WO2019044398A1

WO2019044398A1 - Resin sheet, semiconductor device and method for using resin sheet

Info

Publication number: WO2019044398A1
Application number: PCT/JP2018/029431
Authority: WO
Inventors: 裕介根津; 康貴渡邉; 貴志杉野
Original assignee: リンテック株式会社
Priority date: 2017-08-31
Filing date: 2018-08-06
Publication date: 2019-03-07
Also published as: CN110536796A; JPWO2019044398A1; KR20200047447A; TW201919873A

Abstract

A resin sheet 1 which is used for the formation of an insulating film; and this resin sheet 1 comprises a first supporting sheet 11 and a curable resin composition layer 10. The resin composition layer 10 is formed from a resin composition that contains a thermosetting resin and inorganic fine particles; and the content of the inorganic fine particles is from 50% by mass to 90% by mass (inclusive). The first supporting sheet 11 comprises a supporting substrate 111 and an adhesive layer 112; and the resin composition layer is laminated on the adhesive layer 112-side surface of the first supporting sheet 11. This resin sheet 1 is not susceptible to the occurrence of adhesion loss at the interface between the resin composition layer and the supporting sheet even in cases where the resin composition layer has low surface tackiness; and in cases where this resin sheet 1 is used in a method for producing a semiconductor device, wherein the supporting sheet is separated from a cured layer after forming the cured layer by thermally curing the resin composition layer, the supporting sheet is easily separated from the cured layer.

Description

Resin sheet, semiconductor device, and method of using resin sheet

The present invention relates to a resin sheet used for forming an insulating film, a semiconductor device manufactured using the resin sheet, and a method of using the resin sheet.

In recent years, as a component built-in board in which a multilayer printed wiring board and electronic parts are built in an inner layer circuit board, from the viewpoint of achieving high functionality and miniaturization, a buildup system in which insulating films and conductor layers are alternately laminated Things have been proposed. In such a buildup type multilayer printed wiring board or component-embedded substrate, the insulating film can be formed using a resin sheet provided with a curable resin composition layer.

As the resin sheet as described above, in general, a resin sheet having a structure in which a support sheet is laminated on a resin composition layer may be used in order to improve the handleability at the time of processing or transport. For example, Patent Document 1 discloses, as such a resin sheet, an adhesive film comprising a thermosetting resin composition layer and a support laminated on one side of the thermosetting resin composition layer, Furthermore, a method of manufacturing a component built-in circuit board using the adhesive film is disclosed. For example, Patent Document 2 discloses a method of manufacturing a multilayer printed wiring board using a sheet in which a resin composition layer is laminated on a base material. In the method, after laminating a resin composition layer on a circuit board, the resin composition layer is thermally cured to form an insulating layer, and then the substrate is peeled off from the insulating layer.

In addition, since the resin sheet as described above usually contains a thermosetting resin such as an epoxy resin and a curing accelerator in the resin composition layer, the storage stability tends to be low, and therefore, it is necessary to store under refrigeration. There is a case.

JP, 2015-2295, A JP, 2014-7403, A

By the way, when the resin composition layer in the resin sheet is thermally cured to form a cured layer in a state where the support sheet is laminated on the resin composition layer, it may be difficult to peel the support sheet from the cured layer. For this reason, the peeling force at the time of peeling a support sheet from a hardened layer is reduced to a predetermined range by using as a support sheet the thing in which the field which touches a resin composition layer exfoliated by the silicone type release agent. It is also conceivable.

In the resin sheet described above, when using a resin composition layer having a high inorganic filler content or depending on the type of the resin component, there is also a resin sheet having a small tackiness (tack) on the surface of the resin composition layer. When the resin composition layer having such a small tack is protected by the support sheet treated with a silicone-based release agent as described above, the resin composition layer and the resin sheet are transported, stored, processed, etc. It becomes easy to generate float at the interface with the support sheet. When the floating occurs, problems such as chipping and cracking occur in the resin composition layer during processing and transportation of the resin sheet. In particular, resin sheets are often stored refrigerated, and the floating problem becomes significant when stored refrigerated in this manner.

Also, in recent years, it has been considered to manufacture a wafer level package and a panel scale package using a resin sheet. Although the thing which has a large area as a resin sheet is used for manufacture of such a package, when the size of a resin sheet becomes a comparatively large area, the float mentioned above becomes especially easy to occur.

As mentioned above, in the conventional resin sheet, it is difficult to simultaneously achieve peeling of the support sheet from the cured layer and suppression of the floating at the interface between the resin composition layer and the support sheet.

The present invention has been made in view of such a situation, and even when the tack on the surface of the resin composition layer is small, the floating at the interface between the resin composition layer and the support sheet does not easily occur. And, even when used in a method of manufacturing a semiconductor device in which the support sheet is peeled off from the formed cured layer after heat curing of the resin composition layer, a resin sheet which easily peels the support sheet from the hardened layer is provided. The purpose is to The invention also provides good quality semiconductor devices manufactured using such resin sheets, and methods of using such resin sheets.

In order to achieve the above object, firstly, the present invention is a resin sheet used for forming an insulating film, wherein the resin sheet is laminated on a first support sheet and one side of the first support sheet. And the resin composition layer is formed of a resin composition containing a thermosetting resin and inorganic fine particles, and the inorganic fine particles in the resin composition. Content is 50 mass% or more and 90 mass% or less, Said 1st support sheet is equipped with a support base material and the adhesive layer laminated | stacked on the single-sided side of said support base material, The said resin composition An object layer is laminated on the surface of the first support sheet on the pressure-sensitive adhesive layer side, and a resin sheet is provided (Invention 1).

In the resin sheet according to the invention (Invention 1), the first support sheet is provided with the support base and the pressure-sensitive adhesive layer, and the surface of the pressure-sensitive adhesive layer opposite to the support base is cured. By being in contact with the conductive resin composition layer, the first support sheet adheres well to the curable resin composition layer, whereby the interface between the curable resin composition layer and the first support sheet Even in the case where the first support sheet is peeled off from the cured layer formed by heat curing the curable resin composition layer, the peeling can be easily performed.

In the above invention (Invention 1), the resin composition layer contains a thermoplastic resin, and the content of the thermoplastic resin in the resin composition is 1.0% by mass or more and 30% by mass or less Is preferable (invention 2).

In the said invention (invention 1 and 2), it is preferable that the said adhesive layer is comprised from the acrylic adhesive (invention 3).

In the above inventions (Inventions 1 to 3), the pressure-sensitive adhesive layer is composed of at least one pressure-sensitive adhesive selected from an active energy ray-curable pressure-sensitive adhesive, a thermally foamable pressure-sensitive adhesive and a thermosetting pressure-sensitive adhesive. Is preferred (invention 4).

In the above inventions (Inventions 1 to 4), in the resin sheet obtained by heating the resin sheet at 100 ° C. for 30 minutes and further heating it at 180 ° C. for 60 minutes, the first cured layer is formed by curing the resin composition layer. It is preferable that peeling force (F12) at the time of peeling the support sheet of is 0.5 N / 25 mm or more and 3.0 N / 25 mm or less (invention 5).

In the above inventions (Inventions 1 to 5), the pressure-sensitive adhesive layer in the first support sheet preferably has a storage elastic modulus of 1 × 10 ⁵ Pa or more at 100 ° C. and a measurement frequency of 1 Hz. (Invention 6).

In the above inventions (Inventions 1 to 6), the first support sheet has the pressure-sensitive adhesive layer surface adhered to a copper foil, is heated at 100 ° C. for 30 minutes, and is subsequently heated to 180 ° C. for 30 minutes The adhesive strength at room temperature to the copper foil after heating at 190 ° C. for 1 hour is 0.7 N / 25 mm or more and 2.0 N / 25 mm or less, and the pressure-sensitive adhesive layer surface is It is attached to a polyimide film, heated under conditions of 100 ° C. and 30 minutes, subsequently heated under conditions of 180 ° C. and 30 minutes, and further heated under conditions of 190 ° C. and 1 hour, room temperature relative to the polyimide film It is preferable that the adhesive force in (7) is 0.7 N / 25 mm or more and 2.0 N / 25 mm or less.

In the above inventions (Inventions 1 to 7), the pressure-sensitive adhesive layer in the first support sheet preferably has a 5% weight loss temperature of 250 ° C. or more (Invention 8).

In the above inventions (Inventions 1 to 8), the thermoplastic resin is preferably at least one selected from phenoxy resins, polyvinyl acetal resins and polyvinyl butyral resins (Invention 9).

In the above inventions (Inventions 1 to 9), the inorganic fine particles are preferably surface-treated with a surface treatment agent (Invention 10).

In the above inventions (Inventions 1 to 10), the average particle diameter of the inorganic fine particles is preferably 0.01 μm or more and 3.0 μm or less (Invention 11).

In the above inventions (Inventions 1 to 11), the thickness of the resin composition layer is preferably 5 μm or more and 80 μm or less (Invention 12).

In the above inventions (Inventions 1 to 12), the support substrate is preferably a resin support substrate having a glass transition temperature (Tg) of 50 ° C. or more (Invention 13).

In the above inventions (Inventions 1 to 13), the resin sheet preferably includes a second support sheet laminated on the surface of the resin composition layer opposite to the first support sheet (Invention 14) ).

In the above inventions (Inventions 1 to 14), it is preferable to use for forming the insulating film in a semiconductor device (Invention 15).

In the above invention (Invention 15), the insulating film is preferably an insulation film in a buildup layer of the semiconductor device (Invention 16).

In the above inventions (Inventions 15 and 16), the semiconductor device is preferably at least one of a component built-in substrate, a multilayer printed wiring board, a fanout type wafer level package and a fanout type panel level package (Invention 17) .

Second, the present invention provides an insulating film formed by curing the resin composition layer in the resin sheet (Inventions 1 to 17) (Invention 18).

Thirdly, the present invention provides a semiconductor device comprising a cured layer obtained by curing the resin composition layer in the above-mentioned resin sheet (inventions 1 to 17) as an insulating layer (invention 19).

Fourth, the present invention is a method of using the resin sheet (inventions 1 to 17), wherein the step of curing the resin composition layer to obtain a cured layer, and after curing of the resin composition layer And removing the first support sheet from the cured layer. A method of using the resin sheet is provided (Invention 20).

According to the resin sheet of the present invention, even when the tack on the surface of the resin composition layer is small, it is difficult for the floating at the interface between the resin composition layer and the support sheet to occur, and the heat of the resin composition layer Even in the case of using the method for manufacturing a semiconductor device in which the supporting sheet is peeled off from the formed hardened layer after curing, the supporting sheet is easily peeled off from the hardened layer. Moreover, the semiconductor device which has favorable quality can be manufactured by using the resin sheet of this invention.

It is a sectional view of a resin sheet concerning one embodiment of the present invention. It is sectional drawing explaining the usage method of the resin sheet which concerns on this embodiment. It is sectional drawing explaining the usage method of the resin sheet which concerns on this embodiment.

Hereinafter, embodiments of the present invention will be described.
[Resin sheet]
FIG. 1 shows a cross-sectional view of the resin sheet 1 according to the present embodiment. As shown in FIG. 1, the resin sheet 1 according to the present embodiment includes a first support sheet 11 and a curable resin composition layer 10 laminated on one side of the first support sheet 11 (hereinafter referred to as “resin composition Object layer 10 "). The first support sheet 11 includes a support base 111 and an adhesive layer 112 laminated on one side of the support base 111, and the resin composition layer 10 has adhesion in the first support sheet 11. It is laminated on the surface on the agent layer 112 side. Moreover, the resin sheet 1 which concerns on this embodiment is provided with the 2nd support sheet 12 laminated | stacked on the surface on the opposite side to the 1st support sheet 11 in the resin composition layer 10, as FIG. 1 shows. Is preferred.

In the resin sheet 1 according to the present embodiment, since the resin composition layer 10 is laminated on the surface of the first support sheet 11 on the pressure-sensitive adhesive layer 112 side, the resin composition layer 10 and the first support sheet Lifting at the interface with 11 is less likely to occur. In particular, even when the tack on the surface of the resin composition layer 10 is small, the floating at the interface between the resin composition layer 10 and the first support sheet 11 can be effectively suppressed. Thereby, in the resin sheet 1 which concerns on this embodiment, generation | occurrence | production of the chipping and the crack in the resin composition layer 10 is suppressed at the time of storage or conveyance.

Further, in the resin sheet 1 according to the present embodiment, the resin composition layer 10 is laminated on the surface of the first support sheet 11 on the pressure-sensitive adhesive layer 112 side, so that the resin composition layer 10 is thermally cured. Thus, even when the hardened layer is formed, the first support sheet 11 can be easily peeled off from the hardened layer.

1. Curable Resin Composition Layer The resin composition layer 10 in the present embodiment is formed of a thermosetting resin and a resin composition containing inorganic fine particles. Here, the content of the inorganic fine particles in the resin composition is 50% by mass or more and 90% by mass or less. In addition, the resin composition layer 10 has curability, and a cured layer can be formed by curing the resin composition layer 10. The cured layer formed by curing the resin composition layer 10 exhibits insulation. It is preferable that the resin composition layer 10 does not contain a conductive material from the viewpoint of easily forming a cured layer exhibiting an insulating property. In addition, the cured layer preferably has a surface resistivity of 1 × 10 ¹⁵ Ω / □ or more, and more preferably 1 × 10 ¹⁶ Ω / □ or more. Thereby, in the obtained semiconductor device, defects such as short circuit can be suppressed, and excellent performance can be obtained.

(1) Thermosetting resin The thermosetting resin is not particularly limited, and examples thereof include epoxy resin, phenol resin, naphthol resin, active ester resin, benzoxazine resin, cyanate ester resin, etc. These can be used singly or in combination of two or more.

As the epoxy resin, various known epoxy resins can be used. Specifically, glycidyl ethers of phenols such as bisphenol A, bisphenol F, resorcinol, phenyl novolac, cresol novolac; butanediol, polyethylene glycol, Glycidyl ethers of alcohols such as polypropylene glycol; Glycidyl ethers of carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid; Glycidyl type or alkyl glycidyl in which active hydrogen bonded to a nitrogen atom such as aniline isocyanurate is substituted by glycidyl group Type epoxy resin; vinylcyclohexane diepoxide, 3,4-epoxycyclohexylmethyl-3,4-dicyclohexanecarboxylate, 2- (3,4-epoxy So-called cycloaliphatic epoxides, such as cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m-dioxane etc., in which an epoxy is introduced, eg by oxidation of the carbon-carbon double bond in the molecule Can be mentioned. In addition, an epoxy resin having a biphenyl skeleton, a triphenylmethane skeleton, a dicyclohexadiene skeleton, a naphthalene skeleton and the like can also be used. These epoxy resins can be used singly or in combination of two or more. Among the epoxy resins described above, glycidyl ether of bisphenol A (bisphenol A type epoxy resin), epoxy resin having biphenyl skeleton (biphenyl type epoxy resin), epoxy resin having naphthalene skeleton (naphthalene type epoxy resin), or a combination thereof It is preferred to use.

Examples of the phenolic resin include bisphenol A, tetramethyl bisphenol A, diallyl bisphenol A, biphenol, bisphenol F, diallyl bisphenol F, triphenylmethane-type phenol, tetrakisphenol, novolac-type phenol, cresol novolac resin, biphenylaralkyl skeleton The phenol which has (biphenyl type phenol) etc. is mentioned, It is preferable to use a biphenyl type phenol among these. These phenolic resins can be used singly or in combination of two or more. In addition, when using an epoxy resin as curable resin, it is preferable to use a phenol resin together from a viewpoint of the reactivity with an epoxy resin etc.

The content of the thermosetting resin in the resin composition is preferably 10% by mass or more, particularly preferably 15% by mass or more, and further preferably 20% by mass or more. In addition, the content is preferably 60% by mass or less, particularly preferably 50% by mass or less, and further preferably 40% by mass or less. When the content is 10% by mass or more, curing of the resin composition layer 10 becomes more sufficient, and a stronger insulating film can be formed. In addition, when the content is 60% by mass or less, curing of the resin composition layer 10 in an unintended stage can be further suppressed, and the storage stability becomes more excellent. In addition, the said content of a thermosetting resin is solid content conversion value.

(2) Thermoplastic Resin In addition, the resin composition in the present embodiment may contain a thermoplastic resin. The thermoplastic resin includes, for example, phenoxy resin, olefin resin, polyester resin, polyurethane resin, polyester urethane resin, acrylic resin, amide resin, styrene-isobutylene-styrene copolymer (SIS), etc. Styrene resin, silane resin, rubber resin, polyvinyl acetal resin, polyvinyl butyral resin, polyimide resin, polyamide imide resin, polyether sulfone resin, polysulfone resin, fluorine resin and the like can be mentioned. These can be used alone or in combination of two or more. Moreover, these thermoplastic resins may have a curable functional group.

Here, in the case of manufacturing a semiconductor device using the resin sheet 1 according to the present embodiment in order to miniaturize the semiconductor device and to miniaturize the wiring, a cured layer formed by curing the resin composition layer 10 By forming an electrode on top, a rewiring layer may be provided. In particular, in the case of providing a redistribution layer by a semi-additive method described later, in the process of desmearing, the hardened layer is treated under severe conditions such as being exposed to an alkaline solution. In this case, depending on the type of the thermoplastic resin, the cured layer may be dissolved, and the wiring formability such as a decrease in plating peel strength may be poor. Therefore, it is preferable that the thermoplastic resin does not contain an acrylic resin from the viewpoint of the wiring formation to the cured layer. As the thermoplastic resin, it is preferable to use at least one selected from the group consisting of phenoxy resins, polyvinyl acetal resins, and polyvinyl butyral resins among the above-described thermoplastic resins.

Although it does not specifically limit as a phenoxy resin, For example, bisphenol A type, bisphenol F type, bisphenol A / bisphenol F copolymer type, bisphenol S type, bisphenol acetophenone type, novolak type, fluorene type, dicyclopentadiene type, norbornene Of naphthalene type, naphthalene type, anthracene type, adamantane type, terpene type, trimethylcyclohexane type, biphenol type and biphenyl type phenoxy resins are exemplified, and among these, it is preferable to use bisphenol A type phenoxy resin. The terminal of the phenoxy resin may be any functional group such as phenolic hydroxyl group and epoxy group. A phenoxy resin may be used individually by 1 type, or may use 2 or more types together.

When a phenoxy resin is used as the thermoplastic resin, the tack on the surface of the resin composition layer 10 tends to be small. However, in the resin sheet 1 according to the present embodiment, even when the tack is small as described above, the resin composition layer 10 is laminated on the surface of the first support sheet 11 on the pressure-sensitive adhesive layer 112 side. By being present, the floating at the interface between the resin composition layer 10 and the first support sheet 11 can be effectively suppressed. Therefore, the resin sheet 1 which concerns on this embodiment is suitable also when using a phenoxy type-resin as a thermoplastic resin.

The weight average molecular weight (Mw) of the thermoplastic resin is preferably 100 or more, particularly preferably 1000 or more, and particularly preferably 10,000 or more. The weight average molecular weight (Mw) of the thermoplastic resin is preferably 1,000,000 or less, particularly preferably 800,000 or less, and particularly preferably 100,000 or less. When the weight average molecular weight (Mw) of the thermoplastic resin is in the above range, it becomes easier to form the resin composition layer 10 into a sheet. In addition, the weight average molecular weight in this specification is a standard polystyrene conversion value measured by gel permeation chromatography (GPC) method.

The content of the thermoplastic resin in the resin composition is preferably 1.0% by mass or more, particularly preferably 3.0% by mass or more, and further preferably 5.0% by mass or more preferable. In addition, the content is preferably 30% by mass or less, particularly preferably 20% by mass or less, and further preferably 10% by mass or less. When the content is in the above range, the film forming property is improved, and the handleability of the obtained resin sheet is effectively improved. In addition, the said content of a thermoplastic resin is solid content conversion value.

(3) Inorganic fine particle The resin composition in this embodiment contains an inorganic fine particle by 50 mass% or more and 90 mass% or less. As a result, the thermal expansion coefficient and the water absorption coefficient of the cured layer in which the resin composition layer 10 is cured become relatively small, whereby the resin composition layer 10 exhibits excellent flexibility, fluidity, and adhesiveness. It will be done. From such a viewpoint, the content of the inorganic fine particles in the resin composition is preferably 55% by mass or more, and particularly preferably 60% by mass or more. In addition, the content is preferably 85% by mass or less, particularly 80% by mass from the viewpoint of the wiring formability in the case where the rewiring layer is formed in the cured layer formed by curing of the resin composition layer 10 It is preferable that it is the following. In addition, the said content of inorganic fine particles is a solid content conversion value.

As the inorganic fine particles, for example, silica, alumina, glass, titanium oxide, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, magnesium oxide, aluminum oxide, aluminum nitride, Inorganic fine particles composed of aluminum borate, boron nitride, crystalline silica, amorphous silica, mullite, cordierite and other composite oxides, montmorillonite, smectite, boehmite, talc, iron oxide, silicon carbide, zirconium oxide, etc. These can be used alone or in combination of two or more. Among these, it is preferable to use silica fine particles and alumina fine particles, and it is particularly preferable to use silica fine particles.

The inorganic fine particles are preferably surface-treated with a surface treatment agent. Thereby, the dispersibility and the filling property of the inorganic fine particles in the resin composition become excellent. Examples of the surface treatment agent include epoxysilanes, vinylsilanes, silazane compounds, alkoxysilanes and silane coupling agents. These may be used alone or in combination.

The minimum coating area of the surface treatment agent is preferably less than 550 m ² / g, particularly preferably 520 m ² / g or less, and further preferably 450 m ² / g or less. On the other hand, the lower limit value of the minimum covering area of the surface treatment agent is preferably 100 m ² / g or more, particularly preferably 200 m ² / g or more, and further preferably 300 m ² / g or more . While the dispersibility and filling property of the inorganic fine particle in a resin composition improve by the minimum covering area being the said range, the formation property of the electrode with respect to the hardened layer which the resin composition layer 10 hardens | cures improves.

The minimum coverage area (m ² / g) of the surface treatment agent refers to the area (m ² ) of the monomolecular film when the monomolecular film is formed using 1 g of the surface treatment agent. The minimum coverage area can be theoretically calculated from the structure of the surface treatment agent and the like.

Preferred examples of the surface treatment agent include epoxysilanes such as 3-glycidoxypropyltrimethoxysilane and vinylsilanes such as vinyltrimethoxysilane.

The average particle diameter of the inorganic fine particles is preferably 0.01 μm or more, particularly preferably 0.1 μm or more, and further preferably 0.3 μm or more. The average particle diameter of the inorganic fine particles is preferably 3.0 μm or less, and particularly preferably 1.0 μm or less. When the average particle diameter of the inorganic fine particles is in such a range, the flexibility and flexibility of the resin composition layer 10 are likely to be excellent, and the content of the inorganic fine particles is in the range described above. It becomes easy to adjust to a high filling rate. Furthermore, as described above, when the rewiring layer is formed on the cured layer formed by curing of the resin composition layer 10, the formability of the electrode is likely to be improved.

The maximum particle size of the inorganic fine particles is preferably 0.05 μm or more, and more preferably 0.5 μm or more. Further, the maximum particle size is preferably 5 μm or less, and particularly preferably 3 μm or less. When the maximum particle size of the inorganic fine particles is in the above range, the inorganic fine particles can be easily filled in the resin composition, and the coefficient of thermal expansion at the time of curing can be suppressed low. Further, as described above, when the rewiring layer is formed on the cured layer formed by curing of the resin composition layer 10, fine wiring is easily formed. The average particle size and the maximum particle size of the inorganic fine particles in the present specification were measured by a dynamic light scattering method using a particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., product name “Nanotrac Wave-UT 151”). It will be a value.

(4) Curing Catalyst The resin composition in the present embodiment preferably further contains a curing catalyst. As a result, the curing reaction of the thermosetting resin can be effectively advanced, and the resin composition layer 10 can be favorably cured. Examples of the curing catalyst include imidazole curing catalysts, amine curing catalysts, phosphorus curing catalysts and the like.

The curing catalysts described above may be used alone or in combination of two or more.

The content of the curing catalyst in the resin composition is preferably 0.01% by mass or more, particularly preferably 0.05% by mass or more, and further preferably 0.1% by mass or more preferable. The content is preferably 2.0% by mass or less, particularly preferably 1.5% by mass or less, and further preferably 1.0% by mass or less. When the content is in the above range, the resin composition layer 10 can be cured more favorably. In addition, the said content of a curing catalyst is a solid content conversion value.

(5) Other Components The resin composition in the present embodiment may further contain a plasticizer, a stabilizer, a tackifier, a colorant, a coupling agent, an antistatic agent, an antioxidant, and the like.

(6) Thickness of Resin Composition Layer The thickness of the resin composition layer 10 is preferably 5 μm or more, particularly preferably 10 μm or more, and further preferably 15 μm or more. Further, the thickness is preferably 80 μm or less, particularly preferably 60 μm or less, and further preferably 40 μm or less.

(7) Physical Properties of Curable Resin Composition Layer The tack on the surface of the resin composition layer 10 may be less than 5 g of probe tack at 25 ° C. measured using a probe with a diameter of 25 mm. In the resin sheet 1 according to the present embodiment, even when the tack on the surface of the resin composition layer 10 is very small as described above, the resin composition layer 10 is on the pressure-sensitive adhesive layer 112 side of the first support sheet 11 By being laminated on the surface of the above, the floating at the interface between the resin composition layer 10 and the first support sheet 11 can be effectively suppressed. The lower limit value of the probe tack at 25 ° C. is not particularly limited, and may be, for example, 0.00001 g. Also, the probe tack at 25 ° C. described above can be measured by a probe tack test. Specifically, a stainless steel probe with a diameter of 25 mm was contacted for 10 seconds with a contact load of 0.98 N / cm ² on the surface of the resin composition layer 10 on the first support sheet 11 side under an environment of 25 ° C. After that, the probe is released from the test piece at a speed of 10 mm / sec, and can be measured as the value of the load at that time.

2. First Support Sheet The first support sheet 11 in the present embodiment includes a support base 111 and a pressure-sensitive adhesive layer 112 laminated on one side of the support base 111.

(1) Support base material Although the said support base material 111 is not specifically limited, For example, as the support base material 111, it is preferable to use a resin film, a nonwoven fabric, paper etc. Examples of the resin film include polyester films such as polyethylene terephthalate film, polybutylene terephthalate film and polyethylene naphthalate film; polyolefin films such as polyethylene film and polypropylene film; polyimide film and the like. Examples of the non-woven fabric include non-woven fabrics using fibers such as rayon, acrylic and polyester. Examples of the above-mentioned paper include high-quality paper, glassine paper, impregnated paper, coated paper and the like. You may use these as 2 or more types of laminated bodies.

The material forming the resin film preferably has a glass transition temperature (Tg) of 50 ° C. or higher, particularly preferably 55 ° C. or higher, and more preferably 60 ° C. or higher. When the glass transition temperature (Tg) of the said material is 50 degreeC or more, in the state by which the 1st support sheet 11 was laminated | stacked on the resin composition layer 10, it is a case where the resin composition layer 10 is thermosetting. Also, the first support sheet 11 is unlikely to be thermally deformed, which makes it easy for the first support sheet 11 to be peeled off from the hardened layer. The upper limit of the glass transition temperature (Tg) is not particularly limited, but is preferably 500 ° C. or less, particularly preferably 400 ° C. or less. The glass transition temperature (Tg) is a value measured using a differential scanning calorimeter.

Further, the support base 111 constituting the first support sheet 11 is subjected to primer treatment, corona treatment, if desired, on one side or both sides, as desired, for the purpose of improving the adhesion with the pressure-sensitive adhesive layer 112 laminated on the surface. Surface treatment such as plasma treatment or oxidation treatment may be performed.

The thickness of the support base 111 is not particularly limited, but is preferably 10 μm or more, particularly preferably 15 μm or more, and further preferably 20 μm or more from the viewpoint of the handling property of the resin sheet 1 preferable. In addition, the thickness is preferably 500 μm or less, particularly preferably 100 μm or less, and further preferably 75 μm or less.

The heat shrinkage ratio of the support substrate 111 in the MD direction and the CD direction when heated for 30 minutes at 150 ° C. is preferably 2.0% or less, and particularly preferably 1.5% or less. Is preferred. The lower limit value of the thermal contraction rate in the MD direction of the support base 111 and the lower limit value of the thermal contraction rate in the CD direction are preferably as small as possible, and usually 0.01% or more is preferable.

Further, the thermal contraction rate in the MD direction of the support base 111 and the thermal contraction rate in the CD direction of the support base 111 satisfy the above ranges, and the ratio of the thermal contraction rate in the MD direction and the thermal contraction rate in the CD direction (The thermal contraction rate in the MD direction / the thermal contraction rate in the CD direction) is preferably in the range of 0.03 or more and 30 or less, and particularly preferably in the range of 0.5 or more and 5.0 or less. When the support base material 111 fills these, when peeling the 1st support sheet 11 from the formed cured layer after thermosetting of the resin composition layer 10, the curvature of the semiconductor device obtained can be prevented. it can.

The above-mentioned MD direction is a direction parallel to the direction in which the support base 111 is transported when the support base 111 is formed into a long film, and the CD direction is on the same surface of the support base 111. It is a direction orthogonal to the MD direction.

The thermal contraction rate mentioned above shall be measured by the following method based on JISZ1712. The supporting substrate 111 is cut into a size of 20 mm wide and 200 mm long in the MD direction and the TD direction, suspended in a hot air oven at 150 ° C., and heated for 5 minutes. Then, the length after heating is measured, and the ratio (percentage) of the contracted length to the original length is taken as the thermal contraction rate.

In addition, the thermal contraction rate of the support base material 111 selects the material which satisfy | fills a desired range, carries out the annealing process of the support base material 111, and changes the film-forming method of the support base material 111, for example. It can also adjust by things (for example, changing the extending | stretching method) etc.

Moreover, as the support base material 111, it is preferable to select the thing to which a low molecular-weight component (oligomer) does not precipitate easily. By using such a supporting substrate 111, it is possible to suppress precipitation of the oligomer contained in the supporting substrate 111 by heating at the time of curing of the resin composition layer 10 and transfer to the cured layer, thereby achieving higher quality. Semiconductor devices can be manufactured. The degree of precipitation of the low molecular weight component is as follows: the resin sheet 1 is heated at 100 ° C. for 60 minutes and then heated at 170 ° C. for 60 minutes, and then the resin composition layer 10 is cured. The first support sheet 11 is peeled off from the hardened layer, and the exposed surface of the hardened layer is observed with a digital microscope (500 × magnification) to confirm the presence or absence of residues derived from low molecular weight components. It can be judged by

(2) Pressure-Sensitive Adhesive Layer The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 112 is not particularly limited as long as the first support sheet 11 exhibits desired adhesiveness to the resin composition layer 10. Examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 112 include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, polyester-based pressure-sensitive adhesives, and polyvinyl ether-based pressure-sensitive adhesives. it can.

The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 112 is preferably composed of at least one pressure-sensitive adhesive selected from an active energy ray-curable pressure-sensitive adhesive, a thermally foamable pressure-sensitive adhesive, and a thermosetting pressure-sensitive adhesive. Thereby, the first support sheet 11 exhibits desired adhesiveness to the resin composition layer 10, and the floating between the resin composition layer 10 and the first support sheet 11 is suppressed. On the other hand, the above-mentioned adhesive can reduce the adhesive strength by irradiation or heating of active energy rays, whereby the first support sheet from the cured layer formed by curing the resin composition layer 10 It becomes possible to easily carry out peeling of 11, and it becomes possible to control the occurrence of chipping and cracking of the hardened layer.

(2-1) Acrylic-Based Pressure-Sensitive Adhesive Although the above-mentioned acrylic-based pressure-sensitive adhesive is not particularly limited, it is a pressure-sensitive adhesive prepared using a pressure-sensitive adhesive composition P containing a (meth) acrylic acid ester polymer (A) Is preferred. In the present specification, (meth) acrylic acid ester means both acrylic acid ester and methacrylic acid ester. Other similar terms are also the same.

The (meth) acrylic acid ester polymer (A) preferably contains, as a monomer constituting the polymer, a (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group. Thereby, the obtained adhesive can express desirable adhesiveness.

The (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group may be used alone or in combination of two or more. From the viewpoint of heat resistance, it is preferable to use a (meth) acrylic acid alkyl ester having 6 to 10 carbon atoms in the alkyl group as the above (meth) acrylic acid alkyl ester, and in particular, (meth) acrylic acid 2 Preference is given to using ethylhexyl.

The (meth) acrylic acid ester polymer (A) contains 10% by mass or more of (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group as a monomer unit constituting the polymer The content is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 85% by mass or more, and still more preferably 90% by mass or more. Further, the (meth) acrylic acid ester polymer (A) contains, as a monomer unit constituting the polymer, an (meth) acrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group at 99% by mass or less In particular, the content is preferably 98% by mass or less, and more preferably 97% by mass or less.

Moreover, it is preferable that the (meth) acrylic acid ester polymer (A) contains the monomer (reactive functional group containing monomer) which has a reactive functional group as a monomer which comprises the said polymer. As said reactive functional group containing monomer, a hydroxyl group containing monomer, a carboxyl group containing monomer, an amino group containing monomer etc. are mentioned preferably. One of these reactive functional group-containing monomers may be used alone, or two or more thereof may be used in combination.

The (meth) acrylic acid ester polymer (A) preferably contains 1% by mass or more of the reactive functional group-containing monomer as a monomer unit constituting the polymer, and particularly preferably 2% by mass or more It is preferable to contain 3 mass% or more preferably. Further, the (meth) acrylic acid ester polymer (A) preferably contains, as a monomer unit constituting the polymer, a reactive functional group-containing monomer at 30% by mass or less, and at 20% by mass or less It is more preferable that the content be 10% by mass or less, particularly preferably 7% by mass or less.

Further, the (meth) acrylic acid ester polymer (A) may further contain another monomer as a monomer constituting the polymer. As the other monomer, for example, (meth) acrylic acid ester having aliphatic ring, non-crosslinkable acrylamide, (meth) acrylic acid ester having non-crosslinkable tertiary amino group, vinyl acetate, styrene and the like It can be mentioned. These may be used alone or in combination of two or more.

In addition, a (meth) acrylic acid ester polymer (A) may be used individually by 1 type, and may be used combining 2 or more types.

It is preferable that the adhesive composition P for producing the said acrylic adhesive further contains a crosslinking agent (B), and the said acrylic adhesive is the (meth) acrylic acid ester polymer (A) mentioned above, It is preferable that it is what bridge | crosslinks the adhesive composition P containing a crosslinking agent (B).

The crosslinker (B) may be any one that reacts with the reactive functional group possessed by the (meth) acrylic acid ester polymer (A). For example, an isocyanate crosslinker, an epoxy crosslinker, an amine crosslinker Agent, melamine based crosslinking agent, aziridine based crosslinking agent, hydrazine based crosslinking agent, aldehyde based crosslinking agent, oxazoline based crosslinking agent, metal alkoxide based crosslinking agent, metal chelate based crosslinking agent, metal salt based crosslinking agent, ammonium salt based crosslinking agent Etc. In addition, a crosslinking agent (B) can be used individually by 1 type or in combination of 2 or more types.

The content of the crosslinking agent (B) in the adhesive composition P is preferably 0.1 parts by mass or more, and 1 part by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A). The content is more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more. Further, the content is preferably 20 parts by mass or less, particularly preferably 15 parts by mass or less, and further 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A). It is preferable that it is less than part.

(2-2) Silicone-Based Pressure-Sensitive Adhesive The silicone-based pressure-sensitive adhesive is not particularly limited, and examples thereof include a pressure-sensitive adhesive containing dimethylpolysiloxane. As the silicone-based pressure-sensitive adhesive, for example, a pressure-sensitive adhesive composition containing an organopolysiloxane having an unsaturated group such as a vinyl group, a dimethylpolysiloxane having an SiH group as a crosslinking agent, and a platinum-based catalyst is cured. It is possible to use an addition polymerization type silicone-based pressure-sensitive adhesive or a silicone-based pressure-sensitive adhesive obtained by curing an organopolysiloxane with an organic peroxide such as benzoyl peroxide (BPO). From the viewpoint of heat resistance, addition polymerization type silicone pressure-sensitive adhesives are preferable. In this case, it is possible to adjust the crosslink density according to the density of the unsaturated group in consideration of the adhesive force obtained. The addition polymerization type silicone-based pressure-sensitive adhesive can be favorably formed by performing heating or the like for addition polymerization.

(2-3) Active Energy Ray-Curable Adhesive The active energy ray-curable adhesive cures by irradiation of active energy rays while exhibiting a predetermined adhesive power before irradiation of active energy rays. The pressure-sensitive adhesive is not particularly limited as long as it is sufficiently reduced. The active energy ray curable adhesive may contain an active energy ray curable polymer, and the active energy ray non-curable polymer (polymer having no active energy ray curable) and at least one or more polymers. Or a mixture of monomers and / or oligomers having an active energy ray-curable group of

(2-4) Heat-foamable pressure-sensitive adhesive The heat-foamable pressure-sensitive adhesive is not particularly limited as long as it is a pressure-sensitive adhesive which is foamed by heating to sufficiently reduce the adhesiveness while exhibiting a predetermined adhesiveness before heating. For example, a pressure-sensitive adhesive containing a pressure-sensitive adhesive component as a matrix and a foaming agent is preferable. The heat-foamable pressure-sensitive adhesives are described in detail in JP-A-2004-277749, JP-A-2012-117040, JP-A-2010-094834, etc. Alternatively, it may be used as an adhesive in the present embodiment.

The first support sheet 11 in which the pressure-sensitive adhesive layer 112 is formed of a heat-foamable pressure-sensitive adhesive may be a commercially available product, and as an example, the product name "REVAALPHA" (manufactured by Nitto Denko Corporation) etc. Is preferably mentioned.

(2-5) Thermosetting adhesive The thermosetting adhesive is not particularly limited as long as it is a pressure-sensitive adhesive that cures by heating to sufficiently reduce the adhesion while exhibiting a predetermined adhesion before heating. For example, conventionally known materials such as a pressure-sensitive adhesive containing a pressure-sensitive adhesive component and a thermosetting resin can be used.

Examples of the pressure-sensitive adhesive component include acrylic pressure-sensitive adhesives, rubber pressure-sensitive adhesives, silicone pressure-sensitive adhesives, urethane pressure-sensitive adhesives and the like. One of these may be used alone, or two or more may be used in combination.

(2-6) Additives In the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 112, various additives which are usually used, for example, refractive index modifiers, antistatic agents, tackifiers, silane coupling agents Antioxidants, UV absorbers, light stabilizers, softeners, fillers, light curing agents, photopolymerization initiators and the like can be added.

The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 112 preferably contains, as a tackifier, a rubber-based resin having a reactive group. As said rubber-type resin, the hydrogenation type polybutadiene resin which has a carboxyl group at the terminal, the hydrogenation type polybutadiene resin which has a hydroxyl group at the terminal, etc. are mentioned, for example. As a specific example of the hydrogenation type polybutadiene resin which has a carboxyl group at the terminal, the product name "CI1000" by Nippon Soda Co., Ltd. etc. is mentioned. Moreover, as a specific example of hydrogenation type polybutadiene resin which has a hydroxyl group at the terminal, product names "GI1000", "GI2000", "GI3000" etc. made by Nippon Soda Co., Ltd. are mentioned.

It becomes easy to adjust the peeling force (F11) and peeling force (F12) mentioned later to a desired range by the adhesive which comprises the adhesive layer 112 including the tackifier mentioned above, and also a resin composition layer When the first support sheet 11 is peeled off from the cured layer after the thermal curing of 10, the adhesive residue can be prevented from remaining in the cured layer.

The content of the tackifier in the adhesive composition P is preferably 1 part by mass or more, particularly 5 parts by mass or more based on 100 parts by mass of the (meth) acrylic acid ester polymer (A). Is preferred. Further, the content is preferably 30 parts by mass or less, and particularly preferably 15 parts by mass or less, with respect to 100 parts by mass of the (meth) acrylic acid ester polymer (A).

(2-7) Physical Properties of Pressure-Sensitive Adhesive Layer, Etc. The thickness of the pressure-sensitive adhesive layer 112 is preferably 1 μm or more, particularly preferably 5 μm or more, and further preferably 10 μm or more. Further, the thickness is preferably 500 μm or less, particularly preferably 100 μm or less, and further preferably 50 μm or less.

The pressure-sensitive adhesive layer 112 preferably has a storage elastic modulus of 1 × 10 ⁵ Pa or more at 100 ° C. and a measurement frequency of 1 Hz. If the pressure-sensitive adhesive layer 112 has such a storage elastic modulus, after curing the resin composition layer 10 and forming a cured layer, the first support sheet 11 is more easily peeled off from the cured layer. It is possible to prevent the problem that the pressure-sensitive adhesive remains on the surface of the cured layer (so-called adhesive residue). The upper limit of the storage elastic modulus when the measurement frequency is 1 Hz at 100 ° C. of the pressure-sensitive adhesive layer 112 is not particularly limited, but is preferably 1 × 10 ⁷ Pa or less. The storage elastic modulus is a value measured by a torsional shear method using a dynamic viscoelasticity measuring apparatus, and the details of the measuring method are as described in the examples to be described later.

The first support sheet 11 has a surface on the adhesive layer 112 side adhered to a copper foil, is heated under conditions of 100 ° C. and 30 minutes, and is subsequently heated under conditions of 180 ° C. and 60 minutes, It is preferable that the adhesion at room temperature with respect to is 0.7 N / 25 mm or more and 2.0 N / 25 mm or less. The surface of the first support sheet 11 on the adhesive layer 112 side is attached to a polyimide film, heated at 100 ° C. for 30 minutes, and subsequently heated at 180 ° C. for 60 minutes. The adhesion at room temperature to the film is preferably 0.7 N / 25 mm or more and 2.0 N / 25 mm or less. If the adhesive force after such heating is in the above-mentioned range, the first support sheet 11 is more easily peeled off from the cured layer formed by heat curing the resin composition layer 10. In addition, the detail of the measuring method of the said adhesive force presupposes as it describes in the Example mentioned later. In the present specification, room temperature refers to a temperature of 22 ° C. or more and 24 ° C. or less.

The pressure-sensitive adhesive layer 112 is reduced by 5% from the viewpoint of effectively suppressing the adhesive residue caused by the deterioration of the pressure-sensitive adhesive layer 112 when the first support sheet 11 is peeled off from the cured layer after being heated. The temperature is preferably 250 ° C. or more, more preferably 300 ° C. or more.

3. Second Support Sheet The resin sheet 1 according to the present embodiment preferably includes the second support sheet 12 laminated on the surface of the resin composition layer 10 opposite to the first support sheet 11. By providing the second support sheet 12 with the resin sheet 1 according to the present embodiment, the resin composition layer 10 can be protected from both sides by the first support sheet 11 and the second support sheet 12. As a result, appearance problems and the occurrence of chipping or cracking of the resin composition layer 10 are effectively suppressed.

The second support sheet 12 is not particularly limited, and for example, a polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, a plastic film such as polyolefin film such as polypropylene or polyethylene, high quality paper, glassine paper, impregnated paper And paper such as coated paper, non-woven fabric and the like. You may use these as 2 or more types of laminated bodies. The second support sheet 12 may be subjected to surface treatment such as mud treatment or corona treatment.

The contact surface with the resin composition layer 10 in the 2nd support sheet 12 may be exfoliated by the exfoliation agent. Examples of the release agent include silicone release agents, alkyd release agents, fluorine release agents, long chain alkyl release agents, olefin resin release agents, acrylic release agents, rubber release agents, and the like. Among these, it is preferable to use at least one selected from silicone-based release agents and alkyd-based release agents, and in particular, generation of floating between the second support sheet 12 and the resin composition layer 10 is prevented. In view of the above, it is more preferable to use an alkyd release agent.

The second support sheet 12 may have a pressure-sensitive adhesive layer on the side in contact with the resin composition layer 10. The pressure-sensitive adhesive layer may be the same as the pressure-sensitive adhesive layer 112 included in the first support sheet 11.

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

4. Physical Properties of Resin Sheet The peeling force (F11) at the time of peeling the first support sheet 11 from the resin composition layer 10 before curing is preferably 0.1 N / 25 mm or more, particularly 0.2 N / 25 mm or more Is preferably 0.3 N / 25 mm or more. When the peeling force (F11) is 0.1 N / 25 mm or more, floating of the first support sheet 11 and the resin composition layer 10 during storage (particularly during cold storage) or handling of the resin sheet 1 The occurrence is effectively suppressed.

Moreover, about the upper limit of the said peeling force (F11), when the adhesive which comprises the adhesive layer 112 is neither an active energy ray-curable adhesive, a thermally foamable adhesive nor a thermosetting adhesive The peeling force (F11) is preferably 3.0 N / 25 mm or less, particularly preferably 2.0 N / 25 mm or less, and further preferably 0.5 N / 25 mm or less. When the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer 112 is at least one of an active energy ray-curable pressure-sensitive adhesive, a heat-foamable pressure-sensitive adhesive and a thermosetting pressure-sensitive adhesive, the peeling force (F11) is 30 N / 25 mm. It is preferable that it is the following, It is preferable that it is especially 25 N / 25 mm or less, More preferably, it is 20 N / 25 mm or less. When the upper limit value of the peeling force (F11) is in these ranges, it is possible to effectively suppress chipping and cracking of the resin composition layer 10 when peeling the first support sheet 11.

In addition, the measuring method of the peeling force (F11) mentioned above is as showing to the test example mentioned later.

Further, in the resin sheet 1 in which the resin sheet 1 is heated at 100 ° C. for 30 minutes and further heated at 180 ° C. for 60 minutes, the first support sheet 11 is peeled off from the cured layer formed by heat curing the resin composition layer 10 The peeling force (F12) at the time of carrying out is preferably 0.5 N / 25 mm or more, particularly preferably 0.7 N / 25 mm or more, and further preferably 0.8 N / 25 mm or more. Further, the peeling force (F12) is preferably 3.0 N / 25 mm or less, particularly preferably 2.0 N / 25 mm or less, and further preferably 1.5 N / 25 mm or less. By the said peeling force (F12) being 0.5 N / 25 mm or more, the unintended peeling of the 1st support sheet 11 before and behind thermosetting of the resin composition layer 10 can be suppressed, and the obtained hardened layer is obtained. Can be better protected by the first support sheet 11. Moreover, even after heating the first support sheet 11 because the peeling force (F12) is 3.0 N / 25 mm or less, from the surface of the cured layer formed by curing the resin composition layer 10 The first support sheet 11 can be easily peeled off, and chipping and cracking of the resin composition layer 10 can be effectively suppressed. In addition, the measuring method of the peeling force (F12) mentioned above is as showing to the test example mentioned later.

Moreover, when the resin sheet 1 which concerns on this embodiment is equipped with the 2nd support sheet 12, the peeling force (F2) at the time of peeling the 2nd support sheet 12 from the resin composition layer 10 before hardening is a lower type. (1)
F11 / F2> 1 (1)
It is preferable that the Thereby, the second support sheet 12 can be easily peeled off from the resin composition layer 10 while suppressing the occurrence of floating between the first support sheet 11 and the resin composition layer 10. The peeling force (F2) is preferably 0.05 N / 100 mm or more, and particularly preferably 0.10 N / 100 mm or more. Moreover, it is preferable that the said peeling force (F2) is 2.0 N / 100 mm or less. In addition, the measuring method of the peeling force (F2) mentioned above is as showing to the test example mentioned later.

5. Method of Manufacturing Resin Sheet The method of manufacturing the resin sheet 1 according to the present embodiment is not particularly limited. For example, the second support sheet 12 contains the above-described resin composition and, if desired, further a solvent or dispersion medium. The coating liquid to be applied is applied, dried (or heat-crosslinked as necessary), and the resin composition layer 10 is formed. Then, it can manufacture by bonding together the surface at the side of the adhesive layer 112 in the 1st support sheet 11 prepared separately to the surface on the opposite side to the 2nd support sheet 12 in the said resin composition layer 10 . In addition, the manufacturing method of the 1st support sheet 11 is not specifically limited, either, It can manufacture by a well-known method.

Examples of the coating method include known methods such as spin coating method, spray coating method, bar coating method, knife coating method, roll coating method, roll knife coating method, blade coating method, die coating method and gravure coating method.

Further, examples of the solvent include organic solvents such as toluene, ethyl acetate and methyl ethyl ketone.

6. Use of Resin Sheet The resin sheet 1 according to the present embodiment can be used to form an insulating film. More specifically, in a semiconductor device such as a component built-in substrate, a multilayer printed wiring board, a fan-out type wafer level package, a fan-out type panel level package, etc., it can be suitably used for forming an insulating film. More specifically, the resin sheet 1 according to the present embodiment includes an insulating film in a buildup layer of a semiconductor device such as a component built-in substrate, a multilayer printed wiring board, a fanout type wafer level package, and a fanout type panel level package. It can be suitably used to form.

[Semiconductor device]
The semiconductor device according to the present embodiment includes a cured layer formed by curing the resin composition layer 10 in the resin sheet 1 according to the present embodiment as an insulating film. Examples of such semiconductor devices include component built-in boards, multilayer printed wiring boards and the like. These semiconductor devices can be manufactured by the method described later using the resin sheet 1 according to the present embodiment.

As described above, the resin sheet 1 according to the present embodiment is hard to generate floating at the interface between the resin composition layer 10 and the first support sheet 11, and is cured by heat curing the resin composition layer 10. Peeling of the first support sheet 11 from the layer is easy. Therefore, the semiconductor device according to the present embodiment manufactured using the resin sheet 1 has a good quality by being manufactured using the resin sheet 1 according to the present embodiment described above. It becomes.

[How to use resin sheet]
The resin sheet 1 which concerns on this embodiment can be used for the manufacturing method of a semiconductor device, for example. Below, the manufacturing method of the semiconductor device provided with the cured layer formed by hardening | curing the resin composition layer 10 in the resin sheet 1 which concerns on embodiment as an insulating film is demonstrated. 2 and 3 show cross-sectional views for explaining an example of the manufacturing method. First, as shown in FIG. 2A, the electronic component 2 is provided on one surface of the temporary fixing member 8 as a preparation step. The method of providing the electronic component 2 on the temporary fixing material 8 is not particularly limited, and a general method can be employed.

The temporary fixing material 8 is not particularly limited as long as the electronic component 2 can be temporarily fixed on the temporary fixing material 8, and it is a pressure-sensitive adhesive sheet comprising a substrate and a pressure-sensitive adhesive layer laminated on the substrate A laminated member consisting of a hard support plate and a pressure-sensitive adhesive layer laminated on the hard support plate. It may be. Alternatively, the resin sheet 1 according to the present embodiment can be used as the temporary fixing material 8. In this case, the electronic component 2 is provided on the surface of the curable resin composition layer 10 opposite to the first support sheet 11. As described above, when the resin sheet 1 according to the present embodiment is used as the temporary fixing material 8, heating for forming the sealing resin layer 13 ′ and formation of the insulating film 10 ′ as described later Heating can be performed simultaneously, and the process can be simplified.

The electronic component 2 is not particularly limited as long as it is generally an electronic component to be sealed, and examples thereof include a semiconductor chip and the like. Furthermore, the electronic component 2 may be one in which a semiconductor chip is mounted at a predetermined position of the interposer. In this case, at least a part of the interposer is sealed together with the semiconductor chip and the like in the mounted state. As an example of the said interposer, a lead frame, a polyimide tape, a printed circuit board etc. are mentioned. Furthermore, a frame (also referred to as a frame-like member) such as a frame made of metal such as copper or a resin-made frame may be provided around the electronic component 2 on the temporary fixing material 8. In this case, at least a part of the frame-shaped member may be sealed together with the electronic component 2. The frame-like member usually comprises one or more openings consisting of holes penetrating in the thickness direction, and a frame-like part made of copper or the like, resin or the like.

When using the frame-like member, after the frame-like member is placed on one side of the temporary fixing material 8 in the preparation step, for example, the electronic component 2 is placed at the position of the opening of the frame-like member Do. Thereby, in the subsequent resin composition layer laminating step, the exudation of the sealing resin to the outside of the opening can be suppressed, and the thickness of the obtained semiconductor device can be made uniform, and further, the sealing resin layer It is possible to suppress the occurrence of warpage and to suppress the warpage of the obtained semiconductor device.

Subsequently, the surface of the temporary fixing material 8 on which the electronic component 2 is provided is sealed. Although it can carry out by the conventionally well-known method as a method to seal | block, the case where it seals using the sealing sheet which consists of sealing materials as an example is demonstrated. As shown in FIG. 2 (b), the sealing sheet 13 is laminated on the side of the temporary fixing material 8 on which the electronic component 2 is provided. Thereby, the electronic component 2 provided on the temporary fixing material 8 is covered by the sealing sheet 13. When laminating the sealing sheet 13, it is preferable to laminate so that no space is generated around the electronic component 2. The sealing sheet 13 can be laminated | stacked on conventionally well-known lamination conditions using a conventionally well-known laminating apparatus.

Next, as shown in FIG. 2C, as a curing step, the sealing sheet 13 is cured to form a sealing resin layer 13 '. The curing is preferably performed by heating the sealing sheet 13. By the curing, a sealing body 4 including the sealing resin layer 13 ′ and the electronic component 2 sealed by the sealing resin layer 13 ′ is obtained. Curing of the sealing sheet 13 is preferably performed, for example, by heating at 100 ° C. to 240 ° C. for 15 minutes to 300 minutes.

Next, as shown in FIG. 2D, the temporary fixing material 8 is peeled off from the sealing body 4.

Next, as shown in FIGS. 3A and 3B, an insulating film formation step is performed. First, as shown in FIG. 3A, the first support of the resin composition layer 10 of the resin sheet 1 according to the present embodiment is applied to the exposed surface of the sealing body 4 exposed by the peeling of the temporary fixing material 8. The surface opposite to the sheet 11 is laminated. Subsequently, as shown in FIG. 3B, the resin composition layer 10 is cured to form a cured layer as an insulating film 10 '. The curing is preferably performed by heating, and the heat treatment is preferably performed, for example, at a temperature of 100 ° C. to 240 ° C. for 15 minutes to 300 minutes. Moreover, it is preferable to perform hardening of the resin composition layer 10 by the heating mentioned above in multiple steps by heat processing.

Next, as shown in FIG. 3C, the first support sheet 11 is peeled off from the insulating film 10 '.

Here, when the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 112 includes the above-described active energy ray-curable pressure-sensitive adhesive, it is preferable to cure the pressure-sensitive adhesive layer 112 by irradiating the pressure-sensitive adhesive layer 112 with active energy rays. . As a result, the adhesion of the first support sheet 11 to the insulating film 10 ′ is reduced, and the first support sheet 11 can be easily peeled off. As an active energy ray, an ultraviolet ray, an electron beam or the like can be used. Case of irradiation with ultraviolet rays, a high-pressure mercury lamp, a fusion H lamp, can be carried out by a xenon lamp or the like, the dose of ultraviolet ray is illuminance 50 mW / cm ² or more, 1000 mW / cm ² or less, the amount of light 50 mJ / cm ² or more, 1000 mJ It is preferable to set it as / cm < ² > or less. When irradiating an electron beam, it can be performed by an electron beam accelerator or the like, and the irradiation amount of the electron beam is preferably 10 krad or more and 1000 krad or less. In addition, when an active energy ray curable adhesive is included as an adhesive which comprises the adhesive layer 112, it is preferable that the support base material 111 can permeate | transmit an active energy ray. Thus, active energy rays can be applied to the pressure-sensitive adhesive layer 112 through the support base 111.

When the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 112 includes the thermally foamable pressure-sensitive adhesive, it is preferable to cause the pressure-sensitive adhesive layer 112 to foam by heating the first support sheet 11. As a result, the adhesion of the first support sheet 11 to the insulating film 10 ′ is reduced, and the first support sheet 11 can be easily peeled off. As a means to heat, heating means, such as a hot plate, a hot-air dryer, a near-infrared lamp, an air dryer, an infrared lamp, heating water, can be used, for example. The heating conditions can be appropriately set depending on the type of the foaming agent, the heat resistance of the supporting substrate 111, the insulating film 10 ', etc., the heating method (heat capacity, heating means, etc.), but in particular, the heating temperature is in the adhesive layer 112. It is preferable to set it as the temperature which becomes more than the foaming start temperature (thermal expansion start temperature) of the foaming agent (thermal expansion microsphere etc.). Under general heating conditions, the temperature is 100 ° C. or more and 250 ° C. or less, and the heating time in the case of using a hot plate or the like is 1 second or more and 90 seconds or less, and a hot air drier or the like is used The heating time is 5 minutes or more and 15 minutes or less. The heat treatment for causing foaming in the pressure-sensitive adhesive layer 112 may be performed at a desired stage depending on the purpose of use, and may be performed together with the heat treatment for curing the resin composition layer 10, for example. .

When the pressure-sensitive adhesive that constitutes the pressure-sensitive adhesive layer 112 includes the thermosetting pressure-sensitive adhesive described above, it is preferable to cure the pressure-sensitive adhesive layer 112 by heating the pressure-sensitive adhesive layer 112. As a result, the adhesion of the first support sheet 11 to the insulating film 10 ′ is reduced, and the first support sheet 11 can be easily peeled off. As the heating means and heating conditions in this case, it is preferable to use the heating means and heating conditions in the case where the heat-expandable pressure-sensitive adhesive is included as the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 112.

Following peeling of the first support sheet 11 from the insulating film 10 ', an electrode is formed on the insulating film 10' by any method known in the art. Below, the example formed by the semi-additive method is demonstrated.

As shown in FIG. 3D, the holes 5 penetrating the insulating film 10 'are formed. Specifically, a hole 5 penetrating from the surface of the insulating film 10 ′ opposite to the electronic component 2 to the interface between the insulating film 10 ′ and the electronic component 2 is formed. The cross-sectional view of FIG. 3D shows that two holes 5 are formed in one electronic component 2. The formation of the holes 5 can be carried out in a conventional manner.

Next, in the desmearing process, the sealing body 4 on which the insulating film 10 ′ in which the holes 5 are formed is stacked is exposed to an alkaline solution. The said process can be performed by the conventionally well-known general method.

Finally, as shown in FIG. 3E, the electrode 6 is formed in the hole 5 as an electrode forming step. The electrode 6 is electrically connected to the electronic component 2 through the hole 5. The formation of the electrode 6 can be performed by a general method. By the above, it is possible to obtain a semiconductor device provided with the insulating film 10 ′ formed by curing of the resin composition layer 10 in the resin sheet 1 according to the present embodiment.

In FIGS. 3D and 3E, the example in which the electrode is formed on the insulating film 10 ′ has been described, but the hole formation and the formation on either of the sealing resin layer 13 ′ and the insulating film 10 ′ are described. Electrode formation may be performed, or hole formation and electrode formation may be performed on both of the sealing resin layer 13 ′ and the insulating film 10 ′.

According to the method of using the resin sheet 1 according to the present embodiment, even when the resin sheet 1 is stored under refrigeration, occurrence of floating at the interface between the resin composition layer 10 and the support sheet is effectively suppressed. , Peeling of the first support sheet 11 from the insulating film 10 ′ can be easily performed, as a result, the yield can be improved, and a high quality component built-in substrate, multilayer printed wiring board, fan-out type wafer level package, It becomes possible to manufacture semiconductor devices such as fan-out type panel level packages.

The embodiments described above are described to facilitate the understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents that fall within the technical scope of the present invention.

Hereinafter, the present invention will be described in more detail by showing Examples and Test Examples, but the present invention is not limited to the following Test Examples and the like.

Example 1
(1) Preparation of first support sheet Acrylic acid ester copolymer (92.8 mass% of 2-ethylhexyl acrylate, 7.0 mass% of 2-hydroxyethyl acrylate, 0.2 mass% of acrylic acid, Copolymers), 50 parts by mass of hydrogenated hydroxyl-terminated polybutadiene as a tackifier (product name “GI-1000” manufactured by Nippon Soda Co., Ltd.), and fat having hexamethylene diisocyanate as a crosslinking agent A mixed solution of a pressure-sensitive adhesive composition having a solid content concentration of 30% by mass was mixed with methyl ethyl ketone-based isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., product name "Coronato HX") and 3.5 parts by mass in methyl ethyl ketone Prepared.

Next, a release film obtained by release-treating one side of a polyethylene terephthalate film with a silicone release layer using a roll coater with a coating solution of the prepared pressure-sensitive adhesive composition (product name “SP-PET 382150, manufactured by Lintec Co., Ltd.) (Thickness: 38 μm), coated on a release-treated surface, heated at 90 ° C. for 90 seconds, subsequently dried at 115 ° C. for 90 seconds, and then dried as a supporting substrate Transparent polyethylene terephthalate film (Toyobo Co., Ltd., product name “PET 50A-4300”, thickness: 50 μm, glass transition temperature Tg: 67 ° C., thermal shrinkage in MD): 1.2%, thermal shrinkage in CD: 0.6 A first support sheet comprising a pressure-sensitive adhesive layer composed of an acrylic pressure-sensitive adhesive having a thickness of 50 μm and a supporting substrate by bonding the first support sheet to It was prepared in a state in which the release film is laminated on the surface of the destination agent layer side.

In addition, the storage elastic modulus at a measurement frequency of 1 Hz at 100 ° C. of the obtained pressure-sensitive adhesive layer was 2.36 × 10 ⁵ Pa. Moreover, the adhesive force with respect to the copper foil of the obtained 1st support sheet was 1.2 N / 25 mm. Moreover, the adhesive force with respect to the polyimide film of a 1st support sheet was 1.1 N / 25 mm. The 5% weight loss temperature of the pressure-sensitive adhesive layer was 304.degree. These physical property values are measured by the following methods.

(Measurement of storage modulus)
About the adhesive layer laminated | stacked until the sum total of thickness will be set to 3 mm, the cylinder (3 mm in thickness) of diameter 8 mm is pierced and this is made into the sample. Regarding the sample, according to JIS K7244-4: 1999, the condition of measurement frequency: 1 Hz and measurement temperature: 100 ° C. by a torsional shear method using a visco-elasticity measuring device (product name “DYNAMIC ANALYZER” manufactured by REOMETRICH) Storage elastic modulus (Pa) was measured.

(Adhesion to copper foil and polyimide film)
The first support sheet is cut into a length of 100 mm and a width of 25 mm, and the peelable film is peeled to form a test piece, which is applied to the copper foil at 0.5 MPa and 50 ° C. for 20 minutes for application. Heating was performed for 30 minutes, followed by heating at 180 ° C. and 60 minutes, and then left for 24 hours in a standard environment (23 ° C., 50% RH). Thereafter, using a tensile tester (product name “Autograph AG-IS” manufactured by Shimadzu Corporation) under a standard environment (23 ° C., 50% RH), a peeling angle of 180 ° and a peeling speed of 300 mm / min. The first support sheet was peeled off from the copper foil and the adhesion (mN / 25 mm) was measured. Moreover, the adhesive force with respect to the polyimide film mentioned above measured the measuring method of the adhesive force similar to the above except changing the object which the 1st support sheet sticks to a polyimide film from copper foil.

(Measurement of 5% weight loss temperature)
For the pressure-sensitive adhesive layer, using a differential heat / thermogravimetry simultaneous measurement device (manufactured by Shimadzu Corporation, product name “DTG-60”), using an inflowing gas as nitrogen, the gas inflow rate 100 ml / min, the temperature rising rate 20 ° C./min Then, the thermogravimetric measurement was performed by raising the temperature from 40 ° C. to 550 ° C. (based on JIS K 7120 “Thermogravimetric measurement method of plastic”). Based on the obtained thermal weight curve, a temperature (5% weight loss temperature) at which the weight decreases by 5% with respect to the weight at a temperature of 100 ° C. was determined.

(2) Formation of a curable resin composition layer 5.1 parts by mass (solids conversion, the same applies hereinafter) of a bisphenol A-type phenoxy resin (made by Mitsubishi Chemical Corporation, product name “jER1256”) as a thermoplastic resin Of bisphenol A epoxy resin (Mitsubishi Chemical Co., Ltd., product name "jER 828") as a reactive resin, and biphenyl epoxy resin (Nippon Kayaku Co., Ltd., product name "NC-" as a thermosetting resin "3000-L") 5.7 parts by mass, 4.1 parts by mass of a naphthalene type epoxy resin (made by DIC, product name "HP-4700") as a thermosetting resin, and biphenyl type as a thermosetting resin 14.1 parts by mass of phenol (manufactured by Meiwa Kasei Co., Ltd., product name "MEHC-7851-SS") and 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd.) as an imidazole-based curing catalyst , Product name "2E4MZ") 0.1 parts by mass, and epoxy silane-treated silica filler as inorganic fine particles [Silica filler (manufactured by Admatex Co., product name "SO-C2", average particle size: 0.5 μm, maximum particle size Diameter: 2 μm, shape: spherical, 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name “KBM-403, minimum coverage area: 330 m ² / g)) 65 A mass part was mixed in methyl ethyl ketone, and the coating liquid of the resin composition whose solid content concentration is 40 mass% was obtained.

A release film obtained by release-treating one side of a polyethylene terephthalate film as a second support sheet with an alkyd release agent as a second support sheet (Lintec Corporation, product name “PET 38 AL-5”, It apply | coated to the peeling process surface of thickness: 38 micrometers, and the obtained coating film was dried, and the laminated body of a 20 micrometers thick curable resin composition layer and a 2nd support sheet was obtained.

(3) Preparation of resin sheet The release film is peeled off from the first support sheet produced in the above step (1), and the exposed surface of the exposed pressure-sensitive adhesive layer and the curability in the laminate produced in the above step (2) By bonding the surface on the resin composition layer side, a resin sheet in which the first support sheet, the curable resin composition layer, and the second support sheet are sequentially laminated is obtained.

Example 2
As a second support sheet, a release film (made by Lintec Co., Ltd., product name “SP-PET 38X, thickness: 38 μm) was used, in which one surface of a polyethylene terephthalate film was release-treated with a non-silicone release layer, In the same manner as Example 1, a resin sheet was obtained.

[Example 3]
As a first support sheet, a sheet (a product name “River Alpha” manufactured by Nitto Denko Corporation) is used, in which a pressure-sensitive adhesive layer composed of a heat-expandable pressure-sensitive adhesive is laminated on one side of a polyethylene terephthalate film. In the same manner as Example 1, a resin sheet was obtained.

Example 4
100 parts by mass of an acrylic copolymer obtained by reacting 86% by mass of 2-ethylhexyl acrylate and 14% by mass of 2-hydroxyethyl acrylate and 15 parts by mass of 2-methacryloyloxyethyl isocyanate It was made to react and obtained the polymer which has active energy ray curability. 100 parts by mass of the polymer having the active energy ray curability, 8 parts by mass of a tolylene diisocyanate based crosslinking agent as a crosslinking agent (Nippon Polyurethane Industry Co., Ltd., product name "Corronate L"), 2 as a photopolymerization initiator 5 parts by mass of 2, 2-dimethoxy-1, 2-diphenylethane-1-one (manufactured by Ciba Specialty Chemicals, product name “IRGACURE 651”) in methyl ethyl ketone and coating of the adhesive composition I got a liquid.

The coating solution is coated on a release-treated surface of a release film (Lintec Co., Ltd., product name “SP-PET 382150”, thickness: 38 μm) obtained by release-treating one surface of a polyethylene terephthalate film with a silicone-based release layer And the coating obtained thereby was dried. After that, a transparent polyethylene terephthalate film (made by Toyobo Co., Ltd., product name “PET 50A-4300”, thickness: 50 μm, glass transition temperature: 67 ° C., as a supporting substrate, and the surface opposite to the peeling film in the coating film. The thermal contraction rate in the MD direction: 1.2%, and the thermal contraction rate in the CD direction: 0.6%. Thereby, the laminated body in which a support base material, an adhesive layer, and a peeling film were laminated | stacked in order was obtained. Furthermore, a first supporting substrate and a pressure-sensitive adhesive layer composed of an active energy ray-curable pressure-sensitive adhesive laminated on one side of the supporting substrate by peeling a peeling film from the laminate. I got a support sheet.

A resin sheet was obtained in the same manner as in Example 1 except that the first support sheet was used.

Comparative Example 1
As a first support sheet, a release film (made by Lintec Co., Ltd., product name “SP-PET 3811”, thickness: 38 μm) in which one surface of a polyethylene terephthalate film is release-treated with a silicone release agent is used. Example 1 and Example 1 were used except that a release film (made by Lintec Co., Ltd., product name “SP-PET 381031”, thickness: 38 μm) was used as the support sheet, one side of the polyethylene terephthalate film being release treated with a silicone release agent. A resin sheet was obtained in the same manner.

Comparative Example 2
A polyethylene terephthalate (PET) film (thickness: 38 μm) whose both surfaces are not release-treated with a release agent is used as the first support sheet, and one side of the polyethylene terephthalate film is silicone as the second support sheet. A resin sheet was obtained in the same manner as in Example 1 except that a release film release-treated with a release agent (manufactured by Lintec Corporation, product name "SP-PET 381031", thickness: 38 μm) was used.

[Test Example 1] (Evaluation of peelability after heat curing)
The resin sheet manufactured by the Example and the comparative example was cut | judged to the size of 500 mm x 400 mm. Thereafter, the second support sheet is peeled off from the resin sheet, and the exposed curable resin composition layer is laminated on a copper plate, heated at 100 ° C. for 30 minutes, and further heated at 180 ° C. for 60 minutes. The resin composition layer was cured. Thereafter, the cured layer formed by curing of the curable resin composition layer was cooled to room temperature.

After cooling of the cured layer is completed, the adhesive constituting the adhesive layer in the first support sheet is heated by heating the resin sheet of Example 3 at 200 ° C. for 20 seconds using an oven. It was foamed. Subsequently, after cooling a resin sheet to room temperature, the 1st support sheet was exfoliated from a hardening layer.

Moreover, about the resin sheet of Example 4, the said adhesive layer was hardened by irradiating an ultraviolet-ray with respect to the adhesive layer of a 1st support sheet. Thereafter, the first support sheet was peeled off from the cured layer.

About the resin sheet of Examples 1 and 2 and Comparative Examples 1 and 2, after cooling of a hardened layer was completed, the 1st support sheet was exfoliated from a hardened layer, without performing processings, such as heating and ultraviolet irradiation.

About the condition when the 1st support sheet was exfoliated from a hardening layer as mentioned above, the exfoliation after thermosetting was evaluated based on the following standard. The results are shown in Table 1.
A: The first support sheet could be peeled off.
B: The first support sheet could not be peeled off.

[Test Example 2] (Evaluation of floating during storage)
The resin sheets produced in Examples and Comparative Examples are cut into a size of 500 mm × 400 mm, stored for 1 week in an environment of 5 ° C., and then floated at the interface between the curable resin composition layer and the first support sheet. And the occurrence of floating at the interface between the curable resin composition layer and the second support sheet were evaluated, and the floating during storage was evaluated based on the following criteria. The results are shown in Table 1.
A: Lifting does not occur both at the interface between the curable resin composition layer and the first support sheet and at the interface between the curable resin composition layer and the second support sheet.
AB: Lifting does not occur at the interface between the curable resin composition layer and the first support sheet, but lifting occurs at the interface between the curable resin composition layer and the second support sheet.
B: Lifting occurs both at the interface between the curable resin composition layer and the first support sheet and at the interface between the curable resin composition layer and the second support sheet.

[Test Example 3] (Measurement of Peeling Force)
About the resin sheet manufactured in Example 1 and 2, peeling force (F11) at the time of peeling a 1st support sheet from the resin composition layer before hardening by the following method, and a 1st support sheet Peeling force (F12) at the time of peeling from the cured layer formed by thermosetting the composition layer was measured. Further, with respect to the resin sheets manufactured in Examples 1 to 4, the peeling force (F2) at the time of peeling the second support sheet from the resin composition layer before curing was measured. The results are shown in Table 1.

(1) Measurement of Peeling Force (F11) The resin sheets produced in Examples 1 and 2 were cut into a width of 25 mm and a length of 250 mm. Next, the second support sheet was peeled off, and the exposed surface of the exposed curable resin composition layer was bonded to a stainless steel plate with a double-sided tape to prepare a measurement sample. Then, based on JIS Z 0237; 2009, using an all-purpose tensile tester (Autograph manufactured by Shimadzu Corporation), peeling speed 300 mm / min, peeling angle 180 ° under an environment of 23 ° C. and 50% relative humidity. The first support sheet was peeled off from the curable resin composition layer, and the peeling force (N / 25 mm) was measured to obtain a peeling force (F11).

(2) Measurement of Peeling Force (F12) The measurement sample prepared in the same manner as the above (1) is heated at 100 ° C. for 30 minutes and further heated at 180 ° C. for 60 minutes to cure the curable resin composition layer. did. Thereafter, the cured layer formed by curing of the curable resin composition layer was cooled to room temperature. The peel strength (N / 25 mm) of the measurement sample after cooling was measured in the same manner as the above (1) to obtain a peel strength (F12).

(3) Measurement of Peeling Force (F2) The resin sheets produced in Examples 1 to 4 were cut into a width of 100 mm and a length of 100 mm. Next, the second support sheet is peeled off from the curable resin composition layer by T-peel peeling at a peeling speed of 300 mm / min under an environment of 23 ° C. and a relative humidity of 50% based on JIS K6854-3: 1999. Peeling force (N / 100 mm) at that time was measured, and it was set as peeling force (F2).

[Test Example 4] (Evaluation of Formability of Electrode)
The second support sheet was peeled off from the resin sheet produced in Examples 1 to 4, and the exposed surface of the curable resin composition layer was formed on one side of the core material (manufactured by Hitachi Chemical Co., Ltd., product name "MCL-E-679FG"). Then, using a vacuum laminator (manufactured by Nikko Materials, product name "V130"), lamination was performed under conditions of 90 ° C and 0.3 MPa. Thereafter, the curable resin composition layer was cured by heating at 100 ° C. for 30 minutes and further heating at 180 ° C. for 60 minutes.

Then, about Example 3, the adhesive which comprises the adhesive layer in a 1st support sheet was heated, and it was made to foam by heating for 20 seconds at 200 degreeC using oven. Moreover, about Example 4, the said adhesive layer was hardened by irradiating an ultraviolet-ray with respect to the adhesive layer of a 1st support sheet. After these, the first support sheet was peeled off from the cured layer for each example. Thereby, the laminated body which consists of a core material and the hardened layer as an insulating layer was obtained.

Next, a laser was irradiated to the surface on the insulating layer side in the obtained laminate using a CO ₂ laser processing machine to form a via hole having a diameter of 100 μm on the surface of the insulating layer.

Thereafter, the laminate was immersed at 60 ° C. for 5 minutes in an alkaline swelling solution in which a glycol ether solvent and ethylene glycol monobutyl ether were mixed. Subsequently, the laminate was immersed in a roughening solution (alkaline permanganic acid aqueous solution) at 80 ° C. for 15 minutes. Furthermore, the laminate was neutralized by immersing in an aqueous solution of sulfuric acid at 40 ° C. for 5 minutes. Finally, the desmear treatment was completed by drying the laminate at 80 ° C. for 5 minutes.

Subsequently, the laminate subjected to the desmear treatment is immersed in the solution for electroless plating at 40 ° C. for 6 minutes, and further immersed in the electroless copper plating solution at 25 ° C. for 18 minutes, and then annealed for 30 minutes at 150 ° C. Did. Thereafter, a plating resist layer is attached to the surface on which the via hole is formed, and a predetermined pattern (wiring width (L): 50 μm, wiring spacing (S): 50 μm) in the plating resist layer is obtained by exposure and development. The area was removed. Subsequently, copper sulfate electrolytic plating was performed to form a layer of copper having a thickness of 10 μm in the removed area. Then, the remaining plating resist layer was peeled off, unnecessary portions of electroless copper plating were removed by flash etching, and finally, annealing was performed at 190 ° C. for 60 minutes.

The electrode formed as described above was observed, and the formability of the electrode was evaluated based on the following criteria. The results are shown in Table 1.
:: It was possible to form an electrode having the intended wiring pattern (wiring width (L): 50 μm, wiring spacing (S): 50 μm).
X: The electrode having the intended wiring pattern could not be formed.

As shown in Table 1, in the resin sheet according to the example, even after heat curing, the first support sheet could be peeled well from the cured layer. Moreover, in the resin sheet which concerns on an Example, generation | occurrence | production of the float between the 1st support sheet and curable resin composition layer at the time of storage was suppressed. On the other hand, the resin sheet which concerns on the comparative example 1 had floating generate | occur | produced at the time of storage. Moreover, the resin sheet which concerns on the comparative example 2 was not able to peel a support sheet from the formed cured layer after thermosetting of a resin composition layer.

The resin sheet according to the present invention can be suitably used for the production of semiconductor devices such as component built-in substrates, multilayer printed wiring boards, fan-out type wafer level packages, and fan-out type panel level packages.

DESCRIPTION OF SYMBOLS 1 ... Resin sheet 10 ... Curable resin composition layer 10 '... Insulating film 11 ... 1st support sheet 111 ... Support base material 112 ... Adhesive layer 12 ... 2nd support sheet 2 ... Electronic component 4 ... Sealing body 5 ... hole 6 ... electrode 8 ... temporary fixing material 13 ... sealing sheet 13 '... sealing resin layer

Claims

A resin sheet used to form an insulating film,
The resin sheet includes a first support sheet, and a curable resin composition layer laminated on one side of the first support sheet.
The resin composition layer is formed of a resin composition containing a thermosetting resin and inorganic fine particles,
The content of the inorganic fine particles in the resin composition is 50% by mass or more and 90% by mass or less,
The first support sheet includes a support base and an adhesive layer laminated on one side of the support base,
A resin sheet, wherein the resin composition layer is laminated on the surface of the first support sheet on the pressure-sensitive adhesive layer side.
The resin composition layer contains a thermoplastic resin,
Content of the said thermoplastic resin in the said resin composition is 1.0 mass% or more and 30 mass% or less, The resin sheet of Claim 1 characterized by the above-mentioned.
The said adhesive layer is comprised from the acrylic adhesive, The resin sheet of Claim 1 or 2 characterized by the above-mentioned.
The pressure-sensitive adhesive layer is composed of at least one pressure-sensitive adhesive selected from an active energy ray-curable pressure-sensitive adhesive, a thermally foamable pressure-sensitive adhesive and a thermosetting pressure-sensitive adhesive. The resin sheet as described in any one of the above.
The resin sheet which heated the said resin sheet for 30 minutes at 100 degreeC, and also heated for 60 minutes at 180 degreeC, Peeling force at the time of peeling said 1st support sheet from the cured layer which the said resin composition layer hardens | cures The resin sheet according to any one of claims 1 to 4, wherein (F12) is 0.5 N / 25 mm or more and 3.0 N / 25 mm or less.
The pressure-sensitive adhesive layer in the first support sheet has a storage elastic modulus of 1 × 10 5 Pa or more at 100 ° C. and a measurement frequency of 1 Hz. The resin sheet as described in one item.
The first support sheet is
The pressure-sensitive adhesive layer is attached to a copper foil, heated at 100 ° C. for 30 minutes, subsequently heated at 180 ° C. for 30 minutes, and further heated at 190 ° C. for 1 hour, The adhesion at room temperature to the copper foil is 0.7 N / 25 mm or more and 2.0 N / 25 mm or less,
The pressure-sensitive adhesive layer surface is adhered to a polyimide film, heated at 100 ° C. for 30 minutes, subsequently heated at 180 ° C. for 30 minutes, and further heated at 190 ° C. for 1 hour, The resin sheet according to any one of claims 1 to 6, wherein the adhesion at room temperature to the polyimide film is 0.7 N / 25 mm or more and 2.0 N / 25 mm or less.
The resin sheet according to any one of claims 1 to 7, wherein the pressure-sensitive adhesive layer in the first support sheet has a 5% weight loss temperature of 250 属 C or more.
The resin sheet according to any one of claims 1 to 8, wherein the thermoplastic resin is at least one selected from phenoxy resins, polyvinyl acetal resins and polyvinyl butyral resins.
The resin sheet according to any one of claims 1 to 9, wherein the inorganic fine particles are surface-treated with a surface treatment agent.
The resin sheet according to any one of claims 1 to 10, wherein an average particle diameter of the inorganic fine particles is 0.01 μm or more and 3.0 μm or less.
The resin sheet according to any one of claims 1 to 11, wherein a thickness of the resin composition layer is 5 μm or more and 80 μm or less.
The resin sheet according to any one of claims 1 to 12, wherein the support base is a resin support base having a glass transition temperature (Tg) of 50 属 C or higher.
The said resin sheet is provided with the 2nd support sheet laminated | stacked on the surface on the opposite side to the said 1st support sheet in the said resin composition layer, The any one of the Claims 1-13 characterized by the above-mentioned. Resin sheet as described.
The resin sheet according to any one of claims 1 to 14, which is used for forming the insulating film in a semiconductor device.
The resin sheet according to claim 15, wherein the insulating film is an insulating film in a buildup layer of the semiconductor device.
17. The resin sheet according to claim 15, wherein the semiconductor device is at least one of a component built-in substrate, a multilayer printed wiring board, a fan-out type wafer level package and a fan-out type panel level package.
An insulating film formed by curing the resin composition layer in the resin sheet according to any one of claims 1 to 17.
A semiconductor device comprising, as an insulating layer, a cured layer obtained by curing the resin composition layer in the resin sheet according to any one of claims 1 to 17.
It is a usage method of the resin sheet as described in any one of Claims 1-17, Comprising:
Curing the resin composition layer to obtain a cured layer;
And exfoliating the first support sheet from the cured layer after curing the resin composition layer.