JP2020203961A - Curable resin composition, inorganic substrate laminate, and method for producing the same - Google Patents

Abstract

To provide a curable resin composition which has high heat resistance, has good adhesion to an inorganic substrate and filling property in irregularity and is small in surface waviness by hardening shrinkage, an inorganic substrate laminate using the same, and a method for producing the same.SOLUTION: A curable resin composition that is used for forming an insulating layer having a flat upper surface on a function element formation surface of an inorganic substrate formed with a plurality of function elements contains a silicone compound having 10% or more of a siloxane unit having an Si-H bond in the whole siloxane unit and 10% or more of a T unit (RSiO3/2, R is monovalent substituent (including H)), and a compound having a vinyl group.SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition used for forming an insulating layer having a flat upper surface on a functional element forming surface of an inorganic substrate on which a plurality of functional elements are formed, and an inorganic substrate laminate using the curable resin composition. And the manufacturing method thereof.

Conventionally, in industries such as the semiconductor industry, the MEMS industry, and the display industry, process technologies for rigid flat substrates such as wafer-based or glass substrate-based have been constructed. Further, in recent years, technological development for forming these elements on a polymer film has been carried out for the purpose of weight reduction, miniaturization / thinning, and flexibility of functional elements such as semiconductor elements, MEMS elements, and display elements. There is.

On the other hand, in order to increase the density of functional elements in various devices, a technique for forming a plurality of functional elements in multiple layers is also important. For example, in the semiconductor industry, a semiconductor package in which a plurality of chips are laminated to form a multilayer is manufactured, or a plurality of devices are built in a multilayer wiring board.

In such a multi-layer technology, if only a plurality of chips and the like are bonded and sealed together, high heat resistance is not required for the adhesive and the like, but each layer functions while being sequentially laminated. When forming an element, high heat resistance and the like are required. That is, in the process of forming a desired functional element in each layer, the laminate is often exposed to a high temperature, and for example, in forming a functional element such as polysilicon or an oxide semiconductor, the temperature is about 200 ° C to 600 ° C. Processes in the temperature range may be required.

By the way, as a manufacturing process that requires such high heat resistance, in Patent Document 1, a member for an electronic device such as a display device is formed on a glass substrate of a glass laminate in which a glass substrate and a reinforcing plate are laminated. Later, a method of separating the reinforcing plate from the glass substrate has been proposed. This reinforcing plate has a silicone resin layer fixed on the support plate, and the silicone resin layer and the glass substrate are detachably adhered to each other. When forming the silicone resin layer, a solvent-free addition reaction type silicone for release paper, a platinum-based catalyst, or the like is used.

International Publication No. 2007/018028

However, since the silicone resin layer in Patent Document 1 is formed on a flat support plate and is peeled off from the glass substrate after forming a member for an electronic device, peelability after heating is required. It is a thing.

On the other hand, in the above-mentioned multi-layer technology, when a functional element is formed for each layer, the surface of the lower layer has irregularities due to the functional element, and a resin layer is filled therein to flatten the surface. Is desirable. For this reason, the resin layer is required to have adhesion to the inorganic substrate and fillability to unevenness, and it is also required to reduce the curing shrinkage rate of the silicone resin layer to reduce the surface waviness. It is difficult for the silicone for release paper used in No. 1 to satisfy such a requirement.

The present invention has been made in view of the above-mentioned problems, and an object thereof is to have high heat resistance, good adhesion to an inorganic substrate and good filling property to irregularities, and small surface waviness due to curing shrinkage. An object of the present invention is to provide a curable resin composition, an inorganic substrate laminate using the curable resin composition, and a method for producing the same.

As a result of diligent studies on a curable resin composition having heat resistance after curing, the present inventors have found that the above problems can be solved by containing a silicone compound having a specific structure and a compound having a vinyl group. , The present invention has been completed.

That is, the curable resin composition of the present invention is a curable resin composition used for forming an insulating layer having a flat upper surface on a functional element forming surface of an inorganic substrate on which a plurality of functional elements are formed. Silicone having 10% or more of siloxane units having a Si—H bond and 10% or more of T units (RSiO _3/2 , R is a monovalent substituent (including H)) out of all siloxane units. It is characterized by containing a compound and a compound having a vinyl group.

According to the curable resin composition of the present invention, when forming an insulating layer, it has high heat resistance, good adhesion to an inorganic substrate and good filling property to irregularities, and small surface waviness due to curing shrinkage. It becomes. The details of the reason are not clear, but it can be considered as follows. That is, when the silicone compound has a T unit of 10% or more, it can have high heat resistance and reduce the amount of shrinkage during curing. Further, since the siloxane unit having a Si—H bond and the compound having a vinyl group contribute to the addition type curing reaction, sufficient adhesion (initial peel strength) can be obtained and the amount of shrinkage during curing is small. It is considered that the surface waviness can be reduced. Further, it is considered that by using a compound having a vinyl group, it is not necessary to use a metal catalyst, and the filling property to the unevenness can be improved.

In the above, it is preferable that the compound having a vinyl group is a cross-linking agent having a plurality of vinyl groups or a silane coupling agent having a vinyl group. By using these compounds, it is considered that the crosslink density after curing can be further increased and the adhesion to the inorganic substrate can be further enhanced.

Further, it is preferable that the silicone compound further has a siloxane unit having a vinyl group. When the silicone compound has such a structure, an addition reaction with a siloxane unit having a Si—H bond is likely to occur, and the addition type curing reaction proceeds to realize higher heat resistance and a lower shrinkage amount. It is thought that it will be easier to do.

On the other hand, the inorganic substrate laminate of the present invention includes an inorganic substrate on which a plurality of functional elements are formed and an insulating layer obtained by curing the curable resin composition according to any one of the above. It is characterized in that the recesses between the functional elements are also filled and the upper surface is formed flat.

According to the inorganic substrate laminate of the present invention, since the curable resin composition of the present invention contains an insulating layer formed by curing, it has high heat resistance due to the above-mentioned action and effect, and also has high adhesion to the inorganic substrate. It has an insulating layer having good filling property to unevenness and small surface waviness due to curing shrinkage.

In the above, it is preferable that the upper surface of the insulating layer further contains a heat-resistant polymer film. By including the heat-resistant polymer film, it becomes easier to form a flat surface on the upper surface of the insulating layer, which is advantageous for forming a functional element on the heat-resistant polymer film and further laminating an inorganic substrate.

Further, it is preferable that a plurality of functional elements are formed on the upper surface of the insulating layer or the upper surface of the heat-resistant polymer film. With such a structure, it becomes easy to increase the density and size of various devices.

On the other hand, the method for producing an inorganic substrate laminate of the present invention includes a coating step of applying the curable resin composition according to any one of the above to a functional element forming surface of an inorganic substrate on which a plurality of functional elements are formed. It is characterized by including a curing step of curing the curable resin composition while the upper surface of the curable resin composition is flat.

According to the method for producing an inorganic substrate laminate of the present invention, since the step of applying and curing the curable resin composition of the present invention is included, it has high heat resistance due to the above-mentioned action and effect and adheres to the inorganic substrate. It is possible to obtain an inorganic substrate laminate having an insulating layer having good properties and filling properties to irregularities and having small surface waviness due to curing shrinkage.

In the above, it is preferable that the curing step includes a step of laminating a heat-resistant polymer film after the coating step, and the curing step cures the curable resin composition in a state where the heat-resistant polymer film is laminated. .. By laminating the heat-resistant polymer films in this way and curing them in that state, an insulating layer having a flatter upper surface can be formed. Further, it is possible to include a peeling step of peeling the heat-resistant polymer film.

In the above, it is preferable to further include an element forming step of forming a plurality of functional elements on the upper surface of the insulating layer or the upper surface of the heat-resistant polymer film. By including such an element forming step, it becomes easy to increase the density and miniaturization of various devices.

According to the curable resin composition of the present invention, when forming an insulating layer, it has high heat resistance, good adhesion to an inorganic substrate and good filling property to irregularities, and small surface waviness due to curing shrinkage. It becomes. Further, according to the inorganic substrate laminate of the present invention, it has high heat resistance, good adhesion to the inorganic substrate and good filling property to unevenness, and has an insulating layer having small surface waviness due to curing shrinkage. Further, according to the method for producing an inorganic substrate laminate of the present invention, the inorganic has high heat resistance, good adhesion to the inorganic substrate and good filling property to unevenness, and an insulating layer having a small surface waviness due to curing shrinkage. A substrate laminate can be obtained.

It is sectional drawing which shows an example of each process of the manufacturing method of the inorganic substrate laminated body of this invention. It is sectional drawing which shows an example of each process of the manufacturing method of the inorganic substrate laminated body of this invention. It is sectional drawing which shows an example of each process of the manufacturing method of the inorganic substrate laminated body of this invention. It is sectional drawing which shows an example of each process of the manufacturing method of the inorganic substrate laminated body of this invention. It is sectional drawing which shows an example of each process of the manufacturing method of the inorganic substrate laminated body of this invention. It is sectional drawing which shows an example of each process of the manufacturing method of the inorganic substrate laminated body of this invention. It is sectional drawing which shows an example of each process of the manufacturing method of the inorganic substrate laminated body of this invention. It is sectional drawing which shows an example of each process of the manufacturing method of the inorganic substrate laminated body of this invention. It is sectional drawing which shows the other example of the inorganic substrate laminated body of this invention. It is sectional drawing which shows the other example of the inorganic substrate laminated body of this invention. It is sectional drawing which shows the other example of the inorganic substrate laminated body of this invention. It is a front view of the inorganic substrate for step confirmation obtained in the manufacturing example 2 of the inorganic substrate. It is a front view of the inorganic substrate for step confirmation obtained in the manufacturing example 3 of the inorganic substrate.

[Curable resin composition]
The curable resin composition of the present invention is used for forming an insulating layer having a flat upper surface on a functional element forming surface of an inorganic substrate on which a plurality of functional elements are formed. In the present invention, "the upper surface of the insulating layer is flat" means that the maximum height of the surface irregularities on the surface of the insulating layer opposite to the inorganic substrate is the maximum height (maximum depth) of the irregularities on the inorganic substrate generated by the functional element. The maximum height of the surface unevenness of the insulating layer is preferably 5 μm or less, and more preferably 1 μm or less.

<Inorganic substrate>
The inorganic substrate may be a plate-like substrate that can be used as a substrate made of an inorganic substance. For example, a glass plate, a ceramic plate, a semiconductor wafer, a metal or the like, and these glass plates, ceramic plates, etc. Examples of the semiconductor wafer and the composite of the metal include those in which these are laminated, those in which they are dispersed, and those in which these fibers are contained.

Examples of the glass plate include quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pylex (registered trademark)), borosilicate glass (non-alkali), and the like. Borosilicate glass (microsheet), aluminosilicate glass and the like are included.

Examples of the ceramic plate include those made of ceramics such as alumina, zirconia, mullite, cordylite, steatite, magnesium titanate, calcium titanate, strontium titanate, aluminum nitride, silicon carbide, and silicon nitride.

The semiconductor wafer is not particularly limited, but silicon wafer, germanium, silicon-germanium, gallium-arsenic, aluminum-gallium-indium, nitrogen-phosphorus-arsenide-antimony, SiC, InP (indium phosphorus), InGaAs, GaInNAs, Wafers such as LT, LN, ZnO (zinc oxide), CdTe (cadmium tellurium), and ZnSe (zinc selenide) can be mentioned. Among them, the wafer preferably used is a silicon wafer, and particularly preferably a mirror-polished silicon wafer having a size of 8 inches or more.

Examples of the metal include single element metals such as W, Mo, Pt, Fe, Ni and Au, alloys such as Inconel, Monel, mnemonic, carbon copper, Fe—Ni-based Invar alloys and Super Invar alloys. Further, a multilayer metal plate formed by adding another metal layer or a ceramic layer to these metals is also included.

<Functional element>
In the present invention, a device in which a plurality of functional elements are formed on the above-mentioned inorganic substrate is used. The functional element may be directly formed on an inorganic substrate such as a wafer by a wafer process or the like, or a separately prepared functional element or a wafer chip or the like on which the functional element is formed may be mounted on the inorganic substrate such as a wafer. It may be formed of.

Functional elements include active elements such as transistors and diodes, passive elements such as resistors, capacitors and inductors, sensor elements that sense pressure, temperature, light, humidity, etc., biosensor elements, light emitting elements, liquid crystal displays, and electrophoresis. Examples include image display elements such as displays and self-luminous displays, wireless and wired communication elements, arithmetic elements, storage elements, MEMS elements, power generation elements such as solar cells, power storage elements, and thin film thinning devices.

The plurality of functional elements may be of the same type, but usually, a plurality of types of functional elements are combined and wired on an inorganic substrate to form an electronic circuit or the like. For example, a TFT liquid crystal drive circuit for an image display device is formed on a glass substrate. Further, for example, a calculation element, a storage element, and the like are formed on the wafer by the wafer process.

On the other hand, chips and the like on which a plurality of functional elements are formed are also included in the "functional elements" in the present invention, and an inorganic substrate on which a plurality of such chips and the like are formed can also be used in the present invention.

The maximum height (maximum depth) of the unevenness on the inorganic substrate generated by such a functional element is, for example, 10 to 200 μm, preferably 1 to 20 μm, and the present invention has a sufficiently upper surface even for such unevenness. Can form a flat insulating layer. When the wafer chip or the like is mounted on the inorganic substrate, the maximum height (maximum depth) of the unevenness becomes larger than that when the functional element is directly formed on the inorganic substrate.

<Silicone compound>
The curable resin composition of the present invention contains a silicone compound and a compound having a vinyl group (excluding the silicone compound). Silicone compounds generally have monofunctional M units (R ₃ SiO _1/2 , R is a monovalent substituent (including H)), and bifunctional D units (R ₂ SiO _2/2 , R are). All monovalent substituents (including H), trifunctional T units (RSiO _3/2 , R is monovalent substituents (including H)), and tetrafunctional Q units (SiO _4/2 ) Or it contains a part. The "monovalent substituent" is a monovalent substituent that can be bonded to the Si atom of the silicone compound, and examples thereof include a hydrocarbon group, an oxygen-containing hydrocarbon group, a hydroxy group, and a hydrogen group.

The silicone compound used in the present invention has a T unit of 10% or more of all siloxane units. From the viewpoint of forming an appropriate crosslinked structure for enhancing heat resistance, it preferably has 15 to 23% of T units, and more preferably 18 to 22% of T units. In the present invention, the ratio of each siloxane unit is based on the molar standard. Examples of the monovalent substituent R in the T unit include a methyl group, a phenyl group, a vinyl group, a hydroxy group, a hydrogen group and the like.

Further, the silicone compound preferably has 10 to 25% of D units, and 15 to 20% of D units, from the viewpoint of maintaining an appropriate crosslinked structure while ensuring the filling property to the unevenness. It is more preferable to have. For the same reason, the silicone compound preferably contains 3% or less of Q units among all siloxane units, and more preferably does not contain Q units.

The silicone compound used in the present invention preferably contains 10% or more of siloxane units having a Si—H bond among all siloxane units, and is preferably from the viewpoint of a crosslinked structure for enhancing heat resistance and ease of addition reaction. It has 10 to 25% of siloxane units having a Si—H bond, and more preferably 15 to 22% of siloxane units having a Si—H bond. The siloxane unit having a Si—H bond is classified into a D unit, a T unit, or an M unit, and the D unit is preferably a siloxane unit represented by RHSiO _2/2 (R is a methyl group or a phenyl group).

Further, the silicone compound preferably has a siloxane unit having a vinyl group. The siloxane unit having a vinyl group is classified into D unit, T unit or M unit, and the D unit is a siloxane unit represented by RR'SiO _2/2 (R is a methyl group or a phenyl group and R'is a vinyl group). Is preferable. The content of the siloxane unit having a vinyl group is more preferably 15 to 30%, still more preferably 20 to 27%, from the viewpoint of the crosslinked structure for enhancing the heat resistance and the ease of the addition reaction.

In the present invention, the same type or a plurality of types of the above-mentioned silicone compounds can be mixed and used. When a plurality of types are mixed, it is preferable that each siloxane unit satisfies the above range of content by an average value.

The silicone compound is preferably contained in the curable resin composition in an amount of 50 to 100% by mass, more preferably 80 to 100% by mass, from the viewpoint of exerting a function as a main curable resin component.

<Compound with vinyl group>
The compound having a vinyl group is preferably a cross-linking agent having a plurality of vinyl groups (excluding a silane coupling agent) or a silane coupling agent having a vinyl group. As the cross-linking agent having a plurality of vinyl groups, a cross-linking agent having two vinyl groups in the molecule is preferable, and examples thereof include a divinyl compound and a di (meth) acrylate compound.

Examples of divinyl or vinylphenyl compounds include o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, 4-acetoxystyrene, 3-acetoxystyrene, 2-acetoxystyrene, 4-isopropenyltoluene, and 3-isopropenyltoluene. , 2-Isopropenyltoluene, 4-methylstyrene, 3-methylstyrene, 2-methylstyrene, 1,4-diisopropenylbenzene, 4-ethylstyrene, 1-allyl-4-vinylbenzene, 3-vinyl-4 -Methylphenol, 3,4-divinylphenol, 3,5-divinylphenol, 2,4-divinylphenol, 2,6-divinylphenol, 3-vinyl-5-methylphenol, 2-vinylphenol, 3-vinylphenol , 4-vinylphenol, 4-vinylbenzoic acid, 3-vinylbenzoic acid, 2-vinylbenzoic acid, 2,6-divinylbenzoic acid, 2,5-divinylbenzoic acid, 2,4-divinylbenzoic acid, 2, 3-Divinyl benzoic acid, 2-vinyl-5-methyl benzoic acid, 2-vinyl-4-methyl benzoic acid, 2-vinyl-3-methyl benzoic acid, 2-methyl-5-vinyl benzoic acid, 2-methyl- 4-Vinyl benzoic acid, 2-methyl-3-vinyl benzoic acid, 2-methyl-2-vinyl benzoic acid, 3-methyl-5-vinyl benzoic acid, 3-methyl-4-vinyl benzoic acid, 4-trifluoro Methylstyrene, 3-trifluoromethylstyrene, 2-trifluoromethylstyrene, 4-vinylbenzaldehyde, 3-vinylbenzaldehyde, 2-vinylbenzaldehyde, 2,5-divinylbenzaldehyde, 2-vinyl-5-methylbenzaldehyde, 2- Vinyl-4-methylbenzaldehyde, 2-vinyl-3-methylbenzaldehyde, 2-methyl-5-vinylbenzaldehyde, 2-methyl-4-vinylbenzaldehyde, 2-methyl-3-vinylbenzaldehyde, 2-methyl-2-vinyl Benzaldehyde, 3-methyl-5-vinylbenzaldehyde, 3-methyl-4-vinylbenzaldehyde, 2,6-divinylbenzaldehyde, 2,5-divinylbenzaldehyde, 2,4-divinylbenzaldehyde, 2,3-divinylbenzaldehyde, 4- Vinylbenzonitrile, 3-vinylbenzonitrile, 2-vinylbenzonitrile, 2,6-divinylbenzonitrile, 2,5-divinylbenzonitrile, 2,4-divinylbenzonitrile, 2 , 3-Divinylbenzonitrile, 2-vinyl-5-methylbenzonitrile, 2-vinyl-4-methylbenzonitrile, 2-vinyl-3-methylbenzonitrile, 2-methyl-5-vinylbenzonitrile, 2-methyl -4-Vinylbenzonitrile, 2-methyl-3-vinylbenzonitrile, 2-methyl-2-vinylbenzonitrile, 3-methyl-5-vinylbenzonitrile, 3-methyl-4-vinylbenzonitrile, 4-amino Styrene, 3-aminostyrene, 2-aminostyrene, 2,6-divinylaniline, 2,5-divinylaniline, 2,4-divinylaniline, 2,3-divinylaniline, vinylcyclohexane, o-divinylcyclohexane, m- Divinylcyclohexane, p-divinylcyclohexane, vinylcyclopentane, 1,2-divinylcyclopentane, 1,3-divinylcyclopentane, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-allylnaphthalene, 2-allylnaphthalene, 1- Ethynylnaphthalene, 2-ethynylnaphthalene, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2,5-divinylpyridine, 2,3-divinylpyridine, 2,4-divinylpyridine, 2,5-divinylpyridine , 2,6-Divinylpyridine, 4,4'-divinyl-1,1'-biphenyl and the like.

Examples of the silane coupling agent having a vinyl group include silane coupling agents having a vinyl group, a styryl group, a methacrylic group, an acrylic group and the like in the present invention.

Examples of those having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, vinyltrichlorosilane, vinyltriacetoxysilane and the like. Examples of those having a styryl group include styryltrimethoxysilane. Those having a methacryl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and those having an acrylic group. Examples thereof include 3-acryloxypropyltrimethoxysilane.

When a cross-linking agent having a plurality of vinyl groups is used, the content of the compound having a vinyl group is 20 to 20 to 20 in the curable resin composition from the viewpoint of the cross-linking structure for increasing the heat resistance and the ease of addition reaction. It is preferably contained in an amount of 0.1% by mass, more preferably 10 to 1% by mass. When a silane coupling agent having a vinyl group is used, it is preferably contained in the curable resin composition in an amount of 20 to 0.1% by mass, preferably 10 to 1% by mass, from the viewpoint of enhancing the reactivity of the inorganic substrate. % Is more preferable.

As the compound having a vinyl group, the same type or a plurality of types can be mixed and used.

<Other ingredients>
When the curable resin composition of the present invention contains a silane coupling agent having a vinyl group, it is preferable to contain water from the viewpoint of enhancing the reactivity between the silane coupling agent and the inorganic substrate. In that case, the content of water is, for example, 5 mol times to 0.05 mol times, preferably 2 mol times to 0.1 mol times, more preferably 1.2 times the alkoxy group of the silane coupling agent. It is molar times to 0.2 molar times.

Further, the curable resin composition of the present invention can contain other components such as a solvent, a surfactant, a filler, an antifoaming agent, a curing agent, and a catalyst. The content of these components may be within a range that does not impair the effects of the present invention.

[Inorganic substrate laminate]
1A to 1H are cross-sectional views showing an example of each step of the method for producing an inorganic substrate laminate of the present invention, of which FIG. 1C shows an example of the inorganic substrate laminate of the present invention. .. 2 to 4 are cross-sectional views showing another example of the inorganic substrate laminate of the present invention. Hereinafter, the present invention will be described in detail with reference to the drawings.

As shown in FIG. 1C and the like, the inorganic substrate laminate of the present invention is an insulation obtained by curing the inorganic substrate 10 on which a plurality of functional elements 12 are formed and the curable resin composition 21 of the present invention described above. Layer 22 and the like. Further, in the present invention, the insulating layer 22 is also filled in the recesses between the functional elements 12, and the upper surface 22a is formed flat.

<Inorganic substrate on which multiple functional elements are formed>
In the present embodiment, as shown in FIG. 1A, an inorganic substrate 10 on which a plurality of functional elements 12 are formed by mounting a plurality of semiconductor chips on a wafer 11 having a functional element layer 11a and a wiring layer 11b. Is shown as an example of using. In this example, a functional element layer 11a forming an electronic circuit and a wiring layer 11b for connecting the functional element layer 11a to the outside are formed on the upper portion of the wafer 11, and the wiring layer 11b is connected by bumps 13. Multiple semiconductor chips are mounted. That is, in the inorganic substrate 10, an example is shown in which a plurality of functional elements 12 are formed as the functional element layer 11a of the wafer 11 and a plurality of functional elements 12 are formed as the mounted semiconductor chips.

The functional element layer 11a and the wiring layer 11b of the wafer 11 are usually formed in multiple layers, but in the drawings of the present application, this is simplified and described as a single layer. Further, the functional element layer 11a of the wafer 11 is usually formed in a wide range within the surface of the wafer 11, whereas in the drawing of the present application, two adjacent functional element layers 11a are formed. Only the portion of the wafer 11 is described, and the wafer 11 is continuous in the left-right direction.

In the example shown in FIG. 1C, a plurality of semiconductor chips are mounted on the wafer 11, but in the present invention, various chip components other than the semiconductor chip, resistance elements, capacitor elements, coil elements, light emitting elements, and light receiving elements are mounted. , Switching elements, sensor elements, etc. can also be mounted.

Further, instead of the connection by the bump 13, it is also possible to connect by solder, wire bonding or the like.

<Insulation layer>
The insulating layer 22 is formed by curing the curable resin composition 21 of the present invention. The curing conditions and the like will be described in detail later. The upper surface 22a of the insulating layer 22 is formed flat, but in the case of the process shown in FIG. 1C, the flat state of the upper surface 22a is determined according to the surface roughness of the laminated heat-resistant polymer film 31 and the like. Will be done. This is because the curable resin composition 21 of the present invention has a property of being hard to cure and shrink, and when the curing shrinkage is large, the heat-resistant polymer film 31 is used to form the insulating layer 22. However, undulations are likely to occur on the surface.

<Heat-resistant polymer film>
As shown in FIG. 1C, the upper surface of the insulating layer 22 of the inorganic substrate laminate of the present invention may further contain a heat-resistant polymer film 31. By using the heat-resistant polymer film 31, it is possible to withstand the heat generated when the functional element is formed on the heat-resistant polymer film 31.

In the present specification, the heat-resistant polymer is a polymer having a melting point of 400 ° C. or higher, preferably 500 ° C. or higher, and a glass transition temperature of 250 ° C. or higher, preferably 320 ° C. or higher, more preferably 380 ° C. or higher. .. Hereinafter, it is also simply referred to as a polymer in order to avoid complication. In the present specification, the melting point and the glass transition temperature are determined by differential thermal analysis (DSC). When the melting point exceeds 500 ° C., it may be determined whether or not the melting point has been reached by visually observing the thermal deformation behavior when heated at the corresponding temperature.

Examples of the heat-resistant polymer film (hereinafter, also simply referred to as polymer film) include polyimide resins such as polyimide, polyamideimide, polyetherimide, and fluorinated polyimide (for example, aromatic polyimide resin and alicyclic polyimide resin); polyethylene. , Polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate and other copolymerized polyesters (for example, fully aromatic polyesters, semi-aromatic polyesters); copolymerized (meth) acrylates typified by polymethylmethacrylate; polycarbonate. Polyimide; Polysulphon; Polyethersulphon; Polyetherketone; Cellulose acetate; Cellulite nitrate; Aromatic polyamide; Polyvinyl chloride; Polyphenol; Polyallylate; Polyphenylene sulfide; Polyphenylene oxide; Polystyrene and other films can be exemplified.

However, the polymer film is often used in processes involving heat treatment at 450 ° C. or higher. Among the polymer films, a film using a so-called super engineering plastic is preferable, and more specifically, an aromatic polyimide film, an aromatic amide film, an aromatic amideimide film, an aromatic benzoxazole film, and an fragrance. Examples thereof include group benzothiazole film and aromatic benzoimidazole film.

The thickness of the polymer film is preferably 3 μm or more, more preferably 11 μm or more, further preferably 24 μm or more, and even more preferably 45 μm or more. The upper limit of the thickness of the polymer film is not particularly limited, but it is preferably 250 μm or less, more preferably 150 μm or less, and further preferably 90 μm or less for use as a flexible electronic device.

<Anchor layer>
In the present invention, an anchor layer may be provided between the insulating layer 22 of the inorganic substrate laminate and the inorganic substrate 10 or the heat-resistant polymer film 31 in order to improve the adhesion (not shown). The anchor layer is not particularly limited, but preferably contains a silane coupling agent.

Details of the silane coupling agent are disclosed in, for example, JP-A-2010-283262, JP-A-2011-01145, JP-A-2011-245675, and the like, and thus detailed description thereof will be omitted here. To do. The silane coupling agent physically or chemically intervenes between the inorganic substrate and the resin layer, and has an effect of increasing the adhesive force between the two (the 90 ° initial peel strength).

<Functional element>
As shown in FIGS. 1H or 3 to 4, in the present invention, even if a plurality of functional elements 43 are further formed on the upper surface 22a of the insulating layer 22 or the upper surface of the heat-resistant polymer film 31. Good. Further, a plurality of functional elements 43 may be further formed on the upper surface of the heat-resistant polymer film 31 via an inorganic substrate in close contact with the upper surface of the heat-resistant polymer film 31.

In this embodiment, an example in which the semiconductor chips are formed in multiple layers is shown. As shown in FIG. 1H, the wiring layer 11b of the wafer 11 and the heat-resistant polymer film penetrate the insulating layer 22 and the heat-resistant polymer film 31. A first interlayer connection body 41 for connecting the wiring layer 42 provided on the 31 and a second interlayer connection body 45 for connecting the wiring layer 42 and the land 46 are provided.

In the present invention, when the plurality of functional elements 43 are not further formed, the wiring layer 11b of the wafer 11 and the wiring layer 42 (or land) provided on the heat-resistant polymer film 31 are connected as shown in FIG. 1E. By providing the one-wafer connector 41, it is possible to form a structure capable of connecting the internal electronic circuit and the outside.

[Manufacturing method of inorganic substrate laminate]
In the method for producing an inorganic substrate laminate of the present invention, as shown in FIGS. 1A to 1C, the above-mentioned curable resin composition 21 is applied to the functional element forming surface of the inorganic substrate 10 on which a plurality of functional elements 12 are formed. It is characterized by including a coating step of coating and a curing step of curing the curable resin composition 21 with the upper surface of the curable resin composition 21 flat. Hereinafter, each step will be described.

<Applying process>
In the coating step, as shown in FIG. 1B, the curable resin composition 21 of the present invention is applied to the functional element forming surface of the inorganic substrate 10 on which the plurality of functional elements 12 are formed. In the present embodiment, as described above, the inorganic substrate 10 on which the plurality of functional elements 12 are formed is used by mounting the plurality of semiconductor chips on the wafer 11 having the functional element layer 11a and the wiring layer 11b. An example is shown.

Conventionally known coating steps include spin coating method, curtain coating method, dip coating method, slit die coating method, gravure coating method, bar coating method, comma coating method, applicator method, molding method, screen printing method, spray coating method and the like. Although a solution coating means can be used, a bar coating method, a comma coating method, an applicator method, and a molding method are preferable in order to make the upper surface of the curable resin composition 21 after coating more flat.

From the viewpoint of obtaining a flatter insulating layer, the coating thickness is preferably 0.5 to 10 μm thicker than the maximum height of the unevenness on the inorganic substrate, and 1 to 3 μm thicker than the maximum height of the unevenness on the inorganic substrate. Is more preferable.

As shown in FIG. 1A, when a gap is provided between the semiconductor chip and the wafer 11, it is preferable to fill the gap with the curable resin composition 21 from the viewpoint of suppressing expansion due to heating. In that case, the method of performing the coating process in a vacuum atmosphere, the method of defoaming in a coating vacuum, the method of defoaming in a coating vacuum and further coating, and applying pressure to the resin to inject the resin. It is preferable to adopt a method, a method in which a mold is provided on the outside to be coated and a resin is injected into the mold.

In the present invention, as shown in FIG. 1C, it is preferable to include a step of laminating the heat-resistant polymer film 31 after the coating step. As a result, a flatter insulating layer 22 can be formed after curing. When laminating the heat-resistant polymer film 31, laminating by a vacuum press, laminating using a laminator, pressing in an air atmosphere, or the like is preferable.

When the curable resin composition 21 contains a solvent, it is preferable to carry out a solvent drying step prior to the step of laminating the heat-resistant polymer film 31. When the drying step is carried out, the drying temperature is appropriately set according to the type of solvent.

<Curing process>
In the curing step, as shown in FIG. 1C, the curable resin composition 21 is cured with the upper surface of the curable resin composition 21 being flat. In the present invention, it is possible to cure the curable resin composition 21 after coating in a flat state without laminating the heat-resistant polymer film 31, but as shown in FIG. 1C, this curing step However, it is preferable that the curable resin composition 21 is cured in a state where the heat-resistant polymer film 31 is laminated.

The curing temperature is preferably 250 to 550 ° C, more preferably 350 to 500 ° C, from the viewpoint of obtaining a sufficient curing state. The curing time is preferably 3 to 60 minutes, more preferably 10 to 30 minutes, although it depends on the curing temperature.

In the present invention, the step of peeling off the heat-resistant polymer film 31 may be carried out after the curing step. In that case, as shown in FIG. 2, a laminated body not provided with the heat-resistant polymer film 31 can be obtained. Further, another inorganic substrate can be laminated on the heat-resistant polymer film 31.

<Element formation process>
As shown in FIGS. 1D to 1H, the manufacturing method of the present invention further comprises an element forming step of forming a plurality of functional elements 43 on the upper surface of the insulating layer 22 or the upper surface of the heat-resistant polymer film 31. It is preferable to include it. In this embodiment, an example in which the first interlayer connector 41 is provided while mounting the semiconductor chip as the functional element 43 is shown.

In this embodiment, first, as shown in FIG. 1D, a via hole VH is formed by penetrating the insulating layer 22 and the heat-resistant polymer film 31 to expose the wiring layer 11b of the wafer 11. The via hole VH can be formed by laser irradiation, drilling, etching or the like.

Next, as shown in FIG. 1E, a first interlayer connector 41 for connecting to the wiring layer 11b of the wafer 11 is provided in the via hole VH, and the first interlayer connector 41 is connected to the upper surface of the heat-resistant polymer film 31. A wiring layer 42 is provided. The first interlayer connector 41 can be formed by filling the via hole VH with a metal post, a conductive paste, metal plating, or the like. Further, the wiring layer 42 can be formed by a combination of metal plating and etching.

Next, as shown in FIG. 1F, a plurality of semiconductor chips are mounted as the functional element 43. In the illustrated example, the semiconductor chip is connected to the wiring layer 42 by bumps, but it is also possible to connect by solder, wire bonding, or the like instead of the bumps.

Next, as shown in FIG. 1G, the surface on which the semiconductor chip, which is the functional element 43, is mounted is sealed with the sealing material 44. As the encapsulant 44, various encapsulants such as epoxy resins, phenolic resins, silicone resins and a mixture of these resins and silica particles, which are used in general semiconductor packages, can be used. It is also possible to use the curable resin composition 21 of. These are cured under appropriate conditions according to various sealing materials.

Next, as shown in FIG. 1H, a second interlayer connector 45 and a land 46 for connecting the wiring layer 42 and the land 46 for connecting to the external circuit are provided, and individual packages are obtained by cutting.

The formation of the second interlayer connection body 45 and the land 46 is performed in the same manner as the formation of the first interlayer connection body 41 and the wiring layer 42. A dicer, laser, etc. are used to cut into individual packages.

[Other Embodiments]
(1) In the above embodiment, an example is shown in which a plurality of functional elements 43 are formed on the upper surface of the heat-resistant polymer film 31 without peeling off the heat-resistant polymer film 31, but the inorganic substrate laminate of the present invention has been shown. As shown in FIG. 2, the heat-resistant polymer film 31 may be peeled off to form an inorganic substrate laminate without the heat-resistant polymer film 31.

(2) In the present invention, as shown in FIG. 3, a plurality of functional elements 43 may be formed on the upper surface of the insulating layer 22 without the heat-resistant polymer film 31. In that case, as shown in FIGS. 1D to 1H, the first interlayer connection body 41 and the wiring layer 42 are provided on the inorganic substrate laminate shown in FIG. 2 after the via hole VH is formed, and a plurality of functional elements 43 are provided. The semiconductor chip of the above is mounted, sealed with the sealing material 44, the second interlayer connector 45 and the land 46 are provided, and individual packages can be obtained by cutting.

(3) In the above embodiment, an example in which the wafer 11 having the functional element layer 11a and the wiring layer 11b is used has been shown, but as shown in FIG. 3, the glass substrate 14 having the wiring layer 14b on the upper surface of the glass 14a. May be used as an inorganic substrate 10 on which a plurality of functional elements 12 are formed by mounting a plurality of semiconductor chips on the plurality of semiconductor chips. It is also possible to apply and cure the curable resin composition 21 of the present invention using the wafer 11 having the functional element layer 11a and the wiring layer 11b without mounting the semiconductor chip (not shown). ).

(4) In the above embodiment, by mounting a plurality of semiconductor chips on a wafer, an insulating layer formed by curing the curable resin composition is formed by using an inorganic substrate on which a plurality of functional elements are formed. After that, an example of forming a plurality of functional elements is shown, but the combination of the formed functional elements and the inorganic substrate is not limited to these.

The scope of application of the present invention includes, for example, 1) fabrication of a processor by a three-dimensional TFT with upper and lower wiring after forming an insulating layer, 2) fabrication of a composite sensor element by stacking various sensor chips and a drive TFT, 3 ) Manufacture of a color light receiving element by stacking a transparent light receiving element having spectral characteristics and a driving TFT, 4) A light receiving element with a high-speed image processing layer by performing an operation on each TFT layer after receiving light. 5) Fabrication of a color light emitting display by stacking a combination of a chip type light emitting element that emits light of another color and its driving TFT (in this case, the chip area is very small per light emitting dot, so other If the part is transparent, it can be laminated) and various other uses are conceivable.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The evaluation method of physical properties, etc. in the following examples is as follows.

(1) Reduction viscosity of polyamic acid (ηsp / C)
A solution dissolved in N-methyl-2-pyrrolidone (or N, N-dimethylacetamide) so as to have a polymer concentration of 0.2 g / dl was measured at 30 ° C. using an Ubbelohde type viscosity tube. When the solvent used to prepare the polyamic acid solution was N, N-dimethylacetamide, the polymer was dissolved and measured using N, N-dimethylacetamide.

(2) Thickness of polyimide film or the like The thickness of the film was measured at a random place (n = 10) using a micrometer (Millitron 1245D manufactured by Finereuf Co., Ltd.), and the average value was obtained. Further, the thickness unevenness was obtained by calculating by (maximum value-minimum value) ÷ average value when the thickness was measured at a random place (n = 10).

(3) Tensile elastic modulus, tensile breaking strength and tensile breaking elongation of the polyimide film The polyimide film to be measured is cut into strips of 100 mm × 10 mm in the flow direction (MD direction) and the width direction (TD direction), respectively. Was used as a test piece. Using a tensile tester (manufactured by Shimadzu, Autograph (R), model name AG-5000A), the tensile elastic modulus and tensile strength are obtained in each of the MD and TD directions under the conditions of a tensile speed of 50 mm / min and a chuck distance of 40 mm. The breaking strength and tensile modulus at breaking were measured.

(4) Initial peel strength (90 degree peel strength)
According to the 180 degree peeling method of JIS C6471, the peel strength of the sample was determined by performing a 90 degree peeling test under the following conditions.
Device name; Shimadzu Autograph AG-IS
Measurement temperature; Room temperature peeling speed; 100 mm / min
Atmosphere; Atmosphere measurement sample width; 2.5 cm
At that time, the initial peel strength was measured after the laminate was prepared and stored indoors.

(5) Weight reduction measurement method Thermogravimetric measurement was performed using TGA-50 manufactured by Shimadzu Corporation. Measured at N ₂ flow under went put a sample of approximately 10mg to Al pan. The measurement conditions were such that the temperature was raised to 10 ° C./min, the temperature was 400 ° C., and then 90 minutes was maintained to measure the weight loss during the high temperature holding.

(6) Method for measuring step filling property A curable resin composition is applied to a substrate for step measurement to prepare a sample, and then the curable resin composition is peeled off to make unevenness on both sides of the peeled surface made by KEYENCE. It was measured with a laser microscope VK-9700 / 9710. The height difference (μm) was determined for both peeled surfaces by setting the field of view to 250 μm or more and allowing two observations to be made in both the low step portion and the high step portion. From this height difference, the step filling rate was calculated by the following formula.
Step filling rate = (height difference of peeled surface on film side) / (height difference of peeled surface on inorganic substrate side) X100 (%)
When the portion where this value is 90% or less is 10% or less, the step filling property is judged as ◯, and when it exceeds 10%, the step filling property is judged as x.

(7) Method for Measuring Surface Waviness A curable resin composition was applied to a substrate for measuring steps to prepare a sample, and then the unevenness of the sample surface was measured with a laser microscope VK-9700 / 9710 manufactured by KEYENCE. At this time, the field of view was set to about 250 μm, and the height difference (μm) was determined and used as a swell.

(8) NMR measurement The measurement was carried out under the following measurement conditions.

1) ^{1 1} H-NMR
Device: Fourier Transform Nuclear Magnetic Resonance Device (AVANCE NEO manufactured by Bruker Biospin)
Measurement solution: About 50 mg of the sample was dissolved in 0.6 ml of deuterated chloroform.
¹ H resonance frequency: 600.134 MHz
Flip angle of detection pulse: 30 °
Data acquisition time: 2.75 seconds Delay time: 1.0 seconds Number of integrations: 128 times Measurement temperature: 25 ° C.

2) ²⁹ Si-NMR
Device: Fourier Transform Nuclear Magnetic Resonance Device (AVANCE NEO manufactured by Bruker Biospin)
Measurement solution: About 100 to 300 mg of a sample was dissolved in deuterated chloroform, and about 1 wt% of tris (2,4-pentanedionato) chromium (III) was added to the solution.
²⁹ Si resonance frequency: 119.22MHz
Flip angle of detection pulse: 90 °
Data acquisition time: 1.8 seconds Delay time: 7.0 seconds Proton decoupling: inverse gate decouple.
Number of integrations: Room temperature Number of integrations: About 1000 to 2000 times.

[Production Example 1 of Heat Resistant Polymer Film]
(Preparation of polyamic acid solution)
After replacing the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer and a stirring rod with nitrogen, 223 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole (DAMBO) and N, N-dimethylacetamide 4416 The colloidal silica dispersion was added as a lubricant together with 217 parts by mass of pyromellitic dianhydride (PMDA) to completely dissolve the colloidal silica dispersion, and the silica (lubricant) contained the polymer solid content in the polyamic acid solution. It was added so as to be 0.12% by mass based on the total amount, and the mixture was stirred at a reaction temperature of 25 ° C. for 24 hours to obtain a brown and viscous polyamic acid solution V1 having a reducing viscosity of 3.5ηsp / c.

(Preparation of polyimide film)
The polyamic acid solution V1 obtained above is applied to a smooth surface (non-slip material surface) of a long polyester film (“A-4100” manufactured by Toyobo Co., Ltd.) having a width of 1050 mm using a slit die to have a final film thickness (imide). The film was applied so that the film thickness after conversion was 25 μm, dried at 105 ° C. for 20 minutes, and then peeled off from the polyester film to obtain a self-supporting polyamic acid film having a width of 920 mm.

Next, the obtained self-supporting polyamic acid film was gradually heated in a temperature range of 150 ° C. to 420 ° C. by a pin tenter (first stage 180 ° C. × 5 minutes, second stage 270 ° C. × 10 minutes, The third stage was subjected to heat treatment (420 ° C. for 5 minutes) to imidize, and the pin gripping portions at both ends were dropped by slits to obtain a long polyimide film F1 (1000 m roll) having a width of 850 mm. The characteristics of the obtained film F1 are shown in Table 1.

[Production Example 2 of Heat Resistant Polymer Film]
The film F1 obtained in Film Production Example 1 was slit to a width of 250 mm. Next, the slit 250 mm wide roll was unwound under vacuum and then rewound to release the gas. Next, after waiting until the temperature became 3 × ^10-6 Torr or less, a sputtering step was carried out under the following conditions to form an ITO layer having a thickness of 15 nm on the polyimide film F1.

<Conditions during sputtering>
DC magnetron sputtering method Gas pressure: 2 × 10 ^-3 Torr
Ar flow rate: 50SCCM
O ₂ flow rate: 3SCCM
Target ITO composition: 20 wt% tin oxide with respect to the entire ITO target (manufactured by Mitsui Mining & Smelting Co., Ltd., product name: ITO target)
Power input density to target: 2 W / cm ^{2 with} respect to ITO target
Processing time: Film feed rate 0.1 m / min
Vacuum degree when creating ITO layer: 2 × 10 ^-3 Torr
Let this film be F2.

[Manufacturing Example 1 of Inorganic Substrate] (Glass)
Among the inorganic substrates for measuring the peel strength, as the glass, OA10G glass (manufactured by NEG) having a thickness of 0.7 mm cut into a size of 100 mm × 100 mm was used. Inorganic substrates for peel strength measurement, pure water washing, was used after the optical cleaning by 1min irradiation after drying in UV / _{O 3} irradiation machine (run Technical Services Co. SKR1102N-03).

Further, the inorganic substrate for checking the step was manufactured by performing sputtering, plating and etching on the same glass (100 mm × 100 mm size). First, using a nickel-chromium (3% by mass) alloy target under the conditions of frequency 13.56 MHz, output 400 W, gas pressure 0.8 Pa, and thickness at a rate of 10 Å / sec by RF sputtering in an argon gas atmosphere. A 50 Å nickel-chromium alloy film (underlayer) is formed, then the temperature of the substrate is raised to 100 ° C., and copper is sputter-deposited at a rate of 100 Å / sec to form a copper thin film with a thickness of 0.5 μm. It was.

The obtained copper thin film-forming glass is fixed to a plastic frame, and a copper sulfate plating bath is used to form a thick copper plating layer (thick layer) having a thickness of 10 μm, followed by stripes of 100 μm. The resist was exposed to light in a similar manner, and then etching was performed with a second aqueous solution of iron chloride to form a pattern in which 100 μm wide copper and 100 μm wide copper-free portions were alternated.

[Manufacturing Example 2 of Inorganic Substrate] (Si Wafer)
Among the inorganic substrates for measuring the peel strength, a dummy grade 4-inch wafer was used as the Si wafer. Inorganic substrates for peel strength measurement, pure water washing, was used after the optical cleaning by 1min irradiation after drying in UV / _{O 3} irradiation machine (run Technical Services Co. SKR1102N-03).

Further, as the inorganic substrate for step confirmation, the obtained Si wafer is used in the same manner as in Manufacturing Example 1 of the inorganic substrate, and sputtering, plating, and etching are performed under the same conditions to obtain an inorganic substrate for step confirmation. Manufactured. A plan view of the obtained inorganic substrate for confirming the step is shown in FIG. 5A.

[Manufacturing Example 3 of Inorganic Substrate] (Si Wafer with SiO-based Thin Film)
Among the inorganic substrates for measuring the peel strength, for the Si wafer with a SiO-based thin film, the same Si wafer as in Production Example 2 of the inorganic substrate is cleaned by the above-mentioned cleaning method for the inorganic substrate and then put into a sputtering apparatus to put the SiO-based thin film. Was deposited and manufactured. The sputtering conditions were as follows. A SiO-based film having a thickness of 60 Å was formed at a rate of 3 Å / sec by the RF sputtering method under the conditions of a frequency of 13.56 MHz, an output of 400 W, a gas pressure of 0.8 Pa, and a SiO ₂ target in an argon gas atmosphere. ..

Further, as the inorganic substrate for step confirmation, the obtained Si wafer is used in the same manner as in Manufacturing Example 1 of the inorganic substrate, and sputtering, plating, and etching are performed under the same conditions to obtain an inorganic substrate for step confirmation. Manufactured. A plan view of the obtained inorganic substrate for confirming the step is shown in FIG. 5B.

[Preparation Example 1 of Curable Resin Composition] (Curable Resin Composition A)
5 parts by weight of divinylbenzene was added to 100 parts by weight of a vinyl group-containing phenylmethyl silicone resin (trade name X-40-2667A, manufactured by Shinetsu Silicone Co., Ltd.), and the mixture was stirred to prepare a curable resin composition A. From the results of NMR measurement, it was confirmed that this silicone compound had 11% of siloxane units having a Si—H bond and 21% of T units among all siloxane units. Please add the numerical value.

[Preparation Example 2 of Curable Resin Composition] (Curable Resin Composition B)
0.15 parts by weight of styryltrimethoxysilane ("KBM-1003" manufactured by Shin-Etsu Chemical Co., Ltd.) with respect to 100 parts by weight of vinyl group-containing phenylmethyl silicone resin (trade name X-40-2667A, manufactured by Shin-Etsu Silicone Co., Ltd.). 5 parts by weight of water was added and stirred to prepare a curable resin composition B.

[Preparation Example 3 of Curable Resin Composition] (Curable Resin Composition C)
0.2 parts by weight of vinyl trimethoxysilane (“KBM-1403” manufactured by Shin-Etsu Chemical Co., Ltd.) with respect to 100 parts by weight of vinyl group-containing phenylmethyl silicone resin (trade name X-40-2667A, manufactured by Shin-Etsu Silicone Co., Ltd.). 5 parts by weight of water was added and stirred to prepare a curable resin composition C.

[Preparation Example 4 of Curable Resin Composition] (Curable Resin Composition D)
Only 100 parts by weight of a vinyl group-containing phenylmethyl silicone resin (trade name X-40-2667A, manufactured by Shinetsu Silicone Co., Ltd.) was used as the curable resin composition D.

[Preparation Example 5 of Curable Resin Composition] (Curable Resin Composition E)
3 parts by weight of a platinum catalyst-containing silicone resin (trade name X-40-2667B, manufactured by Shin-Etsu Silicone) with respect to 100 parts by weight of a vinyl group-containing phenylmethyl silicone resin (trade name X-40-2667A, manufactured by Shinetsu Silicone). In addition, the curable resin composition E was prepared by stirring.

[Preparation Example 6 of Curable Resin Composition] (Curable Resin Composition F)
Add 5 parts by weight of silica filler (Leorosyl manufactured by Tokuyama Corporation) to 100 parts by weight of vinyl group-containing phenylmethyl silicone resin (trade name X-40-2667A, manufactured by Shinetsu Silicone Co., Ltd.), and stir to stir to cure the curable resin composition F. Was prepared.

[Preparation Example 7 of Curable Resin Composition] (Curable Resin Composition G)
Vinyl group-containing phenylmethyl silicone resin (trade name X-40-2667A, manufactured by Shinetsu Silicone Co., Ltd.) 100 parts by weight with a platinum catalyst-containing vinyl group-containing phenylmethyl silicone resin (trade name X-40-2667B, manufactured by Shinetsu Silicone Co., Ltd.) (Manufactured) 100 parts by weight was added and stirred to prepare a curable resin composition G. From the results of NMR measurement, it was confirmed that this silicone compound had 7% of siloxane units having a Si—H bond and 8% of T units among all siloxane units.

[Preparation Example 8 of Curable Resin Composition] (Curable Resin Composition H)
Vinyl group-containing phenylmethyl silicone resin (trade name X-40-2667A, manufactured by Shin-Etsu Silicone) with respect to 100 parts by weight, vinyl group-containing phenylmethyl silicone resin containing platinum catalyst (trade name X-40-2667B, manufactured by Shin-Etsu Silicone). (Manufactured) 40 parts by weight and 50 parts by weight of silicone oil (trade name KR-105, manufactured by Shinetsu Silicone Co., Ltd.) were added and stirred to prepare a curable resin composition H. From the results of NMR measurement, it was confirmed that this silicone compound had 12% of siloxane units having a Si—H bond and 8% of T units among all siloxane units.

[Anchor Layer Material Preparation Example 1] (SCA1)
As a silane coupling agent, vinyltrimethoxysilane (“KBM-1003” manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted with isopropyl alcohol to 0.5% by mass to prepare a silane coupling agent diluent SCA1.

[Anchor layer material preparation example 2] (SCA2)
In Anchor Layer Material Preparation Example 1, SCA2 was prepared under the same conditions except that the silane coupling agent was replaced with styryltrimethoxysilane (“KBM-1403” manufactured by Shin-Etsu Chemical Co., Ltd.).

[Anchor layer material preparation example 3] (SCA3)
In Anchor Layer Material Preparation Example 1, SCA3 was prepared under the same conditions except that the silane coupling agent was replaced with methacryloxitrimethoxysilane (“KBM-503” manufactured by Shin-Etsu Chemical Co., Ltd.).

[Anchor Layer Material Preparation Example 4] (SCA4)
In Anchor Layer Material Preparation Example 1, SCA4 was prepared under the same conditions except that the silane coupling agent was replaced with aminomethoxysilane (“KBM-903” manufactured by Shin-Etsu Chemical Co., Ltd.).

[Example of formation of anchor layer 1]
The anchor layer 1 was formed by a spin coater. The anchor layer 1 refers to an anchor layer formed by applying an anchor layer material to an inorganic substrate. After setting the inorganic substrate on a spin coater (MSC-500S manufactured by Japan Create), isopropyl alcohol is dropped, and then the inorganic substrate is rotated at 1000 rpm to spread over the entire surface of the inorganic substrate and then dry. It was washed. After that, the anchor layer material was once dropped, and then the inorganic substrate was rotated at 500 rpm to spread over the entire surface of the inorganic substrate, and then 2000 rotations were performed to shake off and dry the anchor layer material. Then, heating was performed at 100 ° C. × 1 min on a hot plate.

[Example of forming the anchor layer 2]
The anchor layer 2 refers to an anchor layer formed by applying an anchor layer material to a heat-resistant polymer film. When it was applied to a film, it was taped to a glass whose sides were about 50 mm longer than the film, and this glass was set on a spin coater, and the application was performed in the same manner as in the example of forming the anchor layer 1.

[Application example 1 of curable resin composition] (application by applicator)
An inorganic substrate to be coated was fixed to A3 size glass having a thickness of 10 mm with cellophane tape (registered trademark) using an applicator (trade name: Baker Film Applicator, manufactured by Cortec), and then coated with a gap of 15 μm. Inorganic substrates of the same thickness as the sample were placed on both ends of the applicator, and some thickness adjustment was performed by laying a thin film on the inorganic substrates at both ends to ensure a constant film thickness on the sample.

[Application example 2 of curable resin composition] (application by bar coater)
As the bar coater, a wire bar coater # 3 was used to fix the inorganic substrate to be coated to A3 size glass having a thickness of 10 mm with cellophane tape (registered trademark), and then coat the glass.

[Manufacturing example 1 of laminated body] (press method)
The vacuum press uses a press device (manufactured by Imoto Seisakusho Co., Ltd., IMC-1123 type), and after stacking a heat-resistant polymer film of 120 x 120 mm size on an inorganic substrate coated with a curable resin composition and installing it in a chamber. The film was evacuated with a rotary pump and pressed at a pressure of 3 MPa at a pressure of 10 ^{+ 2} Pa or less at 150 ° C. for 30 minutes, then at 200 ° C. for 30 minutes and at 400 ° C. for 60 minutes. The temperature rise time was the rate of temperature rise of the machine, and was performed programmatically without taking time.

[Manufacturing example 2 of laminated body] (lamination method)
Using a laminating device (MRK-1000 manufactured by MCK), a heat-resistant polymer film of 120 x 120 mm size is laminated on an inorganic substrate coated with a curable resin composition, and air is aired at atmospheric pressure atmosphere and room temperature. Lamination was performed by applying roller pressure with a cylinder. At this time, the air source pressure was boosted to a pressure of 0.7 MPa, and the atmosphere was 22 ° C. and 55% RH in a clean room. The laminating speed was 50 mm / sec.

<< Example 1 >>
As shown in Table 2, the glass substrate for peeling strength measurement and step confirmation obtained in Production Example 1 of the inorganic substrate is used as the inorganic substrate, and the curable resin composition A is used as the curable resin composition, and the thermosetting polymer film is used. The film F1 was used as a base. Using these, the curable resin composition is applied to the inorganic substrate according to Application Example 2 (application by a bar coater) of the curable resin composition, and then the inorganic substrate laminate is produced according to Production Example 1 (press method) of the laminate. did. With respect to the obtained inorganic substrate laminate, the initial peel strength, weight loss, step filling property, and surface waviness were measured by the above methods. The results are also shown in Table 2.

<< Examples 2 to 12 >>
Using the inorganic substrate, curable resin composition, and thermosetting polymer film shown in Tables 2 to 3, the curable resin composition is applied to the inorganic substrate according to Application Example 1 or 2 of the curable resin composition, and then the laminate An inorganic substrate laminate was produced according to Production Example 1 or 2 of the above. At that time, for some examples, the anchor layer material was used to form the anchor layer according to the example of forming the anchor layer. With respect to the obtained inorganic substrate laminate, the initial peel strength, weight loss, step filling property, and surface waviness were measured by the above methods. The results are also shown in Tables 2 and 3.

<< Comparative Example 1 >>
As shown in Table 4, in Example 1, instead of applying the curable resin composition A, the anchor layer 1 was formed of the anchor layer material (SCA4) according to the example of forming the anchor layer 1. An inorganic substrate laminate was produced under the same conditions as in Example 1. With respect to the obtained inorganic substrate laminate, the initial peel strength, weight loss, step filling property, and surface waviness were measured by the above methods. The results are also shown in Table 4.

<< Comparative Example 2 >>
As shown in Table 4, the inorganic substrate laminate was prepared under the same conditions as in Example 1 except that the curable resin composition D was used instead of the curable resin composition A in Example 1. Manufactured. With respect to the obtained inorganic substrate laminate, the initial peel strength, weight loss, step filling property, and surface waviness were measured by the above methods. The results are also shown in Table 4.

<< Comparative Example 3 >>
As shown in Table 4, in Example 1, instead of using the curable resin composition A, the curable resin composition E is used, and the anchor layer 1 made of the anchor layer material (SCA1) is used according to the example of forming the anchor layer 1. The inorganic substrate laminate was produced under the same conditions as in Example 1 except that the above was formed. With respect to the obtained inorganic substrate laminate, the initial peel strength, weight loss, step filling property, and surface waviness were measured by the above methods. The results are also shown in Table 4.

<< Comparative Example 4 >>
As shown in Table 4, in Example 1, instead of using the curable resin composition A, the curable resin composition F is used, and the anchor layer 1 is made of the anchor layer material (SCA1) according to the example of forming the anchor layer 1. The inorganic substrate laminate was produced under the same conditions as in Example 1 except that the above was formed. With respect to the obtained inorganic substrate laminate, the initial peel strength, weight loss, step filling property, and surface waviness were measured by the above methods. The results are also shown in Table 4.

<< Comparative Example 5 >>
As shown in Table 4, in Example 1, instead of using the curable resin composition A, the curable resin composition G is used, and the anchor layer 1 is made of the anchor layer material (SCA1) according to the example of forming the anchor layer 1. The inorganic substrate laminate was produced under the same conditions as in Example 1 except that the above was formed. With respect to the obtained inorganic substrate laminate, the initial peel strength, weight loss, step filling property, and surface waviness were measured by the above methods. The results are also shown in Table 4.

<< Comparative Example 6 >>
As shown in Table 4, in Example 1, instead of using the curable resin composition A, the curable resin composition H is used, and the anchor layer 1 made of the anchor layer material (SCA1) is used according to the example of forming the anchor layer 1. The inorganic substrate laminate was produced under the same conditions as in Example 1 except that the above was formed. With respect to the obtained inorganic substrate laminate, the initial peel strength, weight loss, step filling property, and surface waviness were measured by the above methods. The results are also shown in Table 4.

As the results of Tables 2 to 4 show, in the examples of the present invention, it has high heat resistance, good adhesion to an inorganic substrate and good filling property to unevenness, and small surface waviness due to curing shrinkage. A sex resin composition was realized.

On the other hand, in Comparative Example 1 in which the curable resin composition is not used, step filling cannot be performed at all, and in the cases of Comparative Examples 2, 3 and 4 in which the types of the curable resin composition are different, It does not have high heat resistance, has low adhesion to an inorganic substrate, and may have insufficient filling property for irregularities, resulting in surface waviness due to the generation of bubbles. Further, in the cases of Comparative Examples 5 to 6 in which the types of silicone compounds are different, the heat resistance is not high, the adhesion to the inorganic substrate is poor, and the filling property to the unevenness may not be good. Surface swell occurred due to the occurrence of.

10 Inorganic substrate 11 Wafer 12 Functional element (semiconductor chip)
21 Curable resin composition 22 Insulating layer (cured product of curable resin composition)
31 Heat-resistant polymer film 43 Functional element (semiconductor chip)

Claims (10)

A curable resin composition used for forming an insulating layer having a flat upper surface on a functional element forming surface of an inorganic substrate on which a plurality of functional elements are formed.
A silicone compound having 10% or more of siloxane units having a Si—H bond and 10% or more of T units (RSiO _3/2 , R is a monovalent substituent (including H)) among all siloxane units. A curable resin composition comprising a compound having a vinyl group and a vinyl group. The curable resin composition according to claim 1, wherein the compound having a vinyl group is a cross-linking agent having a plurality of vinyl groups or a silane coupling agent having a vinyl group. The curable resin composition according to claim 1 or 2, wherein the silicone compound further has a siloxane unit having a vinyl group. An inorganic substrate on which a plurality of functional elements are formed and an insulating layer obtained by curing the curable resin composition according to any one of claims 1 to 3 are included.
The insulating layer is an inorganic substrate laminate characterized in that the recesses between the functional elements are also filled and the upper surface is formed flat. The inorganic substrate laminate according to claim 4, further comprising a heat-resistant polymer film on the upper surface of the insulating layer. The inorganic substrate laminate according to claim 4 or 5, wherein a plurality of functional elements are formed on the upper surface of the insulating layer or the upper surface of the heat-resistant polymer film. A coating step of applying the curable resin composition according to any one of claims 1 to 3 to a functional element forming surface of an inorganic substrate on which a plurality of functional elements are formed.
A method for producing an inorganic substrate laminate, which comprises a curing step of curing the curable resin composition while the upper surface of the curable resin composition is flat. After the coating step, a step of laminating a heat-resistant polymer film is included.
The method for producing an inorganic substrate laminate according to claim 7, wherein the curing step cures the curable resin composition in a state where the heat-resistant polymer films are laminated. The method for producing an inorganic substrate laminate according to claim 8, further comprising a peeling step of peeling the heat-resistant polymer film. The method for producing an inorganic substrate laminate according to claim 8 or 9, further comprising an element forming step of forming a plurality of functional elements on the upper surface of the insulating layer or the upper surface of the heat-resistant polymer film.

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