CN108966671A

CN108966671A - Composite sheet is used in support chip and protective film formation

Info

Publication number: CN108966671A
Application number: CN201780016815.0A
Authority: CN
Inventors: 小桥力也
Original assignee: Lintec Corp
Current assignee: Lintec Corp
Priority date: 2016-03-24
Filing date: 2017-03-13
Publication date: 2018-12-07
Anticipated expiration: 2037-03-13
Also published as: WO2017163971A1; TWI761335B; SG11201807645SA; CN108966671B; JP6893500B2; KR102313074B1; KR20180124868A; TW201739078A; JPWO2017163971A1

Abstract

The adhesive phase that support chip of the invention has substrate and is laminated on above-mentioned substrate, wherein, the surface roughness (Ra) of the side surface for having above-mentioned adhesive phase of above-mentioned substrate is 0.4 μm or less, above-mentioned substrate is greater than the surface roughness for having a side surface of described adhesive layer with the surface roughness (Ra) on the surface for the side opposite side for having above-mentioned adhesive phase, and is 0.053~0.48 μm.Protective film formation of the invention has with composite sheet to be further equipped with protective film formation on above-mentioned support chip and above-mentioned adhesive phase in above-mentioned support chip and is formed with film.

Description

Composite sheet is used in support chip and protective film formation

Technical field

The present invention relates to support chip and protective film formation composite sheets.

The application is preferential based on Japanese Patent Application 2016-060577 requirement that on March 24th, 2016 files an application in Japan Power, and its content is incorporated herein.

Background technique

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 is may be used at the semiconductor chip with electrodes such as convex blocks in circuit face, the electrode connects with substrate It closes.Therefore, semiconductor chip exposes with the back side of circuit face opposite side sometimes.

The resin film made of organic material is formed as protective film, in this wise at the back side of the semiconductor chip of the exposing The semiconductor chip with protective film obtained from protective film is formed to be mounted sometimes in semiconductor devices.Protective film is in order to anti- So-called clast as rupture, defect only is generated in semiconductor core on piece in the process after cutting action and is utilized 's.

In the formation of such protective film, using having protective film formation film (protective film forming layer) on support chip Made of protective film formation use composite sheet.As above-mentioned support chip, such as it may be used on resin base material and adhesive phase is laminated The laminates Deng made of.For said protection film formation composite sheet, protective film formation with film there is protective film to form energy Power, in addition, support chip can be functioned as cutting sheet, protective film formation film can be formed as one with cutting sheet.

In the above-mentioned substrate being used for before the processing of support chip, usually there is concaveconvex shape in its one or two sides.It is right Substrate before processing, using support chip obtained from the substrate or protective film formation composite sheet for, batched by them And when forming volume, if substrate does not have the face (male and fomale(M&F)) of concaveconvex shape as described above, the contact surface rolled up is pasted each other And lead to adhesion, to cause using becoming difficult.Wherein, in the case where substrate is rolled up, contact surface is the respective surface of substrate, In the case where support chip and protective film formation composite sheet, contact surface is the exposed surface and removing as its undermost substrate The exposed surface of the top layer of film etc..In particular, the composite sheet generates fold if protective film formation composite sheet generates adhesion Deng will lead to top layer's (usually stripping film) and removed from the composite sheet when extracting the composite sheet out from volume.

In contrast, if one of contact surface of volume is the male and fomale(M&F) of substrate, the area for the contact surface rolled up reduces, Therefore it can inhibit adhesion.

On the other hand, in the manufacturing process of semiconductor device, sometimes by laser irradiation to being pasted on semiconductor die The face of the support chip side of the protective film of piece or semiconductor chip carries out lettering, and (in the present specification, sometimes referred to as " laser prints Word ").At this point, irradiating laser across support chip from the opposite side of support chip (substrate) with the side for being formed with protective film.That is, Laser is injected into support chip from the exposing surface side of substrate and reaches protective film.Therefore, in the feelings that the exposed surface of substrate is male and fomale(M&F) Under condition, diffusing reflection occurs for laser on the male and fomale(M&F), so that there are laser letterings to become unintelligible such problems sometimes.

In addition, being checked sometimes using infrared camera etc. across above sheet etc. in the manufacturing process of semiconductor device Have the semiconductor wafer of protective film formation composite sheet or protective film or the state of semiconductor chip.But as described above In the case where irreflexive situation has occurred in the exposed surface laser of substrate, there is also can not obtain to ask as clearly check image Topic.

As the irreflexive protective film formation composite sheet that can prevent the light such as such laser, discloses for example: making It is the substrate of male and fomale(M&F) with only single side, does not make its male and fomale(M&F) as exposed surface, but its male and fomale(M&F) is configured at protective film and is formed The composite sheet obtained from film side (the one-piece type semiconductor back surface protection film of dicing tape) (referring to patent document 1).For this Protective film is formed with for film, and the mist degree for the laminates (dicing tape) that substrate and adhesive phase are laminated is 45% or less.

But protective film formation disclosed in patent document 1 with composite sheet since the exposed surface of substrate is even surface, In the presence of batched and be formed as volume when can not inhibit above-mentioned adhesion such problems.

In addition, in the case where adhesive phase is arranged on the male and fomale(M&F) of substrate, in order to mitigate the male and fomale(M&F) to adhesive phase Bring influences, and there is the layer for needing to make adhesive phase softness, and make its sufficiently thick such problems.If adhesive phase compared with Firmly, then adhesive phase is not filled to the foundation position of the protrusion of substrate surface and generates space part sometimes.In addition, if bonding Oxidant layer is relatively thin, then the concaveconvex shape of substrate surface is reflected, cause the face (back side) of the substrate side of protective film formation film at For male and fomale(M&F).So, the protection of the unfavorable condition become inadequate by the embedment there are the concaveconvex shape of substrate surface Film formation forms protective film with film, if laser lettering is implemented in the face to its support chip side, will lead to lettering becomes unintelligible. In addition, can not also obtain the clearly check image of semiconductor wafer or semiconductor chip.On the other hand, blocked up in adhesive phase In the case where, adhesive phase during due to for example cutting off in cutting action is easy vibration, semiconductor core Piece, the semiconductor wafer in the cutting for the process for being formed as semiconductor chip are also easy vibration, exist to these semiconductor cores Result is easy to generate rupture, defect (being easy to produce clast) on a semiconductor die when piece, semiconductor wafer apply extra power Such problems.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2012-033741 bulletin

Summary of the invention

Problems to be solved by the invention

It is formed the object of the present invention is to provide a kind of protective film formation composite sheet and in said protection film with multiple Support chip used in the manufacture of piece is closed, adhesive phase becomes the embedment of substrate surface in the protective film formation composite sheet Unfavorable condition as insufficient and generation clast, and be able to suppress adhesion, clearly laser print is carried out to protective film Word and the clearly check image for obtaining semiconductor wafer or semiconductor chip.

Solution to the problem

The present invention provides a kind of support chip, the adhesive phase for having substrate and being laminated on above-mentioned substrate, wherein The surface roughness (Ra) of the side surface for having above-mentioned adhesive phase of above-mentioned substrate be 0.4 μm hereinafter, above-mentioned substrate with The surface roughness (Ra) for having the surface of the side opposite side of above-mentioned adhesive phase is greater than the side for having described adhesive layer The surface roughness on surface, and be 0.053~0.48 μm.

In support chip of the invention, the thickness of above-mentioned adhesive phase can be 15 μm or less.

In support chip of the invention, above-mentioned adhesive phase can be non-energy line curability.

In addition, the present invention provides a kind of protective film formation composite sheet, has above-mentioned support chip and in above-mentioned support chip In above-mentioned adhesive phase on be further equipped with protective film formation and formed with film.

The effect of invention

By using support chip of the invention and protective film formation composite sheet, adhesive phase will not be generated to substrate surface Embedment become inadequate and generate unfavorable condition as clast, and be able to suppress adhesion, protective film is carried out it is clear Laser lettering and obtain the clearly check image of semiconductor wafer or semiconductor chip.

Detailed description of the invention

Fig. 1 is the sectional view for schematically showing an embodiment of support chip of the invention.

Fig. 2 is the sectional view for schematically showing an embodiment of protective film formation composite sheet of the invention.

Fig. 3 is the sectional view for schematically showing the other embodiment of protective film formation composite sheet of the invention.

Fig. 4 is the sectional view for schematically showing the other embodiment of protective film formation composite sheet of the invention.

Symbol description

1 ... support chip

11 ... substrates

A surface (the 1st face) for 11a ... substrate

Another surface (the 2nd face) of 11b ... substrate

12 ... adhesive phases

13, film is used in the formation of 23 ... protective films

101, composite sheet is used in 102,103 ... protective films formation

Specific embodiment

Composite sheet is used in ◇ support chip, protective film formation

The adhesive phase that support chip of the invention has substrate and is layered on above-mentioned substrate, on the having of above-mentioned substrate The surface roughness (Ra) for stating a side surface (hereinafter, sometimes referred to as " the 1st face ") for adhesive phase is 0.4 μm hereinafter, above-mentioned base The surface roughness with the surface (hereinafter, sometimes referred to as " the 2nd face ") for the side opposite side for having above-mentioned adhesive phase of material (Ra) it is greater than the surface roughness for having a side surface (the 1st face) for above-mentioned adhesive phase, and is 0.053~0.48 μm.

Above-mentioned support chip is the component for constituting following protective film formation composite sheets, such as can be used as cutting sheet etc. The processing of semiconductor wafer is used with piece.

It should be noted that in the present specification, for convenience's sake, sometimes by surface roughness in the two sides of substrate compared with Small face (such as surface roughness is 0.4 μm of face below, the 1st face) is known as even surface, by the biggish face (example of surface roughness Face, the 2nd face such as surface roughness for 0.053~0.48 μm) it is known as male and fomale(M&F).That is, as the even surface of substrate, male and fomale(M&F) Address not necessarily indicates the absolute smoothness in these faces, but indicates the relative size relationship of the smoothness in these faces.

Protective film formation of the invention is to have above-mentioned support chip and the above-mentioned bonding in above-mentioned support chip with composite sheet It is further equipped in oxidant layer made of protective film formation film.

For said protection film formation composite sheet, the surface roughness by having its 1st face and the 2nd face is in The surface roughness in particular range and the 2nd face is greater than the above-mentioned substrate of the surface roughness in the 1st face, is able to suppress adhesion, right Protective film carries out clearly laser lettering and obtains the clearly check image of semiconductor wafer or semiconductor chip.In addition, For said protection film formation composite sheet, by make the surface roughness in the 1st face of substrate be within a certain range (for Lesser value), camber it is low, do not need to make the layer of adhesive phase softness and keep its sufficiently thick, may also suppress adhesive phase pair The embedment in the 1st face of substrate becomes inadequate and generates the generation of unfavorable condition as clast.

Hereinafter, being said with reference first to overall structure of the attached drawing to support chip of the invention and protective film formation composite sheet It is bright.It should be noted that in order to be easier to understand feature of the invention, for convenience's sake, used in the following description Figure sometimes shows the part amplification as mian part, however it is not limited to dimensional ratios of each component etc. and practical identical feelings Condition.

Support chip 1 depicted herein has adhesive phase 12 on substrate 11, further has stripping on adhesive phase 12 It is formed from film 15.

Be laminated with adhesive phase 12 on a surface (the 1st face) 11a of substrate 11, another surface of substrate 11, i.e. with Surface (the 2nd face) 11b for having the side opposite side of adhesive phase 12 becomes exposed surface.

In substrate 11, the surface roughness of the 1st face 11a is 0.4 μm hereinafter, the surface roughness of the 2nd face 11b is greater than the 1st The surface roughness of face 11a, and be 0.053~0.48 μm.

It should be noted that in the present specification, unless otherwise specified, " surface roughness " refers to based on JIS The so-called arithmetic average roughness that B0601:2001 standard is found out, sometimes referred to simply as " Ra ".

Wherein, on a surface of adhesive phase 12, namely with the surface of the side opposite side that is provided with substrate 11 (with Under, sometimes referred to as " the 1st face ") stripping film 15 is provided on 12a, but when using support chip 1, stripping film 15 is removed, such as Stacking protective film formation replaces the stripping film 15 with film, to constitute protective film formation composite sheet.It should be noted that symbol Number 12b refers to the surface of another surface of adhesive phase 12, the side for being provided with substrate 11 (hereinafter, the sometimes referred to as the " the 2nd Face ").

Fig. 2 is the sectional view for schematically showing an embodiment of protective film formation composite sheet of the invention.It needs It is noted that, with already explained identical constituent element shown in figure, label is said with this in the figure after Fig. 2 Identical symbol in the case where the figure of bright mistake, and description is omitted.

Protective film formation composite sheet 101 depicted herein has adhesive phase 12 and in adhesive phase on substrate 11 Have protective film formation film 13 on 12 to form.The composition of support chip 1 can be used in protective film formation composite sheet 101, can also be with Say it is to be further equipped with protective film formation film 13 on the adhesive phase 12 in support chip 1 to form.

Protective film formation film 13 is layered in the entire surface of the 1st face 12a of adhesive phase 12.

In addition, on the surface of protective film formation film 13 and the side opposite side that is provided with adhesive phase 12 (hereinafter, having When be known as " the 1st face ") a part of 13a, the region namely near peripheral portion be laminated with fixture adhesive layer 14.

Moreover, protective film is formed in the 1st face 13a with film 13, in the face and folder that fixture adhesive layer 14 is not laminated Removing is laminated on the face (the 1st face 14a and side 14c) of tool adhesive layer 14 not being in contact with protective film formation film 13 Film 15.Here, the 1st face 14a of fixture adhesive layer 14 be fixture adhesive layer 14 with 13 phase of protective film formation film The surface of the side opposite side of contact also has the 1st face 14a's and side 14c that can not clearly distinguish fixture adhesive layer 14 The case where boundary.In addition, stripping film 15 is not also in contact with the side 14c of fixture adhesive layer 14 sometimes.Protective film is formed It is usually taken care of with composite sheet 1 with such state for having stripping film 15.It should be noted that in Fig. 2, symbol 15a table What is shown is the surface for the side opposite side of stripping film 15 being in contact with protective film formation film 13 (hereinafter, the sometimes referred to as the " the 1st Face ").

Protective film formation composite sheet 101 passes through the 1st of protective film formation film 13 with the state for eliminating stripping film 15 Face 13a and be pasted on semiconductor wafer (illustration omitted) be formed with the face of circuit (in the present specification, sometimes referred to simply as " circuit forming face ") opposite side face (in the present specification, sometimes referred to simply as " back side ") on and also fixture adhesive layer 14 The 1st face 14a be pasted on the fixtures such as ring frame and used.

Protective film is formed in composite sheet 101, and the surface roughness of the 2nd face 11b of substrate 11 is 0.053~0.48 μm, The surface roughness is greater than the surface roughness of the 1st face 11a of substrate 11, has the concaveconvex shape of appropriateness.As a result, by protective film Formation composite sheet 101 batch and be formed as volume when, can inhibit volume contact surface to each other, namely in the protection being stacked Film is formed with viscous between the 2nd face 11b of a substrate 11 and the 1st face 15a of another stripping film 15 in composite sheet 101 Patch, to can inhibit adhesion.

In addition, protective film formation film 13 is sometimes to be pasted onto semiconductor wafer in the manufacturing process of semiconductor device Or the state on the face (back side) with circuit forming face opposite side of semiconductor chip is by being solidified to form as protective film, then Lettering (laser lettering) is carried out by irradiating laser from the 2nd face side 11b of substrate 11.At this point, laser is from the 2nd face of substrate 11 The side 11b is incident to support chip 1 and reaches protective film.Therefore, as noted previously, as the 2nd face 11b of substrate 11 has the recessed of appropriateness Convex form, camber are low, are suppressed in the diffusing reflection of the laser of the 2nd face 11b of substrate 11, clear so as to carry out to protective film Clear laser lettering.

In addition, in the manufacturing process of semiconductor device, have partly leading for protective film formation composite sheet 101 or protective film Body chip or semiconductor chip are examined across protective film formation with composite sheet 101 or protective film using infrared camera etc. sometimes It looks into.At this point, as noted previously, as the 2nd face 11b of substrate 11 has the concaveconvex shape of appropriateness, camber low, the of substrate 11 The diffusing reflection of the infrared ray of 2 face 11b is suppressed, so as to obtain clearly check image.

In addition, being provided with adhesive phase on the male and fomale(M&F) of substrate as previous protective film formation composite sheet In the case of, it is influenced to mitigate the male and fomale(M&F) to adhesive phase bring, needs to keep adhesive phase soft and keep its sufficiently thick.This It is since if adhesive phase is harder, adhesive phase is not filled to the foundation position of the protrusion of substrate surface and produces sometimes Raw space part, if adhesive phase is relatively thin, the concaveconvex shape of substrate surface is reflected, leads to the base of protective film formation film The face (back side) of material side becomes male and fomale(M&F).Such a adhesive phase becomes not fill to the embedment of the concaveconvex shape of substrate surface In the case where point, when implementing laser lettering to protective film as described above, will lead to lettering becomes unintelligible, and can not also obtain Take the clearly check image of semiconductor wafer or semiconductor chip.But in the case where adhesive phase is blocked up, due to for example Adhesive phase during cutting in cutting action is easy vibration, therefore semiconductor chip, is being formed as semiconductor Semiconductor wafer in the cutting of the process of chip is also easy vibration, extra to these semiconductor chips, semiconductor wafer application Power when be easy to produce rupture, defect (being easy to produce clast).Therefore, the case where adhesive phase is arranged in the male and fomale(M&F) of substrate Under, it is easy to produce various unfavorable conditions.

But the 1st of adhesive phase 12 is provided in substrate 11 in composite sheet 101 in protective film formation of the invention The surface roughness of face 11a is 0.4 μm or less, smoothness is high (camber is low), therefore can be to avoid bad feelings as described above Condition.That is, can be sufficiently embedded to the 1st face 11a of substrate 11 by adhesive phase 12 in protective film formation in composite sheet 101, And thick adhesive phase 12 is not necessarily formed, therefore clast can be inhibited.

Protective film formation composite sheet 102 depicted herein is in addition to the shape of protective film formation film is different and does not have Have other than this point of fixture adhesive layer, it is identical with composite sheet 101 as protective film formation shown in Fig. 2.It is used that is, protective film is formed Composite sheet 102, which has adhesive phase 12 on substrate 11 and has protective film formation film 23 on adhesive phase 12, to be formed, and And has stripping film 15 on protective film formation film 23.

Protective film formation film 23 is laminated in the width of a part of the 1st face 12a of adhesive phase 12, namely support chip 1 Spend the region of the center side on direction (left and right directions in Fig. 3).

It is formed in addition, protective film formation is not laminated in the 1st face 12a of adhesive phase 12 with the face of film 23 and protective film Stripping film 15 is laminated with on the surface (the 1st face 23a and side 23c) of film 23 not being in contact with adhesive phase 12.Here, it protects 1st face 23a of cuticula formation film 23 is the side opposite side of protective film formation film 23 being in contact with adhesive phase 12 Surface, also have can not clearly the boundary of the 1st face 23a and side 23c of distinguishing protection film formation film 23 the case where.In addition, The side 23c of protective film formation film 23 is not also in contact sometimes with stripping film 15.Protective film formation with composite sheet 102 usually with The state for having stripping film 15 in this wise is taken care of.

Protective film formation composite sheet 102 passes through the 1st of protective film formation film 23 with the state for eliminating stripping film 15 Face 23a is pasted on the back side of semiconductor wafer (illustration omitted), and protective film is not laminated in the 1st face 12a of adhesive phase 12 Formation is pasted on the fixtures such as ring frame with the face of film 23 and is used.

Protective film is formed in composite sheet 102, and the surface roughness of the 1st face 11a of substrate 11 is 0.4 μm hereinafter, the 2nd face The surface roughness of 11b is greater than the surface roughness of the 1st face 11a and is

0.053~0.48 μm.Protective film forms the case where being formed with composite sheet 102 and protective film with composite sheet 101 as a result, Similarly, adhesive phase 12 will not be generated and become inadequate and generate clast in this way to the embedment of the 1st face 11a of substrate 11 Unfavorable condition, and be able to suppress adhesion, clearly laser lettering is carried out to protective film and obtain semiconductor wafer or half The clearly check image of conductor chip.

Protective film formation depicted herein is with composite sheet 103 in addition to protective film is not laminated in the 1st face 12a of adhesive phase 12 Other than formation is further laminated with this point of fixture adhesive layer 14 with the region near the face of film 23, namely peripheral portion, with Protective film shown in Fig. 3 forms identical with composite sheet 102.

Protective film formation composite sheet 103 passes through the 1st of protective film formation film 23 with the state for eliminating stripping film 15 Face 23a is pasted on the back side of semiconductor wafer (illustration omitted), and the 1st face 14a of fixture adhesive layer 14 is pasted on ring The fixtures such as shape frame and used.

Protective film is formed in composite sheet 103, and the surface roughness of the 1st face 11a of substrate 11 is 0.4 μm hereinafter, the 2nd face The surface roughness of 11b is greater than the surface roughness of the 1st face 11a and is 0.053~0.48 μm.Protective film is formed with multiple as a result, Piece 103 is closed in the same manner as the case where protective film is formed with composite sheet 101, adhesive phase 12 will not be generated to the 1st face of substrate 11 The embedment of 11a becomes inadequate and generates unfavorable condition as clast, and is able to suppress adhesion, carries out to protective film The clearly clearly check image of laser lettering and acquisition semiconductor wafer or semiconductor chip.

Protective film formation of the invention with composite sheet be not limited to Fig. 2~4 shown in example, do not damaging effect of the present invention In the range of fruit, it is also possible to that a part composition of protective film formation composite sheet shown in Fig. 2~4 is changed or deleted Made of structure, can also be and further add structure made of other compositions in example described above.

Then, the composition of each layer of support chip of the invention and protective film formation composite sheet is illustrated.

◎ substrate

The surface roughness of the side surface (the 1st face) for having above-mentioned adhesive phase of above-mentioned substrate is 0.4 μm hereinafter, can To be set as such as 0.37 μm or less, 0.3 μm or less, 0.2 μm or less, 0.1 μm or less, 0.09 μm or less, 0.08 μm or less, 0.07 μm or less and 0.06 μm of such as the following arbitrary range, but these are an example.

The lower limit value of the surface roughness in the 1st face of above-mentioned substrate is not particularly limited, and can be set to such as 0.01 μm, But this is an example.

The preferred example of surface roughness as above-mentioned 1st face, can enumerate 0.01~0.4 μm, 0.01~0.37 μm, 0.01~0.3 μm, 0.01~0.2 μm, 0.01~0.1 μm, 0.01~0.09 μm, 0.01~0.08 μm, 0.01~0.07 μm and 0.01~0.06 μm.

Above-mentioned substrate is with the surface roughness on the surface (the 2nd face) for the side opposite side for having above-mentioned adhesive phase 0.053~0.48 μm, it can be set to such as 0.055 μm or more, 0.08 μm or more, 0.15 μm or more, 0.25 μm in the range Above, 0.35 μm with first-class, furthermore it is possible to be set as 0.47 μm or less, 0.45 μm or less, 0.35 μm or less, 0.25 μm or less, 0.15 μm such as the following, but these are an example.

The preferred example of surface roughness as above-mentioned 2nd face, can enumerate 0.053~0.47 μm, 0.053~0.45 μm, 0.053~0.35 μm, 0.053~0.25 μm and 0.053~0.15 μm.

Preferred other examples of surface roughness as above-mentioned 2nd face, can enumerate 0.055~0.48 μm, 0.08 ~0.48 μm, 0.15~0.48 μm, 0.25~0.48 μm and 0.35~0.48 μm.

Wherein, the surface roughness in above-mentioned 2nd face is greater than the surface roughness in above-mentioned 1st face.

The substrate (hereinafter, sometimes referred to simply as " raw base substrate ") as raw material can be used for example, using same in above-mentioned substrate When form the method for even surface and male and fomale(M&F) or be respectively formed the method for even surface and male and fomale(M&F) to make.

As the production method for the substrate for being formed simultaneously even surface and male and fomale(M&F), it can be cited for example that following methods: in roller Raw base substrate is sandwiched between the mutually different one group of roller of the smoothness on surface, makes it in roller surface while rotating above-mentioned roller Between pass through, accordingly, for raw base substrate, even surface, small by smoothness is formed by the big roller surface of smoothness (even surface of roller) Roller surface (male and fomale(M&F) of roller) formed male and fomale(M&F), to make substrate.

On the other hand, the production method as the substrate for being respectively formed even surface and male and fomale(M&F), it can be cited for example that below Method: the surface roughness using one or two sides is 0.4 μm of raw base substrate below, determines that finally (surface is thick for even surface Rugosity is 0.4 μm of face below) a surface, smoothing techniques or recessed are carried out for another surface different from the surface Convexification processing, becoming surface roughness, (surface roughness is 0.053~0.48 μm greater than the male and fomale(M&F) of above-mentioned even surface Face), thus make substrate.As the method for smoothing techniques or further provided for contouring processing at this time, it can be cited for example that by raw material Substrate presses on the so-called die pressing of even surface or male and fomale(M&F) of roller as described above etc..

As described above by the shape of transfer roller surface etc. come the case where forming even surface or male and fomale(M&F) to raw base substrate Under, can by adjust the even surface of its roller surface etc. smoothness or male and fomale(M&F) camber it is thick come the surface for adjusting substrate Rugosity.

In the above method, can according to need to raw base substrate eventually become even surface (surface roughness be 0.4 μm with Under face) a surface carry out smoothing techniques or further provided for contouring processing, its rough surface is adjusted in 0.4 μm or less of range Degree.

It should be noted that making the rough surface on a surface of substrate for the even surface or male and fomale(M&F) using roller herein Degree is illustrated for 0.053~0.48 μm of method, but template used in the transfer of even surface or male and fomale(M&F) does not limit In roller, it is also possible to the other shapes of template such as plate, block.

In addition, the further provided for contouring processing method on the surface as raw base substrate can also lift other than above-mentioned die pressing Out such as blasting process, solvent treatment method.

More than, it is the table that 0.4 μm of raw base substrate below makes two sides for using the surface roughness of one or two sides The method that surface roughness meets the substrate of above-mentioned condition respectively is illustrated, but above-mentioned substrate can also be for example, by below Method makes.

That is, the raw base substrate for the use of the surface roughness of one or two sides being 0.053 μm or more, determination eventually become bumps One surface in face (face that surface roughness is 0.053~0.48 μm), smooths another surface being different from Processing or further provided for contouring processing, become surface roughness less than above-mentioned male and fomale(M&F) even surface (surface roughness be 0.4 μm with Under face), thus make substrate.

In this method, can according to need to raw base substrate eventually become male and fomale(M&F) (surface roughness be 0.053~ 0.48 μm of face) a surface carry out smoothing techniques or further provided for contouring processing, adjust it in the range of 0.053~0.48 μm Surface roughness.

Wherein, as above-mentioned base material production method is, it is preferable to use raw base substrate is formed simultaneously even surface and male and fomale(M&F) Method.

The constituent material of above-mentioned substrate is preferably various resins, and above-mentioned resin is well known resin.

Wherein, the light that the light for being preferably 532nm to wavelength is with transmittance, simultaneously 1600nm to wavelength also has transmission The substrate of property.Wavelength is that the light of 532nm is suitable for carrying out the laser lettering of protective film, and wavelength is that the light of 1600nm is suitable for carrying out The infrared inspection of semiconductor wafer or semiconductor chip.

In addition, preferably having to the light of ultraviolet range in the case that adhesive phase described later is energy ray-curable There is radioparent substrate.

About the specific constituent material of substrate, it is described below.

The constituent material of 1 layer of substrate can be only one kind, or and it is two or more, in the case where being two or more, Their combination and ratio can be adjusted arbitrarily.

The tensile modulus of elasticity of above-mentioned substrate is not particularly limited, preferably 240~700MPa, more preferably 280~ 650MPa, particularly preferably 320~600MPa.

Substrate can be made of 1 layer (single layer), can also be made of 2 layers or more of multilayer.The feelings that substrate is made up of multiple layers Under condition, multilayer can be the same or different each other.I.e., it is possible to be that all layers are all the same, it is also possible to all layers not Together, it can also be that only part layer is identical.Moreover, the combination of these multilayers is not particularly limited in the case that multilayer is different. It should be noted that in the present specification, so-called multilayer is different, at least one of material and thickness of each layer are each meant It is different, the case where this is not limited to substrate.

The thickness of above-mentioned substrate can be suitable for selecting according to purpose, and preferably 15~300 μm, more preferably 20~200 μm, It such as can be the arbitrary thickness such as 30~160 μm and 40~120 μm.By make substrate with a thickness of such range, it is above-mentioned The flexibility of protective film formation composite sheet further increases the stickup of semiconductor wafer or semiconductor chip.

Here, " thickness of substrate " refers to the thickness of substrate entirety, for example, the thickness for the substrate being made up of multiple layers refers to structure At all layers of overall thickness of substrate.

It should be noted that the surface roughness of at least one side of substrate is 0.053 μm or more, become with concaveconvex shape Non- even surface, for the thickness of substrate, can at the position comprising protrusion of substrate, using the top of the protrusion as one A starting point and more precisely calculate.

◎ adhesive phase

Above-mentioned adhesive phase can be well known adhesive phase, be not particularly limited.For example, adhesive phase can be energy Any one in line curability and non-energy line curability.

In the present invention, " energy ray-curable " refers to through the cured property of irradiation energy line.In addition, with its phase Instead, not cured property it will be known as " non-energy line curability " irradiation energy line.

In the present invention, " energy line " refers to the ray in electromagnetic wave or beam of charged ions with the quantum of energy, as it Example can enumerate ultraviolet light, radioactive ray, electron beam etc..

Ultraviolet light for example can be by using high-pressure sodium lamp, melting H lamp, xenon lamp, black light lamp or the LED as ultraviolet source Lamp etc. is irradiated.Electron beam can radiate the ray generated by electron-beam accelerator etc..

As the constituent material of adhesive phase, for example, the adhesive of resin of binding property etc., crosslinking agent etc..

Wherein, the light that the light for being 532nm preferably for wavelength is with transmittance, simultaneously 1600nm to wavelength also has The adhesive phase of penetrating property.Wavelength is that the light of 532nm is suitable for carrying out the laser lettering of protective film, and the light that wavelength is 1600nm is suitble to In the infrared inspection for carrying out semiconductor wafer or semiconductor chip.

Above-mentioned adhesive phase is preferably any one of energy ray-curable and non-energy line curability, more preferably non-energy Measure line curability.

The storage modulus of adhesive phase is not particularly limited, it is often preferred that 0.01~1000MPa, more preferably 0.01~ 500MPa, particularly preferably 0.01~300MPa.

The storage modulus of adhesive phase can be adjusted by adjusting the type containing ingredient or the amount of adhesive phase.

It should be noted that in the present specification, unless otherwise specified, the case where adhesive phase is curability Under, " storage modulus of adhesive phase " refers to " storage modulus of the adhesive phase before being solidified ".

The storage modulus of adhesive phase is acquired by following methods.

That is, being bonded adhesive phase each other, the laminated body of the adhesive phase with a thickness of 800 μm is made, which is rushed It is cut into the circle of diameter 10mm, test piece assigns frequency to the test film using measurement devices such as determination of viscoelasticity devices The strain of 1Hz, the storage modulus of -50~150 DEG C of measurement, using the value of the storage modulus at 23 DEG C as above-mentioned adhesive phase Storage modulus.

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 where composition, multilayer can be the same or different each other.Here, " multilayer each other can be identical or not The case where referring to together " with above-mentioned substrate is same.Moreover, the combination of multilayer does not limit especially in the case that multilayer is different It is fixed.

The thickness of adhesive phase can according to purpose be suitable for selection, preferably 1~50 μm, more preferably 1~40 μm, especially Preferably 1~30 μm.By make adhesive phase with a thickness of above-mentioned lower limit value more than, adhesive phase is for protective film formation film Bonding force further increase.In addition, the effect of the concaveconvex shape in the 1st face of embedment substrate further increases, it can be further Reduce adhesive phase is influenced by the concaveconvex shape.On the other hand, by make adhesive phase with a thickness of above-mentioned upper limit value with Under, the inhibitory effect of clast further increases, and cutting action more stabilizes.

Here, " thickness of adhesive phase " refers to the thickness of adhesive phase entirety, for example, the adhesive phase being made up of multiple layers Thickness refer to constitute adhesive phase all layers of overall thickness.

It should be noted that the surface roughness in the 1st face of above-mentioned substrate is 0.4 μm hereinafter, with so as described above Concaveconvex shape it is corresponding, the side surface (the 2nd face) for being provided with substrate of adhesive phase sometimes become have surface roughness For 0.1 μm of non-even surface with first-class concaveconvex shape.In this case, can bonded for the thickness of adhesive phase The position comprising protrusion of oxidant layer is more precisely calculated using the top of the protrusion as a starting point.

Adhesive phase preferably adjusts hardness according to its thickness.As the index for judging the hardness of adhesive phase, example Above-mentioned storage modulus can such as be enumerated.

For example, the thickness of adhesive phase is preferably greater than 15 μm (15 μ m-thicks of ratio), more preferably 18 μm or more such thickness In the case where, the storage modulus of adhesive phase is preferably 30kPa or more, more preferably 40kPa or more, particularly preferably 50kPa More than.The upper limit value of the storage modulus of adhesive phase in this case for example can be set to enumerated supra under common value Upper limit value.So, if adhesive phase is harder, even in the case where adhesive phase is thicker, such as in cutter Adhesive phase in sequence in cutting-off process is also not susceptible to vibrate.Therefore, semiconductor chip, form the process of semiconductor chip Semiconductor wafer in cutting is also not susceptible to vibrate, and can inhibit extra to above-mentioned semiconductor chip, semiconductor wafer application Power and result causes semiconductor chip to generate rupture, so-called clast as defect.

On the other hand, the thickness of adhesive phase is preferably 15 μm or less, more preferably 10 μm or less such lower thickness In the case where, the storage modulus of adhesive phase is not particularly limited.In this case, even if adhesive phase is relatively soft, such as cutting It cuts adhesive phase when cutting off in process to be also not susceptible to vibrate, therefore can get and the hard and thick situation of above-mentioned such adhesive phase Same effect down.

The storage modulus of the adhesive phase of (the relatively thin situation of adhesive phase) for example can be set to listed hereinbefore in this case The common range lifted, but this is an example.Wherein, from the aspect of the inhibitory effect for further increasing clast, the feelings Under condition, it is also preferred that the storage modulus of adhesive phase be set as with above-mentioned adhesive phase it is thicker in the case where same range.

That is, in above-mentioned support chip, by make the thickness of adhesive phase be preferably 15 μm or less, more preferably 10 μm with Under, the higher effect for inhibiting clast can be obtained, influenced without the storage modulus by adhesive phase.

Adhesive phase can be used the adhesive composition containing adhesive and be formed.For example, can be by adhesive Adhesive composition is applied in the formation object surface of layer and is made it dry as needed and is formed adhesive phase in target site. The more specific forming method of adhesive phase is illustrated in detail below together with other layers of forming method.Adhesive combination The mutual content ratio of the ingredient not gasified at normal temperature in object usually with the mentioned component of adhesive phase is mutual contains It is identical to measure ratio.It should be noted that in the present specification, " room temperature ", which refers to, does not carry out cooling especially also without the temperature of heating Degree, namely usual temperature, for example, 15~25 DEG C of temperature etc..

Above-mentioned adhesive composition can be by cooperating other than above-mentioned adhesive, above-mentioned adhesive used as needed Ingredient etc. is used to constitute the ingredient of adhesive composition and obtains.

Order of addition when each ingredient is cooperated is not particularly limited, and can also add two or more ingredients simultaneously.

The method mixed when cooperation to each ingredient is not particularly limited, can from make stirrer or agitating paddle etc. rotate Come mixed method, using method that mixer is mixed, apply the method that ultrasonic wave is mixed etc. well known to side It is 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, is suitable for adjusting, but temperature is preferably 15~30 DEG C.

The coating of adhesive composition can carry out according to known methods, it can be cited for example that using airblade coating Machine, scraper plate coating machine, bar coater, gravure coater, roll coater, roller knife coating machine, curtain stream coating machine, die coating machine, blade coating The method of the various coating machines such as machine, silk screen coating machine, Meyer bar coater, kiss coater.

The drying condition of adhesive composition is not particularly limited, and adhesive composition contains the feelings of solvent described later Under condition, preferably make its heat drying.Adhesive composition containing solvent is for example preferably at 70~130 DEG C, 10 seconds~5 minutes Condition be dried.

As the support chip for having the substrate and adhesive phase that are formed by constituent material as described above, example can be enumerated As: that records in No. 4805549 bulletins of Japanese Patent No. is made of base material film and the adhesive phase being formed on the base material film Bonding sheet；Recorded in No. 4781633 bulletins of Japanese Patent No. by base material film and the adhesive phase structure that is formed on the base material film At bonding sheet；The bonding for having substrate and being layered in its at least one side recorded in No. 5414953 bulletins of Japanese Patent No. The cutting sheet of oxidant layer；At least one side in substrate recorded in Japanese Unexamined Patent Publication 2013-199562 bulletin has pressure-sensitive adhesive The work pieces process piece etc. of resin layer (adhesive phase).

As support chip of the invention, preferably comprise that material is identical as above sheet and the surface in the 1st face and the 2nd face is thick Rugosity is adjusted to the support chip of above-mentioned numberical range.

Film is used in the formation of ◎ protective film

Said protection film formation has curability with film, by being solidified to form protective film.

Said protection film formation film can be any one of thermosetting property and energy ray-curable.

Film is used in the formation of zero thermosetting protective film

As preferred thermosetting protective film formation film, it can be cited for example that containing component of polymer (A) and thermosetting property Film is used in the thermosetting protective film formation of ingredient (B).Component of polymer (A) be can regard as polymerizable compound carry out polymerization reaction and The ingredient of formation.In addition, thermosetting component (B) is to be able to carry out heat as the releaser reacted to solidify (polymerization) and react Ingredient.It should be noted that polymerization reaction also includes polycondensation reaction in present embodiment.

Thermosetting protective film formation film can be made of 1 layer (single layer), can also be made of 2 layers or more of multilayer.Heat In the case that solidity protective film formation is made up of multiple layers with film, multilayer can be the same or different each other.Here, " more Layer can be the same or different each other " the case where referring to above-mentioned substrate is same.Moreover, the situation that multilayer is different Under, the combination of multilayer is not particularly limited.

The thickness of thermosetting protective film formation film is preferably 1~100 μm, more preferably 5~75 μm, particularly preferably 5 ~50 μm.By make thermosetting protective film formation film with a thickness of above-mentioned lower limit value more than, it is higher protective capability can be formed Protective film.In addition, by making being formed as with a thickness of above-mentioned upper limit value hereinafter, can inhibit for thermosetting protective film formation film More thickness.

Here, " thickness of thermosetting protective film formation film " refers to the thickness of thermosetting protective film formation film entirety, Such as the thickness for the thermosetting protective film formation film being made up of multiple layers refers to all of composition thermosetting protective film formation film The overall thickness of layer.

For thermosetting protective film formation is pasted on the back side of semiconductor wafer with film and it is made to be solidified to form protection For condition of cure when film, do not limited especially as long as the curing degree that can reach the degree that protective film gives full play to its function It is fixed, it can be carried out being suitable for selection according to the type of thermosetting protective film formation film.

For example, heating temperature when thermosetting protective film formation is solidified with film is preferably 100~200 DEG C, more preferably 110 ~180 DEG C, particularly preferably 120~170 DEG C.Moreover, heating time when above-mentioned solidification is preferably 0.5~5 hour, more preferably It is 0.5~3 hour, particularly preferably 1~2 hour.

< < thermosetting protective film, which is formed, uses composition > >

The thermosetting protective film formation composition containing its constituent material can be used with film for thermosetting protective film formation 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 for example can be according to the coating with above-mentioned adhesive composition Situation identical method carries out.

The drying condition of thermosetting protective film formation composition is not particularly limited, and thermosetting protective film is formed with 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.

< thermosetting protective film, which is 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 Dividing the thermosetting protective film of (B) to be formed, (in the present specification, sometimes referred to simply as " group is used in protective film formation with composition (III-1) Close object (III-1) ") etc..

[component of polymer (A)]

Component of polymer (A) is the polymerization for assigning film forming, flexibility etc. to thermosetting protective film formation film Close object.

It can be only one kind that composition (III-1) and thermosetting protective film, which form the component of polymer (A) contained by film, Can be to be two or more, in the case where being two or more, their combination and ratio can be selected arbitrarily.

As component of polymer (A), it can be cited for example that: the acrylic resin (tree with (methyl) acryloyl group Rouge), 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.

It should be noted that in the present specification, the concept of " (methyl) acryloyl group " include " acryloyl group " and Both " methylacryloyl ".The term similar with (methyl) acryloyl group is also the same, for example, " (methyl) acrylic acid " it is general Reading includes both " acrylic acid " and " methacrylic acid ", and the concept of " (methyl) acrylate " includes " acrylate " and " first Both base acrylate ".

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.More than the above-mentioned lower limit value of weight average molecular weight by making acrylic resin, thermosetting protective film is formed with film Shape stability (ageing stability when keeping) improves.In addition, by keeping the weight average molecular weight of acrylic resin 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) of adherend with film Addendum and thermosetting protective film are formed with generation gap etc. between film.

It should be noted that in the present specification, unless otherwise specified, weight average molecular weight is by gel infiltration color The polystyrene scaled value of (GPC) method of composing measurement.

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 above-mentioned lower limit value of the Tg of acrylic resin or more, can inhibit bonding between protective film and support chip (adhesive phase) The fissility of power, support chip improves.In addition, by making the above-mentioned upper limit value of Tg of acrylic resin hereinafter, thermosetting property is protected Film is formed to be improved with the bonding force between film and protective film and adherend.

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 Sour stearyl ((methyl) stearyl acrylate) etc. constitutes the chain structure that the carbon atom number of 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 methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 3- hydroxybutyl, (methyl) third (methyl) acrylate of the hydroxyls such as olefin(e) acid 4- hydroxybutyl；

(methyl) acrylate containing substituted-amino such as (methyl) acrylic acid N- methylamino ethyl ester etc..Wherein, " replace Amino " refers to, group made of 1 of amino or 2 hydrogen atoms are replaced by the group other than hydrogen atom.

Acrylic resin is for example also possible to other than above-mentioned (methyl) acrylate, also copolymerization has selected from (methyl) One or more of acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N hydroxymethyl acrylamide etc. Acrylic resin made of monomer.

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, their combination and ratio can be selected arbitrarily.

Acrylic resin can have 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 being bonded by above-mentioned functional group with other compounds, the reliability of encapsulation obtained from protective film formation composite sheet is used The tendency being improved.

In the present invention, as component of polymer (A), acrylic compounds can be used alone without using acrylic resin Thermoplastic resin (hereinafter, sometimes referred to simply as " thermoplastic resin ") other than resin, can also be by itself and acrylic resin group It closes and uses.By using above-mentioned thermoplastic resin, protective film is improved from the fissility on support chip or thermosetting protective film shape At being easy to follow the male and fomale(M&F) of adherend with film, further suppresses to be formed in adherend and thermosetting protective film sometimes and use Gap etc. is generated between film.

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, 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 composition (III-1) and thermosetting protective film formation film can be only one kind, Or it is two or more, in the case where being two or more, their combination and ratio can be selected arbitrarily.

In composition (III-1), the total content of the content of component of polymer (A) relative to the whole components other than solvent Kind of the ratio (that is, content that thermosetting protective film forms the component of polymer (A) with film) independent of component of polymer (A) Class, preferably 5~85 mass %, more preferably 5~80 mass %, such as can for 10~70 mass %, 20~60 mass %, And 30~50 mass % arbitrary range.

Component of polymer (A) is also equivalent to the case where thermosetting component (B).In the present invention, composition (III-1) contains In the case where having the ingredient for being equivalent to both such component of polymer (A) and thermosetting component (B), composition (III-1) can Regard as containing component of polymer (A) and thermosetting component (B).

[thermosetting component (B)]

Thermosetting component (B) be for make thermosetting protective film formation with film be solidified to form hard protective film at Point.

It can be only one kind that composition (III-1) and thermosetting protective film, which form the thermosetting component (B) contained by film, Can be to be two or more, in the case where being two or more, their combination 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).

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 where being two or more, their combination and ratio can be selected arbitrarily.

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 Rouge, 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 do not have 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 uses the semiconductor chip with protective film obtained from protective film formation composite sheet Reliability improves.

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 made of aromatic rings for being bonded to and constituting epoxy resin etc. etc..

Unsaturated alkyl is the unsaturated group with polymerism, sub as its concrete example, can enumerate vinyl (vinyl group), 2- acrylic (allyl), (methyl) acryloyl group, (methyl) acrylamido etc., preferably acryloyl Base.

The number-average molecular weight of epoxy resin (B1) is not particularly limited, from the curability of thermosetting protective film formation film, And from the viewpoint of the protection film strength and heat resistance after solidifying, preferably 300~30000, more preferably 300~ 10000,300~3000 are particularly preferably.

The epoxide equivalent of epoxy resin (B1) is preferably 100~1000g/eq, more preferably 150~950g/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 where, their combination and ratio can be selected arbitrarily.

Thermal curing agents (B2)

Thermal curing agents (B2) as epoxy resin (B1) curing agent and function.

As thermal curing agents (B2), it can be mentioned, for example: have in 1 molecule 2 or more can be with the official of epoxy reaction 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 type phenolic resin, aralkyl-type phenol 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) are also possible to 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 made of group with unsaturated alkyl replaces, the group 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.

Phenols curing agent is used as in the case where 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.

In thermal curing agents (B2), such as multifunctional phenolic resin, novolak phenolics, dicyclopentadiene type phenol The number average molecular weight of the resin components such as resin, aralkyl-type phenol 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 where, their combination and ratio can be selected arbitrarily.

It is formed in composition (III-1) and thermosetting protective film with 100 matter of content in film, relative to epoxy resin (B1) Part is measured, the content of thermal curing agents (B2) is preferably 0.1~500 mass parts, more preferably 1~200 mass parts, such as can be 1 The arbitrary range of~100 mass parts, 1~50 mass parts and 1~25 mass parts.By above-mentioned the containing for making thermal curing agents (B2) Amount is above-mentioned lower limit value or more, it is easier to carry out the solidification of thermosetting protective film formation film.In addition, by making thermal curing agents (B2) above-mentioned content is above-mentioned upper limit value hereinafter, the thermosetting protective film formation hydroscopicity reduction of film, uses protective film shape It is further increased at the reliability of the encapsulation obtained from composite sheet.

It is formed in composition (III-1) and thermosetting protective film with the content 100 in film, relative to component of polymer (A) Mass parts, the content (for example, total content of epoxy resin (B1) and thermal curing agents (B2)) of thermosetting component (B) is preferably 20~ 500 mass parts, more preferably 30~300 mass parts, particularly preferably 40~150 mass parts, such as can be 40~125 mass The arbitrary range of part, 40~100 mass parts and 40~75 mass parts.By make thermosetting component (B) above-mentioned content this The range of sample, can inhibit the bonding force between protective film and support chip, and the fissility of support chip improves.

[curing accelerator (C)]

Composition (III-1) and thermosetting protective film formation film can contain curing accelerator (C).Curing accelerator (C) it is ingredient for adjusting the curing rate of 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- phenylimidazole, 2- phenyl- 4-methylimidazole, 2- phenyl -4,5- bishydroxymethyl imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazole etc. imidazoles (1 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, triphenylphosphine tetraphenyl Tetraphenyl borate salts such as borate etc..

It can be only one kind that composition (III-1) and thermosetting protective film, which form the curing accelerator (C) contained by film, Can be to be two or more, in the case where being two or more, their combination and ratio can be selected arbitrarily.

In the case where using curing accelerator (C), is formed and used in film in composition (III-1) and thermosetting protective film, phase For 100 mass parts of content of thermosetting component (B), the content of curing accelerator (C) is preferably 0.01~10 mass parts, more excellent It is selected as 0.1~7 mass parts.By making the content of curing accelerator (C) more than above-mentioned lower limit value, can be made more significantly The effect brought by curing accelerator (C).In addition, by make the content of curing accelerator (C) in above-mentioned upper limit value hereinafter, Such as highly polar curing accelerator (C) under high temperature/super-humid conditions in thermosetting protective film formation film to quilt The inhibitory effect that the bonding interface side of bur is mobile and is segregated improves, using obtained from protective film formation composite sheet The reliability of semiconductor chip with protective film further increases.

[packing material (D)]

Composition (III-1) and thermosetting protective film formation film can contain packing material (D).By protecting thermosetting property Cuticula formation film contains packing material (D), for the protective film obtained from solidify thermosetting protective film formation film, It is easily adjusted thermal expansion coefficient.Moreover, optimizing the thermal expansion coefficient by the formation object for protective film, thermosetting property is used The reliability of semiconductor chip of the protective film formation obtained from film with protective film further increases.In addition, by making thermosetting Property protective film formation film contain packing material (D), can also reduce protective film hydroscopicity, 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 The modified product in surface；The mono-crystlling fibre of these inorganic filling materials；Glass fibre etc..

In these materials, preferably inorganic filling material is silica or aluminium oxide.

It can be only one kind that composition (III-1) and thermosetting protective film, which form the packing material (D) contained by film, can also Think it is two or more, in the case where two or more, their combination and ratio can be selected arbitrarily.

In the case where using packing material (D), in composition (III-1), relative to the whole components other than solvent The ratio (that is, content that thermosetting protective film forms the packing material (D) with film) of total content, the content of packing material (D) is excellent 5~80 mass %, more preferably 7~60 mass % are selected as, such as can be 10~50 mass %, 15~45 mass % and 20 Any range in~40 mass %.By making the content of packing material (D) in such range, the tune of above-mentioned thermal expansion coefficient It is whole to become more to be easy.

[coupling agent (E)]

Composition (III-1) and thermosetting protective film formation film can contain coupling agent (E).It can by using having Compound with the functional group of inorganic compound or organic compound reaction can make thermosetting protective film shape as coupling agent (E) It is improved at the cementability and adaptation with film relative to adherend.In addition, not will lead to makes heat by using coupling agent (E) The heat resistance of protective film obtained from solidity protective film formation film solidifies is impaired, and water resistance can be improved.

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,hoxysilane, 3- ring Oxygen propoxypropyl methyldiethoxysilane, 3- epoxy propoxy propyl triethoxysilane, 3- glycidyl oxy methyl two Ethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- methacryloxypropyl trimethoxy silicon Alkane, 3- TSL 8330,3- (2- aminoethylamino) 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- urea propyl-triethoxysilicane, 3-mercaptopropyi trimethoxy silane, 3- mercapto propyl methyl dimethoxy silane, double (3- triethoxysilylpropyltetrasulfide) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyl front three Oxysilane, vinyltriacetoxy silane, imidizole silane etc..

It can be only one kind that composition (III-1) and thermosetting protective film, which form the coupling agent (E) contained by film, can also be with Be it is two or more, in the case where two or more, their combination and ratio can be selected arbitrarily.

In the case where using coupling agent (E), is formed and used in film in composition (III-1) and thermosetting protective film, relative to 100 mass parts of total content of component of polymer (A) and thermosetting component (B), the content of coupling agent (E) are preferably 0.03~20 matter Measure part, more preferably 0.05~10 mass parts, particularly preferably 0.1~5 mass parts.By making the content of coupling agent (E) upper Lower limit value or more is stated, the raising of dispersibility of the packing material (D) in resin can be obtained more significantly, thermosetting protective film is formed Raising with film and the cementability of adherend etc. uses effect brought by coupling agent (E).In addition, by making coupling agent (E) Content in above-mentioned upper limit value hereinafter, the generation of degassing (outgas) can be further suppressed.

[crosslinking agent (F)]

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 where, combination Object (III-1) and thermosetting protective film formation film can contain crosslinking agent (F).Crosslinking agent (F) is for making component of polymer (A) the above-mentioned functional group in is bonded with other compounds and the ingredient that is crosslinked, is crosslinked in this way, adjustable thermosetting Property protective film formed use film initial bonding force and cohesiveness.

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 below by polyisocyanate compound and alicyclic polyisocyanates compound Polyisocyanate compound etc. ")；The trimers such as above-mentioned aromatic polyisocyanate compound, isocyanuric acid ester body and adduct； Terminal isocyanate carbamic acid obtained from reacting above-mentioned aromatic polyisocyanate compound etc. and polyol compound 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.As the example of 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 di-isocyanate(TDI)s； 2,6- toluene di-isocyanate(TDI)；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: N, N '-diphenyl methane -4,4 '-bis- (1- aziridine Formamide) ,-three-β of trimethylolpropane-'-aziridino propionic ester ,-three-β of tetramethylol methane-'-aziridino propionic ester, N, N '-Toluene-2,4-diisocyanate, bis- (1- aziridine formamide) triethylenemelanins of 4- etc..

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.In the case where crosslinking agent (F) has hydroxyl with isocyanate group, component of polymer (A), Crosslinking knot easily can be imported to thermosetting protective film formation film with reacting for component of polymer (A) by crosslinking agent (F) Structure.

It can be only one kind that composition (III-1) and thermosetting protective film, which form the crosslinking agent (F) contained by film, can also be with Be it is two or more, in the case where two or more, their combination and ratio can be selected arbitrarily.

In the case where using crosslinking agent (F), relative to 100 mass parts of content of component of polymer (A), composition (III- 1) 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.It more than the above-mentioned lower limit value of above-mentioned content by making crosslinking agent (F), can obtain more significantly using crosslinking agent (F) And bring effect.In addition, by making the above-mentioned upper limit value of above-mentioned content of crosslinking agent (F) hereinafter, can inhibit crosslinking agent (F) It is excessively used.

[energy ray-curable resin (G)]

Composition (III-1) can contain energy ray-curable resin (G).Thermosetting protective film formation film is by containing Energy ray-curable resin (G) can change characteristic by energy line irradiation.

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: intramolecular at least has the change of 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- butanediol 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 where above, their combination and ratio can be selected arbitrarily.

Energy ray-curable resin (G) contained by composition (III-1) can be only one kind, or two kinds with On, in the case where being two or more, their combination and ratio can be selected arbitrarily.

In the case where using energy ray-curable resin (G), the energy ray-curable resin (G) of composition (III-1) Content is preferably 1~95 mass %, more preferably 5~90 mass %, particularly preferably 10~85 mass %.

[Photoepolymerizationinitiater initiater (H)]

In the case that composition (III-1) contains energy ray-curable resin (G), in order to make energy line curable resin (G) polymerization reaction is effectively performed, and can also contain Photoepolymerizationinitiater initiater (H).

As the Photoepolymerizationinitiater initiater (H) in composition (III-1), it can be cited for example that: benzoin, benzoin methylether, The double first of benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether, styrax benzoic acid, styrax methyl benzoate, styrax The benzoins compound such as ether；Acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, 2,2- dimethoxy -1,2- diphenyl The acetophenone compounds such as ethane -1- ketone；Bis- (2,4,6- trimethylbenzoyl) phenyl phosphine oxides, 2,4,6- trimethylbenzoyl The acylphosphine oxide compounds such as base diphenyl phosphine oxide；The sulfide compounds such as benzyl phenyl thioether, tetramethylthiuram monosulfide； The α -one alcoholic compound such as 1- hydroxycyclohexylphenylketone；The azo-compounds such as azodiisobutyronitrile；The titanocenes chemical combination such as titanocenes Object；The thioxanthone compounds such as thioxanthones；Per-compound；The dione compounds such as diacetyl；Dibenzoyl；Bibenzyl；Benzophenone； 2,4- diethyl thioxanthone；1,2- diphenyl methane；2- hydroxy-2-methyl -1- [4- (1- methyl ethylene) phenyl] acetone；2- Chloroanthraquinone etc..

In addition, the naphtoquinone compounds such as 1- chloroanthraquinone can also be enumerated as above-mentioned Photoepolymerizationinitiater initiater；The photosensitizers such as amine Deng.

Photoepolymerizationinitiater initiater (H) contained by composition (III-1) can be only one kind, or and it is two or more, be In the case where two or more, their combination and ratio can be selected arbitrarily.

In the case where using Photoepolymerizationinitiater initiater (H), relative to 100 mass parts of content of energy ray-curable resin (G), The content of the Photoepolymerizationinitiater initiater (H) of composition (III-1) be preferably 0.1~20 mass parts, more preferably 1~10 mass parts, Particularly preferably 2~5 mass parts.

[colorant (I)]

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 acidIt is pigment, azulene (azulenium) 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 Diindyl quinoline ketone system pigment, quinophthalone system pigment, azole series pigment, thioindigo system pigment, metal complex system pigment (metallic complex salt dye 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 series pigment, chromium system pigment, titanium system Pigment, vanadium system pigment, zirconium 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..

It can be only one kind that composition (III-1) and thermosetting protective film, which form the colorant (I) contained by film, can also be with Be it is two or more, in the case where two or more, their combination and ratio can be selected arbitrarily.

In the case where using colorant (I), thermosetting protective film is formed can be according to mesh with the content of the colorant (I) of film Suitable adjusting.For example, forming the content of the colorant (I) of film by adjusting thermosetting protective film and adjusting protective film Translucency, adjustable lettering when carrying out laser lettering to protective film are visual.In addition, by adjusting thermosetting protective film shape At the content of the colorant (I) with film, the design of protective film can also be improved and make the grinding trace of back surface of semiconductor wafer Mark becomes to be not readily apparent.If it is considered that these aspects, then in composition (III-1), the content of colorant (I) is relative to solvent The ratio (that is, content that thermosetting protective film forms the colorant (I) with film) of the total content of all the components in addition is preferably 0.1~10 mass %, more preferably 0.1~7.5 mass %, particularly preferably 0.1~5 mass %.By making colorant (I) Above-mentioned content is above-mentioned lower limit value or more, can be obtained more significantly using effect brought by colorant (I).In addition, by making The above-mentioned content of colorant (I) is above-mentioned upper limit value hereinafter, the translucency that can inhibit thermosetting protective film formation film excessively drops It is low.

[universal additive (J)]

Composition (III-1) and thermosetting protective film formation film can contain within the scope of the effect of the invention 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..

It can be only one kind that composition (III-1) and thermosetting protective film, which form the universal additive (I) contained by film, Can be to be two or more, in the case where being two or more, their combination and ratio can be selected arbitrarily.

The content for the universal additive (I) that composition (III-1) and thermosetting protective film form film is not particularly limited, It can be suitable for selection according to purpose.

[solvent]

Composition (III-1) preferably further contains solvent.The operability of composition (III-1) containing solvent becomes good It 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； The alcohol such as methanol, ethyl alcohol, 2- propyl alcohol, isobutanol (2- methylpropane -1- alcohol), n-butyl alcohol；The esters such as ethyl acetate；Acetone, methyl ethyl ketone Equal ketone；The ethers such as tetrahydrofuran；Amides such as dimethylformamide, N-Methyl pyrrolidone (compound with amido bond) etc..

Solvent contained by composition (III-1) can be only one kind, or and it is two or more, it is two or more feelings Under condition, their combination and ratio can be selected arbitrarily.

Aspect, composition (III-1) institute are mixed from can will more uniformly contain ingredient in composition (III-1) The solvent contained is preferably methyl ethyl ketone etc..

< < thermosetting protective film forms the manufacturing method > > for using composition

Composition (III-1) etc. thermosetting protective film formation composition can be by cooperating each ingredient for constituting it And it obtains.

Cooperate order of addition when each ingredient to be not particularly limited, two or more ingredients can also be added simultaneously.

It, can be and solvent be mixed with any gradation composition other than solvent by the cooperation in the case where using solvent It uses, any gradation composition other than solvent can not also be diluted in advance after ingredient beforehand dilution, but passing through 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 rotate stirrer or agitating paddle etc. 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. It is suitable for 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.

Film is used in the formation of zero energy ray-curable protective film

Energy ray-curable protective film formation film contains energy ray-curable ingredient (a).

Energy ray-curable protective film is formed in film, and energy ray-curable ingredient (a) is preferably uncured, preferably has Adhesiveness, more preferably it is uncured and have adhesiveness.Here, " energy line " and " energy ray-curable " as previously described.

Energy ray-curable protective film formation film can be only 1 layer (single layer), or 2 layers or more of multilayer is In the case where multilayer, multilayer can be the same or different each other, and the combination of these multilayers is not particularly limited.

The thickness of energy ray-curable protective film formation film is preferably 1~100 μm, is more preferably 5~75 μm, is especially excellent It is selected as 5~50 μm.By make energy ray-curable protective film formation film with a thickness of above-mentioned lower limit value more than, guarantor can be formed The higher protective film of shield ability.In addition, by make energy ray-curable protective film formation film with a thickness of above-mentioned upper limit value with Under, it can inhibit the thickness for being formed as excessive.

Here, " thickness of energy ray-curable protective film formation film " refers to energy ray-curable protective film formation film Whole thickness, such as the thickness of energy ray-curable protective film formation film being made up of multiple layers refer to composition energy line curing Property protective film formed use film all layers of overall thickness.

For the formation of energy ray-curable protective film is pasted on the back side of semiconductor wafer with film and solidifies it and shape For condition of cure when at protective film, do not have as long as the curing degree that can reach the degree that protective film gives full play to its function It is particularly limited to, can be carried out being suitable for selection according to the type of energy ray-curable protective film formation film.

For example, in the solidification of energy ray-curable protective film formation film, the illumination of energy line is preferably 120~ 280mW/cm².Moreover, the light quantity of energy line is preferably 200~1000mJ/cm when above-mentioned solidification²。

< < energy ray-curable protective film, which is formed, uses composition > >

The energy ray-curable protective film containing its constituent material can be used with film for the formation of energy ray-curable protective film 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, which is formed, uses composition, makes it dry as needed, it is possible thereby to form energy ray-curable in target site Film is used in protective film formation.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.

Energy ray-curable protective film formation composition coating for example can according to above-mentioned adhesive composition The case where coating, identical method carried out.

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 is for example preferably dried in the condition of 70~130 DEG C, 10 seconds~5 minutes with composition.

< energy ray-curable protective film, which is 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 " composition (IV-1) ") etc..

[energy ray-curable ingredient (a)]

Energy ray-curable ingredient (a) is cured ingredient to be irradiated by energy line, and be used for energy line curing Property protective film formation film assign film forming, flexibility etc., and form the ingredient of the protective film of hard after hardening.

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 the polymer that its at least part is crosslinked by crosslinking agent, can also be with It is the polymer not crosslinked.

(weight average molecular weight with energy ray-curable group is 80000~2000000 polymer (a1))

The polymer (a1) for being 80000~2000000 as the weight average molecular weight with energy ray-curable group, can arrange Illustrate as: as have the acrylic polymer (a11) of functional group that can be reacted with group 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 Acrylic resin (a1-1) made of compound (a12) reaction.

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, be also possible 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, it is also possible to block copolymer, polymerize Method can also use well known method.

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- hydroxyl Ethyl ester, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (first Base) (methyl) hydroxyalkyl acrylates such as acrylic acid 3- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl；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 acid 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 with above-mentioned functional group.

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 where being two or more, their combination and ratio can be selected arbitrarily.

As the acrylic monomer for not having 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 Arrcostab ((methyl) stearyl acrylate) etc. constitutes (the first for the chain structure that the carbon atom number of the alkyl of Arrcostab is 1~18 Base) alkyl acrylate etc..

In addition, also it can be mentioned, for example (methyl) acrylic acid methoxies as the acrylic monomer for not having above-mentioned functional group 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, (methyl) with tertiary amino of the non-crosslinked property such as N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester 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 where being two or more, their combination 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 where being two or more, their combination 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 the such range of aforementioned proportion, by above-mentioned third Above-mentioned acrylic resin obtained from olefin(e) acid quasi polymer (a11) and above-mentioned energy ray-curable compound (a12) are copolymerized (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, can also Think it is two or more, in the case where two or more, their combination and ratio can be selected arbitrarily.

In resin layer formation in composition (IV-1), relative to the total content of the ingredient other than solvent, acrylic compounds tree The ratio (that is, content that energy ray-curable protective film forms the acrylic resin (a1-1) with film) of the content of rouge (a1-1) Preferably 1~70 mass %, more preferably 5~60 mass %, particularly preferably 10~50 mass %, such as can be 15~50 Any range in quality %, 25~50 mass % and 35~50 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 where 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 1~3.

As above-mentioned energy ray-curable compound (a12), it can be mentioned, for example: 2- methacryloxyethyl isocyanic acid 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- methacryloxyethyl is 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 where being two or more, their combination and ratio can be selected arbitrarily.

In above-mentioned acrylic resin (a1-1), relative to the above-mentioned official for coming 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 is multifunctional (with 2 in 1 molecule in above-mentioned energy ray-curable compound (a12) A above above-mentioned group) in the case where 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.

In the case that above-mentioned polymer (a1) is the polymer that its at least part is crosslinked by crosslinking agent, on Stating polymer (a1) can be by being not belonging to be illustrated as the monomer for constituting above-mentioned acrylic polymer (a11) Any one of above-mentioned monomer and have the monomer of group reacted with crosslinking agent aggregated and to be reacted with above-mentioned crosslinking agent Compound made of group crosslinking is also possible to from above-mentioned energy ray-curable compound (a12) and above-mentioned functional group Compound made of the group crosslinking of reaction.

Composition (IV-1) and energy ray-curable protective film form above-mentioned polymer (a1) contained by film It is a kind of, or two or more, in the case where being two or more, their combination and ratio can be selected arbitrarily.

(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 comprising 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: have energy It measures the low molecular weight compound of line curative group, the epoxy resin with energy ray-curable group, there is 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., preferably with the acrylic ester compound of (methyl) acryloyl group.

As above-mentioned acrylic ester compound, it can be mentioned, for example: 2- hydroxyl -3- (methyl) acryloxypropyl Acrylate, polyethylene glycol two (methyl) acrylate, propoxylation Ethoxylated bisphenol A bis- (methyl) acrylate, 2,2- Bis- [4- ((methyl) acryloyl-oxy Quito ethyoxyl) phenyl] propane, Ethoxylated bisphenol A bis- (methyl) acrylate, 2,2- are bis- Bis- [4- (2- (methyl) acryloyloxyethoxy) benzene of [4- ((methyl) acryloxy diethoxy) phenyl] propane, 9,9- Base] fluorenes, 2,2- bis- [4- ((methyl) acryloyl-oxy Quito propoxyl group) phenyl] propane, Tricyclodecane Dimethanol two (methyl) propylene Acid esters, 1,10- decanediol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, two (first of 1,9- nonanediol 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 Bis- [4- ((methyl) acryloyloxyethoxy) benzene of (methyl) acrylate, triethylene glycol two (methyl) acrylate, 2,2- Base] propane, neopentyl glycol two (methyl) acrylate, ethoxylated polypropylene glycol two (methyl) acrylate, 2- hydroxyl -1,3- Two (methyl) acryloxy propane etc. difunctionalities (methyl) acrylate；

Modified three (2- (methyl) acryloyl-oxies of three (2- (methyl) acryloyl-oxyethyl) isocyanuric acid esters, 6-caprolactone 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, have energy ray-curable The tree recorded in such as in the 0043rd section of " Japanese Unexamined Patent Publication 2013-194102 bulletin " can be used in the phenolic resin of group Rouge.Such resin also corresponds to the resin for constituting 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.

Composition (IV-1) and energy ray-curable protective film form above compound (a2) contained by film It is a kind of, or two or more, in the case where being two or more, their combination and ratio can be selected arbitrarily.

[polymer (b) without energy ray-curable group]

Composition (IV-1) and energy ray-curable protective film formation use film containing above compound (a2) as above-mentioned In the case where energy ray-curable ingredient (a), preferably also further contain the polymer without energy ray-curable group (b)。

Above-mentioned polymer (b) can be the polymer that its at least part is crosslinked by crosslinking agent, can also be with It is the polymer not crosslinked.

As the polymer (b) for not having energy ray-curable group, it can be mentioned, for example acrylic polymers, 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 Quasi polymer (b-1) ").

Acrylic polymer (b-1) can be homopolymerization that is those of known, such as can be a kind of acrylic monomer Object is also possible to 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 the above-mentioned acrylic monomer for constituting acrylic polymer (b-1), 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 containing substituted-amino etc..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) stearyl acrylate) etc. constitutes (methyl) propylene for the chain structure that the carbon atom number of 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 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 methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) propylene Sour 2- hydroxybutyl, (methyl) acrylic acid 3- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl etc..

As above-mentioned (methyl) acrylate containing substituted-amino, it can be mentioned, for example: (methyl) acrylic acid N- methylamino Ethyl ester etc..

As the above-mentioned non-acrylic monomer for constituting acrylic polymer (b-1), it can be mentioned, for example: ethylene, drop ice The alkene such as piece alkene；Vinyl acetate；Styrene etc..

Above-mentioned the gathering without energy ray-curable group being crosslinked as at least part by crosslinking agent It closes object (b), it can be mentioned, for example: polymer made of the 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 Stating reactive functional groups is preferably the group other than carboxyl.

As the polymer (b) without energy ray-curable group with above-mentioned reactive functional groups, example can be enumerated 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, then uses the monomer with above-mentioned reactive functional groups to enumerate above-mentioned 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 as hydroxyl, except this with Outside, 1 or 2 or more hydrogen atom in the above-mentioned acrylic monomer or non-acrylic monomer by aforementioned list can also be enumerated 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 the such range of aforementioned proportion, the degree of the crosslinking in above-mentioned polymer (b) can reach To preferred range.

From the viewpoint of the film forming of composition (IV-1) becomes be more good, without energy ray-curable group The weight average molecular weight (Mw) of polymer (b) is preferably 10000~2000000, more preferably 100000~1500000.Here, institute It is as mentioned before to state " weight average molecular weight ".

Composition (IV-1) and energy ray-curable protective film, which are formed, does not have energy ray-curable base with contained by film The polymer (b) of group can be only one kind, or and it is two or more, in the case where being two or more, their combination and ratio Rate can be selected arbitrarily.

As composition (IV-1), can enumerate containing any one in above-mentioned polymer (a1) and above compound (a2) The composition of person or both.Also, in the case where composition (IV-1) contains above compound (a2), preferably also further contain There is the polymer (b) without energy ray-curable group, at this point, further preferably further containing above-mentioned (a1).In addition, composition (IV-1) containing above-mentioned polymer (a1) and can also not have energy ray-curable base simultaneously without above compound (a2) The polymer (b) of group.

Composition (IV-1) is containing above-mentioned polymer (a1), above compound (a2) and does not have energy ray-curable group Polymer (b) in the case where, in composition (IV-1), relative to above-mentioned polymer (a1) and do not have energy ray-curable 100 mass parts of total content of the polymer (b) of group, the content of above compound (a2) is preferably 10~400 mass parts, more excellent It is selected as 30~350 mass parts.

In composition (IV-1), above-mentioned energy ray-curable ingredient (a) and gathering without energy ray-curable group Total content of object (b) is closed (that is, energy ray-curable protective film is formed with the above-mentioned energy ray-curable ingredient (a) of film and not Total content of polymer (b) with energy ray-curable group) relative to the ingredient in addition to solvent total content ratio Example is preferably 5~90 mass %, more preferably 10~80 mass %, particularly preferably 20~70 mass %.By making energy line The aforementioned proportion of the content of curability composition is such range, and energy ray-curable protective film forms the energy line curing for using film Property can become be more good.

It, can also be according to purpose and containing selected from heat in composition (IV-1) other than above-mentioned energy ray-curable ingredient One or both of solidity ingredient, packing material, coupling agent, crosslinking agent, Photoepolymerizationinitiater initiater, colorant and universal additive More than.For example, being formed by by using the composition (IV-1) containing above-mentioned energy ray-curable ingredient and thermosetting component The bonding force relative to adherend of energy ray-curable protective film formation film is improved by heating, is consolidated by the energy line The protection film strength that the property changed protective film formation is formed with film also improves.

Cause as the above-mentioned thermosetting component in composition (IV-1), packing material, coupling agent, crosslinking agent, photopolymerization Agent, colorant and universal additive can be enumerated and the thermosetting component in energy line curing resin composition (III-1) respectively (B), packing material (D), coupling agent (E), crosslinking agent (F), Photoepolymerizationinitiater initiater (H), colorant (I) and universal additive (J) It is those of identical.

In composition (IV-1), above-mentioned thermosetting component, packing material, coupling agent, crosslinking agent, Photoepolymerizationinitiater initiater, Toner and universal additive can use individually one kind, can also be used in combination of two or more, be used in combination of two or more In the case where, their combination and ratio can be selected arbitrarily.

Above-mentioned thermosetting component, packing material, coupling agent, crosslinking agent, Photoepolymerizationinitiater initiater in composition (IV-1), The content of toner and universal additive is suitably adjusted according to purpose, is not particularly limited.

For composition (IV-1), from its operability aspect can be improved by dilution, preferably further contain There is solvent.

As the solvent contained by composition (IV-1), it can be cited for example that with protective film formation with composition (III-1) In the identical solvent of solvent.

Solvent contained by composition (IV-1) can be only one kind, or two or more.

< < energy ray-curable protective film forms the manufacturing method > > for using composition

Composition (IV-1) Isoenergetical line curability protective film formation composition can by will be used to constitute its it is each at Distribution is closed and is obtained.

For the method that each ingredient mixes is not particularly limited when cooperation, from rotate stirrer or agitating paddle etc. 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 manufacturing method of ◇ support chip, protective film form the manufacturing method for using composite sheet

Above-mentioned support chip and protective film formation composite sheet can in the way of the positional relationship of corresponding above layers according to It is secondary to be laminated to manufacture.The forming method of each layer is as previously described.

For example, in the case where adhesive phase is laminated on substrate, above-mentioned bonding is applied on substrate when manufacturing support chip Agent composition simultaneously makes it dry as needed.

On the other hand, such as when manufacturing protective film formation composite sheet, adhesive phase on base material is being laminated In the case that upper further stacking protective film is formed with film, thermosetting protective film can be applied over the binder layer and is formed with combination Object or energy ray-curable protective film formation directly form protective film formation film with composition.So, use is any It, can be further on the layer formed by above-mentioned composition in the case that kind composition forms continuous 2 layers of stepped construction Coating composition and new forming layer.Wherein, it is preferable to use above-mentioned composition is pre-formed in above-mentioned 2 layers on other stripping film The layer being laminated afterwards, then the layer that keeps the formation good the side opposite side being in contact with above-mentioned stripping film exposed surface with formed Thus the exposed surface fitting of good remaining layer forms continuous 2 layers of stepped construction.At this point, above-mentioned composition preferably applies It applies on the lift-off processing face of stripping film.Stripping film is forming the thick removal as needed of stepped construction.

That is, applying adhesive composition on substrate, as needed in the case where manufacturing protective film formation composite sheet It makes it dry, adhesive phase has thus been laminated on substrate, formed in addition, applying thermosetting protective film on stripping film with combination Object or energy ray-curable protective film, which are formed, uses composition, makes it dry as needed, protective film shape is formd on stripping film At with film, then it is bonded the exposed surface of the protective film formation film and the exposed surface for the adhesive phase folded on substrate upper layer, Protective film formation film is laminated on adhesive phase, to obtain protective film formation composite sheet.

On the other hand, it in the case where adhesive phase is laminated on substrate, can be replaced using following methods above-mentioned such On substrate apply adhesive composition method, the method are as follows: adhesive composition is applied on stripping film, according to need It makes it dry, thus forms adhesive phase on stripping film, then by a surface of the exposed surface of the adhesive phase and substrate Fitting, so that adhesive phase be laminated on substrate.

In any one method, stripping film can be in any time removal after the stepped construction for forming target.

In this way, the layer (adhesive phase, protective film, which are formed, uses film) that composition protective film is formed other than the substrate with composite sheet is equal It is previously formed on stripping film, and can be laminated by the method for fitting in the surface of destination layer, it therefore, can basis It needs to be suitable for selecting to manufacture protective film formation composite sheet using the layer of such process.

But in the present invention, the lamination surface of the adhesive phase in substrate, i.e. the surface roughness in the 1st face be 0.1~ 0.4 μm or the value near it, in the case where being the value of the degree of camber that can not ignore the face, preferably by being applied on substrate The method of adhesive composition is applied to form adhesive phase (forming support chip).This is because, making the adhesive being pre-formed In the case that layer fits in such male and fomale(M&F), produced for example, adhesive phase is not filled near the foundation of the protrusion in the face Raw space part, becomes inadequate the embedment in the face (the 1st face) so as to cause adhesive phase.So, the embedment in the 1st face becomes It is insufficient when, then produce it is explained above as unfavorable condition.

In contrast, in the case where forming adhesive phase to the 1st face of substrate coating adhesive composition, there is flowing The adhesive composition of property is fully filled the position near the foundation of the protrusion in the 1st face, as a result, these positions are bonded Oxidant layer is fully embedded to, and therefore, can highly inhibit the generation of above-mentioned such unfavorable condition.But such as to substrate When 1st face paste closes adhesive phase, its softening can also be made to inhibit above-mentioned space part and heating to adhesive phase It generates.Therefore, the method for also thering is the 1st face paste for being able to use the adhesive phase and substrate that will be pre-formed to close.

It should be noted that protective film formation is usually fitted in its support chip opposite side most with stripping film with composite sheet The state on the surface on surface layer (such as protective film forms and uses film) is taken care of.And hence it is also possible to be protected in the following manner Film, which is formed, uses composite sheet, that is, applies thermosetting protective film on the stripping film (preferably its lift-off processing face) and is formed with combination Object or energy ray-curable protective film formation composition etc. are used to form the composition for constituting the layer on most surface layer, make as needed It is dried, and the layer for constituting most surface layer is formd on stripping film, then utilizes above-mentioned arbitrary method by remaining each layer stackup In in the exposed surface of the side opposite side being in contact with stripping film of this layer, do not remove stripping film and keep fitting state and obtain To protective film formation composite sheet.

Embodiment

Hereinafter, being illustrated in more details by specific embodiment to the present invention, but the present invention is not by as shown below Embodiment any restriction.

It should be noted that for example following institute of the composition of each layer of the protective film formation composite sheet in following embodiments etc. Show.

< substrate >

The substrate described below for constituting support chip.

Substrate Bm1: with polypropylene be main constituent material and with a thickness of 80 μm, it is tensile modulus of elasticity 360MPa, smooth The substrate that the surface roughness (Ra) in face is 0.05 μm, the surface roughness (Ra) of male and fomale(M&F) is 0.1 μm.

Substrate Bm2: with polypropylene be main constituent material and with a thickness of 80 μm, it is tensile modulus of elasticity 360MPa, smooth The substrate that the surface roughness (Ra) in face is 0.05 μm, the surface roughness (Ra) of male and fomale(M&F) is 0.2 μm.

Substrate Bm3: with polypropylene be main constituent material and with a thickness of 80 μm, it is tensile modulus of elasticity 360MPa, smooth The substrate that the surface roughness (Ra) in face is 0.05 μm, the surface roughness (Ra) of male and fomale(M&F) is 0.3 μm.

Substrate Bm4: with polybutylene terephthalate (PBT) for main constituent material and with a thickness of 80 μm, tensile elasticity mould Amount be 500MPa, the base that the surface roughness (Ra) of even surface is 0.05 μm, the surface roughness (Ra) of male and fomale(M&F) is 0.3 μm Material.

Substrate Bm5: being main constituent material and with a thickness of 80 μm, tensile modulus of elasticity 360MPa, two sides with polypropylene It is the substrate for the even surface that surface roughness (Ra) is 0.05 μm.

Substrate Bm6: with polypropylene be main constituent material and with a thickness of 80 μm, it is tensile modulus of elasticity 360MPa, smooth The substrate that the surface roughness (Ra) in face is 0.05 μm, the surface roughness (Ra) of male and fomale(M&F) is 0.5 μm.

Substrate Bm7: with polypropylene be main constituent material and with a thickness of 80 μm, it is tensile modulus of elasticity 360MPa, smooth The substrate that the surface roughness (Ra) in face is 0.05 μm, the surface roughness (Ra) of male and fomale(M&F) is 0.055 μm.

Substrate Bm8: with polypropylene be main constituent material and with a thickness of 80 μm, it is tensile modulus of elasticity 360MPa, smooth The substrate that the surface roughness (Ra) in face is 0.03 μm, the surface roughness (Ra) of male and fomale(M&F) is 0.4 μm.

Substrate Bm9: with polypropylene be main constituent material and with a thickness of 80 μm, it is tensile modulus of elasticity 360MPa, smooth The substrate that the surface roughness (Ra) in face is 0.03 μm, the surface roughness (Ra) of male and fomale(M&F) is 0.47 μm.

Substrate Bm10: with polypropylene be main constituent material and with a thickness of 80 μm, it is tensile modulus of elasticity 360MPa, flat The substrate that the surface roughness (Ra) of sliding surface is 0.35 μm, the surface roughness (Ra) of male and fomale(M&F) is 0.4 μm.

Substrate Bm11: with polypropylene be main constituent material and with a thickness of 80 μm, it is tensile modulus of elasticity 360MPa, flat The substrate that the surface roughness (Ra) of sliding surface is 0.37 μm, the surface roughness (Ra) of male and fomale(M&F) is 0.47 μm.

Substrate Bm12: with polypropylene be main constituent material and with a thickness of 80 μm, it is tensile modulus of elasticity 360MPa, flat The substrate that the surface roughness (Ra) of sliding surface is 0.43 μm, the surface roughness (Ra) of male and fomale(M&F) is 0.47 μm.

It should be noted that the tensile modulus of elasticity and surface roughness of above-mentioned substrate are surveyed according to method as shown below The value obtained.

(measurement of the tensile modulus of elasticity of substrate)

Substrate cutting is made into test film, based on the above-mentioned test film of JIS K 7161:1994 standard test at 23 DEG C Under tensile modulus of elasticity (Young's modulus).At this point, width when above-mentioned test film is measured is set as 15mm, by distance between fixture It is set as 100mm.

(measurement of the surface roughness of substrate)

Based on JIS B0601:2001 standard, contact surface-profile measuring instrument (Mitsutoyo corporation is used " SURFTEST SV-3000 "), cutoff value λ c is set as 0.8mm, evaluation length Ln is set as 10mm, determine the table of substrate surface Surface roughness (Ra).

< resin of binding property >

The resin of binding property for being used to form adhesive phase is as shown below.

Resin of binding property (i) -1: n-butyl acrylate (hreinafter referred to as " BA ") (85 mass parts) and acrylic acid 2- hydroxyl The acrylic polymer of weight average molecular weight 600000 made of ethyl ester (hreinafter referred to as " HEA ") (15 mass parts) copolymerization.

Resin of binding property (i) -2: 2-EHA (hreinafter referred to as " 2EHA ") (30 mass parts), acrylic acid Weight average molecular weight 800000 made of isobornyl thiocyanoacetate (hreinafter referred to as " iBA ") (50 mass parts) and HEA (20 mass parts) copolymerization Acrylic polymer.

< protective film forms the manufacture raw material > for using composition

Raw material for manufacturing protective film formation composition is as shown below.

[component of polymer (A)]

(A) -1:BA (10 mass parts), methyl acrylate (70 mass parts), glycidyl methacrylate (5 mass parts) And acrylic resin (- 1 DEG C of weight average molecular weight 800000, glass transition temperature) made of HEA (15 mass parts) copolymerization

[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, number-average molecular weight 370)

(B1) -2: bisphenol A type epoxy resin (Mitsubishi chemical Co., Ltd's system " JER1055 ", 800~900g/ of epoxide equivalent Eq, number-average molecular weight 1600)

(B1) -3: dicyclopentadiene-type epoxy resin (DIC corporation " EPICLON HP-7200HH ", epoxide equivalent 255 ~260g/eq)

Thermal curing agents (B2)

(B2) -1: dicyandiamide (thermal activities latent epoxy resin curing agent, ADEKA corporation " AdekaHardener EH-3636AS ", active hydrogen amount 21g/eq)

[curing accelerator (C)]

(C) -1:2- phenyl -4,5- bishydroxymethyl imidazoles (Shikoku Chem's system " CUREZOL2PHZ ")

[packing material (D)]

(D) -1: (Admatechs company " SC2050MA " has carried out surface with epoxy compounds and has changed silica filler The silica filler of property, 0.5 μm of average grain diameter)

[coupling agent (E)]

(E) -1:3- glycidoxy-propyltrimethoxy silane (3- glycidyloxypropyl trimethoxy silane) (silicon Alkane coupling agent, Shin-Etsu Chemial Co., Ltd's system " KBM403 ", methoxyl group equivalent 12.7mmol/g, molecular weight 236.3)

[crosslinking agent (F)]

(F) -1: toluene di-isocyanate(TDI) class crosslinking agent (TOYOCHEM corporation " BHS8515 ")

[Photoepolymerizationinitiater initiater (H)]

Photoepolymerizationinitiater initiater (H) -1:1- hydroxycyclohexylphenylketone (BASF AG's system " Irgacure (registered trademark) 184”)

[colorant (I)]

(I) -1: carbon black (Mitsubishi chemical Co., Ltd's system " MA600B ", average grain diameter 28nm)

[energy ray-curable ingredient (a)]

Energy ray-curable ingredient (a) -1: make 2- methacryloxyethyl isocyanates (hreinafter referred to as " MOI ") (make the total mole number of the isocyanate group in 2- methacryloxyethyl isocyanates relative to above-mentioned acrylic acid The total mole number of the hydroxyl from HEA in quasi polymer reaches 0.8 times of amount) and 2EHA (80 mass parts) and HEA (20 matter Measure part) copolymerization made of acrylic polymer reaction and obtain, side chain have methacryloxy weight average molecular weight 800000, -10 DEG C of glass transition temperature of ultraviolet hardening acrylic copolymers.

< protective film forms the manufacture > for using composite sheet

[embodiment 1]

(thermosetting protective film forms the manufacture for using composition (III-1))

By component of polymer (A) -1 (40 mass parts), epoxy resin (B1) -1 (5 mass parts), epoxy resin (B1) -2 (4 Mass parts), epoxy resin (B1) -3 (10 mass parts), thermal curing agents (B2) -1 (1 mass parts), -1 (1 matter of curing accelerator (C) Measure part), packing material (D) -1 (36 mass parts), coupling agent (E) -1 (1 mass parts) and colorant (I) -1 (2 mass parts) carry out Mixing, then reach 45 mass % with the concentration that methyl ethyl ketone is diluted to solid component, it has obtained thermosetting protective film and has been formed with combination Object (III-1).It should be noted that the use level of the ingredient other than methyl ethyl ketone depicted herein is solid content.

(protective film forms the formation for using film)

Shell made of lift-off processing handling the single side for being film-made polyethylene terephthalate by organosilicon It is applied on above-mentioned lift-off processing face from film (38 μm of Lindeke Co., Ltd's system " SP-PET381031 ", thickness) obtained above Composition (III-1), it is 3 minutes dry at 100 DEG C, thus form the protective film formation film Pf1 with a thickness of 25 μm.

(manufacture of adhesive composition)

By resin of binding property (i) -1 (100 mass parts) and toluene di-isocyanate(TDI) class crosslinking agent (TOYOCHEM corporation " BHS8515 ") (1 mass parts) are mixed, then reach 35 mass % with the concentration that methyl ethyl ketone is diluted to solid component, it obtains The adhesive composition (I-4) -1 of non-energy line curability.It should be noted that ingredient other than methyl ethyl ketone depicted herein Use level is solid content.

(formation of adhesive phase, the manufacture of support chip)

Adhesive composition obtained above is applied on the even surface that the surface roughness of above-mentioned substrate Bm1 is 0.05 μm (I-4) -1,1 minute dry at 100 DEG C, it is consequently formed with a thickness of the adhesive phase Ad1 of 5 μm, non-energy line curability, obtains Support chip Ss1.

(protective film forms the manufacture for using composite sheet)

By the exposed surface of the side for not having stripping film of protective film formation film Pf1 obtained above and support chip Ss1 The exposed surface of adhesive phase Ad1 be laminated, result in the protective film formation composite sheet of structure shown in Fig. 2.

The protective film formation is according to substrate Bm1, adhesive phase Ad1, protective film formation film Pf1 and removing with composite sheet Made of the sequence of film is laminated on their thickness direction, the face of the side for having adhesive phase Ad1 of substrate Bm1 is smooth Face, substrate Bm1 with the face (exposed surface) of the side opposite side for having adhesive phase Ad1 become male and fomale(M&F).By the protective film It is formed shown in table 1 with the composition of composite sheet.

[embodiment 2]

In the formation of adhesive phase, change adhesive composition (I-4) -1 coating amount, formed with a thickness of 20 μm without It is the adhesive phase Ad2 of 5 μm of non-energy line curability, has obtained support chip Ss2, and the support chip Ss2 obtained using this, removed Other than this, in the same manner as shown in Example 1, protective film formation composite sheet has been manufactured.

That is, the protective film formation with composite sheet be according to substrate Bm1, adhesive phase Ad2, protective film formation film Pf1 and Made of the sequence of stripping film is laminated on their thickness direction, the face of the side for having adhesive phase Ad2 of substrate Bm1 is Even surface, substrate Bm1's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad2.By the guarantor Cuticula forms shown in table 1 with the composition of composite sheet.

[embodiment 3]

(manufacture of adhesive composition)

By resin of binding property (i) -2 (100 mass parts) and toluene di-isocyanate(TDI) system crosslinking agent (TOYOCHEM corporation " BHS8515 ") (10 mass parts) are mixed, then reach 35 mass % と with the concentration that methyl ethyl ketone is diluted to solid component, it obtains The adhesive composition (I-4) -2 of non-energy line curability is arrived.It should be noted that other than methyl ethyl ketone depicted herein at The use level divided is solid content.

(formation of adhesive phase, the manufacture of support chip)

Adhesive composition obtained above is applied on the even surface that the surface roughness of above-mentioned substrate Bm1 is 0.05 μm (I-4) -2, the dry drying in 1 minute at 100 DEG C, forms the adhesive phase Ad3 of the non-energy line curability with a thickness of 5 μm, obtains Support chip Ss3 is arrived.

(protective film forms the manufacture for using composite sheet)

In addition to use support chip Ss3 obtained above replace support chip Ss1 this point other than, according to same as Example 1 Method manufactured protective film formation composite sheet.

That is, the protective film formation with composite sheet be according to substrate Bm1, adhesive phase Ad3, protective film formation film Pf1 and Made of the sequence of stripping film is laminated on their thickness direction, the face of the side for having adhesive phase Ad3 of substrate Bm1 is Even surface, substrate Bm1's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad3.By the guarantor Cuticula forms shown in table 1 with the composition of composite sheet.

[embodiment 4]

(manufacture of adhesive composition)

Adhesive composition (I-4) -2 has been obtained according to method same as Example 3.

(formation of adhesive phase, the manufacture of support chip)

Adhesive composition obtained above is applied on the even surface that the surface roughness of above-mentioned substrate Bm2 is 0.05 μm (I-4) -2,1 minute dry at 100 DEG C, the adhesive phase Ad3 of the non-energy line curability with a thickness of 5 μm is formed, is obtained Support chip Ss4.

(protective film forms the manufacture for using composite sheet)

In addition to use support chip Ss4 obtained above replace support chip Ss1 this point other than, according to same as Example 1 Method manufactured protective film formation composite sheet.

That is, the protective film formation with composite sheet be according to substrate Bm2, adhesive phase Ad3, protective film formation film Pf1 and Made of the sequence of stripping film is laminated on their thickness direction, the face of the side for having adhesive phase Ad3 of substrate Bm2 is Even surface, substrate Bm2's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad3.By the guarantor Cuticula forms shown in table 1 with the composition of composite sheet.

[embodiment 5]

(manufacture of adhesive composition)

(formation of adhesive phase, the manufacture of support chip)

Adhesive composition obtained above is applied on the even surface that the surface roughness of above-mentioned substrate Bm3 is 0.05 μm (I-4) -2,1 minute dry at 100 DEG C, the adhesive phase Ad3 of the non-energy line curability with a thickness of 5 μm is formed, is obtained Support chip Ss5.

(protective film forms the manufacture for using composite sheet)

In addition to use support chip Ss5 obtained above replace support chip Ss1 this point other than, according to same as Example 1 Method manufactured protective film formation composite sheet.

That is, the protective film formation with composite sheet be according to substrate Bm3, adhesive phase Ad3, protective film formation film Pf1 and Made of the sequence of stripping film is laminated on their thickness direction, the face of the side for having adhesive phase Ad3 of substrate Bm3 is Even surface, substrate Bm3's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad3.By the guarantor Cuticula forms shown in table 1 with the composition of composite sheet.

[embodiment 6]

(manufacture of adhesive composition)

(formation of adhesive phase, the manufacture of support chip)

Adhesive composition obtained above is applied on the even surface that the surface roughness of above-mentioned substrate Bm4 is 0.05 μm (I-4) -2,1 minute dry at 100 DEG C, the adhesive phase Ad3 of the non-energy line curability with a thickness of 5 μm is formed, is obtained Support chip Ss6.

(protective film forms the manufacture for using composite sheet)

In addition to use support chip Ss6 obtained above replace support chip Ss1 this point other than, according to same as Example 1 Method manufactured protective film formation composite sheet.

That is, the protective film formation with composite sheet be according to substrate Bm4, adhesive phase Ad3, protective film formation film Pf1 and Made of the sequence of stripping film is laminated on their thickness direction, the face of the side for having adhesive phase Ad3 of substrate Bm4 is Even surface, substrate Bm4's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad3.By the guarantor Cuticula forms shown in table 1 with the composition of composite sheet.

[embodiment 7]

(energy ray-curable protective film forms the manufacture for using composition (IV-1))

By energy line curability composition (a) -1 (42 mass parts), packing material (D) -1 (55 mass parts), coupling agent (E) -1 (0.3 mass parts), crosslinking agent (F) -1 (1 mass parts), Photoepolymerizationinitiater initiater (H) -1 (0.3 mass parts) and colorant (I) -1 (1 Mass parts) it is mixed, then reach 45 mass % with the concentration that methyl ethyl ketone is diluted to solid component, obtain energy ray-curable Protective film, which is formed, uses composition (IV-1).It should be noted that the use level of the ingredient other than methyl ethyl ketone depicted herein is Solid content.

(protective film forms the formation for using film)

Shell made of lift-off processing handling the single side for being film-made polyethylene terephthalate by organosilicon It is applied on above-mentioned lift-off processing face from film (38 μm of Lindeke Co., Ltd's system " SP-PET381031 ", thickness) obtained above Composition (IV-1), it is 3 minutes dry at 100 DEG C, thus form the protective film formation film Pf2 with a thickness of 25 μm.

(manufacture of adhesive composition)

(formation of adhesive phase, the manufacture of support chip)

Adhesive phase Ad3 is formed according to method same as Example 5, has obtained support chip Ss5.

(protective film forms the manufacture for using composite sheet)

By the viscous of the exposed surface of the side for not having stripping film of protective film formation film obtained above and support chip Ss5 The exposed surface of mixture layer Ad3 is laminated, and the protective film formation composite sheet of structure shown in Fig. 2 has been obtained.

The protective film formation is according to substrate Bm3, adhesive phase Ad3, protective film formation film Pf2 and removing with composite sheet Made of the sequence of film is laminated on their thickness direction, the face of the side for having adhesive phase Ad3 of substrate Bm3 is smooth Face, substrate Bm3's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad3.By the protective film It is formed shown in table 1 with the composition of composite sheet.

[embodiment 8]

(protective film forms the formation for using film)

Protective film formation film Pf1 is formd in the same manner as shown in Example 1.

(formation of adhesive phase, the manufacture of support chip)

Substrate Bm1 is replaced using above-mentioned substrate Bm7, and makes the even surface of 0.05 μm of its surface roughness as bonding The forming face of oxidant layer Ad1 has obtained support chip Ss11 in addition to this in the same manner as shown in Example 1.

(protective film forms the manufacture for using composite sheet)

By the exposed surface of the side for not having stripping film of protective film formation film Pf1 obtained above and support chip Ss11 The exposed surface of adhesive phase Ad1 be laminated, obtained the protective film formation composite sheet of structure shown in Fig. 2.

The protective film formation is according to substrate Bm7, adhesive phase Ad1, protective film formation film Pf1 and removing with composite sheet Made of the sequence of film is laminated on their thickness direction, the face of the side for having adhesive phase Ad1 of substrate Bm7 is smooth Face, substrate Bm7's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad1.By the protective film The composition of formation composite sheet is shown in table 2.

[embodiment 9]

(protective film forms the formation for using film)

(formation of adhesive phase, the manufacture of support chip)

Substrate Bm1 is replaced using above-mentioned substrate Bm8, and makes the even surface of 0.03 μm of its surface roughness as bonding The forming face of oxidant layer Ad1 has obtained support chip Ss12 in addition to this in the same manner as shown in Example 1.

(protective film forms the manufacture for using composite sheet)

By the exposed surface of the side for not having stripping film of protective film formation film Pf1 obtained above and support chip Ss12 The exposed surface of adhesive phase Ad1 be laminated, obtained the protective film formation composite sheet of structure shown in Fig. 2.

The protective film formation is according to substrate Bm8, adhesive phase Ad1, protective film formation film Pf1 and removing with composite sheet Made of the sequence of film is laminated on their thickness direction, the face of the side for having adhesive phase Ad1 of substrate Bm8 is smooth Face, substrate Bm8's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad1.By the protective film The composition of formation composite sheet is shown in table 2.

[embodiment 10]

(protective film forms the formation for using film)

(formation of adhesive phase, the manufacture of support chip)

Substrate Bm1 is replaced using above-mentioned substrate Bm9, and makes the even surface of 0.03 μm of its surface roughness as bonding The forming face of oxidant layer Ad1 has obtained support chip Ss13 in addition to this in the same manner as shown in Example 1.

(protective film forms the manufacture for using composite sheet)

By the exposed surface of the side for not having stripping film of protective film formation film Pf1 obtained above and support chip Ss13 The exposed surface of adhesive phase Ad1 be laminated, obtained the protective film formation composite sheet of structure shown in Fig. 2.

The protective film formation is according to substrate Bm9, adhesive phase Ad1, protective film formation film Pf1 and removing with composite sheet Made of the sequence of film is laminated on their thickness direction, the face of the side for having adhesive phase Ad1 of substrate Bm9 is smooth Face, substrate Bm9's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad1.By the protective film The composition of formation composite sheet is shown in table 2.

[embodiment 11]

(protective film forms the formation for using film)

(formation of adhesive phase, the manufacture of support chip)

Substrate Bm1 is replaced using above-mentioned substrate Bm10, and makes the even surface of 0.35 μm of its surface roughness as viscous The forming face of mixture layer Ad1 has obtained support chip Ss14 in addition to this in the same manner as shown in Example 1.

(protective film forms the manufacture for using composite sheet)

By the exposed surface of the side for not having stripping film of protective film formation film Pf1 obtained above and support chip Ss14 The exposed surface of adhesive phase Ad1 be laminated, obtained the protective film formation composite sheet of structure shown in Fig. 2.

The protective film formation is according to substrate Bm10, adhesive phase Ad1, protective film formation film Pf1 and stripping with composite sheet Made of sequence from film is laminated on their thickness direction, the face of the side for having adhesive phase Ad1 of substrate Bm10 is Even surface, substrate Bm10's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad1.By the guarantor The composition of cuticula formation composite sheet is shown in table 2.

[embodiment 12]

(protective film forms the formation for using film)

(formation of adhesive phase, the manufacture of support chip)

Substrate Bm1 is replaced using above-mentioned substrate Bm11, and makes the even surface of 0.37 μm of its surface roughness as viscous The forming face of mixture layer Ad1 has obtained support chip Ss15 in addition to this in the same manner as shown in Example 1.

(protective film forms the manufacture for using composite sheet)

By the exposed surface of the side for not having stripping film of protective film formation film Pf1 obtained above and support chip Ss15 The exposed surface of adhesive phase Ad1 be laminated, obtained the protective film formation composite sheet of structure shown in Fig. 2.

The protective film formation is according to substrate Bm11, adhesive phase Ad1, protective film formation film Pf1 and stripping with composite sheet Made of sequence from film is laminated on their thickness direction, the face of the side for having adhesive phase Ad1 of substrate Bm11 is Even surface, substrate Bm11's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad1.By the guarantor The composition of cuticula formation composite sheet is shown in table 2.

[reference example 1]

(protective film forms the formation for using film)

(formation of adhesive phase, the manufacture of support chip)

In the formation of adhesive phase, change the coating amount of adhesive composition (I-4) -2, form with a thickness of 20 μm and It is not 5 μm of adhesive phase Ad4, in addition to this, has obtained support chip Ss7 according to method same as Example 4.

(protective film forms the manufacture for using composite sheet)

By the exposed surface of the side for not having stripping film of protective film formation film Pf1 obtained above and support chip Ss7 The exposed surface of adhesive phase Ad4 be laminated, obtained the protective film formation composite sheet of structure shown in Fig. 2.

The protective film formation is according to substrate Bm2, adhesive phase Ad4, protective film formation film Pf1 and removing with composite sheet Made of the sequence of film is laminated on their thickness direction, the face of the side for having adhesive phase Ad4 of substrate Bm2 is smooth Face, substrate Bm2's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad4.By the protective film The composition of formation composite sheet is shown in table 3.

[comparative example 1]

(protective film forms the formation for using film)

(formation of adhesive phase, the manufacture of support chip)

Substrate Bm1 is replaced using above-mentioned substrate Bm5, and is formd on one face (even surface) with a thickness of 5 μm Adhesive phase Ad1 has obtained support chip Ss8 in addition to this in the same manner as shown in Example 1.

(protective film forms the manufacture for using composite sheet)

By the exposed surface of the side for not having stripping film of protective film formation film Pf1 obtained above and support chip Ss8 The exposed surface of adhesive phase Ad1 be laminated, obtained the protective film formation composite sheet of structure shown in Fig. 2.

The protective film formation is according to substrate Bm5, adhesive phase Ad1, protective film formation film Pf1 and removing with composite sheet Made of the sequence of film is laminated on their thickness direction, the face of the side for having adhesive phase Ad1 of substrate Bm5 and substrate Bm5's becomes even surface with the face (exposed surface) of the side opposite side for having adhesive phase Ad1.The protective film is formed and is used The composition of composite sheet is shown in table 3.

[comparative example 2]

(protective film forms the formation for using film)

(formation of adhesive phase, the manufacture of support chip)

Substrate Bm1 is replaced using above-mentioned substrate Bm6, and above-mentioned in the male and fomale(M&F) coating that its surface roughness is 0.5 μm Obtained adhesive composition (I-4) -1, forms adhesive phase Ad2, in addition to this, according to method same as Example 2 Support chip Ss9 is obtained.

(protective film forms the manufacture for using composite sheet)

By the exposed surface of the side for not having stripping film of protective film formation film Pf1 obtained above and support chip Ss9 The exposed surface of adhesive phase Ad2 be laminated, obtained the protective film formation composite sheet of structure shown in Fig. 2.

The protective film formation is according to substrate Bm6, adhesive phase Ad2, protective film formation film Pf1 and removing with composite sheet Made of the sequence of film is laminated on their thickness direction, the face of the side for having adhesive phase Ad2 of substrate Bm6 is bumps Face, substrate Bm6's becomes even surface with the face (exposed surface) of the side opposite side for having adhesive phase Ad2.By the protective film The composition of formation composite sheet is shown in table 3.

[comparative example 3]

(protective film forms the formation for using film)

(formation of adhesive phase, the manufacture of support chip)

Substrate Bm1 is replaced using above-mentioned substrate Bm6, and is applied and applied on the even surface that its surface roughness is 0.05 μm The adhesive composition (I-4) -1 stated, forms adhesive phase Ad1, in addition to this, according to side same as Example 1 Method has obtained support chip Ss10.

(protective film forms the manufacture for using composite sheet)

By the exposed surface of the side for not having stripping film of protective film formation film Pf1 obtained above and support chip Ss10 The exposed surface of adhesive phase Ad1 be laminated, obtained the protective film formation composite sheet of structure shown in Fig. 2.

The protective film formation is according to substrate Bm6, adhesive phase Ad1, protective film formation film Pf1 and removing with composite sheet Made of the sequence of film is laminated on their thickness direction, the face of the side for having adhesive phase Ad1 of substrate Bm6 is smooth Face, substrate Bm6's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad1.By the protective film The composition of formation composite sheet is shown in table 3.

[comparative example 4]

(protective film forms the formation for using film)

(formation of adhesive phase, the manufacture of support chip)

Substrate Bm1 is replaced using above-mentioned substrate Bm12, and the even surface for being 0.43 μm using its surface roughness is as viscous The forming face of mixture layer Ad1 has obtained support chip Ss16 in addition to this in the same manner as shown in Example 1.

(protective film forms the manufacture for using composite sheet)

By the exposed surface of the side for not having stripping film of protective film formation film Pf1 obtained above and support chip Ss16 The exposed surface of adhesive phase Ad1 be laminated, obtained the protective film formation composite sheet of structure shown in Fig. 2.

The protective film formation is according to substrate Bm12, adhesive phase Ad1, protective film formation film Pf1 and stripping with composite sheet Made of sequence from film is laminated on their thickness direction, the face of the side for having adhesive phase Ad1 of substrate Bm12 is Even surface, substrate Bm11's becomes male and fomale(M&F) with the face (exposed surface) of the side opposite side for having adhesive phase Ad1.By the guarantor The composition of cuticula formation composite sheet is shown in table 3.

< protective film forms the evaluation > for using composite sheet

For protective film formation composite sheet obtained above, by the following method to laser lettering, infrared inspection Property, resistance to blocking, adhesive phase evaluate the imbedibility of substrate surface and resistance to clasticity, the results are shown in table 1~ Table 3 (is shown in table with " imbedibility ").

[laser lettering]

From protective film formation with stripping film is removed in composite sheet, sticker (Lindeke Co., Ltd system " RAD- is used 2700F/12 ") protective film formation is pasted on stainless steel ring frame with composite sheet, while will be in protective film formation composite sheet Protective film formation be pasted on film be heated to 70 DEG C silicon wafer (8 inches of outer diameter, 100 μm of thickness) the back side.

Next, above-mentioned film is carried out to add within 2 hours at 130 DEG C in the case where protective film formation film is heat cured situation It is heat-treated and makes its solidification, in the case where protective film formation is energy ray-curable with film, with illumination 145mW/cm², light quantity 230mJ/cm²Condition to above-mentioned film irradiate 2 ultraviolet lights and make its solidification, form protective film.

Then, using printing device (KEYENCE corporation " MD-S9910A "), output power 4.8W, frequency 80kHz, From substrate side to the laser of protective film illumination wavelength 532nm under conditions of scanning speed 500mm/ seconds, with 2 following patterns (pattern 1, pattern 2) has carried out laser lettering to protective film.

(pattern)

Pattern 1: text size 0.30mm × 0.5mm, text interval 0.05mm, text number 20

Pattern 2: text size 0.15mm × 0.3mm, text interval 0.05mm, text number 20

Then, it for the text formed on protective film with above-mentioned laser lettering, is observed across support chip, according to Following benchmark evaluate laser lettering.It should be noted that if the gas generated due to laser lettering by protective film The reason of volume is stored between adhesive phase and protective film, then generates clast when can become cutting, therefore, by non-trapped gas Sample is as evaluation object.

(evaluation criteria)

A: all texts of pattern 1 and 2 can clearly carry out lettering.

B: although a part of text in pattern 2 has carried out lettering, all texts in pattern 1 fuzzy, unintelligiblely It can clearly carry out lettering.

C: pattern 1 and 2 some equal text have carried out lettering unintelligiblely.

[infrared inspection]

From protective film formation with stripping film is removed in composite sheet, sticker (Lindeke Co., Ltd system " RAD- is used 2700F/12 ") protective film formation is pasted on stainless steel ring frame with composite sheet, while will be in protective film formation composite sheet Protective film formation be pasted on film be heated to 70 DEG C silicon wafer (8 inches of diameter, 100 μm of thickness) the back side, i.e. #2000 mill On bevel.

Then, using cutter device (DISCO corporation " DFD6361 "), in feed 30mm/ seconds, revolving speed 30000rpm Under the conditions of carry out cutter cutting, thus silicon wafer is split, has obtained the silicon chip of 2mm × 2mm size.

For obtained silicon chip, using infraed microscope (Olympus Co., Ltd's system " BX-IR ") across support Piece observes grinding surface (back side of silicon chip) and divisional plane (side of silicon chip), examines according to following benchmark to infrared ray The property looked into is evaluated.

(evaluation criteria)

A: the grinding trace of grinding surface can be clearly confirmed, also, can also clearly be confirmed from silicon chip Divide the clast for 2 μm of sizes more than and less than 5 μm that the inside towards silicon chip is formed.

B: can clearly confirm the grinding trace of grinding surface, but fail clearly to confirm the divisional plane from silicon chip The clast of the 2 μm of sizes more than and less than 5 μm formed to the inside of silicon chip.

C: the grinding trace of grinding surface can not be confirmed or can not clearly confirmed completely, and can not be confirmed completely Or it can not clearly confirm the clast of any size.

[resistance to blocking]

The protective film formation of length 10m composite sheet is rolled up on 3 inches of diameter of ABS resin coremaking material, with the state 3 days have been stood at room temperature.

Then, the protective film formation of the web-like after keeping is extracted out with composite sheet, removes stripping film, uses sticker The protective film formation of extraction is pasted on stainless steel annular with composite sheet by (Lindeke Co., Ltd's system " RAD-2700F/12 ") Frame, while protective film formation being pasted on the protective film formation in composite sheet with film and is heated to 70 DEG C of silicon wafer (8 English of diameter Very little, 100 μm of thickness) the back side, attempted continuously carry out 10 silicon wafers.Based at this time operability, according to following benchmark Resistance to blocking is evaluated.

(evaluation criteria)

A: not sticking together completely, can with there is no problem carry out aforesaid operations.

B: although protective film formation film can be pasted on silicon wafer, protective film formation is batched with composite sheet Volume in, bonding partially has occurred in substrate and the mutual contact surface of stripping film, when protective film formation is extracted out with composite sheet, Between substrate and adhesive phase or between adhesive phase and protective film formation film, it was found that be partially stripped.

C: in volume made of protective film formation is batched with composite sheet, substrate and the mutual contact surface of stripping film are partly It pastes, it will be apparent that stick together, when protective film formation is extracted out with composite sheet, between adhesive phase and protective film formation film Generation is partially stripped, and support chip (laminates of substrate and adhesive phase) is transferred on stripping film or can not be protected Film forms the extraction for using composite sheet.

[imbedibility of the adhesive phase to substrate surface]

Support chip obtained above is observed using digit microscope (Keyence corporation " VHS-1000 "), is pressed According to imbedibility of following benchmark evaluations adhesive phase to substrate surface.

Zero: not finding bubble between substrate and adhesive phase.

×: bubble is had found between substrate and adhesive phase.

[resistance to clasticity]

The silicon chip of 2mm × 2mm size used in the evaluation of infrared inspection above-mentioned for 10, it is aobvious using optics Micro mirror observes its 4 divisional plane (side of silicon chip), according to the resistance to clasticity of following benchmark evaluations.

Zero: being towards the quantity at the clast position of 30 μm or more sizes of the inside of silicon chip formation from the segmentation of silicon chip Average every 1 silicon chip is less than 1 position.

×: be towards the quantity at the clast position of 30 μm or more sizes of the inside of silicon chip formation from the segmentation of silicon chip It is more than average every 1 silicon chip, 1 position.

" table 1]

[table 2]

[table 3]

As defining the above results, for the protective film formation composite sheet of embodiment 1~12, by making The surface roughness in the 1st face of substrate is 0.37 μm hereinafter, the surface roughness in the 2nd face of substrate is greater than the table in above-mentioned 1st face Surface roughness and be 0.055~0.47 μm, resistance to blocking, laser lettering and infrared inspection are excellent.In addition, in office In the embodiment of meaning, resistance to clasticity and imbedibility are also excellent.Wherein, the protective film of Examples 1 to 3 and embodiment 8 is formed with multiple The surface roughness for closing the 2nd face in the substrate of piece is smaller, and laser lettering and infrared inspection are especially excellent.In contrast, The protective film of embodiment 5~7 and embodiment 9~12, which is formed, uses the surface roughness in the 2nd face of substrate in composite sheet larger, anti-stick Even property is especially excellent.Moreover, the surface roughness in the 2nd face is intermediate in the substrate of the protective film formation composite sheet of embodiment 4 Degree, resistance to blocking, laser lettering and infrared inspection are especially excellent.

In contrast, the protective film of comparative example 1 is formed too small with the surface roughness in the 2nd face of substrate in composite sheet, is resisted Adhesive is poor.

Use the surface roughness in the 1st face of substrate in composite sheet excessive, substrate in addition, the protective film of comparative example 2 is formed The surface roughness in the 2nd face is too small, and resistance to blocking, laser lettering and infrared inspection are poor.In addition, comparative example 2 Protective film, which is formed, uses the surface roughness in the 1st face of substrate in composite sheet excessive, and imbedibility is also poor.

In addition, the protective film of comparative example 3 forms, laser print excessive with the surface roughness in the 2nd face of substrate in composite sheet Word and infrared inspection are poor.

In addition, the protective film of comparative example 4 forms, laser print excessive with the surface roughness in the 1st face of substrate in composite sheet Word, infrared inspection and imbedibility are poor.

For the protective film formation composite sheet of reference example 1, the surface roughness in the 1st face due to meeting substrate Surface roughness for 0.4 μm or less, the 2nd face of substrate is condition as 0.053~0.48 μm, resistance to blocking, laser print Word and infrared inspection are excellent.But since adhesive phase is blocked up, resistance to clasticity is poor.

Industrial applicibility

The present invention can be used in the manufacture of semiconductor device.

Claims

1. a kind of support chip, the adhesive phase for having substrate and being laminated on the substrate, wherein

The surface roughness (Ra) of the side surface for having described adhesive layer of the substrate be 0.4 μm hereinafter,

Being greater than with the surface roughness (Ra) on the surface for the side opposite side for having described adhesive layer for the substrate has institute The surface roughness of a side surface of adhesive phase is stated, and is 0.053~0.48 μm.

2. support chip according to claim 1, wherein described adhesive layer with a thickness of 15 μm or less.

3. support chip according to claim 1 or 2, wherein described adhesive layer is non-energy line curability.

4. a kind of protective film, which is formed, uses composite sheet, has support chip according to any one of claims 1 to 3, and described Protective film formation is further equipped on described adhesive layer in support chip to be formed with film.