CN108701597A - Protective film formation composite sheet - Google Patents
Protective film formation composite sheet Download PDFInfo
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- CN108701597A CN108701597A CN201680081330.5A CN201680081330A CN108701597A CN 108701597 A CN108701597 A CN 108701597A CN 201680081330 A CN201680081330 A CN 201680081330A CN 108701597 A CN108701597 A CN 108701597A
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- protective film
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- film formation
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- composite sheet
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Adhesive Tapes (AREA)
- Dicing (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The protective film formation of the present invention has support chip with composite sheet, has on a surface of the support chip protective film formation film and has overlay on the surface with the side opposite side with the protective film formation film of the support chip and forms; wherein, the surface roughness Ra on the surface for the side opposite side of the overlay being in contact with the support chip is less than the surface roughness Ra of the side surface for having overlay of the support chip.
Description
Technical field
The present invention relates to the protective film formation composite sheets for forming protective film at the back side of semiconductor chip.
The application is required preferential based on the Japanese Patent Application 2016-042689 that on March 4th, 2016 files an application in Japan
Power, and its content is incorporated herein.
Background technology
In recent years, semiconductor device is carried out using the Method for Installation for being referred to as so-called upside-down mounting (face down) mode
Manufacture.In upside-down mounting mode, it may be used at the semiconductor chip with the electrodes such as convex block in circuit face, and the electrode and substrate
Engagement.Therefore, chip exposes with the back side of circuit face opposite side sometimes.
At the back side of the chip of the exposing, the resin film made of organic material is formed sometimes as protective film, and with band
The form installation of the semiconductor chip of protective film is in semiconductor devices.Protective film be in order to prevent in cutting action, encapsulate it
It cracks and utilizes on chip afterwards.
As formation when protective film, formed using having protective film formation protective film made of film on support chip
Use composite sheet.It is above-mentioned as above-mentioned support chip, such as using the laminate structure of resin base material, base material and adhesive phase etc.
The lamination surface of the protective film formation film of base material or adhesive phase etc. is surface-treated sometimes.Said protection film is formed and is used
For composite sheet, protective film formation has protective film Forming ability with film, in addition, support chip can be used as cutting sheet to play work(
Can, protective film formation film can be formed as one with cutting sheet.
In the above-mentioned base material before being used for the processing of support chip, usually there is concaveconvex shape in its one or two sides.This
It is due to if not having such concaveconvex shape, base material being batched when forming volume, base material connecing to each other can be caused
Contacting surface is pasted and is sticked together, to become using difficulty.If at least one of the contact surface of base material to each other has bumps
Shape, then the area of contact surface reduces, therefore can inhibit adhesion.
It is representative for such previous protective film formation composite sheet for having used the base material with male and fomale(M&F)
There is structure as shown in Figure 4.Fig. 4 is the section of an example for schematically showing previous protective film formation composite sheet
Figure.It should be noted that later in the attached drawing used in explanation, such as formed with compound to be easier to understand protective film
The feature of piece sometimes shows the part amplification as mian part, however it is not limited to the size of each integral part for convenience's sake
The situation identical as reality such as ratio.
Previous protective film formation composite sheet 9 depicted herein have protective film formation film 13 on support chip 90 and
At support chip 90 is made of the laminate structure of base material 91 and adhesive phase 12, and has protective film on adhesive phase 12
It is formed and uses film 13.Protective film formation becomes protective film with film 13 by solidification.Protective film formation composite sheet 9 is further being protected
Has stripping film 15 on cuticula formation film 13, when using protective film formation composite sheet 9, stripping film 15 is removed.It is protecting
Cuticula, which is formed, to be used in composite sheet 9, the face with face (surface) the 90a opposite sides for having protective film formation film 13 of support chip 90
(back side) 90b, namely base material 91 become with face (back side) 91b of face (surface) the 91a opposite sides for having adhesive phase 12
Male and fomale(M&F).For protective film formation composite sheet 9, male and fomale(M&F) is become by the back side 91b of base material 91 in this wise,
When batching and becoming volume, adhesion can inhibit.That is, can inhibit the stickup of protective film formation composite sheet 9 to each other after stacking, more
Specifically, the stickup of the back side 91b of base material 91 and exposed surface (surface) 15a of stripping film 15 be can inhibit.
On the other hand, protective film formation with composite sheet sometimes in the support of the protective film formed by protective film formation film
Lettering is carried out on the face of piece side by irradiating laser (hereinafter, sometimes referred to as " laser lettering ").When laser lettering, from support chip
Be irradiated with the opposite side for foring protective film side.At this point, for example, in the case of protective film formation composite sheet 9,
Laser is irradiated to protective film from the back side sides 91b of base material 91 through support chip 90, but since the back side 91b of base material 91 is bumps
Face, herein light diffusing reflection can occur, there are the unintelligible this problems of laser lettering.
As the irreflexive protective film formation composite sheet that can prevent such light, it is known to have shown in Fig. 5 that
The protective film of spline structure, which is formed, uses composite sheet 8 (referring for example to patent document 1).Fig. 5 is to schematically show previous protective film
Another sectional view of formation composite sheet.
It is being supported in the same manner as previous protective film formation composite sheet 8 and protective film formation composite sheet 9 depicted herein
Having protective film formation film 13 on piece 80, support chip 80 is made of the laminate structure of base material 81 and adhesive phase 12, and
Has protective film formation film 13 on adhesive phase 12.But in support chip 80, the configuration of the male and fomale(M&F) of base material 81 and branch
Base material 91 in blade 90 is opposite.That is, in protective film formation in composite sheet 8, the face (table for having adhesive phase 12 of base material 81
Face) 81a becomes male and fomale(M&F), and base material 81 becomes even surface with face (back side) 81b of surface 81a opposite sides.Support chip 80
In base material 81, protective film formation film 13 and stripping film 15 respectively with base material 91, the protective film formation film in support chip 90
13 and stripping film 15 it is identical.
But in the case of protective film formation composite sheet 8, the back side 81b of base material 81, namely support chip 80 with
Face (back side) 80b for having face (surface) 80a opposite sides of adhesive phase 12 becomes even surface, is formed with multiple by protective film
Close piece 8 batch and as volume when, can not inhibit the back side 81b of base material 81 and exposed surface (surface) 15a of stripping film 15 stickup,
Adhesion can not be inhibited.When sticking together, protective film formation is used with generation fold in composite sheet 8 or forming protective film
When composite sheet 8 is continuously extracted out from volume is upper, stripping film 15 is caused to be removed from protective film formation on film 13.In addition, in base material 81
On the 81a of surface, in order to eliminate concave-convex shape, need adhesive phase 12 that there is enough thickness.The thickness of adhesive phase 12 is not
When sufficient, the concaveconvex shape of base material 81 is reflected and is made face (back side) 13b of 80 side of support chip of protective film formation film 13
It is provided with concaveconvex shape, it is real to the face of the support chip side of the protective film formed by such protective film formation film 13 to exist
The laser lettering applied becomes unintelligible this problem.
Therefore, actual conditions are so far, can not have both still and can inhibit adhesion and clearly swash to protective film
The protective film formation composite sheet of light lettering.
Existing technical literature
Patent document
Patent document 1:No. 5432853 bulletins of Japanese Patent No.
Invention content
The subject that the invention solves
Problem of the present invention is that providing a kind of protective film formation composite sheet, it is used at the back side of semiconductor chip
Protective film is formed, which can inhibit adhesion, and can clearly carry out laser print to protective film
Word.
Solution to the problem
The present invention provides a kind of protective film formation composite sheet, has support chip, a surface in the support chip
On have protective film formation film and the table with the side opposite side with the protective film formation film in the support chip
Have overlay on face to form, the rough surface on the surface for the side opposite side of the overlay being in contact with the support chip
Spend the surface roughness Ra that Ra is less than the side surface for having overlay of the support chip.
For the protective film formation composite sheet of the present invention, using further having on the protective film formation film
The protective film formation composite sheet of standby stripping film, the peeling force of the stripping film measured by the following method can be
10mN/50mm hereinafter,
(assay method of the peeling force of stripping film)
By the protective film formation composite sheet of the protective film formation with stripping film and width 50mm, long 100mm on film
Multiple are overlapped in such a way that the overlay is 10~60 μm towards the overall thickness of the same direction and the overlay, by
It is overlay, the laminated body that another outermost layer is stripping film that this, which forms an outermost layer, by the laminated body in the protection
The stacking direction of film formation composite sheet is applied with the power of 980.665mN and stands 3 days at 40 DEG C, then in the stacking side
To will be near the stripping film slave phase of the outermost overlay with the condition of peeling rate 300mm/ points, 180 ° of peel angle
It is removed on adjacent overlay, measures peeling force at this time.
Can be above-mentioned support chip by base material and adhesive layer by layer for the protective film formation composite sheet of the present invention
Folded to form, said protection film formation is to stack gradually above-mentioned overlay, base material, adhesive phase and protective film to form use with composite sheet
Made of film.
For the protective film formation composite sheet of the present invention, above-mentioned adhesive phase can be energy ray-curable or non-
The adhesive phase of energy ray-curable.
In the protective film formation composite sheet of the present invention, said protection film formation film can be thermosetting property or energy line
The film of curability.
The effect of invention
The protective film formation of the present invention is used to form protective film at the back side of semiconductor chip with composite sheet, by using this
Protective film formation composite sheet, can inhibit the adhesion of protective film formation composite sheet, and can to protective film clearly into
Row laser lettering.
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 vertical view for the protective film formation composite sheet for showing to manufacture in embodiment.
Fig. 4 is the sectional view of an example for schematically showing previous protective film formation composite sheet.
Fig. 5 is another sectional view for schematically showing previous protective film formation composite sheet.
Symbol description
1,2 ... protective film formation composite sheets
10 ... support chips
The surface of 10a ... support chips
The back side of 10b ... support chips
11 ... base materials
The surface of 11a ... base materials
The back side of 11b ... base materials
12 ... adhesive phases
The surface of 12a ... adhesive phases
13,23 ... protective film formation films
The surface of 13a, 23a ... protective film formation film
14 ... overlays
The surface of 14a ... overlays
The back side of 14b ... overlays
15 ... stripping films
The surface of 15a ... stripping films
16 ... fixture adhesive layers
The surface of 16a ... fixture adhesive layers
Specific implementation mode
◎ protective film formation composite sheets
The protective film formation composite sheet of the present invention has support chip, has protection on a surface of above-mentioned support chip
Film formation film and has painting on the surface with the side opposite side with said protection film formation film of above-mentioned support chip
Coating forms, and the surface roughness Ra on the surface for the side opposite side of above-mentioned overlay being in contact with above-mentioned support chip is less than upper
State the surface roughness Ra of the side surface for having overlay of support chip.
In said protection film formation composite sheet, the side opposite side of above-mentioned overlay being in contact with above-mentioned support chip
Surface surface roughness Ra be less than above-mentioned support chip the surface for having above-mentioned overlay side surface roughness Ra.
That is, the surface for the side opposite side of overlay being in contact with support chip is even surface, or inhibited for concave-convex degree
Face.Therefore, when having irradiated laser, pressed down in the diffusing reflection of the laser on the small above-mentioned surface of the surface roughness Ra of overlay
System.Accordingly, for the protective film after making protective film formation film cure, when irradiating laser through support chip from overlay side, energy
It is enough that laser lettering is clearly carried out to protective film.
In addition, said protection film formation with the overlay in composite sheet for the contactant of overlay be easy moderately slide
It is dynamic, and there is static electricity resistance.Therefore, when protective film formation being batched with composite sheet and becoming volume, it can inhibit the guarantor after stacking
Stickup of the cuticula formation with composite sheet to each other, you can inhibit adhesion.
It should be noted that in the present specification, in said protection film formation composite sheet, by heating or irradiating energy
After amount line makes protective film formation be solidified to form protective film with film, as long as the stepped construction of above-mentioned support chip and protective film is able to
It keeps, is then also referred to as " protective film formation composite sheet ".In addition, in said protection film formation composite sheet, above-mentioned support chip
In the case of for the laminate structure of base material and adhesive phase, after so that adhesive phase is cured, as long as above-mentioned base material, adhesive phase
Solidfied material and the stepped construction of protective film formation film or protective film are maintained, then are also referred to as that " protective film is formed with compound
Piece ".
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 1 depicted herein has support chip 10, has on a surface 10a of support chip 10
Standby protective film formation film 13 and has overlay 14 on another surface (back side) 10b of support chip 10 and form.In addition,
Support chip 10 is that base material 11 and adhesive phase 12 are laminated, have on a surface 11a of base material 11 adhesive phase 12,
Have overlay 14 on another surface (back side) 11b of base material 11, have protective film formation film on adhesive phase 12
13.In addition, protective film formation composite sheet 1 further has stripping film 15 on protective film formation film 13, stripping film 15 exists
Protective film formation is removed when being used with composite sheet 1.Protective film formation becomes protective film with film 13 by solidification.
In protective film formation in composite sheet 1, adhesive phase 12 is laminated on the above-mentioned surface 11a of base material 11, protective film
Formation film 13 is laminated in a part of surface 12a for adhesive phase 12.Moreover, in the surface 12a of adhesive phase 12 not
The exposed surface of protective film formation film 13 and the surface 13a of protective film formation film 13 are laminated with (in other words as upper surface and side
Face) on be laminated with stripping film 15.
It should be noted that in stripping film 15 and the surface 12a of adhesive phase 12 or the surface of protective film formation film 13
May exist space part between 13a.For example, protective film is formed in the side of film 13, the surface 12a of adhesive phase 12, protect
Region easy tos produce above-mentioned space part near film formation film 13.
In protective film formation in composite sheet 1, support chip 10 with face (surface) 10a for having protective film formation film 13
Face (back side) 10b of opposite side, in other words namely base material 11 with face (surface) 11a opposite sides for having adhesive phase 12
Face (back side) 11b becomes male and fomale(M&F).Moreover, covering the male and fomale(M&F) and being provided with overlay 14.Overlay 14 and support chip
The surface roughness Ra of face (back side) 14b of face (surface) 14a opposite sides that 10 (base materials 11) are in contact is less than support chip 10
The surface roughness Ra of above-mentioned back side 10b (in other words as the above-mentioned back side 11b of base material 11).For by protective film formation film 13
In the case that the protective film (illustration omitted) of formation carries out laser lettering, from 14 side of overlay to 10 side of support chip of protective film
Surface irradiation laser.At this point, as described above, the surface roughness Ra of the above-mentioned back side 14b by reducing overlay 14, can inhibit
The diffusing reflection of laser on overlay 14.Therefore, laser lettering can clearly be carried out to protective film.
It should be noted that in the present specification, unless otherwise specified, " surface roughness Ra " refers to JIS
B0601:So-called arithmetic average roughness specified in 2001.
In addition, protective film formation with composite sheet 1 by with overlay 14, even if batched and the case where as volume
Under, can also inhibition layer poststack the stickup to each other of protective film formation composite sheet 1, can inhibit adhesion.More specifically,
It can inhibit the stickup of the above-mentioned back side 11b of base material 11 and exposed surface (surface) 15a of stripping film 15.
In protective film formation in composite sheet 1, the surface 11a of base material 11 is formed as even surface but it is also possible to be flat herein
The low male and fomale(M&F) of slippery.But as it is explained in detail hereinafter, from the generation for inhibiting the space part between base material 11 and adhesive phase 12, more
It is easy to set out in terms of making protective film formation composite sheet 1 become the composite sheet with ideal characterisitics, the surface 11a of preferred substrates 11
For even surface.
For protective film formation shown in FIG. 1 composite sheet 1, at it in use, stripping film 15 is removed, semiconductor
The back side of chip (illustration omitted) is pasted on the surface 13a of protective film formation film 13.In addition, the surface 12a of adhesive phase 12
In protective film formation be not laminated be pasted on the fixtures such as ring frame with the exposed surface of film 13.
Fig. 2 is the sectional view for another embodiment for schematically showing the protective film formation composite sheet of the present invention.It needs
It is noted that in fig. 2, for inscape same as shown in Figure 1, marking symbol identical with Fig. 1, and omit it in detail
Thin explanation.This is also the same in the figure after Fig. 2.
Protective film as shown here is formed in composite sheet 2, and protective film formation film 23 is laminated in adhesive phase 12
In the entire surface of surface 12a, fixture adhesive layer 16 is laminated in a part of the surface 23a of protective film formation film 23.
In addition, for protective film formation composite sheet 2, fixture is not laminated in surface 23a of the protective film formation with film 23 and uses and glues
It connects and is laminated on the exposed surface of oxidant layer 16 and the surface 16a (in other words as upper surface and side) of fixture adhesive layer 16
Stripping film 15.Other than this above-mentioned several points, protective film, which forms to be formed with protective film shown in FIG. 1 with composite sheet 2, uses composite sheet 1
It is identical.
It should be noted that in the surface 23a or fixture adhesive layer 16 of stripping film 15 and protective film formation film 23
Surface 16a between may exist space part.For example, the table of the side of fixture adhesive layer 16, protective film formation film 23
In the 23a of face, region easy tos produce above-mentioned space part near fixture adhesive layer 16.
In protective film formation in composite sheet 2, with protective film formation composite sheet 1 the case where in the same manner as, support chip 10
Above-mentioned back side 10b (the above-mentioned back side 11b of base material 11) is formed as male and fomale(M&F), but covers the male and fomale(M&F) and be provided with overlay 14.
Therefore, compared with the above-mentioned back side 10b of support chip 10, the surface roughness Ra smaller of the above-mentioned back side 14b of overlay 14.Cause
This, can be for clearly carrying out laser lettering by protective film formation with the protective film that film 23 is formed.
In addition, protective film formation composite sheet 2 becomes the case where volume by having overlay 14, even being batched
Under, can also inhibition layer poststack the stickup to each other of protective film formation composite sheet 2, you can inhibit adhesion.
Protective film shown in Fig. 2 is formed in composite sheet 2, its using when stripping film 15 be removed, semiconductor wafer
The back side of (illustration omitted) is pasted on the surface 23a of protective film formation film 23.In addition, surface of the fixture with adhesive layer 16
The fixtures such as upper surface and ring frame in 16a are pasted.
The present invention protective film formation with composite sheet be not limited to Fig. 1~2 shown in example, do not damaging effect of the present invention
Can also be structure made of the part composition of composite sheet shown in Fig. 1~2 is changed or deleted in the range of fruit,
It can also be and further add structure made of other compositions in example described above.
Hereinafter, being illustrated in more detail to each composition of the protective film formation composite sheet of the present invention.
Zero support chip
As long as said protection film formation film can be arranged in above-mentioned support chip, it is not particularly limited.As support chip,
Such as stripping film for preventing from using in surface adhesive dust of protective film formation film etc. can be enumerated and in cutter
The sheet material for the effect that sequence etc. is used to be protected to the surface of protective film formation film and play cutting sheet etc..
As preferred above-mentioned support chip, can enumerate processing in semiconductor wafer in piece field it is usually used only
The support chip etc. that the support chip and base material and adhesive phase being made of base material are laminated.
Support chip can be made of 1 layer (single layer), can also be made of 2 layers or more of multilayer.Support chip is made up of multiple layers
In the case of, multilayer can be the same or different each other.Can also be all layers i.e., it is possible to be all layers of all same
It is different, it can also be that only part layer is identical.Moreover, in the case that multilayer is different, the combination of these multilayers is not special
It limits.Here, it refers to that at least one of the material of each layer and thickness are different that multilayer is different.
As long as the thickness of support chip according to purpose suitable for selection, but from can more clearly carry out laser to protective film
Lettering and then enough flexibility can be assigned with composite sheet to said protection film formation, the stickup of semiconductor wafer is become
From the perspective of good, preferably 10~500 μm, more preferably 20~350 μm, particularly preferably 30~200 μm, such as can be with
For 40~175 μm and 50~150 μm of arbitrary thickness.
Here, " thickness of support chip " refers to the overall thickness for each layer for constituting support chip, for example, in base material and adhesive phase
In the case of the support chip being laminated, refer to base material thickness and adhesive phase thickness aggregate value.
It should be noted that at least one side of support chip can become male and fomale(M&F), the thickness of support chip can be in support chip
The position comprising the protrusion in the male and fomale(M&F), calculated as a starting point using the top of the protrusion.
Base material
The material of above-mentioned base material is preferably various resins.
As the specific example of above-mentioned resin, can enumerate:Polyethylene (low density polyethylene (LDPE) (LDPE), Zhi Lock low-density
Polyethylene (LLDPE), high density polyethylene (HDPE) (HDPE etc.)), it is polypropylene, ethylene-propylene copolymer, polybutene, polybutadiene, poly-
Methylpentene, vinyl chloride copolymer, polyethylene terephthalate, polyethylene naphthalate, gathers to benzene polyvinyl chloride
Dioctyl phthalate butanediol ester, polyurethane, urethane acrylate, polyimides, vinyl-vinyl acetate copolymer, ionomer tree
Fat, ethylene-(methyl) acrylic copolymer, ethylene-(methyl) acrylate copolymer, polystyrene, makrolon, fluorine tree
Fat and hydrogenation products, modifier, cross-linking agent or the copolymer of arbitrary resin etc. in these.
It should be noted that in the present specification, the concept of " (methyl) acrylic acid " includes " acrylic acid " and " methyl
Both acrylic acid ".
In the case of support chip is made of other component stackings such as base material and adhesive phase, the thickness of base material can be according to mesh
Suitable selection, but preferably 15~300 μm, more preferably 20~200 μm, such as can be 30~175 μm, 40~150 μm
And any thickness in 50~125 μm.By making the thickness of base material be such range, said protection film formation composite sheet
It is flexible and the stickup of semiconductor wafer or semiconductor chip is further increased.
Base material can be made of 1 layer (single layer), can also be made of 2 layers or more of multilayer.The feelings that base material is made up of multiple layers
Under condition, multilayer can be the same or different each other.Here, " multilayer can be the same or different each other " refer to
The case where above-mentioned support chip, is identical.
In the case that base material is made up of multiple layers, as long as the overall thickness of each layer is set as above-mentioned preferred base material thickness.
The surface roughness Ra in the face (surface) for having adhesive phase of base material is preferably 0.001~0.1 μm, is more preferably
0.005~0.08 μm, particularly preferably 0.01~0.04 μm.By making the above-mentioned surface roughness Ra of substrate surface be on above-mentioned
Limit value is hereinafter, laser lettering can more clearly be carried out to protective film.
The above-mentioned surface roughness Ra of substrate surface can for example pass through the surface treatment condition of the condition of molding of base material, base material
Etc. being adjusted.
It should be noted that as the method that monolithic turns to semiconductor chip by the cutting semiconductor chip by, such as can
To enumerate:Using cutter cut semiconductor wafer cutter cutting, by laser irradiation cut semiconductor wafer laser cutting,
Or cut the method using Water Cutting etc. of semiconductor wafer by being blown the water comprising grinding agent.
On the other hand, as the method that semiconductor wafer monolithic is turned to semiconductor chip, in addition to above-mentioned utilization cutting
Other than method, following methods can also be enumerated:The focus that is set in inside semiconductor wafer is focused on to irradiate infrared region
Laser, after the inside of semiconductor wafer forms modified layer, to the semiconductor wafer applied force, thus in above-mentioned modified layer
Forming part is divided and singualtion by semiconductor wafer.
In the case that the above-mentioned surface roughness Ra of substrate surface is, for example, 0.01~0.2 μm, with such base material
Inside of the protective film formation with composite sheet preferably above-mentioned in semiconductor wafer form modified layer and by semiconductor wafer monolithic
It is used when change.
On the other hand, the surface roughness with the face (back side) of face (surface) opposite side for having adhesive phase of base material
Ra, in other words namely support chip it is thick with the surface in the face (back side) of face (surface) opposite side for having protective film formation film
Rugosity Ra is preferably 0.001~4 μm, more preferably 0.005~3.7 μm, is more preferably 0.01~3.4 μm, particularly preferably
It is 0.02~3.1 μm.By making the above-mentioned surface roughness Ra of substrate backside for above-mentioned upper limit value hereinafter, can be easier to reduce
The surface roughness Ra on the surface for the side opposite side of overlay being in contact with support chip is clear to protective film to be easier
Ground carries out laser lettering.
The above-mentioned surface roughness Ra of substrate backside can be for example, by the condition of molding of base material, the surface treatment item of base material
Part etc. is adjusted.
The resin of material as base material, which can also use, passes through crosslinked resin.
In addition, can be the piece formed by the extrusion molding of thermoplastic resin using resin as the base material of constituent material
Material can also be obtained from stretching, and can also be keeps curable resin thin layer and be solidified to form by well known method
Sheet material.
In addition, base material can be by made of coloring, can also be made of implementing printing.
It is from excellent heat resistance and also good with expansion adaptability, pickup adaptability by the flexibility with appropriateness
Aspect set out, preferably comprise polyacrylic base material.
It for example can be the base material for the single-layer or multi-layer being only made of polypropylene containing polyacrylic base material, can also be poly-
The base material for the multilayer (2 layers or more) that propylene layer is laminated with the resin layer other than polypropylene.
In the case of protective film formation film is heat cured, by making base material that there is heat resistance, the heat because of base material can inhibit
Caused by deteriorate, the generation of the unfavorable condition in manufacturing process so as to effectively inhibit semiconductor device.
For base material, in order to make it be carried with the cementability between film with the adhesive phase or protective film formation being arranged on
Height can also implement its surface the further provided for contouring processing based on blasting treatment, solvent processing etc.;Corona discharge Treatment, electron beam
At the oxidations such as treatment with irradiation, corona treatment, ozone/ultraviolet treatment with irradiation, flame treatment, chromic acid processing, hot wind processing
Reason etc..It is carried out the material that primary coat is handled in addition, base material can also be surface.
Adhesive phase
Above-mentioned adhesive phase suitable can use well known adhesive phase.
Adhesive phase can use for constitute its, adhesive composition containing various compositions such as adhesives and shape
At.The ratio for the mutual content of ingredient not gasified under room temperature in adhesive composition usually in adhesive phase it is above-mentioned at
Divide the ratio of mutual content identical.It should be noted that in the present specification, " room temperature " refers to especially cold or not hot temperature
Degree, i.e. usual temperature, it can be mentioned, for example 15~25 DEG C temperature etc..
The thickness of adhesive phase can be according to purpose suitable for selection, preferably 1~100 μm, more preferably 2~80 μm, spy
You Xuanwei not be 3~50 μm, can be such as 3~35 μm, 3~20 μm and 3~10 μm of any thickness.
Adhesive phase can be made of 1 layer (single layer), can also be made of 2 layers or more of multilayer.Adhesive phase is by multilayer
In the case of composition, multilayer can be the same or different each other.Here, " multilayer each other can it is identical can not also
The case where referring to above-mentioned support chip, is same together ".
In the case that adhesive phase is made up of multiple layers, as long as the overall thickness of each layer is set as the thickness of above-mentioned preferred adhesive phase
Degree.
As above-mentioned adhesive, it can be cited for example that acrylic resin, urethane based resin, rubber resin,
The resin of binding property such as organic silicon resin, vinyl ethers resinoid.In addition, as above-mentioned adhesive, from the viewpoint of its function into
In the case of row classification, it can be cited for example that energy ray-curable resin etc..
It should be noted that in the present specification, " energy line " refers to having energy in electromagnetic wave or beam of charged ions
The ray of quantum can enumerate ultraviolet light, radioactive ray, electron beam etc. as its example.Ultraviolet light for example can be by using work
It is irradiated for the high-pressure sodium lamp of ultraviolet source, melting H lamps, xenon lamp, black light or LED light etc..Electron beam, which can radiate, to be passed through
Electron-beam accelerator etc. and generate ray.
In addition, in the present specification, " energy ray-curable " refers to by the cured property of irradiation energy line, " non-energy
Measure line curability " refer to the property not being cured irradiation energy line.
As above-mentioned energy ray-curable resin, it can be cited for example that with polymerizations such as (methyl) acryloyl group, vinyl
The resin of property group.
Above-mentioned resin of binding property is preferably acrylic resin, more preferably includes the knot from (methyl) acrylate
(methyl) acrylate copolymer of structure unit.
In the case that above-mentioned adhesive phase contains the ingredient that energy ray-curable resin etc. polymerize by energy line irradiates,
As energy ray-curable, irradiation energy line and make its adhesiveness reduction, the semiconductor core with protective film described below as a result,
The pickup of piece becomes easy.Such adhesive phase can be used for example containing each of the ingredient polymerizeing by irradiation by energy line
Adhesive composition is planted to be formed.
< < adhesive composition > >
As preferred above-mentioned adhesive composition, can enumerate containing the viscous of the ingredient polymerizeing by irradiation by energy line
Mixture composite.As such adhesive composition, for example,:Contain acrylic resin and energy line polymerism
The composition of compound (hereinafter, sometimes referred to simply as " adhesive composition (i) ");Containing with hydroxyl and side chain is with polymerism
The above-mentioned acrylic resin of group and the composition of isocyanates crosslinking agent are (hereinafter, sometimes referred to simply as " adhesive group
Close object (ii) ") etc..As above-mentioned with the acrylic resin of hydroxyl and side chain with polymerizable group, such as can lift
Provide hydroxyl and side chain via urethane bond and with polymerizable group acrylic resin etc..
< adhesive compositions (i) >
Adhesive composition (i) contains above-mentioned acrylic resin and energy line polymerizable compound as essential component.
Hereinafter, being illustrated to each ingredient.
[Bing Xisuanleishuzhi ]
In above-mentioned acrylic resin in adhesive composition (i), as preferred acrylic resin, such as can be with
Enumerate as the monomer polymerization other than (methyl) acrylate of monomer and (methyl) acrylate used as needed and
Obtained (methyl) acrylate copolymer.
As above-mentioned (methyl) acrylate, it can be cited for example that:(methyl) methyl acrylate, (methyl) acrylic acid second
Ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl)
Heptylacrylate, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (first
Base) the positive nonyl ester of 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) propylene
Sour tetradecane base ester ((methyl) myristyl ester), (methyl) acrylic acid pentadecane base ester, (methyl) acrylic acid hexadecane
Base ester ((methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester, (methyl) octadecyl acrylate ((methyl)
Stearyl acrylate), (methyl) acrylic acid isooctadecane base ester ((methyl) isostearyl acrylate) etc. constitute the alkane of Arrcostab
(methyl) alkyl acrylate for the chain structure that the carbon atom number of base is 1~18;
(methyl) the acrylate base esters such as (methyl) isobornyl acrylate, (methyl) dicyclopentanyl acrylate;
(methyl) benzyl acrylate etc. (methyl) acrylic acid aralkyl ester;
(methyl) acrylic acid cyclenes base ester such as (methyl) acrylic acid dicyclopentenyl ester;
(methyl) acrylic acid cyclenes oxygroup Arrcostab such as (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester;
(methyl) acrylimide;
(methyl) acrylate containing glycidyl such as (methyl) glycidyl acrylate;
(methyl) dihydroxypropyl methyl esters, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters,
(methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 3- hydroxybutyls, (methyl) third
(methyl) acrylate of the hydroxyls such as olefin(e) acid 4- hydroxybutyls etc..
As the monomer other than above-mentioned (methyl) acrylate, it can be cited for example that:(methyl) acrylic acid, itaconic acid, second
Vinyl acetate, acrylonitrile, styrene, N hydroxymethyl acrylamide etc..
It is each to constitute monomer other than above-mentioned (methyl) acrylate of acrylic resin, above-mentioned (methyl) acrylate etc.
Kind monomer can be only one kind, or two or more.
Acrylic resin contained by adhesive composition (i) can be only one kind, or two or more.
Relative to all total amounts containing ingredient other than solvent in adhesive composition (i), adhesive composition (i)
The content of acrylic resin is preferably 40~99 mass %, more preferably 50~91 amount %.
[Energy line Ju Hexinghuahewu ]
Above-mentioned energy line polymerizable compound is irradiated by the compound of polymerizing curable by energy line, as its example,
Intramolecular, which can be enumerated, has the compound of energy ray-curable double bond Isoenergetical line polymerizable group.
As above-mentioned energy line polymerizable compound, it can be cited for example that the low molecular weight with energy line polymerizable group
Compound (simple function or polyfunctional monomer and oligomer).
As above-mentioned energy line polymerizable compound, more specifically, it can be cited for example that:Trimethylolpropane tris acrylic acid
Ester, tetramethylol methane tetraacrylate, pentaerythritol triacrylate, dipentaerythritol monohydroxypentaacryande, two seasons
The acrylate such as penta tetrol, six acrylate, 1,4 butanediol diacrylate, 1,6 hexanediol diacrylate;
The acrylate of the skeletons containing annular aliphatic such as bicyclopentadiene dimethoxy diacrylate;
Polyethyleneglycol diacrylate, oligoester acrylate, urethane acrylate oligomer, epoxy-modified third
Acrylic ester compounds such as olefin(e) acid ester, polyether acrylate, itaconic acid oligomer etc..
The molecular weight of above-mentioned energy line polymerizable compound is preferably 100~30000, more preferably 300~10000.
Energy line polymerizable compound contained by adhesive composition (i) can be only one kind, or two or more.
Relative to 100 mass parts of content of above-mentioned acrylic resin, the energy line polymerism of adhesive composition (i)
The content for closing object is preferably 1~125 mass parts, more preferably 10~125 mass parts.
[Guang Juheyinfaji ]
It, can be with other than above-mentioned acrylic resin and energy line polymerizable compound in adhesive composition (i)
Contain Photoepolymerizationinitiater initiater.
Above-mentioned Photoepolymerizationinitiater initiater can be well known Photoepolymerizationinitiater initiater.
As above-mentioned Photoepolymerizationinitiater initiater, it is specific it can be cited for example that:4- (2- hydroxyl-oxethyls) phenyl (2- hydroxyls -2-
Propyl) ketone, Alpha-hydroxy-α, α '-dimethyl acetophenone, 2- methyl -2- hydroxypropiophenonepreparations, 1- hydroxycyclohexylphenylketones, 2- hydroxyls
Base -1- { 4-[4- (2- hydroxy-2-methyls propiono) Bian Ji ]Phenyl } the α -one alcohol compounds such as -2- methylpropane -1- ketone;
Methoxyacetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- diethoxy acetophenones, 2- methyl-1s -
[4- (methyl mercapto) Ben Jis ]The acetophenone compounds such as -2- morpholino propane -1- ketone;
The benzoin ethers compound such as benzoin ethyl ether, benzoin iso-propylether, anisoin methyl ether;
The ketal compounds such as benzoin dimethylether;
The aromatic sulfonyls class compound such as 2- naphthalene sulfonyl chlorides;
The photolytic activities oxime compounds such as 1- benzophenone -1,1- propanedione -2- (O- ethoxy carbonyls) oxime;
The benzophenone compounds such as benzophenone, benzoylbenzoic acid, 3,3 '-dimethyl -4- methoxy benzophenones;
Thioxanthones, 2-chlorothioxanthone, 2- methyl thioxanthones, 2,4- dimethyl thioxanthones, isopropyl thioxanthone, 2,4- dichloros
The thioxanthene ketone class compounds such as thioxanthones, 2,4- diethyl thioxanthones, 2,4- diisopropylthioxanthones;
Camphorone;Halogenated ketone;Acylphosphine oxide;Acyl phosphonate etc..
Photoepolymerizationinitiater initiater contained by adhesive composition (i) can be only one kind, or two or more.
In the case of using Photoepolymerizationinitiater initiater, relative to 100 mass parts of content of above-mentioned energy line polymerizable compound,
The content of the Photoepolymerizationinitiater initiater of adhesive composition (i) is preferably 0.1~10 mass parts, more preferably 1~5 mass parts.It is logical
Crossing makes the above-mentioned content of Photoepolymerizationinitiater initiater be above-mentioned lower limiting value or more, can fully obtain using caused by Photoepolymerizationinitiater initiater
Effect.In addition, by making the above-mentioned content of Photoepolymerizationinitiater initiater be that above-mentioned upper limit value is drawn hereinafter, can inhibit by excessive photopolymerization
The byproduct compounds that agent generates are sent out, to carry out the solidification of adhesive phase better.
[Jiao Lianji ]
It, can be with other than above-mentioned acrylic resin and energy line polymerizable compound in adhesive composition (i)
Contain crosslinking agent.
As above-mentioned crosslinking agent, it can be cited for example that organic polyisocyanate compound, organic more group with imine moiety etc..
As above-mentioned organic polyisocyanate compound, it can be cited for example that:Aromatic polyisocyanate compound, fat
Race's polyisocyanate compound, the tripolymer of alicyclic polyisocyanates compound and these compounds, isocyanuric acid ester body
And addition body;Above-mentioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanates
Terminal isocyanate carbamate prepolymer etc. obtained from compound is reacted with polyol compound.Above-mentioned addition body refers to
Above-mentioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound or alicyclic polyisocyanates compound and second
The reactant of the low molecules active hydrogen compounds such as glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil.
As above-mentioned organic polyisocyanate compound, more specifically, it can be cited for example that:2,4- toluene diisocynates
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;The addition toluene di-isocyanate(TDI) on all or part of hydroxyl of the polyalcohols such as trimethylolpropane
And compound made of any one of hexamethylene diisocyanate or both;Lysine diisocyanate etc..
As above-mentioned organic more group with imine moiety, it can be mentioned, for example:Bis- (the 1- aziridine of N, N '-diphenyl methane -4,4 ' -
Carboxylic acid amides) ,-three-β of trimethylolpropane-'-aziridino propionic ester ,-three-β of tetramethylol methane-'-aziridino propionic ester, N,
N '-Toluene-2,4-diisocyanates, bis- (1- aziridine carboxylic acid amides) triethylenemelanins of 4- etc..
In the case of using isocyanate compound as crosslinking agent, as acrylic resin, it is preferable to use hydroxyl
Polymer.Crosslinking agent with isocyanate group, acrylic resin with hydroxyl in the case of, pass through above-mentioned isocyanate group
With the reaction of hydroxyl, cross-linked structure can be easily imported within the adhesive layer.
Crosslinking agent contained by adhesive composition (i) can be only one kind, or two or more.
In the case of using crosslinking agent, relative to 100 mass parts of content of above-mentioned acrylic resin, adhesive composition
(i) content of crosslinking agent is preferably 0.01~20 mass parts, more preferably 0.1~16 mass parts.
[Rong Ji ]
In adhesive composition (i), other than above-mentioned acrylic resin and energy line polymerizable compound, preferably into
One step contains solvent.
Above-mentioned solvent is not particularly limited.
As preferred above-mentioned solvent, it can be cited for example that:The hydrocarbon such as toluene, dimethylbenzene;Methanol, ethyl alcohol, 2- propyl alcohol, isobutyl
The alcohol such as alcohol (2- methylpropane -1- alcohol), n-butyl alcohol;The esters such as ethyl acetate;The ketone such as acetone, methyl ethyl ketone;The ethers such as tetrahydrofuran;Diformazan
Amides such as base formamide, N-Methyl pyrrolidone (compound with amido bond) etc..
Solvent contained by adhesive composition (i) can be only one kind, or two or more.
In the case that adhesive composition (i) contains solvent, the solvent content of adhesive composition (i) is preferably 40~90
Quality %, more preferably 50~80 mass %.
[Other Cheng Fen ]
In adhesive composition (i), other than above-mentioned acrylic resin and energy line polymerizable compound, do not damaging
In the range of evil effect of the present invention, the other ingredients for being not belonging to above-mentioned Photoepolymerizationinitiater initiater, crosslinking agent and solvent can also be contained.
Above-mentioned other ingredients can be those of known, can arbitrarily be selected, be not particularly limited according to purpose.As excellent
Above-mentioned other ingredients of choosing, it can be cited for example that:Dyestuff, pigment, deterioration preventing agent, antistatic agent, fire retardant, organosilicon compound
The various additives such as object, chain-transferring agent.
Above-mentioned other ingredients contained by adhesive composition (i) can be only one kind, or two or more.
< adhesive compositions (ii) >
Adhesive composition (ii) contains with hydroxyl and side chain acrylic resin and isocyanide with polymerizable group
Esters of gallic acid crosslinking agent is as essential component.Here, as above-mentioned acrylic resin, it can be cited for example that having hydroxyl and side chain
The acrylic resin with polymerizable group via urethane bond.
In the case of using adhesive composition (ii), acrylic resin in side chain by having polymerizable group, such as
The case where adhesive composition (i), is such, and uses energy line polymerizable compound and is polymerize by irradiation energy line
The case where reaction, is compared, the adhesiveness of the adhesive phase after polymerisation (solidification) reduce and generate from the stripping on the object that is stuck
It is improved from property, the pick of the semiconductor chip with protective film improves.
It should be noted that in the present specification, the note about " acrylic resin " in adhesive composition (ii)
It carries, refers to " there is the acrylic resin of polymerizable group in side chain " unless otherwise specified.
[Bing Xisuanleishuzhi ]
There is the acrylic resin of polymerizable group as above-mentioned side chain, it can be cited for example that:Make as monomer
(methyl) acrylate (in the present specification, sometimes referred to as " not (methyl) acrylate of hydroxyl ") without hydroxyl with
(methyl) acrylate (in the present specification, sometimes referred to as " (methyl) acrylate of hydroxyl ") with hydroxyl etc. contains hydroxyl
The copolymer compound of base, and make that there is the isocyanate group of isocyanate group and the compound of polymerizable group to contain with obtained
The hydroxyl reaction of the copolymer of hydroxyl, to form resin obtained from urethane bond.
As (methyl) acrylate of above-mentioned not hydroxyl, it can be cited for example that (methyl) of adhesive composition (i)
(methyl) acrylate in acrylate other than (methyl) acrylate of hydroxyl.
In addition, the compound as above-mentioned hydroxyl, can enumerate (methyl) with hydroxyl in adhesive composition (i)
The identical compound of acrylate.
The compound of (methyl) acrylate and hydroxyl that constitute the not hydroxyl of above-mentioned acrylic resin respectively can
To be only one kind, or two or more.
As the above-mentioned compound with isocyanate group and polymerizable group, it can be cited for example that 2- methacryloxypropyls
(methyl) acrylate etc. containing isocyanate group such as base ethyl isocyanate.
Constituting the above-mentioned compound with isocyanate group and polymerizable group of above-mentioned acrylic resin can be only
It is a kind of, or two or more.
Acrylic resin contained by adhesive composition (ii) can be only one kind, or two or more.
Relative to all total amounts containing ingredient other than the solvent in adhesive composition (ii), adhesive composition
(ii) content of acrylic resin is preferably 80~99 mass %, more preferably 90~97 mass %.
[Isocyanates Jiao Lianji ]
As above-mentioned isocyanates crosslinking agent, it can be cited for example that middle as crosslinking agent with adhesive composition (i)
The identical substance of above-mentioned organic polyisocyanate compound.
Isocyanates crosslinking agent contained by adhesive composition (ii) can be only one kind, or two or more.
It is preferred that the molal quantity phase of isocyanate group possessed by isocyanates crosslinking agent in adhesive composition (ii)
Molal quantity for hydroxyl possessed by the acrylic resin in adhesive composition (ii) is 0.2~3 times.By making isocyanide
The above-mentioned molal quantity of perester radical is above-mentioned lower limiting value or more, the adhesiveness of the adhesive phase after solidification reduce caused by from being glued
The fissility pasted on object improves, and the pick of the semiconductor chip with protective film improves.In addition, by making the upper of isocyanate group
Molal quantity is stated as above-mentioned upper limit value hereinafter, the pair that the reaction of isocyanates crosslinking agent to each other generates can be further suppressed
Product.
It is preferred that being carried out to the content of the isocyanates crosslinking agent of adhesive composition (ii) suitable for adjusting so that isocyanic acid
The molal quantity of ester group is above-mentioned range.
It is above-mentioned different meeting in addition, for the content of the isocyanates crosslinking agent of adhesive composition (ii)
On the basis of mole said conditions of cyanic acid ester group, relative to 100 mass parts of content of acrylic resin, preferably 0.01~20
Mass parts, more preferably 0.1~15 mass parts, particularly preferably 0.3~12 mass parts.
[Guang Juheyinfaji ]
It, can be with other than above-mentioned acrylic resin and isocyanates crosslinking agent in adhesive composition (ii)
Contain Photoepolymerizationinitiater initiater.
As above-mentioned Photoepolymerizationinitiater initiater, it can be cited for example that the same photopolymerization of with adhesive composition (i) the case where
Initiator.
Photoepolymerizationinitiater initiater contained by adhesive composition (ii) can be only one kind, or two or more.
In the case of using Photoepolymerizationinitiater initiater, relative to 100 mass parts of content of acrylic resin, adhesive combination
The content of the Photoepolymerizationinitiater initiater of object (ii) is preferably 0.05~20 mass parts.Above-mentioned content by making Photoepolymerizationinitiater initiater is
It more than above-mentioned lower limiting value, can fully obtain using effect caused by Photoepolymerizationinitiater initiater.In addition, by making Photoepolymerizationinitiater initiater
Above-mentioned content be above-mentioned upper limit value hereinafter, can inhibit the byproduct compounds generated by excessive Photoepolymerizationinitiater initiater, to more
The solidification of adhesive phase is carried out well.
[Rong Ji ]
In adhesive composition (ii), other than above-mentioned acrylic resin and isocyanates crosslinking agent, preferably into
One step contains solvent.
As above-mentioned solvent, it can be cited for example that with adhesive composition (i) the case where same solvent.
Solvent contained by adhesive composition (ii) can be only one kind, or two or more.
In the case that adhesive composition (ii) contains solvent, the solvent content of adhesive composition (ii) is preferably 40~
90 mass %, more preferably 50~80 mass %.
[Other Cheng Fen ]
In adhesive composition (ii), other than above-mentioned acrylic resin and isocyanates crosslinking agent, do not damaging
In the range of evil effect of the present invention, the other ingredients for being not belonging to above-mentioned Photoepolymerizationinitiater initiater and solvent can also be contained.
As above-mentioned other ingredients, it can be cited for example that with same other ingredients the case where adhesive composition (i).
Above-mentioned other ingredients contained by adhesive composition (ii) can be only one kind, or two or more.
More than, for containing irradiated by energy line by the adhesive composition of ingredient that polymerize is illustrated, but
When the formation of adhesive phase, the adhesive composition without the ingredient polymerizeing by irradiation by energy line can also be used.That is, viscous
Mixture layer can also be the adhesive phase of the non-energy line curability without energy ray-curable.
As preferred above-mentioned non-energy line curing adhesive composition, it can be cited for example that containing acrylic resin
And the adhesive composition (hereinafter, sometimes referred to simply as " adhesive composition (iii) ") etc. of crosslinking agent.Adhesive composition
(iii) any ingredients such as solvent, the other ingredients for being not belonging to solvent can be contained.
< adhesive compositions (iii) >
Above-mentioned acrylic resin, crosslinking agent, solvent and other ingredients contained by adhesive composition (iii) respectively with it is viscous
Acrylic resin, crosslinking agent, solvent and other ingredients in mixture composite (i) is identical.
Relative to all total amounts containing ingredient other than the solvent in adhesive composition (iii), adhesive composition
(iii) content of acrylic resin is preferably 40~99 mass %, more preferably 50~93 mass %.
Relative to 100 mass parts of content of acrylic resin, the content of the crosslinking agent of adhesive composition (iii) is preferred
For 3~30 mass parts, more preferably 5~25 mass parts.
Adhesive composition (iii) is identical as adhesive composition (i) other than this above-mentioned point.
The manufacturing method > > of < < adhesive compositions
The above-mentioned adhesive compositions such as adhesive composition (i)~(iii) can be by coordinating above-mentioned adhesive, as needed
Ingredient other than the above-mentioned adhesive used etc. is used to constitute the ingredient of each adhesive composition and obtains.
Coordinate order of addition when each ingredient to be not particularly limited, two or more ingredients can also be added simultaneously.
The method mixed to each ingredient when cooperation is not particularly limited, can be from making the rotations such as stirrer or agitating paddle
Come mixed method, using method that mixer is mixed, apply the method that ultrasonic wave is mixed etc. well known to side
Suitable for selection in method.
For temperature and time when the addition of each ingredient and mixing, as long as deteriorating each gradation composition,
It is not particularly limited, suitable for adjusting, but temperature is preferably 15~30 DEG C.
Zero protective film formation film
Said protection film formation film can be any one in thermosetting property and energy ray-curable.Protective film, which is formed, to be used
Film eventually becomes the high protective film of impact resistance by solidification.The semiconductor that the protective film for example can prevent cutting action later
The generation of crackle in chip.
Protective film formation film can use thermosetting protective film formation composition described later or energy line curing
Property protective film formation composition (hereinafter, sometimes will be including being known as " protective film formation composition " including them) and formed.
Protective film formation film can be only 1 layer (single layer), or 2 layers or more of multilayer, in the case of being multilayer,
Its multilayer can be the same or different each other, and the combination of multilayer is not particularly limited.
The thickness of protective film formation film is not particularly limited, preferably 1~100 μm, more preferably 5~75 μm, especially
Preferably 5~50 μm.By making the thickness of protective film formation film be above-mentioned lower limiting value or more, for half as the object that is stuck
The adhesion of conductor chip and semiconductor chip further increases.In addition, by making the thickness of protective film formation film be above-mentioned
Upper limit value will more easily can be cut hereinafter, in the pickup of semiconductor chip using shearing force as the protective film of solidfied material
It is disconnected.
Thermosetting protective film formation film
As preferred thermosetting protective film formation film, it can be cited for example that containing component of polymer (A) and thermosetting property
The thermosetting protective film formation film of ingredient (B).Component of polymer (A) be can regard as polymerizable compound carry out polymerisation and
The ingredient of formation.In addition, thermosetting component (B) is that heat can be cured (polymerization) and be reacted as the releaser of reaction
Ingredient.It should be noted that in the present invention, polymerisation also includes polycondensation reaction.
< < thermosetting protective films, which are formed, uses composition > >
Thermosetting protective film formation film can use the thermosetting protective film formation composition containing its constituent material
To be formed.For example, thermosetting protective film formation composition is applied in the formation object surface of thermosetting protective film formation film,
It makes it dry as needed, so as to form thermosetting protective film formation film in target site.Thermosetting protective film is formed
With the content ratio of the ingredient not gasified under room temperature in composition to each other usually with thermosetting protective film formation film
The content ratio of mentioned component to each other is identical.Here, " room temperature " as previously described.
The coating of thermosetting protective film formation composition can carry out according to known methods, it can be cited for example that making
With Kohler coater, scraper plate coating machine, bar coater, gravure coater, roll coater, roller knife coating machine, curtain stream coating machine, die coating
The method of the various coating machines such as machine, knife type coater, silk screen coating machine, Meyer bar coater, kiss coater.
The drying condition of thermosetting protective film formation composition is not particularly limited, thermosetting protective film formation combination
In the case that object contains solvent described later, preferably make its heat drying.Thermosetting protective film formation group containing solvent
Object is closed for example preferably to be dried with the condition of 70~130 DEG C, 10 seconds~5 minutes.
< protective films, which are formed, uses composition (III-1) >
As thermosetting protective film formation composition, it can be cited for example that containing component of polymer (A) and thermosetting property at
The thermosetting protective film of point (B) is formed with composition (III-1) (in the present specification, sometimes referred to simply as " protective film formation group
Close object (III-1) ") etc..
[Component of polymer (A)s ]
Component of polymer (A) is the polymerization for assigning film forming, flexibility etc. to thermosetting protective film formation film
Close object.
Component of polymer (A) contained by protective film formation composition (III-1) and thermosetting protective film formation film can
To be only one kind, or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
As component of polymer (A), it can be cited for example that:Acrylic resin (the tree with (methyl) acryloyl group
Fat), polyester, urethane based resin (with urethane bond resin), propenoic methyl carbamate resin, organosilicon
Resinoid (resin with siloxanes key), rubber resin (resin with rubber structure), phenoxy resin, thermosetting property are poly-
Acid imide etc., preferably acrylic resin.
As the above-mentioned acrylic resin in component of polymer (A), well known acrylic polymer can be enumerated.
The weight average molecular weight (Mw) of acrylic resin is preferably 10000~2000000, more preferably 100000~
1500000.By making the weight average molecular weight of acrylic resin be above-mentioned lower limiting value or more, thermosetting protective film formation film
Shape stability (ageing stability when keeping) improves.In addition, by making the weight average molecular weight of acrylic resin be above-mentioned
Upper limit value can be further suppressed and glued hereinafter, thermosetting protective film formation is easy to follow the male and fomale(M&F) for the object that is stuck with film
It pastes and generates gap etc. between object and thermosetting protective film formation film.
The glass transition temperature (Tg) of acrylic resin is preferably -60~70 DEG C, more preferably -30~50 DEG C.It is logical
Crossing makes the Tg of acrylic resin be above-mentioned lower limiting value or more, can inhibit the bonding force between protective film and support chip, support chip
Fissility improves.In addition, by make acrylic resin Tg be above-mentioned upper limit value hereinafter, thermosetting protective film formation film and
Bonding force between protective film and the object that is stuck improves.
As acrylic resin, it can be cited for example that the polymer of one or more kinds of (methyl) acrylate;Choosing
From two kinds in (methyl) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N hydroxymethyl acrylamide etc. with
The copolymer etc. of upper monomer.
As above-mentioned (methyl) acrylate for constituting acrylic resin, it can be cited for example that:(methyl) acrylic acid first
Ester, (methyl) 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, (first
Base) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (first
Base) n-octyl, 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) acrylic acid 13
Arrcostab, (methyl) acrylic acid tetradecane base ester ((methyl) myristyl ester), (methyl) acrylic acid pentadecane base ester,
(methyl) aliphatic acrylate ((methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester, (methyl) propylene
The chain structure that the carbon atom number that sour stearyl ((methyl) stearyl acrylate) etc. constitutes the alkyl of Arrcostab is 1~18
(methyl) alkyl acrylate;
(methyl) the acrylate base esters such as (methyl) isobornyl acrylate, (methyl) dicyclopentanyl acrylate;
(methyl) benzyl acrylate etc. (methyl) acrylic acid aralkyl ester;
(methyl) acrylic acid cyclenes base ester such as (methyl) acrylic acid dicyclopentenyl ester;
(methyl) acrylic acid cyclenes oxygroup Arrcostab such as (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester;
(methyl) acrylimide;
(methyl) acrylate containing glycidyl such as (methyl) glycidyl acrylate;
(methyl) dihydroxypropyl methyl esters, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters,
(methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 3- hydroxybutyls, (methyl) third
(methyl) acrylate of the hydroxyls such as olefin(e) acid 4- hydroxybutyls;
(methyl) acrylate containing substituted-amino such as (methyl) acrylic acid N- methylamino ethyl esters etc..Wherein, " substitution
Amino " refers to, group made of 1 of amino or 2 hydrogen atoms are replaced by the group other than hydrogen atom.
Acrylic resin for example can also be other than above-mentioned (methyl) acrylate, also copolymerization have be selected from (methyl)
One or more of acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N hydroxymethyl acrylamide etc.
Monomer forms.
The monomer for constituting acrylic resin can be only one kind, or and it is two or more, it is two or more situations
Under, combination thereof and ratio can be selected arbitrarily.
Acrylic resin can lift vinyl, (methyl) acryloyl group, amino, hydroxyl, carboxyl, isocyanate group etc.
The functional group that can be bonded with other compounds.The above-mentioned functional group of acrylic resin can pass through crosslinking agent described later
(F) it is bonded, can not also be directly bonded with other compounds by crosslinking agent (F) with other compounds.Acrylic resin
When above-mentioned functional group is bonded with other compounds, the reliability that is encapsulated obtained from composite sheet using protective film formation
The tendency being improved.
In the present invention, as component of polymer (A), can also by other than acrylic resin thermoplastic resin (with
Under, sometimes referred to simply as " thermoplastic resin ") it is applied in combination with acrylic resin.By using above-mentioned thermoplastic resin, protection
Film is improved from the fissility on support chip or thermosetting protective film formation is easy to follow the male and fomale(M&F) for the object that is stuck with film, is had
When can further suppress to be stuck between object and thermosetting protective film formation film and generate gap etc..
The weight average molecular weight of above-mentioned thermoplastic resin is preferably 1000~100000, more preferably 3000~80000.
The glass transition temperature (Tg) of above-mentioned thermoplastic resin is preferably -30~150 DEG C, is more preferably -20~120
℃。
As above-mentioned thermoplastic resin, it can be cited for example that:Polyester, polyurethane, phenoxy resin, polybutene, polybutadiene
Alkene, polystyrene etc..
Above-mentioned thermoplastic resin contained by protective film formation composition (III-1) and thermosetting protective film formation film can
To be only one kind, or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
Protective film is formed in composition (III-1), the content of component of polymer (A) relative to other than solvent all at
The ratio (that is, content of the component of polymer (A) of thermosetting protective film formation film) of the total content divided is independent of polymer
The type of ingredient (A), preferably 5~50 mass %, more preferably 10~40 mass %, particularly preferably 15~35 mass %.
Component of polymer (A) is also equivalent to the case where thermosetting component (B).In the present invention, protective film formation group
In the case of object (III-1) is closed containing the ingredient for being equivalent to both such component of polymer (A) and thermosetting component (B), protect
Cuticula formation is considered as with composition (III-1) containing component of polymer (A) and thermosetting component (B).
[Thermosetting component (B)s ]
Thermosetting component (B) be for make thermosetting protective film formation with film be solidified to form hard protective film at
Point.
Thermosetting component (B) contained by protective film formation composition (III-1) and thermosetting protective film formation film can
To be only one kind, or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
As thermosetting component (B), it can be cited for example that epoxy-based thermosetting resin, Thermocurable polyimide, polyurethane,
Unsaturated polyester (UP), organic siliconresin etc., preferably epoxy-based thermosetting resin.
(epoxy-based thermosetting resin)
Epoxy-based thermosetting resin includes epoxy resin (B1) and thermal curing agents (B2).
Protective film is formed with the epoxy-based thermosetting resin contained by composition (III-1) and thermosetting protective film formation film
Can be only one kind, or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily
It selects.
Epoxy resin (B1)
As epoxy resin (B1), well known epoxy resin can be enumerated, it can be cited for example that:Multifunctional class asphalt mixtures modified by epoxy resin
Fat, biphenol compound, bis-phenol A glycidyl ether and its hydride, o-cresol phenolic resin varnish, bicyclopentadiene type ring
Oxygen resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenylene matrix type epoxy resin etc.,
Epoxides more than 2 functions.
As epoxy resin (B1), the epoxy resin with unsaturated alkyl can be used.With without unsaturated alkyl
Epoxy resin compare, the compatibility of epoxy resin and acrylic resin with unsaturated alkyl is high.Therefore, by using
Epoxy resin with unsaturated alkyl is improved using the reliability that protective film formation encapsulates obtained from composite sheet.
As the epoxy resin with unsaturated alkyl, it can be cited for example that the PART EPOXY base of multifunctional based epoxy resin
Group is converted into compound made of the group with unsaturated alkyl.Such compound for example can be by making (methyl) third
Olefin(e) acid or derivatives thereof carries out addition reaction with epoxy group and obtains.
In addition, as the epoxy resin with unsaturated alkyl, it can be cited for example that the group with unsaturated alkyl is straight
Connect compound etc. made of aromatic rings for being bonded to and constituting epoxy resin etc..
Unsaturated alkyl is the unsaturated group for having polymerism, sub as its concrete example, can enumerate vinyl
(vinyl group), 2- acrylic (allyl), (methyl) acryloyl group, (methyl) acrylamido etc., preferably acryloyl
Base.
It should be noted that in the present specification, " derivative " refers to, 1 or more hydrogen atom of former compound is by hydrogen original
Compound made of group (substituent group) substitution other than son.
The number average molecular weight of epoxy resin (B1) is not particularly limited, from the solidification of thermosetting protective film formation film
Property and solidification after protection film strength and heat resistance in terms of set out, preferably 300~30000, more preferably 300~
10000,300~3000 are particularly preferably.
The epoxide equivalent of epoxy resin (B1) is preferably 100~1100g/eq, more preferably 150~1000g/eq.
Epoxy resin (B1) can be used alone, and can also be used in combination of two or more, be used in combination of two or more
In the case of, combination thereof and ratio can be selected arbitrarily.
Thermal curing agents (B2)
Thermal curing agents (B2) are functioned as the curing agent of epoxy resin (B1).
As thermal curing agents (B2), it can be mentioned, for example:It can be with the official of epoxy reaction with 2 or more in 1 molecule
The compound that can be rolled into a ball.As above-mentioned functional group, it can be mentioned, for example:Phenolic hydroxyl group, alcoholic extract hydroxyl group, amino, carboxyl, acidic group through acid anhydrides and
At group etc., preferably phenolic hydroxyl group, amino or acidic group are through group made of acid anhydrides, more preferably phenolic hydroxyl group or amino.
As the phenols curing agent with phenolic hydroxyl group in thermal curing agents (B2), it can be mentioned, for example:Multifunctional phenolic resin,
Xenol, novolak phenolics, dicyclopentadiene class phenolic resin, aralkyl phenolic resin etc..
As the amine curing agent with amino in thermal curing agents (B2), it can be mentioned, for example:Dicyandiamide is (below also referred to as
For " DICY ") etc..
Thermal curing agents (B2) can also be the thermal curing agents with unsaturated alkyl.
As the thermal curing agents (B2) with unsaturated alkyl, it can be mentioned, for example:A part of quilt of the hydroxyl of phenolic resin
Compound, the group with unsaturated alkyl made of group substitution with unsaturated alkyl are bonded directly to phenolic resin
Compound made of aromatic ring etc..
Above-mentioned unsaturated alkyl in thermal curing agents (B2) be in the above-mentioned epoxy resin with unsaturated alkyl not
The identical group of saturated hydrocarbyl.
In the case of using phenols curing agent as thermal curing agents (B2), from protective film is improved from the fissility on support chip
From the perspective of, thermal curing agents (B2) are preferably softening point or the high thermal curing agents of glass transition temperature.
Thermal curing agents (B2) are preferably solid-state and not show curing activity to epoxy resin (B1) at normal temperatures, but another
Aspect is dissolved by heating and shows the thermal curing agents of curing activity (hereinafter, sometimes referred to simply as " heat epoxy resin (B1)
Active latent epoxy resin curing agent ").
Above-mentioned thermal activities latent epoxy resin curing agent at normal temperatures in thermosetting protective film formation film steadily
It is scattered in epoxy resin (B1), but compatible with epoxy resin (B1) by heating, is reacted with epoxy resin (B1).By making
It is significantly improved with the storage stability of above-mentioned thermal activities latent epoxy resin curing agent, protective film formation composite sheet.For example,
The curing agent is inhibited with film to the movement of adjacent support chip from protective film formation, can effectively inhibit thermosetting protective film
The thermosetting property of formation film reduces.Moreover, because the heat cure degree based on heating of thermosetting protective film formation film is further
Increase, the pick of the semiconductor chip described later with protective film further increases.
As above-mentioned thermal activities latent epoxy resin curing agent, it can be cited for example that:Salt, binary acid hydrazides, double cyanogen
The amine additives etc. of amine, curing agent.
In thermal curing agents (B2), such as multifunctional phenolic resin, novolak phenolics, bicyclopentadiene class phenolic aldehyde
The number average molecular weight of the resin components such as resin, aralkyl phenolic resin is preferably 300~30000, more preferably 400~
10000,500~3000 are particularly preferably.
In thermal curing agents (B2), such as the molecular weight of the non-resins ingredient such as bis-phenol, dicyandiamide is not particularly limited, such as excellent
It is selected as 60~500.
Thermal curing agents (B2) can be used alone, and can also be used in combination of two or more, be used in combination of two or more
In the case of, combination thereof and ratio can be selected arbitrarily.
In protective film formation composition (III-1) and thermosetting protective film formation film, relative to epoxy resin
(B1) content of 100 mass parts of content, thermal curing agents (B2) is preferably 0.1~500 mass parts, more preferably 1~200 mass
Part.By making the above-mentioned content of thermal curing agents (B2) be above-mentioned lower limiting value or more, it is easier to carry out thermosetting protective film and form use
The solidification of film.In addition, by making the above-mentioned content of thermal curing agents (B2) for above-mentioned upper limit value hereinafter, thermosetting protective film forms use
The hydroscopicity of film reduces, and the reliability encapsulated obtained from composite sheet using protective film formation is further increased.
In protective film formation composition (III-1) and thermosetting protective film formation film, relative to component of polymer
(A) 100 mass parts of content, the content of thermosetting component (B) is (for example, epoxy resin (B1) and thermal curing agents (B2's) always contains
Amount) it is preferably 1~100 mass parts, more preferably 1.5~85 mass parts, particularly preferably 2~70 mass parts.By making thermosetting
Property ingredient (B) above-mentioned content be such range, can inhibit the bonding force between protective film and support chip, the fissility of support chip
It improves.
[Curing accelerator (C)s ]
Protective film formation composition (III-1) and thermosetting protective film formation film can contain curing accelerator (C).
Curing accelerator (C) is the ingredient of the curing rate for adjusting protective film formation composition (III-1).
As preferred curing accelerator (C), it can be mentioned, for example:Triethylenediamine, benzyldimethylamine, 2,4, three ethyl alcohol
The tertiary amines such as amine, dimethylaminoethanol, three (dimethylaminomethyl) phenol;2-methylimidazole, 2- phenylimidazoles, 2- phenyl-
The imidazoles (1 such as 4-methylimidazole, 2- phenyl -4,5- bishydroxymethyls imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazoles
Imidazoles made of the above hydrogen atom is replaced by the group other than hydrogen atom);Tributylphosphine, diphenylphosphine, triphenylphosphine etc. are organic
Phosphine (phosphine made of 1 or more hydrogen atom is replaced by organic group);TetraphenylTetraphenyl borate salts, four benzene of triphenylphosphine
Tetraphenyl borate salts such as ylboronic acid salt etc..
Curing accelerator (C) contained by protective film formation composition (III-1) and thermosetting protective film formation film can
To be only one kind, or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the case of using curing accelerator (C), in protective film formation composition (III-1) and thermosetting protective film shape
At in film, relative to 100 mass parts of content of thermosetting component (B), the content of curing accelerator (C) is preferably 0.01~10
Mass parts, more preferably 0.1~5 mass parts.It, can be more by making the content of curing accelerator (C) more than above-mentioned lower limiting value
It significantly obtains using effect caused by curing accelerator (C).In addition, by making the content of curing accelerator (C) above-mentioned
Upper limit value hereinafter, for example being formed in thermosetting protective film under high temperature/super-humid conditions for highly polar curing accelerator (C)
It is improved with inhibition mobile to the bonding interface side with the object that is stuck and being segregated in film, uses thermosetting protective film shape
It is further increased at the reliability encapsulated obtained from film.
[Packing material (D)s ]
Protective film formation composition (III-1) and thermosetting protective film formation film can contain packing material (D).It is logical
Crossing makes thermosetting protective film formation film contain packing material (D), for making the solidification of thermosetting protective film formation film obtain
Protective film, be easily adjusted coefficient of thermal expansion.Moreover, optimizing the thermal expansion system by formation object for protective film
Number, the reliability encapsulated obtained from film using thermosetting protective film formation are further increased.In addition, by making thermosetting property protect
Cuticula formation film contains packing material (D), can also reduce the hydroscopicity of protective film, improve exothermicity.
Packing material (D) can be any materials in organic filler material and inorganic filling material, but preferably inorganic
Packing material.
As preferred inorganic filling material, it can be mentioned, for example:Silica, aluminium oxide, talcum, calcium carbonate, titanium white, iron
The powder such as red, silicon carbide, boron nitride;Bead made of spherical shape is made in these inorganic filling materials;These inorganic filling materials
Surface be modified product;The mono-crystlling fibre of these inorganic filling materials;Glass fibre etc..
In these materials, preferably inorganic filling material is silica or aluminium oxide.
Packing material (D) contained by protective film formation composition (III-1) and thermosetting protective film formation film can be with
It is only a kind of, or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the case of using packing material (D), in protective film formation in composition (III-1), other than solvent
Whole components total content, the ratio of the content of packing material (D) is (that is, the packing material of thermosetting protective film formation film
(D) content) it is preferably 5~80 mass %, more preferably 7~60 mass %.By making the content of packing material (D) in this way
Range, the adjustment of above-mentioned coefficient of thermal expansion becomes more to be easy.
[Coupling agent (E)s ]
Protective film formation composition (III-1) and thermosetting protective film formation film can contain coupling agent (E).Pass through
Using with heat can be made with the compound of the functional group of inorganic compound or organic compound reaction as coupling agent (E)
Solidity protective film formation film is improved relative to the cementability and adaptation of the object that is stuck.In addition, by using coupling agent (E),
The heat resistance of the 1st protective film 1a obtained from making thermosetting protective film formation film cure will not be caused impaired, and can be improved
Water resistance.
Coupling agent (E) preferably has can be with functional group possessed by component of polymer (A), thermosetting component (B) etc.
The compound of the functional group of reaction, more preferably silane coupling agent.
As preferred above-mentioned silane coupling agent, it can be mentioned, for example:3- glycidoxypropyltrime,hoxysilanes, 3- rings
Oxygen propoxypropyl methyldiethoxysilane, 3- glycidoxypropyl groups triethoxysilane, 3- glycidyl oxy methyls two
Ethoxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- methacryloxypropyl trimethoxy silicon
Alkane, 3- TSL 8330s, 3- (2- aminoethylaminos) propyl trimethoxy silicane, 3- (2- amino-ethyl ammonia
Base) hydroxypropyl methyl diethoxy silane, 3- (phenyl amino) propyl trimethoxy silicane, 3- anilino- propyl trimethoxy silicon
It is alkane, 3- ureas propyl-triethoxysilicane, 3-mercaptopropyi trimethoxy silane, 3- mercapto propyl methyl dimethoxy silanes, double
(3- triethoxysilylpropyltetrasulfides) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyl front three
Oxysilane, vinyltriacetoxy silane and imidizole silane etc..
Coupling agent (E) contained by protective film formation composition (III-1) and thermosetting protective film formation film can be only
For one kind, or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the case of using coupling agent (E), is formed and used in protective film formation composition (III-1) and thermosetting protective film
In film, relative to 100 mass parts of total content of component of polymer (A) and thermosetting component (B), the content of coupling agent (E) is preferred
For 0.03~20 mass parts, more preferably 0.05~10 mass parts, particularly preferably 0.1~5 mass parts.By making coupling agent
(E) content more than above-mentioned lower limiting value, can significantly more obtain packing material (D) in resin dispersibility raising,
Raising of cementability of thermosetting protective film formation film and the object that is stuck etc. uses effect caused by coupling agent (E).In addition,
By making the content of coupling agent (E) in above-mentioned upper limit value hereinafter, the generation of degassing (outgas) can be further suppressed.
[Crosslinking agent (F)s ]
As component of polymer (A), acrylic resin stated in use etc. has and can be bonded with other compounds
The ingredient of functional groups such as vinyl, (methyl) acryloyl group, amino, hydroxyl, carboxyl, isocyanate group in the case of, protection
Film formation composition (III-1) and thermosetting protective film formation film can contain crosslinking agent (F).Crosslinking agent (F) is to be used for
So that the above-mentioned functional group in component of polymer (A) is bonded and crosslinked ingredient with other compounds, be crosslinked in this way,
The initial bonding force and cohesiveness of thermosetting protective film formation film can be adjusted.
As crosslinking agent (F), it can be mentioned, for example:Organic polyisocyanate compound, organic more group with imine moiety, metal chelating
Close species crosslinking agent (crosslinking agent with metallo-chelate structure), aziridines crosslinking agent (crosslinking agent with '-aziridino)
Deng.
As above-mentioned organic polyisocyanate compound, it can be mentioned, for example:Aromatic polyisocyanate compound, aliphatic
These compounds (are also together simply referred to as " aromatic series by polyisocyanate compound and alicyclic polyisocyanates compound below
Polyisocyanate compound etc. ");The trimers such as above-mentioned aromatic polyisocyanate compound, isocyanuric acid ester body and adduct;
Terminal isocyanate carbamic acid obtained from making above-mentioned aromatic polyisocyanate compound etc. and polyol compound react
Ester prepolymer etc..Above-mentioned " adduct " indicates above-mentioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound
Or the low molecules such as alicyclic polyisocyanates compound and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil
The reactant of active hydrogen compounds.Example is obtained as above-mentioned adduct, trimethylolpropane as described later can be enumerated
Benzene dimethylene diisocyanate addition product etc..In addition, " the terminal isocyanate carbamate prepolymer " such as institute above
It states.
As above-mentioned organic polyisocyanate compound, more specifically, it can be mentioned, for example:2,4 toluene diisocyanate;
2,6- toluene di-isocyanate(TDI)s;1,3- benzene dimethylene diisocyanate;1,4- xylene diisocyanate;Diphenyl methane-
4,4 '-diisocyanate;Diphenyl methane -2,4 '-diisocyanate;3- Dimethyl diphenylmethane diisocyanate;Six methylenes
Group diisocyanate;Isophorone diisocyanate;Dicyclohexyl methyl hydride -4,4 '-diisocyanate;Dicyclohexyl methyl hydride -2,
4 '-diisocyanate;Addition has toluene di-isocyanate(TDI), six Asias on all or part of hydroxyl of the polyalcohols such as trimethylolpropane
In methyl diisocyanate and benzene dimethylene diisocyanate any one or it is two or more made of compound;Lysine
Diisocyanate etc..
As above-mentioned organic more group with imine moiety, it can be mentioned, for example:Bis- (the 1- aziridine of N, N '-diphenyl methane -4,4 ' -
Formamide) ,-three-β of trimethylolpropane-'-aziridino propionic ester ,-three-β of tetramethylol methane-'-aziridino propionic ester, N,
N '-Toluene-2,4-diisocyanates, bis- (1- aziridine formamide) triethylenemelanins of 4- etc..
It is excellent as component of polymer (A) in the case where using organic polyisocyanate compound as crosslinking agent (F)
Choosing uses the polymer of hydroxyl.Crosslinking agent (F) with isocyanate group, component of polymer (A) with hydroxyl in the case of,
By crosslinking agent (F) is with reacting for component of polymer (A) easily crosslinking knot can be imported to thermosetting protective film formation film
Structure.
Crosslinking agent (F) contained by protective film formation composition (III-1) and thermosetting protective film formation film can be only
For one kind, or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the case of using crosslinking agent (F), in protective film formation in composition (III-1), relative to component of polymer
(A) 100 mass parts of content, the content of crosslinking agent (F) be preferably 0.01~20 mass parts, more preferably 0.1~10 mass parts,
Particularly preferably 0.5~5 mass parts.By making the above-mentioned content of crosslinking agent (F) more than above-mentioned lower limiting value, can significantly more obtain
Obtain the effect for using crosslinking agent (F) and bringing.In addition, by making the above-mentioned content of crosslinking agent (F) in above-mentioned upper limit value hereinafter, can
Inhibit bonding force, thermosetting protective film formation film and semiconductor wafer between thermosetting protective film formation film and support chip or
Bonding force between semiconductor chip excessively reduces.
In the present invention, the effect of the present invention can be fully obtained without using crosslinking agent (F).
[Energy ray-curable resin (G)s ]
Protective film formation composition (III-1) can contain energy ray-curable resin (G).Thermosetting protective film is formed
With film by containing energy ray-curable resin (G), characteristic can be changed based on the irradiation of energy line.
Energy ray-curable resin (G) is that energy line curability compound is made to polymerize resin obtained from (solidification).
As above-mentioned energy ray-curable compound, it can be mentioned, for example:The intramolecular at least change with 1 polymeric double bond
Close object, it is however preferred to have the acrylic ester compound of (methyl) acryloyl group.
As above-mentioned acrylic ester compound, it can be mentioned, for example:Trimethylolpropane tris (methyl) acrylate, four hydroxyls
Methylmethane four (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, two
Pentaerythrite monohydroxy five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1,4- butanediols two (methyl)
(methyl) acrylate of the races containing chain fatty such as acrylate, 1,6-hexylene glycols two (methyl) acrylate skeleton;Two (first
Base) skeleton containing annular aliphatic such as dicyclopentanyl acrylate (methyl) acrylate;Polyethylene glycol two (methyl) acrylate
Etc. polyalkylene glycol (methyl) acrylate;Oligoester (methyl) acrylate;Carbamate (methyl) acrylate is low
Polymers;Epoxy-modified (methyl) acrylate;Polyethers (methyl) third other than above-mentioned polyalkylene glycol (methyl) acrylate
Olefin(e) acid ester;Itaconic acid oligomer etc..
The weight average molecular weight of above-mentioned energy ray-curable compound is preferably 100~30000, more preferably 300~
10000。
Above-mentioned energy ray-curable compound for polymerization can be only one kind, or and it is two or more, it is two kinds
In the case of above, combination thereof and ratio can be selected arbitrarily.
Energy ray-curable resin (G) contained by protective film formation composition (III-1) can be only one kind, can also
It is two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the case of using energy ray-curable resin (G), protective film forms the energy line curing with composition (III-1)
Property resin (G) content be preferably 1~95 mass %, more preferably 2~90 mass %, particularly preferably 3~85 mass %.
[Photoepolymerizationinitiater initiater (H)s ]
In the case that protective film formation contains energy ray-curable resin (G) with composition (III-1), in order to make energy line
The polymerisation of curable resin (G) is effectively performed, and can also contain Photoepolymerizationinitiater initiater (H).
As Photoepolymerizationinitiater initiater (H) of the protective film formation in composition (III-1), it can enumerate and be combined with adhesive
The identical Photoepolymerizationinitiater initiater of Photoepolymerizationinitiater initiater in object (ii).
Photoepolymerizationinitiater initiater (H) contained by protective film formation composition (III-1) can be only one kind, or two
Kind or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the case of using Photoepolymerizationinitiater initiater (H), in protective film formation in composition (III-1), relative to energy
100 mass parts of content of line curable resin (G), the content of Photoepolymerizationinitiater initiater (H) is preferably 0.1~20 mass parts, more excellent
It is selected as 1~10 mass parts, particularly preferably 2~5 mass parts.
[Colorant (I)s ]
Protective film formation composition (III-1) and thermosetting protective film formation film can contain colorant (I).
As colorant (I), it can be cited for example that well known to inorganic system's pigment, organic system pigment, organic based dye etc.
Toner.
As above-mentioned organic system pigment and organic based dye, it can be cited for example that:Ammonium system pigment, cyanine system pigment, portion are spent
Blueness is pigment, crocic acid system pigment, side's acidBe pigment, azulene (azulenium) it is pigment, polymethine system pigment, naphthoquinones
It is pigment, pyransIt is pigment, phthalocyanine system pigment, naphthalene phthalocyanine system pigment, naphthalene lactim system pigment, azo system pigmen, condensation
Azo system pigmen, purple cyclic ketones system pigment, is pigment, two at indigo system's pigmentPiperazine system pigment, quinacridone pigment, different Yin
(metallic complex salt contaminates for diindyl quinoline ketone system pigment, quinophthalone system pigment, azole series pigment, thioindigo system pigment, metal complex system pigment
Material), dithiol metal complex system pigment, indoles phenol system pigment, triallyl methane system pigment, anthraquinone system pigment, twoPiperazine
It is pigment, naphthols system pigment, azomethine system pigment, benzimidazolone system pigment, pyranthrone system pigment and intellectual circle system pigment etc..
As above-mentioned inorganic system's pigment, it can be cited for example that:Carbon black, cobalt system pigment, iron system pigment, chromium system pigment, titanium system
Pigment, vanadium system pigment, zirconium system pigment, molybdenum system pigment, ruthenium system pigment, platinum group pigment, ITO (tin indium oxide) are pigment, ATO (oxygen
Change antimony tin) it is pigment etc..
Colorant (I) contained by protective film formation composition (III-1) and thermosetting protective film formation film can be only
For one kind, or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the case of using colorant (I), the colorant (I) of thermosetting protective film formation film if content according to mesh
Suitable adjusting.E.g., including protective film passes through and adjusts thermosetting property protection by the way that laser irradiation implements lettering the case where
The content of the colorant (I) of film formation film and the translucency for adjusting protective film, can adjust lettering visibility.In addition,
By adjusting the content of the colorant (I) of thermosetting protective film formation film, the design of protective film can also be improved and made
The grinding trace for obtaining back surface of semiconductor wafer is not readily apparent.If it is considered that this point, then in protective film formation composition (III-
1) in, the content of colorant (I) relative to the total content of the whole components in addition to solvent ratio (that is, thermosetting protective film
Form the content of the colorant (I) of film) it is preferably 0.1~10 mass %, more preferably 0.1~7.5 mass %, particularly preferred
For 0.1~5 mass %, such as it can be the arbitrary content of 0.1~3 mass % and 0.1~1 mass %.By making colorant (I)
Above-mentioned content be above-mentioned lower limiting value more than, can significantly more obtain using effect caused by colorant (I).In addition, passing through
Make colorant (I) above-mentioned content be above-mentioned upper limit value hereinafter, the translucency that can inhibit thermosetting protective film formation film is excessive
It reduces.
[Universal additive (J)s ]
Protective film forms composition (III-1) and thermosetting protective film formation can not damage effect of the present invention with film
In the range of contain universal additive (J).
Universal additive (J) can be well known additive, can select, be not particularly limited according to purpose and arbitrarily, make
For preferred universal additive, it can be mentioned, for example:Plasticizer, antistatic agent, antioxidant, getter etc..
Universal additive (I) contained by protective film formation composition (III-1) and thermosetting protective film formation film can
To be only one kind, or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
Protective film forms the content of the universal additive (I) with composition (III-1) and thermosetting protective film formation film
It is not particularly limited, it can be according to purpose suitable for selection.
[Rong Ji ]
Protective film formation composition (III-1) preferably further contains solvent.Protective film formation group containing solvent
The operability for closing object (III-1) is good.
Above-mentioned solvent is not particularly limited.
As preferred above-mentioned solvent, it can be cited for example that:The hydrocarbon such as toluene, dimethylbenzene;Methanol, ethyl alcohol, 2- propyl alcohol, isobutyl
The alcohol such as alcohol (2- methylpropane -1- alcohol), n-butyl alcohol;The esters such as ethyl acetate, butyl acetate;The ketone such as acetone, methyl ethyl ketone;Tetrahydrofuran
Equal ethers;Amides such as dimethylformamide, N-Methyl pyrrolidone (compound with amido bond) etc..
Solvent contained by protective film formation composition (III-1) can be only one kind, or and it is two or more, it is two
Kind or more in the case of, combination thereof and ratio can be selected arbitrarily.
From can more uniformly ingredient mixing aspect will be contained in protective film formation composition (III-1), protect
It is preferably methyl ethyl ketone etc. that cuticula, which is formed with the solvent contained by composition (III-1),.
The manufacturing method > > of < < thermosetting protective film formation compositions
The thermosetting protective films formation such as protective film formation composition (III-1) composition can be by coordinating for constituting
Its each ingredient and obtain.
Coordinate order of addition when each ingredient to be not particularly limited, two or more ingredients can also be added simultaneously.
It, can be by solvent be mixed with the arbitrary gradation composition other than solvent by the cooperation in the case of using solvent
It uses, the arbitrary gradation composition other than solvent can not also be diluted in advance after ingredient beforehand dilution, but by will be molten
Agent is mixed with these gradation compositions and is used.
For the method that each ingredient mixes is not particularly limited when cooperation, from so that stirrer or agitating paddle etc. is rotated and into
In method well known to the mixed method of row, the method mixed using method that mixer is mixed, application ultrasonic wave etc.
Appropriate selection.
The temperature and time when addition and mixing of each ingredient is not as long as in the case where causing each gradation composition to deteriorate
It is not particularly limited, it is appropriate to adjust, but preferable temperature is 15~30 DEG C.
Energy ray-curable protective film formation film
Energy ray-curable protective film formation film contains energy ray-curable ingredient (a).
Energy ray-curable ingredient (a) is preferably uncured, preferably have adhesiveness, more preferably it is uncured and with bonding
Property.Here, " energy line " and " energy ray-curable " as previously described
< < energy ray-curable protective films, which are formed, uses composition > >
Energy ray-curable protective film formation film can use the energy ray-curable protective film containing its constituent material
Formation composition and formed.For example, applying energy line in the formation object surface of energy ray-curable protective film formation film
Curability protective film formation composition, makes it dry as needed, it is possible thereby to form energy ray-curable in target site
Protective film formation film.The ingredient that does not gasify under room temperature in energy ray-curable protective film formation composition is to each other
Content ratio is usually identical as the content ratio of the mentioned component of energy ray-curable protective film formation film to each other.Here,
" room temperature " as previously described.
The coating of energy ray-curable protective film formation composition can carry out according to known methods, can enumerate
Such as using Kohler coater, scraper plate coating machine, bar coater, gravure coater, roll coater, roller knife coating machine, curtain stream coating machine,
The method of the various coating machines such as die coating machine, knife type coater, silk screen coating machine, Meyer bar coater, kiss coater.
The drying condition of energy ray-curable protective film formation composition is not particularly limited, energy ray-curable protection
In the case that film formation composition contains solvent described later, preferably make its heat drying.Energy line containing solvent is solid
The property changed protective film formation composition preferably drying under conditions of such as 70~130 DEG C, 10 seconds~5 minutes.
< protective films, which are formed, uses composition (IV-1) >
As energy ray-curable protective film formation composition, it can be cited for example that containing above-mentioned energy ray-curable at
The energy ray-curable protective film of point (a) is formed with composition (IV-1) (in the present specification, sometimes referred to simply as " protective film shape
At with composition (IV-1) ") etc..
[Energy ray-curable ingredient (a) ]
Energy ray-curable ingredient (a) is by energy line irradiates cured ingredient, and for energy line curing
Property protective film formation film assign film forming, flexibility etc. ingredient.
As energy ray-curable ingredient (a), it can be cited for example that the weight average molecular weight with energy ray-curable group
For 80000~2000000 polymer (a1) and chemical combination that the molecular weight with energy ray-curable group is 100~80000
Object (a2).Above-mentioned polymer (a1) can be that crosslinked polymer has occurred by crosslinking agent in its at least part, can also
It is the polymer not crosslinked.
(polymer (a1) that the weight average molecular weight with energy ray-curable group is 80000~2000000)
The polymer (a1) for being 80000~2000000 as the weight average molecular weight with energy ray-curable group, can arrange
Citing is such as:By with can with the acrylic polymer (a11) for the functional group that group reacts possessed by other compounds and
Energy ray-curable with group and energy ray-curable double bond Isoenergetical line curative group with above-mentioned functional group reactions
The acrylic resin (a1-1) that compound (a12) is polymerized.
As the above-mentioned functional group that can be reacted with group possessed by other compounds, it can be mentioned, for example:Hydroxyl, carboxylic
Base, amino, substituted-amino (group made of 1 of amino or 2 hydrogen atoms are replaced by the group other than hydrogen atom), epoxy group
Deng.Wherein, from the viewpoint of the circuit etch for preventing semiconductor wafer, semiconductor chip etc., preferably above-mentioned functional group is carboxylic
Group other than base.
In these, above-mentioned functional group is preferably hydroxyl.
Acrylic polymer (a11) with functional group
As the acrylic polymer (a11) with above-mentioned functional group, it can be mentioned, for example:By with above-mentioned functional group
Acrylic monomer and without above-mentioned functional group acrylic monomer copolymerization made of polymer, can also be in addition to these
Copolymer obtained from monomer (non-acrylic monomer) other than monomer other than further co-polypropylene acrylic monomer.
In addition, above-mentioned acrylic polymer (a11) can be random copolymer, can also be block copolymer.
As the acrylic monomer with above-mentioned functional group, it can be mentioned, for example:Hydroxyl monomer, contains carboxyl group-containing monomer
Amino monomers, monomer containing substituted-amino, containing epoxy based monomers etc..
As above-mentioned hydroxyl monomer, it can be mentioned, for example:(methyl) dihydroxypropyl methyl esters, (methyl) acrylic acid 2- hydroxyls
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 above-mentioned carboxyl group-containing monomer, it can be mentioned, for example:The olefinics unsaturated monocarboxylic acids such as (methyl) acrylic acid, crotonic acid
(monocarboxylic acid with ethylenic unsaturated bond);The olefinics unsaturated dicarboxylic acid such as fumaric acid, itaconic acid, maleic acid, citraconic acid
(dicarboxylic acids with ethylenic unsaturated bond);The acid anhydrides of above-mentioned olefinic unsaturated dicarboxylic acid;Methacrylic acid 2- carboxyl second
Ester etc. (methyl) acrylic acid carboxyalkyl ester etc..
The preferred hydroxyl monomer of acrylic monomer, carboxyl group-containing monomer with above-mentioned functional group, more preferable hydroxyl list
Body.
The acrylic monomer with above-mentioned functional group for constituting above-mentioned acrylic polymer (a11) can be only one
Kind, or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
As the acrylic monomer without above-mentioned functional group, it can be cited for example that:(methyl) methyl acrylate, (first
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
(the first for the chain structure that the carbon atom number that Arrcostab ((methyl) stearyl acrylate) etc. constitutes the alkyl of Arrcostab is 1~18
Base) alkyl acrylate etc..
In addition, as the acrylic monomer without above-mentioned functional group, also it can be mentioned, for example:(methyl) acrylic acid methoxy
Base methyl esters, (methyl) methoxyethyl acrylate, (methyl) ethioxy methyl esters, (methyl) ethoxyethyl acrylate etc.
(methyl) acrylate containing alkoxyalkyl;Including having for (methyl) phenyl acrylate etc. (methyl) benzyl acrylate etc.
(methyl) acrylate of aromatic group;(methyl) acrylamide and its derivative of non-crosslinked property;(methyl) acrylic acid N,
N- dimethylamino ethyl esters, (methyl) acrylic acid N, N- dimethylamino propyl ester etc. have (methyl) of the tertiary amino of non-crosslinked property
Acrylate etc..
The acrylic monomer without above-mentioned functional group for constituting above-mentioned acrylic polymer (a11) can be only one
Kind, or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
As above-mentioned non-acrylic monomer, it can be cited for example that:The alkene such as ethylene, norbornene;Vinyl acetate;Benzene
Ethylene etc..
The above-mentioned non-acrylic monomer for constituting above-mentioned acrylic polymer (a11) can be only one kind, or
Two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In above-mentioned 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 above-mentioned functional group is preferably 0.1~50 mass %, more
Preferably 1~40 mass %, particularly preferably 3~30 mass %.By making aforementioned proportion be such range, by above-mentioned third
Alkene acids polymers (a11) and above-mentioned energy ray-curable compound (a12) are through above-mentioned acrylic resin obtained from copolymerization
(a1-1) in, the curing degree of protective film easily can be adjusted to preferred range by the content of energy ray-curable group.
The above-mentioned acrylic polymer (a11) for constituting above-mentioned acrylic resin (a1-1) can be only one kind, also may be used
Think it is two or more, in the case of two or more, combination thereof and ratio can be selected arbitrarily.
In protective film formation in composition (IV-1), the content of acrylic resin (a1-1) is preferably 1~40 matter
Measure %, more preferably 2~30 mass %, particularly preferably 3~20 mass %.
Energy ray-curable compound (a12)
Above-mentioned energy ray-curable compound (a12) preferably has one in isocyanate group, epoxy group and carboxyl
Kind or it is two or more as can with the group of functional group reactions possessed by above-mentioned acrylic polymer (a11), more preferably
With isocyanate group as above-mentioned group.Above-mentioned energy ray-curable compound (a12) is for example made with isocyanate group
In the case of above-mentioned group, which is easy have acrylic polymer of the hydroxyl as functional group with above-mentioned
(a11) the hydroxyl reacts.
Above-mentioned energy ray-curable compound (a12) has 1~5 above-mentioned energy ray-curable base preferably in 1 molecule
Group more preferably has 1~2.
As above-mentioned energy ray-curable compound (a12), it can be mentioned, for example:2- methacryloxyethyl isocyanic acids
Ester, isopropenyl-bis (alpha, alpha-dimethylbenzyl) based isocyanate, methacryl isocyanates, allyl isocyanate, 1,1- are (double
Acryloyloxymethyl) ethyl isocyanate;
By diisocyanate cpd or polyisocyanate compound and (methyl), Hydroxyethyl Acrylate is reacted and obtains
The acryloyl group monoisocyanate compound arrived;
By diisocyanate cpd or polyisocyanate compound, polyol compound and (methyl) dihydroxypropyl second
Acryloyl group monoisocyanate compound etc. obtained from ester is reacted.
In these compounds, above-mentioned energy ray-curable compound (a12) is preferably that 2- methacryloxyethyls are different
Cyanate.
The above-mentioned energy ray-curable compound (a12) for constituting above-mentioned acrylic resin (a1-1) can be only one kind,
Or it is two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In above-mentioned acrylic resin (a1-1), relative to the above-mentioned official from above-mentioned acrylic polymer (a11)
The content that can be rolled into a ball, the ratio of the content of the energy ray-curable group from above-mentioned energy ray-curable compound (a12) are preferred
For 20~120 moles of %, more preferably 35~100 moles of %, particularly preferably 50~100 moles of %.By making above-mentioned content
Ratio be such range, the bonding force of the protective film after solidification further increases.It should be noted that in above-mentioned energy line
In the case that curability compound (a12) is simple function (with 1 above-mentioned group in 1 molecule) compound, above-mentioned content
The upper limit value of ratio is 100 moles of %, but (has 2 in 1 molecule in above-mentioned energy ray-curable compound (a12) to be multifunctional
A above above-mentioned group) in the case of compound, the upper limit value of the ratio of above-mentioned content is sometimes more than 100 moles of %.
The weight average molecular weight (Mw) of above-mentioned polymer (a1) is preferably 100000~2000000, more preferably 300000~
1500000。
Here, described " weight average molecular weight " is as mentioned before.
Above-mentioned polymer (a1) is its at least part in the case that crosslinked polymer has occurred in crosslinking agent, on
It can be by being not belonging to be illustrated as the monomer for constituting above-mentioned acrylic polymer (a11) to state polymer (a1)
Any one of above-mentioned monomer and it is with the monomer of group reacted with crosslinking agent aggregated and to be reacted with above-mentioned crosslinking agent
Compound made of group crosslinking can also be with coming from above-mentioned energy ray-curable compound (a12) with above-mentioned functional group
Compound made of the group crosslinking of reaction.
Protective film is formed with the above-mentioned polymer contained by composition (IV-1) and energy ray-curable protective film formation film
(a1) it can be only one kind, or two or more, in the case of being two or more, combination thereof and ratio can be arbitrary
Selection.
(compound (a2) that the molecular weight with energy ray-curable group is 100~80000)
Energy possessed by the compound (a2) for being 100~80000 as the molecular weight with energy ray-curable group
Line curative group can enumerate the group for including energy ray-curable double bond, preferably enumerate (methyl) acryloyl group, vinyl
Deng.
Above compound (a2) can be enumerated as long as the compound for meeting above-mentioned condition is then not particularly limited:With energy
Measure the low molecular weight compound of line curative group, the epoxy resin with energy ray-curable group, with energy line curing
The phenolic resin etc. of property group.
As the low molecular weight compound with energy ray-curable group in above compound (a2), it can be mentioned, for example
Polyfunctional monomer or oligomer etc., the preferably acrylic ester compound with (methyl) acryloyl group.
As above-mentioned acrylic ester compound, it can be mentioned, for example:2- hydroxyls -3- (methyl) acryloxypropyl
Acrylate, polyethylene glycol two (methyl) acrylate, propoxylation Ethoxylated bisphenol A bis- (methyl) acrylate, 2,2-
Shuan [4- ((methyl) acryloyl-oxy Quito ethyoxyl) phenyl;Propane, Ethoxylated bisphenol A bis- (methyl) acrylate, 2,2- are bis-
[4- ((methyl) acryloxy diethoxy) Ben Ji ]The bis- [ of propane, 9,9-;4- (2- (methyl) acryloyloxyethoxy) benzene
Ji ]The bis- [ of fluorenes, 2,2-;4- ((methyl) acryloyl-oxy Quito propoxyl group) phenyl;Propane, Tricyclodecane Dimethanol two (methyl) propylene
Acid esters, 1,10- decanediols two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, two (first of 1,9- nonanediols
Base) acrylate, dipropylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, two (first of polypropylene glycol
Base) acrylate, polytetramethylene glycol two (methyl) acrylate, ethylene glycol two (methyl) acrylate, diethylene glycol two
(methyl) acrylate, triethylene glycol two (methyl) acrylate, the bis- [ of 2,2-;4- ((methyl) acryloyloxyethoxy) benzene
Ji ]Propane, neopentyl glycol two (methyl) acrylate, ethoxylated polypropylene glycol two (methyl) acrylate, 2- hydroxyls -1,3-
Two (methyl) acryloxy propane etc. difunctionalities (methyl) acrylate;
Three (2- (methyl) acryloyl-oxyethyl) isocyanuric acid esters, 6-caprolactone are modified three (2- (methyl) acryloyl-oxies
Base ethyl) isocyanuric acid ester, ethoxylated glycerol three (methyl) acrylate, pentaerythrite three (methyl) acrylate, three hydroxyls
Methylpropane three (methyl) acrylate, double trimethylolpropane four (methyl) acrylate, four (first of ethoxylation pentaerythrite
Base) acrylate, pentaerythrite four (methyl) acrylate, more (methyl) acrylate of dipentaerythritol, dipentaerythritol six
The multifunctional (methyl) acrylates such as (methyl) acrylate;
Multifunctional (methyl) acrylates oligomer such as carbamate (methyl) acrylate oligomer etc..
As in above compound (a2) the epoxy resin with energy ray-curable group, with energy ray-curable
The tree described in such as in the 0043rd section of " Japanese Unexamined Patent Publication 2013-194102 bulletins " can be used in the phenolic resin of group
Fat.Such resin also corresponds to constitute the resin of the thermosetting component described below, but in the present invention, as above-mentioned chemical combination
Object (a2) processing.
The weight average molecular weight of above compound (a2) is preferably 100~30000, more preferably 300~10000.
Protective film is formed with the above compound contained by composition (IV-1) and energy ray-curable protective film formation film
(a2) it can be only one kind, or two or more, in the case of being two or more, combination thereof and ratio can be arbitrary
Selection.
[Polymer (b) ] without energy ray-curable group;
Protective film formation composition (IV-1) and energy ray-curable protective film formation film are containing above compound
(a2) as in the case of above-mentioned energy ray-curable ingredient (a), preferably also further contain and do not have energy ray-curable base
The polymer (b) of group.
Above-mentioned polymer (b) can be that crosslinked polymer has occurred by crosslinking agent in its at least part, can also
It is the polymer not crosslinked.
As the polymer (b) without energy ray-curable group, it can be mentioned, for example:Acrylic polymer, benzene oxygen
Resin, polyurethane resin, polyester, rubber resin, propenoic methyl carbamate resin etc..
In these polymer, above-mentioned polymer (b) is preferably acrylic polymer (hereinafter, sometimes referred to simply as " acrylic acid
Type of Collective object (b-1) ").
Acrylic polymer (b-1) can be those of known, such as can be a kind of homopolymerization of acrylic monomer
Object can also be the copolymer of two or more acrylic monomers, can also be one or more kinds of acrylic monomers and
The copolymer of monomer (non-acrylic monomer) other than one or more kinds of acrylic monomers.
As constitute acrylic polymer (b-1) above-mentioned acrylic monomer, it can be mentioned, for example:(methyl) acrylic acid
(the first of Arrcostab, (methyl) acrylate with cyclic skeleton, (methyl) acrylate containing glycidyl, hydroxyl
Base) acrylate, (methyl) acrylate etc. containing substituted-amino.Here, described " substituted-amino " is as mentioned before.
As above-mentioned (methyl) alkyl acrylate, it can be cited for example that:(methyl) methyl acrylate, (methyl) acrylic acid
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) propylene for the chain structure that the carbon atom number that ((methyl) stearyl acrylate) etc. constitutes the alkyl of Arrcostab is 1~18
Acid alkyl ester etc..
As above-mentioned (methyl) acrylate with cyclic skeleton, it can be cited for example that:(methyl) isobomyl acrylate
(methyl) the acrylate base esters such as ester, (methyl) dicyclopentanyl acrylate;
(methyl) benzyl acrylate etc. (methyl) acrylic acid aralkyl ester;
(methyl) acrylic acid cyclenes base ester such as (methyl) acrylic acid dicyclopentenyl ester;
(methyl) acrylic acid cyclenes oxygroup Arrcostab such as (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester etc..
As above-mentioned (methyl) acrylate containing glycidyl, it can be cited for example that (methyl) glycidyl
Ester etc..
As (methyl) acrylate of above-mentioned hydroxyl, it can be cited for example that:(methyl) dihydroxypropyl methyl esters, (first
Base) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) propylene
Sour 2- hydroxybutyls, (methyl) acrylic acid 3- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls etc..
As above-mentioned (methyl) acrylate containing substituted-amino, it can be mentioned, for example:(methyl) acrylic acid N- methylaminos
Ethyl ester etc..
As constitute acrylic polymer (b-1) above-mentioned non-acrylic monomer, it can be mentioned, for example:Ethylene, drop ice
The alkene such as piece alkene;Vinyl acetate;Styrene etc..
Crosslinked above-mentioned gathering without energy ray-curable group is had occurred by crosslinking agent as at least part
Object (b) is closed, it can be mentioned, for example:Polymer made of reactive functional groups in above-mentioned polymer (b) are reacted with crosslinking agent.
Above-mentioned reactive functional groups are suitably selected according to type of crosslinking agent etc., are not particularly limited.For example, crosslinking
In the case that agent is polyisocyanate compound, as above-mentioned reactive functional groups, hydroxyl, carboxyl, amino etc. can be enumerated, at this
In a little functional groups, preferably with the hydroxyl with high reactivity of isocyanate group.In addition, the case where crosslinking agent is epoxy compounds
Under, as above-mentioned reactive functional groups, carboxyl, amino, amide groups etc. can be enumerated, in these functional groups, preferably and epoxy
The carboxyl with high reactivity of base.Wherein, from the viewpoint of the circuit etch for preventing semiconductor wafer, semiconductor chip etc., on
It is preferably the group other than carboxyl to state reactive functional groups.
As the polymer (b) without energy ray-curable group with above-mentioned reactive functional groups, example can be enumerated
Such as:At least make polymer obtained from the monomer polymerization with above-mentioned reactive functional groups.If it is acrylic polymer (b-
1) the case where, is then enumerated above-mentioned using the monomer with above-mentioned reactive functional groups as to constitute the monomer of the polymer
In acrylic monomer and non-acrylic monomer any one or both.As with hydroxyl as reactive functional
The above-mentioned polymer (b) of group, it can be mentioned, for example polymer obtained from (methyl) acrylic ester polymerization by hydroxyl, except this with
Outside, it can also enumerate by 1 or 2 or more hydrogen atom in the above-mentioned acrylic monomer of aforementioned list or non-acrylic monomer
Polymer obtained from monomer polymerization made of being replaced by above-mentioned reactive functional groups.
In the above-mentioned polymer (b) with reactive functional groups, relative to the total of the structural unit for constituting the polymer
Amount is preferably 1~20 mass %, more by the ratio (content) of the amount of the structural unit of the monomer derived with reactive functional groups
Preferably 2~10 mass %.By making aforementioned proportion be such range, the crosslinked degree in above-mentioned polymer (b) can reach
To preferred range.
From the viewpoint of the film forming of protective film formation composition (IV-1) becomes more good, do not have energy line
The weight average molecular weight (Mw) of the polymer (b) of curative group is preferably 10000~2000000, more preferably 100000~
1500000.Here, described " weight average molecular weight " is as mentioned before.
Protective film is formed does not have energy with contained by composition (IV-1) and energy ray-curable protective film formation film
The polymer (b) of line curative group can be only one kind, or and it is two or more, in the case of being two or more, they
Combination and ratio can arbitrarily select.
As protective film formation with composition (IV-1), can enumerate containing above-mentioned polymer (a1) and above compound
(a2) in any one or both composition.Also, contain above compound in protective film formation composition (IV-1)
(a2) in the case of, preferably also further contain without energy ray-curable group polymer (b), at this point, further preferably into
One step contains above-mentioned (a1).In addition, protective film formation composition (IV-1) can not also be same containing above compound (a2)
The above-mentioned polymer of Shi Hanyou (a1) and the polymer (b) without energy ray-curable group.
Protective film is formed with composition (IV-1) containing above-mentioned polymer (a1), above compound (a2) and without energy
In the case of the polymer (b) of line curative group, in protective film formation in composition (IV-1), relative to above-mentioned polymer
(a1) and 100 mass parts of the total content of the polymer (b) without energy ray-curable group, the content of above compound (a2)
Preferably 10~400 mass parts, more preferably 30~350 mass parts.
In protective film formation in composition (IV-1), above-mentioned energy ray-curable ingredient (a) and solid without energy line
Change property group polymer (b) total content relative to the ingredient other than solvent total content ratio (that is, energy line curing
The above-mentioned energy ray-curable ingredient (a) of property protective film formation film and the polymer (b) without energy ray-curable group
Total content) be preferably 5~90 mass %, more preferably 10~80 mass %, particularly preferably 20~70 mass %.Pass through
It is such range, the energy of energy ray-curable protective film formation film to make the aforementioned proportion of the content of energy line curability composition
Amount line curability can become more good.
Protective film, which is formed, to be used in composition (IV-1) other than above-mentioned energy ray-curable ingredient, can also be according to purpose
And containing in thermosetting component, Photoepolymerizationinitiater initiater, packing material, coupling agent, crosslinking agent, colorant and universal additive
One or more.For example, by using the protective film shape containing above-mentioned energy ray-curable ingredient and thermosetting component
At with composition (IV-1), the bonding force relative to the object that is stuck for being formed by energy ray-curable protective film formation film is logical
It crosses heating and improves, the protection film strength formed with film by the energy ray-curable protective film formation also improves.
As protective film formation in composition (IV-1) above-mentioned thermosetting component, Photoepolymerizationinitiater initiater, packing material,
Coupling agent, crosslinking agent, colorant and universal additive, can enumerate respectively with energy line curing resin composition (III-1) in
Thermosetting component (B), Photoepolymerizationinitiater initiater (H), packing material (D), coupling agent (E), crosslinking agent (F), colorant (I) and logical
It is those of identical with additive (J).
Protective film, which is formed, to be used in composition (IV-1), above-mentioned thermosetting component, Photoepolymerizationinitiater initiater, packing material, coupling
Agent, crosslinking agent, colorant and universal additive can use individually one kind, can also be used in combination of two or more, combination
In the case of two or more uses, combination thereof and ratio can be selected arbitrarily.
Protective film is formed with the above-mentioned thermosetting component in composition (IV-1), Photoepolymerizationinitiater initiater, packing material, coupling
Agent, crosslinking agent, colorant and universal additive content suitably adjusted according to purpose, be not particularly limited.
For protective film formation composition (IV-1), from its operability aspect can be improved by dilution,
Preferably further contain solvent.
As solvent of the protective film formation contained by composition (IV-1), it can be cited for example that being formed with protective film with combining
The identical solvent of solvent in object (III-1).
Solvent contained by protective film formation composition (IV-1) can be only one kind, or two or more.
The manufacturing method > > of < < energy ray-curable protective film formation compositions
Protective film formation composition (IV-1) Isoenergetical line curability protective film formation composition can be by that will be used for
It constitutes its each components matching and obtains.
Coordinate order of addition when each ingredient to be not particularly limited, two or more ingredients can also be added simultaneously.
It, can be by solvent be mixed with the arbitrary gradation composition other than solvent by the cooperation in the case of using solvent
It uses, the arbitrary gradation composition other than solvent can not also be diluted in advance after ingredient beforehand dilution, but by will be molten
Agent is mixed with these gradation compositions and is used.
For the method that each ingredient mixes is not particularly limited when cooperation, from so that stirrer or agitating paddle etc. is rotated and into
In method well known to the mixed method of row, the method mixed using method that mixer is mixed, application ultrasonic wave etc.
Appropriate selection.
The temperature and time when addition and mixing of each ingredient is not as long as in the case where causing each gradation composition to deteriorate
It is not particularly limited, it is appropriate to adjust, but preferable temperature is 15~30 DEG C.
Zero overlay
For above-mentioned overlay, as long as the surface roughness on the surface of the opposite side of side that is in contact with its support chip
Ra is less than the surface roughness Ra on the surface for having overlay side of support chip, is not particularly limited.
As above-mentioned overlay, such as the solidfied material as obtained from energy line irradiation solidification is preferably comprised, preferably comprised
It is polymerizeing by energy line irradiates, so that coating composition containing energy line polymerizable compound is cured obtained from apply
Layer.Moreover, above-mentioned energy line polymerizable compound is preferably (methyl) acrylic acid or derivatives thereof.
Said protection film formation not only has with composite sheet to be formed for the back side to semiconductor chip obtained from cutting
Function as the protective film protected, the function of cutting sheet when can also have both for example as cutting semiconductor chip.
Moreover, in the cutting of semiconductor wafer, spread sheet is carried out to the semiconductor wafer for being pasted with protective film formation composite sheet sometimes,
In this case, claimed film formation has the flexibility of appropriateness with composite sheet.In order to be assigned with composite sheet to protective film formation
The flexibility of appropriateness selects the resin of the softness such as polypropylene sometimes for example, as the material for constituting above-mentioned support chip.Another party
Face, the resin etc. of such softness cause to deform or generate fold sometimes because of heating.Therefore, for overlay,
It may be said that wish its be can by the composition as raw material by using the solidification that energy line irradiates rather than pass through heat cure
To be formed.
The thickness of above-mentioned overlay is not particularly limited, preferably 0.1~20 μm, more preferably 0.4~15 μm, it is especially excellent
It is selected as 0.8~10 μm.By making the thickness of overlay be above-mentioned lower limiting value or more, it is easier to reducing overlay with above-mentioned support
The surface roughness Ra on the surface for the side opposite side that piece is in contact, and inhibit the adhesion of said protection film formation composite sheet
Effect further increase.In addition, by make the thickness of overlay be above-mentioned upper limit value hereinafter, infrared passing through across sheet above
When camera etc. is checked with the state of the semiconductor wafer after composite sheet having pasted said protection film formation, it can obtain more
Clearly check image, and then can more easily carry out the cutting of the semiconductor wafer with spread sheet.
It should be noted that overlay by covering the male and fomale(M&F) of support chip, the contact surface with support chip as described above
It can be formed as male and fomale(M&F), the thickness of overlay can be at the position, convex with this of the protrusion during overlay is comprising the male and fomale(M&F)
The top in portion is calculated as a starting point.
The surface roughness Ra on the surface for the side opposite side of above-mentioned overlay being in contact with above-mentioned support chip is preferably
0.5 μm or less, more preferably 0.4 μm or less, further preferably 0.3 μm or less, particularly preferably 0.2 μm or less.By making
The above-mentioned surface roughness Ra of overlay is above-mentioned upper limit value hereinafter, laser lettering can more clearly be carried out to protective film.
In addition, the surface roughness Ra on the surface for the side opposite side of above-mentioned overlay being in contact with above-mentioned support chip
Lower limiting value is not particularly limited, such as can be set as 0.005 μm etc..
That is, above-mentioned surface roughness Ra can for example be preferably set to 0.005~0.5 μm, more preferably be set as 0.005~0.4 μ
M, it is further preferably set as 0.005~0.3 μm, is particularly preferably set as 0.005~0.2 μm or less.
For the above-mentioned surface roughness Ra of overlay, such as can have overlay side by support chip
The surface roughness Ra on surface, the thickness of overlay, be used to form overlay coating composition described later coating side
Method etc. is adjusted.
Above-mentioned overlay [Thickness (μm) ] of overlay;/[The surface on the surface for having overlay side of support chip is thick
Rugosity Ra (μm) ]Value be preferably 0.1~30, more preferably 0.3~20, particularly preferably 0.5~10.By making above-mentioned value be
More than above-mentioned lower limiting value, the surface roughness Ra on the surface for the side opposite side of overlay being in contact with above-mentioned support chip is into one
Step reduces.Therefore, laser lettering can more clearly be carried out to protective film, in addition, inhibiting said protection film formation composite sheet
The effect of adhesion further increase.In addition, by making its above-mentioned value for above-mentioned upper limit value hereinafter, can avoid the thickness of overlay
It is superfluous.
The gloss on the surface of side (the above-mentioned support chip side) opposite side of above-mentioned overlay being in contact with above-mentioned support chip
Value preferably 32~95, more preferably 40~90, particularly preferably 45~85, such as can be 50~80.By making overlay
Above-mentioned gloss value be such range, can more clearly carry out laser lettering to protective film.In addition, by making overlay
Above-mentioned gloss value is above-mentioned lower limiting value or more, and use is being formed to having pasted said protection film by infrared camera etc. across sheet above
When the state of semiconductor wafer after composite sheet is checked, clearer check image can be obtained.Moreover, by making coating
Layer above-mentioned gloss value be above-mentioned upper limit value hereinafter, when similarly checking the state of semiconductor wafer, can inhibit painting
The luminous phenomenon of coating, to be easier to carry out the visuognosis of check image using infrared camera.
It should be noted that above-mentioned gloss value is based on JISK7105 standards, from overlay and above-mentioned support chip side phase
Anti- side measures to be worth obtained from 20 ° of mirror surface lusters of coating layer surface.
Protective film formation composite sheet from above-mentioned overlay side measure mist degree measured value be preferably 47% or less, it is more excellent
It is selected as 1~47%, further preferably 2~40%, particularly preferably 3~30%.By making protective film formation composite sheet
Above-mentioned mist degree is above-mentioned upper limit value hereinafter, the scattering of light is can inhibit, so as to more clearly carry out laser lettering to protective film.
In addition, across sheet above by infrared camera etc. to the semiconductor wafer after having pasted said protection film formation composite sheet
When state is checked, clearer check image can be obtained.Here, the above-mentioned mist degree of protective film formation composite sheet measures
Value refers to, in protective film formation composite sheet, from the side opposite side being in contact with above-mentioned support chip of above-mentioned overlay
The value for the mist degree that the direction on surface measures.
It should be noted that above-mentioned mist degree is the value measured based on JIS K7136 standards.
The various characteristics such as the gloss value of above-mentioned overlay for example can by the thickness of overlay, be used to form overlay after
The coating composition of text narration is adjusted containing ingredient etc..
Protective film formation composite sheet from above-mentioned overlay side measure mist degree measured value for example can by overlay,
The thickness of each layer of the composition protective film formation composite sheet of support chip etc. is used to form the composition of above layers (after for example,
The coating composition of text narration) be adjusted containing ingredient etc..
< < coating composition > >
Above-mentioned coating composition is preferably comprised selected from silicon dioxide gel and is bonded with containing free-radical polymerised unsaturation
Any one of silicon dioxide microparticle of organic compound of group or both (α) (hereinafter, sometimes referred to simply as " ingredient (α) "),
And selected from one or more of polyfunctional acrylate's class monomer and esters of acrylic acid prepolymer (β) (hereinafter, having
When be referred to as " ingredient (β) ").
[Ingredient (α)s ]
Mentioned component (α) is while said protection film to be made to be formed with compound for making the refractive index of above-mentioned overlay reduce
The cure shrinkage and the wet shrinkage of heat of piece reduce, to inhibit the protective film formation caused by these shrink to be produced with composite sheet
The ingredient of raw curling.
As the silicon dioxide gel in ingredient (α), it can be cited for example that silicon dioxide microparticle in alcohol, derive from ethylene glycol
The organic solvents such as ether (cellosolve) in suspended with colloidal state made of colloidal silicon dioxide.The above-mentioned silica that left floating
The average grain diameter of particle is preferably 0.001~1 μm, more preferably 0.03~0.05 μm.
The silicon dioxide microparticle for being bonded with the organic compound containing free-radical polymerised unsaturated group in ingredient (α)
It is crosslinked and cures by energy line irradiates.
It, can as the above-mentioned silicon dioxide microparticle for being bonded with the organic compound containing free-radical polymerised unsaturated group
To enumerate for example:It is present in the silanol group on the surface of silicon dioxide microparticle in having containing free-radical polymerised unsaturated group
The average grain diameter of silicon dioxide microparticle made of functional group reactions in machine compound, the silicon dioxide microparticle is preferably 0.005
~1 μm.As long as the above-mentioned functional group in the organic compound containing free-radical polymerised unsaturated group can be micro- with silica
Above-mentioned silanol group reaction in grain, is not particularly limited.
As the organic compound containing free-radical polymerised unsaturated group with above-mentioned functional group, example can be enumerated
The compound that such as the following general formula (1) indicates.
[Chemical formula 1]
(in formula, R1For hydrogen atom or methyl;R2Represented by the arbitrary general formula in halogen atom or following formula (2a)~(2f)
Group.)
[Chemical formula 2]
As R2In above-mentioned halogen atom, it can be cited for example that chlorine element, bromine atom, iodine atom etc..
As the preferred above-mentioned organic compound containing free-radical polymerised unsaturated group, it can be cited for example that:(first
Base) acrylic acid, (methyl) acryloyl chloride, (methyl) acrylic acid 2- isocyanatoethyls, (methyl) glycidyl acrylate,
(methyl) acrylic acid 2,3- imino groups propyl ester, (methyl) acrylic acid 2- hydroxy methacrylates, (3- (methyl) acryloxypropyl) three
Methoxy silane etc..
In the present invention, the above-mentioned organic compound containing free-radical polymerised unsaturated group can be used alone,
It can also be used in combination of two or more.
In ingredient (α), silicon dioxide gel and it is bonded with the organic compound containing free-radical polymerised unsaturated group
Silicon dioxide microparticle respectively can be only one kind, or it is two or more.
As ingredient (α), silicon dioxide gel can be used only, above-mentioned be bonded with containing radical polymerization can also be used only
The silicon dioxide microparticle of the organic compound of conjunction property unsaturated group, can also contain silicon dioxide gel and above-mentioned be bonded with
There is the silicon dioxide microparticle of the organic compound of free-radical polymerised unsaturated group to be applied in combination.
The content of the ingredient (α) of above-mentioned coating composition is preferably selected according to the refractive index of above-mentioned support chip, usually
The content of the silica for coming from ingredient (α) of preferably above-mentioned overlay reaches the amount of 20~60 mass %.By making two
The above-mentioned content of silica is above-mentioned lower limiting value or more, the effect for making the refractive index of overlay reduce and the above-mentioned protection of inhibition
Film formation is further increased with the effect for generating curling in composite sheet.In addition, by making the above-mentioned content of silica be above-mentioned
Upper limit value is hereinafter, the formation of overlay becomes easier to, and the effect for inhibiting the hardness of overlay to reduce further increases.
Volume from the refractive index, formation easiness and hardness and protective film formation composite sheet of above-mentioned overlay
Bent generation inhibition becomes better aspect and sets out, and the content of the silica for coming from ingredient (α) of overlay is more preferable
For 20~45 mass %.
[Ingredient (β)s ]
Mentioned component (β) is the main photo-curable ingredient to form above-mentioned overlay.
Mentioned component (β) as long as in 1 molecule of polyfunctional acrylate's class monomer in have 2 or more (methyl)
(methyl) acrylic acid derivative of acryloyl group, is not particularly limited.
As preferred above-mentioned polyfunctional acrylate's class monomer, it can be cited for example that:1,4- butanediols two (methyl)
Acrylate, 1,6-hexylene glycols two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyethylene glycol two (methyl)
Acrylate, hydroxyl trimethylace tonitric neopentyl glycol two (methyl) acrylate, two (methyl) dicyclopentanyl acrylates, caprolactone
Modified two (methyl) acrylic acid dicyclopentenyl esters, ethylene-oxide-modified di(2-ethylhexyl)phosphate (methyl) acrylate, two (first of allylation
Base) cyclohexyl acrylate, triisocyanate two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, two seasons
Penta tetrol three (methyl) acrylate, propionic acid are modified dipentaerythritol three (methyl) acrylate, pentaerythrite three (methyl) third
Olefin(e) acid ester, epoxy pronane modification trimethylolpropane tris (methyl) acrylate, three (acrylyl oxy-ethyl) triisocyanates, two
Pentaerythrite five (methyl) acrylate, propionic acid are modified dipentaerythritol five (methyl) acrylate, six (first of dipentaerythritol
Base) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc..
Mentioned component (β) as long as in esters of acrylic acid prepolymer have photo-curable (methyl) acrylic ester polymerization
Object or oligomer, are not particularly limited.
As preferred above-mentioned esters of acrylic acid prepolymer, it can be cited for example that:Polyester acrylates prepolymer, epoxy
Esters of acrylic acid prepolymer, urethane acrylate class prepolymer, polyalcohol acrylate class prepolymer etc..
As above-mentioned polyester acrylates prepolymer, it can be cited for example that:Condensation by polyacid and polyalcohol is anti-
To in two ends of molecule there is the above-mentioned hydroxyl of the polyester oligomer of hydroxyl to carry out ester obtained from answering, with (methyl) acrylic acid
Polyester acrylates prepolymer obtained from change;With (methyl) acrylic acid to making oxyalkylene and polyacid carry out addition reaction
Obtained from oligomer terminal hydroxyl be esterified obtained from polyester acrylates prepolymer etc..
As above-mentioned Epoxy Acrylates prepolymer, it can be cited for example that:By making (methyl) acrylic acid and relatively low point
Propylene oxide obtained from the epoxide ring reaction of the bisphenol-type epoxy resin or phenolic resin varnish type epoxy resin of son amount is esterified
Esters of gallic acid prepolymer.
As above-mentioned urethane acrylate class prepolymer, it can be cited for example that:By with (methyl) acrylic acid pair
Urethane acrylate class prepolymer obtained from urethane oligomer is esterified, the urethane oligomer are to pass through
Obtained from the reacting of polyether polyol or polyester polyol and polyisocyanates.
As above-mentioned polyalcohol acrylate class prepolymer, it can be cited for example that:With (methyl) acrylic acid to polyether polyols
Polyalcohol acrylate class prepolymer obtained from the hydroxyl of alcohol is esterified.
In ingredient (β), above-mentioned polyfunctional acrylate's class monomer and esters of acrylic acid prepolymer can be only one respectively
Kind, or it is two or more.
As ingredient (β), above-mentioned polyfunctional acrylate's class monomer can be used only, above-mentioned propylene can also be used only
Above-mentioned polyfunctional acrylate's class monomer and esters of acrylic acid prepolymer can also be applied in combination for esters of gallic acid prepolymer.
[Rong Ji ]
Above-mentioned coating composition preferably further contains solvent other than ingredient (α) and ingredient (β).By making coating group
It closes object and contains solvent, as described hereinafter, coating coating composition can be easier and made it dry, be used to form to be formed
The film of overlay.
Above-mentioned solvent can be used alone, and can also be used in combination of two or more.
As above-mentioned solvent, it can be cited for example that:The aliphatic hydrocarbons such as hexane, heptane, hexamethylene;The fragrance such as toluene, dimethylbenzene
Hydrocarbon;The halogenated hydrocarbons such as dichloromethane, vinyl chloride;The alcohol such as methanol, ethyl alcohol, propyl alcohol, butanol, 1- methoxy-2-propanols;Acetone, first and second
The ketone such as ketone, 2 pentanone, isophorone, cyclohexanone;The esters such as ethyl acetate, butyl acetate;Cellosolvo (ethyl cellosolve)
Equal cellosolves etc..
[Ren Yichengfen ]
For above-mentioned coating composition, other than ingredient (α) and ingredient (β), effect of the present invention is not being damaged
In range, mono-functional's acrylic ester monomer can also be contained, Photoepolymerizationinitiater initiater, photosensitizer, polymerization inhibitor, crosslinking agent, resisted
The various any ingredients such as oxygen agent, ultra-violet absorber, light stabilizer, levelling agent, defoaming drug.
Above-mentioned any ingredient can be used alone, and can also be used in combination of two or more.
(mono-functional's acrylic ester monomer)
Above-mentioned mono-functional's acrylic ester monomer as any ingredient is photo-curable ingredient, as long as at 1 point
(methyl) acrylic acid derivative only in son with 1 (methyl) acryloyl group, is not particularly limited.
As preferred above-mentioned mono-functional's acrylic ester monomer, it can be cited for example that:(methyl) cyclohexyl acrylate,
(methyl) 2-EHA, (methyl) dodecylacrylate ((methyl) lauryl acrylate), (methyl) propylene
Sour stearyl ((methyl) stearyl acrylate), (methyl) isobornyl acrylate etc..
(Photoepolymerizationinitiater initiater)
As the above-mentioned Photoepolymerizationinitiater initiater of any ingredient, can enumerate previous used known for free radical polymerization
Photoepolymerizationinitiater initiater.
As preferred above-mentioned Photoepolymerizationinitiater initiater, it can be cited for example that:Acetophenone compounds, benzophenone chemical combination
Object, alkyl amino benzophenone compound, benzil class based compound, benzoin class compound, benzoin ethers compound,
The aryl ketones light such as benzyl dimethyl ketal class compound, benzoyl benzoate compounds, α-acyl group oxime ester compound are poly-
Close initiator;The sulfur-bearings class Photoepolymerizationinitiater initiater such as thio-ether type compounds, thioxanthene ketone class compound;The acyls such as acyl group diaryl phosphine oxide
Base phosphine oxide-type compound;Anthraquinone analog compound etc..
It should be noted that in the case of keeping above-mentioned coating composition cured by electron beam irradiation, photopolymerization is not needed
Initiator.
In above-mentioned coating composition, relative to 100 mass parts of total content of photo-curable ingredient, Photoepolymerizationinitiater initiater contains
Amount is preferably 0.2~10 mass parts, more preferably 0.5~7 mass parts.
(photosensitizer)
As above-mentioned photosensitizer, it can be cited for example that tertiary amines, ESCAROL 507 ester, mercaptan based sensitisers
Deng.
In above-mentioned coating composition, relative to 100 mass parts of total content of photo-curable ingredient, the content of photosensitizer is preferred
For 1~20 mass parts, more preferably 2~10 mass parts.
(antioxidant, ultra-violet absorber, light stabilizer)
Above-mentioned antioxidant, ultra-violet absorber and light stabilizer can be it is well known those, but preferably intramolecular has (first
Base) acryloyl group etc. response type antioxidant, ultra-violet absorber and light stabilizer.These antioxidant, ultra-violet absorber
And light stabilizer can inhibit due to being bonded on the polymer chain formed by energy line irradiates due to the process of time
The loss from cured layer can play the function of these ingredients for a long time.
Above-mentioned coating composition preferably comprises silicon dioxide gel as ingredient (α), is further preferably hanged with colloidal state
The silicon dioxide gel that the average grain diameter of the silicon dioxide microparticle floated is 0.03~0.05 μm.
By making above-mentioned overlay contain such silicon dioxide gel, inhibit the viscous of said protection film formation composite sheet
Effect even further increases.Moreover, in above-mentioned overlay, compared to other regions, in the table with support chip side opposite side
There are more such silicon dioxide gels in face and its near zone, unevenly exist due to such, inhibit above-mentioned guarantor
The effect of the adhesion of cuticula formation composite sheet further increases.In above-mentioned overlay, in order to make silicon dioxide gel etc. contain
Exist with there are uneven components, the coating condition of above-mentioned coating composition can be adjusted.
The manufacturing method > > of < < coating compositions
Coating composition can for example pass through gradation composition (α) and ingredient (β) Isoenergetical line polymerizable compound, Yi Jigen
It is obtained according to ingredient other than the above to be used etc. is needed for constituting each ingredient of coating composition.For coating composition
Speech, such as other than this different point of gradation composition, can be according to above-mentioned adhesive composition the case where same method and
It obtains.
It, can be by solvent be mixed with the arbitrary gradation composition other than solvent by the cooperation in the case of using solvent
It uses, the arbitrary gradation composition other than solvent can not also be diluted in advance after ingredient beforehand dilution, but by will be molten
Agent is mixed with these gradation compositions and is used.
The ingredient other than solvent in coating composition is soluble in solvent, can not also be dissolved and is scattered in solvent
In.Moreover, for the concentration of each ingredient of coating composition, viscosity, as long as coating composition can be applied, it is right
It is not particularly limited.
The manufacturing method of ◎ protective film formation composite sheets
The protective film formation of the present invention can be manufactured as follows with composite sheet:It is formed with composition using said protection film formation
Protective film formation film forms overlay using above-mentioned coating composition, then successively forms overlay, support chip and protective film
It is laminated with film.In the case that support chip is made up of multiple layers, support chip is made as long as these are multilayer laminated.Example
Such as, support chip is that can form bonding using above-mentioned adhesive composition in the case that base material and adhesive phase are laminated
Oxidant layer.
Constitute the formation sequence of each layer (overlay, support chip, protective film formation film) of protective film formation composite sheet
It is not particularly limited.In addition, can be with the state of protective film formation composite sheet in phase by being formed for composition of above layers
In addition the progress directly on a surface of adjacent layer, can also use stripping film (stripping film) and carry out on the surface thereof, and by the shape
At layer fit in the state of protective film formation composite sheet the surface of adjacent layer.But in order to inhibit overlay with
Space part is generated between the male and fomale(M&F) (back side) of support chip, overlay is preferably directly coated with coating group on the male and fomale(M&F) of support chip
It closes object and is formed.
Hereinafter, being illustrated for an example of the preferable production process of protective film formation composite sheet.
It is preferred that forming overlay by the following method, that is, support chip male and fomale(M&F) (in Fig. 1 and 2, be support chip 10
Back side 10b, i.e. base material 11 back side 11b) on coating coating composition and make it dry, make to be formed by film as needed
Solidification.
Coating of the coating composition to object surface can carry out according to known methods, it can be cited for example that using air knife
Coating machine, scraper plate coating machine, bar coater, gravure coater, roll coater, roller knife coating machine, curtain stream coating machine, die coating machine, scraper
The method of the various coating machines such as coating machine, silk screen coating machine, Meyer bar coater, kiss coater.
In the case where being coated with coating composition on the male and fomale(M&F) of support chip, preferably inhibit in the recessed of overlay and support chip
Space part is generated between convex surface.By inhibiting the generation of above-mentioned space part, can inhibit in the male and fomale(M&F) of overlay and support chip
The diffusing reflection of borderline light, so as to more clearly carry out laser lettering on the surface of protective film.
In order to inhibit the generation of above-mentioned space part, such as it is preferable to use the small coating compositions of viscosity.In addition, containing energy
The coating composition of line polymerizable compound is normally more suitable for inhibiting the generation of above-mentioned space part.
The drying condition of coating composition is not particularly limited, and coating composition is preferably thermally dried, in this case,
Such as it is preferably made it dry under conditions of 70~130 DEG C, 0.5~5 minute.
The condition of cure of the film formed by coating composition is not particularly limited, and carries out according to known methods.
By energy line irradiation carry out it is cured in the case of, such as irradiation ultraviolet light when, can be used as ultraviolet source
High-pressure sodium lamp, melting H lamps, xenon lamp, black light or LED light etc., exposure is preferably set to 100~500mJ/cm2To be shone
It penetrates.On the other hand, if it is irradiating electron beam the case where, then preferably generates electron beam by electron-beam accelerator etc., will irradiate
Amount is preferably set to 150~350kV to be irradiated.Wherein, the formation of overlay is preferably carried out by ultraviolet light irradiation.
It, can be in the table for the base material for having overlay in the case that support chip is, for example, base material and adhesive phase is laminated
Face (being the surface 11a of base material 11 in Fig. 1 and 2) is directly coated with adhesive composition to form adhesive phase.But it is usually excellent
Choosing for example on the lift-off processing face of stripping film using applying adhesive composition and making it dry and form adhesive phase, by institute
The adhesive phase of formation is fitted in the surface of base material, removes above-mentioned stripping film etc., is additionally formed adhesive phase and is fitted in
The method on the surface of base material.
Adhesive composition may be used the same method of the case where with coating composition and be applied to object surface.
Adhesive composition after coating can make its crosslinking by heating, this can also be simultaneous using the crosslinking that heating carries out
Make drying to carry out.Heating condition can for example be set as 100~130 DEG C, 1~5 minute, and but not limited to this.
Support chip is that the case where being made of 1 layer (single layer) and for example, base material and adhesive phase are only made of etc. base material
Be laminated etc. under the either case in the case of being made up of multiple layers, can the support chip for having overlay surface (Fig. 1 and
It is the surface 10a of support chip 10 in 2, i.e. the surface 12a of adhesive phase 12) it is directly coated with protective film formation composition and is formed
Protective film formation film.But with the above-mentioned adhesive phase the case where in the same manner as, it is usually preferred to using the lift-off processing in stripping film
Protective film formation composition is applied on face and makes it dry and forms protective film formation film, then the protective film of formation is formed
Fit in the surface of support chip with film, remove above-mentioned stripping film etc. as needed, be additionally formed protective film formation film and by its
The method for fitting in the surface of support chip.
The same method of the case where protective film formation may be used with composition with coating composition is coated on object surface.
The case where drying condition of protective film formation composition is not particularly limited, may be used with coating composition is same
The method of sample makes it dry.
Support chip is in the case of being laminated by base material and adhesive phase, protective film formation of the invention with composite sheet also
The method other than the above method may be used to manufacture.For example, forming adhesive phase using above-mentioned adhesive composition, using upper
It states protective film formation composition and forms protective film formation film, then overlap above-mentioned adhesive phase and protective film formation with film
And laminated body is made, so that the surface (the surface 11a of the base material 11 in Fig. 1 and 2) for the base material for having overlay is fitted in the layer
The surface (face that protective film formation film is not set of adhesive phase) of the above-mentioned adhesive phase of stack, it is possible thereby to manufacture protection
Film formation composite sheet.
The case where formation condition of adhesive phase and protective film formation film in this case is with the above method is identical.
For example, manufacture it is as shown in Figure 1 when overlooked with composite sheet protective film formation down from above, protection
In the case that the surface area of film formation film is less than the protective film formation composite sheet of the surface area of adhesive phase, in above-mentioned system
It makes in method, as long as the protective film formation for being first cut into given size and shape in advance is set to film on adhesive phase.
The application method of ◎ protective film formation composite sheets
The application method of the protective film formation composite sheet of the present invention is for example as shown below.
Firstly, for protective film formation film be it is heat cured in the case of protective film formation composite sheet application method
It illustrates.
In this case, the protective film that the back side of semiconductor wafer is pasted on to protective film formation composite sheet first is formed and is used
On film, while protective film formation is fixed on cutter device with composite sheet.
Then, so that protective film formation is cured with film by heating and obtain protective film.In the surface (electrode of semiconductor wafer
Forming face) be pasted with back grinding tape (back grinding tape) in the case of, usually removing the back of the body from semiconductor wafer
Protective film is formed after mill adhesive tape.
Then, cutting semiconductor chip and obtain semiconductor chip.Can also since forming protective film to being cut
In a period of being segmented into only, laser is irradiated from the overlay side of protective film formation composite sheet to protective film, in protective film
Surface carries out lettering.In this case, as previously described, the side opposite side of overlay being in contact with support chip
The surface roughness Ra in face (back side) fully reduces, and the above-mentioned back side of overlay is even surface or becomes or concave-convex degree obtains
To the face of inhibition.Therefore, it when irradiating laser, is suppressed in the diffusing reflection of the above-mentioned backside laser of overlay, so as to right
Protective film clearly carries out laser lettering.
In addition, for before cutting semiconductor wafer, cut obtained from semiconductor chip, sometimes with
Infrared camera etc. checks its state from carrying out from its back side (face for having pasted protective film formation composite sheet) side.For example,
If it is semiconductor chip, then check that it there are the breakages such as N/D, fracture sometimes.
On the other hand, the present invention the semiconductor chip with protective film in, as described above, overlay and support chip
The surface roughness Ra in the face (back side) for the side opposite side being in contact fully reduces, in addition, in the recessed of overlay and support chip
Between convex surface (back side), the generation of space part is inhibited.Therefore, using infrared camera etc. from overlay side across protective film
When formation observes semiconductor wafer, semiconductor chip with composite sheet, since clearly check image can be obtained,
Inspection can be accurately proceed.
Then, semiconductor chip is removed together from support chip with the protective film for being pasted on its back side, is picked up, by
This obtains the semiconductor chip with protective film.For example, support chip is laminated by base material and adhesive phase and above-mentioned adhesive phase
In the case of for energy ray-curable, adhesive phase is set to cure by energy line irradiation, it will from the adhesive phase after the solidification
Semiconductor chip picks up together with the protective film for being pasted on its back side, thus can more easily obtain the semiconductor core with protective film
Piece.
For example, using protective film formation shown in FIG. 1 composite sheet 1, by protective film formation composite sheet 1
Protective film formed and pasted with the back side of film 13 and semiconductor wafer, while the support chip of exposing 10 (adhesive phase 12) being pasted
In cuttings such as ring frames with fixture (illustration omitted), to which protective film formation composite sheet 1 is fixed on cutter device.Then,
After so that the solidification of protective film formation film 13 is obtained protective film, laser lettering is carried out to protective film, is then cut, and root
It is regions curing other than the stickup position relative to above-mentioned fixture of adhesive phase 12 according to needing to make by irradiation energy line, so
The semiconductor chip with protective film is picked up afterwards.In this way, using the guarantor that adhesive phase 12 is energy ray-curable
In the case that cuticula is formed with composite sheet 1, need to be adjusted so that protective film formation composite sheet 1 will not be from above-mentioned fixture
Stripping cures the specific region of adhesive phase 12.On the other hand, using protective film formation composite sheet 1,
It is not necessary that the composition for the composite sheet to be pasted on to above-mentioned fixture is in addition arranged.
In contrast, using protective film formation shown in Fig. 2 composite sheet 2, protective film is formed with multiple
The protective film for closing piece 2 forms the back side stickup for using film 23 with semiconductor wafer, while fixture adhesive layer 16 is pasted on ring
The cuttings such as shape frame are with fixture (illustration omitted), to which protective film formation composite sheet 2 is fixed on cutter device.Then, make guarantor
After the solidification of cuticula formation film 23 obtains protective film, laser lettering is carried out to protective film, is then cut, and according to need
The semiconductor chip with protective film is picked up after irradiation energy line makes adhesive phase 12 cure.In this way,
Using protective film formation composite sheet 2 that adhesive phase 12 is energy ray-curable, formed with protective film is used
With difference the case where composite sheet 1, need not be adjusted in order not to make the specific region of adhesive phase 12 be cured.It is another
Aspect is different with composite sheet 1 from protective film formation as protective film formation composite sheet 2, it is necessary to be to have fixture bonding agent
The composite sheet of layer 16.By having fixture adhesive layer 16, the layer of wide in range composition can be selected as adhesive according to purpose
Layer 12.
Then, the use of the protective film formation composite sheet in the case of being energy ray-curable with film to protective film formation
Method illustrates.
In this case, in the same manner as being heat cured situation with above-mentioned protective film formation film first, by semiconductor wafer
The back side be pasted on the protective film formation film of protective film formation composite sheet, while protective film formation being fixed with composite sheet
In cutter device.
Then, become protective film by energy line irradiation makes protective film formation film cure.In the table of semiconductor wafer
In the case that face (electrode forming surface) is pasted with back grinding tape, usually formed after removing the back grinding tape from semiconductor wafer
Protective film.
Then, cutting semiconductor chip and obtain semiconductor chip.Can also since forming protective film to being cut
In a period of being segmented into only, laser is irradiated from the overlay side of protective film formation composite sheet to protective film, in protective film
Surface carries out lettering.Can be that heat cured situation is same with above-mentioned protective film formation film until the lettering to cutting
Ground carries out, with the situation likewise it is possible to clearly carry out laser lettering to protective film, so as to contour using infrared camera
Checked to precision.
Then, semiconductor chip is removed together from support chip with the protective film for being pasted on its back side and is picked up, thus
Obtain the semiconductor chip with protective film.
This method is specially suitable in the case of for example using following protective film formation composite sheets, as the guarantor
Cuticula formation composite sheet, support chip are laminated by base material and adhesive phase, and above-mentioned adhesive phase cures for non-energy line
Property.It should be noted that herein for making protective film formation film cure by energy line irradiation, then cutting semiconductor is brilliant
Piece, then the case where semiconductor chip of pick-up tape protective film, are illustrated, but above-mentioned adhesive phase is non-energy line curability
In the case of, the solidification of protective film formation film carried out by irradiation by energy line can also be before picking up semiconductor chip
Any stage carry out.
For example, be laminated by base material and adhesive phase using support chip and above-mentioned adhesive phase be energy ray-curable
Protective film formation composite sheet in the case of, method preferably described below.
That is, first, in the same manner as the above situation, the back side of semiconductor wafer is pasted on protective film formation composite sheet
On protective film formation film, while protective film formation is fixed on cutter device with composite sheet.
Then, from the overlay side of protective film formation composite sheet to protective film irradiate laser, the surface of protective film into
Row lettering, then cutting semiconductor chip and semiconductor chip is made.It, can be with above-mentioned protective film until the lettering to cutting
Formation is that heat cured situation is carried out similarly with film, with the situation likewise it is possible to clearly carry out laser print to protective film
Word, so as to be accurately proceed inspection using infrared camera etc..
Then, by by energy line irradiation the solidification of protective film formation film is made to become protective film, while adhesive phase is made to consolidate
Change, semiconductor chip is picked up together with the protective film for being pasted on its back side from the adhesive phase after the solidification, is thus obtained
Semiconductor chip with protective film.
On the other hand, it in the case of the protective film formation of strip being batched with composite sheet, is generally used in protective film and is formed
With the protective film formation composite sheet for the state for being laminated with stripping film (being stripping film 15 in Fig. 1 and 2) in the exposed surface of film.And
And protective film formation composite sheet of the invention be formed arbitrarily (for example, protective film formation composite sheet 1 shown in FIG. 1 and
Being formed arbitrarily in protective film formation composite sheet 2 shown in Fig. 2) when, as protective film formation coils into web-like with composite sheet,
The lamination unit for being sequentially laminated with overlay, support chip, protective film formation film and stripping film overlaps successively in the radial direction of volume.Its
As a result, between the lamination unit that the radial direction of volume contacts with each other, the surface of the stripping film of a lamination unit (be provided with
Protective film formed film side opposite side face) with the back side (one to be in contact with base material of the overlay of another lamination unit
The face of side opposite side) contact, become the state of pressing, in the case where keeping the state, the volume of protective film formation composite sheet
It is saved.But by being provided with overlay, between lamination unit, due to the stickup of above-mentioned stripping film and overlay
It is suppressed, therefore, protective film formation of the invention can inhibit adhesion with composite sheet.
By the protective film of the present invention of the wide 50mm for the state for having stripping film on protective film formation film, long 100mm
Formation is overlapped with composite sheet in such a way that overlay reaches 10~60 μm towards the overall thickness in identical direction and overlay
Multi-disc, it is overlay, the laminated body that another outermost layer is stripping film that an outermost layer, which is thus made, to the laminated body in protective film
The stacking direction of formation composite sheet applies the power (external force) of 980.665mN (i.e. 100gf), retains that state for 40 DEG C of standings
3 days, above-mentioned stacking direction will be near above-mentioned outermost painting with the condition of peeling rate 300mm/ points, 180 ° of peel angle
The stripping film of coating is from adjacent overlay (closest to the coating of above-mentioned outermost overlay on above-mentioned stacking direction
Layer) on remove, peeling force at this time is preferably 10mN/50mm or less, more preferably 7.5mN/50mm or less, particularly preferably
5mN/50mm or less.It should be noted that here, the protective film formation of overlapping multi-disc is set as similarly constituting with composite sheet.
In addition, the piece number of the protective film formation composite sheet of overlapping is preferably 10.Can the peeling force based on such stripping film come
Confirm the height of the adhesion inhibition (resistance to blocking) of the protective film formation composite sheet of the present invention.
Embodiment
Hereinafter, the present invention is described in more detail by specific embodiment.But the present invention is not completely by following
Shown in embodiment restriction.
The manufacture > of < protective film formation composite sheets
[Embodiment 1]
The protective film formation composite sheet constituted shown in Fig. 1 is manufactured.By the vertical view of the protective film formation composite sheet
It is shown in Fig. 3.More specifically, as described below.
[The Zhi Zao ] of 1st laminated body;
(preparation of thermosetting protective film formation composition)
Coordinate following compositions with following amounts (solid constituent), then coordinate methyl ethyl ketone, it is 51 matter to have obtained solid component concentration
The protective film for measuring % is formed with composition (III-1).
(component of polymer (A))
(A)-1:10 mass parts of n-butyl acrylate, 70 mass parts of methyl acrylate, 5 matter of glycidyl methacrylate
Measure acrylic resin (weight average molecular weight 400000, vitrifying made of part and the copolymerization of 15 mass parts of acrylic acid 2- hydroxy methacrylates
- 1 DEG C of transition temperature) 150 mass parts
(thermosetting component (B))
Epoxy resin (B1)
(B1)-1:Bisphenol A type epoxy resin (Mitsubishi chemical Co., Ltd's system " JER 828 ", 183~194g/ of epoxide equivalent
Eq, molecular weight 370) 60 mass parts
(B1)-2:Bisphenol A type epoxy resin (Mitsubishi chemical Co., Ltd's system " JER 1055 ", epoxide equivalent 800~
900g/eq, molecular weight 1600) 10 mass parts
(B1)-3:Dicyclopentadiene-type epoxy resin (DIC corporations " EPICLON HP-7200HH ", epoxide equivalent 274
~286g/eq) 30 mass parts
Thermal curing agents (B2)
(B2)-1:Dicyandiamide (solid dispersing latent curing agent, ADEKA corporations " AdekaHardener EH-
3636AS ", active hydrogen amount 21g/eq)
(curing accelerator (C))
(C)-1:2- phenyl -4,5- bishydroxymethyls imidazoles (Shikoku Chem's system " CUREZOL2PHZ ")
(packing material (D))
(D)-1:(Admatechs companies " SC2050MA " have carried out surface with epoxy compounds and have changed silica filler
The silica filler of property, 0.5 μm of average grain diameter) 320 mass parts
(coupling agent (E))
(E)-1:γ-glycidoxypropyltrimethoxy silane (silane coupling agent, Shin-Etsu Chemial Co., Ltd's system
" KBM403 ", methoxyl group equivalent 12.7mmol/g, molecular weight 236.3) 0.4 mass parts
(colorant (I))
(I)-1:Carbon black (pigment, Mitsubishi chemical Co., Ltd's system " MA600B ", average grain diameter 28nm) 1.2 mass parts
(formation of protective film formation film, the manufacture of the 1st laminated body)
On the lift-off processing face of the 1st stripping film (50 μm of Lindeke Co., Ltd's system " SP-P502010* ", thickness), make
It is coated with protective film formation composition (III-1) obtained above with knife type coater, it is 2 minutes dry at 120 DEG C, it forms
Protective film, which is formed, uses film (25 μm of thickness).
Then, the 2nd stripping is bonded on the face for the face opposite side for being provided with the 1st stripping film in the protective film formation film
The lift-off processing face of film (38 μm of Lindeke Co., Ltd's system " SP-PET381031C ", thickness), has obtained being sequentially laminated with the 1st
The laminated body of the strip of stripping film, protective film formation film and the 2nd stripping film.Then, the laminated body of the strip is batched
After volume, by the laminated body, along its width direction, (protective film shown in Fig. 3 forms the symbol w with composite sheet 11Shown in width
Direction) cut into the size of 300mm.
Then, the laminated body for this after cutting is cut in its width direction central portion from the 2nd stripping film side
The hemisection of cut mark so that the circle that the 2nd stripping film and protective film formation are diameter 220mm when depicting vertical view with film.It needs
Illustrate, in the present specification, " vertical view " of laminated body refers to being seen downwards above its stacking direction to laminated body
It sees.Then, the remaining mode of circular portion formed according to the only hemisection is by the 2nd stripping film and protective film formation film from upper
It states and is removed on laminated body, obtained being circular protective film when being sequentially laminated with vertical view on the lift-off processing face of the 1st stripping film
1st laminated body made of formation film and the 2nd stripping film.Circular protective film formation in 1st laminated body is equivalent to film
Protective film shown in Fig. 3 is formed with diameter d in composite sheet 11For the circular protective film formation film 13 of 220mm.
(preparation of coating composition)
(catalyst is melted into dispersion liquid obtained from being scattered in cellosolvo (ethyl cellosolve) in silicon dioxide gel
Industrial Co., Ltd's system " OSCAL1632 ", 30~50nm of grain size of silicon dioxide gel, 30 mass % of solid component concentration) 150
In mass parts, (waste river is chemical for the hard paint that cooperation is formed by urethane acrylate and polyfunctional acrylate's monomer
Industrial Co., Ltd's system " Beamset 575CB ", contains Photoepolymerizationinitiater initiater at 100 mass % of solid component concentration) 100 mass
Part, obtain coating composition (30 mass % of solid component concentration).
(formation of overlay)
Then, the surface roughness Ra of male and fomale(M&F) is 0.4 μm, the surface roughness Ra in the face of the male and fomale(M&F) opposite side is
On the above-mentioned male and fomale(M&F) of 0.02 μm of polypropylene base material (100 μm of thickness, 140~160 DEG C of fusing point), applied using Meyer bar coater
Cloth coating composition obtained above, after 1 minute dry at 80 DEG C, with about 230mJ/cm2Light quantity irradiate ultraviolet light, make to do
Curing of coating after dry forms overlay (3 μm of thickness).
(preparation of adhesive composition)
By 100 mass parts of (methyl) alkyl acrylate copolymer and the (crosslinking of aromatic system polyisocyanate compound
Agent, Mitsui Chemicals, Inc's system " Takenate D110N ") 10 mass parts (solid constituent) mixing, methyl ethyl ketone is being mixed, is being obtained
The adhesive composition (iii) that solid component concentration is 30 mass % is arrived.
Above-mentioned (methyl) alkyl acrylate copolymer is 40 mass parts of n-butyl acrylate, 2-EHA 55
The acrylic resin of weight average molecular weight 600000 made of mass parts and the copolymerization of 5 mass parts of acrylic acid 2- hydroxy methacrylates.
(formation of adhesive phase (support chip), the manufacture of the 2nd laminated body)
Single side carried out by forming organic silicon peeling agent layer 38 μm of thickness obtained from lift-off processing by poly- pair
Ethylene terephthalate is film-made the above-mentioned stripping of the 3rd stripping film to be formed (Lindeke Co., Ltd's system " SP-PET381031C ")
From in process face, it is coated with adhesive composition obtained above (iii) using knife type coater and makes it dry, form bonding
Oxidant layer (5 μm of thickness).
Then, to be formed with overlay above-mentioned base material carried out sided corona treatment with the face of male and fomale(M&F) opposite side after, make
Above-mentioned adhesive phase is closed with the sided corona treatment face paste, has been stacked gradually overlay, base material, adhesive phase and the 3rd stripping
Film and include support chip strip the 2nd laminated body.
Then, by the 2nd laminated body of the strip batch and as volume after, by the 2nd laminated body along its width direction (Fig. 3
Shown in protective film formed with the symbol w of composite sheet 11Shown in width direction) cut into the size of 300mm.
(manufacture of protective film formation composite sheet)
The 2nd stripping film is removed from the 1st laminated body obtained above, and circular protective film formation is made to be exposed with film.In addition,
The 3rd stripping film is removed from the 2nd laminated body obtained above, and adhesive phase is made to expose.Then, make above-mentioned protective film be formed to use
The exposed surface of film is bonded with the exposed surface of the adhesive phase, has obtained stacking gradually overlay, base material, adhesive phase, protective film
The 3rd laminated body of protective film formation composite sheet is equivalent to made of formation film and the 1st stripping film.
For the 3rd laminated body obtained above, the hemisection of incision cut mark is carried out from overlay side so that overlay, base
Material and adhesive phase are described when having vertical view as the circle of diameter 270mm.When the hemisection, to overlay, base material and adhesive phase
The above-mentioned circle of diameter 270mm is formed by diameter 220mm's with protective film formation with film when having cut cut mark, and to overlook
Circle becomes concentric circles.
Then, the position of the radial outside 20mm of the circle apart from above-mentioned diameter 270mm when looking down, from overlay side into
It has gone overlay, base material and adhesive phase and has cut the hemisection for having cut mark, and made width direction (Fig. 3 institutes in the 3rd laminated body
The symbol w for the protective film formation composite sheet 1 shown1Shown in width direction) depict opposite a pair of of circular arc.Be equivalent to this one
The curved of adhesive phase shown in symbol 121 in protective film formation composite sheet 1 shown in Fig. 3 is formed to the cut mark of circular arc
Peripheral portion.It is formed moreover, the distance between the circle of diameter 270mm and above-mentioned circular arc (20mm) are equivalent to protective film shown in Fig. 3
With the symbol w in composite sheet 12。
Such above-mentioned hemisection for describing 2 concentric circles and a pair of of circular arc the 3rd laminated body length direction (with Fig. 3 institutes
The symbol w for the protective film formation composite sheet 1 shown1Shown in the orthogonal direction of width direction) in multiple positions carry out, from painting
Coating side has carried out overlay, base material and adhesive phase and has cut the hemisection for having cut mark, and so that adjacent when depicting vertical view
In above-mentioned length direction by circular arc 2 straight lines connected to each other between the position connect.It is equivalent to the cut mark formation figure of 2 straight lines
Protective film shown in 3 forms the planar peripheral portion of the adhesive phase shown in the symbol 122 in composite sheet 1.
Then, it removes part when overlooking between the circle of above-mentioned diameter 270mm and a pair of of circular arc and is incited somebody to action by above-mentioned
Overlay, base material and the adhesive phase in part clamped by circular arc 2 straight lines connected to each other, results in the institutes of Fig. 1 and 3
The protective film formation composite sheet shown.The protective film is formed is equivalent to figure with the circular adhesive phase (support chip) in composite sheet
Diameter d in 32For the circular adhesive phase 12 (support chip 10) of 270mm.In addition, in the protective film formation composite sheet
1st stripping film is equivalent to the stripping film 15 in Fig. 3.
[Embodiment 2]
As shown in table 1 like that, it is 1 μm rather than 0.4 μm of base material to have used the surface roughness Ra of male and fomale(M&F), in addition to this
Other than point, protective film formation composite sheet has been obtained according to method similarly to Example 1.
[Embodiment 3]
As shown in table 1 like that, the surface roughness Ra of male and fomale(M&F) has been used to be 1 μm rather than 0.4 μm of base material and make
The thickness of overlay replaces 3 μm by 1 μm, and other than this point, protective film shape has been obtained according to method similarly to Example 1
At with composite sheet.
[Embodiment 4]
As shown in table 1 like that, so that the thickness of overlay is replaced 3 μm by 1 μm, in addition to this point other than, according to embodiment 1
Same method has obtained protective film formation composite sheet.
[Embodiment 5]
As shown in table 1 like that, the surface roughness Ra of male and fomale(M&F) has been used to be 1 μm rather than 0.4 μm of base material and make
The thickness of overlay replaces 3 μm by 6 μm, and other than this point, protective film shape has been obtained according to method similarly to Example 1
At with composite sheet.
[Embodiment 6]
As shown in table 1 like that, the surface roughness Ra of male and fomale(M&F) has been used to be 3 μm rather than 0.4 μm of base material and make
The thickness of overlay replaces 3 μm by 6 μm, and other than this point, protective film shape has been obtained according to method similarly to Example 1
At with composite sheet.
[Comparative example 1]
As shown in table 1 like that, it is 1 μm rather than 0.4 μm of base material and not to have used the surface roughness Ra of male and fomale(M&F)
Overlay is formed, other than this point, protective film formation composite sheet has been obtained according to method similarly to Example 1.
[Comparative example 2]
As shown in table 1 like that, it is configured in such a way that male and fomale(M&F) is towards opposite side, namely adhesive phase side (inside) To
Base material and do not form overlay (that is, being formed as previous composition shown in fig. 5), other than this point, according to embodiment
1 same method has obtained protective film formation composite sheet.
[Comparative example 3]
As shown in table 1 like that, it is 1 μm rather than 0.4 μm of base material, according to recessed to have used the surface roughness Ra of male and fomale(M&F)
Mode convex surface facing opposite side, namely adhesive phase side (inside) To configures base material and does not form overlay (that is, shape
As previous composition shown in fig. 5), other than this point, obtains protective film according to method similarly to Example 1 and formed
Use composite sheet.
[Comparative example 4]
Dispersion liquid obtained from being scattered in cellosolvo instead of silicon dioxide gel, has used in terms of solid constituent
It is (Admatechs corporations " SC2050MA ", average for the same amount of spherical silicon dioxide for having carried out surface modification with epoxy group
0.5 μm of grain size), other than this point, coating composition is prepared for according to method similarly to Example 1.
Also, it other than having used this point of the coating composition, is protected according to method similarly to Example 1
Film formation composite sheet.
In obtained protective film formation composite sheet, the surface roughness Ra of substrate side most surface as shown in table 1 that
Sample is 0.8 μm.
The evaluation > of < protective film formation composite sheets
[Laser lettering ]
In the protective film formation composite sheet of each Examples and Comparative Examples obtained above, the 1st stripping film is removed, is used
Adhesive phase is pasted on stainless steel ring frame by sticker (Lindeke Co., Ltd's system " RAD-2700F/12 "), simultaneously will
Protective film formation is pasted on the back side for the silicon wafer (8 inches of outer diameter, 100 μm of thickness) for being heated to 70 DEG C with film.
Then, protective film formation at 130 DEG C heat within 2 hours with film, make protective film formation film thermosetting
Change and forms protective film.
Then, using printing device (KEYENCE corporations " VK9700 "), in output power 0.6W, frequency 40kHz, sweep
Laser of the speed from substrate side to protective film illumination wavelength 532nm under conditions of 100mm/ seconds is retouched, with following 2 patterns (figures
Case 1, pattern 2) laser lettering has been carried out to protective film.
(pattern)
Pattern 1:Character size 0.4mm × 0.5mm, word interval 0.3mm, word number 20
Pattern 2:Character size 0.2mm × 0.5mm, word interval 0.3mm, word number 20
Then, for the word formed on protective film with above-mentioned laser lettering, according to following benchmark for from base material
The visibility (laser lettering) of side is evaluated, and the results are shown in tables 1.
(evaluation criteria)
A:All words of pattern 1 and 2 are clear, can with there is no problem read the word of pattern 1 and 2.
B:Although at least part word in pattern 2 is unintelligible, all words in pattern 1 are clear, can not have
The word of pattern 1 is read problematicly.
C:Any one pattern of pattern 1 and 2 is that at least part word is unintelligible.
[Resistance to blocking (1) ]
The protective film formation of each Examples and Comparative Examples obtained above of 10m length composite sheet is rolled up in 3 English of diameter
On very little ABS resin coremaking material, 3 days have been stood at room temperature with the state.
Then, it for Examples 1 to 6, the protective film formation composite sheet of comparative example 4, has attempted that painting will have been stacked gradually
10 lamination units extraction of coating, base material, adhesive phase, protective film formation film and the 1st stripping film, for comparative example 1~3
Protective film formation composite sheet since there is no overlay attempted that base material, adhesive phase, protective film will have been stacked gradually
10 lamination units of formation film and the 1st stripping film are extracted out, at this point, the protective film to contact with each other when for batching is formed with multiple
Close piece contact site to each other whether there is or not paste, exist stickup in the case of its stickup degree, evaluated according to following benchmark,
Show the result in table 1.
(evaluation criteria)
A:The stickup of above-mentioned contact site to each other is not confirmed completely.
B:Although confirming the slight stickup of above-mentioned contact site to each other, with there is no problem protective film can be formed
It is extracted out with composite sheet.
C:Above-mentioned contact site is pasted a part of completely each other, when protective film formation is extracted out with composite sheet, the 1st stripping
Film is removed from adhesive phase.
[Resistance to blocking (2) ]
The protective film formation of each Examples and Comparative Examples obtained above is cut into wide 50mm, long 100mm rulers with composite sheet
Very little is band-like.It should be noted that when cutting out so that the length direction of the band and the coating direction one of adhesive composition
It causes.
Prepare 10 ribbons obtained in this way, these ribbons are laminated and test film has been made.At this point, implementing
It is that above-mentioned ribbon is laminated upward for overlay in the case of example 1~6, comparative example 4.But comparative example 1~3
In the case of, it is that above-mentioned ribbon is laminated upward for base material since there is no overlay.Then, with 2 glass
The test film is clamped in plate (wide 75mm, long 15mm, thickness 5mm), by the sandwich entirety of these glass plates and test film according to one
Glass plate is positioned over given position as lowest level, and counterweight is placed on the glass plate of another top layer, to above-mentioned test film
It is pressurizeed.At this point, on the stacking direction of above-mentioned ribbon, to the power that above-mentioned test film applies be 980.665mN (i.e.
100gf).In this state by the sandwich entirety of these glass plates and test film in damp and hot promoters (ESPEC corporations)
It is taken care of 3 days at 40 DEG C, having carried out heating pressurization to above-mentioned test film promotes experiment.
Then, above-mentioned test film is taken out from damp and hot promoters, remove undermost 1st stripping film (with it is undermost
The 1st stripping film that glass plate is in contact) and protective film formation film adjacent thereto, using double-faced adhesive tape by the bonding of exposing
Oxidant layer fits in support plate, heating is pressurizeed remove only the undermost 1st from above-mentioned test film after promoting experiment as a result,
Stripping film and protective film formation adjacent thereto are fixed on above-mentioned support plate with the sample after film.
Then, it in the case of Examples 1 to 6, comparative example 4, removes in the sample after above-mentioned fixation farthest away from above-mentioned branch
The sandwich of the top layer of fagging being made of with film overlay, base material, adhesive phase and protective film formation, uses tension test
Machine is shelled the 1st stripping film of exposing with the condition of 300mm/ points of peeling rate, 180 ° of peel angle from adjacent overlay
From determining peeling force at this time.In the case of comparative example 1~3, remove in the sample after above-mentioned fixation farthest away from above-mentioned branch
The sandwich of the top layer of fagging being made of with film base material, adhesive phase and protective film formation, using cupping machine, to shell
Condition from speed 300mm/ points, 180 ° of peel angle removes the 1st stripping film of exposing from adjacent base material, determines this
When peeling force.Using the measured value of the peeling force of the 1st stripping film obtained in this way as the anti-stick of protective film formation composite sheet
The even index of property.
It should be noted that in the case where the peeling force for the 1st stripping film for wanting to measure is sufficiently small, from by damp and hot promotion
It removes on the above-mentioned test film taken out in device and (connects as described above with undermost glass plate with undermost 1st stripping film
The 1st tactile stripping film) adjacent protective film formation film when, sometimes as the 1st stripping film of the measure object of peeling force head
On the layer (be in the case of Examples 1 to 6, comparative example 4 overlay, comparative example 1~3 in the case of be base material) first abutted from it
Stripping.In this case, after removing undermost 1st stripping film on the above-mentioned test film taken out from by damp and hot promoters, with it
Adjacent protective film formation is not removed with film, but protective film formation is fitted in support plate with film using double-faced adhesive tape,
The sample after undermost 1st stripping film will be removed only from above-mentioned test film as a result, and is fixed on above-mentioned support plate, for this
Sample after fixation determines the peeling force of the 1st stripping film as described above.
The results are shown in tables 1.
[The Biao MiancucaoduRa ] of substrate side most surface;
It is thick using contact surface for Examples 1 to 6 obtained above, the protective film formation composite sheet of comparative example 4
Rugosity instrument (Mitutoyo corporations " SURFTEST SV-3000 "), cutoff value λ c are set as 0.8mm, evaluation length Ln is set as
4mm is based on JIS B0601:2001 standards are to substrate side most surface, i.e. overlay is thick with the surface in the face of substrate side opposite side
Rugosity Ra is determined, and the results are shown in table 1.In table 1, for the protective film formation composite sheet of comparative example 1~3,
As the surface roughness Ra of substrate side most surface, the thick with the surface in the face of adhesive phase side opposite side of above-mentioned base material is described
Rugosity Ra.
[Apply the gloss value of layer surface;
For Examples 1 to 6 obtained above, the protective film formation composite sheet of comparative example 4, vancometer (day is used
This electricity Se Co., Ltd. manufacture vancometer " VG2000 "), be based on JIS K7105 standards, from overlay and substrate side phase
Anti- side measures 20 ° of mirror surface lusters on the surface of overlay, using its measured value as the gloss value of coating layer surface, by it
As a result shown in table 1.
[The mist degree Ce Dingzhi ] measured from overlay side;
For Examples 1 to 6 obtained above, the protective film formation composite sheet of comparative example 4, mist degree instrument (Japan is used
Electric color Co. Ltd. system " NDH-2000 "), mist degree determined from overlay side based on JIS K7136 standards, the results are shown in
Table 1.
[Table 1]
The protective film formation composite sheet of Examples 1 to 6 in the outermost layer of substrate side by having overlay, laser print
Word and resistance to blocking are good.
The especially protective film formation composite sheet of embodiment 1,2,4 and 5 is formed with the protective film of embodiment 3 and 6 with multiple
It closes piece to compare, laser lettering is excellent, thus it is speculated that this is because, the " [ of the protective film formation composite sheet of embodiment 1,2,4 and 5;It applies
Thickness (μm) ] of coating;/[Surface roughness Ra (μm) ] of the male and fomale(M&F) of base material;" value bigger, the male and fomale(M&F) relative to base material
Surface roughness Ra, the relative thickness of overlay is thicker, as a result, substrate side most surface (overlay it is opposite with substrate side
The face of side) surface roughness Ra (μm) become smaller.
In addition, compared with the protective film formation composite sheet of embodiment 5 and 6, the protective film of Examples 1 to 4 is formed with multiple
The resistance to blocking for closing piece is excellent, thus it is speculated that this is because, the coating layer thickness of the protective film formation composite sheet of Examples 1 to 4 is more
It is thin.
It should be noted that the protective film formation composite sheet of Examples 1 to 6 is not true between base material and adhesive phase
Recognize space part.
In contrast, the protective film formation composite sheet composite sheet as shown in fig. 4 of comparative example 1 is same, base material with tool
The face (back side) of face (surface) opposite side of the side of standby adhesive phase is male and fomale(M&F), and does not have overlay, thus while
Resistance to blocking is excellent, but laser lettering is poor.
The protective film formation composite sheet of comparative example 2 is same as composite sheet shown in fig. 5, base material with have adhesive phase
The face (back side) of face (surface) opposite side of side be even surface, and do not have overlay, thus while laser lettering
Well, but resistance to blocking is poor.The protective film formation composite sheet of comparative example 3 and the protective film formation composite sheet of comparative example 2 have
There is same composition, not only resistance to blocking is poor, and laser lettering is also poor.Speculate this is because, base material has adhesive phase
The face (surface) of side is male and fomale(M&F), and its surface roughness Ra is more than the protective film formation composite sheet of comparative example 2.For than
For example 3, since the surface roughness Ra of above-mentioned male and fomale(M&F) is big, the shape of male and fomale(M&F) has also obtained instead on the surface of protective film
It reflects, leads to the case where concave-convex degree in the surface of protective film is more than comparative example 2, as a result, the diffusing reflection bigger of light, laser lettering
Property is further deteriorated.In addition it could be speculated that the protective film formation of comparative example 2 and 3 with composite sheet in the male and fomale(M&F) of base material and bonding
There is space part, but compared with comparative example 2 between oxidant layer, the surface roughness Ra bigger of the male and fomale(M&F) of comparative example 3, space part becomes
Greatly, therefore, compared with comparative example 2, the diffusing reflection bigger of the light of comparative example 3, laser lettering is further deteriorated.
The protective film formation composite sheet of comparative example 4 is same as the protective film formation composite sheet of embodiment 1, base material with
The face (back side) for having face (surface) opposite side of the side of adhesive phase is male and fomale(M&F), and has overlay, although resist blocking and that
Property is excellent, but laser lettering is poor.Speculate this is because, in the protective film formation composite sheet of comparative example 4, with base material and tool
The face (back side) of face (surface) opposite side of the side of standby adhesive phase is compared, substrate side most surface (overlay and substrate side
The face of opposite side) surface roughness Ra (μm) bigger.
Industrial applicibility
The present invention can be used in the manufacture of semiconductor chip protected to the back side by protective film etc..
Claims (5)
1. a kind of protective film formation composite sheet has support chip, has protective film on a surface of the support chip
Formation film and has coating on the surface with the side opposite side for having the protective film formation film of the support chip
Layer forms,
The surface roughness Ra on the surface for the side opposite side of the overlay being in contact with the support chip is less than the branch
The surface roughness Ra of the side surface for having overlay of blade.
2. protective film formation composite sheet according to claim 1, wherein used using further being formed in the protective film
Has the protective film formation composite sheet of stripping film on film, the peeling force of the stripping film measured by the following method is
10mN/50mm hereinafter,
The assay method of the peeling force of stripping film:
By on protective film formation film with stripping film and width 50mm, long 100mm the protective film formation composite sheet according to
The mode that the overlay is 10~60 μm towards the overall thickness of the same direction and the overlay overlaps multiple, thus shape
It is overlay, the laminated body that another outermost layer is stripping film at an outermost layer, by the laminated body in the protective film shape
Stand 3 days at the power for being applied with 980.665mN with the stacking direction of composite sheet and at 40 DEG C, then the stacking direction with
Peeling rate 300mm/ points, the condition of 180 ° of peel angle by near the stripping film of the outermost overlay from adjacent
It is removed on overlay, measures peeling force at this time.
3. protective film formation composite sheet according to claim 1 or 2, wherein the support chip is base material and adhesive
Made of layer stackup,
The protective film formation with composite sheet stack gradually the overlay, base material, adhesive phase and protective film formation film and
At.
4. protective film formation composite sheet according to claim 3, wherein described adhesive layer be energy ray-curable or
The adhesive phase of non-energy line curability.
5. protective film formation composite sheet according to any one of claims 1 to 4, wherein the protective film, which is formed, to be used
Film is the film of thermosetting property or energy ray-curable.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-042689 | 2016-03-04 | ||
| JP2016042689 | 2016-03-04 | ||
| PCT/JP2016/086539 WO2017149890A1 (en) | 2016-03-04 | 2016-12-08 | Protective film-forming composite sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108701597A true CN108701597A (en) | 2018-10-23 |
| CN108701597B CN108701597B (en) | 2023-03-31 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680081330.5A Active CN108701597B (en) | 2016-03-04 | 2016-12-08 | Composite sheet for forming protective film |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP6805230B2 (en) |
| KR (1) | KR102574633B1 (en) |
| CN (1) | CN108701597B (en) |
| SG (1) | SG11201805895XA (en) |
| TW (1) | TWI783920B (en) |
| WO (1) | WO2017149890A1 (en) |
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| WO2016027888A1 (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 |
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| JPS5432853U (en) | 1977-08-09 | 1979-03-03 | ||
| JP6091954B2 (en) * | 2013-03-26 | 2017-03-08 | リンテック株式会社 | Adhesive sheet, protective film-forming film, protective film-forming composite sheet, and marking method |
| JP6092035B2 (en) * | 2013-07-30 | 2017-03-08 | 日東電工株式会社 | Surface protective film and optical member |
| JP5607847B1 (en) * | 2013-11-29 | 2014-10-15 | 古河電気工業株式会社 | Adhesive tape for semiconductor processing |
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- 2016-12-08 CN CN201680081330.5A patent/CN108701597B/en active Active
- 2016-12-08 JP JP2018502537A patent/JP6805230B2/en active Active
- 2016-12-08 KR KR1020187022594A patent/KR102574633B1/en active IP Right Grant
- 2016-12-08 SG SG11201805895XA patent/SG11201805895XA/en unknown
- 2016-12-08 WO PCT/JP2016/086539 patent/WO2017149890A1/en active Application Filing
- 2016-12-09 TW TW105140850A patent/TWI783920B/en active
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|---|---|---|---|---|
| JP2000246834A (en) * | 1999-03-01 | 2000-09-12 | Mitsubishi Electric Corp | Manufacture of metal ornament |
| JP2001341263A (en) * | 2000-06-05 | 2001-12-11 | Toyobo Co Ltd | Releasable polyester film, separator, and adhesive sheet using them |
| US20050238879A1 (en) * | 2003-11-11 | 2005-10-27 | Lintec Corporation | Film for optical applications |
| JP2008222894A (en) * | 2007-03-14 | 2008-09-25 | Denki Kagaku Kogyo Kk | Pressure-sensitive adhesive sheet for electronic component fixation, and manufacturing method of electronic component using it |
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| JP2015063584A (en) * | 2013-09-24 | 2015-04-09 | リンテック株式会社 | Release sheet and pressure-sensitive adhesive sheet |
| WO2016027888A1 (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 |
|---|---|
| TW201732002A (en) | 2017-09-16 |
| KR102574633B1 (en) | 2023-09-04 |
| KR20180120148A (en) | 2018-11-05 |
| JP6805230B2 (en) | 2020-12-23 |
| JPWO2017149890A1 (en) | 2018-12-27 |
| WO2017149890A1 (en) | 2017-09-08 |
| SG11201805895XA (en) | 2018-09-27 |
| CN108701597B (en) | 2023-03-31 |
| TWI783920B (en) | 2022-11-21 |
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