CN108778731A - Protective film formation composite sheet - Google Patents
Protective film formation composite sheet Download PDFInfo
- Publication number
- CN108778731A CN108778731A CN201780010062.2A CN201780010062A CN108778731A CN 108778731 A CN108778731 A CN 108778731A CN 201780010062 A CN201780010062 A CN 201780010062A CN 108778731 A CN108778731 A CN 108778731A
- Authority
- CN
- China
- Prior art keywords
- protective film
- film formation
- methyl
- composite sheet
- energy ray
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the groups H01L21/18 - H01L21/326 or H10D48/04 - H10D48/07 e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- 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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
-
- 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
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/72—Cured, e.g. vulcanised, cross-linked
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Dicing (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Physical Vapour Deposition (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
The present invention provides a kind of can form protective film, the protective film formation composite sheet with good cutting adaptive and the protective film formation film that has energy ray-curable at the back side of semiconductor crystal wafer or semiconductor chip.The protective film formation composite sheet 1A of the present invention has the protective film formation film 13 of energy ray-curable on support chip 10; when to the 13 irradiation energy ray of protective film formation film to which protective film be made, the adhesion strength between the protective film and the support chip 10 is 100~2000mN/25mm.
Description
Technical field
The present invention relates to a kind of protective film formation composite sheets.
The Japanese Patent Application 2016-092032 claims priorities that the application is filed an application based on April 28th, 2016 in Japan
Power, and its content is applied at this.
Background technology
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 engages.Therefore, the back side with the circuit face opposite side of semiconductor chip is exposed 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 protective film is formed, support chip can be also used as to cutting sheet, can be made into protective film formation film and the integrated protection of cutting sheet
Film formation composite sheet.
As such protective film formation composite sheet, such as mainly uses to have so far and carried out by heating
Cure 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) after, make the solidification of protective film formation film to which protective film be made by heating, will partly be led by cutting
Body wafer divides that semiconductor chip is made together with protective film.Then, the state for being pasted with the protective film is kept, will partly be led
Body chip is detached and is picked up from support chip.
However, being heating and curing for the protective film formation film of Thermocurable usually requires the long-time of hours or so, because
This it is expected to shorten hardening time.In this regard, studying can be by the cured protective film of the irradiation of the energy-rays such as ultraviolet light
Formation is used for the formation of protective film with film.For example, having been disclosed for being formed in the energy ray-curable protective film on stripping film
(referring to patent document 1) and high rigidity can be formed and to the energy-ray of the excellent protective film of the adherence of semiconductor chip
Cure cake core protection with film (with reference to patent document 2).
Existing technical literature
Patent document
Patent document 1：No. 5144433 bulletins of Japanese Patent No.
Patent document 2：Japanese Unexamined Patent Publication 2010-031183 bulletins
Invention content
The technical problem to be solved in the present invention
However, using in energy ray-curable protective film formation film disclosed in Patent Document 1 or patent document 2
When disclosed energy ray-curable chip protection film, make film solidification to be made due to energy-rays such as irradiation ultraviolet lights
After protective film, when being cut using cutter, protective film is removed with support chip, therefore there are the back sides to have partly leading for protective film
The technical issues of body chip disperses from support chip or cutting water infiltrates between protective film and support chip.
Therefore, the present invention provide it is a kind of can the back side of semiconductor crystal wafer or semiconductor chip formed protective film, have it is good
The protective film formation composite sheet of good cutting adaptive and the protective film formation film that has energy ray-curable.
Solve the technological means of technical problem
In order to solve the above technical problem, the present invention provides a kind of protective film formation composite sheets, have on support chip
The protective film formation film of standby energy ray-curable, to the protective film formation film irradiation energy ray to which protection be made
When film, the adhesion strength between the protective film and the support chip is 100~2000mN/25mm.
In the protective film formation composite sheet of the present invention, the preferably described support chip has adhering agent layer, the protective film
Formation is in direct contact with film and the adhering agent layer.
The adhering agent layer of the further preferably protective film formation composite sheet of the present invention is non-energy ray-curable.
Invention effect
According to the present invention, it is possible to provide a kind of to form protective film at the back side of semiconductor crystal wafer or semiconductor chip, have
The protective film formation composite sheet of the good protective film formation film for cutting adaptive and having energy ray-curable.
Description of the drawings
Fig. 1 is the sectional view for an embodiment for schematically showing the protective film formation composite sheet of the present invention.
Fig. 2 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
Fig. 3 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
Fig. 4 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
Fig. 5 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
Specific implementation mode
◇ protective film formation composite sheets
The protective film that the protective film formation composite sheet of the present invention has energy ray-curable on support chip forms use
Film, when to the protective film formation film irradiation energy ray to which protective film be made, the protective film and the support chip it
Between adhesion strength be 100~2000mN/25mm.
In addition, in the present invention, " protective film formation film " refers to film before curing, and " protective film " is to instigate protective film
Film made of formation film is cured.
The protective film formation film is cured 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 formation film be it is soft,
It can be simply attached to attach object.Moreover, be 100 by making adhesion strength between protective film and the support chip~
2000mN/25mm, protective film formation of the invention have good cutting adaptive with composite sheet.More specifically, cutter are used
When semiconductor crystal wafer is cut together with protective film, the stripping of protective film and support chip is can inhibit, such as can inhibit the back side and have
The semiconductor chip (semiconductor chip with protective film) of protective film disperses from support chip, can prevent cutting water from infiltrating into guarantor
Between cuticula and support chip.
In addition, for the protective film formation composite sheet of the present invention, by making the protective film formation with film be that energy is penetrated
Line curability, can the protective film formation film than having Thermocurable previous protective film formation composite sheet it is shorter
Cured to form protective film in time.
In the present invention, " energy-ray " refers to the ray with the quantum of energy in electromagnetic wave or charged particle beam, 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 lamps (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 " refers to carrying 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 the effect of the present invention, so preferably 30~1000 μm, more preferably
100~300 μm.
Hereinafter, being described in detail to the composition of the present invention.
◎ support chips
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 also be different, as long as not damaging this
The effect of invention, then these multiple layers combinations are not particularly limited.
In addition, in the present specification, the case where being not limited only to support chip, " multiple layers mutually the same can also be different "
Refer to " layer that can be all is identical, and layer that can also be all is different, can be identical with the layer of only a part ", in addition, " multiple layers
It is different from each other " refer to " constituent material of each layer and thickness at least one different from each other ".
As preferred support chip, such as the support that adhering agent layer is in direct contact and is laminated with base material can be enumerated
Support chip and the support chip etc. being only made of base material made of piece, adhering agent layer are laminated via middle layer on base material.
The protective film of the present invention is formed with compound hereinafter, accordinging to the type of such support chip while with reference to attached drawing
The example of piece illustrates.In addition, in order to which the feature of the present invention is more readily understood, for conveniently, will make in following explanation sometimes
The pith of figure expands display, and dimensional ratios of each integral part etc. are not necessarily identical as reality.
Fig. 1 is the sectional view for an embodiment for schematically showing the protective film formation composite sheet of the present invention.
Protective film formation composite sheet 1A shown here has adhering agent layer 12 on base material 11, on adhering agent layer 12
Has protective film formation film 13.Support chip 10 is the laminated body of base material 11 and adhering agent layer 12, and in other words, protective film is formed
There is the composition that protective film formation film 13 is laminated on the surface 10a of the side of support chip 10 with composite sheet 1A.In addition, protecting
Cuticula formation with composite sheet 1A in protective film formation with being further equipped with stripping film 15 on film 13.
" stripping film " is the film with stripping function, refers to specifically to protect the guarantor before being attached at semiconductor crystal wafer
Cuticula formation film is peeled in operation and is used to be attached at the film on the surface of protective film formation film.
In protective film formation in composite sheet 1A, it is laminated with adhering agent layer 12 on the surface 11a of the side of base material 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, adhesion strength between protective film and adhering agent layer 12 is 100~2000mN/25mm.
Fixture adhesive phase 16 for example can be the single layer structure containing adhesive ingredients, or as core material
Sheet material two sides on stacking the layer containing adhesive ingredients made of multilayered structure.
Protective film formation shown in FIG. 1 is used in the following manner with composite sheet 1A：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 makes fixture
It is attached on the fixtures such as annular frame with the upper surface in the surface 16a of adhesive phase 16.
Fig. 2 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
In addition, in the figure after Fig. 2, for inscape identical with the inscape shown in figure being explained,
Label reference numeral identical with the figure that this is explained, and description is omitted.
Protective film formation composite sheet 1B shown here is not other than having 16 this point of fixture adhesive phase, with figure
Protective film shown in 1 forms identical with composite sheet 1A.That is, in protective film formation in composite sheet 1B, in the side of base material 11
It is laminated with adhering agent layer 12 on the 11a of surface, protective film formation film is laminated in the entire surface of the surface 12a of adhering agent layer 12
13, it 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 is used in the following manner with composite sheet 1B：In the shape for eliminating stripping film 15
Semiconductor crystal wafer, which is attached, under state, on a part of region of the center side in surface 13a of the protective film formation with film 13 (saves sketch map
Show) the back side, so that protective film formation is attached on the fixtures such as annular frame with the region near the peripheral part of film 13.
Fig. 3 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
Protective film formation composite sheet 1C shown here is not other than having 12 this point of adhering agent layer, with Fig. 1 institutes
The protective film formation composite sheet 1A shown is identical.That is, in protective film formation in composite sheet 1C, support chip 10 is only by 11 structure of base material
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 base material 11 and being formed
Film 13 is laminated with fixture bonding 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 in surface 13a of the protective film formation with film 13 are used viscous with fixture
It is laminated with stripping film 15 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, adhesion strength between protective film and base material 11 is 100~2000mN/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 is used：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 makes the upper surface in the surface 16a of fixture adhesive phase 16 be attached to annular
On the fixtures such as frame.
Fig. 4 is the sectional view for the another embodiment for schematically showing the protective film formation composite sheet of the present invention.
Protective film formation composite sheet 1D shown here is not other than having 16 this point of fixture adhesive phase, with figure
Protective film shown in 3 forms identical with composite sheet 1C.That is, in protective film formation in composite sheet 1D, in the side of base material 11
It is laminated with protective film formation film 13 on the 11a of surface, stripping is laminated in the entire surface of the surface 13a of protective film formation film 13
From 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 is used：In the state of eliminating stripping film 15, the center side 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 the another embodiment for schematically showing the protective film formation composite sheet of the present 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 1B as protective film formation shown in Fig. 2.That is, protective film formation composite sheet 1E has adhesion on base material 11
Oxidant layer 12 has protective film formation film 23 on adhering agent layer 12.Support chip 10 is the stacking of base material 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 in protective film formation with composite sheet 1E on film 23
15。
In protective film formation in composite sheet 1E, it is laminated with adhering agent layer 12 on the surface 11a of the side of base material 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 with film 23
Layer 12 is small, has the shape 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, adhesion strength between protective film and adhering agent layer 12 is 100~2000mN/25mm.
Protective film formation shown in fig. 5 is used in the following manner with composite sheet 1E：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 makes adhesion
The protective film formation that is not laminated in the surface 12a of oxidant layer 12 is attached to the surface of film 23 on the fixtures such as annular frame.
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
Not being laminated on the surface of protective film formation film 23 in the surface 12a of adhering agent layer 12 is laminated fixture adhesive phase and (saves
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
Film formation is used with composite sheet 1E in a manner of so that the surface of fixture adhesive phase is attached on the fixtures such as annular frame.
As described previously for the protective film formation composite sheet of the present invention, no matter support chip and protective film formation are with film
What kind of form can have fixture adhesive phase.Wherein, usually as shown in Figures 1 and 3, has fixture adhesive
The protective film formation composite sheet of the present invention of layer, preferably in protective film formation with having fixture adhesive phase on film.
The present invention protective film formation with composite sheet be not limited to Fig. 1~5 shown in composite sheet, do not damaging the present invention
In the range of effect, what can be constituted to change or deleting a part for protective film formation composite sheet shown in Fig. 1~5 answers
It closes piece or may be to have added the compound of other compositions on the basis of the protective film formation composite sheet that is illustrated above
Piece.
For example, in Fig. 3 and protective film formation composite sheet shown in Fig. 4, it can be in base material 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 base material 11 and adhering agent layer 12
Between middle layer is set.That is, in the protective film formation composite sheet of the present invention, support chip can stack gradually base material, centre
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 the protective film formation composite sheet of the present invention, can stripping film with and the stripping film be in direct contact
A part of gap is generated between layer.
In addition, in the protective film formation composite sheet of the present invention, the size of each layer can be arbitrarily adjusted according to purpose
And shape.
The present invention protective film formation composite sheet in, 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 is in direct contact.Such protective film formation composite sheet can more be held
It changes places and cuts the semiconductor chip that the back side has protective film.
Support chip can be transparent, can not also be transparent, can also be coloured according to purpose.
Wherein, in protective film formation has the present invention of energy ray-curable with film, preferably support chip penetrates energy
Ray.
For example, in support chip, the transmitance of the light of wavelength 375nm is preferably 30% or more, more preferably 50% or more,
Particularly preferably 70% or more.By making the transmitance of the light be such range, 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 can
To be set as 95%.
In addition, in support chip, the transmitance of the light of wavelength 532nm is preferably 30% or more, more preferably 50% or more,
Particularly preferably 70% or more.By making the transmitance of the light be such range, protective film is formed through support chip and is used
It, being capable of more clearly lettering when film or protective film irradiation laser to it so that carry out lettering.
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 can
To be set as 95%.
In addition, in support chip, the transmitance of the light of wavelength 1064nm is preferably 30% or more, more preferably 50% with
On, particularly preferably 70% or more.Transmitance by making the light is such range, is formed to protective film 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 can
To be set as 95%.
Then, further each layer for constituting support chip is described in detail.
Zero base material
The base material is sheet or membranaceous, as its constituent material, such as can enumerate various resins.
As the resin, for example, can enumerate low density polyethylene (LDPE) (LDPE), straight-chain low density polyethylene (LLDPE),
The polyethylene such as high density polyethylene (HDPE) (HDPE)；Polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin etc. remove
Polyolefin other than polyethylene；Vinyl-vinyl acetate copolymer, ethylene-(methyl) acrylic copolymer, ethylene-(methyl)
The ethene copolymers such as acrylate copolymer, ethylene-norbornene copolymer (are copolymerized using ethylene as obtained from monomer
Object)；The vinyl chloride resins such as polyvinyl chloride, vinyl chloride copolymer (use vinyl chloride as resin obtained from monomer)；Polyphenyl
Ethylene；Polycyclic alkene；Polyethylene terephthalate, polybutylene terephthalate (PBT), gathers at polyethylene naphthalate
Ethylene isophthalate, poly- 2,6- (ethylene naphthalate)s, all structural units have the complete of aromatic series cyclic group
The polyester such as aromatic polyester；The copolymer of the two or more polyester；Poly- (methyl) acrylate；Polyurethane；Polyurethane third
Olefin(e) acid ester；Polyimides；Polyamide；Makrolon；Fluororesin；Polyacetals；Noryl；Polyphenylene sulfide；Polysulfones；Polyether-ketone
Deng.
In addition, as the resin, such as can also enumerate the polyester and gather 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 can also enumerate the one or more of the resin above illustrated
Crosslinked resin made of crosslinking；The modified tree such as one or more kinds of ionomers of the resin above illustrated is used
Fat.
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 base material resin can be only one kind, or it is two or more, for it is two or more when, combination thereof and
Ratio can be selected arbitrarily.
Base material can be made of a layer (single layer), can also be made of two layers or more of multiple layers, be 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 base material is preferably 50~300 μm, more preferably 60~100 μm.By making the thickness of base material be 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 base material " refers to the thickness of base material entirety, such as the thickness for the base material being made of multiple layers refers to
Constitute the thickness of the total of all layers of base material.In addition, the assay method of the thickness as base material, such as use can be enumerated
Contact thickness gauge calculates the average method etc. of measured value in arbitrary five position finding thickness.
Preferred substrates be thickness base material with high accuracy, i.e. no matter what part thickness the base that is inhibited of deviation
Material.As it is in above-mentioned constituent material, can be used as constituting the material of the high base material of such thickness and precision, such as can enumerate poly-
Ethylene, the polyolefin in addition to polyethylene, polyethylene terephthalate, vinyl-vinyl acetate copolymer etc..
Base material can also contain packing material, colorant, anti-quiet other than containing the main compositions material such as described resin
Various additives well known to electric agent, antioxidant, organic lubricant, catalyst, softening agent (plasticizer) etc..
As long as the optical characteristics of base material meets the optical characteristics of support chip described above.That is, base material can be saturating
It is bright, can not also be transparent, it can also be coloured according to purpose, other layers can also be deposited.
Moreover, in protective film formation has the present invention of energy ray-curable with film, preferred substrates are penetrated through energy
Line.
In order to improve and be set to the adherence of other layers of adhering agent layer on it etc., base material can be to implement to surface
At further provided for contouring processing, Corona discharge Treatment, electron beam treatment with irradiation, plasma based on blasting treatment, solvent processing etc.
The base material of the oxidation processes such as reason, the processing of ozone 〃 ultraviolet treatment with irradiation, flame treatment, chromic acid, hot wind processing etc..
In addition, base material can also be base material of the surface through prime treatment.
In addition, overlapping antistatic coating, protective film formation composite sheet and when being preserved, base material can also have and prevent
Base material bonds or prevents the layer etc. that base material is bonded with suction unit with other sheet materials.
Wherein, the point of the generation of the part of base material caused by the friction of knife when inhibiting by cutting, particularly preferably
Base material is the base material that surface implements electron beam treatment with irradiation.
Base material can utilize well known method to manufacture.For example, the base material 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, makrolon, esters resin, preferably acrylic compounds tree
Fat.
In addition, in the present invention, " adherence resin " be comprising with adherence resin and with the resin of adhesiveness
Both concept, for example, include not only the resin that resin itself has adherence, also include by with additive etc. other at
Point while use and show adherence resin or by heat or the triggers (trigger) such as water there are by show bonding
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 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 thickness of the total for all layers for constituting adhering agent layer.In addition, the measurement of the thickness as adhering agent layer
Method, such as can enumerate using contact thickness gauge in arbitrary five position finding thickness, and calculate being averaged for measured value
Method etc..
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 not also be transparent, can also be coloured according to purpose.
Moreover, in protective film formation has the present invention of energy ray-curable with film, preferably adhering agent layer penetrates energy
Measure ray.
Adhering agent layer can be formed using energy ray-curable sticker, can also use non-energy ray-curable
Sticker and formed.It is preceding and solid that the adhering agent layer formed using energy ray-curable sticker can easily adjust solidification
Physical property after change.
< < adhesion agent composition > >
The adhesion agent composition containing sticker can be used to form 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 below be described in detail 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.
Using well known method carry out adhesion agent composition coating, 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, such as the adherence tree containing non-energy ray-curable can be enumerated
Fat (I-1a) (hereinafter, writing a Chinese character in simplified form work " adherence resin (I-1a) " sometimes) is combined with the sticker of energy ray-curable compound
Object (I-1)；Side chain containing the adherence resin (I-1a) in non-energy ray-curable is imported with the energy of unsaturated group
The adhesion agent composition of the adherence resin (I-2a) (hereinafter, writing a Chinese character in simplified form work " adherence resin (I-2a) " sometimes) of ray-curable
(I-2)；Adhesion agent composition (I-3) etc. containing the adherence resin (I-2a) Yu energy ray-curable compound.
< adhesion agent compositions (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 the structure at least having and coming from (methyl) alkyl acrylate can be enumerated
The acrylic polymer of unit.
Structural unit possessed by acrylic resin can be only one kind, or and it is two or more, it is two or more
When, combination thereof and ratio can be selected arbitrarily.
As (methyl) alkyl acrylate, such as it is 1 that can enumerate the carbon atom number for the alkyl for constituting Arrcostab
~20 (methyl) alkyl acrylate, the preferably described alkyl are straight-chain or branched.
As (methyl) alkyl acrylate, more specifically, (methyl) methyl acrylate, (methyl) propylene can be enumerated
Acetoacetic ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid
Isobutyl ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) acrylic acid oneself
Ester, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid are just
Monooctyl ester, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) acrylic acid 11
Arrcostab, (methyl) dodecylacrylate ((methyl) lauryl acrylate), (methyl) tridecyl acrylate, (first
Base) acrylic acid tetradecane base ester ((methyl) myristyl ester), (methyl) acrylic acid pentadecane base ester, (methyl) acrylic acid
Cetyl ester ((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) acrylic 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 2 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 2~12, 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 come from (methyl) alkyl acrylate structural unit other than, preferably into
One step has the structural unit for carrying out self-contained monomer.
Contain monomer as described, such as can enumerate by the functional group is with aftermentioned reacting for crosslinking agent
Generate crosslinked starting point or can be by the unsaturated group in the functional group and the aftermentioned compound containing unsaturated group
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 containing monomer, such as hydroxyl monomer can be enumerated, carboxyl group-containing monomer, emulsion stability, contain ring
Oxygroup monomer etc..
As the hydroxyl monomer, such as (methyl) acrylate, (methyl) acrylic acid 2- hydroxyls can be enumerated
Ethyl ester, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (first
Base) (methyl) hydroxyalkyl acrylates such as acrylic acid 3- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls；Vinyl alcohol, alkene
Non- (methyl) acrylic compounds unsaturated alcohol such as propyl alcohol (unsaturated alcohol for not having (methyl) acryloyl group skeleton) etc..
As the carboxyl group-containing monomer, such as the olefinics unsaturation unitary carboxylic such as can enumerate (methyl) acrylic acid, crotonic acid
Acid (monocarboxylic acid with ethylenic unsaturated bond)；The ethylenically unsaturated dicarboxylics such as fumaric acid, itaconic acid, maleic acid, citraconic acid
(dicarboxylic acids with ethylenic unsaturated bond)；The acid anhydrides of the ethylenically unsaturated dicarboxylic；Methacrylic acid 2- carboxyethyls 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 and it is two or more, be
When two or more, combination thereof and ratio can be selected arbitrarily.
In the acrylic polymer, relative to the total amount of structural unit, carry out the structure list of self-contained monomer
The content of member is preferably 1~29 mass %, more preferably 2~25 mass %, particularly preferably 3~20 mass %.
The acrylic polymer is in addition to having the structural unit for coming from (methyl) alkyl acrylate and coming self-contained
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 and it is two or more, be
When two or more, combination thereof 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, make to have energy-ray polymerism unsaturated group (energy-ray polymerizable group) contains insatiable hunger
With the compound of group and the functional group reactions in the acrylic polymer and the substance that generates, above-mentioned energy can be used as
Measure 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, combination thereof and ratio can be selected arbitrarily.
In the adhesion agent composition (I-1), relative to the gross mass of adhesion agent composition (I-1), adherence resin
(I-1a) content is preferably 5~99 mass %, more preferably 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 the irradiation of energy-ray or oligomer can be passed through.
As the monomer in energy ray-curable compound, such as trimethylolpropane tris (methyl) propylene can be enumerated
Acid esters, pentaerythrite (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylic acid
Polynary (methyl) acrylate such as ester, 1,4- butanediols two (methyl) acrylate, 1,6-HD (methyl) acrylate；Ammonia
Carbamate (methyl) acrylate；Polyester (methyl) acrylate；Polyethers (methyl) acrylate；Epoxy (methyl) acrylic acid
Ester etc..
As the oligomer in energy ray-curable compound, for example, the monomer polymerization above illustrated can be enumerated and
At oligomer etc..
Storage modulus larger with regard to molecular weight, adhering agent layer is not easy for reducing 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
It is two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
In the adhesion agent composition (I-1), relative to the gross mass of adhesion agent composition (I-1), the energy is penetrated
The content of line curability compound is preferably 1~95 mass %, more preferably 5~90 mass %, particularly preferably 10~85 matter
Measure %.
[crosslinking agent]
It will be other than there is the structural unit for coming from (methyl) alkyl acrylate, further with next self-contained functional group
When the acrylic polymer of the structural unit of monomer is used as adherence resin (I-1a), preferred adhesive compositions (I-
1) further contain crosslinking agent.
The crosslinking agent with the functional group for example by reacting adherence resin (I-1a) being cross-linked to each other.
As crosslinking agent, such as toluene di-isocyanate(TDI), hexamethylene diisocyanate, phenylenedimethylidyne two can be enumerated
The isocyanates crosslinking agent such as addition product (crosslinking agent with isocyanate group) of isocyanates, these diisocyanate；Second
The epoxies such as glycol glycidyl ether crosslinking agent (crosslinking agent with glycidyl)；Six [1- (2- methyl) '-aziridinos]
The triazines cross-linkings agent such as triphosphoric acid triazine (Hexa [1- (2-methyl)-aziridinyl] triphosphatriazine) (tool
There is the crosslinking agent of '-aziridino)；The metal-chelatings species such as aluminium chelate compound crosslinking agent (crosslinking agent with metallo-chelate structure)；
Isocyanuric acid esters crosslinking agent (crosslinking agent with isocyanuric acid skeleton) etc..
From the cohesiveness for improving sticker to improve the point of the adhesion strength of adhering agent layer and be pointed out from what is be easy to get etc.
Hair, preferably crosslinking agent are isocyanates crosslinking agent.
Crosslinking agent contained by adhesion agent composition (I-1) can be only one kind, or it is two or more, be two kinds with
When upper, combination thereof 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 containing Photoepolymerizationinitiater initiater
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, such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin can be enumerated
The benzoins such as isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal
Close object；Acetophenone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone etc.
Acetophenone compound；Bis- (2,4,6- trimethylbenzoyls) phosphine oxides of phenyl, 2,4,6- trimethyl benzoyl diphenyl base oxygen
Change the acylphosphine oxides compounds such as phosphine；The sulphur compounds such as benzyl phenyl thioether, tetramethylthiuram monosulfide；1- hydroxy cyclohexylphenyls
The α -one alcoholic compounds such as base phenyl ketone；The azo-compounds such as azodiisobutyronitrile；The titanocenes compound such as titanocenes；Thioxanthones etc.
Thioxanthone compounds；Peroxide compound；The dione compounds such as biacetyl；Benzyl；Dibenzyl；Benzophenone；2,4- diethyls
Base thioxanthones；1,2- diphenyl methanes；2- hydroxy-2-methyls -1- [4- (1- methyl ethylenes) phenyl] acetone；2- chloroanthraquinones
Deng.
In addition, as the Photoepolymerizationinitiater initiater, such as the naphtoquinone compounds such as 1- chloroanthraquinones 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 and it is two or more, be
When two or more, combination thereof 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 can enumerate the response delay in 1 molecule with more than two carbonyls (- C (=O) -)
Agent.
Other additives contained by adhesion agent composition (I-1) can be only one kind, or and it is two or more, it is two
Kind or more when, combination thereof 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 contain solvent.Adhesion agent composition (I-1) is improved by containing solvent to applying
The coating adaptive of cloth subject surface.
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, dioxanes；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 will manufacture adherence resin (I-1a) solvent that uses from adherence resin
(I-1a) it is removed in and is directly used in adhesion agent composition (I-1), can also in addition added when manufacturing adhesion agent composition (I-1)
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 and it is two or more, it is two or more
When, combination thereof 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 compositions (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)]
The adherence resin (I-2a) for example contains insatiable hunger by make to have energy-ray polymerism unsaturated group
It is obtained with the functional group reactions in adherence resin (I-1a) with the compound of group.
The compound containing unsaturated group is other than with energy-ray polymerism unsaturated group, into one
Walk the base that has and can be bonded with adherence resin (I-1a) by being reacted with the functional group in adherence resin (I-1a)
The compound of group.
As the energy-ray polymerism unsaturated group, such as can to enumerate (methyl) acryloyl group, vinyl (secondary
Ethyl), allyl (2- acrylic) etc., preferably (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, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-2), relative to the gross mass of adhesion agent composition (I-2), adherence resin (I-
Content 2a) is preferably 5~99 mass %, more preferably 10~95 mass %, particularly preferably 10~90 mass %.
[crosslinking agent]
For example, will be identical with adherence resin (I-1a), with the structural unit for carrying out self-contained monomer
When the acrylic polymer is used as adherence resin (I-2a), preferred adhesive compositions (I-2) further contain 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 it is two or more, be two kinds with
When upper, combination thereof 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 0.01~25 mass parts, more preferably 0.05~20 mass parts, particularly preferably 0.1~15 mass parts.
[Photoepolymerizationinitiater initiater]
Adhesion agent composition (I-2) can also further contain Photoepolymerizationinitiater initiater.Even if to containing Photoepolymerizationinitiater initiater
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 and it is two or more, be
When two or more, combination thereof 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 and it is two or more, it is two
Kind or more when, combination thereof 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 and it is two or more, it is two or more
When, combination thereof 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 compositions (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), relative to the gross mass of adhesion agent composition (I-3), adherence resin (I-
Content 2a) is preferably 5~99 mass %, more preferably 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 can be enumerated by the cured monomer of the irradiation of energy-ray or oligomer
Energy ray-curable compound identical with the energy ray-curable compound contained by adhesion agent composition (I-1).
The energy ray-curable compound contained by adhesion agent composition (I-3) can be only one kind, can also
It is two or more, when being two or more, combination thereof 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 containing Photoepolymerizationinitiater initiater
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 and it is two or more, be
When two or more, combination thereof 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
The content of 100 mass parts of total content of object, Photoepolymerizationinitiater initiater is 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 and it is two or more, it is two
Kind or more when, combination thereof 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 and it is two or more, it is two or more
When, combination thereof 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 >s 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, can be equally used for combining except these three stickers as their substance being illustrated containing ingredient
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, such as can enumerate containing acrylic resin, amino
Formate ester resin, rubber resin, organic silicon resin, epoxylite, polyvinylether, makrolon, esters resin etc.
The adhesion agent composition (I-4) of the adherence resin (I-1a) of non-energy ray-curable, preferably comprises acrylic resin
The adhesion agent composition of non-energy ray-curable.
It is preferred that the adhesion agent composition in addition to adhesion agent composition (I-1)~(I-3) contains one or more
Crosslinking agent, can be by the setting of its content identical as the situation of above-mentioned adhesion agent composition (I-1) etc..
< adhesion agent compositions (I-4) >
As preferred adhesion agent composition (I-4), such as can enumerate containing the adherence resin (I-1a) and friendship
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, combination thereof and ratio can be selected arbitrarily.
In adhesion agent composition (I-4), relative to the gross mass of adhesion agent composition (I-4), adherence resin (I-
Content 1a) is preferably 5~99 mass %, more preferably 10~95 mass %, particularly preferably 15~90 mass %.
[crosslinking agent]
It will be other than there is the structural unit for coming from (methyl) alkyl acrylate, further with next self-contained functional group
When the acrylic polymer of the structural unit of monomer is used as adherence resin (I-1a), preferred adhesive compositions (I-
4) further contain 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 it is two or more, be two kinds with
When upper, combination thereof 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 and it is two or more, it is two
Kind or more when, combination thereof 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 and it is two or more, it is two or more
When, combination thereof 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 the protective film formation composite sheet of the present 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 makes protective film formation film cure, nothing
Method inhibits to cure while adhering agent layer.If adhering agent layer cures simultaneously with protective film formation film, after solidification can be caused
The attaching for the degree that cannot be removed occurs on their interface for protective film formation film and adhering agent layer.At this time, it is difficult to
By the back side have solidification after protective film formation film, 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 curing, lead to not normally pick up
Semiconductor chip with protective film.It can by making adhering agent layer be non-energy ray-curable for the support chip of the present invention
Definitely avoid such undesirable condition, is capable 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, even if support chip with
The protective film formation layer that the layer that film is in direct contact is in addition to adhering agent layer, as long as the layer is non-energy ray-curable, then
Play same effect.
The preparation method > > of < < adhesion agent compositions
Adhesion agent composition (I-1)~(I-3) or adhesion agent composition (I-4) etc. except adhesion agent composition (I-1)~
(I-3) adhesion agent composition other than can be by blending the sticker and the ingredient in addition to the sticker as needed
It is obtained Deng for constituting each ingredient of adhesion agent composition.
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 by mixing solvent with the arbitrary blending ingredient in addition to solvent when using solvent
Dilution, can not also be by the arbitrary blending ingredient pre-dilution in addition to solvent and by by solvent and these to be used
Ingredient mixing is blended to be used.
The method that each ingredient is mixed when blending is not particularly limited, and 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, then the temperature and time when adding and mix each ingredient are not particularly limited,
Suitably adjust, preferable temperature is 15~30 DEG C.
◎ protective film formation films
In the present invention, the adhesion strength obtained from protective film formation being cured with film between protective film and support chip is
100~2000mN/25mm, more preferably 300~1900mN/25mm.By making the adhesion strength be the lower limiting value or more, use
When cutter cut semiconductor crystal wafer together with protective film, the stripping of protective film and support chip is can inhibit, such as can inhibit the back of the body
The semiconductor chip (semiconductor chip with protective film) that face has protective film disperses from support chip, can prevent cutting water from oozing
Thoroughly between protective film and support chip.In addition, by making the adhesion strength for the upper limit value hereinafter, the half of pick-up tape protective film
When conductor chip, the cracking and defect of semiconductor chip can inhibit.By this method, by making the adhesion strength in specific range
Interior, protective film formation composite sheet has good cutting adaptive and pickup adaptive.
In addition, in the present invention, even if after protective film formation film cures, 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
Formation 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, after irradiation energy ray makes protective film formation film cure to form protective film, with peeling rate
300mm/min removes support chip from the protective film being attached on adherend.Stripping at this time is set as so-called 180 °
Stripping, wherein by support chip along its length in a manner of making the face that protective film and support chip contact with each other be in each other 180 ° of angle
Spend direction (length direction of protective film formation composite sheet) stripping.Then, the load (peeling force) when this 180 ° strippings is measured,
And using its measured value 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, preferably 100~300mm.In addition, when measuring, it is to be attached to preferably to make protective film formation composite sheet
State on adherend, and make 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 can
Think 80mN/25mm with first-class, preferably 100mN/25mm or more, more preferably 150mN/25mm or more, particularly preferably
200mN/25mm or more.By making the adhesion strength be 100mN/25mm or more, being easy to will be viscous between protective film and support chip
Put forth effort to be adjusted to above range.
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,
Such as can be any one of 10000mN/25mm, 5000mN/25mm, 3000mN/25mm etc..But these are one
Example.
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 adhesion strength between protective film formation film and support chip can utilize the adhesion between above-mentioned protective film and support chip
The identical method of power is measured.
For example, can be protected by the setting in the type containing ingredient and amount, support chip of adjusting protective film formation film
The constituent material of the layer of film formation film and the surface state of this layer etc. come suitably adjust above-mentioned protective film and support chip it
Between adhesion strength and protective film formation film and support chip between adhesion strength.
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, constituent material
It can suitably be adjusted by the type containing ingredient and amount to adhering agent layer are adjusted.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.Moreover, passing through
Adhesion agent composition is adjusted containing in ingredient, such as adherence resin type and content, it can be more easily
Adjust the adhesion strength between protective film or protective film formation film and support chip (adhering agent layer).
On the other hand, when the layer for being provided with protective film formation film in support chip is base material, protective film or protective film
Adhesion strength between formation film and support chip, except through base material constituent material be adjusted other than, can also pass through base material
Surface state be adjusted.Moreover, the surface state of base material for example can improve base material and other layers by implementing to be used as
The surface treatment of adherence and in following processing for hereinbefore enumerating any one and be adjusted：At sandblasting
The further provided for contouring processing of reason, solvent processing etc.；Corona discharge Treatment, electron beam treatment with irradiation, corona treatment, ozone 〃 are ultraviolet
The oxidation processes such as line treatment with irradiation, flame treatment, chromic acid processing, hot wind processing；Prime treatment etc..
Protective film formation has energy ray-curable with film, such as can enumerate containing energy ray-curable ingredient
(a) protective film formation film.
Preferred energy ray-curable ingredient (a) is uncured, preferably its with adherence, more preferably its is uncured and has
Adherence.
Protective film formation film can be one layer (single layer), or two layers or more of multiple layers, when being multiple layers, this
A little 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.
Thickness by making protective film formation film is the lower limiting value or more, can form the higher protective film of protective capability.In addition,
Become excessive thickness hereinafter, can inhibit thickness by making the thickness of protective film formation film be the upper limit value.
Herein, " thickness of protective film formation film " refers to the thickness of protective film formation film entirety, such as by multiple layers
The thickness of the protective film formation film of composition refers to the thickness of the total for all layers for constituting protective film formation film.In addition,
The assay method of thickness as protective film formation film, such as can enumerate using contact thickness gauge in arbitrary five positions
Measurement thickness is set, and calculates the average method etc. of measured value.
As long as protective film become fully play its function degree curing degree, then make protective film formation film solidification from
And condition of cure when forming protective film is not particularly limited, and according to the type of protective film formation film suitably select i.e.
It can.
For example, the illumination of energy-ray when solidification 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 films, which are 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 and is dried as needed, energy with composition
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 can be enumerated 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
It when the solvent stated, is preferably 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 films, which are 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) be by the cured ingredient of the irradiation of 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 made of its at least part is crosslinked by aftermentioned crosslinking agent (f)
Substance, or uncrosslinked substance.
In addition, in the present specification, unless otherwise indicated, weight average molecular weight refers to utilizing 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 can with the acrylic polymer (a11) for the functional group that group react 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 without 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, such as (methyl) acrylate, (methyl) acrylic acid 2- hydroxyls can be enumerated
Ethyl ester, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (first
Base) (methyl) hydroxyalkyl acrylates such as acrylic acid 3- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls；Vinyl alcohol, alkene
Non- (methyl) acrylic compounds unsaturated alcohol such as propyl alcohol (unsaturated alcohol for not having (methyl) acryloyl group skeleton) etc..
As the carboxyl group-containing monomer, such as the olefinics unsaturation unitary carboxylic such as can enumerate (methyl) acrylic acid, crotonic acid
Acid (monocarboxylic acid with ethylenic unsaturated bond)；The ethylenically unsaturated dicarboxylics such as fumaric acid, itaconic acid, maleic acid, citraconic acid
(dicarboxylic acids with ethylenic unsaturated bond)；The acid anhydrides of the ethylenically unsaturated dicarboxylic；Methacrylic acid 2- carboxyethyls 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 two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
As the acrylic monomer without the functional group, such as (methyl) methyl acrylate, (first can be enumerated
Base) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl)
Isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) third
The own ester of olefin(e) acid, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) third
Olefin(e) acid n-octyl, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) propylene
Sour hendecane base ester, (methyl) dodecylacrylate ((methyl) lauryl acrylate), (methyl) acrylic acid tridecyl
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) acrylic acid 18
Arrcostab ((methyl) stearyl acrylate acid esters) etc., composition Arrcostab alkyl is the chain structure that carbon atom number is 1~18
(methyl) alkyl acrylate etc..
In addition, as the acrylic monomer without the functional group, such as can also enumerate (methyl) acrylic acid first
Oxygroup methyl esters, (methyl) methoxyethyl acrylate, (methyl) ethioxy methyl esters, (methyl) ethoxyethyl acrylate
Deng (methyl) acrylate containing alkoxyalkyl；Including (methyl) phenyl acrylate etc. (methyl) benzyl acrylate etc.,
(methyl) acrylate with aromatic group；(methyl) acrylamide and its derivative of non-crosslinked property；(methyl) propylene
Sour N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester etc. have the tertiary amino of non-crosslinked property
(methyl) acrylate etc..
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, combination thereof 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
Two or more, when being two or more, combination thereof 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 ratio be such range, pass through described third
Alkene acids polymers (a11) and the acrylic compounds tree obtained from the copolymerization of 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 fat (a1-1)
Range.
The acrylic polymer (a11) for constituting the acrylic resin (a1-1) can be only one kind, also may be used
Think it is two or more, for it is two or more when, combination thereof and ratio can be selected arbitrarily.
In the protective film formation in composition (IV-1), relative to protective film formation total matter of composition (IV-1)
Amount, the content of acrylic resin (a1-1) is preferably 1~40 mass %, more preferably 2~30 mass %, and particularly preferably 3
~20 mass %.
〃 energy ray-curables 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), such as 2- methylacryoyloxyethyl isocyanides can be enumerated
Acid esters, isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate, methacryloyl isocyanate, allyl iso cyanurate, 1,
1- (double acryloyloxymethyls) ethyl isocyanate；
By diisocyanate cpd or polyisocyanate compounds are with (methyl) reacting for 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 two or more, when being two or more, combination thereof 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 %, and when the energy ray-curable compound (a12) be it is multifunctional (in 1 molecule have 2
A above group) 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 any for being not belonging in the above-mentioned monomer illustrated as the monomer for constituting the acrylic polymer (a11)
It person and is copolymerized with the monomer of group reacted with crosslinking agent (f), and at the group reacted with the crosslinking agent (f)
Polymer made of being crosslinked can also be in from the energy ray-curable compound (a12) and the function
Polymer made of being crosslinked at the group of group's reaction.
The polymer (a1) contained by protective film formation composition (IV-1) and protective film formation film can be only
For one kind, or two or more, when being two or more, combination thereof 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 for including energy ray-curable double bond can be enumerated, as preferred group, can be enumerated
(methyl) acryloyl group, vinyl etc..
The compound (a2) is not particularly limited as long as meeting above-mentioned condition, can enumerate with energy ray curing
The low molecular weight compound of property group, the epoxy resin with energy ray-curable group, with energy ray-curable base
The phenol resin etc. of 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., the preferably acrylic ester compound with (methyl) acryloyl group.
As the acrylic ester compound, such as 2- hydroxyls -3- (methyl) acryloxypropyl first can be enumerated
Base acrylate, polyethylene glycol two (methyl) acrylate, propoxylation Ethoxylated bisphenol A bis- (methyl) acrylate, 2,
Bis- [4- ((methyl) acryloxy polyethoxy) phenyl] propane of 2-, Ethoxylated bisphenol A bis- (methyl) acrylate, 2,2-
Bis- [4- ((methyl) acryloxy diethoxy) phenyl] propane, the bis- [4- (2- (methyl) acryloyloxyethoxy) of 9,9-
Phenyl] fluorenes, bis- [4- (the poly- propoxyl group of (methyl) acryloxy) phenyl] propane of 2,2-, Tricyclodecane Dimethanol two (methyl) third
Olefin(e) acid ester (tristane dihydroxymethyl two (methyl) acrylate), 1,10- decanediols two (methyl) acrylate, 1,6- oneself two
Alcohol two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, 3 the third two
Alcohol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate, ethylene glycol two
(methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, the bis- [4- of 2,2-
((methyl) acryloyloxyethoxy) phenyl] propane, neopentyl glycol two (methyl) acrylate, ethoxylated polypropylene glycol two
Difunctionalities (methyl) acrylate such as (methyl) acrylate, 2- hydroxyls -1,3- two (methyl) acryloxy propane；
Three (2- (methyl) acrylyl oxy-ethyl) isocyanuric acid esters, 6-caprolactone are modified three (2- (methyl) acryloyl-oxy second
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)
Described in phenol resin, such as paragraph 0043 that " Japanese Unexamined Patent Publication 2013-194102 bulletins " can be used of the property changed group etc.
Resin.Such resin also corresponds to constitute the resin of aftermentioned thermosetting component (h), but describedization is regarded as in the present invention
Close object (a2).
The weight average molecular weight of the compound (a2) is preferably 100~30000, and more preferably 300~10000.
The compound (a2) contained by protective film formation composition (IV-1) and protective film formation film can be only
For one kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
[polymer (b) for not having 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 that at least part is crosslinked substance made of agent (f) crosslinking, or uncrosslinked
Substance.
As the polymer (b) without 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, 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 of composition acrylic polymer (b-1), such as (methyl) propylene can be enumerated
Acid alkyl ester, (methyl) acrylate with cyclic skeleton, (methyl) acrylate containing glycidyl, hydroxyl
(methyl) acrylate, (methyl) acrylate etc. containing substituted-amino.Herein, " substituted-amino " and the phase being illustrated above
Together.
As (methyl) alkyl acrylate, such as (methyl) methyl acrylate, (methyl) acrylic acid can be enumerated
Ethyl ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid are different
Butyl ester, (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) acrylic acid are just pungent
Ester, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (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 pentadecane base ester, (methyl) acrylic acid ten
Six Arrcostabs ((methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester, (methyl) octadecyl acrylate
((methyl) stearyl acrylate acid esters) etc., constitute Arrcostab alkyl be the chain structure that carbon atom number is 1~18 (first
Base) alkyl acrylate etc..
As described (methyl) acrylate with cyclic skeleton, such as (methyl) isobomyl acrylate can be enumerated
(methyl) the acrylate base esters such as ester, (methyl) acrylic acid bicyclopentyl ester；
(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, such as (methyl) acrylate, (methyl) can be enumerated
Acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2-
Hydroxybutyl, (methyl) acrylic acid 3- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls etc..
As described (methyl) acrylate containing substituted-amino, such as (methyl) acrylic acid N- methylaminos 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 at least partially, agent (f) is crosslinked, the polymer without energy ray-curable group
(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, for the corrosion this point of circuit with regard to preventing semiconductor crystal wafer or semiconductor chip, the preferably described functional group is
Group in addition to carboxyl.
As the polymer (b) with the reactive functional groups and without energy ray-curable group, such as can
Enumerate polymer obtained from at least monomer polymerization with the reactive functional groups of sening as an envoy to.For acrylic polymer
(b-1) it when, is arranged using the monomer with the reactive functional groups 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 it can enumerate (methyl) acrylic ester polymerization of hydroxyl and obtain
The polymer arrived can enumerate the acrylic monomer that will hereinbefore enumerate or non-acrylic monomer in addition to this
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 make the ratio be such range, in the polymer (b), crosslinked degree 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 it is with composition (IV-1) and contained by protective film is formationed film, without energy ray-curable
The polymer (b) of group can be only one kind, or two or more, when being two or more, combination thereof 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 composition.Moreover, when containing the compound (a2), preferably protect
Cuticula is formed further contains the polymer (b) without energy ray-curable group with composition (IV-1), at this point, also excellent
Choosing further contains (a1).In addition, protective film formation composition (IV-1) can not also contain the compound (a2)
And contain the polymer (a1) and the polymer (b) without energy ray-curable group simultaneously.
When protective film formation composition (IV-1) containing the polymer (a1), the compound (a2) and does not have energy
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 the 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, the energy ray-curable ingredient of protective film formation 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
It is such range to make the ratio of total content, and 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 is penetrated without energy
When the polymer (b) of line curative group, in protective film formation composition (IV-1) and protective film formation film, relative to
The content of 100 mass parts of content of energy ray-curable ingredient (a), the polymer (b) is preferably 3~160 mass parts, more
Preferably 6~130 mass parts.By making the content of the polymer (b) be such range, protective film formation film
Energy ray-curable becomes more good.
In addition to contain energy ray-curable ingredient (a) and polymer (b) without energy ray-curable group with
Outside, protective film formation composition (IV-1) can also be according to purpose and containing selected from by Photoepolymerizationinitiater initiater (c), packing material
(d), in the group of coupling agent (e), crosslinking agent (f), colorant (g), Thermocurable ingredient (h) and universal additive (z) composition
It is one or more kinds of.For example, by using containing the energy ray-curable ingredient (a) and Thermocurable ingredient (h)
Protective film, which is formed, uses composition (IV-1), is formed by protective film formation film and is improved because of heating to the bonding force of adherend,
The protection film strength formed with film by the protective film formation is also improved.
[Photoepolymerizationinitiater initiater (c)]
As Photoepolymerizationinitiater initiater (c), such as can to enumerate benzoin, benzoin methylether, benzoin ethyl ether, benzoin different
The benzoins chemical combination such as propyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzoin dimethyl ketal
Object；The benzene such as acetophenone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone
Ethanone compounds；Bis- (2,4,6- trimethylbenzoyls) phosphine oxides of phenyl, the oxidation of 2,4,6- trimethyl benzoyl diphenyl bases
The acylphosphine oxides compound such as phosphine；The sulphur compounds such as benzyl phenyl thioether, tetramethylthiuram monosulfide；1- hydroxy-cyclohexyls
The α -one alcoholic compounds such as phenyl ketone；The azo-compounds such as azodiisobutyronitrile；The titanocenes compound such as titanocenes；The thiophenes such as thioxanthones
Ton ketone compound；Benzophenone, 2- (dimethylamino) -1- (4- morpholinyl phenyls) -2- benzyl -1- butanone, 1- [9- ethyls -6-
(2- methyl benzoyls) -9H- carbazole -3- bases] benzophenone cpds such as ethyl ketone 1- (O- acetyl oxime)；Peroxide chemical combination
Object；The dione compounds such as biacetyl；Benzyl；Dibenzyl；2,4- diethyl thioxanthones；1,2- diphenyl methanes；2- hydroxyl -2- first
Base -1- [4- (1- methyl ethylenes) phenyl] acetone；2- chloroanthraquinones etc..
In addition, as Photoepolymerizationinitiater initiater (c), such as the naphtoquinone compounds such as 1- chloroanthraquinones also can be used；Photosensitizers such as amine etc..
Photoepolymerizationinitiater initiater (c) contained by protective film formation composition (IV-1) can be only one kind, or
Two or more, when being two or more, combination thereof 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 cured with film and is protected obtained from
The adjustment of the coefficient of thermal expansion of cuticula becomes easy, by keeping the coefficient of thermal expansion most suitable relative to the formation object of protective film
Change, the reliability encapsulated obtained from composite sheet using protective film formation is further enhanced.In addition, by making protective film
Formation film contains packing material (d), can reduce the hydroscopicity of protective film, or can improve 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
Surface be modified product；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, preferably 0.01~20 μm, more preferably 0.1~15 μm,
Particularly preferably 0.3~10 μm.Average grain diameter by making packing material (d) is such range, is able to maintain that protective film
Formation object adhesiveness and inhibit simultaneously protective film light transmitance reduction.
In addition, unless otherwise indicated, " average grain diameter " in this specification refers to being acquired using laser diffraction scattering method
In size distribution curve, accumulated value is the value of the grain size (D50) at 50%.
Packing material (d) contained by protective film formation composition (IV-1) and protective film formation film can be only one
Kind, or two or more, when being two or more, combination thereof 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
The content of the packing material (d) of cuticula formation 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 content of packing material (d) be such range
The adjustment of coefficient of thermal expansion becomes easier to.
[coupling agent (e)]
By using with can be with the substance of the functional group of inorganic compound or organic compound reaction as coupling agent
(e), adhesiveness and adherence of the protective film formation film to adherend can be improved.In addition, by using coupling agent (e), it will
Protective film improves water resistance in the state of not damaging heat resistance obtained from protective film formation is cured with film.
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, such as 3- glycydoxy trimethoxy silicon can be enumerated
Alkane, 3- glycydoxies methyldiethoxysilane, 3- glycidyl ether oxypropyltriethoxysilanes, 3- contractings
Water glycerin ether oxygroup methyldiethoxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- methacryls
Oxygroup propyl trimethoxy silicane, 3- TSL 8330s, 3- (2- aminoethylaminos) propyl trimethoxy silicon
Alkane, 3- (2- aminoethylaminos) hydroxypropyl methyl diethoxy silane, 3- (phenyl amino) propyl trimethoxy silicane, 3- aniline
Base propyl trimethoxy silicane, 3- ureas propyl-triethoxysilicane, 3- mercaptopropyl trimethoxysilanes, 3- mercapto hydroxypropyl methyl diformazans
Oxysilane, bis- (3- triethoxy silicon substrates propyl) tetrasulfides, methyltrimethoxysilane, methyltriethoxysilane, second
Alkenyl trimethoxy silane, vinyltriacetoxy silane, imidizole silane etc..
Coupling agent (e) contained by protective film formation composition (IV-1) and protective film formation film can be only one
Kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
When using coupling agent (e), in protective film formation composition (IV-1) and protective film formation 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.The content by making coupling agent (e) is the lower limiting value or more, can significantly more obtain packing material (d) 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 make the content of coupling agent (e) be the upper limit value 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 without 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, such as aromatic polyisocyanate compound, fat can be enumerated
Race's polyisocyanate compound and alicyclic polyisocyanates compound by these compounds (hereinafter, uniformly write a Chinese character in simplified form work " virtue sometimes
Fragrant race's polyisocyanate compound etc. ")；The tripolymer of the aromatic polyisocyanate compound etc., isocyanuric acid ester body and
Addition product；Terminal isocyanate ammonia obtained from making described aromatic polyisocyanate compound etc. be reacted with polyol compound
Carbamate prepolymer etc.." addition product " refers to the aromatic polyisocyanate compound, aliphatic polyisocyante
Compound or alicyclic polyisocyanates compound and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil etc.
The reactant of low molecule active hydrogen-contg compound can enumerate the benzene two of trimethylolpropane as described later as its example
Methylene diisocyanate addition product etc..In addition, " terminal isocyanate carbamate prepolymer " refers to carbamic acid
Ester bond and the terminal part of molecule have isocyanate group prepolymer.
As the organic polyisocyanate compound, more specifically, such as 2,4- toluene diisocynates can be enumerated
Ester；2,6- toluene di-isocyanate(TDI)s；1,3- benzene dimethylene diisocyanate；1,4- benzene dimethylene diisocyanate；Hexichol
Methylmethane -4,4 '-diisocyanate；Diphenyl methane -2,4 '-diisocyanate；3- Dimethyl diphenylmethane diisocyanate；
Hexamethylene diisocyanate；Isophorone diisocyanate；Dicyclohexyl methyl hydride -4,4 '-diisocyanate；Dicyclohexyl first
Alkane -2,4 '-diisocyanate；Addition has toluene diisocyanate on all or part of hydroxyl of the polyalcohols such as trimethylolpropane
In acid esters, hexamethylene diisocyanate and benzene dimethylene diisocyanate any one or it is two or more made of chemical combination
Object；Lysine diisocyanate etc..
As the organic multicomponent group with imine moiety, such as N can be enumerated, diphenyl methane -4 N ' -, 4 '-bis- (1- nitrogen third
Pyridine formamide) ,-three-β of trimethylolpropane-'-aziridino propionic ester ,-three-β of tetramethylol methane-'-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, can cross-linked structure simply be imported into protective film formation film.
Crosslinking agent (f) contained by protective film formation composition (IV-1) and protective film formation film can be only one
Kind, or two or more, when being two or more, combination thereof 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 the 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 limiting value or more, can significantly more obtain by using crosslinking agent (f) and the effect that generates.In addition,
By make crosslinking agent (f) the content be the upper limit value 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, such as amine can be enumerated(aminium) class pigment, cyanine class
Pigment, merocyanine class pigment, crocic acid (croconium) class pigment, sour cyanines (squarylium) the class pigment in side, azulene
(azulenium) class pigment, polymethine class pigment, naphthalene Quinone Pigments, pyran 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 (metal complex salt dyestuff), dithiol metal complexing
Species pigment, indoles phenol sulfonate, triallyl methane class pigment, anthraquinone pigments, aphthols pigment, azomethine class pigment,
Benzimidazole ketone pigment, pyranthrone pigment and intellectual circle (threne) class pigment etc..
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) classes pigment, ATO (oxidations
Antimony tin) class pigment etc..
Colorant (g) contained by protective film formation composition (IV-1) and protective film formation film can be only one
Kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
When using colorant (g), the content that protective film forms the colorant (g) of film according to purpose suitably adjust i.e.
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 of colorant (g) (i.e. the content of the colorant (g) of protective film formation film) 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 %.The content by making colorant (g) is the lower limiting value or more, can significantly more be obtained logical
Cross the effect generated using colorant (g).In addition, by make colorant (g) the content be the upper limit value hereinafter, can
Inhibit being excessively used for colorant (g).
[Thermocurable ingredient (h)]
Thermocurable ingredient (h) contained by protective film formation composition (IV-1) and protective film formation film can be only
For one kind, or two or more, when being two or more, combination thereof 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).
Epoxies heat-curing resin contained by protective film formation composition (IV-1) and protective film formation film can
To be only one kind, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
Epoxy resin (h1)
As epoxy resin (h1), well known epoxy resin can be enumerated, for example, 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 without unsaturated alkyl
Epoxy resin is compared, and the compatibility of epoxy resin and acrylic resin with unsaturated alkyl is high.Therefore, by using tool
The epoxy resin for having unsaturated alkyl, the reliability encapsulated obtained from composite sheet using protective film formation are improved.
As the epoxy resin with unsaturated alkyl, for example, can enumerate multifunctional based epoxy resin epoxy group one
Partial Transformation is at compound made of the group with unsaturated alkyl.Such compound for example can be by making (methyl) propylene
Acid or derivatives thereof 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 can enumerate ethylidine (ethylene as its concrete example
Base), 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, curability, Yi Jibao from protective film formation film
The point of shield film strength and heat resistance sets out, preferably 300~30000, more preferably 400~10000, particularly preferably 500
~3000.
In the present specification, unless otherwise indicated, " number-average molecular weight " refers to be surveyed using gel permeation chromatography (GPC) method
Fixed standard polystyren scaled value and the number-average molecular weight indicated.
The epoxide equivalent of epoxy resin (h1) is preferably 100~1000g/eq, more preferably 150~800g/eq.
In the present specification, " epoxide equivalent " refers to the grams (g/ of the epoxide comprising 1 gram equivalent of epoxy group
It eq), can be according to JIS K 7236:2001 method is measured.
Epoxy resin (h1) can be used alone, can also use simultaneously it is two or more, while using two or more
When, combination thereof 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 group made of change etc., preferably 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
Fat, '-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.
As the thermal curing agents (h2) with unsaturated alkyl, for example, can enumerate phenol resin hydroxyl a part through tool
Compound made of having the group of unsaturated alkyl to replace, Direct Bonding has unsaturated alkyl on the aromatic rings of phenol resin
Compound obtained from group 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), the pointing out from the fissility of support chip from raising protective film
Hair, thermal curing agents (h2) are preferably 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 fat, 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 use simultaneously it is two or more, while using two or more
When, combination thereof and ratio can be selected arbitrarily.
When using Thermocurable ingredient (h), in protective film formation composition (IV-1) and protective film formation 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), in protective film formation composition (IV-1) and protective film formation film, phase
For 100 mass parts of content of the polymer (b) without 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.
[universal additive (z)]
Universal additive (z) can be well known additive, can arbitrarily be selected, be not particularly limited according to purpose, as
Preferred additive, such as plasticizer, antistatic agent, antioxidant, capturing agent (gettering agent) can be enumerated etc..
Universal additive (z) contained by protective film formation composition (IV-1) and protective film formation film can be only
It is a kind of, or two or more, when being two or more, combination thereof and ratio can be selected arbitrarily.
When using universal additive (z), general the adding of protective film formation composition (IV-1) and protective film formation film
Add the content of agent (z) to be not particularly limited, according to purpose suitably select.
[solvent]
Protective film formation composition (IV-1) preferably further contains solvent.Protective film formation combination containing solvent
The operability of object (IV-1) becomes good.
The solvent is not particularly limited, and as preferred solvent, such as can enumerate the hydrocarbon such as toluene, dimethylbenzene；Methanol,
The alcohol such as ethyl alcohol, 2- propyl alcohol, isobutanol (2- methylpropane -1- alcohol), n-butyl alcohol；The esters such as ethyl acetate；Acetone, methyl ethyl ketone etc.
Ketone；The ethers such as tetrahydrofuran；Amides such as dimethylformamide, N-Methyl pyrrolidone (compound with amido bond) etc..
Solvent contained by protective film formation composition (IV-1) can be only one kind, or and it is two or more, be
When two or more, combination thereof 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),.
The preparation method > > of < < protective film formation compositions
The protective films formation such as protective film formation composition (IV-1) composition can be by blending for constituting its
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 by mixing solvent with the arbitrary blending ingredient in addition to solvent when using solvent
Dilution, can not also be by the arbitrary blending ingredient pre-dilution in addition to solvent and by by solvent and these to be used
Ingredient mixing is blended to be used.
The method that each ingredient is mixed when blending is not particularly limited, and 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, then the temperature and time when adding and mix each ingredient are not particularly limited,
Suitably adjust, preferable temperature is 15~30 DEG C.
As with the present invention protective film formation composite sheet it is identical, 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).
It is picked up from support chip together with semiconductor chip however, the adhesive phase that has of chip joint fastener will be cut
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, with regard to by its with together with semiconductor chip from support chip pick up this point for, it is of the invention
Protective film formation film in protective film formation composite sheet is 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, the present invention protective film formation film with cut
The purposes for cutting the adhesive phase in chip joint fastener is different, and the performance sought is certainly also different.Moreover, in general, with cutting core
Adhesive phase in chip bonding piece is compared, and protective film formation film has hard and is difficult to the tendency picked up, on this has also reflected
The difference for the purposes stated.It is therefore often difficult to which the adhesive phase cut in chip joint fastener directly conversion is formed as protective film
With the protective film formation film in composite sheet.As the composite sheet for the protective film formation film for having energy ray-curable, originally
The protective film formation composite sheet of invention is that the pickup adaptive of semiconductor chip in the past no, with protective film is extremely excellent
Protective film formation composite sheet.
In the form of the present invention, protective film formation of the invention has the adhesion containing following substances with composite sheet
Oxidant layer：By 2-EHA (31~41 mass parts, preferably 36 mass parts), butyl acrylate (54~64 mass parts,
Preferably 59 mass parts) and acrylic acid 2- hydroxy methacrylates (3~7 mass parts, preferably 5 mass parts) copolymerization made of acrylic acid
Type of Collective object (weight average molecular weight：600000) (90~110 mass parts, preferably 100 mass parts)；And trifunctional phenylenedimethylidyne
Diisocyanates crosslinking agent (10.0~11.4 mass parts, preferably 10.7 mass parts).
In addition, in the form of the present invention, protective film formation composite sheet of the invention, which has, contains following substances
Adhering agent layer：By butyl acrylate (90~100 mass parts, preferably 95 mass parts) and acrylic acid 2- hydroxy methacrylates (3~7
Mass parts, preferably 5 mass parts) copolymerization made of acrylic polymer (weight average molecular weight：800000) (90~110 mass
Part, preferably 100 mass parts)；And trifunctional benzene dimethylene diisocyanate class crosslinking agent (0.3~0.7 mass parts, preferably
For 0.5 mass parts).
In addition, in the form of the present invention, protective film formation composite sheet of the invention, which has, contains following substances
Adhering agent layer：Make 2-EHA (50~70 mass parts, preferably 60 mass parts), methyl acrylate (20~40
Mass parts, preferably 30 mass parts) and acrylic acid 2- hydroxy methacrylates (8~12 mass parts, preferably 10 mass parts) be copolymerized
Acrylic polymer and 2- methylacryoyloxyethyls isocyanates (in 2- methylacryoyloxyethyl isocyanates
The total mole number of isocyanate group is relative to the hydroxyl from acrylic acid 2- hydroxy methacrylates in the acrylic copolymer
Total mole number is 0.8 times of amount) reacted obtained from, side chain there is the energy ray-curable third of methacryloxy
Alkene acids polymers (weight average molecular weight：600000) (90~110 mass parts, preferably 100 mass parts)；Cause as photopolymerization
The 1- hydroxycyclohexylphenylketones (0.1~0.5 mass parts, preferably 0.3 mass parts) of agent；And the toluene two as crosslinking agent
Isocyanates crosslinking agent (0.1~0.3 mass parts, preferably 0.2 mass parts).
The manufacturing method of ◇ protective film formation composite sheets
Can by make above-mentioned each layer as corresponding position relationship in a manner of stack gradually above-mentioned each layer and make
Make the protective film formation composite sheet of the present invention.The forming method of each layer is identical as what is be illustrated above.
For example, when manufacture support chip, when adhering agent layer is laminated on base material, above-mentioned adhesion agent composition is coated on base
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 composition on adhering agent layer 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, is 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 advance shape on other stripping films
At the layer of the rear stacking in above-mentioned two layers, and by with the side contacted with the stripping film being opposite by the established layer
The exposed surface of side and the fitting of the exposed surface of another layer formed, form continuous two layers of stepped construction.At this point, it is preferred that will
The composition is coated on the lift-off processing face of stripping film.After forming stepped construction, stripping film is removed as needed.
For example, manufacture on base material be laminated adhering agent layer and on the adhering agent layer be laminated protective film formation film and
Obtained protective film formation is with composite sheet (support chip is the protective film formation composite sheet of the sandwich of base material and adhering agent layer)
When, by the way that adhesion agent composition is coated on base material and is dried as needed, sticker is thus laminated on base material
Thus layer, is in addition being removed by being coated on protective film formation on stripping film with composition and being dried as needed again
Protective film formation film is formed on film.Then, by by the exposed surface of the protective film formation film be laminated it is on base material
The exposed surface of adhering agent layer is bonded, and protective film formation is stacked in film layer on adhering agent layer, and protective film can be obtained and formed with multiple
Close piece.
In addition, when adhering agent layer is laminated on base material, as described above, on base material instead of adhesion agent composition to be coated with
Adhesion agent composition is coated on stripping film and is dried as needed, thus forms sticker on stripping film by method
Layer, and the exposed surface of this layer is bonded with the surface of the side of base material, thus adhering agent layer can be layered on base material.
In arbitrary method, the arbitrary opportunity after forming target stepped construction removes stripping film.
As noted previously, as stripping can be previously formed in by constituting the layer in addition to base material of protective film formation composite sheet
It on film, and 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 (such as protective film is formed with the most surface layer of support chip opposite side
With film) surface be fitted with the state of stripping film and taken care of.Therefore, though by protective film formation composition etc., be used for
The composition for forming the layer for constituting most surface layer is coated on stripping film (preferably its lift-off processing face), and is done as needed
It is dry, the layer for constituting most surface layer is thus formed on stripping film, and connect in this layer and same stripping film using above-mentioned arbitrary method
Tactile side is that stacking other each layers also may be used when holding does not remove and is bonded the state of stripping film in the exposed surface of opposite side
Obtain protective film formation composite sheet.
The application method of ◇ protective film formation composite sheets
The protective film formation of the present invention can for example be used with composite sheet using method as shown below.
That is, protective film formation composite sheet is made to pass through its protective film formation film to be attached at the back side of semiconductor crystal wafer
(face with electrode forming surface opposite side).Then, to protective film formation film irradiation energy ray, keep protective film formation film solid
Change to which protective film be made.Then, by cutting, semiconductor crystal wafer is divided together with protective film, semiconductor chip is made.So
Afterwards, to be pasted with the state (that is, as semiconductor chip with protective film) of the protective film, by semiconductor chip from support chip
It detaches 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 package body is made.Then, using the semiconductor package body, mesh is made
Mark semiconductor device.
Embodiment
Hereinafter, according to specific embodiment, the present invention will be described in more detail.But the present invention is not limited to
Embodiment described below.
The ingredient used in the manufacture of protective film formation composition described below.
Energy ray-curable ingredient
(a2)-1：Tristane dihydroxymethyl diacrylate be (manufacture of Nippon Kayaku Co., Ltd.s
" 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 second
Acrylic resin (weight average molecular weight 300000, vitrifying made of ester (hereinafter, writing a Chinese character in simplified form work " HEA ") (15 mass parts) copolymerization
- 1 DEG C of transition temperature).
Photoepolymerizationinitiater initiater
(c)-1：2- (dimethylamino) -1- (4- morpholinyl phenyls) -2- benzyl -1- butanone be (BASF AG's manufacture
" Irgacure (registered trademark) 369 ")
(c)-2：1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] ethyl ketone 1- (O- acetyl oxime) (BASF
" Irgacure (registered trademark) OXE02 " of company's manufacture)
〃 packing materials
(d)-1：Silica filler (vitreous silica filler, 8 μm of average grain diameter)
Coupling agent
(e)-1：3- methacryloxypropyl trimethoxy silanes (Shin-Etsu Chemical Co., Ltd. systems
" 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 mode of the total amount of three kinds of pigments/styrene acrylic resin amount=1/3 (mass ratio) carries out pigmentation and obtains
The pigment arrived.
[embodiment 1]
The manufacture > of < protective film formation composite sheets
(protective film forms the preparation with composition (IV-1))
Energy ray-curable ingredient (a2) -1 (20 mass parts), polymer (b) -1 (22 mass parts), photopolymerization are caused
Agent (c) -1 (0.3 mass parts), Photoepolymerizationinitiater initiater (c) -2 (0.3 mass parts), packing material (d) -1 (56 mass parts), coupling
Agent (e) -1 (0.4 mass parts) and colorant (g) -1 (2 mass parts) are dissolved or dispersed in methyl ethyl ketone, and in 23 DEG C into
Thus row stirring is prepared for the protective film formation composition (IV-1) that solid component concentration is 50 mass %.
(preparation of adhesion agent composition (I-4))
It is prepared for containing acrylic polymer (100 mass parts, solid constituent) and two isocyanide of trifunctional phenylenedimethylidyne
Esters of gallic acid crosslinking agent " the TAKENATE D110N " of manufacture (three fields Jing Wu chemical companies) (10.7 mass parts, solid constituent), simultaneously
Further contain methyl ethyl ketone as solvent, solid component concentration be 30 mass % non-energy ray-curable adhesion
Agent composition (I-4).The acrylic polymer is by 2-EHA (hereinafter, writing a Chinese character in simplified form work " 2EHA ") (36 matter
Measure part), BA (59 mass parts) and HEA (5 mass parts) copolymerization made of weight average molecular weight be 600000 acrylic
Object.
(manufacture of support chip)
Adhesion agent composition obtained above (I-4) is coated on using silicone-treated to polyethylene terephthalate
Stripping film obtained from the single side progress lift-off processing of film (" SP-PET381031 " of Lintec Corporation. manufactures,
38 μm of thickness) the lift-off processing face on, and in 120 DEG C of heat dryings 2 minutes, thus form the non-energy of 10 μm of thickness
The adhering agent layer of ray-curable.
Then, the adhering agent layer will be fitted in as the polypropylene film of base material (80 μm of Young's modulus 400MPa, thickness)
Exposed surface on, result in the support chip (10) -1 for having the adhering agent layer on the surface of the side of the base material.
(manufacture of protective film formation composite sheet)
Protective film formation obtained above is coated on composition (IV-1) using knife type coater and utilizes silicone-treated
Stripping film (Lintec obtained from lift-off processing is carried out to the single side of polyethylene terephthalate film
Corporation. 38 μm of " SP-PET381031 ", the thickness manufactured) the lift-off processing face on, and it is dry in 100 DEG C of heating
Dry 2 minutes, the protective film formation film (13) -1 of the energy ray-curable of 25 μm of thickness is thus made.
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 film (13) -1 in the exposed surface of the adhering agent layer, has been made base material, adhering agent layer, guarantor
Cuticula formed film (13) -1 and stripping film along their thickness direction stack gradually made of protective film formation composite sheet.It will
The composition of obtained protective film formation composite sheet is shown in table 1.
The evaluation > of < protective film formation composite sheets
(adhesion strength between protective film and support chip)
Protective film formation obtained above is cut into the size of 25mm × 140mm with composite sheet, by stripping film from protection
Film formation is removed in composite sheet, to make the surface of the side of protective film formation film (13) -1 expose, before having made solidification
Test film.On the other hand, prepared to be fitted with double-sided adhesive tape on the surface of the support plate (70mm × 150mm) of SUS
Support plate.Then, it will be tried before solidification using laminating machine (" the LAMIPACKER LPD3214 " of FUJI CORPORATION. manufactures)
The exposed surface for testing the protective film formation film (13) -1 of piece attaches on the double-sided adhesive tape on the supporting plate, thus via
Test film attaches on the supporting plate before double-sided adhesive tape will cure.
Then, using ultraviolet lamp (" RAD2000m/8 " of Lintec Corporation. manufactures), in illumination
195mW/cm2, light quantity 170mJ/cm2Under conditions of to before solidification test film irradiate ultraviolet light, thus make protective film formation film
(13) -1 solidifications, test film after being cured.
Then, using accurate universal testing machine " the AUTOGRAPH AG-IS " of manufacture (Shimadzu Corporation),
Under conditions of 180 ° of peel angle, 23 DEG C of measuring temperature, tensile speed 300mm/min, (cure into support chip (10) -1 is about to
The sandwich of adhering agent layer and base material afterwards) from make protective film formation cured with film (13) -1 after protective film on the stretching that peels
Experiment, measure load (peeling force) at this time, as make protective film formation film (13) -1 cure after protective film and support
Adhesion strength between piece (10) -1.Show the result in table 1.
(inhibition of silicon chip when cutting dispersed)
So that protective film formation composite sheet obtained above is passed through its protective film formation film (13) -1 and is attached to 6 inches of silicon
On the #2000 abradant surfaces of wafer (100 μm of thickness), the piece is further fixed on ring-shaped frame, and stood 30 minutes.
Then, using ultraviolet lamp (" RAD2000m/8 " of Lintec Corporation. manufactures), in illumination
195mW/cm2, light quantity 170mJ/cm2Under conditions of, protective film formation composite sheet is irradiated from (10) -1 side of support chip ultraviolet
Thus line cures protective film formation film (13) -1, has made protective film.
Then, using cutting blade, Silicon Wafer is sliced together with protective film, has obtained the silicon chip of 5mm × 5mm.This
When, whether visual confirmation silicon chip disperses from support chip, will by silicon chip is not determined as "○" the case where dispersing completely
Even have a small amount of silicon chip is determined as "×" the case where dispersing, have rated cutting adaptive.Show the result in table 1.In table 1
" inhibition of chip dispersed " column is recorded as corresponding result.
(inhibition of the infiltration of cutting water when cutting)
So that protective film formation composite sheet obtained above is passed through its protective film formation film (13) -1 and is attached to 6 inches of silicon
On the #2000 abradant surfaces of wafer (100 μm of thickness), the piece is further fixed on ring-shaped frame, and stood 30 minutes.
Then, using ultraviolet lamp (" RAD2000m/8 " of Lintec Corporation. manufactures), in illumination
195mW/cm2, light quantity 170mJ/cm2Under conditions of, protective film formation composite sheet is irradiated from (10) -1 side of support chip ultraviolet
Thus line cures protective film formation film (13) -1, has made protective film.
Then, using cutting blade, Silicon Wafer is sliced together with protective film, has obtained the silicon chip of 5mm × 5mm.This
When, visual confirmation whether there is or not the infiltration of cutting water, by completely not the infiltration of cutting water the case where be determined as "○", will be even have few
The case where infiltration for measuring cutting water, is determined as "×", has rated cutting adaptive.Show the result in table 1.In table 1 " cutting water
The inhibition of infiltration " column is recorded as corresponding result.
(evaluation of the stripping of silicon chip when pickup)
So that protective film formation composite sheet obtained above is passed through its protective film formation film (13) -1 and is attached to 6 inches of silicon
On the #2000 abradant surfaces of wafer (100 μm of thickness), the piece is further fixed on ring-shaped frame, and stood 30 minutes.
Then, using ultraviolet lamp (" RAD2000m/8 " of Lintec Corporation. manufactures), in illumination
195mW/cm2, light quantity 170mJ/cm2Under conditions of, protective film formation composite sheet is irradiated from (10) -1 side of support chip ultraviolet
Thus line cures protective film formation film (13) -1, has made protective film.
Then, using cutting blade, Silicon Wafer is sliced together with protective film, has obtained the silicon chip of 5mm × 5mm.
Then, using chip engagement machine (the die bonder) (" BESTEM- of Canon Machinery Inc. manufactures
D02 "), 20 silicon chips with protective film are picked up.At this point, visual confirmation has the stripping of chipless, will successfully remove
The case where (pickup), is determined as "○", by even there is a small amount of unstripped (pickup) successful situation to be determined as "×", has rated and picks up
Take adaptive.Show the result in table 1." stripping of chip " column in table 1 is recorded as corresponding result.
[embodiment 2]
The manufacture > of < protective film formation composite sheets
(preparation of adhesion agent composition (I-4))
It is prepared for containing acrylic polymer (100 mass parts, solid constituent) and two isocyanide of trifunctional phenylenedimethylidyne
Esters of gallic acid crosslinking agent (" the TAKENATE D110N " of the manufacture of three fields Jing Wu chemical companies) (0.5 mass parts, solid constituent) 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 that will again divide equally made of BA (95 mass parts) and HEA (5 mass parts) copolymerization
The acrylic polymer that son amount is 800000.
(manufacture of support chip)
Other than having used adhesion agent composition obtained above (I-4) this point, side same as Example 1 is utilized
Method forms the adhering agent layer of the non-energy ray-curable of 10 μm of thickness on base material, has made support chip (10) -2.
(manufacture of protective film formation composite sheet)
In addition to use support chip (10) -2 obtained above instead of (10) -1 this point of support chip other than, using with implementation
1 identical method of example has manufactured protective film formation composite sheet.The composition of obtained protective film formation composite sheet is shown in table
1。
The evaluation > of < protective film formation composite sheets
For protective film formation composite sheet obtained above, evaluated using method same as Example 1.It will
As a result shown in table 1.
[embodiment 3]
The manufacture > of < protective film formation composite sheets
(preparation of adhesion agent composition (I-2))
It is prepared for containing acrylic polymer (100 mass parts, solid constituent), Photoepolymerizationinitiater initiater (1- hydroxy cyclohexylphenyls
Base phenyl ketone, BASF AG manufacture " Irgacure (registered trademark) 184 ") (0.3 mass parts, solid constituent) and toluene two it is different
Cyanate crosslinking agent (" the CORONATE L " of the manufacture of Nippon Polyurethane Industry Co., Ltd.s) (0.2 matter
Amount part, solid constituent) and further contain methyl ethyl ketone as solvent, solid component concentration for 30 mass % energy
The adhesion agent composition (I-2) of ray-curable.The acrylic polymer is by making 2EHA (60 mass parts), acrylic acid
Acrylic copolymer and 2- methylacryoyloxyethyls made of methyl esters (MA) (30 mass parts) and HEA (10 mass parts) copolymerization
(total mole number of the isocyanate group in 2- methylacryoyloxyethyl isocyanates is relative to the acrylic compounds for isocyanates
The total mole number of the hydroxyl from HEA in copolymer is 0.8 times of amount) reacted obtained from, side chain there is methyl-prop
The energy ray-curable acrylic polymer that the weight average molecular weight of alkene acyloxy is 600000.
(manufacture of support chip)
Other than having used adhesion agent composition obtained above (I-2) this point, side same as Example 1 is utilized
Method forms the adhering agent layer of the energy ray-curable of 10 μm of thickness on base material, has made support chip (10) -3.
(manufacture of protective film formation composite sheet)
In addition to use support chip (10) -3 obtained above instead of (10) -1 this point of support chip other than, using with implementation
1 identical method of example has manufactured protective film formation composite sheet.The composition of obtained protective film formation composite sheet is shown in table
1。
The evaluation > of < protective film formation composite sheets
For protective film formation composite sheet obtained above, evaluated using method same as Example 1.It will
As a result shown in table 1.
[comparative example 1]
The manufacture > of < protective film formation composite sheets
(preparation of adhesion agent composition)
It is prepared for being crosslinked containing acrylic polymer (100 mass parts, solid constituent), hexamethylene diisocyanate class
Agent " the CORONATE HL " of manufacture (Nippon Polyurethane Industry Co., Ltd.s) (9 mass parts, solid at
Point) and Photoepolymerizationinitiater initiater (oligomeric [2- hydroxy-2-methyls -1- (4- (1- methyl ethylenes) phenyl) acetone], DKSH
" KIP-150 " of Management Ltd. manufacture) (3 mass parts, solid constituent) and further contain methyl ethyl ketone conduct
Solvent, solid component concentration be 30 mass % energy ray-curable adhesion agent composition.The acrylic
Object is total by acrylic compounds made of making 2 ethyl methacrylate (2EMA) (70 mass parts) be copolymerized with HEA (30 mass parts)
Polymers and 2- methylacryoyloxyethyls isocyanates (isocyanate group in 2- methylacryoyloxyethyl isocyanates it is total
The amount that molal quantity is 0.7 times relative to the total mole number of the hydroxyl from HEA in the acrylic copolymer) it is reacted
Obtained from, side chain have methacryloxy weight average molecular weight be 600000 energy ray-curable acrylic polymer
Close object.
(manufacture of support chip)
In addition to using the adhesion agent composition of energy ray-curable obtained above instead of adhesion agent composition (I-4)
Other than this point, using method same as Example 1, the non-energy actinic radiation-curable for having 10 μm of thickness on base material has been made
The support chip (10) -4 of the adhering agent layer of property.
(manufacture of protective film formation composite sheet)
In addition to use support chip (10) -4 obtained above instead of (10) -1 this point of support chip other than, using with implementation
1 identical method of example has manufactured protective film formation composite sheet.The composition of obtained protective film formation composite sheet is shown in table
1。
The manufacture of < protective film formation composite sheets and evaluation >
For protective film formation composite sheet obtained above, evaluated using method same as Example 1.It will
As a result shown in table 1.In addition, the record of the "-" in the column of evaluation result in table 1 refers to failing to implement protective film to be formed with compound
The evaluation of piece.
[comparative example 2]
The manufacture > of < protective film formation composite sheets
(preparation of adhesion agent composition)
It is prepared for containing acrylic polymer (100 mass parts, solid constituent) and toluene di-isocyanate(TDI) class crosslinking agent
" the CORONATE L " of manufacture (Nippon Polyurethane Industry Co., Ltd.s) (0.2 mass parts, solid at
Point), further contain methyl ethyl ketone as solvent, solid component concentration be 30 mass % energy ray-curable glue
Agent composition.The acrylic polymer is made of so that BA (91 mass parts) is copolymerized with acrylic acid (AA) (9 mass parts)
The acrylic polymer that weight average molecular weight is 600000.
(manufacture of support chip)
Other than having used acrylic copolymer this point obtained above, using method same as Example 1,
The support chip (10) -5 of the adhering agent layer for the non-energy ray-curable for having 10 μm of thickness on base material is made.
(manufacture of protective film formation composite sheet)
In addition to use support chip (10) -5 obtained above instead of (10) -1 this point of support chip other than, using with implementation
1 identical method of example has manufactured protective film formation composite sheet.The composition of obtained protective film formation composite sheet is shown in table
1。
The evaluation > of < protective film formation composite sheets
For protective film formation composite sheet obtained above, evaluated using method same as Example 1.It will
As a result shown in table 1.
[table 1]
According to the above results it is found that using Examples 1 to 3 protective film formation composite sheet when, protective film and support chip
Between adhesion strength in the range of 100~2000mN/25mm, dispersing for silicon chip and oozing for cutting water can be inhibited in cutting
Thoroughly, and do not observe that other unfavorable conditions, cutting adaptive are excellent yet.It is used moreover, being formed using the protective film of Examples 1 to 3
When composite sheet, the adhesion strength between protective film and support chip, can be in pickup by silicon in the range of 100~2000mN/25mm
Chip is removed from support chip, and pickup adaptive is also excellent.
When in contrast, using the protective film formation composite sheet of comparative example 1, the adhesion strength between protective film and support chip
In the range of less than 100mN/25mm, the adhesion strength is small, fail to inhibit in cutting silicon chip disperse and cutting water
Infiltration, cutting adaptive are poor.
When on the other hand, using the protective film formation composite sheet of comparative example 2, the adhesion strength between protective film and support chip
More than 2000mN/25mm, the adhesion strength is big, and cutting adaptive is excellent, but fails to shell silicon chip from support chip in pickup
From pickup adaptive is poor.Using comparative example 2 protective film formation composite sheet when, although the piece has the guarantor with Examples 1 to 3
The identical protective film formation film of cuticula formation composite sheet, but the adhering agent layer in support chip is strong adherence, thus it is speculated that protection
Adhesion strength between film and support chip is not value appropriate.
Industrial applicibility
The present invention can be used in the manufacture of semiconductor device.
Reference sign
1A, 1B, 1C, 1D, 1E ... protective film are formed with composite sheet, 10 ... support chips, the surface of 10a ... support chips, 11 ...
Base material, the surface of 11a ... base materials, 12 ... adhering agent layers, the surface of 12a ... adhering agent layers, 13,23 ... protective films formed with film,
The surface of 13a, 23a ... protective film formation film, 15 ... stripping films, 16 ... fixtures adhesive phase, 16a ... fixture adhesives
The surface of layer.
Claims (3)
1. a kind of protective film formation composite sheet has the protective film formation film of energy ray-curable on support chip,
When to the protective film formation film irradiation energy ray to which protective film be made, the protective film and the support chip it
Between adhesion strength be 100~2000mN/25mm.
2. protective film formation composite sheet according to claim 1, wherein the support chip has adhering agent layer, described
Protective film formation is in direct contact with film and the adhering agent layer.
3. protective film formation composite sheet according to claim 2, wherein the adhering agent layer is non-energy actinic radiation-curable
Property.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-092032 | 2016-04-28 | ||
| JP2016092032 | 2016-04-28 | ||
| PCT/JP2017/016280 WO2017188213A1 (en) | 2016-04-28 | 2017-04-25 | Composite sheet for protective membrane formation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108778731A true CN108778731A (en) | 2018-11-09 |
Family
ID=60161621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780010062.2A Pending CN108778731A (en) | 2016-04-28 | 2017-04-25 | Protective film formation composite sheet |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6929835B2 (en) |
| KR (1) | KR102441649B1 (en) |
| CN (1) | CN108778731A (en) |
| TW (1) | TWI731964B (en) |
| WO (1) | WO2017188213A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI770371B (en) * | 2018-03-23 | 2022-07-11 | 日商琳得科股份有限公司 | Die bonding film, dicing die bonding sheet, and method for producing semiconductor chip |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375866A (en) * | 2001-03-21 | 2002-10-23 | 琳得科株式会社 | Sheet material for forming chip protection film and method for making semiconductor chip |
| JP2008143104A (en) * | 2006-12-12 | 2008-06-26 | Bridgestone Corp | Transfer sheet for forming coating film and method for forming covering coating film using same |
| CN102472970A (en) * | 2009-07-02 | 2012-05-23 | 太阳控股株式会社 | Photocurable heat-curable resin composition |
| WO2014155756A1 (en) * | 2013-03-26 | 2014-10-02 | リンテック株式会社 | Adhesive sheet, composite sheet for forming protective film, and method for manufacturing chip with protective film |
| WO2016027883A1 (en) * | 2014-08-22 | 2016-02-25 | リンテック株式会社 | Protective-coating-forming sheet and method for manufacturing semiconductor chip provided with protective coating |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5144433B1 (en) | 1970-02-02 | 1976-11-29 | ||
| JP3097619B2 (en) * | 1997-10-02 | 2000-10-10 | 日本電気株式会社 | Method of manufacturing field emission cold cathode |
| JP4364508B2 (en) * | 2002-12-27 | 2009-11-18 | リンテック株式会社 | Protective film forming sheet for chip back surface and manufacturing method of chip with protective film |
| KR20110010601A (en) * | 2008-03-31 | 2011-02-01 | 헨켈 코포레이션 | Multilayer Visco-curable Adhesive Film |
| JP2010031183A (en) | 2008-07-30 | 2010-02-12 | Furukawa Electric Co Ltd:The | Energy ray hardening type chip protecting film |
| JP5144433B2 (en) * | 2008-08-28 | 2013-02-13 | 古河電気工業株式会社 | Chip protection film |
| JP2011204806A (en) * | 2010-03-24 | 2011-10-13 | Nitto Denko Corp | Processing method of wafer |
| JP5439264B2 (en) * | 2010-04-19 | 2014-03-12 | 日東電工株式会社 | Dicing tape integrated semiconductor backside film |
| JP5036887B1 (en) * | 2011-03-11 | 2012-09-26 | 日東電工株式会社 | Dicing film with protective film |
| JP6091955B2 (en) * | 2013-03-26 | 2017-03-08 | リンテック株式会社 | Adhesive sheet, composite sheet for forming protective film, and method for producing chip with protective film |
| SG11201703250YA (en) * | 2014-10-29 | 2017-05-30 | Lintec Corp | Film for forming protective coating and composite sheet for forming protective coating |
-
2017
- 2017-04-24 TW TW106113626A patent/TWI731964B/en active
- 2017-04-25 WO PCT/JP2017/016280 patent/WO2017188213A1/en active Application Filing
- 2017-04-25 KR KR1020187023558A patent/KR102441649B1/en active Active
- 2017-04-25 JP JP2018514603A patent/JP6929835B2/en active Active
- 2017-04-25 CN CN201780010062.2A patent/CN108778731A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375866A (en) * | 2001-03-21 | 2002-10-23 | 琳得科株式会社 | Sheet material for forming chip protection film and method for making semiconductor chip |
| JP2008143104A (en) * | 2006-12-12 | 2008-06-26 | Bridgestone Corp | Transfer sheet for forming coating film and method for forming covering coating film using same |
| CN102472970A (en) * | 2009-07-02 | 2012-05-23 | 太阳控股株式会社 | Photocurable heat-curable resin composition |
| WO2014155756A1 (en) * | 2013-03-26 | 2014-10-02 | リンテック株式会社 | Adhesive sheet, composite sheet for forming protective film, and method for manufacturing chip with protective film |
| WO2016027883A1 (en) * | 2014-08-22 | 2016-02-25 | リンテック株式会社 | Protective-coating-forming sheet and method for manufacturing semiconductor chip provided with protective coating |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI731964B (en) | 2021-07-01 |
| KR20190002423A (en) | 2019-01-08 |
| KR102441649B1 (en) | 2022-09-07 |
| JP6929835B2 (en) | 2021-09-01 |
| WO2017188213A1 (en) | 2017-11-02 |
| TW201741421A (en) | 2017-12-01 |
| JPWO2017188213A1 (en) | 2019-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108713248A (en) | Protective film forms the manufacturing method with film, protective film formation composite sheet and semiconductor chip | |
| JP6388752B1 (en) | Curable resin film and first protective film forming sheet | |
| CN109075047A (en) | The manufacturing method of the manufacturing method and semiconductor device of protective film formation composite sheet and the semiconductor chip with protective film | |
| CN108140567A (en) | Curable resin film and the 1st protective film formation piece | |
| CN109072009A (en) | Protective film formation film and protective film formation composite sheet | |
| JPWO2017188216A1 (en) | Protective film forming film and protective film forming composite sheet | |
| CN108140585A (en) | 1st protective film formation piece | |
| CN108701640A (en) | Protective film formation film and protective film formation composite sheet | |
| TWI743361B (en) | Resin layer forming film and resin layer forming composite sheet | |
| CN108701641A (en) | Protective film forms the manufacturing method with piece, the manufacturing method of protective film formation piece and semiconductor device | |
| CN109287125A (en) | The manufacturing method of semiconductor chip with protective film and the manufacturing method of semiconductor device | |
| CN109071845A (en) | Protective film formation film and protective film formation composite sheet | |
| CN108778721A (en) | Protective film formation composite sheet | |
| CN108778722A (en) | Protective film formation composite sheet | |
| CN108778731A (en) | Protective film formation composite sheet | |
| CN108966656A (en) | Protective film formation film and protective film formation composite sheet | |
| CN108604541A (en) | Protective film formation film and protective film formation composite sheet | |
| CN108883620A (en) | Composite sheet is used in protective film formation | |
| CN108604542A (en) | Protective film formation film and protective film formation composite sheet | |
| CN108886023A (en) | Protective film formation film and protective film formation composite sheet | |
| CN109005667A (en) | Protective film formation film and protective film formation composite sheet | |
| CN113214745B (en) | Composite sheet for forming protective film and method for manufacturing chip with protective film | |
| CN108701597A (en) | Protective film formation composite sheet | |
| CN116891700A (en) | Protective film forming film, composite sheet for forming protective film, kit, and use of protective film forming film | |
| CN116891612A (en) | Protective film forming film, roller body and application of protective film forming film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181109 |