CN110536796A

CN110536796A - The application method of resin sheet, semiconductor device and resin sheet

Info

Publication number: CN110536796A
Application number: CN201880026660.3A
Authority: CN
Inventors: 根津裕介; 渡边康贵; 杉野贵志
Original assignee: Lindeko Corp
Current assignee: Lindeko Corp; Lintec Corp
Priority date: 2017-08-31
Filing date: 2018-08-06
Publication date: 2019-12-03
Also published as: TW201919873A; JPWO2019044398A1; KR20200047447A; WO2019044398A1

Abstract

The present invention provides a kind of resin sheet (1), its formation for being used for insulating film, the resin sheet (1) has the first support chip (11) and cured resin composition layer (10), resin composition layer (10) is formed by the resin combination containing thermosetting resin and inorganic particles, the content of the inorganic particles is 50 mass % or more, 90 mass % or less, first support chip (11) has supporting base material (111) and adhering agent layer (112), the resin composition layer is layered on the face of adhering agent layer (112) side of the first support chip (11).According to the resin sheet (1), even if when the viscosity of resin combination layer surface is smaller, do not allow to be also easy to produce to float at the interface of resin composition layer and support chip yet, even and if be used in after the heat cure of resin composition layer, by support chip from the manufacturing method for being formed by the semiconductor device removed on cured layer when, also be easy support chip is removed from the cured layer.

Description

The application method of resin sheet, semiconductor device and resin sheet

Technical field

The present invention relates to a kind of resin sheets of formation for insulating film, the semiconductor device manufactured using the resin sheet And the application method of the resin sheet.

Background technique

In recent years, as multilayer printed-wiring board or will be built in the electronic component-embedded component made of internal layer circuit substrate Substrate, from the angle for seeking multifunction or miniaturization, propose by insulating film and conductor layer it is alternately laminated made of increasing The multilayer printed-wiring board and built-in substrate of layer (build-up) mode.In the multilayer printed-wiring board of this increasing layer mode Or in built-in substrate, it is able to use and has the resin sheet of cured resin composition layer to form insulating film.

It is used sometimes as resin sheet as described above generally for the operability improved in its processing or when carrying Resin sheet with following compositions is laminated with the composition of support chip on resin composition layer.For example, as such resin Piece, patent document 1 disclose a kind of bonding film, have compositions of thermosetting resin layer and are layered in thermosetting resin combination Supporter on one face of nitride layer further discloses a kind of manufacturer of component internal circuit board for having used the bonding film Method.It is laminated with the piece of resin composition layer on substrate and manufactures multilayer in addition, disclosing a kind of use in such as patent document 2 The method of printed wiring board.In this method, after resin composition layer is layered on circuit substrate, to the resin composition layer It carries out heat cure and forms insulating layer, then, substrate is removed from the insulating layer.

In addition, resin sheet as described above contains the thermosetting resins such as epoxy resin usually in resin composition layer, consolidates Change promotor, therefore storage stability is easy to be lower, thus keeping must be refrigerated sometimes.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2015-2295 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2014-7403 bulletin

Summary of the invention

The technical problem to be solved in the present invention

However, to be laminated with the state of support chip on resin composition layer, by the resin composition layer heat in resin sheet When being solidified to form cured layer, it is difficult to remove support chip from the cured layer sometimes.Therefore, also it is contemplated that silicone will be utilized The face that remover pair is contacted with resin composition layer has carried out the sheet material after lift-off processing and has been used as support chip, thus makes support chip Peeling force when removing from cured layer is reduced to prescribed limit.

When resin composition layer higher using inorganic filling material content or according to the type of resin component, above-mentioned resin There is also the resin composition layers that the adherence of resin combination layer surface (viscosity) is small in piece.Use utilization silicone remover The support chip handled come protect viscosity be so small resin composition layer when, in the carrying of resin sheet, keeping in, It processes medium, is easy to float at the interface of resin composition layer and support chip.When this occurs floating, in the processing of resin sheet When and carry when, it may occur that defect or crackle etc. are led to the problem of on resin composition layer.Especially resin sheet most cases Lower to be taken care of by refrigeration, when by such refrigeration keeping, it is especially pronounced that this floats problem.

In addition, in recent years, also studying using resin sheet manufacture wafer-level packaging (wafer level package) and Face Board level packaging (panel scale package).Although using the sheet material with large area in the manufacture of such encapsulation As resin sheet, but when the size of resin sheet is larger area, it is particularly easy to occur above-mentioned to float.

As described above, previous resin sheet is difficult to take into account support chip from simply stripping off on cured layer and to resin combination The inhibition of the interface of nitride layer and support chip floated.

The present invention is in view of such actual situation to complete, and its purpose is to provide a kind of resin sheets, even if It when the viscosity of resin combination layer surface is smaller, is also not easy to float at the interface of resin composition layer and support chip, and i.e. Just be used in after the heat cure of resin composition layer, by support chip from being formed by the semiconductor device removed on cured layer Manufacturing method when, be also easy to remove support chip from the cured layer.In addition, the present invention provides a kind of use such resin The application method of the semiconductor device and such resin sheet with good quality of piece manufacture.

Solve the technological means of technical problem

In order to achieve the above objectives, first, the present invention provides a kind of resin sheet, is used for the formation of insulating film, feature It is, the resin sheet has the first support chip and the curable resin being layered on a face of first support chip combination Nitride layer, the resin composition layer are formed by the resin combination containing thermosetting resin and inorganic particles, the inorganic particles It is 50 mass % or more, 90 mass % hereinafter, first support chip has branch support group in the content in the resin combination Material and be layered in the supporting base material a surface side adhering agent layer, the resin composition layer is layered in first support chip The adhering agent layer side face on (invention 1).

In the resin sheet of foregoing invention (invention 1), by making the first support chip have supporting base material and adhering agent layer and making The adhering agent layer is contacted with the face that supporting base material is opposite side with cured resin composition layer, and the first support chip is close well It closes in cured resin composition layer, is not easy to occur at the interface of cured resin composition layer and the first support chip as a result, Float, even and if when the first support chip is removed from cured layer made of cured resin composition layer heat cure, also can Enough it is easy to carry out the removing.

In foregoing invention (invention 1), the preferably described resin composition layer contains thermoplastic resin, and the thermoplastic resin exists Content in the resin combination is 1.0 mass % or more, 30 mass % or less (invention 2).

In foregoing invention (invention 1,2), the preferably described adhering agent layer is made of (invention 3) acrylic compounds sticker.

In foregoing invention (invention 1~3), the preferably described adhering agent layer by selected from active energy ray-curable sticker, At least one of thermally foamable sticker and thermosetting property sticker sticker constitute (invention 4).

In foregoing invention (invention 1~4), preferably: the resin sheet is heated 30 minutes with 100 DEG C, further with 180 It DEG C heated in 60 minutes resin sheets, by first support chip from cured layer made of resin composition layer solidification Peeling force (F12) when removing is 0.5N/25mm or more, 3.0N/25mm or less (invention 5).

In foregoing invention (invention 1~5), the adhering agent layer of preferably described first support chip at 100 DEG C, will measurement Storage modulus when frequency is set as 1Hz is 1 × 10⁵Pa or more (invention 6).

In foregoing invention (invention 1~6), preferably: the adhering agent layer face paste of first support chip is invested into copper foil, It is heated with the condition of 100 DEG C and 30 minutes, is then heated with the condition of 180 DEG C and 30 minutes, further with 190 DEG C And after 1 hour condition is heated, the adhesion strength to the copper foil of first support chip at room temperature is 0.7N/ 25mm or more, 2.0N/25mm are hereinafter, invest polyimide film for the adhering agent layer face paste of first support chip, with 100 DEG C and 30 minutes conditions heated, then heated with the condition of 180 DEG C and 30 minutes, it is further small with 190 DEG C and 1 When condition heated after, the adhesion strength to the polyimide film of first support chip at room temperature be 0.7N/ 25mm or more, 2.0N/25mm or less (invention 7).

In foregoing invention (invention 1~7), 5% weightless temperature of the adhering agent layer in preferably described first support chip For 250 DEG C or more (inventions 8).

In foregoing invention (invention 1~8), the preferably described thermoplastic resin is to contract selected from phenoxy group resinoid, polyvinyl alcohol At least one of air aldehyde resin and polyvinyl butyral resin (invention 9).

In foregoing invention (invention 1~9), the preferably described inorganic particles are surface-treated (hair using surface treating agent It is bright 10).

In foregoing invention (invention 1~10), the average grain diameter of the preferably described inorganic particles is 0.01 μm or more, 3.0 μm with Under (invention 11).

In foregoing invention (invention 1~11), the preferably described resin composition layer (is sent out with a thickness of 5 μm or more, 80 μm or less It is bright 12).

In foregoing invention (invention 1~12), the preferably described supporting base material is that glass transition temperature (Tg) is 50 DEG C or more Resin supporting base material (invention 13).

In foregoing invention (invention 1~13), the preferably described resin sheet have be layered in the resin composition layer with institute State the second support chip (invention 14) on the face that the first support chip is opposite side.

In foregoing invention (invention 1~14), the resin sheet is preferably used for the insulating film in semiconductor device Form (invention 15).

In foregoing invention (invention 15), the preferably described insulating film is the increasing layer layer (build-up of the semiconductor device Layer the insulating film (invention 16) in).

In foregoing invention (invention 15,16), the preferably described semiconductor device is built-in substrate, multilayer printed circuit At least one of plate, fan-out-type wafer-level packaging and fan-out-type face Board level packaging (invention 17).

Second, the present invention provides a kind of insulating film, which is characterized in that it is by by above-mentioned resin sheet (invention 1~17) Resin composition layer solidification forms (invention 18).

Third, the present invention provide a kind of semiconductor device, which is characterized in that it has above-mentioned resin sheet (invention 1~17) Resin composition layer solidification made of cured layer as insulating layer (invent 19).

4th, the present invention provides a kind of application method of resin sheet, is the user of above-mentioned resin sheet (invention 1~17) Method, which is characterized in that it has: the resin composition layer is solidified to the process for obtaining cured layer；And in the resin After the solidification of composition layer, process that first support chip is removed from the cured layer (invention 20).

Invention effect

Resin sheet according to the present invention is also not easy even if the viscosity on the surface of resin composition layer is smaller in resin The interface of composition layer and support chip floats, even and if be used in after resin composition layer heat cure, by support chip When from the manufacturing method for being formed by the semiconductor device removed on cured layer, it is also easy to shell support chip from the cured layer From.In addition, the semiconductor device with good quality can be manufactured by using resin sheet of the invention.

Detailed description of the invention

Fig. 1 is the sectional view of the resin sheet of an embodiment of the invention.

Fig. 2 is the sectional view for illustrating the application method of resin sheet of present embodiment.

Fig. 3 is the sectional view for illustrating the application method of resin sheet of present embodiment.

Specific embodiment

Hereinafter, embodiments of the present invention will be described.

[resin sheet]

Fig. 1 shows the sectional views of the resin sheet 1 of present embodiment.As shown in Figure 1, the resin sheet 1 of present embodiment has First support chip 11 is with the cured resin composition layer 10 being layered on a face of the first support chip 11 (hereinafter, sometimes referred to as For " resin composition layer 10 ").First support chip 11 has supporting base material 111 and is layered in a surface side of supporting base material 111 Adhering agent layer 112, resin composition layer 10 are layered on the face of 112 side of adhering agent layer of the first support chip 11.In addition, such as Fig. 1 Shown, it is opposite side with the first support chip 11 that the resin sheet 1 of preferably present embodiment, which has be layered in resin composition layer 10, Face on the second support chip 12.

In the resin sheet 1 of present embodiment, since resin composition layer 10 is layered in the adhering agent layer of the first support chip 11 On the face of 112 sides, therefore it is not easy to float in resin composition layer 10 and the interface of the first support chip 11.Even if especially existing When the viscosity on 10 surface of resin composition layer is smaller, resin composition layer 10 and the first support chip 11 can be also effectively inhibited Interface floats.Accordingly, for the resin sheet 1 of present embodiment, resin composition layer 10 can be inhibited in keeping and when carrying Defect and crackle generation.

In addition, in the resin sheet 1 of present embodiment, by making resin composition layer 10 be layered in the viscous of the first support chip 11 On the face of 112 side of oxidant layer, even if when making 10 heat cure of resin composition layer to form cured layer, also can easily by First support chip 11 is removed from the cured layer.

1. cured resin composition layer

Resin composition layer 10 in present embodiment is by the resin combination shape containing thermosetting resin and inorganic particles At.Herein, content of the inorganic particles in resin combination is 50 mass % or more, 90 mass % or less.In addition, resin combination Nitride layer 10 has curability, can be by making the solidification of resin composition layer 10 to form cured layer.By resin composition layer 10 Cured layer made of solidification shows insulating properties.From the angle of the cured layer of display insulating properties easy to form, resin combination Layer 10 is preferably free of conductive material.In addition, the surface resistivity of the cured layer is preferably 1 × 10¹⁵Ω/ or more, more preferably It is 1 × 10¹⁶Ω/ or more.As a result, in obtained semiconductor device, a problem that being able to suppress short circuit, it can obtain Excellent performance.

(1) thermosetting resin

It as thermosetting resin, is not particularly limited, such as epoxy resin, phenol resin, naphthols resinoid, work can be enumerated Property esters resin, benzoxazine resinoid, cyanate resin etc., these thermosetting resins can be used alone one kind, Huo Zheye It can be used in combination two or more.

As above-mentioned epoxy resin, well known various epoxy resin are able to use, specifically, bisphenol-A, double can be enumerated The glycidol ether of the phenols such as phenol F, resorcinol, phenyl novolac (phenyl novolac), cresol novolak；Fourth two The glycidol ether of the alcohols such as alcohol, polyethylene glycol, polypropylene glycol；Phthalic acid, M-phthalic acid, tetrahydrophthalic acid etc. The glycidol ether of carboxylic acid；Made of the reactive hydrogen being bonded on the nitrogen-atoms of aniline isocyanuric acid ester etc. is replaced by glycidyl The epoxy resin of glycidyl type or alkyl glycidyl fundamental mode (alkyl glycidyl)；Such as vinylcyclohexene diepoxy Compound, 3,4- epoxycyclohexylmethyl -3,4- dicyclohexene carboxylate, 2- (3,4- epoxy group) cyclohexyl -5,5- spiral shell (3,4- Epoxy group) oxidation is carried out as hexamethylene-dioxanes etc., for example by the carbon-to-carbon double bond to intramolecular to import ring Made of oxygroup, so-called alicyclic ring type ring oxide.Additionally it is possible to using having biphenyl backbone, triphenyl methane skeleton, two The epoxy resin of cyclohexadiene skeleton, naphthalene skeleton etc..These epoxy resin can be used alone one kind, or also can be used in combination two Kind or more.In above-mentioned epoxy resin, it is preferable to use the glycidol ether (bisphenol A type epoxy resin) of bisphenol-A, have biphenyl backbone Epoxy resin (biphenyl type epoxy resin), epoxy resin (naphthalene type epoxy resin) or their combination with naphthalene skeleton.

As above-mentioned phenol resin, such as bisphenol-A, bisphenol-A, diallyl bisphenol, 4 can be enumerated, 4 '-dihydroxies Base biphenyl (biphenol), Bisphenol F, diallyl Bisphenol F, triphenyl methane type phenol, four phenol (tetrakisphenol), phenolic aldehyde Varnish type phenol, cresol novolac resin, phenol (biphenyl type phenol) with xenyl aralkyl skeleton etc., wherein it is preferable to use Biphenyl type phenol.These phenol resin can be used alone one kind, or also can be used in combination two or more.In addition, using epoxy resin When as curable resin, from the angle of reactivity with epoxy resin etc., phenol resin is preferably used simultaneously.

The content of thermosetting resin in resin combination is preferably 10 mass % or more, particularly preferably 15 mass % with On, further preferably 20 mass % or more.In addition, the content is preferably 60 mass % hereinafter, particularly preferably 50 mass % Hereinafter, further preferably 40 mass % or less.By making the 10 mass % of content or more, the solidification of resin composition layer 10 Become more sufficiently, to be capable of forming more robust insulating film.In addition, by making 60 mass % of the content hereinafter, can be into one Step inhibits be cured the stage of resin composition layer 10 beyond the consideration, and storage stability becomes more excellent.In addition, thermosetting property The above-mentioned content of resin is solid component scaled value.

(2) thermoplastic resin

In addition, the resin combination in present embodiment can also contain thermoplastic resin.As thermoplastic resin, such as can Enumerate phenoxy group resinoid, olefine kind resin, polyester resin, polyurethane based resin, polyester urethane resinoid, third The styrene resins, silanes tree such as olefin(e) acid resinoid, amide resinoid, styreneisobutylene-styrol copolymer (SIS) Rouge, rubber resin, polyvinyl acetal-based resin, polyvinyl butyral resin, polyimide based resin, polyamide acyl are sub- Amine resins, polyether sulfone resin, polysulfones resinoid, fluorine resin etc., these thermoplastic resins can be used alone one kind, or Also it can be used in combination two or more.In addition, these thermoplastic resins can also have curability functional group.

Herein, it for the miniaturization of semiconductor device or the miniaturization of wiring, is manufactured using the resin sheet 1 of present embodiment When semiconductor device, sometimes through electrode is formed on the cured layer made of the solidification of resin composition layer 10, so that cloth again be arranged Line layer.When especially with aftermentioned semi-additive process, wiring layer again is set, in the engineering of desmearing (desmear) processing, meeting Be exposed to alkaline solution etc. it is harsh under conditions of handle cured layer.At this point, can have solidification according to the type of thermoplastic resin The situation for the wiring formative differences such as layer dissolves, the peel strength of plating is lower.Therefore, from the angle of the wiring formative to cured layer Degree sets out, and preferred thermoplastic resin is free of acrylic resin.As thermoplastic resin, among above-mentioned thermoplastic resin, preferably Using in the group being made of phenoxy group resinoid, polyvinyl acetal-based resin, polyvinyl butyral resin at least It is a kind of.

It as phenoxy group resinoid, is not particularly limited, such as can to illustrate bisphenol A-type, bisphenol-f type, bisphenol-A/Bisphenol F total Poly- type, bisphenol S type, bis-phenol acetophenone type, phenolic varnish type, fluorenes type, dicyclopentadiene-type, norbornene-type, naphthalene type, anthracene type, Adamantane type, terpenes type, trimethyl-cyclohexane type, 4,4 '-dihydroxybiphenyl types, phenoxy group resinoid of biphenyl type etc., wherein It is preferable to use bisphenol A-type phenoxy resins.The end of phenoxy group resinoid can be any one in phenolic hydroxyl group, epoxy group etc. Functional group.Phenoxy group resinoid can be used alone one kind, or also can be used simultaneously two or more.

In addition, there are the viscosity on 10 surface of resin composition layer to become when using phenoxy group resinoid as thermoplastic resin Small tendency.But in the resin sheet 1 of present embodiment, even if being set in the case where viscosity becomes smaller as described above by making Oil/fat composition layer 10 is layered on the face of 112 side of adhering agent layer of the first support chip 11, can effectively inhibit resin combination Layer 10 floats with the interface of the first support chip 11.Therefore, the resin sheet 1 of present embodiment is also suitable for using phenoxy group class tree The case where rouge is as thermoplastic resin.

The weight average molecular weight (Mw) of thermoplastic resin is preferably 100 or more, and particularly preferably 1000 or more, further especially Preferably 10,000 or more.In addition, the weight average molecular weight (Mw) of thermoplastic resin be preferably 1,000,000 hereinafter, particularly preferably 800,000 with Under, further particularly preferably 100,000 or less.If the weight average molecular weight (Mw) of thermoplastic resin is above range, being easier will Resin composition layer 10 is formed as sheet.In addition, the weight average molecular weight in this specification is using gel permeation chromatography (GPC) method The standard polystyren scaled value of measurement.

The content of thermoplastic resin in resin combination is preferably 1.0 mass % or more, particularly preferably 3.0 mass % More than, further preferably 5.0 mass % or more.In addition, the content is preferably 30 mass % hereinafter, particularly preferably 20 matter % is measured hereinafter, further preferably 10 mass % or less.By making the content above range, makes film property and be improved, and institute The operability of obtained resin sheet is effectively improved.In addition, the above-mentioned content of thermoplastic resin is solid component scaled value.

(3) inorganic particles

Resin combination in present embodiment contains 50 mass % or more, 90 mass % inorganic particles below.As a result, The thermal expansion coefficient and water absorption rate of cured layer made of resin composition layer 10 solidifies are smaller, and resin composition layer 10 is sent out as a result, Wave excellent flexibility, mobility and adhesiveness.From this angle, the content of the inorganic particles in resin combination is preferred For 55 mass % or more, particularly preferably 60 mass % or more.In addition, from the cured layer made of the solidification of resin composition layer 10 Upper formation again wiring layer when the angle of wiring formative set out, which is preferably 85 mass % hereinafter, particularly preferably 80 Quality % or less.In addition, the above-mentioned content of inorganic particles is solid component scaled value.

As inorganic particles, such as can exemplify with silica, aluminium oxide, glass, titanium oxide, aluminium hydroxide, hydrogen Magnesia, calcium carbonate, magnesium carbonate, calcium silicates, magnesium silicate, calcium oxide, magnesia, aluminium oxide, aluminium nitride, aluminium borate whisker, nitrogen Change boron, crystallinity silica, amorphism silica, mullite, the composite oxides of cordierite etc., montmorillonite, smectite, Diaspore, talcum, iron oxide, silicon carbide, zirconium oxide etc. are the inorganic particles of material, these inorganic particles can be used alone one Kind, or also can be used in combination two or more.Wherein, it is preferable to use silicon dioxide microparticle, alumina particulate, particularly preferably use Silicon dioxide microparticle.

Above-mentioned inorganic particles are surface-treated preferably by surface treating agent.It is inorganic in resin combination as a result, The dispersibility and fillibility of particle are excellent.As above-mentioned surface treating agent, epoxy silane, vinyl silanes, silicon nitrogen can be enumerated Hydride compounds, alkoxy silane, silane coupling agent etc..These surface treating agents can be used alone, and also can be used in combination.

The minimum vertex-covering area of above-mentioned surface treating agent is preferably smaller than 550m²/ g, particularly preferably 520m²/ g is hereinafter, into one Step is preferably 450m²/ g or less.On the other hand, the lower limit value of the minimum vertex-covering area of surface treating agent is preferably 100m²/ g with On, particularly preferably 200m²/ g or more, further preferably 300m²/ g or more.By making minimum vertex-covering area above range, The dispersibility and fillibility of inorganic particles in resin combination are improved, and electrode solidifies resin composition layer 10 The formative of cured layer be improved.

In addition, the minimum vertex-covering area (m of surface treating agent²/ g) refer to using 1g surface treating agent formed monomolecular film When the monomolecular film area (m²).Minimum vertex-covering area can theoretically be calculated according to structure of surface treating agent etc..

As the preferred example of surface treating agent, 3- glycidyl ether oxypropyltrimethoxysilane etc. can be enumerated The vinyl silanes such as epoxy silane and vinyltrimethoxysilane.

The average grain diameter of above-mentioned inorganic particles is preferably 0.01 μm or more, and particularly preferably 0.1 μm or more, further preferably It is 0.3 μm or more.In addition, the average grain diameter of above-mentioned inorganic particles is preferably 3.0 μm hereinafter, particularly preferably 1.0 μm or less.If The average grain diameter of above-mentioned inorganic particles is such range, then the pliability and flexibility of resin composition layer 10 are easy to become excellent It is different, while being easy to for the content of inorganic particles to be adjusted to the higher filling rate such as above range.Further, as described above, In When forming wiring layer again on cured layer made of resin composition layer 10 solidifies, the formative of electrode is easy to improve.

In addition, the maximum particle diameter of above-mentioned inorganic particles is preferably 0.05 μm or more, particularly preferably 0.5 μm or more.In addition, The maximum particle diameter is preferably 5 μm hereinafter, particularly preferably 3 μm or less.By making the maximum particle diameter above range of inorganic particles, It is easy to fill inorganic particles into resin combination, can coefficient of thermal expansion when solidifying is inhibited lower.In addition, institute as above It states, when forming wiring layer again on the cured layer made of the solidification of resin composition layer 10, fine wiring easy to form.In addition, The average grain diameter and maximum particle diameter of inorganic particles in this specification be using particle size distribution device (Nikkiso Co., Ltd. manufacture, name of product " Nanotrack Wave-UT151 "), the value that is measured using dynamic light scattering method.

(4) curing catalysts

It is preferred that the resin combination in present embodiment further contains curing catalysts.Heat can be effectively performed as a result, The curing reaction of thermosetting resin can be such that resin composition layer 10 solidifies well.As curing catalysts, such as can enumerate Imidazoles curing catalysts, amine-type cure catalyst, Phosphorus curing catalysts etc..

Above-mentioned curing catalysts can be used alone one kind, also can be used simultaneously two or more.

Curing catalysts content in resin combination is preferably 0.01 mass % or more, particularly preferably 0.05 mass % More than, further preferably 0.1 mass % or more.In addition, the content is preferably 2.0 mass % hereinafter, particularly preferably 1.5 matter % is measured hereinafter, further preferably 1.0 mass % or less.By making the content above range, resin composition layer can be made 10 solidify better.In addition, the above-mentioned content of curing catalysts is solid component scaled value.

(5) other ingredients

Resin combination in present embodiment can also further contain plasticizer, stabilizer, tackifier, colorant, idol Join agent, antistatic agent, antioxidant etc..

(6) thickness of resin composition layer

The thickness of resin composition layer 10 is preferably 5 μm or more, particularly preferably 10 μm or more, further preferably 15 μm More than.In addition, the thickness be preferably 80 μm hereinafter, particularly preferably 60 μm hereinafter, further preferably 40 μm or less.

(7) physical property of cured resin composition layer

For the viscosity on 10 surface of resin composition layer, 25 DEG C of the probe tack measured using the probe of diameter 25mm It is smaller than 5g.In the resin sheet 1 of present embodiment, even if the viscosity feelings very small like this on 10 surface of resin composition layer Under condition, also can effectively it be pressed down by the way that resin composition layer 10 is laminated on the face of 112 side of adhering agent layer of the first support chip 11 Resin composition layer 10 processed floats with the interface of the first support chip 11.In addition, the lower limit value of above-mentioned 25 DEG C of probe tack does not have There is special limitation, such as can be 0.00001g.In addition, above-mentioned 25 DEG C of probe tack can be carried out by probe tack test Measurement.Specifically, the stainless steel manufacturing probe of diameter 25mm can be made with 0.98N/cm in the environment of 25 DEG C²Contact The surface of 11 side of the first support chip of loading contact pressure resin composition layer 10 10 seconds, then by probe with 10mm/ seconds speed It separates from test piece, and is measured as loading value at this time.

2. the first support chip

First support chip 11 of present embodiment has supporting base material 111 and is layered in a surface side of supporting base material 111 Adhering agent layer 112.

(1) supporting base material

Above-mentioned supporting base material 111 is not particularly limited, such as it is preferable to use resin film, non-woven fabrics, paper etc. to be used as branch support group Material 111.As the example of the resin film, can enumerate polyethylene terephthalate film, polybutylene terephthalate film, The polyester films such as poly (ethylene naphthalate) film；The polyolefin films such as polyethylene film, polypropylene screen；Polyimide film etc..As upper The example of non-woven fabrics is stated, the non-woven fabrics using fibers such as artificial silk, acrylic acid, polyester can be enumerated.As the example of above-mentioned paper, Vellum, glassine paper can be enumerated, containing impregnated paper, coated paper etc..These supporting base materials two or more laminated bodies can be made and It uses.

The glass transition temperature (Tg) for constituting the material of above-mentioned resin film is preferably 50 DEG C or more, and particularly preferably 55 DEG C More than, further preferably 60 DEG C or more.By make the material glass transition temperature (Tg) be 50 DEG C or more, even if with The state of the first support chip 11 is laminated on resin composition layer 10, when by 10 heat cure of resin composition layer, the first support chip 11 are also not easy thermal deformation, are easy to remove the first support chip 11 from cured layer as a result,.In addition, above-mentioned glass transition temperature The upper limit of degree (Tg) is not particularly limited, but preferably generally 500 DEG C hereinafter, particularly preferably 400 DEG C or less.In addition, above-mentioned Glass transition temperature (Tg) is the value measured using Differential Scanning Calorimetry analyzer.

In addition, constituting the first support for the purpose for the adaptation for improving the adhering agent layer 112 with stacking on the surface thereof The supporting base material 111 of piece 11 can impose prime treatment, sided corona treatment to one or both sides, at plasma according to required The surface treatment such as reason, oxidation processes.

The thickness of above-mentioned supporting base material 111 is not particularly limited, but from the angle of the operability of resin sheet 1, preferably It is 10 μm or more, particularly preferably 15 μm or more, further preferably 20 μm or more.In addition, the thickness be preferably 500 μm with Under, particularly preferably 100 μm hereinafter, further preferably 75 μm or less.

For supporting base material 111, the direction MD of the supporting base material 111 when being heated 30 minutes with 150 DEG C and the heat in the direction CD Shrinking percentage is preferably 2.0% hereinafter, particularly preferably 1.5% or less.The lower limit of the percent thermal shrinkage in the direction MD of supporting base material 111 The lower limit value of the percent thermal shrinkage in value and the direction CD is smaller then the more preferred, it is often preferred that 0.01% or more.

Furthermore it is preferred that the percent thermal shrinkage in the direction CD of the percent thermal shrinkage and supporting base material 111 in the direction MD of supporting base material 111 It meets the above range, while the ratio between the percent thermal shrinkage in the direction MD and the percent thermal shrinkage in the direction the CD (percent thermal shrinkage/side CD in the direction MD To percent thermal shrinkage) be 0.03 or more, 30 ranges below, particularly preferably 0.5 or more, 5.0 ranges below.By making to prop up Support group material 111 meets these ranges, after the heat cure of resin composition layer 10, by the first support chip 11 from be formed by solidification When removing on layer, the warpage of obtained semiconductor device can be prevented.

The above-mentioned direction MD refers to when supporting base material 111 is filmed in a manner of strip, and carries supporting base material 111 The parallel direction in direction, the direction CD refer to the direction to intersect vertically in the direction the same face Shang YuMD of supporting base material 111.

Above-mentioned percent thermal shrinkage is measured according to JIS Z1712 and using the following method.By supporting base material 111 with wide 20mm, The size of long 200mm is cut along the direction MD, the direction TD respectively, is suspended in 150 DEG C of hot-air oven and is heated 5 minutes.So Afterwards, the length after measurement heating, the ratio (percentage) by the length of contraction relative to the original length are used as percent thermal shrinkage.

In addition, the percent thermal shrinkage of supporting base material 111, such as can also be adjusted in the following manner: selection can meet The material of required range；Supporting base material 111 is made annealing treatment；And the film build method of change supporting base material 111 is (for example, change Become extension method) etc..

Furthermore it is preferred that low molecular weight compositions (oligomer) is selected to be not easy the material being precipitated as supporting base material 111.By making With such supporting base material 111, the heating being able to suppress when curable resin composition layer 10 due to, leads to institute in supporting base material 111 The oligomer contained is precipitated and the oligomer is shifted to cured layer, can manufacture higher-quality semiconductor device.On in addition, The precipitation degree for stating low molecular weight compositions can be judged by following manner: heat tree with 100 DEG C and 60 minutes of condition After then being heated with the condition of 170 DEG C and 60 minutes, the first support chip 11 is solidified from resin composition layer 10 for rouge piece 1 Made of remove on cured layer, the table of the cured layer then exposed using numerical digit microscope (500 times of magnifying power of observation) observation Face, whether there is or not the residues from low molecular weight compositions for confirmation.

(2) adhering agent layer

For constituting the sticker of above-mentioned adhering agent layer 112, as long as the first support chip 11 shows resin composition layer 10 Required adherence is not particularly limited.As the example for the sticker for constituting adhering agent layer 112, it is able to use acrylic compounds Sticker, rubber sticker, silicone sticker, carbamates sticker, polyesters sticker, polyvinyl ether Sticker etc..

In addition, constituting the sticker of adhering agent layer 112 preferably by being selected from active energy ray-curable sticker, heat foamable Property at least one of sticker and thermosetting property sticker sticker constitute.The first support chip 11 is to resin composition layer as a result, Adherence needed for 10 displays, can inhibit floating between resin composition layer 10 and the first support chip 11.On the other hand, above-mentioned The adhesion strength of sticker may be reduced because of the irradiation of active energy beam or heating, as a result, can be easily by the first support chip It is removed on 11 cured layers made of the solidification of resin composition layer 10, can inhibit the defect of cured layer or the generation of crackle.

(2-1) acrylic compounds sticker

Though above-mentioned acrylic compounds sticker is not particularly limited, preferably uses and contain (methyl) acrylate polymer (A) adherence composition P and the sticker prepared.In addition, in the present specification, (methyl) acrylate refers to acrylate And both methacrylates.Other similar terms are also identical.

It is preferred that (methyl) propylene that above-mentioned carbon atom number of (methyl) acrylate polymer (A) containing alkyl is 1~20 Acid alkyl ester is as the monomer for constituting the polymer.Obtained sticker can show preferred adherence as a result,.

(methyl) alkyl acrylate that the carbon atom number of alkyl is 1~20 can be used alone one kind, also can be used in combination It is two or more.As above-mentioned (methyl) alkyl acrylate, from the angle of heat resistance, it is preferable to use the carbon atom number of alkyl For 6~10 (methyl) alkyl acrylate, (methyl) 2-EHA is particularly preferably used.

(methyl) acrylate polymer (A) preferably comprise 10 mass % or more, particularly preferably containing 50 mass % or more, Further preferably 70 mass % or more, particularly preferably containing 85 mass % or more, further preferably 90 mass % or more (methyl) alkyl acrylate that the carbon atom number of alkyl is 1~20 is as the monomeric unit for constituting the polymer.In addition, (first Base) acrylate polymer (A) preferably comprise 99 mass % or less, particularly preferably containing 98 mass % or less, further preferably (methyl) alkyl acrylate that the carbon atom number for containing 97 mass % alkyl below is 1~20 is as the composition polymer Monomeric unit.

In addition, (methyl) acrylate polymer (A) preferably comprises the monomer with reactive functional groups (containing reactive official Energy single group body) as the monomer for constituting the polymer.As above-mentioned monomer containing reactive functional groups, hydroxyl is preferably enumerated Monomer, carboxyl group-containing monomer, emulsion stability etc..These monomers containing reactive functional groups can be used alone one kind, and can also combine makes With two or more.

(methyl) acrylate polymer (A) preferably comprise 1 mass % or more, particularly preferably containing 2 mass % or more, into One step preferably comprises the monomer containing reactive functional groups of 3 mass % or more as the monomeric unit for constituting the polymer.In addition, (methyl) acrylate polymer (A) preferably comprises 30 mass % or less, further preferably 20 mass % or less, particularly preferably contains There is 10 mass % or less, further preferably 7 mass % monomer containing reactive functional groups below as the composition polymer Monomeric unit.

In addition, (methyl) acrylate polymer (A) can also further contain other monomers as the composition polymerization The monomer of object.As other monomers, for example, can enumerate (methyl) acrylate with aliphatic ring, non-crosslinked property third Acrylamide, (methyl) acrylate of tertiary amino with non-crosslinked property, vinyl acetate, styrene etc..These other monomers It can be used alone, also can be used in combination two or more.

One kind in addition, (methyl) acrylate polymer (A) can be used alone, also can be used in combination two or more.

The adherence composition P for being preferred for preparing above-mentioned acrylic compounds sticker further contains crosslinking agent (B), above-mentioned Acrylic compounds sticker preferably makes to combine containing the adherence of above-mentioned (methyl) acrylate polymer (A) and crosslinking agent (B) Sticker made of object P crosslinking.

As above-mentioned crosslinking agent (B), as long as can be with reactive functional groups possessed by (methyl) acrylate polymer (A) It is reacted, such as isocyanates crosslinking agent, epoxies crosslinking agent, amine cross-linking agent, melamine class can be enumerated Crosslinking agent, aziridines crosslinking agent, hydrazine crosslinking agent, aldehyde crosslinking agent, oxazoline class crosslinking agent, metal alkoxide class crosslinking agent, Metal chelate class crosslinking agent, metallic salt crosslinking agent, ammonium salt class crosslinking agent etc..In addition, crosslinking agent (B) can be used alone one Kind, or also can be used in combination two or more.

Relative to 100 mass parts of (methyl) acrylate polymer (A), crosslinking agent (B's) in adherence composition P contains Amount is preferably 0.1 mass parts or more, and it is more than more preferably 1 mass parts, it is more than particularly preferably 2 mass parts, further preferably 3 It is more than mass parts.In addition, relative to 100 mass parts of (methyl) acrylate polymer (A), the content be preferably 20 mass parts with Under, particularly preferably 15 below the mass, and further preferably 10 below the mass.

(2-2) silicone sticker

Silicone sticker is not particularly limited, such as can enumerate the sticker containing dimethyl polysiloxane.As Silicone sticker, for example, be able to use adhesion agent composition is solidified made of addition polymerization type silicone sticker, it is described Composition contains the organopolysiloxane with unsaturated groups such as vinyl, the dimethyl with SiH base as crosslinking agent Polysiloxanes and platinum-type catalyst；Or use organic peroxides such as benzoyl peroxide (BPO) by organic poly- silicon oxygen Silicone sticker obtained from alkane solidification etc..From the angle of heat resistance, preferably addition polymerization type silicone sticker.This When, consider obtained adhesion strength, crosslink density can be adjusted according to the density of above-mentioned unsaturated group.Above-mentioned addition polymerization type Silicone sticker can heat etc. to carry out addition polymerization, thus be formed well.

(2-3) active energy ray-curable sticker

As long as active energy ray-curable sticker is to play defined adhesion strength before the irradiation of active energy beam, The sticker that thus adhesion strength fully reduces is solidified by the irradiation of active energy beam simultaneously, is not particularly limited. Active energy ray-curable sticker may include the polymer of active energy ray-curable, also may include non-live Property energy ray-curable polymer (polymer without active energy ray-curable) with work more than at least one The property monomer of energy ray-curable group and/or the mixture of oligomer.

(2-4) thermally foamable sticker

As long as thermally foamable sticker is to play defined adhesion strength before heating, while thus gluing by heating foaming Put forth effort the sticker fully reduced, be not particularly limited, such as preferably comprises the adhesion ingredient as matrix (matrix) With the sticker of foaming agent.In addition, thermally foamable sticker is recorded in Japanese Unexamined Patent Publication 2004-277749 bulletin, Japan in detail These thermally foamable stickers, can be used as by special open 2012-117040 bulletin, Japanese Unexamined Patent Publication 2010-094834 bulletin etc. The sticker of present embodiment.

In addition, commercial goods can be used in the first support chip 11 that adhering agent layer 112 is made of thermally foamable sticker, as Its example preferably enumerates name of product " REVALPHA " (Nitto Denko Corporation manufacture) etc..

(2-5) thermosetting property sticker

As long as thermosetting property sticker is to play defined adhesion strength before heating, while thus adhering by heating solidification The sticker that power fully reduces, is not particularly limited, such as is able to use viscous containing adhesion ingredient and thermosetting resin The known sticker such as agent.

As the example of above-mentioned adhesion ingredient, acrylic compounds sticker, rubber sticker, silicone adhesion can be enumerated Agent, carbamates sticker etc..They can be used alone one kind, or also can be used in combination two or more.

(2-6) additive

Usually used various additives can be added into the sticker for constituting above-mentioned adhering agent layer 112 according to required, Such as it is adjustable refractive index agent, antistatic agent, tackifier, silane coupling agent, antioxidant, ultraviolet absorbing agent, light stabilizer, soft Agent, filler, light curing agent, Photoepolymerizationinitiater initiater etc..

The sticker for preferably comprising above-mentioned adhering agent layer 112 includes the rubber resin with reactive group as thickening Agent.As the rubber resin, such as the hydrogenation type polybutadiene that there is carboxyl in end can be enumerated, had in end Hydrogenation type polybutadiene of hydroxyl etc..It, can as the concrete example of the hydrogenation type polybutadiene in end with carboxyl Enumerate NIPPON SODA CO., the name of product " CI1000 " etc. of LTD. manufacture.In addition, there is hydroxyl as in end The concrete example of hydrogenation type polybutadiene can enumerate NIPPON SODA CO., the name of product of LTD. manufacture " GI1000 ", " GI2000 ", " GI3000 " etc..

The sticker of adhering agent layer 112 is constituted by containing above-mentioned tackifier, is easy to aftermentioned peeling force (F11) and stripping It is adjusted to required range from power (F12), further from admittedly after the heat cure of resin composition layer 10, by the first support chip 11 When being removed on change layer, it is able to suppress sticker residue and remains on cured layer.

Relative to 100 mass parts of (methyl) acrylate polymer (A), the content of the tackifier in adherence composition P More than preferably 1 mass parts, more than particularly preferably 5 mass parts.In addition, relative to (methyl) acrylate polymer (A) 100 Mass parts, the content are preferably that 30 below the mass, particularly preferably 15 below the mass.

The physical property etc. of (2-7) adhering agent layer

The thickness of adhering agent layer 112 is preferably 1 μm or more, particularly preferably 5 μm or more, further preferably 10 μm with On.In addition, the thickness be preferably 500 μm hereinafter, particularly preferably 100 μm hereinafter, further preferably 50 μm or less.

Storage modulus of the adhering agent layer 112 at 100 DEG C, when measurement frequency is set as 1Hz is preferably 1 × 10⁵Pa or more. If adhering agent layer 112 has such storage modulus, after making resin composition layer 10 solidify and form cured layer, Neng Gougeng The first support chip 11 is removed from the cured layer easily, and can prevent from remaining the bad of sticker on solidifying layer surface Situation (so-called residue glue).The upper limit of storage modulus of the adhering agent layer 112 at 100 DEG C, when measurement frequency is set as 1Hz does not have It is particularly limited to, but preferably 1 × 10⁷Pa or less.In addition, above-mentioned storage modulus is using measurement of dynamic viscoelasticity device and to pass through Torsional shear method and the value measured, recorded in the details of measuring method embodiment as be described hereinafter.

The face paste of 112 side of adhering agent layer of first support chip 11 is invested into copper foil, is carried out with 100 DEG C and 30 minutes of condition Heating, after then being heated with the condition of 180 DEG C and 60 minutes, the adhesion to copper foil of the first support chip 11 at room temperature Power is preferably 0.7N/25mm or more, 2.0N/25mm or less.In addition, by the face paste of 112 side of adhering agent layer of the first support chip 11 Polyimide film is invested, is heated with the condition of 100 DEG C and 30 minutes, is then added with the condition of 180 DEG C and 60 minutes After heat, the first support chip 11 at room temperature be preferably 0.7N/25mm or more, 2.0N/ to the adhesion strength of polyimide film 25mm or less.If carrying out the adhesion strength after such heating is above range, it is easier the first support chip 11 from resin It is removed on cured layer made of 10 heat cure of composition layer.In addition, the details of the measuring method of above-mentioned adhesion strength is implemented as be described hereinafter Recorded in example.In addition, in the present specification, room temperature refers to 22 DEG C or more, 24 DEG C of temperature below.

From effectively inhibit the first support chip 11 is heated after it is removed from cured layer when, by adhering agent layer The angle of residue glue caused by 112 deterioration is set out, and 5% weightless temperature of adhering agent layer 112 is preferably 250 DEG C or more, more preferably It is 300 DEG C or more.

3. the second support chip

It is preferred that the resin sheet 1 of present embodiment has the second support chip 12, be layered in resin composition layer 10 with One support chip 11 is on the face of opposite side.Resin sheet 1 by making present embodiment has the second support chip 12, can be using the One support chip 11 and the second support chip 12 protect resin composition layer 10 from two sides.It is apparent thereby, it is possible to effectively inhibit The generation of problem, the defect of resin composition layer 10 and crackle.

Second support chip 12 is not particularly limited, such as can enumerate polyethylene terephthalate, poly- terephthaldehyde It is the plastic foil of the polyolefin films such as the polyester films such as sour butanediol ester, polyethylene naphthalate, polypropylene, polyethylene etc., first-class Paper, glassine paper, containing paper, the non-woven fabrics such as impregnated paper, coated paper etc..They can be made two or more laminated bodies and use.It can also The surface treatment such as delustring processing, sided corona treatment is implemented to the second support chip 12.

It can also be used remover to the contact surface progress lift-off processing with resin composition layer 10 of the second support chip 12.Make For the remover, silicone remover, alcohol acids remover, fluorine class remover, chain alkyl class remover, alkene can be enumerated Resinae remover, acrylic compounds remover and rubber remover etc..Wherein, it is preferable to use being selected from silicone remover, alcohol At least one of acids remover, especially from preventing from floating between the second support chip 12 and resin composition layer 10 Angle set out, more preferably use alcohol acids remover.

In addition, the second support chip 12 can also have adhering agent layer on the face of the side contacted with resin composition layer 10. The adhering agent layer can be identical as the adhering agent layer 112 that the first support chip 11 has.

Though the thickness of the second support chip 12 is not particularly limited, and usually 20 μm or more, 250 μm or less.

4. the physical property of resin sheet

Peeling force (F11) when first support chip 11 is removed from resin composition layer 10 before curing is preferably 0.1N/25mm or more, particularly preferably 0.2N/25mm or more, further preferably 0.3N/25mm or more.By making above-mentioned stripping It is 0.1N/25mm or more from power (F11), when can effectively inhibit keeping (especially refrigeration keeping) and operation resin sheet 1, In Float between first support chip 11 and resin composition layer 10.

In addition, the upper limit value of above-mentioned peeling force (F11) is directed to, when the sticker for constituting adhering agent layer 112 is not active energy When measuring any one in ray-curable sticker, thermally foamable sticker and thermosetting property sticker, the peeling force (F11) is excellent 3.0N/25mm is selected as hereinafter, particularly preferably 2.0N/25mm is hereinafter, further preferably 0.5N/25mm or less.It is viscous when constituting Oxidant layer 112 sticker be active energy ray-curable sticker, thermally foamable sticker and thermosetting property sticker in When at least one, which is preferably 30N/25mm hereinafter, particularly preferably 25N/25mm is hereinafter, further preferably For 20N/25mm or less.By making the upper limit value range of above-mentioned peeling force (F11), removed by the first support chip 11 When, the defect or crackle of resin composition layer 10 can be effectively inhibited.

In addition, shown in the measuring method test example as be described hereinafter of above-mentioned peeling force (F11).

In addition, in the resin sheet 1 for heating 30 minutes resin sheet 1 with 100 DEG C and heated 60 minutes with 180 DEG C, it will Peeling force (F12) when first support chip 11 is removed from cured layer made of 10 heat cure of resin composition layer is preferably 0.5N/25mm or more, particularly preferably 0.7N/25mm or more, further preferably 0.8N/25mm or more.In addition, the peeling force It (F12) is preferably 3.0N/25mm hereinafter, particularly preferably 2.0N/25mm is hereinafter, further preferably 1.5N/25mm or less.It is logical Crossing makes above-mentioned peeling force (F12) to be 0.5N/25mm or more, is able to suppress the first support chip 11 in the thermosetting of resin composition layer 10 The unexpected removing for changing front and back, can protect the table of more obtained cured layer by the first support chip 11 Face.In addition, by make above-mentioned peeling force (F12) even if for 3.0N/25mm hereinafter, by the first support chip 11 heating after, can also Easily the first support chip 11 is removed well from solidification layer surface made of the solidification of resin composition layer 10, it can be effective The defect and crackle of ground inhibition resin composition layer 10.In addition, the measuring method of above-mentioned peeling force (F12) test example institute as be described hereinafter Show.

In addition, when the resin sheet 1 of present embodiment has the second support chip 12, preferably by the second support chip 12 from solidification Peeling force (F2) when removing on preceding resin composition layer 10 meets following formula (1),

F11/F2>1…(1)。

It can inhibit and float between the first support chip 11 and resin composition layer 10 as a result, while being easy second Support chip 12 is removed from resin composition layer 10.In addition, peeling force (F2) is preferably 0.05N/100mm or more, particularly preferably For 0.10N/100mm or more.In addition, the peeling force (F2) is preferably 2.0N/100mm or less.In addition, above-mentioned peeling force (F2) Shown in measuring method test example as be described hereinafter.

5. the manufacturing method of resin sheet

The manufacturing method of the resin sheet 1 of present embodiment is not particularly limited, for example, will containing above-mentioned resin combination, And the coating fluid according to required and further containing solvent or decentralized medium is coated on the second support chip 12, and is made it dry (making its heat cross-linking according to required), resin composition layer 10 is consequently formed.It then, can be by the way that in addition prepare first be supported It is that the face of 112 side of adhering agent layer of piece 11 is fitted in the resin composition layer 10 on the second support chip 12 is opposite side face and It is manufactured.In addition, the manufacturing method of the first support chip 11 is also not particularly limited, it is able to use well known method system It makes.

As coating method, spin-coating method, spray coating method, stick coating method, scraper for coating method (knife coating can be enumerated Method), rolling method, roller knife rubbing method, scraping blade rubbing method (blade coating method), die coating methods, intaglio plate apply Method well known to cloth method etc..

In addition, the organic solvent etc. of toluene, ethyl acetate, methyl ethyl ketone can be enumerated as above-mentioned solvent.

6. the purposes of resin sheet

The resin sheet 1 of present embodiment can be used in the formation of insulating film.More specifically, in built-in substrate, more In the semiconductor devices such as layer printed wiring board, fan-out-type wafer-level packaging, fan-out-type face Board level packaging, it can be suitably used for absolutely The formation etc. of velum.More specifically, the resin sheet 1 of present embodiment can be suitably used to form base built in component It is exhausted in the increasing layer layers of semiconductor devices such as plate, multilayer printed-wiring board, fan-out-type wafer-level packaging, fan-out-type face Board level packaging Velum.

[semiconductor device]

The semiconductor device of present embodiment have the resin composition layer 10 in the resin sheet 1 of present embodiment solidification and At cured layer as insulating film.As the example of such semiconductor device, built-in substrate, multi-sheet printed can be enumerated Wiring plate etc..These semiconductor devices can be by using the resin sheet 1 of present embodiment and according to aftermentioned method system It makes.

As described above, the resin sheet 1 of present embodiment is not easy at the interface of resin composition layer 10 and the first support chip 11 Float, and can easily remove the first support chip 11 from cured layer made of 10 heat cure of resin composition layer.Cause This, using the resin sheet 1 manufacture present embodiment semiconductor device by using above-mentioned present embodiment resin sheet 1 into Row manufacture, to have good quality.

[application method of resin sheet]

The resin sheet 1 of present embodiment for example can be used in the manufacturing method of semiconductor device.Hereinafter, to having by implementing Manufacturing method of the cured layer as the semiconductor device of insulating film made of the resin composition layer 10 of the resin sheet 1 of mode solidifies It is illustrated.The sectional view for illustrating an example of the manufacturing method is shown in Fig. 2 and Fig. 3.Firstly, as shown in (a) of Fig. 2, As preparatory process, electronic component 2 is mounted on a temporarily face of fixed material 8.Electronic component 2 is mounted on temporarily solid The method determined on material 8 is not particularly limited, and usual way can be used.

As above-mentioned temporary fixed material 8, as long as electronic component 2 can be temporarily fixed on the temporary fixed material 8 Be not particularly limited, can be the adhesive sheet that is made of substrate and stacking adhering agent layer on the substrate, can for The substrate of tack can be rigid support plate, or may be by rigid support plate and to be layered on the rigid support plate Adhering agent layer constitute laminate component.Alternatively, being also able to use the resin sheet of present embodiment as temporary fixed material 8 1.At this point, what electronic component 2 was arranged in cured resin composition layer 10 is on the face of opposite side with the first support chip 11.Such as This, when using the resin sheet 1 of present embodiment as temporary fixed material 8, can carry out as described later for shape simultaneously At sealing resin layer 13 ' heating and be used to form the heating of insulating film 10 ', process can be made to simplify.

As above-mentioned electronic component 2, if it is not particularly limited for the electronic component usually as sealed object, such as Semiconductor chip etc. can be enumerated.Further, above-mentioned electronic component 2 can also be carried in the specified position of intermediary layer (interposer) It is equipped with semiconductor chip.At this point, in the state of being loaded by this method, at least part of intermediary layer also with the semiconductor core Piece etc. is sealed together.As the example of above-mentioned intermediary layer, lead frame, Kapton Tape, printed base plate etc. can be enumerated. Further, the frame being made of metals such as copper, resin system can also be set around the electronic component 2 on temporary fixed material 8 The frames such as frame (also referred to as frame member).At this point, can also by least part of the frame member with the electronic component 2 together Sealing.Above-mentioned frame member is usually made of 1 or more opening portion and frame-shaped portion, which runs through comprising through-thickness Hole；The frame-shaped portion is made of copper etc. or resin etc..

When using above-mentioned frame member, in preparatory process, for example, above-mentioned frame member is positioned in temporarily fixed material After on 8 face, electronic component 2 is positioned in the position of the opening portion of above-mentioned frame member.As a result, in subsequent resin It in composition layer lamination process, is able to suppress sealing resin and is exuded to except opening portion, obtained semiconductor device can be made Thickness it is uniform, be further able to inhibit sealing resin layer occur warpage, be able to suppress the warpage of obtained semiconductor device.

Then, the surface side for being provided with electronic component 2 of temporary fixed material 8 is sealed.As encapsulating method, it is able to use Known method carries out, as an example, to the case where using the diaphragm seal being made of sealing material to be sealed into Row explanation.As shown in (b) of Fig. 2, diaphragm seal 13 is layered in the surface side for being provided with electronic component 2 of temporarily fixed material 8.By This, the electronic component 2 being arranged on temporarily fixed material 8 is covered by diaphragm seal 13.When diaphragm seal 13 is laminated, preferably not in electricity The mode that space is generated around subassembly 2 is laminated.Diaphragm seal 13 be able to use known laminater and with It is laminated under the conditions of toward well known stacking.

Then, as shown in (c) of Fig. 2, as curing process, diaphragm seal 13 is solidified to form sealing resin layer 13 '. The solidification is preferably carried out by heating diaphragm seal 13.By the solidification, can obtain having sealing resin layer 13 ' and being sealed The seal 4 for the electronic component 2 that resin layer 13 ' seals.The solidification of diaphragm seal 13 preferably for example by 100 DEG C~240 DEG C, It heats 15 minutes~300 minutes and carries out.

Then, as shown in (d) of Fig. 2, it will temporarily fix material 8 and be removed from seal 4.

Then, as shown in (b) of (a) of Fig. 3 and Fig. 3, insulating film formation process is carried out.Firstly, as shown in (a) of Fig. 3, By being stacked in for the surface layer of opposite side by temporary with the first support chip 11 for the resin composition layer 10 of the resin sheet 1 of present embodiment When fixed material 8 removing and in the exposed surface of seal 4 exposed.Then, as shown in (b) of Fig. 3, by by the resin group It closes nitride layer 10 to solidify, forms cured layer as insulating film 10 '.The solidification is preferably carried out by heating, is heated for example excellent It is selected at 100 DEG C~240 DEG C of temperature and heats 15 minutes~300 minutes.In addition, the resin composition layer 10 based on above-mentioned heating Solidification is preferably handled by heating for multiple times and is periodically carried out.

Then, as shown in (c) of Fig. 3, the first support chip 11 is removed from insulating film 10 '.

Herein, when the sticker for constituting adhering agent layer 112 contains above-mentioned active energy ray-curable sticker, preferably Solidify adhering agent layer 112 and irradiating active energy beam to adhering agent layer 112.11 pairs of first support chip insulation as a result, The adhesion strength of film 10 ' reduces, and can easily remove the first support chip 11.As active energy beam, be able to use ultraviolet light, Electron beam etc..When irradiating ultraviolet light, be able to use high-pressure mercury-vapor lamp, photocuring H lamp (Fusion H lamp), xenon lamp etc. into Row, about ultraviolet irradiation amount, is preferably set as 50mW/cm for illumination²Above, 1000mW/cm²Hereinafter, light quantity is set as 50mJ/cm²Above, 1000mJ/cm²Below.In irradiating electron beam, it is able to use the progress such as electron-beam accelerator, it preferably will be electric The exposure of beamlet is set as 10krad or more, 1000krad or less.In addition, making when containing active energy ray-curable sticker For constitute adhering agent layer 112 sticker when, preferably supporting base material 111 is transmissive to active energy beam.Thereby, it is possible to across Supporting base material 111 irradiates active energy beam to adhering agent layer 112.

When the sticker for constituting adhering agent layer 112 contains above-mentioned thermally foamable sticker, preferably pass through heating first Blade 11 in adhering agent layer 112 so that generate foaming.The first support chip 11 reduces the adhesion strength of insulating film 10 ' as a result, can Easily the first support chip 11 is removed.As the means heated, such as it is able to use heating plate, air drier, close The heating meanss such as infrared lamp, dried-air drier (air dryer), infrared lamp, heating water.Heating condition can be according to foaming Heat resistance, heating means (thermal capacity, heating means etc.) of type, supporting base material 111 or the insulating film 10 ' of agent etc. etc. and it is appropriate Ground setting, particularly preferred heating temperature are the foaming initial temperature of the foaming agent (heat-expandable microsphere etc.) in adhering agent layer 112 Temperature more than (thermal expansion initial temperature).Under common heating condition, temperature be 100 DEG C or more, 250 DEG C hereinafter, use Heating time whens heating plate etc. is 1 second or more, 90 seconds hereinafter, heating time whens using air drier etc. be 5 minutes with Above, 15 minutes or less.In addition, for generated in adhering agent layer 112 foaming heat treatment can according to use purpose and in need The stage wanted carries out, such as can also carry out together with the cured heat treatment for resin composition layer 10.

When the sticker for constituting adhering agent layer 112 contains above-mentioned thermosetting property sticker, preferably pass through heating adhering agent layer 112 to be such that adhering agent layer 112 solidifies.The first support chip 11 reduces the adhesion strength of insulating film 10 ' as a result, can easily by The removing of first support chip 11.As at this time heating means and heating condition, it is viscous as constituting when containing thermally foamable sticker The sticker of oxidant layer 112 when, it is preferable to use heating means as described above and heating condition.

After first support chip 11 is removed from insulating film 10 ', by known any means to 10 ' shape of insulating film At electrode.Hereinafter, being illustrated to the example for using semi-additive process and being formed.

As shown in (d) of Fig. 3, the hole 5 for running through insulating film 10 ' is formed.Specifically, being formed from insulating film 10 ' and electricity Subassembly 2 is that the face of opposite side starts the hole 5 for being through to the interface of insulating film 10 ' and electronic component 2.In the section of (d) of Fig. 3 In figure, shows and the case where there are two hole 5 is formed to an electronic component 2.The formation in hole 5 is able to use usual way progress.

Then, as desmearing treatment process, the seal 4 for being formed with the insulating film 10 ' in hole 5 will be laminated and be exposed to alkali Property solution.The process is able to use known usual way and carries out.

Finally, as electrode forming process, forming electrode 6 in hole 5 as shown in (e) of Fig. 3.6 through hole 5 of electrode It is electrically connected with electronic component 2.The formation of electrode 6 is able to use usual way progress.To sum up, it can obtain having insulating film 10 ' semiconductor device, insulating film 10 ' are solidified by the resin composition layer 10 of the resin sheet 1 of present embodiment.

In addition, the example that electrode is formed on insulating film 10 ' is illustrated in (d) of Fig. 3 and (e) of Fig. 3, But hole formation can also be carried out to any one of sealing resin layer 13 ' and insulating film 10 ' and electrode is formed, or can also be right Both sealing resin layer 13 ' and insulating film 10 ' carry out hole formation and electrode is formed.

The application method of resin sheet 1 according to the present embodiment also can be effective even if resin sheet 1 is refrigerated keeping Ground inhibition floats in resin composition layer 10 and the interface of support chip, while by the first support chip 11 easily from insulating film It is removed on 10 ', as a result, it is possible to improve yield rate, built-in substrate, the multilayer printed circuit of high quality can be manufactured The semiconductor devices such as plate, fan-out-type wafer-level packaging, fan-out-type face Board level packaging.

The implementation described above be for easy understanding the present invention and records, be not intended to limit it is of the invention and It records.Therefore, the objective of each element disclosed in above embodiment also includes to belong to the whole of technical scope of the invention Design alteration and equipollent.

Embodiment

Hereinafter, the present invention is described in more detail by showing embodiment and test example etc., but it is of the invention Not by any restriction of following test examples etc..

[embodiment 1]

The manufacture of (1) first support chip

By acrylate copolymer (92.8 mass % of 2-EHA, 7.0 mass % of acrylic acid 2- hydroxy methacrylate And the copolymer of 0.2 mass % of acrylic acid) 40 mass parts, the two terminal hydroxyl hydrogenated butadiene polymer (NIPPON as tackifier SODA CO., LTD. manufacture, name of product " GI-1000 ") 5 mass parts, as crosslinking agent there is hexa-methylene diisocyanate Aliphatic category isocyanates (manufacture of Nippon Polyurethane Industry Co., Ltd., the name of product of ester " CORONATE HX ") 3.5 mass parts are mixed in methyl ethyl ketone, prepare the sticker that solid component concentration is 30 mass % The coating fluid of composition.

Then, the coating fluid of prepared adhesion agent composition is coated on using roll coater and utilizes silicone remover pair One face of polyethylene terephthalate film carried out lift-off processing stripping film (LINTEC CORPORATION manufacture, Name of product " SP-PET382150 ", thickness: 38 μm) lift-off processing face on, with 90 DEG C heat 90 seconds, then with 115 DEG C Heating 90 seconds, after thus making dried coating film, is fitted in the transparent polyethylene terephthalate film as supporting base material (TOYOBO CO., LTD. manufacture, name of product " PET50A-4300 ", thickness: 50 μm, glass transition temperature Tg: 67 DEG C, MD Direction percent thermal shrinkage: the direction 1.2%, CD percent thermal shrinkage: 0.6%) on a face, thus on the face upper layer of adhering agent layer side The state for being laminated with stripping film manufactures the first support chip being made of the adhering agent layer and supporting base material, and the adhering agent layer is by thickness It is constituted for 50 μm of acrylic compounds stickers.

In addition, obtained adhering agent layer at 100 DEG C, will measure storage modulus of frequency when being set as 1Hz be 2.36 × 10⁵pa.In addition, obtained first support chip is 1.2N/25mm to the adhesion strength of copper foil.In addition, the first support chip is to polyamides The adhesion strength of imines film is 1.1N/25mm.In addition, 5% weightless temperature of adhering agent layer is 304 DEG C.These physics values by with Under method be measured.

(measurement of storage modulus)

For the adhering agent layer for being laminated to thickness and adding up to 3mm, the cylindrical body (thickness 3mm) that punching diameter is 8mm, and will It is as sample.Determination of viscoelasticity device (REOMETRIC corporation is used according to JIS K7244-6:1999 for the sample Make, name of product " DYNAMIC ANALYZER ") and by torsional shear method, to measure frequency: 1Hz and measuring temperature: 100 DEG C Condition measure storage modulus (Pa).

(to the adhesion strength of copper foil and polyimide film)

By the first support chip severing growth 100mm, width 25mm, the first support chip of stripping film will have been removed as test Piece is heated, then after pressurizeing 20 minutes with 0.5MPa, 50 DEG C to be attached at copper foil with the condition of 100 DEG C and 30 minutes It is heated with the condition of 180 DEG C and 60 minutes, then (23 DEG C, 50%RH) are placed 24 hours under standard environment.Then, In Under standard environment (23 DEG C, 50%RH), using cupping machine, (Shimadzu Corporation is manufactured, name of product " AUTOGRAPH AG-IS "), with 180 ° of peel angle, 300mm/ minutes peeling rates, by the first support chip from copper foil Removing measures adhesion strength (mN/25mm).In addition, in addition to the attaching object of the first support chip is changed to acid imide film from copper foil In addition, the above-mentioned adhesion strength to polyimide film is measured with the measuring method of adhesion strength similar to the above.

(measurement of 5% weightless temperature)

For adhering agent layer, using the hot thermogravimetric amount of differential simultaneously measurement device (Shimadzu Corporation is manufactured, Name of product " DTG-60 "), inflow gas is set as nitrogen, with 20 DEG C gas inflow velocity 100ml/min, heating rate/min It is set to be warming up to 550 DEG C from 40 DEG C, to carry out thermogravimetric amount measurement (according to " the thermogravimetric amount measurement side of plastics JIS K7120 Method ").Based on obtained thermogravimetric curves, find out relative to the quality at 100 DEG C of temperature, the temperature (5% of Mass lost 5% Weightless temperature).

(2) formation of cured resin composition layer

It will be as the bisphenol A-type phenoxy resin of thermoplastic resin (Mitsubishi Chemical Corporation system Make, name of product " jER1256 ") 5.1 mass parts (solid component conversion, same as below), as the bisphenol A-type of thermosetting resin Epoxy resin (Mitsubishi Chemical Corporation manufacture, name of product " jER828 ") 5.7 mass parts, conduct The biphenyl type epoxy resin (manufacture of Nippon Kayaku Co., Ltd., name of product " NC-3000-L ") 5.7 of thermosetting resin Mass parts, the naphthalene type epoxy resin (DIC CORPORATION manufacture, name of product " HP-4700 ") 4.1 as thermosetting resin Mass parts, biphenyl type phenol (MEIWA PLASTIC INDUSTRIES, LTD. manufacture, name of product as thermosetting resin " MEHC-7851-SS ") 14.1 mass parts, the 2-ethyl-4-methylimidazole (SHIKOKU as imidazoles curing catalysts CHEMICALS CORPORATION. manufacture, name of product " 2E4MZ ") 0.1 mass parts and the epoxy silane as inorganic particles Handle silica filler [using 3- glycidyl ether oxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. it manufactures, name of product " KBM-403 ", minimum vertex-covering area: 330m²/ g) to silica filler (Admatechs. system Make, name of product " SO-C2 ", average grain diameter: 0.5 μm, maximum particle diameter: 2 μm, shape: spherical) be surface-treated made of fill out Material] 65 mass parts are mixed in methyl ethyl ketone, obtain the coating fluid for the resin combination that solid component concentration is 40 mass %.

Will as described above obtained from coating fluid be coated on it is as the second support chip, using alcohol acids remover to poly- pair One face of ethylene terephthalate film has carried out stripping film (LINTEC CORPORATION manufacture, the product of lift-off processing Title " PET38AL-5 ", thickness: 38 μm) lift-off processing face on, thus obtained dried coating film obtains with a thickness of 20 μ The laminated body of the cured resin composition layer of m and the second support chip.

(3) manufacture of resin sheet

It will be removed on the first support chip that stripping film is manufactured from the above-mentioned operation (1), and by the dew of the adhering agent layer of exposing It appears to close with the face paste of the cured resin composition layer side of the laminated body manufactured in above-mentioned operation (2), thus obtains successively layer Resin sheet made of folded first support chip, cured resin composition layer and the second support chip.

[embodiment 2]

Lift-off processing has been carried out using using a face of the non-silicone remover to polyethylene terephthalate film Stripping film (LINTEC CORPORATION manufacture, name of product " SP-PET38X ", thickness: 38 μm) be used as the second support chip, In addition to this, resin sheet is obtained in the same manner as example 1.

[embodiment 3]

Use the adhesion that stacking is made of thermally foamable sticker on a face of polyethylene terephthalate film Piece made of oxidant layer (Nitto Denko Corporation manufacture, name of product " REVALPHA ") is used as the first support chip, removes Other than this, resin sheet is obtained in the same manner as example 1.

[embodiment 4]

Propylene obtained from reacting the own 86 mass % of ester of acrylic acid 2- hydroxyl with 14 mass % of acrylic acid 2- hydroxy methacrylate 100 mass parts of acid copolymer are reacted with 15 mass parts of 2- methylacryoyloxyethyl isocyanates, obtain active energy The polymer of ray-curable.By 100 mass parts of polymer of the active energy ray-curable, as the first of crosslinking agent Phenylene diisocyanate class crosslinking agent (manufacture of Nippon Polyurethane Industry Co., Ltd., name of product " CORONATE L ") 8 mass parts and the 2,2- dimethoxy -1,2- diphenylethane -1- ketone as Photoepolymerizationinitiater initiater (manufacture of Ciba Specialty Chemicals company, name of product " IRGACURE 651 ") 5 mass parts are mixed in methyl second In base ketone, the coating fluid of adhesion agent composition is obtained.

The coating fluid is coated on and is carried out using a face of the silicone remover to polyethylene terephthalate film The stripping film of lift-off processing (LINTEC CORPORATION manufacture, name of product " SP-PET382150 ", thickness: 38 μm) On lift-off processing face, and by thus obtained dried coating film.Then, being fitted in the film with stripping film for the face of opposite side Transparent polyethylene terephthalate film (TOYOBO CO., LTD. manufacture, name of product " PET50A- as supporting base material 4300 ", thickness: 50 μm, glass transition temperature: 67 DEG C, the percent thermal shrinkage in the direction MD: the percent thermal shrinkage in the direction 1.2%, CD: 0.6%) on a face.Obtain stacking gradually laminated body made of supporting base material, adhering agent layer and stripping film as a result,.Into one Step obtains the first support chip for having supporting base material and adhering agent layer by removing stripping film from the laminated body, described viscous Oxidant layer be layered on a face of the supporting base material and be made of active energy ray-curable sticker.

Other than using above-mentioned first support chip, resin sheet is obtained in the same manner as example 1.

[comparative example 1]

Lift-off processing has been carried out using using a face of the silicone remover to polyethylene terephthalate film Stripping film (LINTEC CORPORATION manufacture, name of product " SP-PET3811 ", thickness: 38 μm) is used as the first support chip, And the stripping film of lift-off processing has been carried out using using a face of the silicone remover to polyethylene terephthalate film (LINTEC CORPORATION manufacture, name of product " SP-PET381031 ", thickness: 38 μm) is used as the second support chip, removes this In addition, resin sheet is obtained in the same manner as example 1.

[comparative example 2]

Polyethylene terephthalate (PET) film (thickness: 38 of lift-off processing is not carried out using remover using two sides μm) it is used as the first support chip, and carried out using using a face of the silicone remover to polyethylene terephthalate film The stripping film of lift-off processing (LINTEC CORPORATION manufacture, name of product " SP-PET381031 ", thickness: 38 μm) is made Resin sheet is obtained in the same manner as example 1 in addition to this for the second support chip.

[test example 1] (evaluation of the fissility after heat cure)

The resin sheet manufactured in Examples and Comparative Examples is cut into the size of 500mm × 400mm.Then, by second Blade is removed from resin sheet, after the cured resin composition layer of exposing is layered on copper sheet, heats 30 points with 100 DEG C Clock is further heated 60 minutes with 180 DEG C, thus solidifies cured resin composition layer.Then, by curable resin Cured layer made of composition layer solidification is cooled to room temperature.

After the completion of the cooling of cured layer, for the resin sheet of embodiment 3,20 seconds are heated with 200 DEG C using baking oven, thus Heating constitutes the sticker of the adhering agent layer of the first support chip and makes its foaming.Then, after resin sheet being cooled to room temperature, by One support chip is removed from cured layer.

In addition, irradiating ultraviolet light by the adhering agent layer to the first support chip for the resin sheet of embodiment 4, keep this viscous Oxidant layer solidification.Then, the first support chip is removed from cured layer.

For the resin sheet of embodiment 1 and 2 and comparative example 1 and 2, after the cooling for completing cured layer, without heating Or ultraviolet light irradiation etc processing and the first support chip is removed from cured layer.

For situation when as described above removing the first support chip from cured layer, based on standard below evaluation heat Fissility after solidification.Show the result in table 1.

A: the first support chip can be removed.

B: the first support chip can not be removed.

(test example 2) (evaluation floated when keeping)

The resin sheet manufactured in Examples and Comparative Examples is cut into the size of 500mm × 400mm, and in 5 DEG C of environment The generation floated and curability after lower keeping 1 week, in the interface of confirmation cured resin composition layer and the first support chip The generation floated in the interface of resin composition layer and the second support chip, and floating when taking care of is evaluated based on standard below It rises.Show the result in table 1.

A: the interface and cured resin composition layer of cured resin composition layer and the first support chip and second The interface of blade does not float.

AB: do not float in cured resin composition layer and the interface of the first support chip, but in curable resin group It closes nitride layer and the interface of the second support chip is floated.

B: the interface and cured resin composition layer of cured resin composition layer and the first support chip and second The interface of blade is floated.

[test example 3] (measurement of peeling force)

For the resin sheet manufactured in embodiment 1 and 2, using following methods measurement by the first support chip from tree before curing Peeling force (F11) when being removed on oil/fat composition layer, by the first support chip from cured layer made of resin composition layer heat cure Peeling force (F12) when upper removing.In addition, measurement is by the second support chip from admittedly for the resin sheet manufactured in Examples 1 to 4 Peeling force (F2) when being removed on the resin composition layer before change.Show the result in table 1.

(1) measurement of peeling force (F11)

The resin sheet manufactured in embodiment 1 and 2 is cut into wide 25mm, long 250mm.Then, the second support chip is removed, The exposed surface of the cured resin composition layer of exposing is fitted in into stainless steel plate using double faced adhesive tape, to manufacture measurement sample Product.Then, it is based on JIS Z 0237:2009, (Shimadzu Corporation is manufactured using universal tensile testing machine AUTOGRAPH), in the environment of 23 DEG C, relative humidity 50%, with peeling rate 300mm/ minutes, 180 ° of peel angle, by One support chip is removed from cured resin composition layer, measures its peeling force (N/25mm), and as peeling force (F11)。

(2) measurement of peeling force (F12)

30 minutes are heated with 100 DEG C to the measurement sample manufactured in a manner of identical with above-mentioned (1), further with 180 DEG C Heating 60 minutes, thus solidifies cured resin composition layer.Then, cured resin composition layer is solidified Cured layer be cooled to room temperature.For measurement sample after cooling, peeling force (N/ is measured in a manner of identical with above-mentioned (1) 25mm), and as peeling force (F12).

(3) measurement of peeling force (F2)

The resin sheet manufactured in Examples 1 to 4 is cut into wide 100mm, long 100mm.Then, it is based on JIS K6854-3: 1999, in the environment of 23 DEG C, relative humidity 50%, with peeling rate 300mm/ minutes, by T-type removing by the second support chip It is removed from cured resin composition layer, measures peeling force (N/100mm) at this time, and as peeling force (F2).

[test example 4] (evaluation of the formative of electrode)

Second support chip is removed from the resin sheet manufactured in Examples 1 to 4, uses vacuum laminator (Nikko The manufacture of materials company, name of product " V130 "), the curable resin of exposing is combined with 90 DEG C and 0.3MPa of condition Nitride layer surface layer is stacked in a face of core material (manufacture of Hitachi Chemical Co., Ltd., name of product " MCL-E-679FG ") On.Then, with 100 DEG C heat 30 minutes, further with 180 DEG C heat 60 minutes, thus cured resin composition layer is consolidated Change.

Then, it for embodiment 3, is heated 20 seconds using baking oven in 200 DEG C, constitutes the viscous of the first support chip to heat The sticker of oxidant layer and make its foaming.In addition, being irradiated by the adhering agent layer to the first support chip ultraviolet for embodiment 4 Line, so that the adhering agent layer be made to solidify.Then, for each example, the first support chip is removed from cured layer.As a result, To the laminated body being made of core material with the cured layer as insulating layer.

Then, using CO₂Laser machine is to the surface irradiation laser of the insulating layer side of obtained laminated body, in insulating layer Surface forms the through-hole (via hole) that diameter is 100 μm.

Then, by laminated body with 60 DEG C in the alkaline swelling solution that glycol ethers solvent and ethylene glycol monobutyl ether mix Dipping 5 minutes.Then, by the laminated body with 80 DEG C of dipping 15 minutes in coarsening solution (alkaline permanganic acid aqueous solution).Further, By the laminated body is impregnated in the aqueous solution of sulfuric acid with 40 DEG C carry out within 5 minutes in and.Finally, by by the laminated body in 80 DEG C of dryings 5 minutes and complete desmearing processing.

Then, the laminated body for having carried out desmearing processing is impregnated 6 minutes in electroless plating solution with 40 DEG C, into After one step is impregnated 18 minutes in electroless plating copper liquid with 25 DEG C, carry out making annealing treatment for 30 minutes in 150 DEG C.Then, it will be electroplated The face for being formed with through-hole is fitted in resist layer, by exposing, developing, removing in the plating resist layer has regulation The region of pattern (cloth line width (L): 50 μm, routing space (S): 50 μm).Then, copper sulfate bath plating is carried out, is gone above-mentioned The region removed forms the layer being made of the copper of 10 μ m-thicks.Then, remaining plating is removed with resist layer, and by rapidly losing It carves (flash etching) to remove unwanted electroless copper-plated parts, finally carries out making annealing treatment for 60 minutes in 190 DEG C.

The electrode being formed as described above is observed, standard below is based on, evaluates the formative of electrode.Show the result in table 1。

Zero: be capable of forming have meet expected wiring pattern (cloth line width (L): 50 μm, routing space (S): 50 μm) Electrode.

×: it can not be formed with the electrode for meeting expected wiring pattern.

[table 1]

It as shown in table 1, also can be good from cured layer by the first support chip even if the resin sheet of embodiment is after heat cure It removes well.In addition, when the resin sheet of embodiment can inhibit keeping between the first support chip and cured resin composition layer Float.On the other hand, the resin sheet of comparative example 1 is floated in keeping.In addition, the resin sheet of comparative example 2 is being set After the heat cure of oil/fat composition layer, support chip can not be removed from being formed by cured layer.

Industrial applicibility

Resin sheet of the invention can be suitably used for built-in substrate, multilayer printed-wiring board, fan-out-type wafer scale In the manufactures of semiconductor devices such as encapsulation, fan-out-type face Board level packaging.

Description of symbols

1: resin sheet；10: cured resin composition layer；10 ': insulating film；11: the first support chips；111: supporting base material； 112: adhering agent layer；12: the second support chips；2: electronic component；4: seal；5: hole；6: electrode；8: temporarily fixing material；13: Diaphragm seal；13 ': sealing resin layer.

Claims

1. a kind of resin sheet is used for the formation of insulating film, which is characterized in that

The resin sheet has the first support chip and the curable resin being layered on a face of first support chip combination Nitride layer,

The resin composition layer is formed by the resin combination containing thermosetting resin and inorganic particles,

The inorganic particles the content in the resin combination be 50 mass % or more, 90 mass % hereinafter,

First support chip has supporting base material and is layered in the adhering agent layer of a surface side of the supporting base material,

The resin composition layer is layered on the face of the adhering agent layer side of first support chip.

2. resin sheet according to claim 1, which is characterized in that

The resin composition layer contains thermoplastic resin,

The thermoplastic resin is 1.0 mass % or more, 30 mass % or less in the content in the resin combination.

3. resin sheet according to claim 1 or 2, which is characterized in that the adhering agent layer is by acrylic compounds sticker structure At.

4. resin sheet described in any one of claim 1 to 3, which is characterized in that the adhering agent layer is by selected from activity At least one of energy ray-curable sticker, thermally foamable sticker and thermosetting property sticker sticker is constituted.

5. resin sheet according to any one of claims 1 to 4, which is characterized in that adding the resin sheet with 100 DEG C Heat 30 minutes further heated with 180 DEG C in 60 minutes resin sheets, by first support chip from the resin combination Peeling force (F12) when removing on cured layer made of layer solidifies is 0.5N/25mm or more, 3.0N/25mm or less.

6. resin sheet according to any one of claims 1 to 5, which is characterized in that described in first support chip Storage modulus of the adhering agent layer at 100 DEG C, when measurement frequency is set as 1Hz is 1 × 10⁵Pa or more.

7. resin sheet described according to claim 1~any one of 6, which is characterized in that

The adhering agent layer face paste of first support chip is invested into copper foil, is heated with the condition of 100 DEG C and 30 minutes, Then it is heated with the condition of 180 DEG C and 30 minutes, it is described after further being heated with the condition of 190 DEG C and 1 hour The adhesion strength to the copper foil of first support chip at room temperature be 0.7N/25mm or more, 2.0N/25mm hereinafter,

The adhering agent layer face paste of first support chip is invested into polyimide film, with 100 DEG C and 30 minutes of condition into Row heating, is then heated with the condition of 180 DEG C and 30 minutes, further carries out heating it with 190 DEG C and 1 hour of condition Afterwards, the adhesion strength to the polyimide film of the first support chip at room temperature is 0.7N/25mm or more, 2.0N/25mm or less.

8. resin sheet according to any one of claims 1 to 7, which is characterized in that described in first support chip 5% weightless temperature of adhering agent layer is 250 DEG C or more.

9. resin sheet described according to claim 1~any one of 8, which is characterized in that the thermoplastic resin is selected from benzene At least one of oxygroup resinoid, polyvinyl acetal-based resin and polyvinyl butyral resin.

10. resin sheet described according to claim 1~any one of 9, which is characterized in that the inorganic particles are using at surface Reason agent is surface-treated.

11. resin sheet described according to claim 1~any one of 10, which is characterized in that the average grain of the inorganic particles Diameter is 0.01 μm or more, 3.0 μm or less.

12. resin sheet described according to claim 1~any one of 11, which is characterized in that the thickness of the resin composition layer Degree is 5 μm or more, 80 μm or less.

13. resin sheet described according to claim 1~any one of 12, which is characterized in that the supporting base material is vitrifying The supporting base material for the resin that transition temperature (Tg) is 50 DEG C or more.

14. resin sheet described according to claim 1~any one of 13, which is characterized in that the resin sheet, which has, to be layered in The resin composition layer is the second support chip on the face of opposite side with first support chip.

15. resin sheet described according to claim 1~any one of 14, which is characterized in that it is used in semiconductor device The formation of the insulating film.

16. resin sheet according to claim 15, which is characterized in that the insulating film is the increasing layer of the semiconductor device Insulating film in layer.

17. resin sheet according to claim 15 or 16, which is characterized in that the semiconductor device is base built in component At least one of plate, multilayer printed-wiring board, fan-out-type wafer-level packaging and fan-out-type face Board level packaging.

18. a kind of insulating film, which is characterized in that it is by by the resin of resin sheet described in any one of claim 1~17 Composition layer solidifies.

19. a kind of semiconductor device, which is characterized in that it has the resin sheet as described in any one of claim 1~17 Cured layer made of resin composition layer solidification is as insulating layer.

20. a kind of application method of resin sheet is the application method of resin sheet described in any one of claim 1~17, It is characterized in that, it has:

The resin composition layer is solidified to the process for obtaining cured layer；And

After the solidification of the resin composition layer, process that first support chip is removed from the cured layer.