CN108884244A - Protective film formation film and protective film formation composite sheet - Google Patents

Protective film formation film and protective film formation composite sheet Download PDF

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Publication number
CN108884244A
CN108884244A CN201780018817.3A CN201780018817A CN108884244A CN 108884244 A CN108884244 A CN 108884244A CN 201780018817 A CN201780018817 A CN 201780018817A CN 108884244 A CN108884244 A CN 108884244A
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protective film
film formation
methyl
film
energy ray
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Granted
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CN201780018817.3A
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CN108884244B (en
Inventor
山本大辅
稻男洋
稻男洋一
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Lintec Corp
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Lintec Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/017—Additives being an antistatic agent

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Dicing (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polymerisation Methods In General (AREA)
  • Paints Or Removers (AREA)

Abstract

The present invention provides the protective film formation film that can prevent semiconductor chip from charging and protective film formation composite sheet.The protective film formation is with the protective film formation film that film is energy ray-curable, when irradiation energy ray solidifies the protective film formation film, surface resistivity 1012Ω cm or less.The protective film formation preferably comprises antistatic agent with film, and the antistatic agent is preferably selected from least one of the group being made of anionic surfactant class antistatic agent, cationic surfactant class antistatic agent, nonionic surfactants antistatic agent, zwitterionic surfactant class antistatic agent and nonionic surfactants antistatic agent.

Description

Protective film formation film and protective film formation composite sheet
Technical field
The present invention relates to protective film formation film and protective film formation composite sheets.
The Japanese Patent Application 2016-092101 claims priority that the application is filed an application based on April 28th, 2016 in Japan Power, and its content is applied at this.
Background technique
In recent years, it is carrying out applying partly leading for the so-called Method for Installation referred to as upside-down mounting (face down) mode The manufacture of body device.In upside-down mounting mode, using the semiconductor chip with the electrodes such as convex block in circuit face, the electrode with Substrate engagement.Therefore, semiconductor chip exposes with the back side of circuit face opposite side sometimes.
It is formed with the resin film containing organic material as protective film at the back side of the semiconductor chip of the exposing, sometimes Semiconductor device is packed into as the semiconductor chip with protective film.It is partly being led after cutting action or encapsulation in order to prevent It cracks to utilize protective film on body chip.
In order to form such protective film, such as use a kind of protective film for having on support chip and being used to form protective film The protective film formation composite sheet of formation film.In protective film formation composite sheet, protective film formation film can pass through solidification And form protective film.In addition, also support chip can be used as cutting sheet, it is integrated with cutting sheet to can be made into protective film formation film Composite sheet is used in protective film formation.
As such protective film formation composite sheet, such as mainly uses to have so far and carried out by heating Solidify and be consequently formed the protective film formation composite sheet of the protective film formation film of the Thermocurable of protective film.At this point, for example Protective film formation is attached at the back side of semiconductor crystal wafer (with electrode with composite sheet with film using the protective film formation of Thermocurable The face of forming face opposite side).Then, make the solidification of protective film formation film to which protective film be made by heating, it will by cutting Semiconductor crystal wafer divides that semiconductor chip (referring to patent document 1, patent document 2) is made together with protective film.
Existing technical literature
Patent document
Patent document 1：No. 5144433 bulletins of Japanese Patent No.
Patent document 2：Japanese Unexamined Patent Publication 2010-031183 bulletin
Fig. 7 indicates the diagrammatic cross-section that previous semiconductor chip is enclosed to the state of reel in embossed carrier tape.Pass through Cutting semiconductor chip (illustration omitted) and divide the obtained semiconductor chip 101 with protective film and picked up one by one.Then, quilt It is accommodated in the pocket 102a for the film for packaging (embossed carrier tape 102) for being continuously provided with multiple depressed sections (pocket 102a), with The state of sticking cover band 103 (enclosed reel) is sent out and is carried to next process on the embossed carrier tape 102.In next process In, the lid band 103 for being accommodated with the embossed carrier tape 102 of the semiconductor chip 101 with protective film is removed, and take out and be accommodated in pocket The semiconductor chip 101 with protective film of 102a, and then for subsequent process.
Summary of the invention
The technical problem to be solved in the present invention
However, friction etc. of the protective film when being divided together with semiconductor crystal wafer in cutting action sometimes due tos generate it is quiet Electricity, the semiconductor chip 101 with protective film for being accommodated in embossed carrier tape 102 charge.If 101 band of semiconductor chip with protective film Electricity is then removing embossing to take out the semiconductor chip 101 with protective film for the pocket 102a for being accommodated in embossed carrier tape 102 When the lid band 103 of carrier band 102, the semiconductor chip 101 with protective film is attached on the lid band 103 of removing.Therefore, band protective film Semiconductor chip 101 and the lid band 103 of removing removed from embossed carrier tape 102 together.It can not be suitable as a result, there is generation It is carried to a problem that foreign matters such as unfavorable condition or the dust of next process are attached on semiconductor chip because of electrostatic sharply The problem of.
Invention that the present invention was completed to solve the above problem.Even if that is, its purpose is to provide one kind to carry out It cuts and the semiconductor chip storage packaging (enclosed reel) with protective film picked up is in embossed carrier tape, can also prevent from receiving It is contained in the protective film formation film and protective film formation composite sheet of the semiconductor chip electrification therein with protective film.
Solve the technological means of technical problem
In order to solve the above-mentioned technical problem present inventor has made intensive studies.As a result, it has been found that by making to protect It is 10 that film, which is formed and formed with film or protective film with the surface resistivity of composite sheet,12Ω cm is asked hereinafter, being able to solve above-mentioned technology Topic, so as to complete the present invention.
That is, the present invention is a kind of protective film formation film, it is the protective film formation film of energy ray-curable, In, when irradiation energy ray solidifies the protective film formation film, surface resistivity 1012Ω cm or less.
In protective film formation film of the invention, the preferably described protective film formation film contains antistatic agent.
In addition, in protective film formation film of the invention, the preferably described antistatic agent is selected from being lived by anionic surface Property agent class antistatic agent, cationic surfactant class antistatic agent, nonionic surfactants antistatic agent, amphoteric ion At least one of the group of surfactant-based antistatic agent and nonionic surfactants antistatic agent composition.
Further, the preferably described antistatic agent is alkaline metal salt.
Preferably with respect to the quality of the resin component contained in the protective film formation film, the content of the antistatic agent For 6~20 mass %.
It is preferred that the protective film formation film further contains energy ray-curable ingredient (a) and does not have energy-ray The polymer (b) of curative group.
It is preferred that relative to the energy ray-curable ingredient (a) and not having energy in the protective film formation film Measure the gross mass of the polymer (b) of ray-curable group, the antistatic agent containing 6~20 mass %.
In addition, the present invention can be a kind of protective film formation composite sheet, with the guarantor of above-mentioned record on support chip Film is used in cuticula formation.
Invention effect
According to the present invention, it is possible to provide even if one kind is also capable of partly leading for anti-stop-band protective film when being accommodated in embossed carrier tape The protective film formation film and protective film formation composite sheet of body chip electrification.
Detailed description of the invention
Fig. 1 is the sectional view for schematically showing an embodiment of protective film formation composite sheet of the invention.
Fig. 2 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Fig. 3 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Fig. 4 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Fig. 5 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Fig. 6 is the sectional view for schematically showing an embodiment of protective film formation film of the invention.
Fig. 7 is to schematically show that the semiconductor chip with protective film is accommodated in the pocket of embossed carrier tape and pastes lid Sectional view with the state to be covered and the state for having removed the lid band.
Specific embodiment
Film is used in the formation of ◇ protective film
Protective film formation of the invention is with the protective film formation film that film is energy ray-curable, surface resistivity 1012Ω cm or less.
It is preferred that protective film formation film of the invention contains antistatic agent.
In protective film formation film of the invention, the preferably described antistatic agent is selected from by anionic surfactant class Antistatic agent, cationic surfactant class antistatic agent, nonionic surfactants antistatic agent, amphoteric ion surface are living Property agent class antistatic agent and nonionic surfactants antistatic agent composition at least one of group.
It is preferred that the antistatic agent is alkaline metal salt.
It is preferred that the protective film formation film further contains energy ray-curable ingredient (a) and does not have energy-ray The polymer (b) of curative group.
It is preferred that relative to the energy ray-curable ingredient (a) and not having energy in the protective film formation film Measure the gross mass of the polymer (b) of ray-curable group, the antistatic agent containing 6~20 mass %.
Protective film formation film of the invention can have the first stripping film on the surface of at least side, can also be another Further there is the second stripping film on the surface of side.Protective film formation film of the invention can be to be wound into the strip of roll The form of shape film provides.Fig. 6 is the sectional view for schematically showing an embodiment of protective film formation film of the invention. In Fig. 6, it is sequentially laminated with the first stripping film 15b, protective film formation film 13 (23) and the second stripping film 15a.
Composite sheet is used in the formation of ◇ protective film
The protective film that protective film formation composite sheet of the invention has energy ray-curable on support chip, which is formed, to be used Film, it is 10 that the protective film, which is formed with the surface resistivity of film,12Ω cm or less.
Herein, " surface resistivity 1012Ω cm protective film below forms film " refer to the protective film shape When at protective film is made with film irradiation energy ray, the surface resistivity of the protective film is 1012Ω cm protection below Film is used in film formation.
In addition, in the present invention, " protective film forms film " refers to film before curing, and " protective film " is to instigate protective film Form film made of using film cured.
In addition, the surface resistivity relative to protective film formation film before curing, the surface resistivity after solidification increases, Antistatic property decline.Therefore, in order to make the surface resistivity 10 of the protective film after solidifying12Ω cm is hereinafter, must make to solidify It is 10 that preceding protective film, which is formed with the surface resistivity of film,11Ω cm or less.
The surface resistivity of protective film formation film is preferably 1011Ω cm is hereinafter, more preferably 1010Ω cm hereinafter, Further preferably 109Ω cm or less.The lower limit value of the surface resistivity of protective film formation film is not particularly limited.Such as It can be set as 108Ω·cm。
In addition, the surface resistivity of protective film is preferably 1012Ω cm is hereinafter, more preferably 1011Ω cm hereinafter, into One step is preferably 1010Ω cm or less.The lower limit value of the surface resistivity of protective film is not particularly limited.Such as 10 can be set as9 Ω·cm。
The protective film formation film is solidified by the irradiation of energy-ray, becomes protective film.The protective film is for protecting Protect the back side (face with electrode forming surface opposite side) of semiconductor crystal wafer or semiconductor chip.Protective film formed with film be it is soft, It can be simply attached to attach object.
Moreover, surface resistivity when being solidified and energy-ray that protective film formation is illuminated with film is set as 1012Ω cm is hereinafter, protective film formation of the invention has antistatic property with composite sheet.For example, even across cutting action, It can prevent semiconductor chip from charging.In addition, further, enclose reel and send out, and in next process peel-off covers band, it can It prevents from semiconductor chip to be attached to lid to take.
Adhere to further, since preventing semiconductor chip itself to charge, therefore dust or dust can be prevented etc. because of electrostatic On a semiconductor die.
In the present invention, " energy-ray " refers to the ray in electromagnetic wave or charged particle beam with the quantum of energy, as it Example can enumerate ultraviolet light, radioactive ray, electron beam etc..
Ultraviolet light for example can be by using high-pressure sodium lamp, fusion H lamp (fusion H lamp), xenon lamp, black light lamp or LED Lamp etc. is irradiated as ultraviolet source.Electron beam can irradiate the electron beam using generations such as electron-beam accelerators.
In the present invention, " energy ray-curable ", which refers to, carries out cured property by irradiation energy ray, " non-energy Amount ray-curable " refers to irradiation energy ray without cured property.
The semiconductor crystal wafer of object or the thickness of semiconductor chip are used as protective film formation composite sheet of the invention Degree is not particularly limited.Due to can significantly more obtain effect of the invention, so preferably 30~1000 μm, more preferably 100~300 μm.
Hereinafter, being described in detail to composition of the invention.
◎ support chip
The support chip can be made of a layer (single layer), can also be made of two layers or more of multiple layers.Support chip When being made of multiple layers, these multiple layers constituent materials and thickness mutually the same can be can also be different, as long as not damaging this The effect of invention, these multiple layers combinations are not particularly limited.
In addition, in the present specification, the case where being not limited to support chip, " multiple layers mutually the same can also be different " is Refer to that " layer that can be all is identical.Layer that can also be all is different, can be identical with the layer of only a part ", in addition, " multiple layers that This is different " refer to " at least one of the constituent material of each layer and thickness are different from each other ".
As preferred support chip, such as the support that adhering agent layer is directly contacted and is laminated with substrate can be enumerated Support chip and the support chip being only made of substrate etc. made of piece, adhering agent layer are laminated on substrate via middle layer.
Protective film of the invention is formed with compound hereinafter, accordinging to the type of such support chip while referring to attached drawing The example of piece is illustrated.In addition, for conveniently, will make in following explanation sometimes in order to which feature of the invention is more readily understood The pith of figure expands display, and dimensional ratios of each component etc. are not necessarily identical as reality.
Fig. 1 is the sectional view for schematically showing an embodiment of protective film formation composite sheet of the invention.This Shown in protective film formation composite sheet 1A have adhering agent layer 12 on substrate 11, have protective film on adhering agent layer 12 It is formed and uses film 13.Support chip 10 is the laminated body of substrate 11 and adhering agent layer 12, and in other words, protective film, which is formed, uses composite sheet 1A With the composition for being laminated with protective film formation film 13 on the surface 10a of the side of support chip 10.It is used in addition, protective film is formed Composite sheet 1A is in protective film formation with being further equipped with stripping film 15 on film 13.
In protective film formation in composite sheet 1A, adhering agent layer 12 is laminated on the surface 11a of the side of substrate 11.? Protective film formation film 13 is laminated in the entire surface of the surface 12a of adhering agent layer 12, on the protective film formation surface of film 13 A part of 13a, the region i.e. near peripheral part are laminated with fixture adhesive phase 16.On the protective film formation surface of film 13 The surface 16a (upper surface and side) on the surface that fixture adhesive phase 16 is not laminated and fixture adhesive phase 16 in 13a On be laminated with stripping film 15.
In protective film formation in composite sheet 1A, the protective film after solidification is formed with film 13 (i.e. protective film) and support chip 10 Between adhesion strength, in other words, the adhesion strength between protective film and adhering agent layer 12 is preferably 50~1500mN/25mm.
Fixture adhesive phase 16 for example can be the single layer structure containing adhesive ingredients.In addition it is also possible to make The multilayered structure of the layer containing adhesive ingredients is laminated on two sides for the sheet material of core material.
Protective film formation shown in FIG. 1 carried out in the following manner with composite sheet 1A using：In the shape for eliminating stripping film 15 Under state, the back side of semiconductor crystal wafer (illustration omitted) is attached on surface 13a of the protective film formation with film 13.Further, make to press from both sides Upper surface in the surface 16a of tool adhesive phase 16 is attached on the fixtures such as annular frame.
Fig. 2 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention. In addition, in the figure after Fig. 2, for constituent element identical with the constituent element shown in figure being explained, Appended drawing reference identical with the figure that this is explained is marked, and description is omitted.
Protective film formation composite sheet 1B shown here other than not having 16 this point of fixture adhesive phase, with Protective film shown in FIG. 1 forms identical with composite sheet 1A.That is, in protective film formation in composite sheet 1B, in the side of substrate 11 Surface 11a on be laminated with adhering agent layer 12.It is laminated with protective film in the entire surface of the surface 12a of adhering agent layer 12 and forms use Film 13 is laminated with stripping film 15 in the entire surface of the surface 13a of protective film formation film 13.
Protective film formation shown in Fig. 2 carried out in the following manner with composite sheet 1B using：In the shape for eliminating stripping film 15 Under state, semiconductor crystal wafer is attached on a part of region of the center side in surface 13a of the protective film formation with film 13 and (saves sketch map Show) the back side.It is attached to protective film formation on the fixtures such as annular frame with the region near the peripheral part of film 13.
Fig. 3 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Protective film formation composite sheet 1C shown here is not other than having 12 this point of adhering agent layer, with Fig. 1 institute The protective film formation composite sheet 1A shown is identical.That is, support chip 10 is only by 11 structure of substrate in protective film formation in composite sheet 1C At.It is used moreover, being laminated with protective film on the surface 11a (the surface 10a of the side of support chip 10) of the side of substrate 11 and being formed Film 13.Fixture bonding is laminated on the region near a part of the surface 13a of protective film formation film 13, i.e. peripheral part Oxidant layer 16, the surface that fixture adhesive phase 16 is not laminated and fixture in surface 13a of the protective film formation with film 13 are used viscous Stripping film 15 is laminated on the surface 16a (upper surface and side) of mixture layer 16.
In protective film formation in composite sheet 1C, the protective film after solidification is formed with film 13 (i.e. protective film) and support chip 10 Between adhesion strength, in other words, the adhesion strength between protective film and substrate 11 is preferably 50~1500mN/25mm.
Identical with composite sheet 1A as protective film formation shown in FIG. 1, protective film shown in Fig. 3, which is formed, uses composite sheet 1C or less The mode of stating carry out using：In the state of eliminating stripping film 15, attaches on surface 13a of the protective film formation with film 13 and partly lead The back side of body wafer (illustration omitted).Further, the upper surface in the surface 16a of fixture adhesive phase 16 is made to be attached to annular On the fixtures such as frame.
Fig. 4 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Protective film formation composite sheet 1D shown here other than not having 16 this point of fixture adhesive phase, with Protective film shown in Fig. 3 forms identical with composite sheet 1C.That is, in protective film formation in composite sheet 1D, in the side of substrate 11 Surface 11a on be laminated with protective film formation film 13.It is laminated in the entire surface of the surface 13a of protective film formation film 13 Stripping film 15.
Identical with composite sheet 1B as protective film formation shown in Fig. 2, protective film shown in Fig. 4, which is formed, uses composite sheet 1D or less The mode of stating carry out using：Center side in the state of eliminating stripping film 15, in surface 13a of the protective film formation with film 13 A part of region on attach semiconductor crystal wafer (illustration omitted) the back side.Further make the peripheral part of protective film formation film 13 Neighbouring region is attached on the fixtures such as annular frame.
Fig. 5 is the sectional view for schematically showing the another embodiment of protective film formation composite sheet of the invention.
Protective film formation shown here with composite sheet 1E other than the shape difference this point of protective film formation film, It is identical with composite sheet 1A as protective film formation shown in FIG. 1.That is, protective film formation composite sheet 1E has adhesion on substrate 11 Oxidant layer 12 has protective film formation film 23 on adhering agent layer 12.Support chip 10 is the stacking of substrate 11 and adhering agent layer 12 Body.In other words, protective film formation has with composite sheet 1E is laminated with protective film shape on the surface 10a of the side of support chip 10 At the composition with film 23.In addition, protective film formation is further equipped with stripping film on film 23 in protective film formation with composite sheet 1E 15。
In protective film formation in composite sheet 1E, adhering agent layer 12 is laminated on the surface 11a of the side of substrate 11.? A part of the surface 12a of adhering agent layer 12 is laminated with protective film formation film 23 on the region of center side.Moreover, The surface on the surface that protective film formation film 23 is not laminated and protective film formation film 23 in the surface 12a of adhering agent layer 12 23a is laminated with stripping film 15 on (upper surface and side).
When overlooking protective film formation down from above with composite sheet 1E, protective film forms the surface area ratio sticker for using film 23 Layer 12 is small.For example, having the shapes such as circle.
In protective film formation in composite sheet 1E, the protective film after solidification is formed with film 23 (i.e. protective film) and support chip 10 Between adhesion strength, in other words, the adhesion strength between protective film and adhering agent layer 12 is preferably 50~1500mN/25mm.
Protective film formation shown in fig. 5 carried out in the following manner with composite sheet 1E using：In the shape for eliminating stripping film 15 Under state, the back side of semiconductor crystal wafer (illustration omitted) is attached on surface 23a of the protective film formation with film 23.Further make to adhere The protective film formation that is not laminated in the surface 12a of oxidant layer 12 is attached on the fixtures such as annular frame with the surface of film 23.
It is used in composite sheet 1E in addition, protective film shown in Fig. 5 is formed, it can be in a manner of identical with shown in Fig. 1 and Fig. 3 Fixture adhesive phase is laminated on the surface that protective film formation film 13 is not laminated in the surface 12a of adhering agent layer 12 (to save Sketch map shows).It is identical as Fig. 1 and protective film formation composite sheet shown in Fig. 3, have the protection of such fixture adhesive phase Mode that film formation is attached to the surface of fixture adhesive phase on the fixtures such as annular frame and made With.
As described previously for protective film formation composite sheet of the invention, no matter support chip and protective film formation with film are What kind of form can have fixture adhesive phase.Wherein, usually as shown in Figures 1 and 3, has fixture adhesive The protective film of the invention of layer, which is formed, uses composite sheet, preferably in protective film formation with having fixture adhesive phase on film.
Protective film formation of the invention with composite sheet be not limited to Fig. 1~5 shown in composite sheet.That is, not damaging this hair In the range of bright effect, it can be constituted to change or deleting a part of protective film formation composite sheet shown in Fig. 1~5 Composite sheet or may be to have added other compositions on the basis of the protective film formation composite sheet that is illustrated above Composite sheet.
For example, in Fig. 3 and protective film formation composite sheet shown in Fig. 4, it can be in substrate 11 and protective film formation film Middle layer is set between 13.As middle layer, arbitrary middle layer can be selected according to purpose.
In addition, in Fig. 1, Fig. 2 and protective film formation composite sheet shown in fig. 5, it can be in substrate 11 and adhering agent layer 12 Between middle layer is set.That is, support chip can stack gradually substrate, centre in protective film formation composite sheet of the invention Layer and adhering agent layer form.Herein, middle layer refers to and can be arranged in Fig. 3 and protective film formation composite sheet shown in Fig. 4 The identical middle layer of middle layer.
In addition, protective film formation composite sheet shown in Fig. 1~5 can be arranged on arbitrary position remove the middle layer with Outer layer.
In addition, in protective film formation composite sheet of the invention, can stripping film with and the stripping film directly contact A part of gap is generated between layer.
In addition, can arbitrarily adjust the size of each layer according to purpose in protective film formation composite sheet of the invention And shape.
In protective film formation composite sheet of the invention, as described below, it is preferably adhering agent layer etc., support chip with Protective film formation is non-energy ray-curable with the layer that film directly contacts.Such protective film formation composite sheet can more be held It changes places and picks up the semiconductor chip that the back side has protective film.
Support chip can be transparent, can also be opaque, can also be coloured according to purpose.
Wherein, in the present invention that protective film formation has energy ray-curable with film, preferably support chip penetrates energy Ray.
For example, the transmitance of the light of wavelength 375nm is preferably 30% or more in support chip, more preferably 50% or more, Particularly preferably 70% or more.By making the such range of transmitance of the light, protective film is formed through support chip and is used When film irradiation energy ray (ultraviolet light), the curing degree of protective film formation film is further enhanced.
On the other hand, in support chip, the upper limit value of the transmitance of the light of wavelength 375nm is not particularly limited.Such as it can To be set as 95%.
In addition, the transmitance of the light of wavelength 532nm is preferably 30% or more in support chip, more preferably 50% or more, Particularly preferably 70% or more.By making the such range of transmitance of the light, protective film is formed through support chip and is used It, being capable of more clearly lettering when film or protective film irradiation laser are to carry out lettering to it.
On the other hand, in support chip, the upper limit value of the transmitance of the light of wavelength 532nm is not particularly limited.Such as it can To be set as 95%.
In addition, the transmitance of the light of wavelength 1064nm is preferably 30% or more in support chip, more preferably 50% with On, particularly preferably 70% or more.By making the such range of transmitance of the light, protective film is formed through support chip It, being capable of more clearly lettering when with film or protective film irradiation laser to carry out lettering to it.
On the other hand, in support chip, the upper limit value of the transmitance of the light of wavelength 1064nm is not particularly limited.Such as it can To be set as 95%.
Then, further each layer for constituting support chip is described in detail.
Zero substrate
The substrate is sheet or membranaceous, as its constituent material, such as can enumerate various resins.
As the resin, following resin can be enumerated.Such as can to enumerate low density polyethylene (LDPE) (LDPE), straight chain low close Spend the polyethylene such as polyethylene (LLDPE), high density polyethylene (HDPE) (HDPE)；Polypropylene, polybutene, polybutadiene, polymethylpentene, The polyolefin in addition to polyethylene such as norbornene resin；Vinyl-vinyl acetate copolymer, ethylene-(methyl) acrylic acid are total The ethene copolymers such as polymers, ethylene-(methyl) acrylate copolymer, ethylene-norbornene copolymer (use ethylene as Copolymer obtained from monomer)；The vinyl chloride resins such as polyvinyl chloride, vinyl chloride copolymer (use vinyl chloride as monomer and Obtained resin)；Polystyrene；Polycyclic alkene；Polyethylene terephthalate, gathers to benzene at polyethylene naphthalate Dioctyl phthalate butanediol ester, polyethylene glycol isophthalate, poly- 2,6- (ethylene naphthalate), all structural units have The polyester such as the Wholly aromatic polyester of aromatic series cyclic group；The copolymer of the two or more polyester；Poly- (methyl) acrylate； Polyurethane；Urethane acrylate；Polyimides；Polyamide；Polycarbonate；Fluororesin；Polyacetals；Noryl；Polyphenyl Thioether；Polysulfones；Polyether-ketone etc..
In addition, as the resin, such as the polyester can also be enumerated and gathered with the mixture of resin etc. in addition to it Close object alloy.It is preferred that the amount of the polyester and the resin in addition to polyester in the polymer alloy of resin in addition to it be compared with On a small quantity.
In addition, as the resin, such as the one or more of the resin above illustrated can also be enumerated Crosslinked resin made of crosslinking；The modified tree such as one or more kinds of ionomers of the resin above illustrated is used Rouge.
In addition, in the present specification, " (methyl) acrylic acid " be comprising " acrylic acid " and " methacrylic acid " both Concept.It is also identical as term as (methyl) acrylic compounds.
Constitute substrate resin can be only one kind, or it is two or more, for it is two or more when, their combination and Ratio can be selected arbitrarily.
Substrate can be made of a layer (single layer), can also be made of two layers or more of multiple layers.It is made of multiple layers When, these multiple layers mutually the same can also be different, these multiple layers combinations are not particularly limited.
The thickness of substrate is preferably 50~300 μm, and more preferably 60~100 μm.By make substrate with a thickness of such Range, the pliability of the protective film formation composite sheet and to the adhesion of semiconductor crystal wafer or semiconductor chip obtain into One step improves.
Herein, " thickness of substrate " refers to the thickness of substrate entirety.For example, the thickness for the substrate being made of multiple layers refers to Constitute the overall thickness of all layers of substrate.
Preferred substrates be the high substrate of thickness and precision, i.e. no matter what part thickness the base that is inhibited of deviation Material.As material in above-mentioned constituent material, can be used as constituting the high substrate of such thickness and precision, following object can be enumerated Matter.Such as polyethylene, the polyolefin in addition to polyethylene, polyethylene terephthalate, ethane-acetic acid ethyenyl can be enumerated Ester copolymer etc..
Substrate other than containing the main compositions material such as the resin, can also containing packing material, colorant, resist it is quiet Various additives well known to electric agent, antioxidant, organic lubricant, catalyst, softening agent (plasticizer) etc..
As long as the optical characteristics of substrate meets the optical characteristics of support chip described above.That is, substrate can be saturating It is bright, it can also be opaque.It can also be coloured according to purpose, other layers can also be vapor-deposited with.
Moreover, preferred substrates are penetrated through energy in the present invention that protective film formation has energy ray-curable with film Line.
In order to improve and be set to other layers of adhering agent layer on it etc. of adherence, substrate can be for surface implementation At further provided for contouring processing, Corona discharge Treatment, electron beam treatment with irradiation, plasma based on blasting treatment, solvent processing etc. The substrate of the oxidation processes such as reason, the processing of ozone-ultraviolet line treatment with irradiation, flame treatment, chromic acid, hot wind processing etc..
In addition, substrate can also be substrate of the surface through prime treatment.
In addition, substrate also can have and prevent when overlapping antistatic coating, protective film formation composite sheet and being saved The layer etc. that substrate and other sheet materials bond or prevent substrate and suction unit from bonding.
Wherein, the point of the generation of the part of the substrate caused by the friction of knife when inhibiting as cutting, particularly preferably Substrate is the substrate that surface implements electron beam treatment with irradiation.
Substrate can be manufactured using well known method.For example, the substrate containing resin can be by that will contain the resin Resin combination molding and manufacture.
Zero adhering agent layer
The adhering agent layer is sheet or membranaceous, and contains sticker.
As the sticker, for example, can enumerate acrylic resin, urethane based resin, rubber resin, The adherences resin such as organic silicon resin, epoxylite, polyvinylether, polycarbonate, esters resin, preferably acrylic compounds tree Rouge.
In addition, in the present invention, " adherence resin " is comprising the resin with adherence and with the resin of adhesiveness The concept of both.For example, not only include that resin itself has the resin of adherence, also comprising by with additive etc. other at It is used while dividing and shows the resin of adherence or bonding is shown by the presence of the triggers (trigger) such as heat or water The resin etc. of property.
Adhering agent layer can be made of a layer (single layer), can also be made of two layers or more of multiple layers.By multiple layers When composition, these multiple layers mutually the same can be can also be different, these multiple layers combinations are not particularly limited.
The thickness of adhering agent layer is preferably 1~100 μm, more preferably 1~60 μm, particularly preferably 1~30 μm.
Herein, " thickness of adhering agent layer " refers to the thickness of adhering agent layer entirety.Such as the sticker being made of multiple layers The thickness of layer refers to the overall thickness for constituting all layers of adhering agent layer.
As long as the optical characteristics of adhering agent layer meets the optical characteristics of support chip described above.That is, sticker Layer can be transparent, can also be opaque.It can also be coloured according to purpose.
Moreover, preferably adhering agent layer penetrates energy in the present invention that protective film formation has energy ray-curable with film Measure ray.
Energy ray-curable sticker can be used and form adhering agent layer, non-energy ray-curable also can be used Sticker and form adhering agent layer.The adhering agent layer formed using the sticker of energy ray-curable can easily adjust Physical property before solidifying and after solidifying.
< < adhesion agent composition > >
It is able to use the adhesion agent composition containing sticker and forms adhering agent layer.For example, by by adhesion agent composition It is coated in the formation object surface of adhering agent layer and is dried as needed, adhering agent layer can be formed in target site.It is viscous The more specific forming method of oxidant layer will be described in detail below together with other layers of forming method.Sticker group In object, the mutual content of ingredient that does not gasify under room temperature is closed than usually comparing phase with the mutual content of the ingredient of adhering agent layer Together.In addition, in the present specification, " room temperature " refers to the temperature for especially not cooled down or being heated, i.e. usual temperature.Such as 15~25 DEG C of temperature etc. can be enumerated.
The coating of adhesion agent composition is carried out using well known method.Such as can enumerate using Kohler coater, Scraping blade coating machine, bar coater, gravure coater, roll coater, roller knife coating machine, curtain coater, die coating machine, knife type coater, silk screen The method of the various coating machines such as coating machine (screen coater), Meyer rod coater, kiss painting machine (kiss coater).
The drying condition of adhesion agent composition is not particularly limited.But when adhesion agent composition contains aftermentioned solvent, It is preferred that being thermally dried.At this point, being for example preferably dried with the condition of 70~130 DEG C, 10 seconds~5 minutes.
When adhering agent layer is energy ray-curable, as the sticker combination containing energy ray-curable sticker The adhesion agent composition of object, i.e. energy ray-curable can enumerate following substance.Such as it can enumerate containing non-energy ray The adherence resin (I-1a) (hereinafter, writing a Chinese character in simplified form work " adherence resin (I-1a) " sometimes) and energy ray-curable of curability Close the adhesion agent composition (I-1) of object；Side chain containing the adherence resin (I-1a) in non-energy ray-curable is imported with The adherence resin (I-2a) of the energy ray-curable of unsaturated group (hereinafter, write a Chinese character in simplified form work " adherence resin (I- sometimes Adhesion agent composition (I-2) 2a) ")；Adhesion containing adherence resin (I-2a) and energy ray-curable compound Agent composition (I-3) etc..
< adhesion agent composition (I-1) >
As described above, adherence resin (I-1a) of the adhesion agent composition (I-1) containing non-energy ray-curable With energy ray-curable compound.
[adherence resin (I-1a)]
It is preferred that the adherence resin (I-1a) is acrylic resin.
As the acrylic resin, such as can enumerate at least with the structure from (methyl) alkyl acrylate The acrylic polymer of unit.
Structural unit possessed by acrylic resin can be only one kind, or two or more.It is two or more When, their combination and ratio can be selected arbitrarily.
As (methyl) alkyl acrylate, such as can enumerate the carbon atom number of the alkyl of composition Arrcostab is 1 ~20 (methyl) alkyl acrylate.It is preferred that the alkyl is straight-chain or branched.
As (methyl) alkyl acrylate, more specifically, following substance can be enumerated.Such as (methyl) can be enumerated Methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) propylene Sour N-butyl, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) propylene Sour pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) acrylic acid Different monooctyl ester, (methyl) n-octyl, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) acrylic acid Last of the ten Heavenly stems ester, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate ((methyl) lauryl acrylate), (methyl) Tridecyl acrylate, (methyl) acrylic acid tetradecane base ester ((methyl) myristyl ester), (methyl) acrylic acid ten Five Arrcostabs, (methyl) aliphatic acrylate ((methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester, (methyl) octadecyl acrylate ((methyl) stearyl acrylate acid esters), (methyl) acrylic acid nonadecane base ester, (methyl) third Olefin(e) acid eicosane base ester etc..
From the point for the adhesion strength for improving adhering agent layer, the preferably described acrylic polymer, which has, comes from the alkyl Carbon atom number be 4 or more (methyl) alkyl acrylate structural unit.Moreover, from the viscous of adhering agent layer is further increased The point puted forth effort sets out, and the carbon atom number of the alkyl is preferably 4~12, and more preferably 4~8.Furthermore it is preferred that the carbon of the alkyl (methyl) alkyl acrylate that atomicity is 4 or more is alkyl acrylate.
The acrylic polymer in addition to have from (methyl) alkyl acrylate structural unit other than, preferably into One step has from the structural unit containing monomer.
Contain monomer as described, such as reacting by the functional group and aftermentioned crosslinking agent can be enumerated The starting point or the functional group and the unsaturated group in the aftermentioned compound containing unsaturated group can be passed through that generation is crosslinked Group reaction and the side chain of acrylic polymer import unsaturated group contain monomer.
As containing the functional group in monomer, such as hydroxyl, carboxyl, amino, epoxy group can be enumerated etc..
That is, as monomer is contained, such as hydroxyl monomer can be enumerated, carboxyl group-containing monomer, emulsion stability, contain ring Oxygroup monomer etc..
As the hydroxyl monomer, following substance can be enumerated.Such as can enumerate (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) third (methyl) the acrylic acid hydroxyls such as olefin(e) acid 2- hydroxybutyl, (methyl) acrylic acid 3- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl Base Arrcostab；Non- (methyl) the acrylic compounds unsaturated alcohol such as vinyl alcohol, allyl alcohol (does not have (methyl) acryloyl group skeleton not Saturated alcohols) etc..
As the carboxyl group-containing monomer, following substance can be enumerated.Such as (methyl) acrylic acid, crotonic acid can be enumerated etc. Olefinic unsaturated monocarboxylic acid (monocarboxylic acid with ethylenic unsaturated bond)；Fumaric acid, itaconic acid, maleic acid, citraconic acid etc. Ethylenically unsaturated dicarboxylic (dicarboxylic acids with ethylenic unsaturated bond)；The acid anhydrides of the ethylenically unsaturated dicarboxylic；Methyl-prop Olefin(e) acid 2- carboxyethyl etc. (methyl) acrylic acid carboxyalkyl ester etc..
It is preferably hydroxyl monomer, carboxyl group-containing monomer, more preferably hydroxyl monomer containing monomer.
Constitute the acrylic polymer can be only one kind containing monomer, or two or more.For When two or more, their combination and ratio can be selected arbitrarily.
In the acrylic polymer, relative to the total amount of structural unit, from the structure list containing monomer The content of member is preferably 1~35 mass %, more preferably 2~32 mass %, particularly preferably 3~30 mass %.
The acrylic polymer is in addition to having structural unit from (methyl) alkyl acrylate and from containing Other than the structural unit of monomer, can further have the structural unit from other monomers.
As long as the other monomers can be not particularly limited with copolymerization such as (methyl) alkyl acrylates.
As the other monomers, such as styrene, α-methylstyrene, vinyltoluene, vinyl formate can be enumerated Ester, vinyl acetate, acrylonitrile, acrylamide etc..
The other monomers for constituting the acrylic polymer can be only one kind, or two or more.For When two or more, their combination and ratio can be selected arbitrarily.
The acrylic polymer can be used as the adherence resin (I-1a) of above-mentioned non-energy ray-curable.
On the other hand, contain unsaturation with energy-ray polymerism unsaturated group (energy-ray polymerizable group) Functional group reactions in the compound of group and the acrylic polymer and the substance generated, can be used as above-mentioned energy The adherence resin (I-2a) of ray-curable.
Adherence resin (I-1a) contained by adhesion agent composition (I-1) can be only one kind, or two kinds with On.When being two or more, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-1), the content of adherence resin (I-1a) is preferably 5~99 mass %, more preferably For 10~95 mass %, particularly preferably 15~90 mass %.
[energy ray-curable compound]
The energy ray-curable compound contained by as adhesion agent composition (I-1), can enumerate with energy It measures ray polymerization unsaturated group and the cured monomer of irradiation or oligomer of energy-ray can be passed through.
As the monomer in energy ray-curable compound, following substance can be enumerated.Such as three hydroxyl first can be enumerated Base propane three (methyl) acrylate, pentaerythrite (methyl) acrylate, pentaerythrite four (methyl) acrylate, two seasons penta Tetrol six (methyl) acrylate, 1,4- butanediol two (methyl) acrylate, 1,6-HD (methyl) acrylate etc. are more First (methyl) acrylate；Carbamate (methyl) acrylate；Polyester (methyl) acrylate；Polyethers (methyl) acrylic acid Ester；Epoxy (methyl) acrylate etc..
As the oligomer in energy ray-curable compound, for example, the monomer polymerization above illustrated can be enumerated and At oligomer etc..
For storage modulus larger with regard to molecular weight, adhering agent layer does not tend to decrease this point, energy ray-curable chemical combination Object is preferably carbamate (methyl) acrylate, carbamate (methyl) acrylate oligomer.
The energy ray-curable compound contained by adhesion agent composition (I-1) can be only one kind, can also be with It is two or more.When being two or more, their combination and ratio can be selected arbitrarily.
In the adhesion agent composition (I-1), the content of the energy ray-curable compound is preferably 1~95 matter Measure %, more preferably 5~90 mass %, particularly preferably 10~85 mass %.
[crosslinking agent]
Sometimes will further have other than there is the structural unit from (methyl) alkyl acrylate from containing official The acrylic polymer of the structural unit of energy single group body is used as adherence resin (I-1a).At this point, it is preferred that sticker group It closes object (I-1) and further contains crosslinking agent.
The crosslinking agent with the functional group for example by reacting for adherence resin (I-1a) to be cross-linked to each other.
As crosslinking agent, following substance can be enumerated.Such as toluene di-isocyanate(TDI), two isocyanide of hexa-methylene can be enumerated Acid esters, benzene dimethylene diisocyanate, these diisocyanate the isocyanates crosslinking agent such as addition product (there is isocyanic acid The crosslinking agent of ester group)；The epoxies such as ethylene glycol glycidyl ether crosslinking agent (crosslinking agent with glycidyl)；Six [1- (2- methyl) '-aziridino] triphosphoric acid triazine (Hexa [1- (2-methyl)-aziridinyl] triphosphatriazine) Equal triazines cross-linkings agent (crosslinking agent with '-aziridino)；The metal-chelatings species such as aluminium chelate compound crosslinking agent (has metal chelating Close the crosslinking agent of object structure)；Isocyanuric acid esters crosslinking agent (crosslinking agent with isocyanuric acid skeleton) etc..
Point from the cohesiveness for improving sticker to improve the adhesion strength of adhering agent layer and be easy to get etc., it is excellent Selecting crosslinking agent is isocyanates crosslinking agent.
Crosslinking agent contained by adhesion agent composition (I-1) can be only one kind, or two or more.For two kinds with When upper, their combination and ratio can be selected arbitrarily.
In the adhesion agent composition (I-1), relative to 100 mass parts of content of adherence resin (I-1a), crosslinking The content of agent is preferably 0.01~50 mass parts, more preferably 0.1~20 mass parts, particularly preferably 0.3~15 mass parts.
[Photoepolymerizationinitiater initiater]
Adhesion agent composition (I-1) can also further contain Photoepolymerizationinitiater initiater.Even if to Photoepolymerizationinitiater initiater is contained Adhesion agent composition (I-1) irradiation ultraviolet light etc. compared with the energy-ray of low energy, be also sufficiently carried out curing reaction.
As the Photoepolymerizationinitiater initiater, following substance can be enumerated.Such as can enumerate benzoin, benzoin methylether, Benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin diformazan The benzoins compound such as base ketal；Acetophenone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 2,2- dimethoxy -1,2- The acetophenone compounds such as diphenylethane -1- ketone；Bis- (2,4,6- trimethylbenzoyl) phosphine oxides of phenyl, 2,4,6- trimethyl The acylphosphine oxides compound such as benzoyl diphenyl phosphine oxide；The sulphur such as benzyl phenyl thioether, tetramethylthiuram monosulfide Compound；The α -one alcoholic compound such as 1- hydroxycyclohexylphenylketone；The azo-compounds such as azodiisobutyronitrile；Two cyclopentadienyl such as titanocenes Titanium compound；The thioxanthone compounds such as thioxanthones；Peroxide compound；The dione compounds such as biacetyl；Benzyl；Dibenzyl； Benzophenone；2,4- diethyl thioxanthone；1,2- diphenyl methane；2- hydroxy-2-methyl -1- [4- (1- methyl ethylene) benzene Base] acetone；2- chloroanthraquinone etc..
In addition, as the Photoepolymerizationinitiater initiater, such as the naphtoquinone compounds such as 1- chloroanthraquinone also can be used；The photosensitizers such as amine Deng.
Photoepolymerizationinitiater initiater contained by adhesion agent composition (I-1) can be only one kind, or two or more.For When two or more, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-1), relative to 100 mass parts of content of the energy ray-curable compound, The content of Photoepolymerizationinitiater initiater is preferably 0.01~20 mass parts, more preferably 0.03~10 mass parts, particularly preferably 0.05 ~5 mass parts.
[other additives]
Within the scope of the effect of the invention, adhesion agent composition (I-1) can also be above-mentioned containing not corresponding to Other additives of any ingredient.
As other described additives, such as antistatic agent, antioxidant, softening agent (plasticizer), filling can be enumerated Material (filler), antirust agent, colorant (pigment, dyestuff), sensitizer, tackifier, response delay agent, crosslinking accelerator (catalysis Agent) etc. well known to additive.
In addition, response delay agent refers to, such as pass through the effect of mixed catalyst in adhesion agent composition (I-1), suppression The additive of the progress of the cross-linking reaction of the non-purpose in adhesion agent composition (I-1) in system preservation.As response delay Agent, such as can enumerate and form chelate complex (chelate complex) using chelate corresponding with catalyst Response delay agent.More specifically, the response delay in 1 molecule with more than two carbonyls (- C (=O) -) can be enumerated Agent.
Other additives contained by adhesion agent composition (I-1) can be only one kind, or two or more.It is two Kind or more when, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-1), the content of other additives is not particularly limited, and it is appropriate to be carried out according to its type Selection.
[solvent]
Adhesion agent composition (I-1) can also contain solvent.By containing solvent, adhesion agent composition (I-1) is to coating The coating adaptive of object surface is improved.
It is preferred that the solvent is organic solvent.As the organic solvent, such as methyl ethyl ketone, acetone can be enumerated etc. Ketone；The esters such as ethyl acetate (carboxylate)；The ethers such as tetrahydrofuran, dioxane；The aliphatic hydrocarbons such as hexamethylene, n-hexane；Toluene, diformazan The aromatic hydrocarbons such as benzene；Alcohol such as 1- propyl alcohol, 2- propyl alcohol etc..
As the solvent, for example, when can not also will manufacture adherence resin (I-1a) solvent that uses from adherence tree It is removed in rouge (I-1a) and is directly used in adhesion agent composition (I-1).In addition it is also possible in manufacture adhesion agent composition (I-1) When, in addition add the solvent with the identical or different type of solvent used when manufacture adherence resin (I-1a).
Solvent contained by adhesion agent composition (I-1) can be only one kind, or two or more.It is two or more When, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-1), the content of solvent is not particularly limited, and can suitably be adjusted.
< adhesion agent composition (I-2) >
As described above, the adhesion agent composition (I-2) contains the adherence resin (I- in non-energy ray-curable Side chain 1a) is imported with the adherence resin (I-2a) of the energy ray-curable of unsaturated group.
[adherence resin (I-2a)]
For example, passing through the compound containing unsaturated group and the adhesion that make that there is energy-ray polymerism unsaturated group Functional group reactions in property resin (I-1a) and obtain the adherence resin (I-2a).
The compound containing unsaturated group be other than with the energy-ray polymerism unsaturated group, Further having can be bonded and being reacted with the functional group in adherence resin (I-1a) with adherence resin (I-1a) Group compound.
As the energy-ray polymerism unsaturated group, such as can to enumerate (methyl) acryloyl group, vinyl (secondary Ethyl), allyl (2- acrylic) etc..It is preferred that (methyl) acryloyl group.
As the group that can be bonded with the functional group in adherence resin (I-1a), such as can enumerate can be with hydroxyl or ammonia The isocyanate group and glycidyl and the hydroxyl that can be bonded with carboxyl or epoxy group and amino etc. of base bonding.
As the compound containing unsaturated group, such as (methyl) acryloyl-oxyethyl isocyanic acid can be enumerated Ester, (methyl) propenoyl isocyanate, (methyl) glycidyl acrylate etc..
Adherence resin (I-2a) contained by adhesion agent composition (I-2) can be only one kind, or two kinds with On.When being two or more, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-2), the content of adherence resin (I-2a) is preferably 5~99 mass %, more preferably For 10~95 mass %, particularly preferably 10~90 mass %.
[crosslinking agent]
For example, will it is identical with adherence resin (I-1a), with from the structural unit containing monomer When the acrylic polymer is used as adherence resin (I-2a), preferred adhesive compositions (I-2) are further containing crosslinking Agent.
As the crosslinking agent in adhesion agent composition (I-2), can enumerate and the friendship in adhesion agent composition (I-1) Join the identical crosslinking agent of agent.
Crosslinking agent contained by adhesion agent composition (I-2) can be only one kind, or two or more.For two kinds with When upper, their combination and ratio can be selected arbitrarily.
In the adhesion agent composition (I-2), relative to 100 mass parts of content of adherence resin (I-2a), crosslinking The content of agent is preferably 0.01~50 mass parts, more preferably 0.1~20 mass parts, particularly preferably 0.3~15 mass parts.
[Photoepolymerizationinitiater initiater]
Adhesion agent composition (I-2) can also further contain Photoepolymerizationinitiater initiater.Even if to Photoepolymerizationinitiater initiater is contained Adhesion agent composition (I-2) irradiation ultraviolet light etc. compared with the energy-ray of low energy, be also sufficiently carried out curing reaction.
As the Photoepolymerizationinitiater initiater in adhesion agent composition (I-2), can enumerate and adhesion agent composition (I-1) In the identical Photoepolymerizationinitiater initiater of Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater contained by adhesion agent composition (I-2) can be only one kind, or two or more.For When two or more, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-2), relative to 100 mass parts of content of adherence resin (I-2a), photopolymerization is drawn The content for sending out agent is preferably 0.01~20 mass parts, more preferably 0.03~10 mass parts, particularly preferably 0.05~5 mass Part.
[other additives]
Within the scope of the effect of the invention, adhesion agent composition (I-2) can also be above-mentioned containing not corresponding to Other additives of any ingredient.
As other described additives in adhesion agent composition (I-2), can enumerate with adhesion agent composition (I-1) in Other identical additives of other additives.
Other additives contained by adhesion agent composition (I-2) can be only one kind, or two or more.It is two Kind or more when, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-2), the content of other additives is not particularly limited, and it is appropriate to be carried out according to its type Selection.
[solvent]
The case where for adhesion agent composition (I-1) identical purpose, adhesion agent composition (I-2) can also contain molten Agent.
As the solvent in adhesion agent composition (I-2), can enumerate and the solvent in adhesion agent composition (I-1) Identical solvent.
Solvent contained by adhesion agent composition (I-2) can be only one kind, or two or more.It is two or more When, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-2), the content of solvent is not particularly limited, and can suitably be adjusted.
< adhesion agent composition (I-3) >
As described above, the adhesion agent composition (I-3) containing the adherence resin (I-2a) with it is energy ray curing Property compound.
In adhesion agent composition (I-3), the content of adherence resin (I-2a) is preferably 5~99 mass %, more preferably For 10~95 mass %, particularly preferably 15~90 mass %.
[energy ray-curable compound]
The energy ray-curable compound contained by as adhesion agent composition (I-3), can enumerate with energy It measures ray polymerization unsaturated group and the cured monomer of irradiation or oligomer of energy-ray can be passed through.That is, can enumerate Energy ray-curable compound identical with the energy ray-curable compound contained by adhesion agent composition (I-1) out.
The energy ray-curable compound contained by adhesion agent composition (I-3) can be only one kind, can also be with It is two or more.When being two or more, their combination and ratio can be selected arbitrarily.
It is described relative to 100 mass parts of content of adherence resin (I-2a) in the adhesion agent composition (I-3) The content of energy ray-curable compound is preferably 0.01~300 mass parts, more preferably 0.03~200 mass parts, especially Preferably 0.05~100 mass parts.
[Photoepolymerizationinitiater initiater]
Adhesion agent composition (I-3) can also further contain Photoepolymerizationinitiater initiater.Even if to Photoepolymerizationinitiater initiater is contained Adhesion agent composition (I-3) irradiation ultraviolet light etc. compared with the energy-ray of low energy, be also sufficiently carried out curing reaction.
As the Photoepolymerizationinitiater initiater in adhesion agent composition (I-3), can enumerate and adhesion agent composition (I-1) In the identical Photoepolymerizationinitiater initiater of Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater contained by adhesion agent composition (I-3) can be only one kind, or two or more.For When two or more, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-3), relative to adherence resin (I-2a) and the energy ray-curable chemical combination 100 mass parts of total content of object, the content of Photoepolymerizationinitiater initiater are preferably 0.01~20 mass parts, more preferably 0.03~10 matter Measure part, particularly preferably 0.05~5 mass parts.
[other additives]
Within the scope of the effect of the invention, adhesion agent composition (I-3) can also be above-mentioned containing not corresponding to Other additives of any ingredient.
As other described additives, can enumerate it is identical with other additives in adhesion agent composition (I-1) its His additive.
Other additives contained by adhesion agent composition (I-3) can be only one kind, or two or more.It is two Kind or more when, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-3), the content of other additives is not particularly limited, and it is appropriate to be carried out according to its type Selection.
[solvent]
The case where for adhesion agent composition (I-1) identical purpose, adhesion agent composition (I-3) can also contain molten Agent.
As the solvent in adhesion agent composition (I-3), can enumerate and the solvent in adhesion agent composition (I-1) Identical solvent.
Solvent contained by adhesion agent composition (I-3) can be only one kind, or two or more.It is two or more When, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-3), the content of solvent is not particularly limited, and can suitably be adjusted.
Adhesion agent composition > of the < in addition to adhesion agent composition (I-1)~(I-3)
So far, mainly to adhesion agent composition (I-1), adhesion agent composition (I-2) and adhesion agent composition (I-3) It is illustrated.The substance being illustrated containing ingredient as them can be equally used for combining except these three stickers All adhesion agent compositions other than object are (in the present specification, referred to as " in addition to adhesion agent composition (I-1)~(I-3) Adhesion agent composition ") in.
As the adhesion agent composition in addition to adhesion agent composition (I-1)~(I-3), in addition to energy ray-curable Other than adhesion agent composition, the adhesion agent composition of non-energy ray-curable can be also enumerated.
As the adhesion agent composition of non-energy ray-curable, following substance can be enumerated.Such as can enumerate containing Acrylic resin, rubber resin, organic silicon resin, epoxylite, polyvinylether, gathers urethane based resin The adhesion agent composition (I-4) of the adherence resin (I-1a) of the non-energy ray-curable such as carbonic ester, esters resin, preferably contains There is the adhesion agent composition of the non-energy ray-curable of acrylic resin.
It is preferred that the adhesion agent composition in addition to adhesion agent composition (I-1)~(I-3) contains one or more Crosslinking agent.Its content can be set as to content identical with the situation of above-mentioned adhesion agent composition (I-1) etc..
< adhesion agent composition (I-4) >
As preferred adhesion agent composition (I-4), such as it can enumerate containing the adherence resin (I-1a) and hand over Join the adhesion agent composition of agent.
[adherence resin (I-1a)]
As the adherence resin (I-1a) in adhesion agent composition (I-4), can enumerate and adhesion agent composition (I-1) In the identical adherence resin (I-1a) of adherence resin (I-1a).
Adherence resin (I-1a) contained by adhesion agent composition (I-4) can be only one kind, or two kinds with On.When being two or more, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-4), the content of adherence resin (I-1a) is preferably 5~99 mass %, more preferably For 10~95 mass %, particularly preferably 15~90 mass %.
[crosslinking agent]
It sometimes will be other than with the structural unit from (methyl) alkyl acrylate, further with from containing official The acrylic polymer of the structural unit of energy single group body is used as adherence resin (I-1a).At this point, it is preferred that sticker group It closes object (I-4) and further contains crosslinking agent.
As the crosslinking agent in adhesion agent composition (I-4), can enumerate and the crosslinking agent in adhesion agent composition (I-1) Identical crosslinking agent.
Crosslinking agent contained by adhesion agent composition (I-4) can be only one kind, or two or more.For two kinds with When upper, their combination and ratio can be selected arbitrarily.
In the adhesion agent composition (I-4), relative to 100 mass parts of content of adherence resin (I-1a), crosslinking The content of agent is preferably 0.01~50 mass parts, more preferably 0.1~20 mass parts, particularly preferably 0.3~15 mass parts.
[other additives]
Within the scope of the effect of the invention, adhesion agent composition (I-4) can also be above-mentioned containing not corresponding to Other additives of any ingredient.
As other described additives, can enumerate it is identical with other additives in adhesion agent composition (I-1) its His additive.
Other additives contained by adhesion agent composition (I-4) can be only one kind, or two or more.It is two Kind or more when, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-4), the content of other additives is not particularly limited, and it is appropriate to be carried out according to its type Selection.
[solvent]
The case where for adhesion agent composition (I-1) identical purpose, adhesion agent composition (I-4) can also contain molten Agent.
As the solvent in adhesion agent composition (I-4), can enumerate and the solvent in adhesion agent composition (I-1) Identical solvent.
Solvent contained by adhesion agent composition (I-4) can be only one kind, or two or more.It is two or more When, their combination and ratio can be selected arbitrarily.
In adhesion agent composition (I-4), the content of solvent is not particularly limited, and can suitably be adjusted.
In protective film formation composite sheet of the invention, preferably adhering agent layer is non-energy ray-curable.This be by In, if adhering agent layer is energy ray-curable, when the irradiation by energy-ray solidifies protective film formation film, nothing Method inhibits to solidify while adhering agent layer.If adhering agent layer solidifies simultaneously with protective film formation film, after will lead to solidification The attaching that not can be carried out the degree of removing occurs over their surface for protective film formation film and adhering agent layer.At this time, it is difficult to By the back side have the protective film formation film after solidifying, i.e. protective film semiconductor chip (in the present specification, sometimes referred to as " semiconductor chip with protective film ") it is removed from the support chip for having the adhering agent layer after solidifying, lead to not normally pick up Semiconductor chip with protective film.It can by making adhering agent layer non-energy ray-curable for support chip of the invention Definitely avoid such undesirable condition.That is, capableing of the semiconductor chip of more easily pick-up tape protective film.
Herein, to adhering agent layer be non-energy ray-curable when effect be illustrated.However, even if support chip It is layer in addition to adhering agent layer with protective film formation with the layer that film directly contacts, as long as the layer is non-energy ray-curable, Then play same effect.
The preparation method > > of < < adhesion agent composition
It can be by blending the sticker and the ingredient in addition to the sticker as needed etc., being used to constitute adhesion Each ingredient of agent composition and obtain adhesion agent composition (I-1)~(I-3) or adhesion agent composition (I-4) etc. except adhesion Adhesion agent composition other than agent composition (I-1)~(I-3).
Order of addition when blending each ingredient is not particularly limited, and can also add two or more ingredients simultaneously.
It, can be pre- by the blending ingredient and mixing solvent with any blending ingredient in addition to solvent when using solvent Dilution to carry out using.In addition it is also possible to not by any blending ingredient pre-dilution in addition to solvent, but by by solvent With these blend ingredients mix thus carry out using.
The method that each ingredient is mixed when blending is not particularly limited.It is suitably selected from following well known methods：Make Blender or stirring blade etc. rotate and mixed method；The method mixed using blender；Apply ultrasonic wave and Mixed method etc..
As long as respectively blending ingredient not deteriorate, the temperature and time when adding and mix each ingredient are not particularly limited, Suitably adjust.It is preferable, however, that temperature is 15~30 DEG C.
Film is used in the formation of ◎ protective film
In the present invention, the adhesion strength obtained from protective film formation film being solidified between protective film and support chip is preferred For 50~1500mN/25mm, more preferably 52~1450mN/25mm, further preferably 53~1430mN/25mm.By making The adhesion strength is the lower limit value or more, in the semiconductor chip of pick-up tape protective film, can inhibit non-targeted band protection The pickup of the semiconductor chip of film.As a result, it is possible to pick up the semiconductor chip with protective film as target with high selectivity. In addition, can inhibit and partly lead by making the adhesion strength upper limit value hereinafter, in the semiconductor chip of pick-up tape protective film The cracking and defect of body chip.By this method, by making the adhesion strength in a specific range, composite sheet is used in protective film formation With good pickup adaptive.
In addition, in the present invention, even if after protective film formation film solidifies, as long as support chip and protective film is maintained to be formed With the stepped construction of the solidfied material (in other words, support chip and protective film) of film, then the laminate structure is thus referred to as " protective film It is formed and uses composite sheet ".
The adhesion strength between protective film and support chip is measured using the following method.
That is, being 25mm by width, the arbitrary protective film formation of length is attached by its protective film formation with film with composite sheet On adherend.
Then, irradiation energy ray makes the solidification of protective film formation film to form protective film.Then, with peeling rate 300mm/min removes support chip from the protective film being attached on adherend.Removing at this time is set as so-called 180 ° Removing, i.e., it is in such a way that the face for contacting with each other protective film and support chip is in 180 ° of angle each other that support chip is square along its length To (protective film forms the length direction with composite sheet) removing.Then, the load (peeling force) when this 180 ° removings is measured, and will Its measured value is as the adhesion strength (mN/25mm).
As long as the length of the protective film formation composite sheet for measurement is in the range of steadily can detect adhesion strength It is not particularly limited.Wherein, preferably 100~300mm.In addition, preferably making protective film formation composite sheet patch when measurement The state being attached on adherend makes attaching in stable conditionization of protective film formation composite sheet.
In the present invention, the adhesion strength between protective film formation film and the support chip is not particularly limited.Such as it can Think 80mN/25mm with first-class, but preferably 100mN/25mm or more, more preferably 150mN/25mm or more, particularly preferably 200mN/25mm or more.By making the adhesion strength 100mN/25mm or more, when being cut, can inhibit protective film and formed With the removing of film and support chip.For example, can inhibit the semiconductor chip for overleaf having protective film formation film from support chip It disperses.
On the other hand, the upper limit value of the adhesion strength between protective film formation film and the support chip is not particularly limited. For example, it may be any of 4000mN/25mm, 3500mN/25mm, 3000mN/25mm etc..But these values are only an example Son.
In addition to do not carry out the protective film formation film for measurement, irradiation based on energy-ray solidification this point with Outside, the identical method of the adhesion strength between above-mentioned protective film and support chip measurement protective film formation film and branch can be utilized Adhesion strength between blade.
Adhesion strength and protective film between above-mentioned protective film and support chip are formed with the adhesion strength between film and support chip It can be suitably regulated.For example, can by adjust protective film formation film the type containing ingredient and amount, support chip in The constituent material of the layer of protective film formation film and the surface state of this layer etc. are set to be adjusted.
For example, the type containing ingredient and amount of protective film formation film can pass through aftermentioned protective film formation composition The type containing ingredient and amount be adjusted.Moreover, by protective film formation composition containing in ingredient, for example The type and content of polymer (b) without energy ray-curable group, the content of packing material (d) or crosslinking agent (f) Content be adjusted, can more easily adjust the adhesion strength between protective film or protective film formation film and support chip.
In addition, for example, when the layer for being provided with protective film formation film in support chip is adhering agent layer, it can be by viscous Oxidant layer the type containing ingredient and amount be adjusted and suitably adjust its constituent material.Moreover, adhering agent layer contains The type and amount of ingredient can be adjusted by the type containing ingredient and amount of above-mentioned adhesion agent composition.
On the other hand, when the layer for being provided with protective film formation film in support chip is substrate, protective film or protective film Formed with adhesion strength between film and support chip, except through substrate constituent material be adjusted other than, substrate can also be passed through Surface state be adjusted.Moreover, the surface state of substrate for example can be by implementing as raising substrate and other layers The surface treatment of adherence and in following processing for hereinbefore enumerating any one and be adjusted.That is, implementation can be passed through Further provided for contouring processing based on blasting treatment, solvent processing etc.；Corona discharge Treatment, electron beam treatment with irradiation, corona treatment, The oxidation processes such as ozone-ultraviolet line treatment with irradiation, flame treatment, chromic acid processing, hot wind processing；It is any in prime treatment etc. It is a kind of and be adjusted.
Protective film formation has energy ray-curable with film.Such as it can enumerate containing energy ray-curable ingredient (a) protective film, which is formed, uses film, preferably comprises energy ray-curable ingredient (a), without energy ray-curable group Film is used in the formation of the protective film of polymer (b) and antistatic agent (j).
Preferred energy ray-curable ingredient (a) is uncured.It is preferred that it is with adherence, more preferably its is uncured and has Adherence.
Protective film formation film can be only one layer (single layer), or two layers or more of multiple layers.When being multiple layers, These multiple layers mutually the same can also be different, these multiple layers combinations are not particularly limited.
The thickness of protective film formation film is preferably 1~100 μm, more preferably 5~75 μm, particularly preferably 5~50 μm. By make protective film formation film with a thickness of the lower limit value more than, be capable of forming the higher protective film of protective capability.In addition, By make protective film formation film with a thickness of the upper limit value hereinafter, can inhibit thickness as excessive thickness.
Herein, " thickness of protective film formation film " refers to the thickness of protective film formation film entirety.For example, by multiple layers The thickness of the protective film formation film of composition refers to the overall thickness for constituting all layers of protective film formation film.
As long as protective film become fully play its function degree curing degree, make protective film formation film solidification from And condition of cure when forming protective film is not particularly limited.Suitably select i.e. according to the type of protective film formation film It can.
For example, the illumination of energy-ray when solidifying protective film formation film is preferably 4~280mW/cm2.Moreover, described The light quantity of energy-ray when solidification is preferably 3~1000mJ/cm2。
< < protective film, which is formed, uses composition > >
Protective film formation film can be used the protective film formation composition containing its constituent material and be formed.For example, logical It crosses and protective film formation is coated in the formation object surface of protective film formation film with composition and is dried as needed, energy It is enough to form protective film formation film in target site.Ingredient in protective film formation composition, not gasifying under room temperature is each other Content than usually with the mutual content of the ingredient of protective film formation film than identical.Herein, " room temperature " with hereinbefore What is illustrated is identical.
The coating of protective film formation composition is carried out using well known method.Such as it can enumerate and be applied using air knife Cloth machine, scraping blade coating machine, bar coater, gravure coater, roll coater, roller knife coating machine, curtain coater, die coating machine, knife type coater, The method of the various coating machines such as silk screen coating machine, Meyer rod coater, kiss painting machine.
The drying condition of protective film formation composition is not particularly limited.But after protective film formation composition contains When the solvent stated, preferably it is thermally dried.At this point, for example preferably being done with the condition of 70~130 DEG C, 10 seconds~5 minutes It is dry.
< protective film, which is formed, uses composition (IV-1) >
As protective film formation composition, such as the guarantor containing the energy ray-curable ingredient (a) can be enumerated Cuticula is formed with composition (IV-1) etc..
[energy ray-curable ingredient (a)]
Energy ray-curable ingredient (a) is the cured ingredient of irradiation by energy-ray, and for protection Film formation film assigns the ingredient for making film property, pliability etc..
As energy ray-curable ingredient (a), for example, can enumerate it is with energy ray-curable group, divide equally again Polymer (a1) that son amount is 80000~2000000 and with energy ray-curable group, molecular weight be 100~ 80000 compound (a2).The polymer (a1) can be its at least part made of the crosslinking of aftermentioned crosslinking agent (f) Substance, or uncrosslinked substance.
In addition, in the present specification, unless otherwise indicated, weight average molecular weight, which refers to, utilizes gel permeation chromatography (GPC) method The polystyrene scaled value of measurement.
(polymer (a1) that with energy ray-curable group, weight average molecular weight is 80000~2000000)
The polymer (a1) for being 80000~2000000 as with energy ray-curable group, weight average molecular weight, Such as can enumerate with the acrylic polymer (a11) of functional group that can react with group possessed by other compounds and Energy-ray with group and the energy ray-curables group such as energy ray-curable double bond with the functional group reactions The acrylic resin (a1-1) that curability compound (a12) is polymerized.
As the functional group that can be reacted with group possessed by other compounds, for example, can enumerate hydroxyl, carboxyl, Amino, substituted-amino (group made of one or two hydrogen atom of amino is replaced by the group in addition to hydrogen atom), epoxy Base etc..Wherein, from the point of the corrosion for the circuit for preventing semiconductor crystal wafer or semiconductor chip etc., the preferably described functional group is Group in addition to carboxyl.
Wherein, the preferably described functional group is hydroxyl.
Acrylic polymer (a11) with functional group
As the acrylic polymer (a11) with functional group, such as can enumerate with the functional group Acrylic monomer and polymer made of the acrylic monomer copolymerization for not having the functional group.Or remove these lists Further copolymerization has the polymer of the monomer (non-acrylic monomer) in addition to acrylic monomer other than body.
In addition, the acrylic polymer (a11) can be random copolymer, or block copolymer.
As the acrylic monomer with the functional group, such as hydroxyl monomer can be enumerated, carboxyl group-containing monomer, contained Amino monomers, monomer containing substituted-amino, containing epoxy based monomers etc..
As the hydroxyl monomer, following substance can be enumerated.Such as can enumerate (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) third (methyl) the acrylic acid hydroxyls such as olefin(e) acid 2- hydroxybutyl, (methyl) acrylic acid 3- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl Base Arrcostab；Non- (methyl) the acrylic compounds unsaturated alcohol such as vinyl alcohol, allyl alcohol (does not have (methyl) acryloyl group skeleton not Saturated alcohols) etc..
As the carboxyl group-containing monomer, following substance can be enumerated.Such as (methyl) acrylic acid, crotonic acid can be enumerated etc. Olefinic unsaturated monocarboxylic acid (monocarboxylic acid with ethylenic unsaturated bond)；Fumaric acid, itaconic acid, maleic acid, citraconic acid etc. Ethylenically unsaturated dicarboxylic (dicarboxylic acids with ethylenic unsaturated bond)；The acid anhydrides of the ethylenically unsaturated dicarboxylic；Methyl-prop Olefin(e) acid 2- carboxyethyl etc. (methyl) acrylic acid carboxyalkyl ester etc..
It is preferred that the acrylic monomer with the functional group is hydroxyl monomer or carboxyl group-containing monomer, more preferably contain hydroxyl Base monomer.
Constitute the acrylic polymer (a11), the acrylic monomer with the functional group can be only one Kind, or it is two or more.When being two or more, their combination and ratio can be selected arbitrarily.
As the acrylic monomer for not having the functional group, following substance can be enumerated.Such as (first can be enumerated Base) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) third Olefin(e) acid N-butyl, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) third Olefin(e) acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) propylene The different monooctyl ester of acid, (methyl) n-octyl, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) propylene Sour last of the ten Heavenly stems ester, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate ((methyl) lauryl acrylate), (first Base) tridecyl acrylate, (methyl) acrylic acid tetradecane base ester ((methyl) myristyl ester), (methyl) acrylic acid Pentadecane base ester, (methyl) aliphatic acrylate ((methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester, (methyl) octadecyl acrylate ((methyl) stearyl acrylate acid esters) etc., composition Arrcostab alkyl is that carbon atom number is (methyl) alkyl acrylate of 1~18 chain structure etc..
In addition, following substance can be enumerated as the acrylic monomer for not having the functional group.Such as it can also enumerate (methyl) methoxyethyl methyl esters, (methyl) methoxyethyl acrylate, (methyl) ethioxy methyl esters, (methyl) out (methyl) acrylate containing alkoxyalkyl such as ethoxyethyl acrylate；Include (methyl) third such as (methyl) phenyl acrylate Olefin(e) acid aryl ester etc., (methyl) acrylate with aromatic group；(methyl) acrylamide of non-crosslinked property and its spread out Biology；The non-crosslinked property such as (methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester (methyl) acrylate etc. with tertiary amino.
Constitute the acrylic polymer (a11), the acrylic monomer without the functional group can be only It is a kind of, or two or more.When being two or more, their combination and ratio can be selected arbitrarily.
As the non-acrylic monomer, such as the alkene such as ethylene, norbornene can be enumerated；Vinyl acetate；Benzene Ethylene etc..
The non-acrylic monomer for constituting the acrylic polymer (a11) can be only one kind, or It is two or more.When being two or more, their combination and ratio can be selected arbitrarily.
In the acrylic polymer (a11), relative to the total amount for the structural unit for constituting the polymer, by having The ratio (content) of the amount of structural unit derived from the acrylic monomer of the functional group is preferably 0.1~50 mass %, more Preferably 1~40 mass %, particularly preferably 3~30 mass %.By making the such range of the ratio, pass through described third The acrylic compounds tree obtained from the copolymerization of olefin(e) acid quasi polymer (a11) and the energy ray-curable compound (a12) The curing degree of first protective film can be easily adjusted to preferably by the content of the energy ray-curable group in rouge (a1-1) Range.
The acrylic polymer (a11) for constituting the acrylic resin (a1-1) can be only one kind, can also Think two or more.When being two or more, their combination and ratio can be selected arbitrarily.
In protective film formation in composition (IV-1), the content of acrylic resin (a1-1) is preferably 1~40 matter Measure %, more preferably 2~30 mass %, particularly preferably 3~20 mass %.
Energy ray-curable compound (a12)
It is preferred that the energy ray-curable compound (a12), which has, selects free isocyanate group, epoxy group and carboxyl group At one or more of group as can be with the base of functional group reactions possessed by the acrylic polymer (a11) Group more preferably has isocyanate group as the group.For example, when the energy ray-curable compound (a12) has When isocyanate group is as the group, which is easy and has acrylic polymer of the hydroxyl as the functional group The hydroxyl for closing object (a11) is reacted.
It is preferred that the energy ray-curable compound (a12) is described energy ray curing with 1~5 in 1 molecule Property group, more preferably have 1~3 energy ray-curable group.
As the energy ray-curable compound (a12), following substance can be enumerated.Such as 2- methyl can be enumerated Acryloyloxyethyl isocyanate, isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate, methacryloyl isocyanate, Allyl iso cyanurate, 1,1- (double acryloyloxymethyls) ethyl isocyanate；
Pass through reacting for diisocyanate cpd or polyisocyanate compounds and (methyl) Hydroxyethyl Acrylate Obtained acryloyl group monoisocyanate compound；
Pass through diisocyanate cpd or polyisocyanate compounds, polyol compound and (methyl) dihydroxypropyl Acryloyl group monoisocyanate compound etc. obtained from the reaction of ethyl ester.
Wherein, the preferably described energy ray-curable compound (a12) is 2- methylacryoyloxyethyl isocyanates.
The energy ray-curable compound (a12) for constituting the acrylic resin (a1-1) can be only one Kind, or it is two or more.When being two or more, their combination and ratio can be selected arbitrarily.
In the acrylic resin (a1-1), the energy from the energy ray-curable compound (a12) is penetrated The content of line curative group is excellent relative to the ratio of the content of the functional group from the acrylic polymer (a11) It is selected as 20~120 moles of %, more preferably 35~100 moles of %, particularly preferably 50~100 moles of %.By making described contain The ratio of amount is such range, is become much larger by the bonding force for the protective film being solidified to form.In addition, when the energy is penetrated When line curability compound (a12) is simple function (having 1 group in 1 molecule) compound, the ratio of the content Upper limit value be 100 moles of %.However, when the energy ray-curable compound (a12) (has to be multifunctional in 1 molecule Have 2 or more the groups) compound when, the upper limit value of the ratio of the content is sometimes more than 100 moles of %.
The weight average molecular weight (Mw) of the polymer (a1) is preferably 100000~2000000, more preferably 300000~ 1500000。
When the polymer (a1) is that its at least part is crosslinked substance made of agent (f) crosslinking, the polymer (a1) can be not belonging to as the monomer for constituting the acrylic polymer (a11) and any in the above-mentioned monomer illustrated Person and there is the monomer of group reacted with crosslinking agent (f) to be copolymerized, and at the group reacted with the crosslinking agent (f) Polymer made of being crosslinked.In addition it is also possible in from the energy ray-curable compound (a12) and institute State polymer made of being crosslinked at the group of functional group reactions.
Protective film, which forms to be formed with composition (IV-1) and protective film, uses the polymer (a1) contained by film can be only For one kind, or two or more.When being two or more, their combination and ratio can be selected arbitrarily.
(compound (a2) that with energy ray-curable group, molecular weight is 100~80000)
Energy possessed by the compound (a2) for being 100~80000 as with energy ray-curable group, molecular weight Ray-curable group is measured, the group comprising energy ray-curable double bond can be enumerated.As preferred group, can enumerate (methyl) acryloyl group, vinyl etc..
The compound (a2) is not particularly limited as long as meeting above-mentioned condition.Wherein, it can enumerate and be penetrated with energy The low molecular weight compound of line curative group, the epoxy resin with energy ray-curable group are consolidated with energy-ray The phenol resin etc. of the property changed group.
As the low molecular weight compound with energy ray-curable group in the compound (a2), such as can arrange Enumerate polyfunctional monomer or oligomer etc..It is preferred that the acrylic ester compound with (methyl) acryloyl group.
As the acrylic ester compound, following substance can be enumerated.Such as 2- hydroxyl -3- (methyl) can be enumerated Acryloxypropyl acrylate, polyethylene glycol two (methyl) acrylate, propoxylation Ethoxylated bisphenol A bis- (methyl) acrylate, 2,2- bis- [4- ((methyl) acryloxy polyethoxy) phenyl] propane, Ethoxylated bisphenol A bis- (methyl) acrylate, 2,2- bis- [4- ((methyl) acryloxy diethoxy) phenyl] propane, the bis- [4- (2- (first of 9,9- Base) acryloyloxyethoxy) phenyl] fluorenes, 2,2- bis- [4- (the poly- propoxyl group of (methyl) acryloxy) phenyl] propane, tricyclic Decane dimethanol two (methyl) acrylate (also referred to as tristane dihydroxymethyl two (methyl) acrylate), the 1,10- last of the ten Heavenly stems two Alcohol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate, dipropyl Glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polybutadiene Alcohol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, 2,2- bis- [4- ((methyl) acryloyloxyethoxy) phenyl] propane, neopentyl glycol two (methyl) third Olefin(e) acid ester, ethoxylated polypropylene glycol two (methyl) acrylate, 2- hydroxyl -1,3- two (methyl) acryloxy propane etc. are double Function (methyl) acrylate；
Modified three (2- (methyl) the acryloyl-oxy second of three (2- (methyl) acrylyl oxy-ethyl) isocyanuric acid esters, 6-caprolactone Base) isocyanuric acid ester, ethoxylated glycerol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, trihydroxy methyl Propane three (methyl) acrylate, two trimethylolpropane four (methyl) acrylate, ethoxylation pentaerythrite four (methyl) Poly- (methyl) acrylate of acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol, six (first of dipentaerythritol Base) multifunctional (methyl) acrylates such as acrylate；
Multifunctional (methyl) acrylates oligomer such as carbamate (methyl) acrylate oligomer etc..
As the epoxy resin with energy ray-curable group, solid with energy-ray in the compound (a2) It is recorded in phenol resin, such as [0043] section for being able to use " Japanese Unexamined Patent Publication 2013-194102 bulletin " of the property changed group etc. Resin.Such resin also corresponds to constitute the resin of aftermentioned thermosetting component (h), but is regarded as in the present invention described Compound (a2).
The weight average molecular weight of the compound (a2) is preferably 100~30000, and more preferably 300~10000.
Protective film, which forms to be formed with composition (IV-1) and protective film, uses the compound (a2) contained by film can be only For one kind, or two or more.When being two or more, their combination and ratio can be selected arbitrarily.
[polymer (b) without energy ray-curable group]
When protective film formation composition (IV-1) and protective film formation use film to contain the compound (a2) described in When energy ray-curable ingredient (a), preferably further also contain the polymer (b) without energy ray-curable group.
The polymer (b) can be crosslinked substance made of agent (f) crosslinking at least part, or uncrosslinked Substance.
As the polymer (b) for not having energy ray-curable group, such as acrylic polymer, benzene can be enumerated Oxygroup resin, carbamate resins, polyester, rubber resin, propenoic methyl carbamate resin, polyvinyl alcohol (PVA), fourth Urea formaldehyde, polyester urethane resin etc..
Wherein, the preferably described polymer (b) is acrylic polymer (hereinafter, writing a Chinese character in simplified form work " acrylic polymer sometimes (b-1)”)。
Acrylic polymer (b-1) can be well known acrylic polymer.It such as can be a kind of acrylic compounds The homopolymer of monomer, or the copolymer of two or more acrylic monomers can also be one or more kinds of The copolymerization of acrylic monomer and one or more kinds of monomers (non-acrylic monomer) in addition to acrylic monomer Object.
As the acrylic monomer for constituting acrylic polymer (b-1), following substance can be enumerated.Such as it can Enumerate (methyl) alkyl acrylate, (methyl) acrylate with cyclic skeleton, (methyl) third containing glycidyl Olefin(e) acid ester, (methyl) acrylate of hydroxyl, (methyl) acrylate containing substituted-amino etc..Herein, " substituted-amino " with What is be illustrated above is identical.
As (methyl) alkyl acrylate, following substance can be enumerated.Such as (methyl) acrylic acid can be enumerated Methyl esters, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, the positive fourth of (methyl) acrylic acid Ester, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) n-octyl, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (first Base) acrylic acid hendecane base ester, (methyl) dodecylacrylate ((methyl) lauryl acrylate), (methyl) acrylic acid ten Trialkyl ester, (methyl) acrylic acid tetradecane base ester ((methyl) myristyl ester), (methyl) acrylic acid pentadecane base ester, (methyl) aliphatic acrylate ((methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester, (methyl) propylene Sour stearyl ((methyl) stearyl acrylate acid esters) etc., composition Arrcostab alkyl is the chain that carbon atom number is 1~18 (methyl) alkyl acrylate of shape structure etc..
As described (methyl) acrylate with cyclic skeleton, following substance can be enumerated.Such as (first can be enumerated Base) (methyl) the acrylate base ester such as isobornyl acrylate, (methyl) dicyclopentyl acrylate；
(methyl) benzyl acrylate etc. (methyl) acrylic acid aralkyl ester；
(methyl) acrylic acid cyclenes base ester such as (methyl) acrylic acid dicyclopentenyl base ester；
(methyl) acrylic acid cycloalkenyl oxy Arrcostab such as (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester etc..
As described (methyl) acrylate containing glycidyl, such as (methyl) glycidyl can be enumerated Ester etc..
As (methyl) acrylate of the hydroxyl, following substance can be enumerated.Such as (methyl) third can be enumerated Olefin(e) acid hydroxyl methyl esters, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxyl third Ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 3- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl etc..
As described (methyl) acrylate containing substituted-amino, such as (methyl) acrylic acid N- methylamino can be enumerated Ethyl ester etc..
As the non-acrylic monomer of composition acrylic polymer (b-1), such as ethylene, drop ice can be enumerated The alkene such as piece alkene；Vinyl acetate；Styrene etc..
As being crosslinked agent (f) crosslinking, the polymer without energy ray-curable group at least partially (b), for example, the reactive functional groups that can enumerate in the polymer (b) reacted with crosslinking agent (f) obtained from polymer.
The reactive functional groups are suitably selected according to progress such as the types of crosslinking agent (f), are not particularly limited.Example Such as, when crosslinking agent (f) is polyisocyanate compounds, as the reactive functional groups, hydroxyl, carboxyl, ammonia can be enumerated Base etc., wherein preferably with the hydroxyl with high reactivity of isocyanate group.In addition, when crosslinking agent (f) is epoxy compounds, As the reactive functional groups, carboxyl, amino, amide groups etc. can be enumerated.Wherein, preferably with high reactivity with epoxy group Carboxyl.However, from the point of the corrosion for the circuit for preventing semiconductor crystal wafer or semiconductor chip, the preferably described functional group be except Group other than carboxyl.
It, such as can as with the reactive functional groups and not having the polymer (b) of energy ray-curable group Enumerate polymer obtained from at least monomer polymerization with the reactive functional groups of sening as an envoy to.For acrylic polymer (b-1) when, the monomer with the reactive functional groups is used to arrange as the monomer for constituting the acrylic polymer (b-1) It is lifting, in the acrylic monomer and non-acrylic monomer any one or both.For example, as with hydroxyl As the polymer (b) of reactive functional groups, such as (methyl) acrylic ester polymerization by hydroxyl can be enumerated and obtained The polymer arrived.In addition to this, the acrylic monomer or non-acrylic monomer that will hereinbefore enumerate can be enumerated One or two of more than hydrogen atom be substituted by polymer obtained from monomer polymerization made of the reactive functional groups.
In the polymer (b) with reactive functional groups, by the knot of the monomer derived with reactive functional groups The amount of structure unit is preferably 1~25 mass % relative to the ratio (content) of the total amount for the structural unit for constituting the polymer (b), More preferably 2~20 mass %.By making the such range of the ratio, in the polymer (b), the degree of crosslinking at For preferred range.
The more good point of film property is made from protective film formation composition (IV-1), is not had energy ray curing The weight average molecular weight (Mw) of the polymer (b) of property group is preferably 10000~2000000, more preferably 100000~ 1500000。
Protective film formed with composition (IV-1) and protective film formed with it is contained by film, do not have energy ray-curable The polymer (b) of group can be only one kind, or two or more.When being two or more, their combination and ratio can Arbitrarily to select.
As protective film formation with composition (IV-1), can enumerate containing the polymer (a1) and the compound (a2) in any one or both protective film formation use composition.Moreover, preferably being protected when containing the compound (a2) Cuticula, which is formed, further contains the polymer (b) without energy ray-curable group with composition (IV-1).At this point, also excellent Choosing is further containing (a1).In addition, protective film, which is formed, can also not contain the compound (a2) with composition (IV-1) And contain the polymer (a1) and the polymer (b) without energy ray-curable group simultaneously.
When protective film formation containing the polymer (a1), the compound (a2) and does not have energy with composition (IV-1) When measuring the polymer (b) of ray-curable group, in protective film formation in composition (IV-1), relative to the polymer (a1) and 100 mass parts of total content of the polymer (b) without energy ray-curable group, compound (a2's) contains Amount is preferably 10~400 mass parts, more preferably 30~350 mass parts.
In protective film formation in composition (IV-1), the energy ray-curable ingredient (a) and penetrated without energy Total content of the polymer (b) of line curative group is (that is, protective film forms the energy ray-curable ingredient for using film (a) and total content of the polymer (b) without energy ray-curable group) relative to the total of the ingredient in addition to solvent The ratio of content is preferably 5~90 mass %, more preferably 10~80 mass %, particularly preferably 15~70 mass %.Pass through Make the such range of ratio of total content, the energy ray-curable of protective film formation film becomes more good.
When protective film formation contains the energy ray-curable ingredient (a) with composition (IV-1) and penetrates without energy When the polymer (b) of line curative group, is formed and used in film in protective film formation composition (IV-1) and protective film, relative to 100 mass parts of content of energy ray-curable ingredient (a), the content of the polymer (b) are preferably 3~160 mass parts, more Preferably 6~130 mass parts.By making the such range of the content of the polymer (b), protective film is formed with film Energy ray-curable becomes more good.
In addition to containing energy ray-curable ingredient (a), the polymer (b) without energy ray-curable group with Outside, protective film formation can also be contained the following substances with composition (IV-1).That is, can be according to purpose and containing selected from by photopolymerization Initiator (c), packing material (d), coupling agent (e), crosslinking agent (f), colorant (g), Thermocurable ingredient (h) and general add One or more of the group for adding agent (z) to form.For example, by using the energy ray-curable ingredient (a) is contained And the protective film of Thermocurable ingredient (h) forms and uses composition (IV-1), is formed by protective film formation film to adherend Bonding force is improved because of heating.In addition, being also improved by the protection film strength that the protective film formation is formed with film.
[Photoepolymerizationinitiater initiater (c)]
As Photoepolymerizationinitiater initiater (c), following substance can be enumerated.Such as benzoin, benzoin methylether, benzene can be enumerated Benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl The benzoins compound such as ketal；Acetophenone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 2,2- dimethoxy -1,2- two The acetophenone compounds such as diphenylphosphino ethane -1- ketone；Bis- (2,4,6- trimethylbenzoyl) phosphine oxides of phenyl, 2,4,6- trimethylbenzene The acylphosphine oxides compound such as formoxyl diphenyl phosphine oxide；The vulcanization such as benzyl phenyl thioether, tetramethylthiuram monosulfide Close object；The α -one alcoholic compound such as 1- hydroxycyclohexylphenylketone；The azo-compounds such as azodiisobutyronitrile；The titanocenes such as titanocenes Compound；The thioxanthone compounds such as thioxanthones；Benzophenone, 2- (dimethylamino) -1- (4- morpholinyl phenyl) -2- benzyl -1- The benzophenone chemical combination such as butanone, 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] ethyl ketone 1- (O- acetyl oxime) Object；Peroxide compound；The dione compounds such as biacetyl；Benzyl；Dibenzyl；2,4- diethyl thioxanthone；1,2- diphenyl Methane；2- hydroxy-2-methyl -1- [4- (1- methyl ethylene) phenyl] acetone；2- chloroanthraquinone etc..
In addition, as Photoepolymerizationinitiater initiater (c), such as the naphtoquinone compounds such as 1- chloroanthraquinone also can be used；Photosensitizers such as amine etc..
It can be only one kind that protective film, which is formed with the Photoepolymerizationinitiater initiater (c) contained by composition (IV-1), or It is two or more.When being two or more, their combination and ratio can be selected arbitrarily.
When using Photoepolymerizationinitiater initiater (c), in protective film formation in composition (IV-1), relative to energy ray curing 100 mass parts of content of property ingredient (a), the content of Photoepolymerizationinitiater initiater (c) is preferably 0.01~20 mass parts, more preferably 0.03~10 mass parts, particularly preferably 0.05~5 mass parts.
[packing material (d)]
By making protective film formation film contain packing material (d), protective film formation is solidified with film and is protected obtained from The adjustment of the thermal expansion coefficient of cuticula becomes easy.As a result, by making the thermal expansion coefficient relative to the formation pair of protective film As object optimization, it is further enhanced using the reliability of protective film formation encapsulation obtained from composite sheet.In addition, passing through So that protective film formation film is contained packing material (d), can reduce the hydroscopicity of protective film, or also can be improved thermal diffusivity.
As packing material (d), such as the packing material being made of Heat Conduction Material can be enumerated.
Packing material (d) can be any one of organic filler material and inorganic filling material, preferably inorganic fill Material.
As preferred inorganic filling material, for example, can enumerate silica, aluminium oxide, talcum, calcium carbonate, titanium white, The powder such as colcother, silicon carbide, boron nitride；By pearl made of these inorganic filling material spheroidizations；These inorganic filling materials The modified product in surface；The mono-crystlling fibre of these inorganic filling materials；Glass fibre etc..
Wherein, preferably inorganic filling material is silica or aluminium oxide.
The average grain diameter of packing material (d) is not particularly limited.Wherein, preferably 0.01~15 μm, more preferably 0.03 ~10 μm, particularly preferably 0.05~8 μm.
By making the such range of average grain diameter of packing material (d), it is able to maintain that protective film to formation object Adhesiveness, and simultaneously inhibit protective film light transmitance decline.
In addition, unless otherwise indicated, " average grain diameter " in this specification refers to be acquired using laser diffraction scattering method In size distribution curve, accumulated value is the partial size (D at 50%50) value.
It can be only one that protective film, which forms composition (IV-1) and protective film formation with the packing material (d) contained by film, Kind, or it is two or more.When being two or more, their combination and ratio can be selected arbitrarily.
When using packing material (d), in protective film formation in composition (IV-1), the content of packing material (d) (is protected Cuticula forms the content with the packing material (d) of film) relative to the total content of all the components in addition to solvent ratio it is preferred For 5~83 mass %, more preferably 7~78 mass %.It is above-mentioned by making the such range of content of packing material (d) The adjustment of thermal expansion coefficient becomes easier to.
[coupling agent (e)]
It can be with the substance of the functional group of inorganic compound or organic compound reaction as coupling agent by using having (e), it can be improved protective film formation film to the adhesiveness and adherence of adherend.In addition, by using coupling agent (e), it will The water resistance of protective film obtained from protective film formation is solidified with film is improved without damaging heat resistance.
Coupling agent (e) preferably have can with energy ray-curable ingredient (a), do not have energy ray-curable group Polymer (b) etc. possessed by functional group reactions functional group compound.More preferably silane coupling agent.
As the preferred silane coupling agent, following substance can be enumerated.Such as 3- glycidyl ether oxygen can be enumerated Base propyl trimethoxy silicane, 3- glycydoxy methyldiethoxysilane, 3- glycydoxy Triethoxysilane, 3- glycidyl ether oxygen ylmethyl diethoxy silane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy Silane, 3- methacryloxypropyl trimethoxy silane, 3- TSL 8330,3- (2- amino-ethyl ammonia Base) propyl trimethoxy silicane, 3- (2- aminoethylamino) hydroxypropyl methyl diethoxy silane, 3- (phenyl amino) propyl three Methoxy silane, 3- anilino- propyl trimethoxy silicane, 3- urea propyl-triethoxysilicane, 3- mercapto propyl trimethoxy silicon Alkane, 3- mercapto hydroxypropyl methyl dimethoxysilane, bis- (3- triethoxy silicon substrate propyl) tetrasulfides, methyltrimethoxysilane, Methyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxy silane, imidizole silane etc..
It can be only one that protective film, which forms composition (IV-1) and protective film formation with the coupling agent (e) contained by film, Kind, or it is two or more.When being two or more, their combination and ratio can be selected arbitrarily.
When using coupling agent (e), is formed and used in film in protective film formation composition (IV-1) and protective film, relative to energy 100 mass parts of total content of ray-curable ingredient (a) and the polymer (b) without energy ray-curable group are measured, it is even The content for joining agent (e) is preferably 0.03~20 mass parts, more preferably 0.05~10 mass parts, particularly preferably 0.1~5 mass Part.More than the content lower limit value by making coupling agent (e), packing material (d) can be significantly more obtained in resin In the raising of dispersibility, protective film formation film and adherend the raising of adhesiveness etc., produced by using coupling agent (e) Raw effect.In addition, by making the content upper limit value of coupling agent (e) hereinafter, the production of degassing can be further suppressed It is raw.
[crosslinking agent (f)]
Above-mentioned energy ray-curable ingredient (a) is crosslinked by using crosslinking agent (f) or is not had energy ray curing The polymer (b) of property group, can adjust the initial bond power and cohesiveness of protective film formation film.
As crosslinking agent (f), such as organic polyisocyanate compound, organic multicomponent group with imine moiety, gold can be enumerated Belong to chelates crosslinking agent (crosslinking agent with metallo-chelate structure), (friendship with '-aziridino of aziridines crosslinking agent Join agent) etc..
As the organic polyisocyanate compound, following substance can be enumerated.Such as aromatic series polyisocyanate can be enumerated Cyanate esters, aliphatic polyisocyanate compound and alicyclic polyisocyanates compound are (hereinafter, sometimes change these It closes object and uniformly writes a Chinese character in simplified form work " aromatic polyisocyanate compound etc. ")；The trimerization of the aromatic polyisocyanate compound etc. Body, isocyanuric acid ester body and addition product；Described aromatic polyisocyanate compound etc. is set to react and obtain with polyol compound Terminal isocyanate carbamate prepolymer arrived etc.." addition product " refers to the aromatic polyisocyanate chemical combination Object, aliphatic polyisocyanate compound or alicyclic polyisocyanates compound and ethylene glycol, propylene glycol, neopentyl glycol, three The reactant of the low molecules active hydrogen-contg compound such as hydroxymethyl-propane or castor oil can enumerate as described later as its example The benzene dimethylene diisocyanate addition product of trimethylolpropane etc..In addition, " terminal isocyanate carbamate pre-polymerization Object " refers to urethane bond and has the prepolymer of isocyanate group in the terminal part of molecule.
As the organic polyisocyanate compound, more specifically, following substance can be enumerated.Such as it can enumerate 2,4 toluene diisocyanate；2,6- toluene di-isocyanate(TDI)；1,3- benzene dimethylene diisocyanate；1,4- phenylenedimethylidyne Diisocyanate；Diphenyl methane -4,4 '-diisocyanate；Diphenyl methane -2,4 '-diisocyanate；3- methyldiphenyl base Methane diisocyanate；Hexamethylene diisocyanate；Isophorone diisocyanate；- two isocyanide of dicyclohexyl methyl hydride -4,4 ' Acid esters；Dicyclohexyl methyl hydride -2,4 '-diisocyanate；On all or part of hydroxyl of the polyalcohols such as trimethylolpropane Addition has any one or two in toluene di-isocyanate(TDI), hexamethylene diisocyanate and benzene dimethylene diisocyanate Kind or more compound；Lysine diisocyanate etc..
As the organic multicomponent group with imine moiety, following substance can be enumerated.Such as N, N '-diphenylmethyl can be enumerated Alkane -4,4 '-bis- (1- aziridine formamides),-three-β of trimethylolpropane-'-aziridino propionic ester, tetramethylol methane-three - β-'-aziridino propionic ester, N, N '-Toluene-2,4-diisocyanate, bis- (1- aziridine formamide) triethylenemelanins of 4- etc..
When using organic polyisocyanate compound as crosslinking agent (f), as energy ray-curable ingredient (a) or not Polymer (b) with energy ray-curable group, it is preferable to use hydroxyl polymer.When crosslinking agent (f) has isocyanide When perester radical, energy ray-curable ingredient (a) or the polymer (b) without energy ray-curable group have hydroxyl, By crosslinking agent (f) with energy ray-curable ingredient (a) or the polymer (b) without energy ray-curable group it is anti- It answers, cross-linked structure simply can be imported into protective film formation film.
It can be only one that protective film, which forms composition (IV-1) and protective film formation with the crosslinking agent (f) contained by film, Kind, or it is two or more.When being two or more, their combination and ratio can be selected arbitrarily.
When using crosslinking agent (f), in protective film formation in composition (IV-1), relative to energy ray-curable ingredient (a) and 100 mass parts of total content of the polymer (b) without energy ray-curable group, the content of crosslinking agent (f) are preferred For 0.01~20 mass parts, more preferably 0.1~10 mass parts, particularly preferably 0.5~5 mass parts.By making crosslinking agent (f) The content be the lower limit value or more, can significantly more obtain by using crosslinking agent (f) and the effect that generates.In addition, By making the content upper limit value of crosslinking agent (f) hereinafter, can inhibit being excessively used for crosslinking agent (f).
[colorant (g)]
As colorant (g), such as well known to inorganic pigment, organic pigment, organic dyestuff being enumerated etc. Toner.
As the organic pigment and organic dyestuff, following substance can be enumerated.Such as amine can be enumerated (aminium) class pigment, anthocyanins, merocyanine class pigment, crocic acid (croconium) class pigment, the sour cyanines in side (squarylium) class pigment, azulene(azulenium) class pigment, polymethine class pigment, naphthalene Quinone Pigments, pyrans Class pigment, phthalocyanines pigment, naphthalene cyanines class pigment, naphthalene lactim (naphtholactam) class pigment, azo pigment, condensation Azo pigment, indigoid type pigment, purple cyclic ketones (perinone) class pigment, class pigment, dioxazines pigment, quinacridine ketone Pigment, isoindoline ketone pigment, quinophthalone class pigment, pyroles pigment, thioindigo class pigment, metal complex species pigment (gold Belong to complexing salt dyestuff), dithiol metal complex class pigment, indoles phenol sulfonate, triallyl methane class pigment, Anthraquinones color Element, aphthols pigment, azomethine class pigment, benzimidazole ketone pigment, pyranthrone pigment and intellectual circle (threne) class pigment Deng.
As the inorganic pigment, such as carbon black, cobalt class pigment, iron class pigment, chromium class pigment, titanium class color can be enumerated Element, vanadium class pigment, zirconium class pigment, molybdenum class pigment, ruthenium class pigment, platinum class pigment, ITO (tin indium oxide) class pigment, ATO (oxidation Antimony tin) class pigment etc..
It can be only one that protective film, which forms composition (IV-1) and protective film formation with the colorant (g) contained by film, Kind, or it is two or more.When being two or more, their combination and ratio can be selected arbitrarily.
When using colorant (g), the content that protective film forms the colorant (g) of film suitably adjust i.e. according to purpose It can.For example, protective film is subjected to lettering sometimes through laser irradiation, pass through containing for the colorant (g) to protective film formation film Amount is adjusted and the translucency of protective film is adjusted, and thus, it is possible to adjust lettering visuality.At this point, being formed in protective film With in composition (IV-1), the content (i.e. protective film forms the content for using the colorant (g) of film) of colorant (g) is relative to except molten The ratio of the total content of all the components other than agent is preferably 0.1~10 mass %, more preferably 0.4~7.5 mass %, especially Preferably 0.8~5 mass %.It more than the content lower limit value by making colorant (g), can significantly more obtain logical Cross the effect generated using colorant (g).In addition, by making the content upper limit value of colorant (g) hereinafter, can Inhibit being excessively used for colorant (g).
[Thermocurable ingredient (h)]
Protective film, which forms to be formed with composition (IV-1) and protective film, uses the Thermocurable ingredient (h) contained by film can be only For one kind, or two or more.When being two or more, their combination and ratio can be selected arbitrarily.
As Thermocurable ingredient (h), for example, can enumerate epoxies heat-curing resin, Thermocurable polyimides, Polyurethane, unsaturated polyester (UP), organic siliconresin etc., preferably epoxies heat-curing resin.
(epoxies heat-curing resin)
Epoxies heat-curing resin is made of epoxy resin (h1) and thermal curing agents (h2).Composition is used in protective film formation (IV-1) and the epoxies heat-curing resin contained by protective film formation film can be only one kind, or two kinds with On.When being two or more, their combination and ratio can be selected arbitrarily.
Epoxy resin (h1)
As epoxy resin (h1), well known epoxy resin can be enumerated.Such as can enumerate multifunctional based epoxy resin, Biphenol compound, bisphenol A diglycidyl ether and its hydride, o-cresol phenolic resin varnish, dicyclopentadiene type ring Oxygen resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenylene matrix type epoxy resin etc. Epoxide more than difunctionality.
As epoxy resin (h1), the epoxy resin with unsaturated alkyl can be used.With do not have unsaturated alkyl Epoxy resin is compared, and the compatibility of epoxy resin and acrylic resin with unsaturated alkyl is high.Therefore, by using tool There is the epoxy resin of unsaturated alkyl, is improved using the reliability of protective film formation encapsulation obtained from composite sheet.
As the epoxy resin with unsaturated alkyl, for example, can enumerate multifunctional based epoxy resin epoxy group one Partial Transformation at the group with unsaturated alkyl compound.Such compound for example can by make (methyl) acrylic acid or Its derivative carries out addition reaction with epoxy group and obtains.
In addition, as the epoxy resin with unsaturated alkyl, such as can enumerate in the aromatic rings for constituting epoxy resin There is the compound etc. of the group with unsaturated alkyl Deng upper Direct Bonding.Unsaturated alkyl is the unsaturated group with polymerism Group, as its concrete example, can enumerate ethylidine (vinyl), 2- acrylic (allyl), (methyl) acryloyl group, (methyl) Acrylamido etc., preferably acryloyl group.
The number-average molecular weight of epoxy resin (h1) is not particularly limited.But from the curability of protective film formation film, with And the point of film strength and heat resistance is protected to set out, preferably 300~30000, more preferably 400~10000, particularly preferably 500~3000.
The epoxide equivalent of epoxy resin (h1) is preferably 100~1000g/eq, more preferably 150~800g/eq.
Epoxy resin (h1) can be used alone, can also be simultaneously using two or more.Simultaneously using two or more When, their combination and ratio can be selected arbitrarily.
Thermal curing agents (h2)
Thermal curing agents (h2) play a role as the curing agent for epoxy resin (h1).
As thermal curing agents (h2), such as can enumerate has two or more can be with the official of epoxy reaction in 1 molecule The compound that can be rolled into a ball.As the functional group, such as phenolic hydroxyl group, alcohol hydroxyl group, amino, carboxyl, acidic group acid anhydrides can be enumerated Group made of change etc..Preferably group made of phenolic hydroxyl group, amino or acidic group acid anhydrides, more preferably phenolic hydroxyl group or Amino.
As the phenols curing agent with phenolic hydroxyl group in thermal curing agents (h2), such as multifunctional phenol tree can be enumerated Rouge, '-biphenyl diphenol, novolak type phenol resin, bicyclopentadiene class phenol resin, aralkyl-phenol resin etc..
As the amine curing agent with amino in thermal curing agents (h2), such as dicyandiamide can be enumerated (hereinafter, sometimes Write a Chinese character in simplified form work " DICY ") etc..
Thermal curing agents (h2) can have unsaturated alkyl.
Had as the thermal curing agents (h2) with unsaturated alkyl, such as a part that the hydroxyl of phenol resin can be enumerated Compound, group of the Direct Bonding with unsaturated alkyl on the aromatic rings of phenol resin for thering is the group of unsaturated alkyl to replace Obtained from compound etc..
In the unsaturated alkyl and the above-mentioned epoxy resin with unsaturated alkyl in thermal curing agents (h2) not Saturated hydrocarbyl is identical.
When using phenols curing agent as thermal curing agents (h2), from improving protective film pointing out from the fissility of support chip Hair, preferably thermal curing agents (h2) are softening point or the high thermal curing agents of glass transition temperature.
Phenol resin in thermal curing agents (h2), for example multifunctional, novolak type phenol resin, bicyclopentadiene class phenol tree The number-average molecular weight of the resin components such as rouge, aralkyl-phenol resin is preferably 300~30000, and more preferably 400~10000, especially Preferably 500~3000.
In thermal curing agents (h2), the molecular weight of non-resin ingredient such as '-biphenyl diphenol, dicyandiamide is not particularly limited, Such as preferably 60~500.
Thermal curing agents (h2) can be used alone, can also be simultaneously using two or more.Simultaneously using two or more When, their combination and ratio can be selected arbitrarily.
When using Thermocurable ingredient (h), is formed and used in film in protective film formation composition (IV-1) and protective film, phase For 100 mass parts of content of epoxy resin (h1), the content of thermal curing agents (h2) is preferably 0.01~20 mass parts.
When using Thermocurable ingredient (h), is formed and used in film in protective film formation composition (IV-1) and protective film, phase For not having 100 mass parts of content of the polymer (b) of energy ray-curable group, the content of Thermocurable ingredient (h) (for example, total content of epoxy resin (h1) and thermal curing agents (h2)) is preferably 1~500 mass parts.
[antistatic agent (j)]
As long as the surface resistivity that protective film forms film can be adjusted to institute's phase by antistatic agent (j) used in the present invention The value of prestige, is not particularly limited.
Such as it can enumerate selected from antistatic by anionic surfactant class antistatic agent, cationic surfactant class Agent, nonionic surfactants antistatic agent, zwitterionic surfactant class antistatic agent and nonionic surfactant At least one of group of class antistatic agent composition etc..
Furthermore, it is possible to use Polymer Antistatic Agent.Such as polyether ester amides class, ethylene oxide-epichlorohydrin can be used The nonionics class Polymer Antistatic Agent such as class and polyethers esters, the anionic species polymer electrolyte such as polystyrene sulfone class are antistatic Agent, the cationics Polymer Antistatic Agent such as acrylate polymer class containing quaternary ammonium salt base.
Further, the Dan Yue such as Span-20, polyoxyethylene sorbitan monolaurate can be used Cinnamic acid esters antistatic agent；
Fatty acid glyceride monoglyceride, fatty acid glyceride acetylation monoglyceride, fatty acid glyceride organic acid monoglyceride, And the glyceride types antistatic agent such as fatty acid glyceride MCT Oil；
Polyglyceryl fatty acid ester, sorbitan fatty acid ester, methyl glycol fatty acid ester, special fatty acid ester and higher alcohol The ester type antistatic agent such as aliphatic ester.
In above antistatic agent (j), preferred as alkali salt antistatic agent, further preferred Li salt is antistatic Agent.
In the present invention, the quality relative to the resin component contained by the protective film formation film, it is described antistatic The content of agent (j) is preferably 1~20 mass %, further preferably 3~10 mass %.That is, in the protective film formation film Further containing energy ray-curable ingredient (a) and when polymer (b) without energy ray-curable group, described Protective film, which is formed, to be used in film, relative to the energy ray-curable ingredient (a) and without energy ray-curable group The gross mass of polymer (b), the antistatic agent are preferably 1~20 mass %, further preferably 3~10 mass %.
If the content of antistatic agent (j) is lower than the lower limit value, exists and be unable to get sufficient electric conductivity, antistatic property The problem of not improving.On the other hand, if the content of antistatic agent is higher than the upper limit value, exist at the interface of protective layer and Si The problem of exudation, reliability decrease occurs.
[usability methods]
In the present invention, it as the method for being applicable in antistatic agent (j), is not particularly limited.Antistatic agent (j) can be added Adduction is blended in protective film formation and is kneaded in composition, can also be in protective film formation composition or protective film shape Antistatic agent (j) is coated on the surface with film.Layer containing antistatic agent (j) can also be coated on protective film shape with membranaceous At on the surface of composition or protective film formation film.It further, can also be by being attached at protective film formation film table The peeling layer (surface) of the stripping film in face assigns antistatic agent (j) to seek the antistatic of protective film formation film.
[universal additive (z)]
Universal additive (z) can be well known additive, can arbitrarily be selected, be not particularly limited according to purpose.Wherein, As preferred additive, such as plasticizer, antistatic agent, antioxidant, capturing agent (gettering agent) can be enumerated Deng.
Protective film forms composition (IV-1) and protective film formation with the universal additive (z) contained by film It is a kind of, or two or more.When being two or more, their combination and ratio can be selected arbitrarily.
When using universal additive (z), protective film forms general the adding with composition (IV-1) and protective film formation film Add the content of agent (z) to be not particularly limited, suitably select according to purpose.
[solvent]
Protective film, which is formed, preferably further contains solvent with composition (IV-1).Protective film containing solvent is formed with combination The operability of object (IV-1) becomes good.
The solvent is not particularly limited.Wherein, as preferred solvent, such as the hydrocarbon such as toluene, dimethylbenzene can be enumerated； The alcohol such as methanol, ethyl alcohol, 2- propyl alcohol, isobutanol (2- methylpropane -1- alcohol), n-butyl alcohol；The esters such as ethyl acetate；Acetone, methyl second The ketone such as base ketone；The ethers such as tetrahydrofuran；The amides such as dimethylformamide, N-Methyl pyrrolidone (compound with amido bond) Deng.
It can be only one kind that protective film, which is formed with the solvent contained by composition (IV-1), or two or more.For When two or more, their combination and ratio can be selected arbitrarily.
From can by the point that containing ingredient more uniformly mixes of the protective film formation in composition (IV-1), protect It is preferably methyl ethyl ketone, toluene or ethyl acetate etc. that film, which is formed with the solvent contained by composition (IV-1),.
< < protective film forms the preparation method > > for using composition
Protective film is formed can be by blending for constituting its with the protective films formation such as composition (IV-1) composition Each ingredient and obtain.
Order of addition when blending each ingredient is not particularly limited, and can also add two or more ingredients simultaneously.
It, can be pre- by the blending ingredient and mixing solvent with any blending ingredient in addition to solvent when using solvent Dilution to carry out using.In addition it is also possible to not by any blending ingredient pre-dilution in addition to solvent, and by by solvent with These blend ingredients mixing to carry out using.
The method that each ingredient is mixed when blending is not particularly limited.It is suitably selected from following well known methods：Make Blender or stirring blade etc. rotate and mixed method；The method mixed using blender；Apply ultrasonic wave and Mixed method etc..
As long as respectively blending ingredient not deteriorate, the temperature and time when adding and mix each ingredient are not particularly limited, Suitably adjust, preferable temperature is 15~30 DEG C.
As it is identical with protective film formation composite sheet of the invention, be attached at and semiconductor crystal wafer or semiconductor chip Circuit face opposite side the back side, and have on support chip the composite sheet of the layer of display adhesiveness, there is cutting chip engagement Piece (dicing die bonding sheet).
However, being picked up the adhesive phase that chip joint fastener has is cut from support chip together with semiconductor chip Afterwards, the adhesive phase is as the bonding whens semiconductor chip to be attached to substrate, lead frame or other semiconductor chips etc. Agent and play a role.On the other hand, of the invention for it is picked up this point from support chip together with semiconductor chip Protective film, which forms to be formed with the protective film in composite sheet, uses film identical as described adhesive layer, but it becomes eventually by solidification Protective film has the function of protecting the back side of attached semiconductor chip.In this way, protective film formation film of the invention with cut The purposes for cutting the adhesive phase in chip joint fastener is different, and the performance sought is certainly also different.Moreover, being engaged with cutting chip Adhesive phase in piece is compared, and protective film formation film usually has hard and is difficult to the tendency picked up, this has also reflected above-mentioned Purposes difference.It is therefore often difficult to which the adhesive phase cut in chip joint fastener, which is directly converted, is used as protective film formation Film is used in protective film formation in composite sheet.As the composite sheet for the protective film formation film for having energy ray-curable, this hair Bright protective film formation composite sheet is the extremely excellent guarantor of the pickup adaptive of semiconductor chip in the past no, with protective film Composite sheet is used in cuticula formation.
◇ protective film forms the manufacturing method for using composite sheet
It can stack gradually above-mentioned each layer in a manner of making above-mentioned each layer become corresponding positional relationship and make Make protective film formation composite sheet of the invention.The forming method of each layer is identical as what is be illustrated above.
For example, when adhering agent layer is laminated on substrate, above-mentioned adhesion agent composition is coated on base when manufacture support chip It is dried on material and as needed.
On the other hand, such as when protective film formation film is further laminated on adhering agent layer on base material has been laminated, Protective film formation can be coated on adhering agent layer with composition and directly form protective film formation film.For removing protective film shape At with the layer other than film, same method can be also utilized, be laminated on adhering agent layer using the composition for being used to form this layer The layer.It like this, can be in the layer formed by the composition when forming continuous two layers of stepped construction using arbitrary composition Upper further coating composition is to form new layer.Wherein, it is preferable to use the composition preparatory shape on other stripping films At the layer of the rear stacking in above-mentioned two layers, and passing through the established layer is opposite with the side contacted with the stripping film The exposed surface of side and the fitting of the exposed surface of another layer formed, to form continuous two layers of stepped construction.At this point, excellent The composition is coated on the lift-off processing face of stripping film by choosing.After forming stepped construction, stripping film is removed as needed ?.
For example, adhering agent layer is laminated on substrate in the presence of manufacture, and protective film is laminated on the adhering agent layer and forms use With composite sheet, (support chip is that the protective film of the sandwich of substrate and adhering agent layer is formed with compound to the formation of protective film made of film Piece) the case where.At this point, by the way that adhesion agent composition is coated on substrate and is dried as needed, thus on substrate Adhering agent layer is laminated, in addition again by being coated on protective film formation on stripping film with composition and being dried as needed, Thus protective film formation film is formed on stripping film.Then, by by the exposed surface of the protective film formation film be laminated The exposed surface of adhering agent layer on base material is bonded, and protective film formation is stacked on adhering agent layer with film layer, can be protected Composite sheet is used in film formation.
In addition, adhesion agent composition can also be coated on stripping film as described above when adhering agent layer is laminated on substrate It above and is as needed dried to replace for adhesion agent composition being coated with method on base material, thus the shape on stripping film It is bonded at adhering agent layer, and by the exposed surface of this layer with the surface of the side of substrate, so that adhering agent layer is layered on substrate.
In arbitrary method, the arbitrary opportunity after forming target stepped construction removes stripping film.
As noted previously, as removing can be previously formed in by constituting the layer in addition to substrate of protective film formation composite sheet On film, and it is laminated in the method for being fitted in the surface of destination layer.Therefore, appropriate selection uses such process as needed Layer manufacture protective film formation composite sheet.
In addition, protective film formation with composite sheet usually with the most surface layer of its support chip opposite side (such as protective film shape At with film) surface on be fitted with the state of stripping film and taken care of.Therefore, though by protective film formation composition etc., The composition for being used to form the layer on composition most surface layer is coated on the stripping film (preferably its lift-off processing face), and as needed It is dried, thus forms the layer for constituting most surface layer on stripping film, and using above-mentioned arbitrary method in this layer and same stripping Side from film contact is the other each layers of stacking in the exposed surface of opposite side, keeps the state for not removing and being bonded stripping film When, protective film formation composite sheet also can be obtained.
◇ protective film forms the application method for using composite sheet
Protective film formation of the invention can for example be carried out using method as shown below with composite sheet using.
That is, protective film formation composite sheet is made to be attached at the back side of semiconductor crystal wafer with film by its protective film formation (face with electrode forming surface opposite side).Then, to protective film formation film irradiation energy ray, keep protective film formation film solid Change that protective film is made.Then, by cutting, semiconductor crystal wafer is divided together with protective film, semiconductor chip is made.So Afterwards, by semiconductor chip to be pasted with the state (that is, as semiconductor chip with protective film) of the protective film from support chip It separates and picks up.
Later, using method identical with previous method, by the semiconductor of the obtained semiconductor chip with protective film After flip-chip is connected to the circuit face of substrate, semiconductor packages is made by using resin seal entirety.Then, this is used Semiconductor packages makes target semiconductor device.
In addition, carried out to the case where making protective film formation film solidify after forming protective film, be cut herein Illustrate, but when using protective film formation composite sheet of the invention, the sequence for carrying out these processes be may be reversed.That is, After protective film formation is attached on the back side of semiconductor crystal wafer with composite sheet, by cutting semiconductor crystal wafer and protective film shape Divide together at film, semiconductor chip is made.Then, to the protective film formation film irradiation energy ray divided, make to protect The solidification of cuticula formation film is to form protective film.Later in the same manner as described above, by the semiconductor chip with protective film It separates, be picked up from support chip, make target semiconductor device.
◇ roll shape
Fig. 6 is the sectional view for schematically showing the protective film formation film of another embodiment of the invention.
As shown in fig. 6, the protective film of present embodiment, which is formed, is referred to as " roll shape " with film 1F.It, which has, forms protective film Stripping film 15a (hereinafter, sometimes referred to as " the first stripping film ") is suitable for stripping film 15b (hereinafter, having with stratiform with composition 13 When be referred to as " the second stripping film ") between structure.
It is formed with above-mentioned protective film with combination for the protective film formation protective film formation of film 1F with composition 13 Object is standard.
The protective film formation can for example be formed with film 1F by following manner：It is fitted in the release surface of the first stripping film 15a With protective film formation composition 13, further, in a manner of making to remove side to 13 side of protective film formation composition It is applicable in the second stripping film 15b thereon, is pressed and is formed.The usability methods of protective film formation composition are with above-mentioned protection The usability methods of film formation composition are standard.
◇ protective film forms the application method for using film
Protective film formation of the invention can for example be carried out using method as shown below with film using.
That is, protective film formation to be attached to the back side (face with electrode forming surface opposite side) of semiconductor crystal wafer with film.It connects , to protective film formation film irradiation energy ray, make the solidification of protective film formation film to which protective film be made.Then, pass through Cutting, semiconductor crystal wafer is divided together with protective film, semiconductor chip is made.Then, to be pasted with the state of the protective film Semiconductor chip is separated and is picked up from support chip by (that is, as semiconductor chip with protective film).
The semiconductor chip 101 with protective film picked up is incorporated in the pocket 102a of embossed carrier tape 102 as shown in Figure 7 In, lid band 103 is pasted at the opening portion of pocket 102a.The opening portion is closed as a result, and is packed.Then, it will emboss Carrier band 102 take care of, carried or is traded to be rolled into the state of reel shape, as next process, by with protective film partly The semiconductor chip upside-down mounting of conductor chip 101 be connected in the process of the circuit face of substrate carry out using.
In the present specification, " embossed carrier tape " refers in polystyrene, polyethylene terephthalate or polypropylene etc. The packaging for the multiple recess portions (sometimes referred to as pocket) being arranged at certain intervals is formed on the strip sheet material of resin Material, such as the semiconductor chip of the invention with protective film can be stored in the multiple pocket.The multiple pocket is usual To be accommodated with the state of the stored object such as the semiconductor chip of the invention with protective film, the lid of strip is pasted in its opening portion Thus band is covered.Be packaged with the semiconductor chip with protective film embossed carrier tape can be wound into a roll the state of plate-like into It exercises and uses.Such as the reel can be mounted on chip mounter, and the semiconductor chip with protective film is installed on substrate.Pressure The pocket of line carrier band can be designed and process according to the size of stored object.As each of the embossed carrier tape in this specification Pocket, such as the mouth of longitudinal size 0.5mm~30mm, lateral dimension 0.5mm~30mm and depth 0.1mm~10mm can be enumerated Bag.The lid band of the strip with a thickness of 10~100 μm, formed by materials such as PET, polyethylene.
Later, using method identical with previous method, by the semiconductor of the obtained semiconductor chip with protective film After flip-chip is connected to the circuit face of substrate, semiconductor packages is made by using resin seal entirety.Then, this is used Semiconductor packages makes target semiconductor device.
In addition, carried out to the case where making protective film formation film solidify after forming protective film, be cut herein Illustrate, but when using protective film formation film of the invention, the sequence for carrying out these processes be may be reversed.That is, that will protect After cuticula formation is attached on the back side of semiconductor crystal wafer with film, by cutting semiconductor crystal wafer and protective film formation film one With segmentation, semiconductor chip is made.Then, to the protective film formation film irradiation energy ray divided, form protective film Solidified to form protective film with film.Later in the same manner as described above, by the semiconductor chip with protective film from support chip Upper separation is simultaneously picked up, and target semiconductor device is made.
Embodiment
Hereinafter, being illustrated in more details according to specific embodiment to the present invention.But the present invention is not limited to Embodiment described below.
Protective film described below forms ingredient used in the preparation with composition.
Energy ray-curable ingredient
(a2)-1：Tristane dihydroxymethyl diacrylate be (Nippon Kayaku Co., Ltd. manufacture " KAYARAD R-684 ", the ultra-violet solidified compound of difunctionality, molecular weight 304)
Polymer without energy ray-curable group
(b)-1：By butyl acrylate (hereinafter, writing a Chinese character in simplified form work " BA ") (10 mass parts), methyl acrylate (hereinafter, writing a Chinese character in simplified form work " MA ") (70 mass parts), glycidyl methacrylate (hereinafter, writing a Chinese character in simplified form work " GMA ") (5 mass parts) and acrylic acid 2- hydroxyl Acrylic resin (weight average molecular weight 300000, glass made of ethyl ester (hereinafter, writing a Chinese character in simplified form work " HEA ") (15 mass parts) copolymerization Change -1 DEG C of transition temperature)
Photoepolymerizationinitiater initiater
(c)-1：2- (dimethylamino) -1- (4- morpholinyl phenyl) -2- benzyl -1- butanone be (BASF AG's manufacture " Irgacure (registered trademark) 369 ")
(c)-2：1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] ethyl ketone 1- (O- acetyl oxime) (BASF " Irgacure (registered trademark) OXE02 " of company's manufacture)
Packing material
(d)-1：Silica filler (vinyl surface modification, average grain diameter 50nm)
Coupling agent
(e)-1：3- methacryloxypropyl trimethoxy silane (Shin-Etsu Chemical Co., Ltd. system " KBM-503 " made, silane coupling agent)
Colorant
(g)-1：By phthalocyanines blue pigment (Pigment Blue 15:3) 32 mass parts, isoindoline ketone yellow color Plain (Pigment Yellow 139) 18 mass parts and the mixing of Anthraquinones red pigments (Pigment Red 177) 50 mass parts, So that the total amount of three kinds of pigments/styrene acrylic resin amount=1/3 (mass ratio) mode carries out pigmentation and obtains The pigment arrived
Antistatic agent：
(j)-1：Using tetraethyleneglycol dimethyl ether as antistatic agent (the Sanko Chemical of the imide li type of carrier " the Sankonol TGR " of Industry Co., Ltd. manufacture)
[embodiment 1]
< protective film forms the manufacture > for using composite sheet
(protective film forms the preparation for using composition (IV-1))
So that energy ray-curable ingredient (a2) -1, polymer (b) -1, Photoepolymerizationinitiater initiater (c) -1, photopolymerization initiation Agent (c) -2, packing material (d) -1, coupling agent (e) -1, colorant (g) -1 and antistatic agent (j) -1 content (solid component, Mass parts) become the mode of value shown in table 1 and is dissolved or dispersed in methyl ethyl ketone, and be stirred in 23 DEG C, thus make The protective film that standby solid component concentration is 50 mass %, which is formed, uses composition (IV-1).
(preparation of adhesion agent composition (I-4))
Preparation contains acrylic polymer (100 mass parts, solid component) and trifunctional phenylenedimethylidyne diisocyanate Esters crosslinking agent (" the TAKENATE D110N " of the manufacture of three field Jing Wu chemical companies) (10.7 mass parts, solid component) is gone forward side by side One step contain methyl ethyl ketone as solvent, solid component concentration be 30 mass % non-energy ray-curable sticker Composition (I-4).The acrylic polymer is by 2-EHA (hereinafter, writing a Chinese character in simplified form work " 2EHA ") (36 mass Part), BA (59 mass parts) and HEA (5 mass parts) copolymerization made of weight average molecular weight be 600000 acrylic polymer.
(manufacture of support chip)
Adhesion agent composition obtained above (I-4) is coated on using silicone-treated to polyethylene terephthalate The single side of film has carried out stripping film (" SP-PET381031 " of Lintec Corporation. manufacture, the thickness of lift-off processing 38 μm, be denoted as " P1 " sometimes below) the lift-off processing face on, and in 120 DEG C heat drying 2 minutes, thickness is consequently formed The adhering agent layer of 10 μm of non-energy ray-curable.
It then, will be as the polypropylene film of substrate (Young's modulus 400MPa, is denoted as " S1 " sometimes below by 80 μm of thickness) It is fitted in the exposed surface of the adhering agent layer, thus obtains having the adhering agent layer on the surface of the side of the substrate Support chip (10) -1.
(protective film forms the manufacture for using composite sheet)
Protective film formation obtained above is coated on composition (IV-1) using knife type coater and utilizes silicone-treated Stripping film (the Lintec Corporation. system of lift-off processing has been carried out to the single side of polyethylene terephthalate film " SP-PET381031 " made, 38 μm of thickness, P1) the lift-off processing face on, and it is 2 minutes dry in 100 DEG C, thus make The protective film for the energy ray-curable that 25 μm of thickness, which is formed, uses film (13) -1.
Then, stripping film is removed from the adhering agent layer of support chip (10) -1 obtained above, by guarantor obtained above Cuticula formation is fitted in the exposed surface of the adhering agent layer with the exposed surface of film (13) -1, is made substrate, adhering agent layer, protection Film formed film (13) -1 and stripping film along their thickness direction stack gradually made of protective film formation composite sheet.By institute The composition of obtained protective film formation composite sheet is shown in table 2.
< protective film forms the evaluation > for using film
(protective film forms the surface resistivity for using film)
Use surface resistivity measurement device (the DIGITAL ELECTRONMETER of ADVANTEST Co., Ltd. manufacture R8252), for obtained protective film formation film, using ultraviolet lamp, (LINTEC Corporation is manufactured " RAD2000m/8 "), in illumination 195mW/cm2, light quantity 170mJ/cm2Under conditions of, protective film formation composite sheet is irradiated purple Outside line and make its solidification, measure surface resistivity at this time.
Protective film when being set as by being irradiated, and solidifying protective film formation film.Show the result in table 2.
In addition, " antistatic agent [the quality %] " in table 2 refer to it is in protective film formation film, solid relative to energy-ray The content of the antistatic agent of the gross mass of the property changed ingredient (a) and the polymer (b) without energy ray-curable group.
(lid band adhesion is tested)
Protective film formation composite sheet obtained above is attached to 6 inches of silicon by its protective film formation film (13) -1 On the #2000 abradant surface of wafer (100 μm of thickness), then the piece is fixed on ring-shaped frame, stands 30 minutes.
Then, using ultraviolet lamp (" RAD2000m/8 " of LINTEC Corporation manufacture), in illumination 195mW/cm2, light quantity 170mJ/cm2Under conditions of, it is irradiated from (10) -1 side of support chip to protective film formation composite sheet ultraviolet Thus line solidifies protective film formation film (13) -1, protective film is made.
Then, using cutting blade, Silicon Wafer is sliced together with protective film, obtains vertical 3mm × horizontal 3mm, protection film thickness The silicon chip of 25 μm of degree, 350 μm of Si thickness degree.
Then, using chip engagement machine (the die bonder) (" BESTEM- of Canon Machinery Inc manufacture D02 "), 20 silicon chips with protective film are picked up.
On the iron plate for indulging 12cm × horizontal 12cm, thickness 5mm, by 16 silicon chips obtained above with protective film with that The equal mode in this interval is placed on the position of the trellis of the square of vertical 4 × cross 4, and covers vertical 12cm on it The lid band (manufacture of Sumitomo Bakelite Co., Ltd., CSL-Z7302) of × horizontal 3.8cm, is positioned in and is heated to 40 DEG C In hot plate, and metal plate is loaded on it, and carried out in a manner of making the pressure 350gf applied to the silicon chip with protective film Installation carries out heating in one minute.Then metallic plate is gone, the lid band is removed, detection lid takes whether be attached with band protection The silicon chip of film.Show the result in table 2.
As determination method, will sentence thering is one to be attached to the case where lid takes in 16 silicon chips with protective film It is set to " having ", is attached to the case where lid takes by none of in 16 silicon chips with protective film and is determined as "None".
< protective film forms the evaluation > for being formed with the manufacture of composite sheet and protective film and using film
[embodiment 2]
Other than the content of antistatic agent (h) -1 is set as 6 mass parts, production is protected in the same manner as in Example 1 Cuticula, which is formed, uses film (13) -2.Further, protective film formation composite sheet is manufactured using protective film formation film (13) -2, commented Valence protective film forms the characteristic for using film.Show the result in table 2.
[embodiment 3] [roll shape]
< protective film forms the manufacture > for using film
Protective film formation obtained above stripping film 1 is coated on composition (IV-1) using knife type coater (to utilize Silicone-treated has carried out the stripping film (Lintec of lift-off processing to the single side that polyethylene terephthalate is film-made Corporation. " SP-PET381031 " manufactured, 38 μm of thickness, P1)) removing surface side surface on, after making it dry, Fitting stripping film 2 (has carried out lift-off processing to the single side that polyethylene terephthalate is film-made using silicone-treated on it Stripping film (LINTEC Corporation manufacture " SP-PET382150 ", 38 μm of thickness, hereinafter sometimes referred to as " P2 ")), Then, 2 minutes dry in 100 DEG C, the protective film for thus making 25 μm of thickness of energy ray-curable, which is formed, uses film (14) -1.
< protective film forms the evaluation > for using film
(surface resistivity)
Use surface resistivity measurement device (the DIGITAL ELECTRONMETER of ADVANTEST Co., Ltd. manufacture R8252), for obtained protective film formation film, using ultraviolet lamp, (LINTEC Corporation is manufactured " RAD2000m/8 "), in illumination 195mW/cm2, light quantity 170mJ/cm2Under conditions of, protective film formation composite sheet is irradiated purple Outside line and make its solidification, measure surface resistivity at this time.Measure the surface resistivity of obtained protective film formation film.It will knot Fruit is shown in table 2.
(lid band adhesion is tested)
Protective film formation obtained above is attached to the #2000 abradant surface of 6 inches of Silicon Wafers (100 μm of thickness) with film On, stand 30 minutes.
Then, using ultraviolet lamp (" RAD2000m/8 " of LINTEC Corporation manufacture), in illumination 195mW/cm2, light quantity 170mJ/cm2Under conditions of, ultraviolet light is irradiated from protective film formation film side, thus forms protective film Solidified with film (14) -1, protective film is made.Then, using cutting blade, Silicon Wafer is sliced together with protective film, is indulged 3mm × horizontal 3mm, the silicon chip for protecting 25 μm of film thickness, 350 μm of Si thickness degree.
Then, using chip engagement machine (" BESTEM-D02 " of Canon Machinery Inc manufacture), 20 bands are protected The silicon chip of cuticula is picked up.
On the iron plate for indulging 12cm × horizontal 12cm, thickness 5mm, by 16 silicon chips obtained above with protective film with that The equal mode in this interval is placed on the position of the trellis of the square for adding up to 16 of vertical 4 × cross 4, and at it The upper lid band (manufacture of Sumitomo Bakelite Co., Ltd., CSL-Z7302) for covering vertical 12cm × horizontal 3.8cm, is positioned in It is heated in 40 DEG C of hot plate, and loads metal plate on it, and so that the pressure applied to the silicon chip with protective film is The mode of 350gf is installed, and heating in one minute is carried out.Then metallic plate is gone, the lid band is removed, detection lid, which takes, is It is no to be attached with the silicon chip with protective film.Show the result in table 2.
[embodiment 4] [roll shape]
< protective film forms the manufacture > for using composite sheet
(protective film forms the preparation for using composition (IV-1))
As shown in table 1, in addition to the content (blended amount) of antistatic agent is set as 6 mass parts to replace 3 mass parts this point In addition, protective film formation composition (IV-1) is prepared in method same as Example 3, and makes protective film formation film, Evaluate characteristic.Show the result in table 2.
[comparative example 1] [one-piece type]
Other than the blended amount of antistatic agent is set as 0 parts by weight, protective film is made in the same manner as example 1 It is formed and uses composite sheet, and evaluate the characteristic of protective film formation film.Show the result in table 2.
[comparative example 2] [roll shape]
Other than the blended amount of antistatic agent is set as 0 parts by weight, protective film is made in mode same as Example 3 It is formed and uses film, and evaluate its characteristic.Show the result in table 2.
< protective film forms the evaluation > for being formed with the manufacture of composite sheet and protective film and using film
For protective film formation film obtained above, evaluated using method same as Example 1.Result is shown In table 2.
[table 1]
[table 2]
From the above results, in the protective film of protective film formation composite sheet, embodiment 3,4 using embodiment 1,2 When being formed with film, it is 1.0 × 10 that protective film, which is formed with the surface resistivity of film,12Ω cm is hereinafter, after carrying out enclosed reel again In the lid band adhiesion test of peel-off covers band, the silicon chip with protective film for being accommodated in embossed carrier tape is not attached to lid and takes.
In contrast, the protective film formation composite sheet, comparative example 2 for not blending the comparative example 1 of antistatic agent are being used When protective film, the surface resistivity of protective film is greater than 1.0 × 1012Ω cm, the lid of peel-off covers band again after carrying out enclosed reel In band adhiesion test, the silicon chip with protective film for being accommodated in embossed carrier tape is attached to lid and takes.
Industrial applicibility
The present invention can be used for the manufacture of semiconductor device.
Description of symbols
1A,1B,1C,1D,1E：Composite sheet is used in protective film formation；1F：Diaphragm is used in protective film formation；10：Support chip；10a： The surface of support chip；11：Substrate；11a：The surface of substrate；12：Adhering agent layer；12a：The surface of adhering agent layer；13,23：Protection Film is used in film formation；13a,23a：Protective film forms the surface for using film；15：Stripping film；16：Fixture adhesive phase；16a：Fixture Use adhesive phase.

Claims (6)

  1. It is that the protective film of energy ray-curable is formed with film, wherein penetrated in irradiation energy 1. a kind of protective film, which is formed, uses film Line and when solidifying the protective film formation film, surface resistivity 1012Ω cm or less.
  2. 2. protective film according to claim 1, which is formed, uses film, wherein the protective film formation film contains antistatic agent.
  3. 3. protective film according to claim 2, which is formed, uses film, wherein the antistatic agent is selected from being lived by anionic surface Property agent class antistatic agent, cationic surfactant class antistatic agent, nonionic surfactants antistatic agent, amphoteric ion At least one of the group of surfactant-based antistatic agent and nonionic surfactants antistatic agent composition.
  4. 4. protective film according to claim 2 or 3, which is formed, uses film, wherein the antistatic agent is alkaline metal salt.
  5. 5. the protective film formation film according to any one of claim 2~4, wherein the protective film formation film into One step contains energy ray-curable ingredient (a) and the polymer (b) without energy ray-curable group,
    In the protective film formation film, consolidate relative to the energy ray-curable ingredient (a) and without energy-ray The gross mass of the polymer (b) of the property changed group, the antistatic agent containing 6~20 mass %.
  6. 6. a kind of protective film, which is formed, uses composite sheet, has protective film according to any one of claims 1 to 5 on support chip Formation film.
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KR20210098994A (en) * 2018-12-05 2021-08-11 린텍 가부시키가이샤 Composite sheet for forming a protective film, and manufacturing method of a semiconductor chip
CN113169124A (en) * 2018-12-05 2021-07-23 琳得科株式会社 Composite sheet for forming protective film and method for manufacturing semiconductor chip
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