass, 2 to 5 parts by mass.
[著色劑(I)]
組成物(III-1)及熱硬化性保護膜形成用薄膜亦可含有著色劑(I)。
著色劑(I)係可舉例如:無機系顏料、有機系顏料、有機系染料等公知物。[Colorant (I)]
The composition (III-1) and the film for forming a thermosetting protective film may contain a colorant (I).
Examples of the colorant (I) include known substances such as inorganic pigments, organic pigments, and organic dyes.
上述有機系顏料及有機系染料係可舉例如:銨（aminium）系色素、花青（cyanine）系色素、部花青素（merocyanine）系色素、克酮酸(croconium)系色素、方酸菁（squarylium）系色素、甘菊環鎓（azulenium）系色素、聚次甲基(polymethine)系色素、萘醌(naphthoquinone)系色素、吡喃(pyrylium)系色素、酞青素(phthalocyanine)系色素、萘酞青素(naphthalocyanine)系色素、萘內醯亞胺(naphtholactam)系色素、偶氮（azo）系色素、縮合偶氮系色素、靛藍（indigo）系色素、培利芘酮（perinone）系色素、苝（Perylene）系色素、雙噁嗪（dioxazine）系色素、喹吖酮（quinacridone）系色素、異吲哚啉酮（isoindolinone）系色素、喹啉黃（quinophthalone）系色素、吡咯（pyrrole）系色素、硫靛藍（thioindigo）系色素、金屬錯合物系色素(金屬錯鹽染料)、二硫酚（dithiol）金屬錯合物系色素、吲哚酚（indole phenol）系色素、三烯丙基甲烷（triallyl methane）系色素、蒽醌（anthraquinone）系色素、雙噁嗪系色素、萘酚（naphthol）系色素、甲亞胺（azomethine）系色素、苯并咪唑酮（benzimidazolone）系色素、皮蒽酮（pyranthrone）系色素及士林（threne）系色素等。Examples of the organic pigments and organic dyes include: ammonium-based pigments, cyanine-based pigments, merocyanine-based pigments, croconium-based pigments, and square acid cyanine. (Squarylium) pigment, azulenium pigment, polymethine pigment, naphthoquinone pigment, pyrylium pigment, phthalocyanine pigment, naphthalene Naphthalocyanine-based pigments, naphtholactam-based pigments, azo-based pigments, condensed azo-based pigments, indigo-based pigments, and perinone-based pigments , Perylene pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, quinophthalone pigments, pyrrole Pigments, thioindigo pigments, metal complex pigments (metal salt dyes), dithiol metal complex pigments, indole phenol pigments, three Allyl methane pigments, anthraquinone pigments, dioxazine pigments, naphthol pigments, azomethine pigments, benzimidazolone pigments Pigments, pyranthrone-based pigments, and threne-based pigments.
上述無機系顏料係可舉例如: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、白金系色素、ITO(氧化銦錫)系色素、ATO(氧化銻錫)系色素等。Examples of the inorganic pigment system include carbon black, cobalt-based pigment, iron-based pigment, chromium-based pigment, titanium-based pigment, vanadium-based pigment, zirconium-based pigment, molybdenum-based pigment, ruthenium-based pigment, platinum-based pigment, and ITO ( Indium tin oxide) based pigments, ATO (antimony tin oxide) based pigments, and the like.
組成物(III-1)及熱硬化性保護膜形成用薄膜所含有的著色劑(I)，係可僅為1種、亦可為2種以上，若2種以上的情況，該等的組合與比率係可任意選擇。The coloring agent (I) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one kind, or two or more kinds, and in the case of two or more kinds, a combination of these The ratio can be selected arbitrarily.
當使用著色劑(I)的情況，熱硬化性保護膜形成用薄膜的著色劑(I)含有量係只要配合目的再行適當調整便可。例如藉由調整熱硬化性保護膜形成用薄膜的著色劑(I)含有量而調整保護膜的光穿透性，便可調整對保護膜施行雷射刻印時的刻印檢視性。又，藉由調整熱硬化性保護膜形成用薄膜的著色劑(I)含有量，亦可提升保護膜的設計性、不易看到半導體晶圓背面的研削痕等。若考慮此點，在組成物(III-1)中，著色劑(I)含有量相對於溶劑以外所有成分總含有量的比例(即，熱硬化性保護膜形成用薄膜的著色劑(I)含有量)，較佳係0.1~10質量%、更佳係0.1~7.5質量%、特佳係0.1~5質量%。藉由著色劑(I)的上述含有量達上述下限值以上，便可使由使用著色劑(I)所造成效果更加明顯。又，藉由著色劑(I)的上述含有量在上述上限值以下，便抑制熱硬化性保護膜形成用薄膜的光穿透性的過度降低。When the colorant (I) is used, the content of the coloring agent (I) in the film for forming a thermosetting protective film may be adjusted as appropriate for the purpose. For example, by adjusting the content of the coloring agent (I) of the thin film for forming a thermosetting protective film and adjusting the light transmittance of the protective film, the marking visibility when the laser marking is performed on the protective film can be adjusted. In addition, by adjusting the content of the coloring agent (I) of the thin film for forming a thermosetting protective film, the design of the protective film can be improved, and it is difficult to see the grinding marks on the back surface of the semiconductor wafer. Taking this into consideration, in the composition (III-1), the ratio of the content of the colorant (I) to the total content of all components except the solvent (that is, the coloring agent (I) of the film for forming a thermosetting protective film (Content)), preferably 0.1 to 10% by mass, more preferably 0.1 to 7.5% by mass, and particularly good 0.1 to 5% by mass. When the content of the colorant (I) is at least the above-mentioned lower limit, the effect caused by using the colorant (I) can be made more pronounced. Moreover, when the said content of the coloring agent (I) is below the said upper limit, excessive reduction of the light transmittance of the film for thermosetting protective film formation is suppressed.
[通用添加劑(J)]
組成物(III-1)及熱硬化性保護膜形成用薄膜在不致損及本發明效果之範圍內，亦可含有通用添加劑(J)。
通用添加劑(J)係可為公知物，可配合目的再行任意選擇，並無特別的限定，、較佳係可舉例如:可塑劑、抗靜電劑、抗氧化劑、吸氣(gettering)劑等。[General additives (J)]
The composition (III-1) and the film for forming a thermosetting protective film may contain a general-purpose additive (J) as long as it does not impair the effects of the present invention.
The general additive (J) can be a publicly known substance, and can be arbitrarily selected according to the purpose, and is not particularly limited. Preferred examples include plasticizers, antistatic agents, antioxidants, gettering agents, etc. .
組成物(III-1)及熱硬化性保護膜形成用薄膜所含有的通用添加劑(J)，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。
組成物(III-1)及熱硬化性保護膜形成用薄膜中的通用添加劑(J)含有量，並無特別的限定，只要配合目的再行適當選擇便可。The general additive (J) contained in the composition (III-1) and the film for forming a thermosetting protective film may be only one type, or two or more types. In the case of two or more types, the combination and ratio thereof Department can be arbitrarily selected.
The content of the general additive (J) in the composition (III-1) and the film for forming a thermosetting protective film is not particularly limited, and may be appropriately selected depending on the purpose.
[溶劑]
組成物(III-1)以進一步含有溶劑為佳。含有溶劑的組成物(III-1)係處置性呈良好。
上述溶劑並無特別的限定，較佳係可舉例如:甲苯、二甲苯等烴類；甲醇、乙醇、2-丙醇、異丁基醇(2-甲基丙烷-1-醇)、1-丁醇等醇類；醋酸乙酯等酯類；丙酮、甲乙酮等酮類；四氫呋喃等醚類；二甲基甲醯胺、N-甲基吡咯啶酮等醯胺類(具醯胺鍵的化合物)等。
組成物(III-1)所含有的溶劑係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。[Solvent]
The composition (III-1) preferably further contains a solvent. The solvent-containing composition (III-1) has good disposability.
The above-mentioned solvent is not particularly limited, and preferred examples include hydrocarbons such as toluene and xylene; methanol, ethanol, 2-propanol, isobutyl alcohol (2-methylpropane-1-ol), 1- Alcohols such as butanol; Esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone; Ethers such as tetrahydrofuran; Amines such as dimethylformamide and N-methylpyrrolidone (compounds with amidine bonds) )Wait.
The solvent contained in the composition (III-1) may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be arbitrarily selected.
組成物(III-1)所含有的溶劑，就從使組成物(III-1)中的含有成分能更均勻混合的觀點，較佳係甲乙酮等。The solvent contained in the composition (III-1) is preferably methyl ethyl ketone or the like from the viewpoint that the components contained in the composition (III-1) can be more uniformly mixed.
＜＜熱硬化性保護膜形成用組成物之製造方法＞＞
組成物(III-1)等熱硬化性保護膜形成用組成物，係藉由摻合構成其的各成分便可獲得。
各成分摻合時的添加順序並無特別的限定，亦可2種以上的成分同時添加。
使用溶劑時，可將溶劑與除溶劑以外的任一摻合成分進行混合，再將該摻合成分施行預稀釋後才使用，亦可在未將溶劑以外的任一摻合成分施行預稀釋狀態下，便將溶劑與這些摻合成分施行混合使用。
摻合時，將各成分施行混合的方法並無特別的限定，可從例如:使攪拌子或攪拌葉片等旋轉而進行混合的方法；使用混合機進行混合的方法；施加超音波進行混合的方法等公知方法中適當選擇。
各成分的添加及混合時的溫度與時間係在各摻合成分不會劣化前提下，並無特別的限定，只要適當調整便可，溫度較佳係15~30℃。＜ Method for manufacturing a composition for forming a thermosetting protective film ＞＞
The composition for forming a thermosetting protective film such as the composition (III-1) can be obtained by blending the respective components constituting the composition.
The order of addition of each component is not particularly limited, and two or more components may be added simultaneously.
When using a solvent, the solvent can be mixed with any blending ingredient other than the solvent, and then the blending ingredient can be pre-diluted before use. It can also be used in a state where any blending ingredient other than the solvent is not pre-dilution Then, the solvent is mixed with these blended components and used.
The method of mixing the components during blending is not particularly limited. For example, a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, or a method of mixing by applying an ultrasonic wave. It is appropriately selected from other known methods.
The temperature and time during the addition and mixing of each component are not particularly limited as long as each blending component does not deteriorate, as long as it is appropriately adjusted, the temperature is preferably 15 to 30 ° C.
○能量線硬化性保護膜形成用薄膜
能量線硬化性保護膜形成用薄膜，可列舉含有能量線硬化性成分(a)者，較佳係含有能量線硬化性成分(a)與填充材。
能量線硬化性保護膜形成用薄膜中，能量線硬化性成分(a)以未硬化為佳，較佳係具有黏著性、更佳係未硬化且具有黏著性。此處所謂「能量線」與「能量線硬化性」係同前所說明。○ Thin film for forming energy ray curable protective film The thin film for forming energy ray curable protective film includes those containing an energy ray curable component (a), and preferably contains the energy ray curable component (a) and a filler.
In the film for forming an energy ray-curable protective film, the energy ray-curable component (a) is preferably uncured, and preferably has adhesiveness, and more preferably has uncured and adhesive properties. The so-called "energy ray" and "energy ray hardenability" are the same as described above.
將能量線硬化性保護膜形成用薄膜貼附於半導體晶圓的背面之後，使硬化時的硬化條件係在使硬化物成為能充分發揮機能之程度的硬化度前提下，並無特別的限定，只要配合能量線硬化性保護膜形成用薄膜的種類再行適當選擇便可。
例如能量線硬化性保護膜形成用薄膜進行硬化時，能量線的照度較佳係120~280mW/cm2
。而，上述硬化時，能量線的光通量較佳係100~1000mJ/cm2
。After the thin film for forming an energy ray-curable protective film is attached to the back surface of a semiconductor wafer, the curing conditions during curing are not specifically limited, provided that the cured product has a degree of curing that is capable of fully performing its functions. What is necessary is just to select suitably according to the kind of thin film for energy-ray-curable protective film formation.
For example, when the thin film for forming an energy ray-curable protective film is cured, the illuminance of the energy ray is preferably 120 to 280 mW / cm 2 . In the above curing, the luminous flux of the energy ray is preferably 100 to 1000 mJ / cm 2 .
＜能量線硬化性保護膜形成用組成物(IV-1)＞
較佳的能量線硬化性保護膜形成用組成物可列舉:含有上述能量線硬化性成分(a)的能量線硬化性保護膜形成用組成物(IV-1)(本說明書中亦簡稱為「組成物(IV-1)」)等。<Energy-ray-curable protective film-forming composition (IV-1)>
Examples of a preferable composition for forming an energy ray-curable protective film include the composition (IV-1) for forming an energy ray-curable protective film containing the energy ray-curable component (a) (also referred to simply as " Composition (IV-1) ") and the like.
[能量線硬化性成分(a)]
能量線硬化性成分(a)係藉由能量線照射會硬化的成分，亦屬於供對能量線硬化性保護膜形成用薄膜賦予造膜性、可撓性等，且經硬化後形成硬質保護膜用的成分。
能量線硬化性成分(a)可列舉例如:具有能量線硬化性基且重量平均分子量80000~2000000的聚合體(a1)；以及具能量線硬化性基且分子量100~80000的化合物(a2)。上述聚合體(a1)係可至少其中一部分利用交聯劑進行交聯、亦可並未被交聯。[Energy ray hardening component (a)]
The energy ray-curable component (a) is a component that is hardened by irradiation with energy rays, and also belongs to the ability to impart film-forming properties and flexibility to a film for forming an energy ray-curable protective film, and forms a hard protective film after curing. Used ingredients.
Examples of the energy ray-curable component (a) include a polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000; and a compound (a2) having an energy ray-curable group, and a molecular weight of 100 to 80,000. The polymer (a1) may be at least partially crosslinked with a crosslinking agent, or may not be crosslinked.
(具有能量線硬化性基且重量平均分子量80000~2000000的聚合體(a1))
具有能量線硬化性基且重量平均分子量80000~2000000的聚合體(a1)可列舉例如:由具有能與其他化合物所具有基產生反應之官能基的丙烯酸系聚合體(a11)，與具有會與上述官能基產生反應之基及具有能量線硬化性雙鍵等能量線硬化性基的能量線硬化性化合物(a12)，進行反應而生成的丙烯酸系樹脂(a1-1)。(Polymer (a1) with an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000)
Examples of the polymer (a1) having an energy ray-curable group and a weight average molecular weight of 80,000 to 2,000,000 include, for example, an acrylic polymer (a11) having a functional group capable of reacting with a group possessed by another compound, The acrylic resin (a1-1) produced by the reaction of the functional group with a functional group and an energy ray-curable compound (a12) having an energy ray-curable group such as an energy ray-curable double bond.
能與其他化合物所具有之基產生反應的上述官能基，係可舉例如: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之基所取代的基)、環氧基等。但，就從防止半導體晶圓、半導體晶片等的電路糟腐蝕之觀點，上述官能基較佳係羧基以外的基。
這些之中，上述官能基較佳係羥基。The above-mentioned functional group capable of reacting with a group possessed by other compounds may be, for example, a hydroxyl group, a carboxyl group, an amine group, or a substituted amine group (one or two hydrogen atoms of the amine group are replaced by a group other than a hydrogen atom Group), epoxy group, and the like. However, from the viewpoint of preventing circuit corrosion of a semiconductor wafer, a semiconductor wafer, and the like, the functional group is preferably a group other than a carboxyl group.
Among these, the functional group is preferably a hydroxyl group.
・具有官能基的丙烯酸系聚合體(a11)
具有上述官能基的丙烯酸系聚合體(a11)係可舉例如:由具有上述官能基的丙烯酸系單體、與未具上述官能基的丙烯酸系單體進行共聚合而形成者，除這些單體之外，尚亦可由丙烯酸系單體以外的單體(非丙烯酸系單體)進行共聚合者。
再者，上述丙烯酸系聚合體(a11)係可為無規共聚物、亦可為嵌段共聚物，關於聚合方法亦可採用公知方法。・ Acrylic polymer with functional group (a11)
Examples of the acrylic polymer (a11) having the above-mentioned functional group include those formed by copolymerizing an acrylic monomer having the above-mentioned functional group and an acrylic monomer having no above-mentioned functional group. Alternatively, it is also possible to copolymerize a monomer (non-acrylic monomer) other than the acrylic monomer.
The acrylic polymer (a11) may be a random copolymer or a block copolymer, and a known method may be adopted for the polymerization method.
具有上述官能基的丙烯酸系單體係可舉例如:含羥基單體、含羧基單體、含胺基單體、取代含胺基單體、含環氧基單體等。Examples of the acrylic single system having the above functional group include a hydroxyl-containing monomer, a carboxyl-containing monomer, an amine-containing monomer, a substituted amine-containing monomer, and an epoxy-containing monomer.
上述含羥基單體係可舉例如:(甲基)丙烯酸羥甲酯、(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸-3-羥丙酯、(甲基)丙烯酸-2-羥丁酯、(甲基)丙烯酸-3-羥丁酯、(甲基)丙烯酸-4-羥丁酯等(甲基)丙烯酸羥烷基酯；乙烯醇、烯丙醇等非(甲基)丙烯酸系不飽和醇(未具(甲基)丙烯醯基骨架的不飽和醇)等。Examples of the above-mentioned hydroxyl-containing monosystem include: hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and -3 (meth) acrylate -Hydroxyalkyl (meth) acrylates such as hydroxypropyl ester, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. ; Non- (meth) acrylic unsaturated alcohols such as vinyl alcohol and allyl alcohol (unsaturated alcohols without a (meth) acrylfluorenyl skeleton) and the like.
上述含羧基單體係可舉例如:(甲基)丙烯酸、巴豆酸等乙烯性不飽和單羧酸(具乙烯性不飽和鍵的單羧酸)；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(具乙烯性不飽和鍵的二羧酸)；上述乙烯性不飽和二羧酸的酸酐；甲基丙烯酸-2-羧乙酯等(甲基)丙烯酸羧烷基酯等等。Examples of the carboxyl-containing monosystem include: (meth) acrylic acid, crotonic acid and other ethylenically unsaturated monocarboxylic acids (monocarboxylic acids with ethylenically unsaturated bonds); fumaric acid, itaconic acid, cis Ethylene unsaturated dicarboxylic acids such as butenedioic acid and citraconic acid (dicarboxylic acids with ethylenically unsaturated bonds); anhydrides of the above ethylenically unsaturated dicarboxylic acids; 2-carboxyethyl methacrylate, etc. Carboxyalkyl (meth) acrylates and the like.
上述具有官能基的丙烯酸系單體較佳係含羥基單體。The acrylic monomer having a functional group is preferably a hydroxyl-containing monomer.
構成上述丙烯酸系聚合體(a11)、且具有上述官能基的丙烯酸系單體，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The acrylic monomer constituting the acrylic polymer (a11) and having the functional group may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be arbitrarily selected. .
未具上述官能基的丙烯酸系單體係可舉例如:(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)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(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)丙烯酸肉荳蔻酯)、(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，構成烷基酯的烷基係碳數1~18之鏈狀構造的(甲基)丙烯酸烷基酯等。Examples of the acrylic single system without the above functional groups include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( N-butyl methacrylate, isobutyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, amyl (meth) acrylate, (meth) acrylic acid Hexyl ester, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate , Isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), ( Tridecyl (meth) acrylate, Tetradecyl (meth) acrylate (Myristyl (meth) acrylate), Pentadecyl (meth) acrylate, Hexadecyl (meth) acrylate Esters (palmit (meth) acrylate), heptadecyl (meth) acrylate, stearyl (meth) acrylate (stearyl (meth) acrylate), etc. Alkyl chain structure with 1 to 18 carbon atoms ( Yl) acrylate and the like.
再者，未具上述官能基的丙烯酸系單體，係可舉例如:(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烷基之(甲基)丙烯酸酯；含(甲基)丙烯酸苯酯等(甲基)丙烯酸芳酯等且具芳香族基的(甲基)丙烯酸酯；非交聯性(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-二甲胺基丙酯等具非交聯性三級胺基的(甲基)丙烯酸酯等。In addition, examples of the acrylic monomer having no functional group include methoxymethyl (meth) acrylate, methoxyethyl (meth) acrylate, and ethoxymethyl (meth) acrylate. (Meth) acrylic acid esters containing alkoxyalkyl groups such as esters, ethoxyethyl (meth) acrylate; aromatic (meth) acrylic acid esters containing phenyl (meth) acrylate, etc. ( (Meth) acrylic acid esters; non-crosslinkable (meth) acrylamidonium and its derivatives; (meth) acrylic acid-N, N-dimethylaminoethyl ester, (meth) acrylic acid-N, N-dicarboxylic acid Non-crosslinkable tertiary amino groups (meth) acrylates and the like such as methylaminopropyl esters.
構成上述丙烯酸系聚合體(a11)、且未具上述官能基的丙烯酸系單體，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The acrylic monomer constituting the acrylic polymer (a11) and not having the functional group may be only one type, or may be two or more types. In the case of two or more types, the combination and ratio may be arbitrary. select.
上述非丙烯酸系單體係可舉例如:乙烯、降莰烯等烯烴；醋酸乙烯酯；苯乙烯等。
構成上述丙烯酸系聚合體(a11)的上述非丙烯酸系單體，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。Examples of the non-acrylic monosystem include: olefins such as ethylene and norbornene; vinyl acetate; styrene and the like.
The non-acrylic monomers constituting the acrylic polymer (a11) may be only one type, or two or more types. In the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
上述丙烯酸系聚合體(a11)中，由具有上述官能基的丙烯酸系單體所衍生之構成單元量，相對於構成其之構成單元總量的比例(含有量)，較佳係0.1~50質量%、更佳係1~40質量%、特佳係3~30質量%。藉由上述比例在此種範圍內，由上述丙烯酸系聚合體(a11)與上述能量線硬化性化合物(a12)共聚合獲得的上述丙烯酸系樹脂(a1-1)中，能量線硬化性基的含有量便可輕易將保護膜的硬化程度調整於較佳範圍內。In the above-mentioned acrylic polymer (a11), the ratio of the amount of the constituent units derived from the acrylic monomer having the functional group to the total amount of the constituent units (content) is preferably 0.1 to 50 masses. %, 1-40% by mass, and 3-30% by mass. When the above ratio is within this range, the acrylic resin (a1-1) obtained by copolymerizing the acrylic polymer (a11) and the energy ray-curable compound (a12), the The content can easily adjust the hardening degree of the protective film to a better range.
構成上述丙烯酸系樹脂(a1-1)的上述丙烯酸系聚合體(a11)，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The acrylic polymer (a11) constituting the acrylic resin (a1-1) may be one type or two or more types. In the case of two or more types, the combination and ratio thereof may be arbitrarily selected.
組成物(IV-1)中，丙烯酸系樹脂(a1-1)含有量相對於溶劑除外之成分總含有量的比例(即，能量線硬化性保護膜形成用薄膜中的丙烯酸系樹脂(a1-1)含有量)，較佳係1~70質量%、更佳係5~60質量%、特佳係10~50質量%。In the composition (IV-1), the ratio of the content of the acrylic resin (a1-1) to the total content of components other than the solvent (i.e., the acrylic resin (a1- 1) Content), preferably 1 to 70% by mass, more preferably 5 to 60% by mass, and particularly good 10 to 50% by mass.
・能量線硬化性化合物(a12)
上述能量線硬化性化合物(a12)中，能與上述丙烯酸系聚合體(a11)所具有官能基產生反應的基，較佳係具有從異氰酸酯基、環氧基及羧基所構成群組中選擇1種或2種以上，更佳係上述基係具有異氰酸酯基。上述能量線硬化性化合物(a12)係例如當上述基具有異氰酸酯基的情況，此異氰酸酯基輕易與具有上述官能基為羥基之丙烯酸系聚合體(a11)的羥基反應。・ Energy ray hardening compound (a12)
Among the energy ray-curable compound (a12), a group capable of reacting with the functional group of the acrylic polymer (a11), preferably has a group selected from the group consisting of an isocyanate group, an epoxy group, and a carboxyl group. One kind or two or more kinds, more preferably, the above-mentioned group has an isocyanate group. The energy ray-curable compound (a12) is, for example, when the group has an isocyanate group, the isocyanate group easily reacts with a hydroxyl group of the acrylic polymer (a11) having the functional group as a hydroxyl group.
上述能量線硬化性化合物(a12)的1分子中之上述能量線硬化性基，較佳係具有1~5個、更佳係具有1~3個。The energy ray-curable group in one molecule of the energy ray-curable compound (a12) preferably has 1 to 5 groups, and more preferably 1 to 3 groups.
上述能量線硬化性化合物(a12)係可舉例如:異氰酸-2-甲基丙烯醯氧基乙酯、間異丙烯基-α,α-二甲苄基異氰酸酯、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；
由二異氰酸酯化合物或聚異氰酸酯化合物、與(甲基)丙烯酸羥乙酯進行反應，而獲得的丙烯醯基單異氰酸酯化合物；
由二異氰酸酯化合物或聚異氰酸酯化合物、多元醇化合物、及(甲基)丙烯酸羥乙酯進行反應，而獲得的丙烯醯基單異氰酸酯化合物等。
這些之中，上述能量線硬化性化合物(a12)較佳係異氰酸-2-甲基丙烯醯氧基乙酯。Examples of the energy ray-curable compound (a12) include: 2-methacryl isoethyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, and methacryl isocyanate. Allyl isocyanate, 1,1- (bispropenyloxymethyl) ethyl isocyanate;
A propylene fluorenyl monoisocyanate compound obtained by reacting a diisocyanate compound or a polyisocyanate compound with hydroxyethyl (meth) acrylate;
Acrylic fluorenyl monoisocyanate compounds and the like obtained by reacting a diisocyanate compound or a polyisocyanate compound, a polyol compound, and hydroxyethyl (meth) acrylate.
Among these, the energy ray-curable compound (a12) is preferably 2-methacryloxyethyl isocyanate.
構成上述丙烯酸系樹脂(a1-1)的上述能量線硬化性化合物(a12)，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The energy ray-curable compound (a12) constituting the acrylic resin (a1-1) may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio can be arbitrarily selected. .
上述丙烯酸系樹脂(a1-1)中，由上述能量線硬化性化合物(a12)所衍生的能量線硬化性基的含有量，相對於由上述丙烯酸系聚合體(a11)所衍生的上述官能基的含有量的比例，較佳係20~120莫耳%、更佳係35~100莫耳%、特佳係50~100莫耳%。藉由上述含有量的比例在此種範圍內，經硬化後的保護膜接著力變為更大。另外，當上述能量線硬化性化合物(a12)係單官能基(上述基在1分子中僅具有1個)化合物的情況，上述含有量的比例上限值成為100莫耳%，但當上述能量線硬化性化合物(a12)係多官能基(上述基在1分子中具有2個以上)化合物的情況，上述含有量的比例上限值便會超過100莫耳%。The content of the energy-ray-curable group derived from the energy-ray-curable compound (a12) in the acrylic resin (a1-1) is higher than the functional group derived from the acrylic polymer (a11). The content ratio is preferably 20 to 120 mol%, more preferably 35 to 100 mol%, and particularly good 50 to 100 mol%. When the above-mentioned content ratio is within such a range, the cured film has a stronger adhesion force. In addition, when the energy ray-curable compound (a12) is a monofunctional group (the above-mentioned group has only one in one molecule), the upper limit value of the content ratio becomes 100 mole%. In the case of a wire-curable compound (a12) based on a polyfunctional compound (the above-mentioned group has two or more in one molecule), the upper limit value of the content ratio will exceed 100 mole%.
上述聚合體(a1)的重量平均分子量(Mw)較佳係100000~2000000、更佳係300000~1500000。The weight average molecular weight (Mw) of the polymer (a1) is preferably 100,000 to 2,000,000, and more preferably 300,000 to 1,500,000.
當上述聚合體(a1)係至少其一部分利用交聯劑而被交聯的情況，上述聚合體(a1)係可並不屬於就構成上述丙烯酸系聚合體(a11)所說明的上述任一單體，且可以是由具有會與交聯劑反應之基的單體進行聚合，在會與上述交聯劑進行反應的基被交聯者，亦可以是在上述能量線硬化性化合物(a12)所衍生會與上述官能基產生反應的基進行交聯者。When the polymer (a1) is at least a part of which is crosslinked with a cross-linking agent, the polymer (a1) may not belong to any one of the above-mentioned units that constitute the acrylic polymer (a11). The polymer may be polymerized from a monomer having a group capable of reacting with a cross-linking agent, and the group to be reacted with the cross-linking agent may be cross-linked, or may be the energy-ray-curable compound (a12). The derivatized group which reacts with the above-mentioned functional group is crosslinked.
組成物(IV-1)與能量線硬化性保護膜形成用薄膜所含有的上述聚合體(a1)，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The polymer (a1) contained in the composition (IV-1) and the energy-ray-curable protective film-forming film may be only one kind, or two or more kinds, and in the case of two or more kinds, the combination thereof The ratio can be selected arbitrarily.
(具能量線硬化性基、且分子量100~80000的化合物(a2))
具能量線硬化性基、且分子量100~80000的化合物(a2)中，上述能量線硬化性基可列舉含有能量線硬化性雙鍵的基，較佳可列舉:(甲基)丙烯醯基、乙烯基等。(Compound (a2) with an energy ray hardening group and a molecular weight of 100 to 80,000)
In the compound (a2) having an energy ray-curable group and having a molecular weight of 100 to 80,000, examples of the energy ray-curable group include a group containing an energy-ray-curable double bond, and preferably, a (meth) acryl group, Vinyl, etc.
上述化合物(a2)係在滿足上述條件前提下，並無特別的限定，可例如:具有能量線硬化性基的低分子量化合物、具有能量線硬化性基的環氧樹脂、具有能量線硬化性基的酚樹脂等。The compound (a2) is not particularly limited as long as the above conditions are satisfied, and examples thereof include a low-molecular-weight compound having an energy-ray-curable group, an epoxy resin having an energy-ray-curable group, and an energy-ray-curable group. Phenol resin and so on.
上述化合物(a2)中，具有能量線硬化性基的低分子量化合物可列舉:多官能基的單體或寡聚物等，較佳係具有(甲基)丙烯醯基的丙烯酸酯系化合物。
上述丙烯酸酯系化合物係可舉例如:2-羥-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)丙烯氧基聚丙氧基)苯基]丙烷、三環癸烷二甲醇二[(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]、聚伸丁二醇二[(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-1,3-二(甲基)丙烯氧基丙烷等雙官能基(甲基)丙烯酸酯；
異三聚氰酸參[2-(甲基)丙烯氧基乙酯]、ε-己內酯改質異三聚氰酸參[2-(甲基)丙烯氧基乙酯]、乙氧基化甘油三[(甲基)丙烯酸酯]、新戊四醇三[(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]、乙氧基化新戊四醇四[(甲基)丙烯酸酯]、新戊四醇四[(甲基)丙烯酸酯]、二新戊四醇聚(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等多官能基(甲基)丙烯酸酯；
胺甲酸乙酯(甲基)丙烯酸酯寡聚物等多官能基(甲基)丙烯酸酯寡聚物等。Examples of the low molecular weight compound having an energy ray-curable group in the compound (a2) include polyfunctional monomers and oligomers, and the like is preferably an acrylate compound having a (meth) acrylfluorene group.
Examples of the acrylate-based compound include 2-hydroxy-3- (meth) acryloxypropyl methacrylate, polyethylene glycol di [(meth) acrylate], and propoxylated ethylene. Oxidized bisphenol A di [(meth) acrylate], 2,2-bis [4-((meth) acryloxy polyethoxy) phenyl] propane, ethoxylated bisphenol A di [(Meth) acrylate], 2,2-bis [4-((meth) acryloxydiethoxy) phenyl] propane, 9,9-bis [4- (2- (methyl) Acrylic ethoxyethoxy) phenyl] pyrene, 2,2-bis [4-((meth) acryloxypolypropoxy) phenyl] propane, tricyclodecanedimethanol dim [(methyl) Acrylate], 1,10-decanediol di [(meth) acrylate], 1,6-hexanediol di [(meth) acrylate], 1,9-nonanediol di [(methyl ) Acrylate], dipropylene glycol di [(meth) acrylate], tripropylene glycol di [(meth) acrylate], polypropylene glycol di [(meth) acrylate], polybutylene glycol di [(formaldehyde Base) acrylate], ethylene glycol di [(meth) acrylate], diethylene glycol di [(meth) acrylate], triethylene glycol di [(meth) acrylate], 2, 2 -Bis [4-((meth) acryloxyethoxy) phenyl] propane, Bifunctional groups such as pentanediol di [(meth) acrylate], ethoxylated polypropylene glycol di [(meth) acrylate], 2-hydroxy-1,3-di (meth) propenyloxypropane (Meth) acrylates;
Isocyanuric acid [2- (meth) acryloxyethyl], ε-caprolactone modified Isocyanuric acid [2- (meth) acryloxyethyl], ethoxy Glycerol tri [(meth) acrylate], neopentaerythritol tri [(meth) acrylate], trimethylolpropane tri [(meth) acrylate], bis (trimethylolpropane) tetra [(Meth) acrylate], ethoxylated neopentaerythritol tetra [(meth) acrylate], neopentaerythritol tetra [(meth) acrylate], dinepentaerythritol poly (methyl) ) Polyfunctional (meth) acrylates such as acrylate, dipentaerythritol hexa (meth) acrylate;
Polyfunctional (meth) acrylate oligomers, such as a urethane (meth) acrylate oligomer, etc.
上述化合物(a2)中，具能量線硬化性基之環氧樹脂、具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」中在段落0043等處所記載者。此種樹脂亦屬於後述構成熱硬化性成分的樹脂，在本發明中視為上述化合物(a2)。Among the compounds (a2), the epoxy resin having an energy ray-curable group and the phenol resin having an energy ray-curable group can be, for example, those described in paragraph 0043 and the like in Japanese Patent Laid-Open No. 2013-194102. . Such a resin also belongs to a resin constituting a thermosetting component described later, and is regarded as the above-mentioned compound (a2) in the present invention.
上述化合物(a2)的重量平均分子量較佳係100~30000、更佳係300~10000。The weight average molecular weight of the compound (a2) is preferably 100 to 30,000, and more preferably 300 to 10,000.
組成物(IV-1)與能量線硬化性保護膜形成用薄膜所含有的上述化合物(a2)，係可僅為1種、亦可為2種以上，若2種以上的情況，該等的組合與比率係可任意選擇。The compound (a-1) contained in the composition (IV-1) and the energy-ray-curable protective film-forming film may be only one kind, or two or more kinds. In the case of two or more kinds, such The combination and ratio can be selected arbitrarily.
[未具能量線硬化性基的聚合體(b)]
組成物(IV-1)及能量線硬化性保護膜形成用薄膜的上述能量線硬化性成分(a)含有上述化合物(a2)的情況，以亦更進一步含有未具能量線硬化性基的聚合體(b) 為佳。
上述聚合體(b)係可至少其中一部分利用交聯劑進行交聯，亦可未被交聯。[Polymer (b) without energy ray hardening group]
When the above-mentioned energy-ray-curable component (a) of the composition (IV-1) and the energy-ray-curable protective film-forming film contains the above-mentioned compound (a2), it further contains polymerization without an energy-ray-curable group. Body (b) is preferred.
The polymer (b) may be at least partially crosslinked with a crosslinking agent, or may not be crosslinked.
未具能量線硬化性基的聚合體(b)係可舉例如:丙烯酸系聚合體、苯氧樹脂、胺甲酸乙酯樹脂、聚酯、橡膠系樹脂、丙烯酸胺甲酸乙酯樹脂等。
這些之中，上述聚合體(b)較佳係丙烯酸系聚合體(以下亦簡稱「丙烯酸系聚合體(b-1)」)。Examples of the polymer (b) having no energy ray-curable group include acrylic polymers, phenoxy resins, urethane resins, polyesters, rubber resins, and acrylic urethane resins.
Among these, the polymer (b) is preferably an acrylic polymer (hereinafter also referred to as "acrylic polymer (b-1)").
丙烯酸系聚合體(b-1)係可為公知物，例如:可為單1種丙烯酸系單體的單聚物，亦可為2種以上丙烯酸系單體的共聚物，亦可由1種或2種以上丙烯酸系單體、與1種或2種以上的丙烯酸系單體以外的單體(非丙烯酸系單體)的共聚物。The acrylic polymer (b-1) may be a known substance. For example, the acrylic polymer (b-1) may be a single polymer of a single acrylic monomer, or a copolymer of two or more acrylic monomers. A copolymer of two or more acrylic monomers and a monomer (non-acrylic monomer) other than one or two or more acrylic monomers.
構成丙烯酸系聚合體(b-1)的上述丙烯酸系單體，係可舉例如:(甲基)丙烯酸烷基酯、具環狀骨架的(甲基)丙烯酸酯、含環氧丙基的(甲基)丙烯酸酯、含羥基的(甲基)丙烯酸酯、含取代胺基的(甲基)丙烯酸酯等。此處，所謂「取代胺基」係如同前所說明。Examples of the acrylic monomers constituting the acrylic polymer (b-1) include (meth) acrylic acid alkyl esters, (meth) acrylic acid esters having a cyclic skeleton, and epoxypropyl group-containing ( (Meth) acrylates, hydroxyl-containing (meth) acrylates, substituted amine-group-containing (meth) acrylates, and the like. Here, the "substituted amino group" is as described above.
上述(甲基)丙烯酸烷基酯係可舉例如:(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)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(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)丙烯酸肉荳蔻酯)、(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，構成烷基酯的烷基係碳數1~18之鏈狀構造的(甲基)丙烯酸烷基酯等。Examples of the above (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (methyl) Base) n-butyl acrylate, isobutyl (meth) acrylate, secondary butyl (meth) acrylate, tertiary butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate Ester, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, Isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), (formyl) Tridecyl acrylate, tetradecyl (meth) acrylate (myristyl (meth) acrylate), pentadecyl (meth) acrylate, cetyl (meth) acrylate Esters (palm (meth) acrylate), heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), and the like, constituting alkyl alkyl esters (Meth) acrylic acid with a chain structure of 1 to 18 carbon atoms Acid alkyl ester and the like.
上述具環狀骨架的(甲基)丙烯酸酯係可舉例如:(甲基)丙烯酸異莰酯、(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等。Examples of the (meth) acrylic acid ester having a cyclic skeleton include: (meth) acrylic acid isopropyl ester, (meth) acrylic acid dicyclopentyl ester, and the like;
Aryl (meth) acrylate, such as benzyl (meth) acrylate;
Cycloalkenyl (meth) acrylate such as dicyclopentenyl (meth) acrylate;
Cycloalkenyl alkyl (meth) acrylate and the like such as dicyclopentenyloxyethyl (meth) acrylate and the like.
上述含有環氧丙基的(甲基)丙烯酸酯係可舉例如:(甲基)丙烯酸環氧丙酯等。
上述含有羥基的(甲基)丙烯酸酯係可舉例如:(甲基)丙烯酸羥甲酯、(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸-3-羥丙酯、(甲基)丙烯酸-2-羥丁酯、(甲基)丙烯酸-3-羥丁酯、(甲基)丙烯酸-4-羥丁酯等。
上述含有取代胺基的(甲基)丙烯酸酯係可舉例如:(甲基)丙烯酸-N-甲胺基乙酯等。Examples of the (meth) acrylic acid ester-containing (meth) acrylic acid esters include propylene glycol (meth) acrylate.
Examples of the hydroxyl-containing (meth) acrylic acid esters include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and (methyl) Methyl) 3-hydroxypropyl acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.
Examples of the (meth) acrylic acid ester containing a substituted amino group include (N) -methylaminoethyl (meth) acrylate and the like.
構成丙烯酸系聚合體(b-1)的上述非丙烯酸系單體係可舉例如:乙烯、降莰烯等烯烴；醋酸乙烯酯；苯乙烯等。Examples of the non-acrylic single system constituting the acrylic polymer (b-1) include olefins such as ethylene and norbornene; vinyl acetate; and styrene.
至少其中一部分利用交聯劑進行交聯的上述未具能量線硬化性基的聚合體(b)，係可舉例如:由上述聚合體(b)中的反應性官能基與交聯劑產生反應後者。
上述反應性官能基係只要依照交聯劑的種類等再行適當選擇便可，其餘並無特別的限定。例如當交聯劑係聚異氰酸酯化合物的情況，上述反應性官能基可列舉:羥基、羧基、胺基等，這些之中較佳係與異氰酸酯基的反應性高之羥基。又，當交聯劑係環氧系化合物的情況，上述反應性官能基可列舉:羧基、胺基、醯胺基等，這些之中較佳係與環氧基的反應性高之羧基。但，就從防止半導體晶圓、半導體晶片的電路遭腐蝕之觀點，上述反應性官能基較佳係羧基以外的基。At least a part of the polymer (b) having no energy ray-curable group which is crosslinked by a crosslinking agent may be, for example, a reaction between a reactive functional group in the polymer (b) and a crosslinking agent. the latter.
The above-mentioned reactive functional group may be appropriately selected according to the type of the crosslinking agent and the like, and the rest is not particularly limited. For example, when the crosslinking agent is a polyisocyanate compound, examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amine group. Among these, a hydroxyl group having high reactivity with an isocyanate group is preferred. When the crosslinking agent is an epoxy compound, examples of the reactive functional group include a carboxyl group, an amine group, and a sulfonylamino group. Among these, a carboxyl group having high reactivity with an epoxy group is preferred. However, from the viewpoint of preventing the semiconductor wafer or the circuit of the semiconductor wafer from being corroded, the reactive functional group is preferably a group other than a carboxyl group.
上述具有反應性官能基的未具能量線硬化性基之聚合體(b)，可列舉:由至少具有上述反應性官能基的單體進行聚合而獲得者。丙烯酸系聚合體(b-1)的情況，只要將就構成其的單體所列舉之上述丙烯酸系單體及非丙烯酸系單體中之任一者或雙方，使用為具有上述反應性官能基者便可。反應性官能基係具有羥基的上述聚合體(b)，可列舉:由含羥基之(甲基)丙烯酸酯進行聚合而獲得者，除此之外，尚亦可列舉由前所列舉的上述丙烯酸系單體或非丙烯酸系單體中，1個或2個以上氫原子被上述反應性官能基所取代形成的單體，進行聚合而獲得者。Examples of the polymer (b) without an energy ray-curable group having a reactive functional group include those obtained by polymerizing a monomer having at least the reactive functional group. In the case of the acrylic polymer (b-1), any one or both of the above-mentioned acrylic monomers and non-acrylic monomers listed for the monomers constituting the acrylic polymer (b-1) may be used as having the above-mentioned reactive functional group. Those who can. Examples of the polymer (b) having a reactive functional group having a hydroxyl group include those obtained by polymerizing a (meth) acrylic acid ester containing a hydroxyl group. In addition, the above-mentioned acrylic acid may also be mentioned. A monomer obtained by polymerizing one or two or more hydrogen atoms with the above-mentioned reactive functional group among the monomers or non-acrylic monomers.
具有反應性官能基的上述聚合體(b)中，由具反應性官能基的單體所衍生構成單元的量，相對於構成具有反應性官能基的上述聚合體(b)的構成單元總量之比例(含有量)，較佳係1~20質量%、更佳係2~10質量%。藉由上述比例在此種範圍內，上述聚合體(b)的交聯程度便可成為更佳範圍。In the polymer (b) having a reactive functional group, the amount of constituent units derived from a monomer having a reactive functional group is relative to the total amount of constituent units constituting the polymer (b) having a reactive functional group. The proportion (content) is preferably 1 to 20% by mass, and more preferably 2 to 10% by mass. When the above-mentioned ratio is within such a range, the degree of crosslinking of the polymer (b) can become a more preferable range.
未具能量線硬化性基的聚合體(b)的重量平均分子量(Mw)，就從使組成物(IV-1)的造膜性更良好之觀點，較佳係10000~2000000、更佳係100000~1500000。此處所謂「重量平均分子量」係如前所說明。The weight average molecular weight (Mw) of the polymer (b) having no energy ray-curable group is preferably from 10,000 to 2,000,000, and more preferably from the viewpoint of making the film forming property of the composition (IV-1) better. 100000 ~ 1500000. The "weight average molecular weight" herein is as described above.
組成物(IV-1)與能量線硬化性保護膜形成用薄膜所含有未具能量線硬化性基的聚合體(b)，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The composition (IV-1) and the energy ray-curable protective film-forming film (b), which does not have an energy ray-curable group, may be only one kind, or two or more kinds, and if two In the above cases, the combination and ratio can be arbitrarily selected.
組成物(IV-1)可列舉:含有上述聚合體(a1)與上述化合物(a2)中任一者或雙方者。而，當組成物(IV-1)係含有上述化合物(a2)的情況，較佳係更進一步亦含有未具能量線硬化性基的聚合體(b)，此情況亦較佳進一步含有上述(a1)。又，組成物(IV-1)亦可未含有上述化合物(a2)，而是上述聚合體(a1)、與未具能量線硬化性基的聚合體(b)均含有。Examples of the composition (IV-1) include one or both of the polymer (a1) and the compound (a2). When the composition (IV-1) contains the above-mentioned compound (a2), it is more preferable that the composition (IV-1) further contains the polymer (b) having no energy ray-curable group, and in this case, it further preferably contains the above-mentioned ( a1). Moreover, the composition (IV-1) may not contain the said compound (a2), but both the said polymer (a1) and the polymer (b) which does not have an energy ray hardening group may be contained.
當組成物(IV-1)係含有上述聚合體(a1)、上述化合物(a2)及未具能量線硬化性基的聚合體(b)的情況，組成物(IV-1)中，上述化合物(a2)的含有量，相對於上述聚合體(a1)與未具能量線硬化性基的聚合體(b)的總含有量100質量份，較佳係10~400質量份、更佳係30~350質量份。When the composition (IV-1) is the polymer (a1), the compound (a2), and the polymer (b) having no energy ray-curable group, the composition (IV-1) includes the compound The content of (a2) is 100 parts by mass relative to the total content of the polymer (a1) and the polymer (b) having no energy ray-curable group, preferably 10 to 400 parts by mass, and more preferably 30 ~ 350 parts by mass.
組成物(IV-1)中，上述能量線硬化性成分(a)與未具能量線硬化性基之聚合體(b)的合計含有量，相對於溶劑以外成分總含有量的比例(即，能量線硬化性保護膜形成用薄膜中的上述能量線硬化性成分(a)與未具能量線硬化性基的聚合體(b)之合計含有量)，較佳係5~90質量%、更佳係10~80質量%、特佳係20~70質量%。藉由能量線硬化性成分的含有量的上述比例設在此種範圍內，便可使能量線硬化性保護膜形成用薄膜的能量線硬化性更良好。In the composition (IV-1), the ratio of the total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group to the total content of components other than the solvent (i.e., The total content of the energy ray-curable component (a) and the polymer (b) having no energy ray-curable group in the film for forming an energy ray-curable protective film is preferably 5 to 90% by mass, more The best line is 10 to 80% by mass, and the best line is 20 to 70% by mass. When the above-mentioned ratio of the content of the energy-ray-curable component is within such a range, the energy-ray-curability of the film for forming an energy-ray-curable protective film can be made better.
組成物(IV-1)係上述能量線硬化性成分以外，配合目的尚亦可含有從熱硬化性成分、填充材、偶合劑、交聯劑、光聚合起始劑、著色劑及通用添加劑所構成群組中選擇1種或2種以上。The composition (IV-1) is in addition to the above-mentioned energy ray-curable components. For the purpose of blending, the composition may further include a thermosetting component, a filler, a coupling agent, a crosslinking agent, a photopolymerization initiator, a colorant, and a general additive. Select one or two or more in the composition group.
例如藉由使用上述含有能量線硬化性成分與熱硬化性成分的組成物(IV-1)，便可提升所形成的能量線硬化性保護膜形成用薄膜利用加熱對被黏物的接著力，且由此能量線硬化性保護膜形成用薄膜所形成保護膜的強度亦獲提升。
再者，藉由使用上述含有能量線硬化性成分及著色劑的組成物(IV-1)，所形成的能量線硬化性保護膜形成用薄膜，便可顯現出與前所說明熱硬化性保護膜形成用薄膜含有著色劑(I)情況同樣的效果。For example, by using the composition (IV-1) containing the energy ray-curable component and the thermosetting component described above, the formed film for forming an energy ray-curable protective film can be heated to adhere to the adherend, In addition, the strength of the protective film formed by the thin film for forming an energy ray-curable protective film is also improved.
Furthermore, by using the above-mentioned composition (IV-1) containing an energy-ray-curable component and a coloring agent, the formed film for forming an energy-ray-curable protective film can exhibit the thermosetting protection described above. The same effect is obtained when the film for film formation contains the colorant (I).
組成物(IV-1)的上述熱硬化性成分、填充材、偶合劑、交聯劑、光聚合起始劑、著色劑及通用添加劑，分別可列舉與組成物(III-1)的熱硬化性成分(B)、填充材(D)、偶合劑(E)、交聯劑(F)、光聚合起始劑(H)、著色劑(I)及通用添加劑(J)相同物。The thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general additives of the composition (IV-1) can be listed respectively as heat curing with the composition (III-1). The same as the component (B), the filler (D), the coupling agent (E), the cross-linking agent (F), the photopolymerization initiator (H), the colorant (I), and the general additive (J).
組成物(IV-1)中，上述熱硬化性成分、填充材、偶合劑、交聯劑、光聚合起始劑、著色劑及通用添加劑分別係可單獨使用1種、亦可併用2種以上，若倂用2種以上的情況，其組合與比率係可任意選擇。In the composition (IV-1), the above thermosetting components, fillers, coupling agents, crosslinking agents, photopolymerization initiators, colorants, and general additives may be used alone or in combination of two or more kinds. If two or more types are used, the combination and ratio can be arbitrarily selected.
組成物(IV-1)的上述熱硬化性成分、填充材、偶合劑、交聯劑、光聚合起始劑、著色劑及通用添加劑之含有量，係只要配合目的再行適當調整便可，並無特別的限定。The content of the above-mentioned thermosetting component, filler, coupling agent, cross-linking agent, photopolymerization initiator, colorant, and general-purpose additive of the composition (IV-1) can be adjusted appropriately according to the purpose. There is no particular limitation.
組成物(IV-1)因為利用稀釋便可提升處置性，因而以進一步含有溶劑為佳。
組成物(IV-1)所含有的溶劑可列舉同上述組成物(III-1)的溶劑。
組成物(IV-1)所含有的溶劑係可僅為1種、亦可為2種以上。Since the composition (IV-1) can improve the disposability by dilution, it is preferable to further contain a solvent.
Examples of the solvent contained in the composition (IV-1) include the same solvents as those of the composition (III-1).
The solvent contained in the composition (IV-1) may be only one kind, or two or more kinds.
＜＜能量線硬化性保護膜形成用組成物之製造方法＞＞
組成物(IV-1)等能量線硬化性保護膜形成用組成物係藉由摻合用於構成其的各成分便可獲得。
各成分摻合時的添加順序並無特別的限定，亦可2種以上的成分同時添加。
使用溶劑時，可將溶劑與除溶劑以外的任一摻合成分進行混合，再將此摻合成分施行預稀釋後才使用，亦可在未將溶劑以外的任一摻合成分施行預稀釋狀態下，便將溶劑與這些摻合成分施行混合使用。
摻合時，將各成分施行混合的方法並無特別的限定，可從例如:使攪拌子或攪拌葉片等旋轉而進行混合的方法；使用混合機進行混合的方法；施加超音波進行混合的方法等公知方法中適當選擇。
各成分的添加、及混合時的溫度與時間係在各摻合成分不會劣化前提下，並無特別的限定，只要適當調整便可，溫度較佳係15~30℃。＜〈 Method for manufacturing composition for forming energy ray curable protective film 〉＞
The composition for forming an energy ray-curable protective film such as the composition (IV-1) can be obtained by blending the components for constituting the same.
The order of addition of each component is not particularly limited, and two or more components may be added simultaneously.
When using a solvent, the solvent can be mixed with any blended component other than the solvent, and then the blended component can be pre-diluted before use. It can also be used in a state where any blended component other than the solvent is not pre-diluted. Then, the solvent is mixed with these blended components and used.
The method of mixing the components during blending is not particularly limited. For example, a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, or a method of mixing by applying an ultrasonic wave. It is appropriately selected from other known methods.
The addition of each component, and the temperature and time during mixing are not particularly limited as long as each blending component does not deteriorate, as long as it is appropriately adjusted, the temperature is preferably 15 to 30 ° C.
○非硬化性保護膜形成用薄膜
上述非硬化性保護膜形成用薄膜雖不會因硬化而呈現特性變化，但本發明中，在貼附於半導體晶圓的上述背面等目標地方之階段，視同已形成保護膜。○ Film for forming non-curable protective film Although the film for forming non-curable protective film does not exhibit characteristics change due to curing, in the present invention, at the stage of being attached to a target place such as the back surface of a semiconductor wafer, Same as protective film.
較佳非硬化性保護膜形成用薄膜可列舉:含有熱可塑性樹脂者。Examples of preferred non-curable protective film-forming films include those containing a thermoplastic resin.
＜非硬化性保護膜形成用組成物(V-1)＞
非硬化性保護膜形成用組成物係可舉例如:含有上述熱可塑性樹脂的非硬化性保護膜形成用組成物(V-1)(本說明書中亦簡稱「組成物(V-1)」)等。<Composition (V-1) for forming a non-curable protective film>
Examples of the composition for forming a non-curable protective film include a composition (V-1) for forming a non-curable protective film containing the thermoplastic resin (also referred to as "composition (V-1)" in this specification). Wait.
[熱可塑性樹脂]
上述熱可塑性樹脂並無特別的限定。
上述熱可塑性樹脂更具體可列舉例如上述組成物(III-1)的含有成分所列舉丙烯酸系樹脂、聚酯、聚氨酯、苯氧樹脂、聚丁烯、聚丁二烯、聚苯乙烯等非硬化性的樹脂為同樣者。[Thermoplastic resin]
The thermoplastic resin is not particularly limited.
Examples of the thermoplastic resin include, for example, non-hardened materials such as acrylic resin, polyester, polyurethane, phenoxy resin, polybutene, polybutadiene, and polystyrene. Sexual resin is the same.
組成物(V-1)及非硬化性保護膜形成用薄膜所含有的上述熱可塑性樹脂，係可僅為1種、亦可為2種以上，若2種以上的情況，其組合與比率係可任意選擇。The thermoplastic resin contained in the composition (V-1) and the film for forming a non-curable protective film may be only one kind, or two or more kinds. In the case of two or more kinds, the combination and ratio are Can be chosen arbitrarily.
組成物(V-1)中，上述熱可塑性樹脂的含有量相對於溶劑以外成分的總含有量的比例(即，非硬化性保護膜形成用薄膜的上述熱可塑性樹脂含有量)，較佳係5~90質量%，例如可為10~80質量%、及20~70質量%等中之任一者。In the composition (V-1), the ratio of the content of the thermoplastic resin to the total content of components other than the solvent (that is, the content of the thermoplastic resin of the non-curable protective film-forming film) is preferably 5 to 90% by mass, for example, any of 10 to 80% by mass and 20 to 70% by mass.
組成物(V-1)係上述熱可塑性樹脂之外，配合目的尚亦可含有從填充材、偶合劑、交聯劑、著色劑及通用添加劑所構成群組中選擇1種或2種以上。The composition (V-1) is in addition to the above-mentioned thermoplastic resin, and it may contain one or two or more types selected from the group consisting of a filler, a coupling agent, a cross-linking agent, a coloring agent, and a general-purpose additive in addition to the above-mentioned thermoplastic resin.
例如藉由使用上述含有熱可塑性樹脂與著色劑的組成物(V-1)，則所形成的非硬化性保護膜形成用薄膜，便可顯現出與前所說明當熱硬化性保護膜形成用薄膜含有著色劑(I)情況同樣的效果。For example, by using the composition (V-1) containing a thermoplastic resin and a coloring agent as described above, the formed non-curable protective film-forming film can be used as the thermosetting protective film-forming film described above. The same effect is obtained when the film contains the colorant (I).
組成物(V-1)中的上述填充材、偶合劑、交聯劑、著色劑及通用添加劑，分別可列舉與組成物(III-1)的填充材(D)、偶合劑(E)、交聯劑(F)、著色劑(I)及通用添加劑(J)為相同者。Examples of the filler, coupling agent, cross-linking agent, colorant, and general additives in the composition (V-1) include the filler (D), the coupling agent (E), and The cross-linking agent (F), the colorant (I), and the general additive (J) are the same.
組成物(V-1)中，上述填充材、偶合劑、交聯劑、著色劑及通用添加劑，分別係可單獨使用1種、亦可併用2種以上，若倂用2種以上的情況，其組合與比率係可任意選擇。In the composition (V-1), the fillers, coupling agents, cross-linking agents, colorants, and general additives may be used alone or in combination of two or more. If two or more are used, The combination and ratio can be arbitrarily selected.
組成物(V-1)中，上述填充材、偶合劑、交聯劑、著色劑及通用添加劑的含有量，係只要配合目的再行適當調整便可，並無特別的限定。In the composition (V-1), the content of the filler, coupling agent, cross-linking agent, colorant, and general-purpose additive is not particularly limited as long as it is appropriately adjusted for the purpose.
組成物(V-1)係利用稀釋便可提升處置性，因而以進一步含有溶劑為佳。
組成物(V-1)所含有的溶劑可列舉同上述組成物(III-1)的溶劑。
組成物(V-1)所含有的溶劑係可僅為1種、亦可為2種以上。The composition (V-1) is capable of improving disposability by dilution, so it is preferable to further contain a solvent.
Examples of the solvent contained in the composition (V-1) include the same solvents as those of the composition (III-1).
The solvent contained in the composition (V-1) may be only one kind, or two or more kinds.
＜＜非硬化性保護膜形成用組成物之製造方法＞＞
組成物(V-1)等非硬化性保護膜形成用組成物係藉由摻合構成其的各成分便可獲得。
各成分摻合時的添加順序並無特別的限定，亦可2種以上的成分同時添加。
使用溶劑時，可將溶劑與溶劑以外的任一摻合成分進行混合，再將此摻合成分施行預稀釋後才使用，亦可在未將溶劑以外的任一摻合成分施行預稀釋狀態下，便將溶劑與這些摻合成分施行混合使用。
摻合時，將各成分施行混合的方法並無特別的限定，可從例如:使攪拌子或攪拌葉片等旋轉而進行混合的方法；使用混合機進行混合的方法；施加超音波進行混合的方法等公知方法中適當選擇。
各成分的添加、及混合時的溫度與時間係在各摻合成分不會劣化前提下，並無特別的限定，只要適當調整便可，溫度較佳係15~30℃。<<< Manufacturing method of non-curable protective film-forming composition >>
A composition for forming a non-curable protective film such as the composition (V-1) can be obtained by blending the components constituting it.
The order of addition of each component is not particularly limited, and two or more components may be added simultaneously.
When a solvent is used, the solvent can be mixed with any blended component other than the solvent, and then the blended component can be used after being pre-diluted. It can also be used without any blending component other than the solvent being pre-diluted. Then, the solvent is mixed with these blended components for use.
The method of mixing the components during blending is not particularly limited. For example, a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, or a method of mixing by applying an ultrasonic wave. It is appropriately selected from other known methods.
The addition of each component, and the temperature and time during mixing are not particularly limited as long as each blending component does not deteriorate, as long as it is appropriately adjusted, the temperature is preferably 15 to 30 ° C.
◎其他層
上述支撐片係在不致損及本發明效果之範圍內，在基材與黏著劑層之外，尚亦可包括上述中間層等其他層。
再者，上述保護膜形成用複合片係在不致損及本發明效果之範圍內，在基材、黏著劑層及保護膜形成用薄膜之外，尚亦可包括其他層，此情況的上述其他層係可為支撐片所包括的上述其他層，亦可配置成未直接接觸支撐片狀態。
上述其他層係可配合目的再行任意選擇，且種類並無特別的限定。◎ Other layers The above-mentioned supporting sheet is within a range that does not impair the effect of the present invention. In addition to the substrate and the adhesive layer, other layers such as the above-mentioned intermediate layer may also be included.
In addition, the above-mentioned composite sheet for forming a protective film is within a range that does not impair the effect of the present invention, and may include other layers in addition to the substrate, the adhesive layer, and the film for forming a protective film. The layer system may be the other layers included in the support sheet, and may also be configured in a state where the support sheet is not in direct contact with the support sheet.
The other layers mentioned above can be arbitrarily selected according to the purpose, and the type is not particularly limited.
上述支撐片與保護膜形成用複合片之一實施形態，可列舉:黏著劑層係非能量線硬化性，且黏著劑層含有至少具由(甲基)丙烯酸烷基酯所衍生構成單元的上述丙烯酸系聚合體、與交聯劑，在黏著劑層中，相對於上述丙烯酸系聚合體的含有量100質量份，交聯劑的含有量係0.3~50質量份，且基材第1面的上述最大高度粗糙度(Rz)係0.01~8μm。One embodiment of the support sheet and the composite sheet for forming a protective film includes the following: the adhesive layer is non-energy ray hardenable, and the adhesive layer contains the above-mentioned structural unit derived from at least an alkyl (meth) acrylate The content of the acrylic polymer and the crosslinking agent in the adhesive layer is 100 parts by mass relative to the content of the acrylic polymer, and the content of the crosslinking agent is 0.3 to 50 parts by mass. The maximum height roughness (Rz) is 0.01 to 8 μm.
上述支撐片與保護膜形成用複合片之一實施形態，可列舉例如:黏著劑層為非能量線硬化性，黏著劑層含有至少具由(甲基)丙烯酸烷基酯所衍生構成單元的上述丙烯酸系聚合體、與交聯劑，在黏著劑層中，相對於上述丙烯酸系聚合體的含有量100質量份，交聯劑的含有量係0.3~50質量份，上述丙烯酸系聚合體係具有由烷基碳數達4以上之(甲基)丙烯酸烷基酯所衍生構成單元、與由含羥基單體所衍生構成單元，且基材第1面的上述最大高度粗糙度(Rz)係0.01~8μm。One embodiment of the support sheet and the composite sheet for forming a protective film includes, for example, that the adhesive layer is non-energy ray-curable, and the adhesive layer contains the above-mentioned structural unit derived from at least an alkyl (meth) acrylate. The acrylic polymer and the cross-linking agent in the adhesive layer contain 100 parts by mass of the content of the acrylic polymer, and the content of the cross-linking agent is 0.3 to 50 parts by mass. The above-mentioned maximum height roughness (Rz) of the structural unit derived from an alkyl (meth) acrylate having an alkyl carbon number of 4 or more and the structural unit derived from a hydroxyl-containing monomer is 0.01 ~ 8 μm.
上述支撐片與保護膜形成用複合片之一實施形態，可列舉例如:黏著劑層為非能量線硬化性，黏著劑層含有至少具由(甲基)丙烯酸烷基酯所衍生構成單元的上述丙烯酸系聚合體與交聯劑，在黏著劑層中，相對於上述丙烯酸系聚合體的含有量100質量份，交聯劑的含有量係0.3~50質量份，上述丙烯酸系聚合體係具有由烷基碳數達4以上之(甲基)丙烯酸烷基酯所衍生構成單元與由含羥基單體所衍生構成單元，在上述丙烯酸系聚合體中，相對於構成單元總量，由含羥基單體所衍生構成單元的含有量係1~35質量%，且基材第1面的上述最大高度粗糙度(Rz)係0.01~8μm。One embodiment of the support sheet and the composite sheet for forming a protective film includes, for example, that the adhesive layer is non-energy ray-curable, and the adhesive layer contains the above-mentioned structural unit derived from at least an alkyl (meth) acrylate. The acrylic polymer and the cross-linking agent are contained in the adhesive layer in an amount of 100 parts by mass with respect to the content of the acrylic polymer, and the content of the cross-linking agent is 0.3 to 50 parts by mass. In the above-mentioned acrylic polymer, the structural unit derived from an alkyl (meth) acrylate having a base carbon number of 4 or more and the structural unit derived from a hydroxyl-containing monomer are composed of a hydroxyl-containing monomer. The content of the derived structural unit is 1 to 35% by mass, and the above-mentioned maximum height roughness (Rz) of the first surface of the substrate is 0.01 to 8 μm.
上述支撐片與保護膜形成用複合片之一實施形態，可列舉:黏著劑層為非能量線硬化性，且黏著劑層含有至少具由(甲基)丙烯酸烷基酯所衍生構成單元的上述丙烯酸系聚合體、與交聯劑，在黏著劑層中，相對於上述丙烯酸系聚合體的含有量100質量份，交聯劑的含有量係0.3~50質量份，上述丙烯酸系聚合體係具有由烷基碳數達4以上之(甲基)丙烯酸烷基酯所衍生構成單元與由含羥基單體所衍生構成單元，在上述丙烯酸系聚合體中，相對於構成單元總量，由含羥基單體所衍生構成單元的含有量係1~35質量%，上述交聯劑係異氰酸酯系交聯劑，且基材第1面的上述最大高度粗糙度(Rz)係0.01~8μm。One embodiment of the support sheet and the composite sheet for forming a protective film includes the following: the adhesive layer is non-energy ray hardenable, and the adhesive layer contains the above-mentioned structural unit derived from at least an alkyl (meth) acrylate The acrylic polymer and the cross-linking agent in the adhesive layer contain 100 parts by mass of the content of the acrylic polymer, and the content of the cross-linking agent is 0.3 to 50 parts by mass. In the above-mentioned acrylic polymer, the structural unit derived from an alkyl (meth) acrylate having an alkyl carbon number of 4 or more and the structural unit derived from a hydroxyl-containing monomer are composed of hydroxyl-containing monomers. The content of the structural unit-derived unit is 1 to 35% by mass, the cross-linking agent is an isocyanate-based cross-linking agent, and the maximum height roughness (Rz) of the first surface of the substrate is 0.01 to 8 μm.
◇保護膜形成用複合片之製造方法
上述保護膜形成用複合片係例如藉由以下製造方法(本說明書中亦稱「製造方法(S1)」)來製造，其包括:依照基材、黏著劑層及保護膜形成用薄膜的順序來製作在其厚度方向積層而構成的積層片之步驟(本說明書中亦稱「積層片製作步驟(1)」)；以及將上述積層片在其厚度方向加壓狀態下保存的步驟(本說明書中亦稱「積層片保存步驟」)。
各層(基材、黏著劑層及保護膜形成用薄膜)的形成方法係如前所說明。
以下，針對上述製造方法(S1)，依照各步驟分別進行更詳細說明。◇ Manufacturing method of protective film-forming composite sheet Step of producing a laminated sheet formed by laminating layers and a protective film forming film in its thickness direction (also referred to as "laminate sheet producing step (1)" in this specification); and adding the laminated sheet in its thickness direction The step of saving in a compressed state (also referred to as a "layered sheet storing step" in this specification).
The method for forming each layer (the substrate, the adhesive layer, and the protective film-forming film) is as described above.
Hereinafter, the manufacturing method (S1) will be described in more detail in accordance with each step.
◎製造方法(S1)
＜＜積層片製作步驟(1)＞＞
上述積層片製作步驟(1)中，製作依照基材、黏著劑層及保護膜形成用薄膜的順序，在其厚度方向上積層構成的積層片。
本步驟中，例如藉由依對應上述層(基材、黏著劑層、保護膜形成用薄膜等)位置關係的方式進行積層，而製作具有與目標保護膜形成用複合片相同積層構造的積層片。
另外，本說明書中，所謂「積層片」在無特別聲明前提下，係指如上述具有與目標保護膜形成用複合片相同積層構造，且尚未施行上述積層片保存步驟者。◎ Manufacturing method (S1)
<<< Laminated sheet production step (1) >>
In the above-mentioned laminated sheet manufacturing step (1), a laminated sheet composed of a substrate, an adhesive layer, and a film for forming a protective film is laminated in the thickness direction in the order.
In this step, for example, a laminated sheet having the same laminated structure as the target sheet for forming a protective film is produced by laminating in a manner corresponding to the positional relationship of the above-mentioned layers (the substrate, the adhesive layer, and the film for forming a protective film).
In addition, in this specification, a "laminated sheet" refers to a person having the same laminated structure as the composite sheet for forming a target protective film as described above, and has not yet performed the above-mentioned laminated sheet storage step unless otherwise specified.
例如製造支撐片時，當在基材上積層黏著劑層時，只要在基材上塗佈上述黏著劑組成物，視需要施行乾燥便可。For example, when manufacturing a support sheet, when an adhesive layer is laminated on a substrate, the adhesive composition may be coated on the substrate and dried as necessary.
另一方面，例如當在已積層於基材上的黏著劑層上，進一步積層保護膜形成用薄膜的情況，在黏著劑層上塗佈保護膜形成用組成物，便可直接形成保護膜形成用薄膜。保護膜形成用薄膜以外的層亦是使用供形成此層的組成物，依照同樣方法，便可在黏著劑層上積層此層。依此，當使用任一組成物，形成連續的雙層積層構造的情況，在由上述組成物所形成的層上，進一步塗佈組成物便可形成新的層。但，在這2層之後才積層的層，較好預先在其他剝離薄膜上使用上述組成物形成，再將會與此已形成層中與上述剝離薄膜接觸一面的相反側的露出面，與已形成的剩餘層的露出面貼合，可形成連續雙層積層構造。此時，上述組成物以塗佈於剝離薄膜的剝離處理面上為佳。剝離薄膜係只要在積層構造形成後，視需要去除便可。On the other hand, for example, when a protective film-forming film is further laminated on an adhesive layer that has been laminated on a substrate, a protective film-forming composition is coated on the adhesive layer to directly form a protective film. With film. The layer other than the thin film for forming a protective film also uses the composition for forming this layer. According to the same method, this layer can be laminated on the adhesive layer. Accordingly, when any composition is used to form a continuous two-layer laminated structure, a new layer can be formed by further coating the composition on the layer formed of the composition. However, the layers that are laminated after these two layers are preferably formed by using the above composition on other release films in advance, and then the exposed surface on the opposite side of the formed layer from the surface that is in contact with the release film is formed in advance. The exposed surfaces of the formed remaining layers are bonded together to form a continuous double-layer laminated structure. In this case, the composition is preferably applied to a release-treated surface of a release film. The release film may be removed as required after the laminated structure is formed.
例如當製造在基材上積層黏著劑層、在上述黏著劑層上積層保護膜形成用薄膜而成的保護膜形成用複合片(支撐片係基材與黏著劑層之積層物的保護膜形成用複合片)時，在基材上塗佈黏著劑組成物，視需要施行乾燥，而在基材上積層黏著劑層，另外在剝離薄膜上塗佈保護膜形成用組成物，視需要施行乾燥，而在剝離薄膜上形成保護膜形成用薄膜。然後，將此保護膜形成用薄膜的露出面，與已積層於基材上的黏著劑層露出面貼合，使保護膜形成用薄膜積層於黏著劑層上，便可獲得上述積層片。For example, when a protective film-forming composite sheet is formed by laminating an adhesive layer on a substrate and a protective film-forming film on the adhesive layer (a protective film formed of a laminate of a supporting sheet-based substrate and an adhesive layer) When using a composite sheet), the adhesive composition is coated on the substrate and dried if necessary, and the adhesive layer is laminated on the substrate, and the protective film-forming composition is coated on the release film, and dried as necessary A protective film-forming film is formed on the release film. Then, the exposed surface of the protective film-forming film is bonded to the adhesive layer-exposed surface laminated on the substrate, and the protective film-forming film is laminated on the adhesive layer to obtain the laminated sheet.
另外，當在基材上積層黏著劑層時，如上述，亦可取代在基材上塗佈黏著劑組成物的方法，改為在剝離薄膜上塗佈黏著劑組成物，視需要施行乾燥，而在剝離薄膜上形成黏著劑層，再藉由將此層的露出面與基材其中一表面貼合，而將黏著劑層積層於基材上。
不管何種方法，剝離薄膜均係在形成目標積層構造後的任意時序中去除便可。In addition, when the adhesive layer is laminated on the substrate, as described above, instead of coating the adhesive composition on the substrate, the adhesive composition may be coated on the release film and dried as necessary. An adhesive layer is formed on the release film, and then the exposed surface of this layer is bonded to one surface of the substrate to laminate the adhesive on the substrate.
Regardless of the method, the release film may be removed at any timing after the target laminated structure is formed.
依此，構成保護膜形成用複合片的基材以外之層，均以預先形成於剝離薄膜上再貼合於目標層的表面之方法便可積層，因而視需要適當選擇採用此種步驟的層，便可製造上述積層片。According to this, the layers other than the base material constituting the protective film-forming composite sheet can be laminated by previously forming on the release film and then bonding to the surface of the target layer. Therefore, if necessary, a layer using such a step is appropriately selected. , The laminated sheet can be manufactured.
例如保護膜形成用複合片，通常以在臨支撐片之一面的相反側的最表層(例如保護膜形成用薄膜)表面貼合剝離薄膜的狀態下進行保管。所以，在此剝離薄膜(較佳係剝離處理面)上，塗佈保護膜形成用組成物等供形成構成最表層的組成物，再視需要施行乾燥，而在剝離薄膜上形成構成最表層的層，再將剩餘的各層依照上述任一方法，積層於與此層中與剝離薄膜接觸側的相反側的露出面上，即便未去除剝離薄膜而維持貼合狀態仍可獲得上述積層片。For example, a protective film-forming composite sheet is usually stored in a state where a release film is bonded to the surface of the outermost layer (for example, the film for protective film formation) on the side opposite to one side of the support sheet. Therefore, on this release film (preferably, a release-treated surface), a composition for forming a protective film, such as a composition for forming a protective film, is applied to form a composition that constitutes the outermost layer, and then dried if necessary, to form the outermost layer on the release film Layer, and the remaining layers are laminated on the exposed surface on the side opposite to the side in contact with the release film in accordance with any of the methods described above, and the laminated sheet can be obtained even if the release film is not removed and the bonding state is maintained.
當保護膜形成用複合片係包括上述其他層的情況，只要在上述積層片製作步驟(1)的適合時序，以成為適當配置位置的方式，適當追加設置上述其層的步驟便可。In the case where the protective film-forming composite sheet system includes the above-mentioned other layers, the steps of providing the above-mentioned layers may be appropriately added so as to be in an appropriate position at the appropriate timing of the above-mentioned laminated sheet production step (1).
積層片製作步驟(1)中所製作的上述積層片的形狀，並無特別的限定。例如可製作適於呈捲筒狀捲取的長條積層片，但亦可製作非為長條的其他形狀的積層片。The shape of the laminated sheet produced in the laminated sheet production step (1) is not particularly limited. For example, a long laminated sheet suitable for winding in a roll shape can be produced, but laminated sheets of other shapes other than long strips can also be produced.
＜＜積層片保存步驟＞＞
上述積層片保存步驟中，將上述積層片在其厚度方向加壓的狀態下保存。
本步驟中，將上述積層片在加壓狀態下保存的方法，可列舉例如:將長條的上述積層片捲取呈捲筒狀，在保持此已捲取的積層片狀態下，在將由捲取所生成的壓力施加於積層片單面或雙面狀態下保存的方法；針對未將長條的上述積層片捲取呈捲筒狀而維持展開狀態的積層片、或非為長條的上述積層片，在其單面或雙面施加壓力狀態下保管的方法等。＜ How to save multilayer film ＞＞
In the laminated sheet storage step, the laminated sheet is stored in a state of being pressed in a thickness direction thereof.
In this step, the method for storing the laminated sheet in a pressurized state may include, for example, winding the long laminated sheet into a roll shape, and keeping the rolled laminated sheet in a state of being rolled by a roll. The method of taking the generated pressure and applying it to one or both sides of the laminated sheet for storage; for the laminated sheet that has not been rolled up into a roll shape and maintained in a rolled state, or the above-mentioned non-long sheet How to store laminated sheets under pressure on one or both sides.
將長條積層片捲取呈捲筒狀時，積層片以朝長邊方向進行捲取為佳。
捲取積層片時，例如捲取張力較佳係150~170N/m，捲取速度較佳係45~55m/min，捲取張力的漸縮比(taper ratio) (降低率)較佳係85~95%。藉由採用此種捲取條件，便可以更恰當的壓力加壓保存積層片。此種捲取條件係針對例如厚度100~300μm、寬度300~500mm、長度40~60m的積層片特別適用，惟積層片大小並不僅侷限於此。When winding a long laminated sheet into a roll shape, it is preferable that the laminated sheet is wound in a long side direction.
When winding the laminated sheet, for example, the winding tension is preferably 150 to 170 N / m, the winding speed is preferably 45 to 55 m / min, and the taper ratio (reduction rate) of the winding tension is preferably 85. ~ 95%. By adopting such a winding condition, the laminated sheet can be stored under pressure with a more appropriate pressure. Such winding conditions are particularly applicable to laminated sheets having a thickness of 100 to 300 μm, a width of 300 to 500 mm, and a length of 40 to 60 m, but the size of the laminated sheet is not limited to this.
積層片係例如可在常溫下或室溫下進行捲取，如後述，亦可在與對所捲取積層片施行加熱加壓保存時的同樣溫度條件下進行捲取。The laminated sheet can be wound up at, for example, normal temperature or room temperature. As described later, the laminated sheet can also be wound up under the same temperature conditions as when the rolled laminated sheet is stored under heat and pressure.
呈捲筒狀捲取的積層片係可在常溫下或室溫下保存，但以在加熱狀態下保存為佳。藉由依此施行加熱加壓保存，便可獲得黏著劑層與保護膜形成用薄膜間之積層性、以及保護膜或保護膜形成用薄膜隔著支撐片的刻印檢視性均更優異的保護膜形成用複合片。The laminated sheet wound in a roll shape can be stored at room temperature or room temperature, but it is preferably stored under heating. By carrying out heat and pressure storage in this way, it is possible to obtain a protective film formation that is superior in the lamination property between the adhesive layer and the film for forming a protective film, and the marking visibility of the protective film or the film for forming a protective film through the support sheet. Use composite tablets.
將積層片呈捲筒狀捲取時，保存時的加熱溫度並無特別的限定，較佳係53~75℃、更佳係55~70℃、特佳係57~65℃。When the laminated sheet is wound in a roll shape, the heating temperature during storage is not particularly limited, but is preferably 53 to 75 ° C, more preferably 55 to 70 ° C, and particularly preferably 57 to 65 ° C.
將積層片呈捲筒狀捲取時的保存時間並無特別的限定，較佳係24~720小時(1~30天)、更佳係48~480小時(2~20天)、特佳係72~240小時(3~10天)。The storage time when the laminated sheet is wound in a roll shape is not particularly limited, preferably 24 to 720 hours (1 to 30 days), more preferably 48 to 480 hours (2 to 20 days), and particularly good 72 ~ 240 hours (3 ~ 10 days).
呈捲筒狀捲取的積層片亦可例如將保護膜形成用薄膜與支撐片加工成特定形狀，再將依此加工的支撐片與保護膜形成用薄膜之複數片積層物，於其臨保護膜形成用薄膜之一面貼合於長條剝離薄膜，同時將此剝離薄膜長邊方向呈整齊排列配置。此情況的保護膜形成用薄膜以具有與半導體晶圓相同或幾近相同的平面形狀(通常係圓形狀) 為佳。又，此情況的支撐片較好具有與切割裝置中供固定支撐片用的夾具相同或幾近相同的外周的形狀。又，此情況，剝離薄膜的上述積層物貼合面中，以在短邊方向的周緣部附近，依不會重疊上述積層物的方式設置帶狀片為佳。此帶狀片係在將積層片呈捲筒狀捲取時，供抑制上述積層物表面出現高度差(本說明書中亦稱「積層痕」)用。上述積層痕係因積層片捲筒中，上述積層物(經加工的支撐片與保護膜形成用薄膜之積層物)的積層位置在捲筒徑向上未一致，導致對上述積層物表面施加較高壓力造成。若上述帶狀片設置於上述周緣部附近，則不會對上述積層物表面施加此種較高壓力，便抑制出現上述積層痕。The laminated sheet wound in a roll shape can also be processed into a specific shape, for example, by forming a protective film and a supporting sheet into a specific shape, and then laminating a plurality of laminated sheets of the supporting sheet and the protective film forming process to protect the protective sheet. One side of the film for forming a film is bonded to the long release film, and at the same time, the longitudinal direction of the release film is arranged in an aligned manner. The protective film-forming film in this case preferably has a planar shape (usually a circular shape) that is the same as or nearly the same as that of the semiconductor wafer. The support sheet in this case preferably has the same or nearly the same outer periphery shape as the jig for fixing the support sheet in the cutting device. In this case, it is preferable that a strip-shaped sheet is provided on the laminate bonding surface of the release film in the vicinity of the peripheral portion in the short-side direction so that the laminate is not overlapped. This strip-shaped sheet is used to suppress the height difference (also referred to as a "lamination mark" in the present specification) on the surface of the laminate when the laminated sheet is wound in a roll shape. The above-mentioned lamination marks are due to the fact that the lamination position of the above-mentioned laminates (laminates of the processed support sheet and the film for forming a protective film) in the laminate sheet roll is not consistent in the radial direction of the roll, which causes a high pressure on the surface of the laminate Cause. If the strip-shaped sheet is provided near the peripheral edge portion, such a high pressure is not applied to the surface of the laminate, and the occurrence of the laminate mark is suppressed.
當長條積層片非呈捲筒狀捲取而呈展開狀態時，以及積層片非為長條的情況，複數片的這些積層片以進一步積層保存為佳。而，依此將積層片積層時，以使複數片的這些積層片的方向與周緣部位置呈相互對準的狀態為佳。When the long laminated sheets are not rolled up and rolled up, and when the laminated sheets are not long, the laminated sheets of a plurality of sheets may be further laminated and stored. When the laminated sheets are laminated accordingly, it is preferable that the directions of the plural laminated sheets and the position of the peripheral edge portion are aligned with each other.
非為長條的積層片(換言之單片式積層片)的形狀與大小並無特別的限定。例如較好使用切割裝置，依適於單片半導體晶圓加工的方式，配合半導體晶圓的形狀與大小、切割裝置中供固定支撐片用的夾具的形狀與大小，調整積層片的形狀與大小。The shape and size of the non-long laminated sheet (in other words, a single-piece laminated sheet) are not particularly limited. For example, it is better to use a dicing device to adjust the shape and size of the laminated sheet according to the shape and size of the semiconductor wafer and the shape and size of the fixture for fixing the support piece in the dicing device in a manner suitable for the processing of a single semiconductor wafer. .
呈積層狀態的上述積層片係可在常溫下或室溫下保存，但以在加熱狀態下保存為佳。藉由依此施行加熱加壓保存，便可獲得黏著劑層與保護膜形成用薄膜間之積層性、以及保護膜或保護膜形成用薄膜隔著支撐片的刻印檢視性均更優異的保護膜形成用複合片。
再者，當對呈積層狀態的上述積層片施行加壓保存時，加熱溫度與保存時間均可設為與上述積層片呈捲筒狀捲取的情況相同。The laminated sheet in a laminated state can be stored at normal temperature or room temperature, but is preferably stored under a heated state. By carrying out heat and pressure storage in this way, it is possible to obtain a protective film formation that is superior in the lamination property between the adhesive layer and the film for forming a protective film, and the marking visibility of the protective film or the film for forming a protective film through the support sheet. Use composite tablets.
Furthermore, when the laminated sheet in the laminated state is stored under pressure, the heating temperature and the storage time can be set to be the same as those in the case where the laminated sheet is rolled up in a roll shape.
製造方法(S1)中，待積層片保存步驟結束後，藉由解除積層片的加壓、以及視需要的加熱，便可獲得目標之保護膜形成用複合片。In the manufacturing method (S1), after the storing step of the laminated sheet is finished, the target composite film for forming a protective film can be obtained by releasing the pressure of the laminated sheet and heating if necessary.
製造方法(S1)的積層片製作步驟(1)中，基材、黏著劑層及保護膜形成用薄膜的積層(貼合)順序並無特別的限定，當預先製作支撐片(預先在基材上積層黏著劑層)、預先製作保護膜形成用薄膜、再於支撐片上積層保護膜形成用薄膜時，將支撐片與保護膜形成用薄膜中之任一者或雙方，於將其積層之前，單獨依照與上述積層片情況相同方法施行加壓保存。藉由將積層前的支撐片單獨施行加壓保存，便可更有效抑制基材與黏著劑層間發生上述未貼合區域。又，藉由單獨將積層前的保護膜形成用薄膜施行加壓保存，便可降低保護膜形成用薄膜與保護膜臨黏著劑層之面(第2面)的凹凸度(增加平滑度)，俾提升保護膜形成用薄膜與保護膜的設計性。In the laminated sheet manufacturing step (1) of the manufacturing method (S1), the order of laminating (bonding) of the base material, the adhesive layer, and the protective film-forming film is not particularly limited. When the protective film forming film is prepared in advance, and then the protective film forming film is laminated on the supporting sheet, one or both of the supporting sheet and the protective film forming film are laminated before the laminating, Separately, pressurized storage was performed in the same manner as in the case of the above-mentioned laminated sheet. By separately preserving the support sheet before lamination, it is possible to more effectively suppress the occurrence of the above-mentioned non-adhered area between the substrate and the adhesive layer. In addition, by separately preserving the protective film forming film before lamination under pressure, the unevenness (increasing smoothness) of the surface (second surface) of the protective film forming film and the protective film adjacent to the adhesive layer can be reduced,俾 Improve the design of protective films and protective films.
即，上述保護膜形成用複合片亦可例如藉由以下製造方法(本說明書中亦稱「製造方法(S2)」)來製造，其包括:在已積層基材與黏著劑層的支撐片之上述黏著劑層上，積層保護膜形成用薄膜而製作依照基材、黏著劑層及保護膜形成用薄膜的順序在其厚度方向積層而構成的積層片之步驟(本說明書中亦稱「積層片製作步驟(2)」)；以及將上述積層片在其厚度方向加壓的狀態下保存的步驟(保存步驟)；其中，在上述積層片製作步驟(2)之前，進一步包括:將上述支撐片與保護膜形成用薄膜其中任一者或雙方在其厚度方向施行加壓並保存的步驟(本說明書中，將保存支撐片的步驟稱「支撐片保存步驟」，將保存保護膜形成用薄膜的步驟稱「保護膜形成用薄膜保存步驟」)。That is, the above-mentioned composite sheet for forming a protective film can also be manufactured by, for example, the following manufacturing method (also referred to as "manufacturing method (S2)" in the present specification), which includes: The above-mentioned adhesive layer is a step of laminating a protective film-forming film to produce a laminated sheet that is laminated in the thickness direction in the order of the substrate, the adhesive layer, and the protective film-forming film (also referred to as "laminated sheet in this specification"). Manufacturing step (2) "); and a step of storing the laminated sheet under pressure in its thickness direction (save step); before the laminated sheet manufacturing step (2), the method further includes: Either or both of the protective film forming film and the protective film forming step are pressurized and stored in the thickness direction (in this specification, the step of storing the supporting sheet is referred to as a "support sheet storing step". The step is referred to as a "thin film storage step for forming a protective film").
◎製造方法(S2)
上述製造方法(S2)係除了上述積層片製作步驟(1)係施行積層片製作步驟(2)，更追加施行上述支撐片保存步驟及保護膜形成用薄膜保存步驟中之任一步驟或雙方之外，與上述製造方法(S1)相同。◎ Manufacturing method (S2)
The above-mentioned manufacturing method (S2) is in addition to the above-mentioned laminated sheet manufacturing step (1), the laminated sheet manufacturing step (2) is performed, and one or both of the above-mentioned supporting sheet storing step and protective film forming film storing step are additionally performed. Otherwise, it is the same as the manufacturing method (S1).
＜＜積層片製作步驟(2)＞＞
上述積層片製作步驟(2)，如上述，除了預先製作支撐片、預先製作保護膜形成用薄膜、依在支撐片上積層保護膜形成用薄膜的方式限定各層的積層順序之外，與製造方法(S1)的積層片製作步驟(1)相同。<<< Laminated sheet production step (2) >>
In the above-mentioned laminated sheet manufacturing step (2), as described above, in addition to preparing a supporting sheet in advance, preparing a protective film-forming film in advance, and limiting the laminating order of each layer in a manner of laminating the protective film-forming film on the supporting sheet, and the manufacturing method Step (1) of manufacturing a laminated sheet in S1) is the same.
＜＜支撐片保存步驟、保護膜形成用薄膜保存步驟＞＞
上述支撐片保存步驟與保護膜形成用薄膜保存步驟係各自的保存標的物並非積層片而是支撐片或保護膜形成用薄膜之外，可依照與製造方法(S1)的積層片保存步驟同樣地實行。
此情況，例如支撐片與保護膜形成用薄膜的保存時間，係與積層片的情況同樣，可設為24~720小時(1~30天)、48~480小時(2~20天)、及72~240小時(3~10天)中之任一者。<<< Support sheet storage procedure, protective film formation film storage procedure >>
The above-mentioned support sheet storage step and the protective film formation film storage step are the respective preservation targets, not the laminated sheet, but the support sheet or the protective film formation film, and they can be performed in the same manner as the laminated sheet storage step of the manufacturing method (S1). Implemented.
In this case, for example, the storage time of the support sheet and the film for forming a protective film is the same as that of the laminated sheet, and can be set to 24 to 720 hours (1 to 30 days), 48 to 480 hours (2 to 20 days), and Any of 72 ~ 240 hours (3 ~ 10 days).
另一方面，上述支撐片保存步驟與保護膜形成用薄膜保存步驟係分別如上述變更保存標的物之外，還有變更保存標的物(支撐片或保護膜形成用薄膜)的保存時間，除這些變更事項之外，依照與製造方法(S1)的積層片保存步驟同樣地實行。
此情況，例如支撐片與保護膜形成用薄膜的保存時間係可設為12~720小時(0.5~30天)、12~480小時(0.5~20天)、及12~240小時(0.5~10天)中之任一者。但，此僅為上述保存時間一例。
[實施例]On the other hand, the support sheet storage step and the protective film formation film storage step are as described above. In addition to changing the storage target, there are also changes in the storage time of the storage target (support sheet or protective film formation film). Except for the changes, it is carried out in the same manner as the multilayer sheet storage procedure of the manufacturing method (S1).
In this case, for example, the storage time of the support sheet and the film for forming the protective film can be set to 12 to 720 hours (0.5 to 30 days), 12 to 480 hours (0.5 to 20 days), and 12 to 240 hours (0.5 to 10). Days). However, this is only an example of the storage time mentioned above.
[Example]
以下，利用具體實施例，針對本發明進行更詳細說明。惟，本發明並不僅侷限於以下所示實施例。Hereinafter, the present invention will be described in more detail using specific embodiments. However, the present invention is not limited to the embodiments shown below.
＜保護膜形成用組成物之製造原料＞
用於保護膜形成用組成物的製造的原料，如下所示。
・聚合體成分(A)
(A)-1:由丙烯酸甲酯(85質量份)與丙烯酸-2-羥乙酯(15質量份)進行共聚合，而形成的丙烯酸系聚合體(重量平均分子量370000、玻璃轉移溫度6℃)
・熱硬化性成分(B1)
(B1)-1:雙酚A型環氧樹脂(三菱化學公司製「jER828」、環氧當量184~194g/eq)
(B1)-2:雙酚A型環氧樹脂(三菱化學公司製「jER1055」、環氧當量800~900g/eq)
(B1)-3:二環戊二烯型環氧樹脂(DIC公司製「Epicron HP-7200HH」、環氧當量255~260g/eq)
・熱硬化劑(B2)
(B2)-1:二氰二胺(ADEKA公司製「ADK HARDENER EH-3636AS」、熱活性潛在性環氧樹脂硬化劑、活性氫量21g/eq)
・硬化促進劑(C)
(C)-1:2-苯基-4,5-二羥甲基咪唑(四國化成工業公司製「Curezol 2PHZ-PW」)
・填充劑(D)
(D)-1:二氧化矽填料(Admatechs公司製「SC2050MA」、經環氧系化合物施行表面修飾後的二氧化矽填料、平均粒徑0.5μm)
・偶合劑(E)
(E)-1:3-胺基丙基三甲氧基矽烷(NUC公司製「A-1110」)
・著色劑(I)
(I)-1:黑色顏料(大日精化公司製)<Materials for producing a protective film-forming composition>
The raw materials used for the production of the protective film-forming composition are as follows.
・ Polymer composition (A)
(A) -1: An acrylic polymer (weight average molecular weight 370,000, glass transition temperature 6 ° C) formed by copolymerization of methyl acrylate (85 parts by mass) and 2-hydroxyethyl acrylate (15 parts by mass). )
・ Thermosetting component (B1)
(B1) -1: Bisphenol A epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 184 ~ 194g / eq)
(B1) -2: Bisphenol A epoxy resin ("jER1055" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 800 ~ 900g / eq)
(B1) -3: Dicyclopentadiene type epoxy resin ("Epicron HP-7200HH" manufactured by DIC, epoxy equivalent 255 ~ 260g / eq)
・ Heat hardener (B2)
(B2) -1: Dicyandiamine ("ADK HARDENER EH-3636AS" manufactured by ADEKA Corporation, thermally active latent epoxy resin hardener, active hydrogen content 21g / eq)
・ Hardening accelerator (C)
(C) -1: 2-phenyl-4,5-dimethylol imidazole ("Curezol 2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd.)
・ Filling agent (D)
(D) -1: Silicon dioxide filler ("SC2050MA" manufactured by Admatechs, a silicon dioxide filler surface-modified with an epoxy-based compound, average particle size 0.5 μm)
・ Coupling agent (E)
(E) -1: 3-Aminopropyltrimethoxysilane ("A-1110" manufactured by NUC Corporation)
・ Colorant (I)
(I) -1: Black pigment (manufactured by Daiichi SEIKA)
[實施例1]
＜支撐片之製造＞
(黏著劑組成物(I-4)之製造)
製造固形份濃度30質量%的非能量線硬化性黏著劑組成物(I-4)，其含有丙烯酸系聚合體(100質量份、固形份)、與三官能基二異氰酸伸苯二甲酯系交聯劑(三井武田化學公司製「TAKENATE D110N」)(40質量份(固形份))，還含有甲乙酮、甲苯及醋酸乙酯的混合溶劑作為溶劑。上述丙烯酸系聚合體係由丙烯酸-2-乙基己酯(2EHA)(80質量份)、及丙烯酸-2-羥乙酯(HEA)(20質量份)進行共聚合而成的重量平均分子量800000的預共聚物。[Example 1]
＜ Manufacture of support sheet ＞
(Manufacture of Adhesive Composition (I-4))
Production of a non-energy ray-curable adhesive composition (I-4) with a solid content concentration of 30% by mass, which contains an acrylic polymer (100 parts by mass, solid content) and trifunctional diisocyanate phthalate An ester-based cross-linking agent ("TAKENATE D110N" manufactured by Mitsui Takeda Chemical Co., Ltd.) (40 parts by mass (solid content)), and a mixed solvent of methyl ethyl ketone, toluene, and ethyl acetate as a solvent. The acrylic polymerization system is obtained by copolymerizing 2-ethylhexyl acrylate (2EHA) (80 parts by mass) and 2-hydroxyethyl acrylate (HEA) (20 parts by mass). Pre-copolymer.
(支撐片之製造)
使用聚對苯二甲酸乙二酯製薄膜的單面經利用聚矽氧處理而施行剝離處理過的剝離薄膜(Lintec公司製「SP-PET381031」、厚度38μm)，在其剝離處理面，塗佈上述所獲得黏著劑組成物(I-4)，於120℃下施行2分鐘加熱乾燥，而形成非能量線硬化性黏著劑層。此時，依黏著劑層厚度成為4μm方式設定條件，塗佈黏著劑組成物(I-4)。(Manufacture of support sheet)
A peeling film ("SP-PET381031" manufactured by Lintec Corporation, thickness: 38 µm) was used on one side of a polyethylene terephthalate film that had been subjected to a peeling treatment with a polysiloxane treatment. The obtained adhesive composition (I-4) was heated and dried at 120 ° C for 2 minutes to form a non-energy-ray-curable adhesive layer. At this time, conditions were set so that the thickness of the adhesive layer became 4 μm, and the adhesive composition (I-4) was applied.
在聚丙烯製薄膜(三菱樹脂公司製、厚度80μm)其中一表面上，藉由使金屬輥的凹凸面在加熱狀態下旋轉而施行按壓，藉此便製得其中一面為凹凸面、另一面為平滑面(亮澤面)的基材。針對此基材的凹凸面，根據JIS B 0601:2013測定最大高度粗糙度(Rz)，結果為5μm。又，經測定此基材臨黏著劑層側的面所相鄰的凹部的最深點間的節距，結果為5μm。On one surface of a polypropylene film (manufactured by Mitsubishi Resin Co., Ltd., with a thickness of 80 μm), the uneven surface of the metal roller is rotated under heating to apply pressure, thereby producing one surface as an uneven surface and the other surface as Base material with smooth surface (glossy surface). The maximum height roughness (Rz) of the uneven surface of this substrate was measured according to JIS B 0601: 2013, and it was 5 μm. In addition, the pitch between the deepest points of the recesses adjacent to the surface of the base material adjacent to the side of the adhesive layer was measured, and it was 5 μm.
其次，藉由在上述所獲得黏著劑層的露出面，貼合上述基材的凹凸面，獲得依照基材、黏著劑層及剝離薄膜的順序在其厚度方向積層的支撐片。所獲得的支撐片的寬度(換言之，基材與黏著劑層的寬度)係400mm。
依上述獲得本發明的支撐片。Next, the uneven surface of the substrate is bonded to the exposed surface of the obtained adhesive layer to obtain a support sheet laminated in the thickness direction in the order of the substrate, the adhesive layer, and the release film. The width of the obtained support sheet (in other words, the width of the substrate and the adhesive layer) was 400 mm.
The support sheet of the present invention is obtained as described above.
接著，針對此支撐片，馬上施行後述關於基材與黏著劑層間之未貼合區域的評價。又，將此支撐片維持此狀態而使用於後述的保護膜形成用複合片的製造。Next, regarding this support sheet, the evaluation of the non-adhesion area between a base material and an adhesive layer mentioned later is performed immediately. In addition, this support sheet was used in the manufacture of a composite sheet for protective film formation described later while maintaining this state.
＜保護膜形成用複合片之製造＞
(保護膜形成用組成物(III-1)之製造)
使聚合體成分(A)-1(150質量份)、熱硬化性成分(B1)-1(60質量份)、(B1)-2(10質量份)、(B1)-3(30質量份)、(B2)-1(2質量份)、硬化促進劑(C)-1(2質量份)、填充劑(D)-1(320質量份)、偶合劑(E)-1(2質量份)、及著色劑(I)-1(18質量份)，溶解或分散於甲乙酮、甲苯及醋酸乙酯的混合溶劑中，在23℃下施行攪拌，而獲得固形份濃度51質量%的熱硬化性保護膜形成用組成物(III-1)。另外，此處所示摻合量全部均指「固形份量」。<Production of a protective film-forming composite sheet>
(Production of the protective film-forming composition (III-1))
Polymer component (A) -1 (150 parts by mass), thermosetting component (B1) -1 (60 parts by mass), (B1) -2 (10 parts by mass), (B1) -3 (30 parts by mass) ), (B2) -1 (2 parts by mass), hardening accelerator (C) -1 (2 parts by mass), filler (D) -1 (320 parts by mass), coupling agent (E) -1 (2 parts by mass) Parts), and coloring agent (I) -1 (18 parts by mass), dissolved or dispersed in a mixed solvent of methyl ethyl ketone, toluene, and ethyl acetate, and stirred at 23 ° C to obtain a heat with a solid concentration of 51% by mass. Composition (III-1) for forming a curable protective film. In addition, all the compounding quantity shown here means "solid content."
(保護膜形成用薄膜之製造)
使用聚對苯二甲酸乙二酯製薄膜單面經聚矽氧處理施行剝離處理過的剝離薄膜(第2剝離薄膜、Lintec公司製「SP-PET381031」、厚度38μm)，在其剝離處理面使用刀塗機塗佈上述所獲得的保護膜形成用組成物(III-1)，於100℃下施行2分鐘乾燥，便製得厚度25μm的熱硬化性保護膜形成用薄膜。(Manufacture of protective film-forming film)
A peeling film (second peeling film, "SP-PET381031" manufactured by Lintec Corporation, thickness: 38 μm) was used on one side of a polyethylene terephthalate film subjected to a polysiloxane treatment for peeling treatment, and used on the peeled surface The above-mentioned composition (III-1) for forming a protective film was applied by a knife coater and dried at 100 ° C. for 2 minutes to obtain a thin film for forming a thermosetting protective film having a thickness of 25 μm.
再者，在所獲得的保護膜形成用薄膜未設有第2剝離薄膜之一側的露出面，貼合剝離薄膜(第1剝離薄膜、Lintec公司製「SP-PET381031」、厚度38μm)的剝離處理面，便獲得在保護膜形成用薄膜其中一面上設有第1剝離薄膜、在另一面上設有第2剝離薄膜的積層薄膜。所獲得的積層薄膜的寬度(換言之，保護膜形成用薄膜、第1剝離薄膜及第2剝離薄膜的寬度)係400mm。In addition, the obtained protective film-forming film was not provided with an exposed surface on one side of the second release film, and the release film (the first release film, "SP-PET381031" manufactured by Lintec Corporation, and a thickness of 38 µm) was laminated. By processing the surface, a laminated film in which a first release film is provided on one side of the film for forming a protective film and a second release film is provided on the other side is obtained. The width (in other words, the width of the protective film-forming film, the first release film, and the second release film) of the obtained laminated film was 400 mm.
(保護膜形成用複合片之製造)
準備直徑5cm、截至距表面深度3mm的區域係由硬度50度的耐熱性聚矽氧橡膠構成之1組(2支)輥。
從上述所獲得的支撐片的黏著劑層除去剝離薄膜。又，從上述所獲得的積層薄膜除去第1剝離薄膜。
然後，使上述經除去剝離薄膜而生成的黏著劑層露出面、與上述經除去第1剝離薄膜而生成的保護膜形成用薄膜露出面呈相對向，使這些支撐片與保護膜形成用薄膜重疊而形成積層物，同時將此積層物以0.3m/min的速度通過溫度設定在60℃的這些輥間之間隙，而以0.5MPa的壓力施行加熱按壓(加熱層壓)。藉此製得依照基材、黏著劑層、保護膜形成用薄膜及第2剝離薄膜的順序在其厚度方向積層而構成之具有與目標保護膜形成用複合片相同積層構造的積層片(保存前的保護膜形成用複合片)。
所獲得的上述積層片的寬度(換言之係支撐片寬度)係400mm，保護膜形成用薄膜的外徑係330mm(Manufacture of protective film-forming composite sheet)
An area of 5 cm in diameter and 3 mm in depth from the surface was prepared as a set (two) of rollers made of heat-resistant silicone rubber having a hardness of 50 degrees.
The release film was removed from the adhesive layer of the support sheet obtained above. The first release film was removed from the laminated film obtained as described above.
Then, the exposed surface of the adhesive layer formed by removing the release film is opposed to the exposed surface of the protective film-forming film formed by removing the first release film, and these supporting sheets are overlapped with the protective film-forming film. A laminate was formed, and at the same time, the laminate was passed through a gap between the rollers whose temperature was set at 60 ° C. at a speed of 0.3 m / min, and a heating press (heat lamination) was performed at a pressure of 0.5 MPa. In this way, a laminated sheet having the same laminated structure as that of the target sheet for forming a protective film is formed by laminating in the order of the substrate, the adhesive layer, the protective film-forming film, and the second release film in the order of thickness (before storage) Protective film forming composite sheet).
The width of the obtained laminated sheet (in other words, the width of the supporting sheet) was 400 mm, and the outer diameter of the protective film-forming film was 330 mm.
其次，將依上述所獲得全體大小400mm×50m的積層片，將其長邊方向設為捲取方向，在捲取張力160N/m、捲取速度50m/min、捲取張力的漸縮比90%的條件下，捲繞於ABS樹脂製的芯上，而捲取呈捲筒狀。此時，依基材在輥的徑向上朝外側的方式(換言之，使第2剝離薄膜接觸於芯)，捲取積層片。
其次，將此捲筒狀積層片在空氣環境下、60℃溫度條件下，靜置保存7天(168小時)。
依上述，獲得具有圖2所示構造的本發明保護膜形成用複合片。Next, the laminated sheet having an overall size of 400 mm × 50 m obtained as described above was set as the winding direction, and the winding tension was 160 N / m, the winding speed was 50 m / min, and the tapering ratio of the winding tension was 90. Under the condition of%, it is wound on a core made of ABS resin, and it is wound into a roll shape. At this time, the laminated sheet was wound such that the substrate faced outward in the radial direction of the roll (in other words, the second release film was brought into contact with the core).
Next, this rolled laminated sheet was left to stand for 7 days (168 hours) under an air environment and a temperature of 60 ° C.
As described above, a composite sheet for forming a protective film of the present invention having a structure shown in FIG. 2 was obtained.
其次，針對經在此種加熱加壓條件下完成保存後的本發明保護膜形成用複合片，施行以下所示項目的評價。Next, the protective sheet forming composite sheet of the present invention after completion of storage under such heat and pressure conditions was evaluated for the items shown below.
＜支撐片及保護膜形成用複合片之評價＞
(黏著劑層的相鄰凸部頂點間之節距測定)
從上述所獲得的保護膜形成用複合片的5個地方，切取大小3mm×3mm的試驗片。此5個地方的切取位置係設為在圓形狀保護膜形成用薄膜中，相當於中心處的1個地方，以及靠近周緣部位且相對於此中心處幾乎呈點對稱位置的4個地方。這5個地方的切取位置中，相當於中心處的1個地方、與其餘靠近周緣部位的4個地方之中心間距離係100mm。<Evaluation of support sheet and composite sheet for protective film formation>
(Measurement of pitch between apexes of adjacent convex parts of the adhesive layer)
A test piece having a size of 3 mm × 3 mm was cut out from five places of the obtained protective film-forming composite sheet. The cutting positions of these five places are set in the film for forming a protective film in a circular shape, corresponding to one place in the center, and four places close to the periphery and almost point-symmetrical with respect to the center. The cutting position of these 5 places is equivalent to one place in the center and the distance between the centers to the other four places near the periphery is 100 mm.
使用截面試料製作裝置(JEOL公司製「截面拋光機SM-09010」)，將間歇式閘門的條件設為「in」10秒、「out」5秒，離子源電壓設為3kV、總拋光時間設為24小時，從上述試驗片形成其截面。新形成的截面係設為每1片試驗片僅有1面。Using a cross-section sample making device ("Section Cross-Surface Polisher SM-09010" manufactured by JEOL), the conditions of the intermittent gate were set to "in" for 10 seconds and "out" for 5 seconds. The cross-section was formed from the test piece for 24 hours. The newly formed cross section was set to have only one side per one test piece.
使用掃描式電子顯微鏡(SEM)，觀察這5個試驗片新形成的截面，在每個試驗片分別針對黏著劑層臨基材之相鄰凸部的頂點間的節距，求取其平均值，計算出P值。此時的試驗片截面觀察區域係上述截面寬度方向的1mm區域。結果如表1所示。Using a scanning electron microscope (SEM), observe the newly formed cross-sections of these five test pieces. For each test piece, the pitch between the vertices of the adjacent convex parts of the adhesive layer adjacent to the substrate is calculated, and the average value is calculated. To calculate the P value. The cross-sectional observation area of the test piece at this time was a 1 mm area in the cross-sectional width direction. The results are shown in Table 1.
(保護膜之刻印檢視性評價)
從上述所獲得的保護膜形成用複合片中除去第2剝離薄膜，將藉此生成的保護膜形成用薄膜的露出面(臨黏著劑層側的相反側的面)，貼附於8吋半導體晶圓的背面。此時的貼附係使用貼膜機(Lintec公司製「RAD2700」)實行。藉此，製得依照基材、黏著劑層、保護膜形成用薄膜及半導體晶圓的順序在其厚度方向上積層構成的第1積層構造體。(Evaluation of engraving of protective film)
The second release film is removed from the protective film-forming composite sheet obtained above, and the exposed surface of the protective film-forming film (the surface opposite to the side of the adhesive layer side) thus produced is attached to an 8-inch semiconductor The back of the wafer. At this time, the application was performed using a film application machine ("RAD2700" manufactured by Lintec). Thereby, a first laminated structure having a structure in which the substrate, the adhesive layer, the protective film-forming film, and the semiconductor wafer are laminated in the thickness direction is obtained.
其次，使用雷射刻印裝置(EO TECHNICS公司製「CSM300M」)，藉由對第1積層構造體中的保護膜形成用薄膜臨黏著劑層側的面(第2面)，隔著支撐片照射雷射光而施行刻印。此時刻印0.3mm×0.2mm大小的文字。Next, a laser engraving device ("CSM300M" manufactured by EO TECHNICS) was used to irradiate the surface (second surface) of the protective film-forming film in the first multilayer structure on the side near the adhesive layer through the support sheet. Laser light engraving. At this moment, characters with a size of 0.3mm × 0.2mm are printed.
其次，隔著支撐片目視觀察此保護膜形成用薄膜的刻印(雷射刻印)，依照下述基準評價刻印(文字)的檢視性。結果如表1所示。此處評價的保護膜形成用薄膜之刻印檢視性，係視為等同保護膜的刻印檢視性。
A:刻印清晰、可輕易檢視。
B:刻印稍微模糊、無法輕易檢視。
C:刻印不清晰、無法檢視。Next, the imprint (laser imprint) of this protective film-forming film was visually observed through a support sheet, and the visibility of the imprint (letter) was evaluated in accordance with the following criteria. The results are shown in Table 1. The marking visibility of the thin film for protective film formation evaluated here is considered to be equivalent to the marking visibility of the protective film.
A: The marking is clear and can be easily viewed.
B: The marking is slightly blurred and cannot be easily viewed.
C: The marking is not clear and cannot be viewed.
其次，從此保護膜形成用薄膜上撕開支撐片(基材與黏著劑層)。然後，使用光學顯微鏡(KEYENCE公司製)，測定在保護膜形成用薄膜上所形成的刻印(文字)的線條粗細度。結果，線條粗細度達40μm以上，呈清晰刻印。Next, the support sheet (the base material and the adhesive layer) was peeled from the film for forming a protective film. Then, using an optical microscope (manufactured by KEYENCE), the thickness of the lines of the engraved (letter) formed on the thin film for forming a protective film was measured. As a result, the thickness of the line was more than 40 μm, and the marking was clearly marked.
(基材與黏著劑間之密接性評價)
根據JIS K 5600-5-6，使用旋切機(rotary cutter)，在支撐片的黏著劑層賦予的1mm四方格子狀計100小方格，經壓貼黏貼帶(賽珞膠帶[NICHIBAN公司製、註冊商標])後，依約60°角度、0.5秒~1.0秒撕開黏貼帶，計數100小方格中殘留的小方格數，藉此針對基材與黏著劑層間之密接性施行測試。密接性評價係依照下述判定基準實行。然後依照下述基準，施行基材與黏著劑層之密接性的相關評價。結果如表1所示。
A:殘留小方格數達90以上。
B:殘留小方格數達70以上且未滿90。
C:殘留小方格數未滿70。(Evaluation of adhesion between substrate and adhesive)
According to JIS K 5600-5-6, using a rotary cutter, 100 small squares of 1 mm square grid pattern provided on the adhesive layer of the support sheet were pressed and pasted by a pressure-sensitive adhesive tape (said tape [manufactured by NICHIBAN) , Registered trademark]), then peel the adhesive tape at an angle of about 60 °, 0.5 seconds to 1.0 seconds, count the number of small squares remaining in the 100 small squares, thereby performing a test on the adhesion between the substrate and the adhesive layer . Adhesion evaluation was performed in accordance with the following judgment criteria. Then, according to the following criteria, a correlation evaluation of the adhesion between the substrate and the adhesive layer was performed. The results are shown in Table 1.
A: The number of small residual squares is more than 90.
B: The number of remaining small squares is 70 or more and less than 90.
C: The number of remaining small squares is less than 70.
＜支撐片及保護膜形成用複合片之製造、以及支撐片與保護膜形成用複合片之評價＞
[實施例2]
在聚丙烯製薄膜(三菱樹脂公司製、厚度80μm)其中一表面，藉由使金屬輥的凹凸面在加熱狀態下旋轉而施行按壓，藉此製得其中一面為凹凸面、另一面為平滑面(亮澤面)的基材。此時所使用的金屬輥凹凸面中，相鄰凸部頂點間的節距，係大於實施例1所使用金屬輥的上述節距，所製得的基材臨黏著劑層側的面相鄰凹部最深點間的節距，係大於實施例1所製得基材的上述節距。<Production of a support sheet and a protective film-forming composite sheet, and evaluation of a support sheet and a protective film-forming composite sheet>
[Example 2]
On one surface of a polypropylene film (manufactured by Mitsubishi Resin Co., Ltd., with a thickness of 80 μm), the uneven surface of the metal roller is rotated under heating to apply pressure, whereby one surface is an uneven surface and the other surface is a smooth surface. (Glossy surface). In the uneven surface of the metal roller used at this time, the pitch between the apexes of adjacent convex portions is larger than the above-mentioned pitch of the metal roller used in Example 1, and the prepared substrate is adjacent to the surface on the side of the adhesive layer. The pitch between the deepest points of the recesses is greater than the above-mentioned pitch of the substrate obtained in Example 1.
使用上述所獲得的基材之外，依照與實施例1同樣的方法製造支撐片，並評價。
然後，使用此種支撐片之外，依照與實施例1同樣的方法製造保護膜形成用複合片，並評價。
結果如表1所示。A support sheet was produced in the same manner as in Example 1 except that the substrate obtained above was used, and evaluated.
Then, a protective sheet-forming composite sheet was produced and evaluated in the same manner as in Example 1 except that such a support sheet was used.
The results are shown in Table 1.
[實施例3]
在聚丙烯製薄膜(三菱樹脂公司製、厚度80μm)其中一表面，藉由使金屬輥的凹凸面在加熱狀態下旋轉而施行按壓，藉此便製得其中一面為凹凸面、另一面為平滑面(亮澤面)的基材。此時所使用的金屬輥凹凸面中，相鄰凸部頂點間的節距，係大於實施例1所使用金屬輥的上述節距，所製得的基材臨黏著劑層側的面相鄰凹部最深點間的節距，係大於實施例1所製得的基材的上述節距。[Example 3]
On one surface of a polypropylene film (manufactured by Mitsubishi Resin Co., Ltd., with a thickness of 80 μm), the uneven surface of the metal roller is rotated while being heated to perform pressing, so that one surface is uneven and the other surface is smooth. Surface (glossy surface). In the uneven surface of the metal roller used at this time, the pitch between the apexes of adjacent convex portions is larger than the above-mentioned pitch of the metal roller used in Example 1, and the prepared substrate is adjacent to the surface on the side of the adhesive layer. The pitch between the deepest points of the recesses is larger than the above-mentioned pitch of the substrate prepared in Example 1.
使用上述所獲得基材之外，依照與實施例1同樣的方法製造支撐片，並評價。
然後，使用此種支撐片之外，依照與實施例1同樣的方法製造保護膜形成用複合片，並評價。
結果如表1所示。A support sheet was produced in the same manner as in Example 1 except that the obtained substrate was used, and evaluated.
Then, a protective sheet-forming composite sheet was produced and evaluated in the same manner as in Example 1 except that such a support sheet was used.
The results are shown in Table 1.
[比較例1]
在聚丙烯製薄膜(三菱樹脂公司製、厚度80μm)其中一表面，藉由使金屬輥的凹凸面在加熱狀態下旋轉而施行按壓，藉此製得其中一面為凹凸面、另一面為平滑面(亮澤面)的基材。此時所使用的金屬輥凹凸面中，相鄰凸部頂點間的節距，係大於實施例1所使用金屬輥的上述節距，所製得的基材臨黏著劑層側的面相鄰凹部最深點間的節距，係大於實施例1所製得基材的上述節距。[Comparative Example 1]
On one surface of a polypropylene film (manufactured by Mitsubishi Resin Co., Ltd., with a thickness of 80 μm), the uneven surface of the metal roller is rotated under heating to apply pressure, whereby one surface is an uneven surface and the other is a smooth surface. (Glossy surface). In the uneven surface of the metal roller used at this time, the pitch between the apexes of adjacent convex portions is larger than the above-mentioned pitch of the metal roller used in Example 1, and the prepared substrate is adjacent to the surface on the side of the adhesive layer. The pitch between the deepest points of the recesses is greater than the above-mentioned pitch of the substrate obtained in Example 1.
使用上述所獲得基材之外，依照與實施例1同樣的方法製造支撐片，並評價。
然後，使用此種支撐片之外，依照與實施例1同樣的方法製造保護膜形成用複合片，並評價。
結果如表1所示。A support sheet was produced in the same manner as in Example 1 except that the obtained substrate was used, and evaluated.
Then, a protective sheet-forming composite sheet was produced and evaluated in the same manner as in Example 1 except that such a support sheet was used.
The results are shown in Table 1.
[比較例2]
在聚丙烯製薄膜(三菱樹脂公司製、厚度80μm)其中一表面，藉由使金屬輥的凹凸面在加熱狀態下旋轉而施行按壓，藉此製得其中一面為凹凸面、另一面為平滑面(亮澤面)的基材。此時所使用的金屬輥凹凸面中，相鄰凸部頂點間的節距，係小於實施例1所使用金屬輥的上述節距，所製得基材臨黏著劑層側的面相鄰凹部最深點間的節距，係小於實施例1所製得基材的上述節距。[Comparative Example 2]
On one surface of a polypropylene film (manufactured by Mitsubishi Resin Co., Ltd., with a thickness of 80 μm), the uneven surface of the metal roller is rotated under heating to apply pressure, whereby one surface is an uneven surface and the other surface is a smooth surface. (Glossy surface). At this time, the pitch between the apexes of adjacent convex portions in the concave-convex surface of the metal roller used at this time is smaller than the above-mentioned pitch of the metal roller used in Example 1, and the surface adjacent to the adhesive layer on the side of the substrate is formed with concave portions The pitch between the deepest points is smaller than the above-mentioned pitch of the substrate obtained in Example 1.
使用上述所獲得的基材之外，依照與實施例1同樣的方法製造支撐片，並評價。
然後，使用此種支撐片之外，依照與實施例1同樣的方法製造保護膜形成用複合片，並評價。
結果如表1所示。A support sheet was produced in the same manner as in Example 1 except that the substrate obtained above was used, and evaluated.
Then, a protective sheet-forming composite sheet was produced and evaluated in the same manner as in Example 1 except that such a support sheet was used.
The results are shown in Table 1.
[表1]
由上述結果得知，實施例1~3的黏著劑層的P值在10μm以下(5~10μm)，基材與黏著劑層間之密接性特優。又，這些實施例的黏著劑層的P值均達5μm以上(5~10μm)，保護膜(保護膜形成用薄膜)的刻印檢視性特優。From the above results, it is known that the P value of the adhesive layer of Examples 1 to 3 is 10 μm or less (5 to 10 μm), and the adhesion between the substrate and the adhesive layer is particularly excellent. In addition, the P values of the adhesive layers in these examples were all 5 μm or more (5 to 10 μm), and the marking of the protective film (thin film for forming a protective film) was excellent in visibility.
相對於此，在比較例1，黏著劑層的P值係18μm，基材與黏著劑層的密接性差。所以，基材與黏著劑層間有出現剝離。In contrast, in Comparative Example 1, the P value of the adhesive layer was 18 μm, and the adhesiveness between the substrate and the adhesive layer was poor. Therefore, peeling occurs between the substrate and the adhesive layer.
再者，關於比較例2，黏著劑層的P值係2μm，隔著支撐片的保護膜(保護膜形成用薄膜)刻印檢視性差。Further, in Comparative Example 2, the P value of the adhesive layer was 2 μm, and the protective film (thin film for protective film formation) via the support sheet was imprinted with poor visibility.
另外，在實施例1~3、比較例1~2，在基材臨黏著劑層側的面，經確認與黏著劑層的P值同樣定義的節距平均值，均呈呈現與黏著劑層的P值相同的值。In addition, in Examples 1 to 3 and Comparative Examples 1 to 2, on the surface of the base material adjacent to the adhesive layer side, it was confirmed that the average pitch value defined as the P value of the adhesive layer was the same as the adhesive layer The P value is the same value.
再者，在實施例1~3，雖數據未特別顯示，但黏著劑層的S值達2μm以上，黏著劑層與保護膜形成用薄膜間之積層性優異。又，在這些實施例中，雖數據未特別顯示，但黏著劑層的L值在8μm以下，保護膜(保護膜形成用薄膜)的刻印檢視性更優異。In addition, in Examples 1 to 3, although the data is not particularly shown, the S value of the adhesive layer was 2 μm or more, and the lamination property between the adhesive layer and the film for forming a protective film was excellent. In these examples, although the data is not particularly shown, the L value of the adhesive layer is 8 μm or less, and the marking visibility of the protective film (thin film for protective film formation) is more excellent.
另外，在實施例1~3，在基材與黏著劑層之間、黏著劑層與保護膜形成用薄膜之間均完全沒有未貼合區域，或者即便有但層間距離仍小，保護膜形成用複合片仍具良好特性。
再者，關於實施例1~3，保護膜形成用薄膜第2面的凹凸度小，保護膜形成用薄膜係外觀優異，可形成設計性高的保護膜。
(產業上之可利用性)In addition, in Examples 1 to 3, there were no unattached areas between the substrate and the adhesive layer, and between the adhesive layer and the film for forming a protective film, or even if there were, the distance between the layers was small, and the protective film was formed. The composite sheet still has good characteristics.
In addition, in Examples 1 to 3, the degree of unevenness on the second surface of the protective film-forming film is small, the protective film-forming film is excellent in appearance, and a protective film having high designability can be formed.
(Industrial availability)
本發明係可利用於半導體裝置之製造。The present invention is applicable to the manufacture of semiconductor devices.
1A,1B,1C‧‧‧保護膜形成用複合片1A, 1B, 1C‧‧‧composite sheet for protective film formation
10‧‧‧支撐片 10‧‧‧ support sheet
10a‧‧‧支撐片臨保護膜形成用薄膜側的面(第1面) 10a‧‧‧ Support sheet facing the side of the film for forming a protective film (first side)
10b‧‧‧支撐片臨保護膜形成用薄膜側的相反側的面(第2面) 10b‧‧‧Support sheet is opposite to the side of the film for forming a protective film (second surface)
11‧‧‧基材 11‧‧‧ Substrate
11a‧‧‧基材臨黏著劑層側的面(第1面、凹凸面) 11a‧‧‧ The surface of the substrate facing the adhesive layer side (the first surface, the uneven surface)
11b‧‧‧基材臨黏著劑層側的相反側的面(第2面) 11b‧‧‧ The surface on the opposite side of the substrate from the side of the adhesive layer (second surface)
12‧‧‧黏著劑層 12‧‧‧ Adhesive layer
12a‧‧‧黏著劑層臨基材側的相反側的面(第1面) 12a‧‧‧ Adhesive layer surface opposite to the substrate side (first surface)
12b‧‧‧黏著劑層臨基材側的面(第2面) 12b‧‧‧ Adhesive layer side surface (second side)
13,23‧‧‧保護膜形成用薄膜 13,23‧‧‧Thin film for protective film formation
13a‧‧‧保護膜形成用薄膜臨黏著劑層側的相反側的面(第1面) 13a‧‧‧ film for forming a protective film, the side opposite to the side of the adhesive layer (first side)
13b‧‧‧保護膜形成用薄膜臨黏著劑層側的面(第2面) 13b‧‧‧Protective film forming surface on the side near the adhesive layer (second surface)
15‧‧‧剝離薄膜 15‧‧‧ release film
16‧‧‧夾具用接著劑層 16‧‧‧ Adhesive layer for jig
16a‧‧‧夾具用接著劑層未接觸到保護膜形成用薄膜之一面 16a‧‧‧ Adhesive layer for jig is not in contact with one side of the film for forming a protective film
23b‧‧‧保護膜形成用薄膜臨黏著劑層側的面(第2面) 23b‧‧‧Protective film forming surface on the side near the adhesive layer (second surface)
91,92‧‧‧未貼合區域 91,92‧‧‧Unapplied area
Pa1,Pa2,Pa3‧‧‧黏著劑層節距P a1 , P a2 , P a3 ‧‧‧ Adhesive layer pitch
Ta‧‧‧黏著劑層厚度T a ‧‧‧ thickness of adhesive layer
Ta1‧‧‧黏著劑層厚度最小值T a1 ‧‧‧Minimum thickness of adhesive layer
Ta2‧‧‧黏著劑層厚度最大值T a2 ‧‧‧Maximum thickness of the adhesive layer
圖1係本發明一實施形態的支撐片及保護膜形成用複合片之示意剖視圖。FIG. 1 is a schematic cross-sectional view of a support sheet and a composite sheet for forming a protective film according to an embodiment of the present invention.
圖2係本發明一實施形態的保護膜形成用複合片與支撐片一起顯示之示意剖視圖。 FIG. 2 is a schematic cross-sectional view showing a protective film-forming composite sheet and a supporting sheet according to an embodiment of the present invention.
圖3係本發明一實施形態的保護膜形成用複合片與支撐片一起顯示之示意剖視圖。 3 is a schematic cross-sectional view showing a protective film-forming composite sheet and a supporting sheet according to an embodiment of the present invention.
圖4係圖1所示支撐片及保護膜形成用複合片的放大剖視圖。 4 is an enlarged cross-sectional view of the supporting sheet and the composite sheet for forming a protective film shown in FIG. 1.
Claims (3)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| WOPCT/JP2018/013576 | 2018-03-30 | ||
| PCT/JP2018/013576 WO2019186995A1 (en) | 2018-03-30 | 2018-03-30 | Support sheet and composite sheet for protective film formation |
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| Publication Number | Publication Date |
|---|---|
| TW201945488A true TW201945488A (en) | 2019-12-01 |
| TWI812687B TWI812687B (en) | 2023-08-21 |
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| TW108109743A TWI812687B (en) | 2018-03-30 | 2019-03-21 | Supporting sheet and composite sheet for forming protective film |
Country Status (5)
| Country | Link |
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| JP (1) | JP6410386B1 (en) |
| KR (1) | KR102534931B1 (en) |
| CN (1) | CN111630631B (en) |
| TW (1) | TWI812687B (en) |
| WO (1) | WO2019186995A1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5432853B2 (en) | 1971-10-11 | 1979-10-17 | ||
| US6638602B2 (en) * | 2000-09-04 | 2003-10-28 | Asahi Kasei Kabushiki Kaisha | Adhesive wrapping film |
| SG11201807645SA (en) * | 2016-03-24 | 2018-10-30 | Lintec Corp | Supporting sheet and composite sheet for protective film formation |
| TWI796297B (en) * | 2016-04-28 | 2023-03-21 | 日商琳得科股份有限公司 | Composite sheet for forming protective film |
| JP6298226B1 (en) * | 2017-03-30 | 2018-03-20 | リンテック株式会社 | Composite sheet for protective film formation |
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2018
- 2018-03-30 JP JP2018540073A patent/JP6410386B1/en active Active
- 2018-03-30 CN CN201880086844.9A patent/CN111630631B/en active Active
- 2018-03-30 KR KR1020207018807A patent/KR102534931B1/en active IP Right Grant
- 2018-03-30 WO PCT/JP2018/013576 patent/WO2019186995A1/en active Application Filing
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| Publication number | Publication date |
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| TWI812687B (en) | 2023-08-21 |
| KR20200136879A (en) | 2020-12-08 |
| WO2019186995A1 (en) | 2019-10-03 |
| CN111630631A (en) | 2020-09-04 |
| KR102534931B1 (en) | 2023-05-19 |
| JPWO2019186995A1 (en) | 2020-04-30 |
| CN111630631B (en) | 2023-07-14 |
| JP6410386B1 (en) | 2018-10-24 |
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