KR101939122B1 - The laminate - Google Patents

Abstract

Provided is a laminate capable of achieving good processability of a device wafer even when a circuit surface of a device wafer is covered with a molding material, an adhesive layer is provided on the surface thereof, and a device wafer and a carrier substrate are laminated.
1. A laminate having a device wafer having a circuit surface, a molding layer covering the surface of the circuit surface, and an adhesive layer located on the surface of the molding layer, , The number of voids having a maximum length of 30 占 퐉 or more is 3 or less per 700 cm ² of the film surface of the adhesive layer, and the arithmetic mean surface roughness Ra of the adhesive layer is Ra? 10 占 퐉.

Description

The laminate

The present invention relates to a laminate. More particularly, the present invention relates to a laminate used for processing a wafer device using a carrier substrate.

In the process of manufacturing a semiconductor device such as an integrated circuit (IC) or a large-scale integrated circuit (LSI), a plurality of IC chips are formed on a device wafer and are separated by dicing.

Further miniaturization and high integration of IC chips mounted on electronic devices are required due to the demand for further miniaturization and high performance of electronic devices, but the integration of integrated circuits in the plane direction of device wafers is approaching the limit.

Conventionally, a wire bonding method has been widely known as an electrical connection method from an integrated circuit in an IC chip to an external terminal of an IC chip. In order to miniaturize the IC chip, a device wafer has recently been provided with a through hole (A method of forming a so-called silicon penetration electrode (TSV)) is known in which a metal plug as an external terminal is connected to an integrated circuit so as to penetrate through the through hole. However, the method of forming the silicon through electrode alone can not sufficiently meet the recent demand for higher integration of the IC chip.

In view of the above, there is known a technique for improving the degree of integration per unit area of a device wafer by making the integrated circuit in the IC chip multilayered. However, since the thickness of the IC chip is increased in the multilayered structure of the integrated circuit, it is necessary to reduce the thickness of the member constituting the IC chip. As for the thickness reduction of such a member, for example, thinning of a device wafer has been studied, leading not only to miniaturization of the IC chip but also to reduction of the manufacturing process of the through-hole of the device wafer in the production of the silicon through- In terms of being able, it is becoming promising. In addition, in semiconductor devices such as power devices and image sensors, thinning has been attempted from the viewpoints of improvement of the degree of integration and freedom of device structure.

As device wafers, those having a thickness of about 700 to 900 mu m are widely known. In recent years, attempts have been made to thin device wafer thicknesses to 200 mu m or less for the purpose of miniaturization of IC chips and the like.

However, a device wafer having a thickness of 200 占 퐉 or less is very thin, and since a semiconductor device manufacturing member made of the substrate is very thin, additional processing is performed on such a member, or when such a member is simply moved, It is difficult to stably support the member without damaging it.

In order to solve the above problems, the device wafer and the carrier substrate before thinning are temporarily fixed (adhered) with an adhesive, and the back surface of the device wafer is ground to be thinned. Then, the carrier substrate is peeled ) Is known.

For example, Patent Document 1 discloses a peeling method in which a support attached to a wafer through an adhesive layer is peeled off from a wafer, wherein a solvent which swells the adhesive layer to lower the adhesiveness of the surface thereof, And a peeling step of peeling off the swollen adhesive layer from the wafer. The peeling method according to claim 1,

On the other hand, in the device manufacturing process for fan-out purposes, since the number of circuits increases, the circuit surface is covered with the molding material, and then the device wafer is made thin by using the adhesive.

Here, as a technique using a molding material, for example, Patent Document 1 discloses a technique for manufacturing a semiconductor device having a substrate, a semiconductor element provided on at least one side of the substrate, a substrate, a semiconductor element, And a second resin which is obtained by curing the second resin composition after the first resin composition is cured, the first resin and the second resin being obtained by curing the resin composition, Is 18 MPa or more at room temperature.

Patent Document 1: JP-A-2014-49698 Patent Document 2: WO2010 / 029726 brochure

Here, as in Patent Document 2, when the circuit surface of the device wafer is covered with a molding material, an adhesive layer is provided on the surface of the device wafer, and when the device wafer is laminated with the carrier substrate, Could know.

It is an object of the present invention to solve such a problem, and it is an object of the present invention to provide a method for manufacturing a semiconductor device, which comprises covering a circuit surface of a device wafer with a molding material, providing an adhesive layer on the surface thereof, Which is capable of achieving a laminated body.

Under these circumstances, the inventor of the present invention has found that a satisfactory processability of a device wafer can be achieved by setting the number of voids and surface roughness of the adhesive layer to a predetermined value or less. It came. Concretely, the above problem is solved by the following means <1>, preferably by <2> to <15>.

&Lt; 1 > A laminate having a device wafer having a circuit surface, a molding layer covering the surface of the circuit surface, and an adhesive layer positioned on the surface of the molding layer,

And wherein not more than one observed with an optical microscope from the direction perpendicular to the film surface, the number of more than the maximum length 30μm voids, the adhesive layer film surface 700cm ² per, 3 of the adhesive layer, wherein the roughness arithmetic average of the surface of the adhesive layer Ra Is Ra? 10.0 占 퐉.

&Lt; 2 > The laminate according to < 1 >, wherein the component having a molecular weight of 1000 or less in the molding layer is 5 mass% or less.

<3> The laminate according to <1> or <2>, wherein the molding layer is formed by baking a liquid molding material.

<4> The laminate according to <1> or <2>, wherein the molding layer is formed by a solid compression molding material.

<5> A method for producing a molded article, comprising: providing an adhesive layer after applying a treatment to a molding layer; and heating the molded layer after heating to 100 ° C to 200 ° C at a rate of 10 ° C / % Or less, based on the total weight of the layered product.

&Lt; 6 > The laminate according to < 5 >, wherein the molding layer covering the surface of the circuit surface is subjected to heat treatment at 100 DEG C to 250 DEG C, followed by provision of an adhesive layer.

<7> The laminate according to <5> or <6>, wherein the surface of the molding layer covering the surface of the circuit surface is cleaned with an organic solvent and then an adhesive layer is provided.

<8> The laminate according to any one of <5> to <7>, wherein the surface of the molding surface covering the surface of the circuit surface is ashed and then an adhesive layer is provided.

<9> A method for producing a circuit board, comprising: heating a molding layer covering the surface of the circuit surface at 100 ° C. to 250 ° C.; cleaning the surface of the molding layer covering the surface of the circuit surface with an organic solvent; The laminate according to any one of < 1 > to < 8 >, wherein at least two of the surfaces of the molding layer covering the surface are subjected to an ashing treatment and further provided with an adhesive layer.

<10> The laminate according to <8> or <9>, wherein the ashing treatment is performed with an oxygen plasma.

<11> The laminate according to any one of <1> to <10>, wherein the molding layer and the adhesive layer each independently comprise a resin.

<12> The laminate according to any one of <1> to <11>, wherein the laminate has a carrier base on the side of the adhesive layer opposite to the side in contact with the molding layer.

<13> The laminate according to any one of <1> to <12>, wherein the thickness of the device wafer is 200 μm or less.

<14> The laminate according to any one of <1> to <13>, wherein the adhesive layer is in contact with the carrier substrate.

<15> The laminate according to <14>, wherein the adhesive layer is one layer.

According to the present invention, there is provided a laminate capable of achieving good processability of a device wafer even when a circuit surface of a device wafer is covered with a molding material, an adhesive layer is provided on the surface thereof, and a device wafer and a carrier substrate are laminated together It became possible.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic view showing the layer structure of a laminate of the present invention. FIG.
2 is a schematic view of a first embodiment showing a manufacturing method of a semiconductor device.
3 is a schematic view of a second embodiment showing a manufacturing method of a semiconductor device.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, " ~ " is used to mean that the numerical values described before and after the numerical value are included as the lower limit value and the upper limit value.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term " active ray " or " radiation " in this specification includes, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

In the present specification, the term " light " means an actinic ray or radiation.

As used herein, the term " exposure " means not only exposure by deep ultraviolet rays, X-rays, extreme ultraviolet light (EUV light) represented by mercury lamps, ultraviolet rays and excimer lasers, but also particles such as electron beams and ion beams It also means drawing by lines.

In the present specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the composition.

As used herein, "(meth) acrylate" refers to acrylate and methacrylate, "(meth) acryl" refers to acrylic and methacryl, "(meth) acryloyl" Quot; and " methacryloyl ".

In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene reduced values by gel permeation chromatography (GPC) unless otherwise stated. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by TOSOH CORPORATION) and TSKgel Super AWM-H , ID (ID) 6.0 mm x 15.0 cm) can be obtained by using 10 mmol / L lithium bromide NMP (N-methylpyrrolidone) solution as an eluent.

In the present specification, the term "hydrophilic group" means a functional group not containing a hydrophilic group. The term " hydrophilic group " means a functional group exhibiting affinity with water.

In the embodiments described below, the members described in the drawings already referred to are denoted by the same reference numerals or signs in the drawings, thereby simplifying or omitting the description.

The laminate of the present invention is a laminate having a device wafer having a circuit surface, a molding layer covering the surface of the circuit surface, and a curing agent layer located on the surface of the molding layer, Wherein the number of voids having a maximum length of 30 占 퐉 or more observed under an optical microscope is 3 or less per 700 cm ² of the film surface of the adhesive layer, and the arithmetic mean surface roughness Ra of the adhesive layer is Ra? 10.0 占 퐉. With this configuration, the processing characteristics of the device wafer can be improved. In particular, occurrence of cracks in the device wafer can be effectively suppressed. The laminate of the present invention is effective for manufacturing a device for fan-out use.

This mechanism is presumed, however, by providing an adhesive layer on the surface of the molding layer, an outgass derived from the molding layer is generated, and this outgas forms voids in the adhesive layer, or roughenes the surface of the adhesive layer . It has been found that although the surface roughness and the surface roughness of the adhesive layer are small, they have a great influence on the thinning of the device wafer. The workability of the device wafer is remarkably improved by setting the number of voids in the adhesive layer to a predetermined value or less and setting the arithmetic average surface roughness (Ra) to a predetermined value or less. It is surprising that the small voids and surface roughness of the adhesive layer greatly affect the processability of the device wafer.

Hereinafter, the laminate of the present invention will be described with reference to the drawings. Needless to say, the present invention is not limited to the embodiment shown in the drawings.

Fig. 1 is a schematic cross-sectional view showing the layer structure of the layered product 1 of the present invention, in which 61 is a substrate (device substrate) of a device wafer, 62 is a circuit surface located on the surface of the device wafer, 11 is a cured adhesive layer located on the surface of the molding layer, and 12 is a carrier substrate. The laminate 1 of the present invention is formed by covering the circuit surface 62 of the surface of the substrate 61 with the molding layer 15 and then peeling the adhesive layer 11 from the side of the adhesive layer 11 which is in contact with the molding layer 15 A carrier substrate 12 is provided. 1, the carrier substrate 12 is in contact with the adhesive layer 11, but another layer may be provided between the carrier substrate 12 and the adhesive layer 11.

A detailed description of each component of the layered product 1 will be described later.

1, since the molding layer 15 and the adhesive layer 11 are in contact with each other, the outgassing derived from the molding layer damages the adhesive layer 11, Or the surface of the adhesive layer was rough. It has been found that such voids and surface roughness cause damages when the device substrate 61 is processed, causing cracks to occur.

In the present invention, the number of voids having a maximum length of 30 占 퐉 or more, which is observed with an optical microscope from a direction perpendicular to the film surface of the adhesive layer, is 3 or less per 700 cm ² of the film surface of the adhesive layer, And Ra is an arithmetic average surface roughness Ra of 10 mu m.

Here, the maximum length refers to the longest length of two points on the outer periphery of the void portion observed by an optical microscope from a direction perpendicular to the film surface of the adhesive layer. For example, when the void is circular, the diameter of the circle becomes the maximum length.

The voids in the present invention may be formed by forming a film surface of the adhesive layer, or may be a void formed inside the adhesive layer. The void formed inside the adhesive layer is usually spherical.

Further, "per 700 cm ² of the film surface of the adhesive layer" means an area of the film surface assuming that the adhesive layer is flat. That is, the number of voids is obtained with respect to the area of the surface observed with an optical microscope.

In the present invention, the number of voids is 3 or less, preferably 2 or less, more preferably 1 or less, and more preferably 0. The number of voids per 300 mm wafer is, for example, not more than 0.05 pieces / cm ² per unit area (not more than three), whereby the yield of chips per wafer (ratio of products to raw materials) can be improved.

The method of measuring the number of voids is specifically based on the method described in the examples. However, when the apparatuses described in the embodiments are difficult to obtain by discontinuation or the like, apparatuses having different functions can be employed.

In the present invention, the arithmetic mean surface roughness (Ra) is preferably Ra? 10.0 占 퐉, Ra? 5.0 占 퐉, more preferably Ra? 3.0 占 퐉, more preferably Ra? 2.0 占 퐉, It is possible.

Subsequently, various means can be used as means for reducing the voids of the backing adhesive layer and reducing the surface roughness. However, it is needless to say that the present invention is not limited to these examples.

In the first embodiment, an embodiment in which the component having a molecular weight of 1,000 or less in the molding layer is 5 mass% or less is exemplified. In this manner, by reducing the components that are easily volatilized in the molding layer, the generation of outgas can be effectively suppressed. Particularly, in the present invention, the amount of highly volatile components may be reduced with respect to the molding material itself, but it is also possible to form the molding layer by using the molding material, or after the molding layer is formed, By doing so, the volatile components of the molding layer may be reduced.

The amount of the volatile component is more preferably 1% by mass or less with respect to the molding layer. The amount of the component having a molecular weight of 1,000 or less is more preferably 2% by mass or less, still more preferably 1.5% by mass or less, and 0.9% by mass or less. With respect to the lower limit value, 0 mass% is preferable, but an example of the embodiment is 0.001 mass% or more.

The method for measuring the amount of the component having a molecular weight of 1000 or less according to the present invention is according to the method described in the following examples.

In the second embodiment, an embodiment in which the molding layer is formed by baking a liquid molding material is exemplified. As such, by baking, the low molecular components contained in the molding material can be reduced, and the low molecular components contained in the molding layer can be reduced. Here, the liquid phase means a fluid having a viscosity of, for example, 0.1 占^10-3 Pa 占 퐏 to 150 Pa 占 퐏 at 25 占 폚.

The bake temperature varies depending on the type of molding material and the like. For example, the bake temperature can be set to 100 to 200 캜, and furthermore, to 150 to 300 캜.

In the third embodiment, an embodiment in which the molding layer is formed by a solid compression molding material is exemplified. As described above, generation of outgassing of the molding layer can be suppressed by using a molding layer formed by a compression method in which a low-molecular component originating from the outgass contained in the molding material is originally small or approximately zero.

In the fourth embodiment, the adhesive layer is provided after the molding layer is treated, and when the temperature of the molding layer after the heat treatment is raised from 100 占 폚 to 200 占 폚 at 10 占 폚 / By mass is 5% by mass or less. The thermal mass reduction degree is preferably 3 mass% or less. By lowering the thermal mass reduction degree, generation of outgas can be reduced even by heating at 100 to 200 ° C. As a means for reducing the thermal mass reduction degree, a material having a low thermal mass reduction degree may be employed for the molding material. However, after the molding layer is formed using the molding material, or after the molding layer is formed, The lowering degree of the thermal mass of the molding layer may be set to 5% by mass or less. The degree of thermal mass reduction is preferably 3 mass% or less, more preferably 2 mass% or less, more preferably 1.5 mass% or less, and particularly preferably 1.4 mass% or less. The lower limit of the degree of thermal mass reduction is preferably 0% by mass, but may be 0.001% by mass or more as an example of the embodiment.

The method of measuring the degree of reduction of the thermal mass in the present invention is based on the method described in the following embodiments.

In the fifth embodiment, there is exemplified a mode in which a molding layer covering the surface of a circuit surface is subjected to heat treatment at 100 ° C to 250 ° C and then an adhesive layer is provided. Before heating the adhesive layer on the surface of the molding layer, it is possible to reduce the low molecular component that can be an outgass contained in the molding layer by baking by heating in advance. As a result, the generation of outgas from the molding layer can be reduced. The heat treatment temperature is preferably 100 to 200 占 폚. The heat treatment time is, for example, 1 to 15 hours, preferably 1 to 10 hours.

In the sixth embodiment, there is exemplified a mode in which a molding layer covering the surface of a circuit surface is cleaned with an organic solvent and then a temporary adhesive layer is provided. By cleaning the molding layer or the like with an organic solvent, it is possible to remove the low-molecular component attributable to outgas adhering to the surface portion of the molding layer. Examples of the organic solvent include organic solvents such as benzene, long-chain alkene-based, petroleum-based, and ketone-based solvents, depending on the molding material.

The cleaning may be performed by immersing the molding layer in an organic solvent or rinsing the surface of the molding layer with an organic solvent in a state where the molding layer is spun.

In the seventh embodiment, an embodiment in which the surface of the molding layer covering the surface of the circuit surface is subjected to an ashing treatment and a temporary adhesive layer is provided is exemplified. The outgas can be reduced by removing the low molecular component attributable to the outgas adhering to the surface of the molding layer by ashing.

As the ashing treatment, ashing treatment by ozone, an ashing treatment by oxygen plasma and argon plasma, and an ashing treatment by oxygen plasma are exemplified, and the ashing treatment by oxygen plasma is more preferable.

As the eighth embodiment, a combination of the above-described first to seventh embodiments is exemplified. Preferably, the molding layer covering the surface of the circuit surface is subjected to heat treatment at 100 ° C to 250 ° C .; the surface of the molding layer covering the surface of the circuit surface is cleaned with an organic solvent; There are exemplified embodiments in which two or more of the surfaces of the covering molding layer subjected to ashing treatment are subjected to an adhesive layer.

By combining two or more kinds of means in this manner, the number of voids in the adhesive layer can be reduced more effectively, and the surface roughness can be suppressed. In the present invention, in particular, it is preferable to combine 2 to 4 types of the above means, more preferably 2 kinds or 3 types, and particularly preferably 2 types.

<Molding Layer>

The molding material for forming the molding layer is not particularly limited so far as it does not deviate from the object of the present invention, but it preferably contains a resin, and more preferably includes a curable resin. Further, the molding material preferably includes at least one of an inorganic filler and a curing agent, and may further contain other components.

Examples of the curable resin include phenol resins such as phenol novolac resins, cresol novolak resins and novolac phenol resins such as bisphenol A novolac resin, resol type phenol resins, phenol novolak type epoxy resins, Bisphenol A type epoxy resins and bisphenol F type epoxy resins; hydroquinone type epoxy resins; biphenyl type epoxy resins; stilbene type epoxy resins; and triphenol methane type epoxy resins A resin having a phenylene skeleton and / or a biphenylene skeleton, a resin having a phenylene skeleton and a phenylene skeleton, an epoxy resin having a phenylene skeleton, an epoxy resin having a phenylene skeleton, a dicyclopentadiene-modified phenol type epoxy resin, a naphthol type epoxy resin, Phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins having phenylene and / or biphenylene skeleton A resin having a triazine ring such as an epoxy resin, a urea (urea) resin or a melamine resin such as a resin, an unsaturated polyester resin, a bismaleimide resin, a polyurethane resin, a diallyl phthalate resin, a silicone resin, And cyanate ester resin. These resins may be used singly or in combination. The term "epoxy resin" as used herein refers to all monomers, oligomers, and polymers having two or more epoxy groups in one molecule. Of these, an epoxy resin is preferable. As a result, the electric characteristics can be improved. Further, even if a large amount of inorganic filler is added, fluidity capable of molding can be maintained.

Particularly, it is preferable to use an epoxy resin as the main component resin of the molding layer and a styrene-based elastomer as the main component resin of the adhesive layer. By adopting such a combination, it is possible to easily peel off at the time of peeling while maintaining the necessary adhesiveness at the time of polishing the device wafer, which is preferable. Here, the resin of the main component means the component having the largest content among the resin components contained in the molding layer or the adhesive layer, and is generally 80% by mass or more of the resin component.

The content of the resin is not particularly limited, but is preferably from 3 to 30 mass%, particularly preferably from 5 to 20 mass%, of the entire molding material. When the content is above the lower limit value, the lowering of the fluidity can be suppressed and the sealing of the semiconductor element can be made better. In addition, by lowering the upper limit value or less, deterioration of the solder heat resistance can be effectively suppressed. The resin may be used alone, or two or more resins may be used.

Examples of the curing agent include aliphatic polyamines such as diethylene triamine (DETA), triethylene tetramine (TETA) and meta xylene diamine (MXDA), diaminodiphenylmethane (DDM), m- Amine type curing agents such as polyamine compounds including dicyandiamide (DICY), organic acid dihydrazide and the like in addition to aromatic polyamines such as dimethylamine (MPDA) and diaminodiphenylsulfone (DDS), novolak type phenol resins, Cyclic fatty acid anhydrides (liquid acid anhydrides) such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (TMA) such as phenol type curing agents (phenolic hydroxyl group-containing curing agents) , Acid anhydride-based curing agents such as anhydrous pyromellitic acid (PMDA) and benzophenone tetracarboxylic acid (BTDA), polyamide resins, and polysulfide resins.

When the above-mentioned epoxy resin is used as the resin, the curing agent is not particularly limited, but it is preferable to use a curing agent having a phenolic hydroxyl group. The curing agent having a phenolic hydroxyl group easily controls the reaction of the resin as compared with other curing agents, and thus it is possible to secure good fluidity in the production of a semiconductor device. Further, since the curing agent having a phenolic hydroxyl group is easily controlled in its reactivity, it is also possible to call the inorganic filler at high speed. As a result, excellent reliability of the semiconductor device can be secured. Here, the curing agent having a phenolic hydroxyl group is generally a monomer, an oligomer, or a polymer having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. Specific examples thereof include novolak type phenol resins such as phenol novolac resin and cresol novolak resin, modified phenol resins such as triphenol methane type phenol resin, terpene modified phenol resin and dicyclopentadiene modified phenol resin, phenylene and / Phenol aralkyl resins having a biphenylene skeleton, aralkyl-type phenol resins such as a naphthol aralkyl resin having a phenylene skeleton and / or a biphenylene skeleton, and bisphenol compounds, which may be used singly or in combination do.

The content of the curing agent is not particularly limited, but is preferably from 2 to 10% by mass, particularly preferably from 4 to 7% by mass, based on the entire molding material. The curing agent may be used alone or in combination of two or more.

When the resin is an epoxy resin, a curing agent having a phenolic hydroxyl group is preferably used as a curing agent. In this case, an equivalent ratio of the epoxy group of the epoxy resin to the phenolic hydroxyl group of the curing agent having a phenolic hydroxyl group Is not particularly limited, but is preferably 0.5 to 2.0, particularly preferably 0.7 to 1.5. When the equivalent ratio is within the above range, the curability and moisture resistance reliability are particularly excellent.

The molding material preferably contains an inorganic filler. Examples of the inorganic filler include oxides such as silicates such as talc, calcined clay, uniaxial clay, mica and glass, and silica powders such as titanium oxide, alumina, fused silica (fused spherical silica, fused silica) , Hydroxides such as calcium carbonate, magnesium carbonate and hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate and calcium sulfite, zinc borate, barium metaborate, aluminum borate, Borates such as calcium borate and sodium borate, and nitrides such as aluminum nitride, boron nitride and silicon nitride. The above inorganic fillers may be used singly or in combination. Of these, silica powder such as fused silica and crystalline silica is preferable, and spherical fused silica is particularly preferable. As a result, heat resistance, moisture resistance, strength and the like can be improved. The shape of the inorganic filler is not particularly limited, but it is preferably a spherical shape, and it is preferable that the particle size distribution is wide. As a result, the flowability of the molding material can be particularly improved. The surface of the inorganic filler may be surface-treated with a coupling agent.

The content of the inorganic filler contained in the molding material is not particularly limited, but is preferably 20 to 95% by mass, particularly preferably 30 to 90% by mass, based on the whole of the molding material. When the content is above the lower limit value, deterioration of moisture resistance is suppressed, and when the content is lower than the upper limit value, good fluidity can be maintained. Only one type of inorganic filler may be used, or two or more types may be used.

The molding material may contain various additives such as diazabicycloalkene and derivatives thereof such as 1,8-diazabicyclo [5.4.0] undecene-7, tributylamine, benzyldimethylamine , Imidazole compounds such as 2-methylimidazole, organic phosphines such as triphenylphosphine and methyldiphenylphosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrabenzoate Curing accelerators such as tetra substituted phosphonium tetra substituted borates such as tetrabutylphosphonium tetrabromide, borate, tetraphenylphosphonium tetranaphthoate acid borate, tetraphenylphosphonium tetranaphthoyloxyborate and tetraphenylphosphonium tetranaphthyloxyborate; Silane coupling agents such as silane, mercaptosilane, amino silane, alkyl silane, ureido silane and vinyl silane, A coupling agent such as a coupling agent, an aluminum coupling agent and an aluminum / zirconium coupling agent, a coloring agent such as carbon black and spinach wax, a natural wax such as carnauba wax, a synthetic wax such as polyethylene wax, a higher fatty acid such as stearic acid or zinc stearate And metal salts thereof, releasing agents such as paraffin, low-stress components such as silicone oil and silicone rubber, antioxidants such as brominated epoxy resin, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, molybdenum zinc, An inorganic ion exchanger such as a flame retardant, a bismuth hydrate, or the like can be added. These components may be used individually or in combination of two or more.

Examples of commercially available molding materials used in the present invention include G750 series, G760 series, G770 series, G790 series, Hitachi Kasei CEL-C-5020, CEL-C-5400 and CEL-C-5800 manufactured by Sumitomo Bakelite have.

The thickness of the molding layer is preferably 100 占 퐉 or more in the thinnest portion, and more preferably 1000 占 퐉 or more. The uppermost limit of the thickness is preferably 3000 m or less at the thinnest portion, and more preferably 5000 m or less.

As a method of forming the molding layer, there may be mentioned a method of baking a liquid molding material or a method of heating using a solid compression molding material as described above.

In the case of baking using a liquid molding material, the molding material can be formed by further baking at 120 ° C to 150 ° C for 2 hours to 4 hours after pre-baking at 90 ° C to 110 ° C for 15 minutes to 30 minutes.

In the present invention, a mode in which a molten resin is used at the time of forming the molding layer can also be adopted. In this case, the viscosity of the molding material when covering the circuit surface is preferably about 3.0 to 20.0 Pa · s.

In the case of using a molten resin, the molding material is obtained by sufficiently uniformly mixing the raw materials by using, for example, a mixer, and then further melt-kneading the mixture with a kneader such as a heat roll, a kneader or an extruder.

The viscosity at the time of sealing with a molding material is not particularly limited, but is, for example, 3.0 Pa · s or more, and preferably 5.0 Pa · s or more. On the other hand, such a viscosity is preferably 30.0 Pa · s or less, and more preferably 20.0 Pa · s or less. As a result, generation of voids can be suppressed.

The viscosity can be determined, for example, by a high-purity flow tester or the like.

After sealing with a molding material, the molding material is cured. Examples of the method of curing the molding material include a method of heating, a method of irradiating light, and the like.

In the case of using a molten resin, the heating condition of the heating method is not particularly limited, but is preferably 30 to 180 seconds at 160 to 185 DEG C, more preferably 50 to 120 seconds at 170 to 185 DEG C. By setting the heating condition to the lower limit value or more, generation of defective moldings such as runner separation can be suppressed. By setting the heating condition within the upper limit value, the cycle time of molding can be shortened and productivity is improved.

After the heat curing of the molding material, it is also preferable to further heat the molding material to post-cure.

It may be heated by using a solid compression molding material. That is, it is preferable that a solid compression molding material is molded in a mold by heating and pressing to form a molding layer. Examples of the solid compression molding material include resin pellets obtained by melt-kneading the above-mentioned molten resin, cooling it, and then pelletizing it.

&Lt; Device wafer having a circuit surface &

The device wafer has a device substrate and a circuit surface located on the surface thereof. As the device substrate, any known substrate can be used without limitation, and examples thereof include a silicon substrate and a compound semiconductor substrate. Specific examples of the compound semiconductor substrate include SiC substrate, SiGe substrate, ZnS substrate, ZnSe substrate, GaAs substrate, InP substrate, GaN substrate and the like.

The surface of the device wafer has a circuit surface. Examples of device wafers having circuit surfaces include micro electro mechanical systems (MEMS), power devices, image sensors, micro sensors, light emitting diodes (LEDs), optical devices, interposers, embedded devices, .

The device wafer preferably has a structure such as a metal bump. According to the present invention, it is possible to stably adhere to a device wafer having a structure on the surface, and to easily release adhesion to the device wafer. The height of the structure is not particularly limited, but is preferably 1 to 150 mu m, more preferably 5 to 100 mu m.

In the present invention, the film thickness of the device wafer before thinning is preferably 500 탆 or more, more preferably 600 탆 or more, and more preferably 700 탆 or more. The upper limit is preferably, for example, 2000 占 퐉 or less, more preferably 1500 占 퐉 or less.

The film thickness of the device wafer after thinning is preferably less than 500 탆, more preferably 400 탆 or less, more preferably 300 탆 or less, more preferably 200 탆 or less, even more preferably 100 탆 or less, Is more preferable. The lower limit is, for example, preferably 1 μm or more, more preferably 5 μm or more, and more preferably 20 μm or more.

<Carrier substrate>

Examples of the carrier substrate include various wafers such as silicon wafers, SiC wafers and GaN wafers, substrates made of various materials such as glass and organic substrates, and organic films or inorganic films formed on the substrates. The thickness of the carrier base material is not particularly limited, but is preferably 300 占 퐉 to 100 mm, more preferably 300 占 퐉 to 10 mm, for example.

<Other Layers>

As described above, the laminate of the present invention may have another layer between the carrier substrate (12 in Fig. 1) and the adhesive layer (11 in Fig. 1). As another layer, a layer (sometimes referred to as a separation layer or a release layer) for facilitating the separation of the carrier substrate and the adhesive layer is exemplified. Examples of the layer for facilitating the separation of the carrier substrate and the adhesive layer include a layer for separating between the device substrate and the adhesive layer or a layer for dissolving in a specific solvent, And a mode in which the device substrate of the sieve is thinned and then immersed in a specific solvent to separate the device substrate and the carrier substrate are exemplified. As examples of these layers, reference can be made, for example, to the description of paragraphs 0025 to 0055 of Japanese Laid-Open Patent Publication No. 2014-212292 and the description of paragraphs 0069 to 0124 of the pamphlet of WO2013-065417, the contents of which are incorporated herein by reference .

&Lt; Adhesive layer >

The adhesive layer is used to bond the molding layer with the carrier substrate. The bonding can be usually carried out by hot pressing. Conventionally, out-gas is generated at the time of hot-pressing, and cracks are generated in the device wafer. In the present invention, however, this problem is avoided by setting the number of voids and the surface roughness of the adhesive layer to a predetermined value or less have.

The pressure bonding conditions are, for example, a temperature of 100 to 210 DEG C, a pressure of 0.01 to 1 MPa, and a time of 1 to 15 minutes.

The material of the adhesive layer in the present invention is not particularly limited so long as it satisfies the above various physical properties, but it is preferable that the adhesive layer includes at least one kind of binder. The means for obtaining the adhesive layer that satisfies the above various physical properties can be suitably determined, and for example, a combination of two or more specified binders is exemplified. It is also possible to adjust by blending a specific kind of binder with a plasticizer or the like.

In the case where the adhesive layer of the present invention includes a binder, the binder is preferably contained in a proportion of 50.00 to 99.99% by mass, more preferably 70.00 to 99.99% by mass, and more preferably 88.00% To 99.99 mass% is particularly preferable.

When an elastomer is used as the binder, the elastomer is preferably contained in a proportion of 50.00 to 99.99% by mass, more preferably 70.00% to 99.99% by mass, and particularly preferably 88.00% to 99.99% by mass in the entire solid content of the adhesive layer desirable.

Details of the binder will be described later.

The adhesive layer of the present invention preferably contains a fluorinated liquid compound. The adhesive layer of the present invention preferably contains the fluorine-containing liquid compound in an amount of 0.03 mass% or more and less than 0.5 mass%, more preferably 0.04 to 0.4 mass%, more preferably 0.04 to 0.4 mass%, in the total solid content of the adhesive layer. To 0.2% by mass is more preferable. Details of the fluorine-based liquid phase compound will be described later.

The adhesive layer of the present invention may further contain other additives such as an antioxidant. Details of these will be described later.

In the present invention, the backing adhesive layer may be a single layer or two or more layers, but one layer (for example, a single layer) is preferable.

The adhesive layer of the present invention preferably has an average film thickness of 0.1 to 500 mu m. The lower limit is preferably 1 m or more. The upper limit is preferably 200 占 퐉 or less, more preferably 100 占 퐉 or less. In the case where the adhesive layer has two or more adhesive layers, it is preferable that the total thickness is in the above range.

Next, a method for manufacturing the adhesive layer will be described.

The adhesive layer is formed so as to be located on the surface of the molding layer as described above. The adhesive layer may be formed on the surface of the molding layer, or it may be provided on the carrier substrate and coalesced with the molding layer. The molding layer may be formed on the surface of another support and transferred. Alternatively, the adhesive layer A may be provided on the molding layer and the adhesive layer B may be provided on the carrier substrate to bond the adhesive layer A and the adhesive layer B. In this case, the adhesive layer A and the adhesive layer B may be the same or different. In other cases, the peeling selectivity (peeling selectivity at the interface between the molding layer and the carrier substrate) and the peeling force can be appropriately adjusted by changing the type of the binder component to be described later, or by changing the kind or amount of the additive other than the binder component.

Hereinafter, a method of producing the adhesive layer will be described as an example of forming the adhesive layer on the surface of another support, but the same process can also be carried out on the surface of the molding layer and on the carrier substrate.

In the method for producing the adhesive layer, it is preferable to form a layer by applying an adhesive composition comprising an adhesive and a solvent on the surface of the substrate, and dry the solvent to prepare a adhesive layer.

Examples of the application method of the adhesive composition include a spin coating method, a blade coating method, a spraying method, a roller coating method, a float coating method, a doctor coating method, a screen printing method and a dip coating method. The coating method is preferable. Alternatively, the adhesive composition may be extruded from a slit-shaped opening under pressure to apply the adhesive composition onto the support.

The application amount of the adhesive composition varies depending on the use, but is preferably, for example, a coating amount in which the average thickness of the dried adhesive layer becomes 0.1 to 500 mu m. The lower limit is preferably 1 m or more. The upper limit is preferably 200 占 퐉 or less, more preferably 100 占 퐉 or less.

In the present invention, the average thickness of the adhesive layer is preferably in a range from the one end face to the other end face in the cross section along one direction of the adhesive layer, Is defined as the average value of the values measured by the micrometer. In the present invention, " a cross section along one direction of the adhesive layer " means a cross section orthogonal to the long side direction when the adhesive layer has a polygonal shape. When the backing adhesive layer is in the form of a square, it is a cross section orthogonal to either one of the sides. In the case where the adhesive layer is circular or elliptical, it is a section passing through the center.

The drying conditions depend on the kind of the adhesive composition and the film thickness of the adhesive layer. The drying conditions are preferably 10 to 600 seconds at 60 to 220 DEG C, for example. The drying temperature is more preferably 80 to 200 占 폚. The drying time is preferably 30 to 500 seconds, more preferably 40 to 400 seconds.

Drying may be carried out by increasing the temperature stepwise by dividing into two steps. For example, heating at 90 to 130 ° C for 30 seconds to 250 seconds and then heating at 170 to 220 ° C for 30 seconds to 250 seconds.

The type of the support on which the adhesive layer is formed is not particularly limited, but a support having releasability is preferable in consideration of transferring to the surface of the molding layer and to one side of the carrier substrate.

When the adhesive layer (film) is formed on the support, the film-like adhesive layer may be a film composed of only the adhesive layer which is peeled off from the support, a curing adhesive layer having a release sheet on one surface, Or an adhesive layer having a release sheet.

By performing these treatments continuously, a roll-shaped long film can be obtained. The length of the long film is not particularly limited, but the lower limit is preferably 5000 mm or more, for example, and more preferably 1000 mm or more. The upper limit is preferably, for example, 500000 mm or less, and more preferably 200000 mm or less. The release sheet is peeled off when used.

When an adhesive layer is formed on a support, it is preferable that a film-like adhesive layer is applied to the surface of the molding layer and the carrier substrate, and the adhesive layer is laminated by application of heat and pressure.

On the other hand, when an adhesive layer is formed on the surface of the molding layer and the carrier substrate in place of the substrate, the adhesive layer can be left without peeling off from these substrates, and the device wafer can be processed. Processing of the device wafer will be described later. When the adhesive layer is directly provided on the surface of the substrate, it is preferable that the adhesive layer includes a step of cleaning the excess adhesive layer adhering to the back surface of the substrate or the outer peripheral portion of the substrate. The cleaning at this time is preferably a cleaning with a solvent, and such a solvent is suitably determined in relation to the composition of the adhesive composition, and for example, mesitylene can be cited.

<< Binder >>

The adhesive composition used in the present invention preferably contains at least one binder. In the present invention, the type and the like of the binder are not particularly limited as long as the binder can attain various properties of the adhesive layer.

The binder includes a block copolymer, a random copolymer and a graft copolymer, and a block copolymer is preferable. If the block copolymer is used, it is possible to suppress the flow of the adhesive composition during the heating process, so that adhesion can be maintained even during the heating process, and an effect that the peelability does not change even after the heating process can be expected.

The type of the binder is not particularly limited and examples thereof include polystyrene copolymers, polyester copolymers, polyolefin copolymers, polyuretene copolymers, polyamide copolymers, polyacrylic copolymers, silicone copolymers, Based copolymer or the like can be used. In particular, a polystyrene-based copolymer, a polyester-based copolymer and a polyamide-based copolymer are preferable, and a polystyrene-based copolymer is more preferable from the viewpoint of heat resistance and releasability. Among them, the binder is preferably a block copolymer of styrene and another monomer, and a styrene block copolymer having one terminal or both terminals of styrene block is particularly preferable.

The binder is preferably a hydrogenated product of a block copolymer. If the binder is a hydrogenated material, the thermal stability and the storage stability are improved. Further, the peelability and the removability of the adhesive layer after peeling can be improved. The hydrogenated product means a polymer having a structure in which a block copolymer is hydrogenated.

In the present invention, the binder is preferably an elastomer. By using an elastomer as a binder, it is possible to form an adhesive layer having excellent adhesiveness by an appropriate anchoring effect following the fine unevenness of the carrier substrate and the device wafer. The elastomer may be used alone or in combination of two or more.

In the present specification, the elastomer refers to a polymer compound exhibiting elastic deformation. That is, when an external force is applied, the polymer is instantaneously deformed according to the external force, and when the external force is excluded, it is defined as a polymer compound having a property of restoring the original shape in a short time.

<<< Elastomer >>>

In the present invention, the weight average molecular weight of the elastomer is preferably 2,000 to 200,000 or less, more preferably 10,000 to 200,000, and still more preferably 50,000 to 100,000. Within this range, even when the carrier substrate is peeled from the device wafer and the residue derived from the elastomer remaining on the device wafer and / or the carrier substrate is removed, the solubility in the solvent is excellent, There is an advantage that no residue is left.

In the present invention, examples of the elastomer include, but not particularly limited to, an elastomer (polystyrene elastomer) containing a repeating unit derived from styrene, a polyester elastomer, a polyolefin elastomer, a polyurethane elastomer, a polyamide elastomer, Acrylic elastomer, silicone-based elastomer, polyimide-based elastomer, and the like. In particular, a polystyrene-based elastomer, a polyester-based elastomer, and a polyamide-based elastomer are preferable, and a polystyrene-based elastomer is most preferable from the viewpoint of heat resistance and releasability.

In the present invention, the elastomer is preferably a hydrogenated product. Particularly, a hydrogenated product of a polystyrene type elastomer is preferable. When the elastomer is a hydrogenated material, thermal stability and storage stability are improved. Further, the peelability and the removability of the adhesive layer after peeling can be improved. When the hydrogenated product of the polystyrenic elastomer is used, the above effect is remarkable. Further, the hydrogenated substance means a polymer in which the elastomer is hydrogenated.

In the present invention, the elastomer preferably has a 5% thermal mass reduction temperature of 25 ° C or higher at 20 ° C / minute, preferably 250 ° C or higher, more preferably 300 ° C or higher, still more preferably 350 ° C or higher, And most preferably at least 400 ° C. The upper limit value is not particularly limited, but is preferably 1000 占 폚 or lower, for example, and more preferably 800 占 폚 or lower. According to this embodiment, it is easy to form an adhesive layer having excellent heat resistance.

The elastomer used in the present invention can be deformed to 200% at a room temperature (20 DEG C) with a small external force, assuming that the original size is 100%, and when the external force is excluded, the elastomer returns to 130% It is preferable to have properties.

<<<< Polystyrene based elastomer >>>>

The polystyrene-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer ), Styrene-butadiene-butylene-styrene copolymers (SBBS) and their hydrogenated products, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene- Block copolymer (SEPS), and styrene-ethylene-ethylene-propylene-styrene block copolymer.

The content of the repeating unit derived from styrene in the polystyrene-based elastomer is preferably from 10 to 90% by mass. From the viewpoint of releasability, the lower limit value is preferably 25 mass% or more, more preferably 51 mass% or more.

In the present invention, the polystyrene-based elastomer comprises an elastomer A containing repeating units derived from styrene in a proportion of 10% by mass or more and 50% by mass or less in the total repeating units, and an elastomer A containing repeating units derived from styrene, It is also preferable to use elastomer B containing more than 50 mass% and not more than 95 mass% in combination. By using the elastomer A and the elastomer B in combination, the occurrence of warpage can be effectively suppressed. The mechanism by which such an effect can be obtained is presumed to be as follows.

That is, since elastomer A is a relatively soft material, it is easy to form an adhesive layer having elasticity. Thus, when a laminate of a substrate and a support is manufactured by using the adhesive composition for use in the present invention, and the substrate is polished to form a thin film, even if the pressure at the time of polishing is locally applied, So that it can be easily returned to the original shape. As a result, excellent flat polishing performance can be obtained. Also, even if the laminated body after the polishing is subjected to heat treatment and then cooled, the internal stress generated at the time of cooling can be alleviated by the adhesive layer, and occurrence of warpage can be effectively suppressed.

Further, since the elastomer B is a relatively solid material, by including the elastomer B, a tacky adhesive layer having excellent peelability can be produced.

The elastomer A preferably contains 13 to 45 mass%, more preferably 15 to 40 mass%, of the repeating units derived from styrene in the total repeating units. In this embodiment, more excellent flat polishing performance can be obtained. Further, occurrence of warping of the base material after polishing can be effectively suppressed.

The hardness of the elastomer A is preferably from 20 to 82, more preferably from 60 to 79. The hardness is a value measured by a Type A durometer according to the method of JIS (Japanese Industrial Standard) K6253.

The elastomer B preferably contains 55 to 90 mass% of repeating units derived from styrene in the total repeating units, more preferably 60 to 80 mass%. According to this embodiment, the peelability can be improved more effectively.

The hardness of the elastomer B is preferably 83 to 100, more preferably 90 to 99. [

The mass ratio of the elastomer A and the elastomer B is preferably from 5:95 to 95: 5, more preferably from 10:90 to 80:20, further preferably from 15:85 to 60:40, in terms of the mass ratio of the elastomer A to the elastomer B And most preferably 25 to 75: 60 to 40. Within the above range, the above-mentioned effect can be obtained more effectively.

The polystyrene-based elastomer is preferably a block copolymer of styrene and another monomer, more preferably a block copolymer in which one terminal or both terminals are styrene block, and particularly preferably both terminals are styrene block. When both ends of the polystyrene-based elastomer are made of styrene block (a repeating unit derived from styrene), the heat resistance tends to be further improved. This is because the repeating unit derived from styrene having high heat resistance is present at the terminal. Particularly, since the block portion of the repeating unit derived from styrene is a reactive polystyrene-based hard block, heat resistance and chemical resistance tends to be more excellent, which is preferable. When these are used as a block copolymer, it is considered that phase separation is performed between the hard block and the soft block at 200 캜 or higher. It is considered that the shape of the phase separation contributes to suppression of the generation of irregularities on the surface of the device wafer. In addition, such an elastomer is more preferable in terms of solubility in a solvent and resistance to a resist solvent.

In addition, if the polystyrene-based elastomer is a hydrogenated product, stability against heat is improved, and deterioration such as decomposition or polymerization is hardly caused. In view of solubility in a solvent and resistance to a resist solvent, it is more preferable.

The amount of the unsaturated double bond of the polystyrene-based elastomer is preferably less than 15 mmol, more preferably less than 5 mmol, and most preferably less than 0.5 mmol, per 1 g of the polystyrene-based elastomer from the viewpoint of releasability. The amount of the unsaturated double bond referred to herein does not include an unsaturated double bond in the benzene ring derived from styrene. The amount of unsaturated double bonds can be calculated by NMR (nuclear magnetic resonance) measurement.

In the present specification, the "repeating unit derived from styrene" is a structural unit derived from styrene contained in the polymer when the styrene or styrene derivative is polymerized, and may have a substituent. Examples of the styrene derivative include? -Methylstyrene, 3-methylstyrene, 4-propylstyrene and 4-cyclohexylstyrene. Examples of the substituent include an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, an alkoxyalkyl group of 2 to 5 carbon atoms, an acetoxy group, and a carboxyl group.

Examples of commercially available polystyrene elastomers include toughprene A, toughprene 125, toughprene 126S, solfrene T, asaprene T-411, asaprene T-432, asaprene T-437, Toughtech H1052, Tuftec H1052, Tuftec M1943, Tuftec M1911, Tuftec H1041, Tuftec MP10, Tuftec M1913, Tuftec H1051, Tuftec H1053, Tuftec H1052, Elastomer AR-850C, elastomer AR-830C, elastomer AR860C, elastomer AR-875C, elastomer AR-885C, elastomer (trade name: Elastomer AR-SC-15, elastomer AR-SC-15, elastomer AR-SC-15, elastomer AR-SC-5, elastomer AR- -45, Elastomer AR-720, Elastomer AR-741, Elastomer AR-731, Elastomer AR-750, Elastomer AR- Elastomer AR-FL-85N, elastomer AR-FL-60N, elastomer AR-1050, elastomer AR-1060, elastomer AR-760, elastomer AR- 1040 (Aaron Gassée), Creighton D1111, Creighton D1113, Creighton D1114, Creighton D1117, Creighton D1119, Creighton D1124, Creighton D1126, Creayton D1161, Creayton D1162, Creayton D1163, Creighton D1164 , Kraton D1165, Kraton D1183, Kraton D1193, Kraton DX406, Kraton D4141, Kraton D4150, Kraton D4153, Kraton D4158, Kraton D4270, Kraton D4271, Kraton D4433, Kraton D1170, Kr Creighton D1171, Creighton D1173, Creighton D1153, Creayt D1152, Creighton D1153, Creighton D1124, Creighton D1101, Creighton D1102, Creayton D1116, Creayton D1118, Creayton D1133, Creayton D1152, , Creighton D1155, Creighton D1184, Creighton D1186, Creighton D1189, Creighton D1191, Creighton D1192, Creighton DX405, Creighton DX408, Creayton DX410, Creayton DX414, Creayton DX415, Creayton A1535, Creayton A1536, Creighton FG1901 , Kraton FG1924, Kraton G1640, Kraton G1641, Kraton G1642, Kraton G1643, Kraton G1645, Kraton G1633, Kraton G1650, Kraton G1651, Kraton G1652 (G1652MU-1000) Kraton G1657, Kraton G1660, Kraton G1726, Kraton G1701, Kraton G1702, Kraton G1730, Kraton G1750, Kraton G1765, Kraton G4609, Kraton G4610 (Kraton), TR2000, TR2001, TR2003, DYNARON 6600P, DYNARON 6200P, DYNARON 4630P, DYNARON 8601P, DYNARON 8630P, DYNARON 8630P, DYNARON 8630P, DYNARON 8630P, DYNARON 8630P, DYNARON 8630P, DYNARON 8630P, DYNARON 8630P, DYNARON 8630P, DYNARON 8630P, DYNARON 8630P, DYNARON 8630P, Dynalon 8600P, Dynalon 8903P, DENARON 1320P, DYNARON 1320P, DYNARON 2324P, DYNARON 9901P (manufactured by JSR Corporation), Denka STR series (manufactured by Denki Kagaku Kogyo K.K.), Quintex 3520, Quintex 3433N, Quintax 3421, (Manufactured by Mitsubishi Kagaku Co., Ltd.), Septon 1001, Septon, 8004, Septon 4033 (manufactured by Sumitomo Chemical Co., Ltd.) , Septon 2104, Septon 8007, Septon 2007, Septon 2004, Septon 2063, Septon HG 252, Septon 8076, Septon 2002, Septon 1020, Septon 8104, Septon 2005, Septon 2006, Septon 4055, Septon 4044, Septon 4077, Septon 4099, (Manufactured by Sumitomo Bakelite Co., Ltd.), Rheostomer, and Aroma &lt; (R) &gt; (Manufactured by Riken Vinyl Corporation), and the like.

<<<< Polyester elastomer >>>>

The polyester-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, those obtained by polycondensation of a dicarboxylic acid or a derivative thereof with a diol compound or a derivative thereof.

Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, aromatic dicarboxylic acids in which the hydrogen atoms of these aromatic rings are substituted with methyl, ethyl, phenyl and the like, adipic acid, An aliphatic dicarboxylic acid having 2 to 20 carbon atoms such as a carboxylic acid, and an alicyclic dicarboxylic acid such as cyclohexane dicarboxylic acid. These may be used alone or in combination of two or more.

Examples of the diol compounds include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, , Alicyclic diols such as 4-cyclohexane diol, alicyclic diols, and divalent phenols represented by the following structural formula.

[Chemical Formula 1]

^Wherein Y ^DO represents any one of an alkylene group having 2 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, -O-, -S-, and -SO ₂ -, or a direct bond between benzene rings Bond (single bond). R ^DO1 and R ^DO2 each independently represent a halogen atom or an alkyl group having 1 to 12 carbon atoms. p ^do1 and p ^do2 each independently represent an integer of 0 to 4, and n ^do1 represents 0 or 1;

Specific examples of the polyester elastomer include bisphenol A, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) propane and resorcin. These may be used alone or in combination of two or more.

As the polyester elastomer, an aromatic polyester (e.g., polystyrene terephthalate) portion is used as a hard segment component, an aliphatic polyester (e.g., a polytetramethylene glycol) portion is used as a soft segment component One multi-block copolymer may be used. As the multi-block copolymer, various grades can be cited by the difference in kind, ratio, and molecular weight of the hard segment and the soft segment. Specific examples thereof include Hytrel (manufactured by Du Pont-Toray Co., Ltd.), Pelprene (manufactured by Toyobo Co., Ltd.), Primaloy (manufactured by Mitsubishi Kagaku Co., Ltd.) Ltd.) and the like.

<<<< Polyolefinic Elastomer >>>>

The polyolefin elastomer is not particularly limited and may be appropriately selected depending on the purpose. Examples of the copolymer include copolymers of C2-C20? -Olefins such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-pentene. Examples thereof include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM) and the like. The non-conjugated dienes having 2 to 20 carbon atoms such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, ethylidene norbornene, butadiene, and isoprene, Olefin copolymers, and the like. Further, carboxy modified nitrile rubber obtained by copolymerizing methacrylic acid with a butadiene-acrylonitrile copolymer may be mentioned. Specific examples include ethylene-? -Olefin copolymer rubbers, ethylene-? - olefin-nonconjugated diene copolymer rubbers, propylene-? -Olefin copolymer rubbers, and butene-? -Olefin copolymer rubbers.

(Manufactured by Mitsui Chemicals Co., Ltd.), Thermolun (Mitsubishi Kagaku Co., Ltd.), EXACT (Exxogaku Co., Ltd.), ENGAGE (manufactured by DOW CHEMICAL Co., Ltd.), S-pollex (Sumitomo Chemical Co., (New Jersey), EXCELINK (manufactured by JSR), and the like.

<<<< Polyurethane-based elastomer >>>>

The polyurethane-based elastomer is not particularly limited and may be appropriately selected according to the purpose. For example, an elastomer containing a structural unit of a soft segment composed of a polymer (long chain) diol and diisocyanate, and a hard segment composed of low molecular weight glycol and diisocyanate can be given.

Examples of the polymer (long chain) diol include polypropylene glycol, polytetramethylene oxide, poly (1,4-butylene adipate), poly (ethylene 1,4-butylene adipate), polycaprolactone, poly (1,6-hexylene carbonate), and poly (1,6-hexylene-neopentylene adipate). The number average molecular weight of the polymer (long chain) diol is preferably from 500 to 10,000.

As a low molecular weight glycol, short chain diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and bisphenol A can be used. The number-average molecular weight of the short-chain diol is preferably 48 to 500.

Examples of commercially available products of the polyurethane-based elastomer include PANDEX T-2185, T-2983N (manufactured by DIC Corporation), miractran (manufactured by Nippon Miraclast), ELASTOLAN (manufactured by BASF) , Pelletan (manufactured by Dow Chemical), Iron Rubber (manufactured by NOK), Mobil Ron (manufactured by Nisshinbo Chemical), and the like.

<<<< Polyamide elastomer >>>>

The polyamide-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, a polyamide such as polyamide-6, 11, 12, or the like may be used for the hard segment and a polyether and / or polyester such as polyoxyethylene, polyoxypropylene, polytetramethylene glycol, And the like. The elastomer is broadly divided into two types, a polyether block amide type and a polyetherester block amide type.

UBESTA XPA (manufactured by Ube Gosan Co., Ltd.), diamide (manufactured by Daicel Ebonic Co., Ltd.), PEBAX (manufactured by ARKEMA), and Grilon ELX (manufactured by EMK Chemie Japan K.K.) as commercial products, PAA-200, PA-201, TPAE-12, TPAE-32, polyester amide TPAE-617, TPAE- 617C (manufactured by T & K TOKA Co., Ltd.).

<<<< Polyacrylic elastomer >>>>

The polyacrylic elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, there may be mentioned acrylic acid esters such as ethyl acrylate, butyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate and the like as the main components, acrylic esters and glycidyl methacrylate, allyl glycidyl ether And the like. And those obtained by copolymerizing acrylonitrile and crosslinking point monomers such as ethylene and the like. Specific examples include acrylonitrile-butyl acrylate copolymer, acrylonitrile-butyl acrylate-ethyl acrylate copolymer, acrylonitrile-butyl acrylate-glycidyl methacrylate copolymer, and the like. .

<<<< Silicone Elastomer >>>>

The silicone-based elastomer is not particularly limited and may be appropriately selected depending on the purpose. For example, an organopolysiloxane as a main component, and examples thereof include polydimethylsiloxane-based, polymethylphenylsiloxane-based, and polydiphenylsiloxane. Specific examples of commercially available products include KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, and SH series (manufactured by Toray Dow Corning Silicone Co., Ltd.).

<<<< Other elastomers >>>>

In the present invention, a rubber-modified epoxy resin (epoxy-based elastomer) can be used as the elastomer. The epoxy-based elastomer can be obtained by copolymerizing a part or all of the epoxy groups of a bisphenol F type epoxy resin, a bisphenol A type epoxy resin, a salicylaldehyde type epoxy resin, a phenol novolak type epoxy resin or a cresol novolak type epoxy resin, Carboxylic acid modified form, butadiene-acrylonitrile rubber, and terminal amino-modified silicone rubber.

<<< Other Polymer Compound >>>

In the present invention, as the binder, a polymer compound other than the above-described elastomer (also referred to as another polymer compound) can be used. The other polymer compound may be used alone or in combination of two or more.

Specific examples of other polymer compounds include hydrocarbon resins, novolac resins, phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyamide resins, polyimide resins, polyamideimide resins , Polybenzimidazole resin, polybenzoxazole resin, polyvinyl chloride resin, polyvinyl acetate resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polystyrene terephthalate resin, polyethylene terephthalate resin, Polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyarylate resin, polyetheretherketone resin, and the like. Among them, a hydrocarbon resin, a polyimide resin, and a polycarbonate resin are preferable, and a hydrocarbon resin is more preferable.

In the present invention, as the binder, those containing a fluorine atom described later can be used, but it is preferable that a binder containing fluorine atoms (hereinafter also referred to as a fluorine-based binder) is substantially not included. The term "substantially not containing the fluorine-based binder" means that the content of the fluorine-based binder is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, relative to the total mass of the binder, Do.

<<<< Hydrocarbon resin >>>>

In the present invention, any hydrocarbon resin may be used.

A hydrocarbon resin basically means a resin composed only of carbon atoms and hydrogen atoms. However, if the basic skeleton is a hydrocarbon resin, it may contain other atoms as side chains. That is, when a functional group other than a hydrocarbon group is directly bonded to a main chain such as an acrylic resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, and a polyvinyl pyrrolidone resin to a hydrocarbon resin composed only of carbon atoms and hydrogen atoms In this case, the content of the repeating unit in which the hydrocarbon group is directly bonded to the main chain is preferably 30 mol% or more with respect to the total repeating units of the resin.

Examples of hydrocarbon resins conforming to the above conditions include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, hydrogenated terpenephenol resins, rosins, rosin esters, hydrogenated rosins, hydrogenated rosin esters, An aromatic petroleum resin, an aromatic petroleum resin, a hydrogenated petroleum resin, a modified petroleum resin, a cyclic aliphatic petroleum resin, a coumarone petroleum resin, an indene petroleum resin, a polystyrene -Olefin polymers (e.g., methylpentene copolymers), and cycloolefin polymers (e.g., norbornene copolymers, dicyclopentadiene copolymers, tetracyclododecene copolymers) .

The hydrocarbon resin is preferably a terpene resin, a rosin, a petroleum resin, a hydrogenated rosin, a polymerized rosin, an olefin polymer, or a cycloolefin polymer, more preferably a terpene resin, a rosin, an olefin polymer, or a cycloolefin polymer And is particularly preferably a cycloolefin polymer.

Examples of the cycloolefin polymer include norbornene polymers, polymers of monocyclic cycloolefins, polymers of cyclic conjugated dienes, vinyl alicyclic hydrocarbon polymers, and hydrides of these polymers. Preferable examples of the cycloolefin polymer include an addition (co) polymer containing at least one repeating unit represented by the following general formula (II), and a copolymer comprising at least one repeating unit represented by the general formula (I) (Co) polymer. Another preferred example of the cycloolefin polymer is a ring-opening (co) polymer containing at least one cyclic repeating unit represented by the general formula (III).

(2)

In the formula, m represents an integer of 0 to 4. R ¹ to R ⁶ each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; X ¹ to X ³ and Y ¹ to Y ³ each represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, (CH ₂ ) n COOR ¹¹ , - (CH ₂ ) n OCOR ¹² , - (CH ₂ ) nNCO, - (CH ₂ ) nNO ₂ , - (CH _{2) nCN, - (CH 2} ) nCONR 13 R 14, - (CH 2) nNR 15 R 16, - (CH 2) nOZ, - (CH 2) nW, or X ¹ and Y ^1, X ² and Y ² , Or (-CO) ₂ O, (-CO) ₂ NR ¹⁷ composed of X ³ and Y ³ . Each of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ represents a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 20 carbon atoms) W represents SiR ¹⁸ _p D _3-p (R ¹⁸ represents a hydrocarbon group of 1 to 10 carbon atoms, D represents a halogen atom, -OCOR ¹⁸ or a group represented by -OR ¹⁸⁾ -OR ¹⁸ , and p represents an integer of 0 to 3). n represents an integer of 0 to 10;

The norbornene polymer is disclosed in, for example, Japanese Unexamined Patent Application Publication No. 10-7732, Japanese Unexamined Patent Publication No. 2002-504184, US2004 / 229157A1, and WO2004 / 070463A1. The norbornene polymer can be obtained by addition polymerization of norbornene polycyclic unsaturated compounds. If necessary, norbornene polycyclic unsaturated compounds and ethylene, propylene, butene; Conjugated dienes such as butadiene, isoprene; And non-conjugated dienes such as ethylidene norbornene may be addition polymerized. This norbornene polymer is commercially available under the trade name APEL from Mitsui Chemicals, Inc. and has a glass transition temperature (Tg) of, for example, APL8008T (Tg 70 DEG C), APL6013T (Tg 125 DEG C) or APL6015T ° C) and the like. Pellets such as TOPAS8007, 5013, 6013 and 6015 are available from Polyplastics. Appear3000 is also being released at Ferrania.

The hydrides of the norbornene-based polymers are disclosed in JP-A-1-240517, JP-A-7-196736, JP-A-60-26024, JP-A-62-19801, As disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-1159767 or Japanese Patent Application Laid-Open No. 2004-309979, by subjecting a polycyclic unsaturated compound to addition polymerization or metathesis ring-opening polymerization, followed by hydrogenation.

In the general formula (III), R ⁵ and R ⁶ are preferably a hydrogen atom or a methyl group, and X ³ and Y ³ are preferably a hydrogen atom, and other groups are appropriately selected. This norbornene polymer is commercially available under the trade name of Arton G or Aton F from JSR Corporation and Zeonor ZF14, ZF16, Zeonex 250, 280, and 480R, and they can be used.

<<<< Polyimide resin >>>>

As the polyimide resin, those obtained by condensation reaction of tetracarboxylic acid dianhydride and diamine by a known method can be used.

As a known method, for example, a method of dehydrating and cyclizing a polyamic acid obtained by mixing tetracarboxylic dianhydride and diamine in approximately equimolar mixing in an organic solvent at a reaction temperature of 80 ° C or lower, and the like can be given. Here, approximately equimolar means that the molar ratio of tetracarboxylic dianhydride to diamine is in the vicinity of 1: 1. If necessary, the composition ratio of the tetracarboxylic dianhydride and the diamine may be adjusted so that the total amount of the diamine is 0.5 to 2.0 moles relative to 1.0 moles of the tetracarboxylic dianhydride in total. The weight average molecular weight of the polyimide resin can be adjusted by adjusting the composition ratio of tetracarboxylic dianhydride and diamine within the above range.

Examples of the tetracarboxylic acid dianhydride include, but are not limited to, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'- Bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2- Bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4 (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylene tetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether Dianhydride, benzene-1,2,3,4-tetracarboxylic acid dianhydride, 3,4,3 ', 4'-benzophenone tetracarboxylic acid dianhydride, 2,3,2', 3'-benzophenone tetracarboxylic acid dianhydride Water, 2,3,3 ', 4'-benzophenone tetracarboxylic acid imine Water, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,2,4- 5-naphthalenetetracarboxylic acid dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, phenanthrene-1,8,9,10-tetracarboxylic acid dianhydride, pyrazine-2,3,5,6 -Tetracarboxylic acid dianhydride, thiophene-2,3,5,6-tetracarboxylic acid dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic acid dianhydride, 3,4,3', 4'- (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) diisocyanate dianhydride, 2,3,4'- Methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyl di Cyclohexane dianhydride, p-phenylene bis (trimellitate anhydride), ethylene tetracarboxylic acid dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, decahydronaphthalene-1,4,5,8 -Tetracarboxylic acid dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid dianhydride, cyclopentane- Tetracarboxylic acid dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid dianhydride, 1,2,3,4-cyclobutante tetracarboxylic acid dianhydride, bis (exo- bicyclo [2.2 Heptane-2,3-dicarboxylic acid dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 2,2- -Dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) phenyl] (2,2-bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane dianhydride, 2,2-bis Bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitic anhydride), dianhydride dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 1,4- , 1,3-bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl- , 2-dicarboxylic acid dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic dianhydride, 1,2- (ethylene) bis (trimellitate anhydride) (Trimellitate anhydride), 1,3- (trimethylene) bis (trimellitate anhydride), 1,4- (tetramethylene) bis (trimellitate anhydride) , 6- ( (Trimellitate anhydride), 1,7- (heptamethylene) bis (trimellitate anhydride), 1,8- (octamethylene) bis (trimellitate anhydride) ), Bis (trimellitate anhydride), 1,10- (decamethylene) bis (trimellitate anhydride), 1,12- (dodecamethylene) bis (trimellitate anhydride) ), Bis (trimellitate anhydride), and 1,18- (octadecamethylene) bis (trimellitate anhydride). These may be used singly or in combination of two or more. Among them, 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3'-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetra Carboxylic acid dianhydride is preferable, and 3,4,3 ', 4'-benzophenonetracarboxylic acid dianhydride is more preferable.

The diamine is not particularly limited, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylether, 3,4'- Aminodiphenylether, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (4-amino- (4-amino-3,5-diisopropylphenyl) methane, 3,3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyl Diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diamino Diphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 4'-diaminodiphenyl ketone, 4,4'-di Aminophenyl ketone, 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindene, 2,2-bis Bis (3-aminophenyl) hexafluoropropane, 2,2- (3-aminophenyl) propane, Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ' 2, 4 '- (1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4' Bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- 4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminophenoxy) phenyl) sulfide, (4-aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) (Aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxy) aminophenoxy, 2,2-bis Phenyl) propane, polyoxypropylene diamine, 4,9-dioxadodecane-1,12-diamine, 4,9,14-trioxaheptadecane-1,17- Diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, Diaminodecane, 1,1-diaminododecane, 1,12-diaminododecane, 1,1-diaminododecane, 1,1-diaminododecane, Hexane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, and the like.

Among these diamines, it is preferable to use at least one selected from the group consisting of 3- (4-aminophenyl) -1,1,3-trimethyl-5-aminoindene, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, Diamine, 1,6-diaminohexane, and 4, 9, 14-diamine, Trioxaheptadecane-1,17-diamine, and more preferably at least one selected from the group consisting of 3- (4-aminophenyl) -1,1,3-trimethyl-5- desirable.

Examples of the solvent used in the reaction of the tetracarboxylic acid dianhydride with diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone and N, N-dimethylformamide. In order to adjust the solubility of raw materials and the like, a nonpolar solvent (for example, toluene or xylene) may be used in combination.

The reaction temperature of the tetracarboxylic dianhydride and the diamine is preferably less than 100 占 폚, more preferably less than 90 占 폚. Imidization of polyamic acid is typically performed by heat treatment under an inert atmosphere (typically, a vacuum or a nitrogen atmosphere). The heat treatment temperature is preferably 150 占 폚 or higher, more preferably 180 to 450 占 폚.

The weight average molecular weight (Mw) of the polyimide resin is preferably 10,000 to 1,000,000, more preferably 20,000 to 100,000.

In the present invention, the polyimide resin is preferably at least one selected from the group consisting of? -Butyrolactone, cyclopentanone, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, cyclohexanone, glycol ether, Side and tetramethylurea are preferably polyimide resins having a solubility of 10 g / 100 g Solvent or more at 25 캜.

The polyimide resin having such a solubility can be obtained, for example, by reacting 3,4,3 ', 4'-benzophenonetetracarboxylic dianhydride with 3- (4-aminophenyl) -1,1,3- And polyimide resins obtained by reacting a polyimide resin with an aminoindine. This polyimide resin is particularly excellent in heat resistance.

As the polyimide resin, a commercially available product may be used. (All manufactured by Fuji Photo Film Co., Ltd.), GPT-LT (manufactured by Gunpo Aigaku Co., Ltd.), SOXR-S, SOXR-M, SOXR-U, SOXR- Manufactured by KODOSHI KOGYO CO., LTD.).

<<<< Polycarbonate Resin >>>>

In the present invention, the polycarbonate resin preferably has a repeating unit represented by the following general formula (1).

(3)

In the general formula (1), Ar ¹ and Ar ² each independently represent an aromatic group, and L represents a single bond or a divalent linking group.

Ar ¹ and Ar ² in the general formula (1) each independently represent an aromatic group. Examples of the aromatic group include a benzene ring, a naphthalene ring, a pentane ring, an indane ring, an azole ring, a heptane ring, an indene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, , A fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophen ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazin ring, , Benzofuran ring, benzothiophen ring, isobenzofuran ring, quinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, Acridine ring, phenanthroline ring, thianthrene ring, chromane ring, xanthene ring, phenoxathiine ring, phenothiazine ring, and phenanthrene ring. Among them, a benzene ring is preferable.

These aromatic groups may or may not have a substituent, but are preferably not present.

Examples of the substituent which the aromatic group may have include a halogen atom, an alkyl group, an alkoxy group, and an aryl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group includes an alkyl group having 1 to 30 carbon atoms. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group may be linear or branched. Further, a part or all of the hydrogen atoms of the alkyl group may be substituted with a halogen atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

As the alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. The carbon number of the alkoxy group is more preferably from 1 to 20, and even more preferably from 1 to 10. The alkoxy group may be linear, branched or cyclic.

The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 20 carbon atoms.

The weight average molecular weight (Mw) of the polycarbonate resin is preferably 1,000 to 1,000,000, more preferably 10,000 to 80,000. Within the above range, the solubility in solvents and the heat resistance are good.

Examples of commercially available products of the polycarbonate resin include PCZ-200, PCZ-300, PCZ-500, PCZ-800 (Mitsubishi Gas Gas Company), APEC 9379 (manufactured by Bayer), Panlite L-1225LM .

The binder for use in the present invention preferably contains the binder in an amount of 50.00 to 99.99% by mass, more preferably 70.00 to 99.99% by mass, and more preferably 88.00 to 99.99% by mass, based on the total solid content of the adhesive composition. Is particularly preferable. When the content of the binder is within the above range, the adhesive property and the peeling property are excellent.

When an elastomer is used as the binder, the elastomer is preferably contained in a proportion of 50.00 to 99.99 mass%, more preferably 70.00 to 99.99 mass%, and particularly preferably 88.00 to 99.99 mass% in the total solid content of the adhesive composition Do. When the content of the elastomer is within the above range, the adhesive property and the peelability are excellent. When two or more kinds of elastomers are used, it is preferable that the total is in the above range.

When an elastomer is used as the binder, the content of the elastomer in the total mass of the binder is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% To 100% by mass is more preferable. The binder may be substantially only an elastomer. The content of the elastomer in the total mass of the binder is preferably 99% by mass or more, more preferably 99.9% by mass or more, still more preferably only the elastomer, and the binder is substantially only an elastomer.

<< Fluorine-based liquid phase compound >>

The adhesive composition of the present invention preferably contains a fluorinated liquid compound.

In the present invention, the liquid phase means a compound having fluidity at 25 ° C, for example, a compound having a viscosity at 25 ° C of 1 to 100,000 mPa · s. Here, the viscosity can be measured using a B-type viscometer, and the viscosity is measured by a viscosity measurement using a B-type viscometer (Visco Lido Advance, manufactured by Funnel Laboratories).

The viscosity of the fluorine-based liquid phase compound at 25 占 폚 is more preferably 10 to 20,000 mPa 占 퐏, and still more preferably 100 to 15,000 mPa 占 퐏. When the viscosity of the fluorine-based liquid-phase compound is within the above range, the fluorine-based liquid-phase compound tends to be unevenly distributed in the surface layer of the pressure-sensitive adhesive layer.

In the present invention, the fluorine-based liquid phase compound may be any of oligomer and polymer compounds. It may also be a mixture of an oligomer and a polymer. These mixtures may further contain monomers. The fluorine-based liquid-phase compound may be a monomer.

The fluorine-based liquid phase compound is preferably an oligomer, a polymer and a mixture thereof from the viewpoint of heat resistance and the like.

Examples of the oligomer and polymer include a radical polymer, a cationic polymer, and an anionic polymer, all of which can be preferably used. Vinyl polymers are particularly preferred.

The weight average molecular weight of the fluorine-based liquid phase compound is preferably from 500 to 100,000, more preferably from 1,000 to 50,000, and still more preferably from 2,000 to 20,000.

In the present invention, the fluorine-based liquid phase compound is preferably a compound which is not denatured during the treatment of the substrate provided for adhesion. For example, a compound which can be present as a liquid phase even after heating at 250 DEG C or higher or after treating the substrate with various chemical solutions is preferable. As a specific example, the viscosity at 25 ° C after heating from 250 ° C to 25 ° C at a temperature elevation rate of 10 ° C / min from 25 ° C is preferably from 1 to 100,000 mPa · s, more preferably from 10 to 20,000 mPa · s · S is more preferable, and 100 to 15,000 mPa · s is even more preferable.

The fluorine-based liquid phase compound having such characteristics is preferably a non-thermosetting compound having no reactive group. The term reactive group as used herein refers to the whole period of the reaction in the heating at 250 ° C, and includes a polymerizable group and a hydrolyzable group. Specific examples thereof include a metha (acryl) group, an epoxy group, and an isocyanate group.

The fluorine-based liquid-phase compound preferably has a 10% thermal mass reduction temperature at 25 ° C or higher and 20 ° C / minute at 250 ° C or higher, more preferably 280 ° C or higher. The upper limit value is not particularly limited, but is preferably 1000 占 폚 or lower, for example, and more preferably 800 占 폚 or lower. According to this embodiment, it is easy to form an adhesive layer having excellent heat resistance. The thermal mass reduction temperature is a value measured under the above-mentioned temperature increasing condition under a nitrogen stream by TG / DTA (thermal mass measuring apparatus).

The fluorine-based liquid-phase compound used in the present invention contains a lipophilic group. Examples of the lipophilic group include a linear or branched alkyl group, a cycloalkyl group, and an aromatic group.

The number of carbon atoms of the alkyl group is preferably from 2 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, and particularly preferably from 12 to 20. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, , Isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group and 2-ethylhexyl group.

The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, and an aromatic group.

Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The carbon number of the alkoxy group is preferably from 1 to 30, more preferably from 1 to 20, and even more preferably from 1 to 10. The alkoxy group is preferably straight-chain or branched.

The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 14, and most preferably from 6 to 10.

The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms of the cycloalkyl group is preferably from 3 to 30, more preferably from 4 to 30, still more preferably from 6 to 30, and most preferably from 12 to 20. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a vinyl group, a camphanyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoryl group, a dicyclohexyl group, .

The cycloalkyl group may have the substituent described above.

The aromatic group may be monocyclic or polycyclic. The carbon number of the aromatic group is preferably from 6 to 20, more preferably from 6 to 14, and most preferably from 6 to 10. It is preferable that the aromatic group does not contain a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom, etc.) in the element constituting the ring. Specific examples of the aromatic group include a benzene ring, a naphthalene ring, a pentane ring, an indene ring, an azole ring, a heptylene ring, an indene ring, a perylene ring, a pentacene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, A thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazin ring, an indolizine ring, A benzofuran ring, an isobenzofuran ring, a quinoline ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, a quinoxazoline ring, an isoquinoline ring, a carbazole ring, a phenanthrene ring, Pyran, acridine, phenanthroline, thianthrene, chroman, zenthene, phenoxathiine, phenothiazine, and phenanthrene.

The aromatic group may have the substituent described above.

The fluorine-based liquid-phase compound may be a compound containing only one kind of oil-cooling group, or may contain two or more kinds. The organic group may contain a fluorine atom. That is, the fluorine-based liquid-phase compound in the present invention may be a compound in which only a hydrophilic group contains a fluorine atom. Further, in addition to a hydrophilic group, a compound having a fluorine atom-containing group (also referred to as a fluorine group) may be used. Preferably, it is a compound containing a mineral oil and a fluorine group. When the fluorine-based liquid-phase compound is a compound having a lipophilic group and a fluorine group, the lipophilic group may or may not contain a fluorine atom, but is preferably not included.

The fluorine-based liquid-phase compound preferably has 2 to 100, more preferably 6 to 80, groups having at least one lipophilic group in one molecule.

As the fluorine group, a known fluorine group can be used. For example, fluorinated alkyl groups, fluorinated alkylene groups and the like. Among the fluorine groups, those functioning as a lipophilic group are assumed to be included in lipophilic groups.

The carbon number of the fluorinated alkyl group is preferably from 1 to 30, more preferably from 1 to 20, and still more preferably from 1 to 15. The fluorine alkyl group may be linear, branched or cyclic. It may also have an ether bond. The fluorinated alkyl group may also be a perfluoroalkyl group in which all of the hydrogen atoms are substituted with fluorine atoms.

The carbon number of the fluorine-containing alkylene group is preferably from 2 to 30, more preferably from 2 to 20, and still more preferably from 2 to 15. The fluorine-containing alkylene group may be linear, branched or cyclic. It may also have an ether bond. The fluorinated alkylene group may be a perfluoroalkylene group in which all of the hydrogen atoms are substituted with fluorine atoms.

The fluorine-based liquid-phase compound preferably has a fluorine atom content of 1 to 90 mass%, more preferably 2 to 80 mass%, and still more preferably 5 to 70 mass%. When the fluorine content is in the above range, the releasability is excellent.

The content of fluorine atoms is defined as "{(the number of fluorine atoms in one molecule x the mass of fluorine atoms) / the mass of all atoms in one molecule} x 100".

As the fluorine-based liquid phase compound, a commercially available product may be used. For example, F-251, F-281, F-477, F-553, F-554, F-555, F-556, F-557, F- F-560, F-561, F-563, F-565, F-567, F-568, F-571, R-40, R-41, R- 710F, 710FM, 710FS, 730FL, and 730LM.

The content of the fluorinated liquid compound in the adhesive composition of the present invention is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, based on the mass of the adhesive composition excluding the solvent Do. When the content of the fluorine-based liquid phase compound is within the above range, the adhesive property and the peeling property are excellent. The fluorinated liquid-phase compound may be used singly or in combination of two or more. When two or more kinds are used in combination, it is preferable that the total content is in the above range.

The adhesive composition used in the present invention preferably has a mass ratio of the fluorine-based liquid compound and the binder to the fluorine-based liquid compound: binder = 0.001: 99.999 to 10: 90.00, more preferably 0.001: 99.999 to 5:95.00, 0.010: 99.99 to 5: 95.00 is more preferable. By setting the mass ratio of the fluorine-based liquid-phase compound and the binder within the above range, it is easy to make the fluorine-based liquid compound more localized on the air interface side of the adhesive layer.

<< Plasticizer >>

The adhesive composition used in the present invention may contain a plasticizer if necessary. By mixing a plasticizer, an adhesive layer that satisfies the above performance can be obtained.

As the plasticizer, phthalic acid ester, fatty acid ester, aromatic polycarboxylic acid ester, polyester and the like can be used.

Examples of the phthalic acid ester include DMP, DEP, DBP, # 10, BBP, DOP, DINP, DIDP (hereinafter referred to as Daihachi Kagaku), PL-200, DOIP Manufactured by Shin-Nippon Rika KK).

Examples of the fatty acid ester include butyl stearate, Unistar M-9676, Unistar M-2222SL, Unistar H-476, Unistar H-476D, Panaset 800B, Panaset 875, Panaset 810 DIBA, DBA, DOA, DINA, DIDA, DOS, BXA, DOZ, DESU (available from Daihachi Chemical).

Examples of the aromatic polycarboxylic acid ester include TOTM (Daihachi Kagaku), Monoisizer W-705 (Daihachi Kagaku), UL-80 and UL-100 (manufactured by ADEKA).

Examples of the polyester include Polysizer TD-1720, Polysizer S-2002, Polysizer S-2010 (manufactured by DIC) and BAA-15 (manufactured by Daihachi Kagaku).

Among the above plasticizers, DIDP, DIDA, TOTM, Unistar M-2222SL and Polysizer TD-1720 are preferable, DIDA and TOTM are more preferable, and TOTM is particularly preferable.

The plasticizer may be used alone or in combination of two or more.

From the viewpoint of prevention of sublimation during heating, the molecular weight of the plasticizer is preferably 250 ° C or more when the mass is reduced by 1% by mass when measured under a constant rate of 20 ° C / min under a nitrogen stream, Particularly preferably 300 DEG C or higher. The upper limit is not specifically defined, but can be set to, for example, 500 ° C or lower.

The addition amount of the plasticizer is preferably 0.01% by mass to 5.0% by mass, more preferably 0.1% by mass to 2.0% by mass, based on the total solid content of the adhesive composition.

<< Antioxidants >>

The adhesive composition used in the present invention may contain an antioxidant. As the antioxidant, phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, quinone antioxidants, amine antioxidants and the like can be used.

Examples of the phenolic antioxidant include p-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol, Irganox1010, Irganox1330, Irganox3114, Irganox1035, Sumilizer MDP-S " and " Sumilizer GA-80 " manufactured by Sumitomo Chemical Co.,

Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate di-stearyl, Sumilizer TPM, Sumilizer TPS, Sumilizer TP-D and the like available from Sumitomo Chemical Co., .

Examples of the phosphorus antioxidant include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, poly Dialkyldiphenylphosphite, triphenylphosphite, "Irgafos 168", "Irgafos 38" manufactured by BASF Co., Ltd., and the like.

Examples of the quinone antioxidant include p-benzoquinone, 2-tert-butyl-1,4-benzoquinone, and the like.

Examples of the amine-based antioxidant include dimethyl aniline and phenothiazine.

The antioxidant is preferably Irganox 1010, Irganox 1330, 3,3'-thiodipropionate distearyl, Sumilizer TP-D, Irganox 1010 and Irganox 1330 are more preferable, and Irganox 1010 is particularly preferable.

Among the above-mentioned antioxidants, phenol-based antioxidants and sulfur-based antioxidants or phosphorus-based antioxidants are preferably used in combination, and phenol-based antioxidants and sulfur-based antioxidants are most preferably used in combination. Particularly when a polystyrene-based elastomer is used as the elastomer, it is preferable to use a phenolic antioxidant and a sulfur-based antioxidant in combination. By using such a combination, the effect of effectively suppressing the deterioration of the binder due to the oxidation reaction can be expected. When the phenolic antioxidant and the sulfur antioxidant are used in combination, the mass ratio of the phenol antioxidant to the sulfur antioxidant is preferably 95: 5 to 5:95, : 75 is more preferable.

As the combination of the antioxidants, Irganox 1010, Sumilizer TP-D, Irganox 1330 and Sumilizer TP-D, Sumilizer GA-80 and Sumilizer TP-D are preferable, Irganox 1010 and Sumilizer TP-D, Irganox 1330 and Sumilizer TP- Irganox 1010 and Sumilizer TP-D are particularly preferred.

From the viewpoint of preventing sublimation during heating, the molecular weight of the antioxidant is preferably 400 or more, more preferably 600 or more, and particularly preferably 750 or more.

The content of the antioxidant is preferably 0.001 to 20.0% by mass, more preferably 0.005 to 10.0% by mass, based on the total solid content of the adhesive composition.

The antioxidant may be of one kind alone or in combination of two or more kinds. When the amount of the antioxidant is two or more, the total amount is preferably in the above range.

<< Solvent >>

The adhesive composition used in the present invention preferably contains a solvent. As the solvent, any known solvent can be used without limitation, and an organic solvent is preferable.

Examples of the organic solvent used in the present invention include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, And examples thereof include methyl, ethyl lactate, alkyloxyacetate (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetic acid Ethyl, etc.), 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate, ethyl 3-oxypropionate (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl propionate, ethyl 3-ethoxypropionate, etc.)), 2-oxypropionic acid alkyl esters (e.g., methyl 2-oxypropionate, 2-oxypropionate Ethyl propionate, propyl 2-oxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate and ethyl 2-ethoxypropionate) Methyl 2-methylpropionate and ethyl 2-oxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- , Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and 1-methoxy-2-propyl acetate;

Diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol mono Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, Ethers such as acetate, propylene glycol monopropyl ether acetate;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and gamma butyrolactone;

Butylbenzene, isobutylbenzene, tert-butylbenzene, amylbenzene, isoamylbenzene, (2,2-dimethylbenzyl) benzene, toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexylbenzene, 2-ethyltoluene, 1 , 2-diethylbenzene, o-cymene, indene, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m-cymene, 1,3-diisopropylbenzene, , 1,4-diethylbenzene, p-cymene, 1,4-diisopropylbenzene, 4-tert-butyltoluene, 1,4-di-tert-butylbenzene, , 2,3-trimethylbenzene, 1,2,4-trimethylbenzene, 4-tert-butyl-ozylene, 1,2,4-triethylbenzene, 1,3,5- 1,3,5-triisopropylbenzene, 5-tert-butyl-m-xylene, 3,5-di-tert-butyltoluene, 1,2,3,5-tetramethyl Zhen, 1,2,4,5-tetramethyl benzene, be an aromatic hydrocarbon such as pentamethyl benzene, decahydronaphthalene soryu;

Aliphatic hydrocarbons such as ethylcyclohexane, limonene (especially d-limonene), p-mentine, nonene, decane, dodecane and decalin are exemplified.

These solvents are also preferably mixed with two or more kinds in view of improving the application surface shape and the like. In this case, particularly preferable examples include mesitylene, tert-butylbenzene, 1,2,4-trimethylbenzene, p-mentine, gamma butyrolactone, anisole, methyl 3-ethoxypropionate, Ethyl propionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethylcarbitol acetate, butylcarbitol acetate , Propylene glycol methyl ether, and propylene glycol methyl ether acetate.

When the adhesive composition contains a solvent, the content of the solvent in the adhesive composition is preferably such that the total solid content of the adhesive composition is 5 to 80% by mass, more preferably 5 to 70% By mass, more preferably from 10 to 60% by mass.

The solvent may be a single kind or two or more types. When two or more kinds of solvents are used, the total amount is preferably in the above range.

The adhesive composition used in the present invention preferably contains a surfactant.

As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants may be used, but preferred surfactants are nonionic surfactants.

Preferable examples of the nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, and silicone surfactants.

The adhesive composition preferably contains a silicone surfactant as a surfactant from the viewpoint of coatability. In general, when a high-viscosity adhesive composition is used, it is difficult to apply the composition in a uniform thickness. However, since it is easy to apply the composition in a uniform thickness, the silicone-based surfactant can be more preferably used.

As a silicone surfactant, there are, for example, those described in JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A- Japanese Patent Application Laid-Open No. 63-34540, Japanese Patent Application Laid-Open Nos. 7-230165, 8-62834, 9-54432, 9-5988, A surfactant described in each of Japanese Patent Application Laid-Open No. 2001-330953, or a commercially available surfactant may be used.

Examples of commercially available silicone surfactants include KP-301, KP-306, KP-109, KP-310, KP-310B, KP-323, KP-326, KP-341, KP- KP-361, KP-366, KP-361, KP-361, KP-361, KP- 368, KP-369, KP-330, KP-650, KP-651, KP-390, KP-391 and KP-392 available from Shin-Etsu Chemical Co.,

When the adhesive composition contains a surfactant, the content of the surfactant is preferably from 0.001 to 5% by mass, more preferably from 0.005 to 1% by mass, based on the total solid content of the adhesive composition, from the viewpoint of coatability , And particularly preferably from 0.01 to 0.5 mass%. The surfactant may be one kind or two or more kinds. When two or more kinds of surfactants are used, the total amount is preferably in the above range.

<< Other additives >>

The adhesive composition for use in the present invention may contain various additives such as a curing agent, a curing catalyst, a silane coupling agent, a filler, an adhesion promoter, an ultraviolet absorber, an aggregate An antioxidant and the like. When these additives are compounded, the total amount of these additives is preferably 3% by mass or less based on the total solid content of the adhesive composition.

The adhesive composition used in the present invention preferably does not contain impurities such as metals. The content of the impurities contained in these materials is preferably 1 mass ppm or less, more preferably 1 mass ppb or less, more preferably 100 mass ppt or less, even more preferably 10 mass ppt or less, (Which is not more than the detection limit of the measuring apparatus) is particularly preferable.

Examples of the method for removing impurities such as metals from the adhesive composition include filtration using a filter. The filter hole diameter is preferably 10 nm or less in pore size, more preferably 5 nm or less, and further preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. The filter may be previously washed with an organic solvent. In the filter filtering step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different hole diameters and / or different materials may be used in combination. In addition, the various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.

As a method for reducing impurities such as metals contained in the adhesive composition, a raw material having a small metal content is selected as a raw material constituting the adhesive composition, and a raw material constituting the adhesive composition is subjected to filter filtration Followed by lining the inside of the device with polytetrafluoroethylene or the like, and performing distillation under the condition that the contamination is suppressed as much as possible. Is the same as the above-mentioned conditions in the filter filtration performed on the raw material constituting the adhesive composition.

In addition to filter filtration, impurities may be removed by the adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

<Preparation of Adhesive Composition>

The adhesive composition for use in the present invention can be prepared by mixing the respective components described above. The mixing of each component is usually carried out in the range of 0 ° C to 100 ° C. It is also preferable to mix the respective components and then filter them with a filter, for example. The filtration may be performed in multiple steps or repeated a plurality of times. In addition, the filtrate may be re-filtered.

The filter is not particularly limited as long as it is conventionally used for filtration. For example, a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon-6 or nylon-6,6, a polyolefin resin such as polyethylene or polypropylene (PP) And the like). Of these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore diameter of the filter is suitably about 0.003 to 5.0 mu m, for example. By setting this range, it becomes possible to reliably remove fine foreign matters such as impurities and aggregates contained in the composition while suppressing filtration clogging.

When using a filter, other filters may be combined. At this time, the filtering using the first filter may be performed once, or may be performed two or more times. When filtering is performed two or more times in combination with other filters, it is preferable that the hole diameters of the second and subsequent times are equal to or smaller than the hole diameters of the first filtering. The first filter having different pore diameters may be combined within the above-described range. The hole diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, there may be selected, for example, various filters provided by Nippon Oil Corporation, Advantech Toyokawa Co., Ltd., Nippon Integrity Corporation (formerly Nihon Micro-Roller Corporation) or Kitsch Microfilter .

<Method of Manufacturing Semiconductor Device>

&Lt; First Embodiment &gt;

Hereinafter, one embodiment of a method of manufacturing a semiconductor device through a step of manufacturing a laminate will be described with reference to FIG. The present invention is not limited to the following embodiments.

2 (A) to 2 (E) are schematic cross-sectional views (Figs. 2A and 2B) for describing adhesion between a carrier substrate and a device wafer provided with a molding layer (Fig. 2 (C)), the device substrate on which the carrier substrate and the molding layer are provided is peeled off (Fig. 2 (D)), the adhesive layer is removed from the device wafer having the molding layer (Fig. 2 (E)). Fig.

In this embodiment, as shown in Fig. 2 (A), first, an adhesive carrier base material 100 having an adhesive layer 11 on the carrier base material 12 is prepared.

It is preferable that the adhesive layer 11 does not substantially contain a solvent.

The device wafer 60 is formed by providing a plurality of circuit surfaces 62 on the surface 61a of the device substrate 61. [

The thickness of the device substrate 61 is preferably, for example, 200 to 1200 占 퐉. The circuit surface 62 is preferably a metal structure, for example, and preferably has a height of 10 to 100 mu m.

Further, the molding layer 15 is provided on the surface of the device wafer so as to cover the circuit surface. The molding layer is preferably a flat layer provided on the substrate surface of the device substrate so as to cover the circuit surface.

Further, in the present invention, when the height of the circuit surface is X m and the thickness of the molding layer is Y m, it is preferable to satisfy the relation of " X + 100 >

This is effective when the molding layer 15 is intended to further lower the TTV (Total Thickness Variation) of the thinning device wafer due to the flat layer (that is, to further improve the flatness of the thinning device wafer).

Subsequently, as shown in Fig. 2 (B), the device wafer 60 provided with the adhesive carrier substrate 100 and the molding layer 15 is pressed and pressed so that the adhesive layer 11 and the molding layer 15 are in contact with each other And the carrier substrate 12 and the molding layer are adhered to each other.

Next, as shown in Fig. 2 (C), the back surface 61b of the device substrate 61 is subjected to a mechanical or chemical treatment (thinning such as gliding or chemical mechanical polishing (CMP) Treatment with high temperature and vacuum such as chemical vapor deposition (CVD) or physical vapor deposition (PVD), treatment with chemicals such as organic solvents, acidic treatment solution or basic treatment solution, plating treatment, irradiation with active rays, heating The thinning device wafer 60a is obtained by thinning the thickness of the device substrate 61 (for example, by thinning the device substrate 61 to the thickness described above) as shown in Fig. 2 (C) .

As a mechanical or chemical treatment, a through hole (not shown) passing through the device substrate is formed from the back surface 61b1 of the thinned device wafer 60a after the thinning process, and a silicon penetration electrode (Not shown) may be formed.

Alternatively, the carrier substrate 12 and the device wafer 60 provided with the molding layer may be adhered to each other, and the heat treatment may be performed during the peeling. As an example of the heat treatment, there is a treatment with heating accompanied with mechanical or chemical treatment.

The maximum attained temperature in the heat treatment is preferably 80 to 400 占 폚, more preferably 130 to 400 占 폚, and even more preferably 180 to 350 占 폚. It is preferable that the maximum attained temperature in the heat treatment is lower than the decomposition temperature of the adhesive layer. The heat treatment is preferably heating for 30 seconds to 30 minutes at the maximum attained temperature, and more preferably for 1 minute to 10 minutes at the maximum attained temperature.

Subsequently, as shown in Fig. 2D, the carrier substrate 12 is separated from the thinned device wafer 60a provided with the molding layer. The method of separation is not particularly limited, but one of the carrier substrate 12 and the thinned device wafer 60a is fixed, and the other is pulled in a direction perpendicular to the substrate side fixed from the end It is preferable to separate them up.

In this embodiment, it is preferable that the carrier substrate 12 and the adhesive layer 11 are peeled from each other at the interface.

After the thinning device wafer 60a having the molding layer 15 provided on the carrier substrate 12 is slid as required, the adhesive layer 11 is brought into contact with the peeling liquid described later, As shown in FIG.

The temperature at the time of separation is preferably 40 DEG C or lower, and may be 30 DEG C or lower. The lower limit of the temperature at the time of peeling is, for example, 0 DEG C or more, and preferably 10 DEG C or more. In the present invention, it is also possible to carry out the separation at a room temperature of about 15 to 35 占 폚.

Then, as shown in Fig. 2 (E), by removing the adhesive layer 11 from the thinned device wafer 60a provided with the molding layer, a thinned device wafer having a molding layer on its surface can be obtained. The method of removing the adhesive layer 11 may be, for example, a method in which the adhesive layer is peeled and removed as it is, a method in which the adhesive layer is removed by using a peeling solution (a method in which the adhesive layer is swollen A method in which the adhesive layer is peeled off and removed, a method in which the peeling solution is sprayed on the adhesive layer to destroy and remove the adhesive layer, a method in which the adhesive layer is dissolved and removed in the peeling solution, etc.) , And a method of removing by vaporization. From the viewpoint of reducing the use amount of the solvent, it is preferable to remove it in the form of a film. From the viewpoint of reducing the damage on the surface of the molding layer, dissolution and removal are preferable. A method in which the adhesive layer is peeled off in its original state means that the adhesive layer is peeled off without any chemical treatment such as the use of a peeling solution and the peeling is carried out in the form of a film desirable. Mechanical peeling is preferable when peeling off the adhesive layer as it is. It is preferable that the adhesion strength B of the molding layer and the pressure-sensitive adhesive layer 11 satisfy the following formula (2).

B? 4 N / cm (2)

In the case where the adhesive layer is removed using a peeling solution, the following peeling solution can be preferably used.

<Release liquid>

As the peeling solution, water and a solvent (organic solvent) can be used.

As the peeling solution, an organic solvent which dissolves the adhesive layer is preferable. Examples of the organic solvent include aliphatic hydrocarbon such as aliphatic hydrocarbon such as hexane, heptane, Isofa E, H, G (manufactured by Esso Chemical), limonene, p-mentine, nonene, decane, dodecane, Decalin and the like), aromatic hydrocarbon (toluene, xylene, anisole, mesitylene, ethylbenzene, propylbenzene, cumene, n-butylbenzene, sec-butylbenzene, isobutylbenzene, tert- (1-phenyloctane, 1-phenyloctane, 1-phenylnonane, 1-phenyldecane, cyclopropylbenzene, cyclohexane, Cyclohexanone, hexylbenzene, 2-ethyltoluene, 1,2-diethylbenzene, o-cymene, indene, 1,2,3,4-tetrahydronaphthalene, 3-ethyltoluene, m- Diisopropylbenzene, 4-ethyltoluene, 1,4-diethylbenzene, p-cymene, 1,4-diisopropylbenzene, 4-tert-butyltoluene, 1,3-diethylbenzene, 1,2,3-trimethylbenzene, 1,2, 4-trimethylbenzene, 4-tert-butyl-o-xylene, 1,2,4-triethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, 5- tert-butyl-m-xylene, 3,5-di-tert-butyltoluene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, Halogenated hydrocarbons (e.g., methylene dichloride, ethylene dichloride, trichlorethylene, and monochlorobenzene), and polar solvents. Examples of polar solvents include alcohols (such as methanol, ethanol, propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, But are not limited to, 1-hexanol, 1-nonanol, 1-decanol, benzyl alcohol, ethylene glycol monomethyl ether, 2-ethoxy ethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl Ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol Ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol Etc.), ketones (acetone, methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) And examples thereof include esters (such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, methyl lactate, butyl lactate, ethylene glycol monobutyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol acetate, N-phenyldiethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, N-phenyldiethanolamine, N- (2-hydroxyethyl) morpholine, N, N-dimethylacetamide, N-methylpyrrolidone, etc.).

Further, from the viewpoint of releasability, the release liquid may contain an alkali, an acid, and a surfactant. When these components are blended, the blending amount is preferably 0.1 to 5.0 mass% of the peeling solution.

From the viewpoint of releasability, a mode of mixing two or more kinds of organic solvents and water, two or more kinds of alkali, acid and surfactant is also preferable.

The alkali includes, for example, sodium tertiary phosphate, potassium tertiary phosphate, ammonium tertiary phosphate, sodium secondary phosphate, potassium secondary phosphate, ammonium secondary phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, An inorganic alkali agent such as potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, ammonium borate, sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithium hydroxide, and organic alkali agents such as monomethylamine, dimethylamine, trimethylamine, But are not limited to, ethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, ethyleneimine , Ethylenediamine, pyridine, tetramethylammonium hydroxide and the like can be used. These alkaline agents may be used alone or in combination of two or more.

Examples of the acid include inorganic acids such as hydrogen halide, sulfuric acid, nitric acid, phosphoric acid and boric acid, and organic acids such as methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, , Gluconic acid, lactic acid, oxalic acid, and tartaric acid.

As the surfactant, anionic, cationic, nonionic or amphoteric surfactants can be used. In this case, the content of the surfactant is preferably 1 to 20% by mass, more preferably 1 to 10% by mass with respect to the total amount of the alkali aqueous solution.

By setting the content of the surfactant within the above-described range, the peeling property of the adhesive layer 11 and the thinning device wafer 60a can be further improved.

Examples of the anionic surfactant include, but are not limited to, fatty acid salts, abietic acid salts, hydroxyalkane sulfonic acid salts, alkane sulfonic acid salts, dialkyl sulfosuccinic acid salts, straight chain alkylbenzene sulfonic acid salts, Benzene sulfonic acid salts, alkyl naphthalene sulfonic acid salts, alkyl diphenyl ether (di) sulfonic acid salts, alkylphenoxy polyoxyethylene alkyl sulfonic acid salts, polyoxyethylene alkyl sulfophenyl ether salts, N-alkyl- Sodium oleyl taurate, disodium N-alkylsulfosuccinic acid monoamide, petroleum sulfonic acid salts, sulfated castor oil, sulfurized waxy oil, sulfuric acid ester salts of fatty acid alkyl esters, alkyl sulfate ester salts, polyoxyethylene alkyl Sulfuric acid ester salts, fatty acid monoglyceride sulfuric acid ester salts, polyoxyethylene alkylphenyl ether sulfuric acid ester salts, polyoxyethylene styrylphenyl ether sulfuric acid ester salts, Phosphoric acid ester salts, polyoxyethylene alkyl ether phosphate ester salts, polyoxyethylene alkylphenyl ether phosphate ester salts, partial saponification products of styrene-maleic anhydride copolymer, partial saponification products of olefin-maleic anhydride copolymer, naphthalene sulfone And acid phosphomoline condensation products. Among them, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts and alkyldiphenylether (di) sulfonic acid salts are particularly preferably used.

The cationic surfactant is not particularly limited, but conventionally known ones can be used. Examples thereof include alkylamine salts, quaternary ammonium salts, alkylimidazolium salts, polyoxyethylene alkylamine salts, and polyethylene polyamine derivatives.

Examples of nonionic surfactants include, but are not particularly limited to, polyethylene glycol type higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, alkylnaphthol ethylene oxide adducts, phenol ethylene oxide adducts, naphthol ethylene oxide adducts, Fatty acid ethylen oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, high alkylamine ethylene oxide adducts, fatty acid amide ethylene oxide adducts, ethylene oxide adducts of oils, polypropylene glycol ethylene oxide adducts, Ethylene oxide block copolymer, dimethylsiloxane- (propylene oxide-ethylene oxide) block copolymer, fatty acid esters of polyhydric alcohol type glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitol, sucrose Of fatty acids , Polyol and the like can be given to the emitter of an alkyl alcohol, fatty acid amides of alkanol amines. Of these, those having an aromatic ring and an ethylene oxide chain are preferable, and alkyl-substituted or unsubstituted phenol ethylene oxide adducts or alkyl-substituted or unsubstituted naphthol ethylene oxide adducts are more preferable.

Examples of the amphoteric surfactant include, but are not limited to, amine oxides such as alkyl dimethyl amine oxide, betaine based ones such as alkyl betaine, and amino acid based ones such as alkylamino fatty acid sodium. In particular, alkyldimethylamine oxide which may have a substituent, alkylcarboxybetaine which may have a substituent, and alkylsulfobetaine which may have a substituent are preferably used. Specifically, the compound represented by the formula (2) in paragraph [0256] of Japanese Laid-Open Patent Publication No. 2008-203359, the compound represented by the formula (I), the formula (II) Compounds represented by the formula (VI) and compounds represented by the paragraphs [0022] to [0029] of JP-A No. 2009-47927 can be used.

If necessary, additives such as a defoaming agent and a water softening agent may also be contained.

The carrier substrate 12 is peeled from the thinned device wafer 60a provided with the molding layer and then subjected to various known processes to the thinned device wafer 60a on which the molding layer is provided as required, (60a).

When the adhesive layer is adhered to the carrier substrate, the carrier substrate can be regenerated by removing the adhesive layer. Examples of the method of removing the adhesive layer include a method of physically removing the adhesive layer in the form of a film by spraying a brush, an ultrasonic wave, an ice particle, or an aerosol, a method of dissolving and removing the solution in an aqueous solution or an organic solvent, And a method of chemical removal such as a method of decomposing and vaporizing by a conventional method, but conventionally known cleaning methods can be used depending on the carrier substrate.

For example, when a device substrate is used as a carrier substrate, conventionally known silicon wafer cleaning methods can be used. Examples of the aqueous solution or organic solvent that can be used for chemical removal include strong acids, strong bases, strong oxidizing agents And specific examples thereof include acids such as sulfuric acid, hydrochloric acid, hydrofluoric acid, nitric acid, and organic acids, bases such as tetramethylammonium, ammonia and organic bases, oxidizing agents such as hydrogen peroxide, , A mixture of hydrochloric acid and hydrogen peroxide, a mixture of sulfuric acid and hydrogen peroxide, a mixture of hydrofluoric acid and hydrogen peroxide, and a mixture of hydrofluoric acid and ammonium fluoride.

From the viewpoint of adhesiveness when a recycled carrier substrate is used, it is preferable to use a carrier substrate cleaning liquid.

The carrier substrate cleaning liquid preferably contains an acid (strong acid) having a pKa of less than 0 and hydrogen peroxide. The acid having a pKa of less than 0 is selected from an inorganic acid such as hydrogen iodide, perchloric acid, hydrogen bromide, hydrogen chloride, nitric acid, sulfuric acid, or an organic acid such as alkylsulfonic acid or arylsulfonic acid. From the viewpoint of the cleaning property of the adhesive layer on the carrier substrate, it is preferably an inorganic acid, and sulfuric acid is most preferable.

As the hydrogen peroxide, 30 mass% hydrogen peroxide can be preferably used. The mixing ratio of the strong acid and the 30 mass% hydrogen peroxide is preferably 0.1: 1 to 100: 1, more preferably 1: 1 to 10: And most preferably from 3: 1 to 5: 1.

&Lt; Embodiment 2 &gt;

A second embodiment of a method of manufacturing a semiconductor device through a process of manufacturing a laminate will be described with reference to FIG. The same portions as those of the first embodiment described above are denoted by the same reference numerals and the description thereof is omitted.

3 (A) to 3 (E) are schematic cross-sectional views (Figs. 3A and 3B) for explaining adhesion between a carrier substrate and a device wafer provided with a molding layer (Fig. 3 (C)), a state in which a device wafer having a carrier substrate and a molding layer are peeled off (Fig. 3 (D)), a state in which a device wafer having a molding layer is removed State (Fig. 3 (E)).

This embodiment differs from the first embodiment in that the adhesive layer 11 is formed on the surface of the molding layer 15 as shown in Fig.

When the adhesive layer 11 is provided on the surface of the molding layer 15, the adhesive composition is preferably applied (preferably applied) to the surface of the molding layer 15 and then dried (baked) . The drying can be performed at, for example, 60 to 150 ° C for 10 seconds to 2 minutes.

Subsequently, as shown in Fig. 3 (B), the carrier base 12 and the device wafer 60 provided with the molding layer 15 are pressed to bond the carrier base 12 and the molding layer 15 together. Subsequently, as shown in Fig. 3 (C), the back surface 61b of the device substrate 61 is subjected to a mechanical or chemical treatment so that the surface of the device substrate 61 The thinned device wafer 60a having a molding layer is obtained. Subsequently, as shown in Fig. 3 (D), the carrier substrate 12 is separated from the thinned device wafer 60a provided with the molding layer. Then, as shown in Fig. 3 (E), the adhesive layer 11 is removed from the thinned device wafer 60a provided with the molding layer.

The manufacturing method of the semiconductor device in the present invention is not limited to the above-described embodiment, but can be appropriately modified and improved.

In the above-described embodiment, the thinning process of the device wafer and the process of forming the silicon through electrode are described as the mechanical or chemical process for the device wafer (device substrate). However, the present invention is not limited to this, And any process necessary for the production method.

In addition, the shapes, dimensions, numbers, locations and the like of the circuit surface in the device wafer exemplified in the above-described embodiments are arbitrary and not limited.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it is beyond the ordinary knowledge. Unless otherwise stated, " part " and "% " are based on mass.

&Lt; Method of Forming Molding Layer X >

A Sumikon EME-G770 (made by Sumitomo Bakelite), which is a solid compression molding material, was molded by a transfer molding machine at a mold temperature of 175 占 폚, an injection pressure of 7.8 MPa and a curing time of 2 minutes, Thereby forming a molding layer.

&Lt; Method of Forming Molding Layer Y >

The molding layer X was changed to CEL-C-5020, which is a molding material for liquid, of Sumicon EME-G770 (made by Sumitomo Bakelite), baked at 100 ° C for 30 minutes, then at 150 ° C for 2 hours, .

&Lt; Method of Forming Molding Layer Z >

The molding layer X was changed to CEL-C-5400, which is a molding material for liquid, of Sumicon EME-G770 (made by Sumitomo Bakelite), baked at 100 ° C for 30 minutes and then at 150 ° C for 2 hours, .

&Lt; Adhesive composition 1 >

Septone S2104 (Kuraray Co., Ltd.): 45 parts by mass

- Tuftec P2000 (manufactured by Asahi Kasei Chemicals Co., Ltd.): 45 parts by mass

Irganox 1010 (made by BASF): 5 parts by mass

Sumilizer TP-D (Sumitomo Chemical Co., Ltd.): 5 parts by mass

- Megafac F-553 (made by DIC): 0.1 parts by mass

Mesitylene (manufactured by Toyo Kosei Kogyo Co., Ltd.): 190 parts by mass

&Lt; Adhesive composition 2 >

Septone S2104 (Kuraray Co., Ltd.): 90 parts by mass

Irganox 1010 (made by BASF): 5 parts by mass

Sumilizer TP-D (Sumitomo Chemical Co., Ltd.): 5 parts by mass

- Megafac F-553 (made by DIC): 0.1 parts by mass

Mesitylene (manufactured by Toyo Kosei Kogyo Co., Ltd.): 190 parts by mass

&Lt; Preparation of laminate &

A molding layer was formed on the surface of a 12-inch silicon wafer (1 inch is 2.54 cm) provided with a circuit surface on the surface by any of the methods for forming the molding layers X to Z as shown in Table 1 , Thereby obtaining a layered product A.

Thereafter, as shown in Table 1, at least one of a heat treatment, a solvent cleaning treatment and an ashing treatment to be described later was performed.

Subsequently, 15.0 mL of the adhesive composition 1 or the adhesive composition 2 was dropped on the surface of the molding layer in 30 seconds while being rotated at 50 rpm by a wafer bonding apparatus (Synapse V, manufactured by Tokyo Electron Co., Ltd.). Using a hot plate, the laminate B was heated at 110 占 폚 for 3 minutes and further heated at 190 占 폚 for 3 minutes to form an adhesive layer on the surface of the silicon wafer.

Subsequently, another 12-inch silicon wafer (carrier substrate) was vacuum-bonded to the side of the laminate B on which the adhesive layer was formed by means of a wafer bonder wafer bonding apparatus (Synapse V, Tokyo Electron) Followed by compression at 190 DEG C and a pressure of 0.11 MPa for 3 minutes to obtain a layered product C. The thickness of the adhesive layer at this time was 40 m.

Subsequently, the previously used silicon wafer side of the layered product C was polished down to a thickness of 35 탆 by using a back grinder DFG 8540 (Disco) to obtain a thin layered laminate D.

<Heat Treatment>

The laminate A was heat-treated at 120 ° C for 8 hours.

<Solvent Cleaning Treatment>

Cyclohexane was spin-coated on the surface of the molding layer of the layered product A at a rotation speed of 800 rpm for 5 minutes, then the solution was blown off, spin-dried at 2000 rpm for 1 minute, and then dried at 100 DEG C for 1 minute Baked.

<Ashing process>

The surface of the molding layer of the laminate A was cleaned by ashing treatment with oxygen plasma.

&Lt; Measurement of amount of component having molecular weight 1000 or less of molding layer >

(Mass%) of a component having a molecular weight of 1000 or less was measured by GCMS (Shimadzu Seisakusho, product number: P2010) for the molding layer after performing at least one of heat treatment, solvent cleaning treatment and ashing treatment, A carrier gas of 140 kPa, a gas chromatography column vaporization chamber temperature of 220 占 폚, an Rtx column (length of 60 m) manufactured by Lutech Co., and a 310 Deg.] C, a mass spectrometer in a scan mode, an interface temperature of 220 [deg.] C, and an ion source temperature of 200 [deg.] C.

&Lt; Measurement of the number of voids &

The film surface of the obtained laminate B on the side of the adhesive layer was observed at a magnification of 50 times by an optical microscope (manufactured by Olympus Corporation, product number: MX-80) from the direction perpendicular to the film surface of the adhesive layer, The number of voids having a maximum length of 30 m or more per 700 cm ² of the film surface of the adhesive layer was measured.

<Arithmetic Surface Roughness (Ra)>

The arithmetic mean surface roughness (Ra) of the surface of the obtained laminate B on the side of the backing adhesive layer was measured using a contact surface type surface roughness meter (manufacturer: KLA-Tencor, part number: P-15). The unit is expressed in μm.

&Lt; Reduction of heat mass after heat treatment >

The degree of decrease in thermal mass when the laminate B was heated from 100 占 폚 to 200 占 폚 at 10 占 폚 / min was measured. The thermal mass reduction degree was measured by a thermogravimetric analyzer Q500 (manufactured by TA) on the aluminum pan at a constant rate of 10 DEG C / min at an initial temperature of 25 DEG C under a stream of nitrogen gas at 60 mL / Lt; 0 &gt; C, and the residual weight when the temperature reached 400 DEG C was measured.

&Lt; Crack in Device Wafer >

With respect to the thinned layered product D, the presence or absence of cracks was visually confirmed.

The results are shown in the following table.

[Table 1]

A molding layer was formed on the surface of a 12-inch silicon wafer having a surface on the surface thereof according to the method of the above-mentioned molding layer X to obtain a laminate A, and then the surface of the molding layer was subjected to a solvent cleaning treatment. Each of the surface of the molding layer of the laminate A and the surface of another 12-inch silicon wafer (carrier substrate) was rotated at 50 rpm by a wafer bonding apparatus (Synapse V, manufactured by Tokyo Electron Co., Ltd.) , 7.5 mL was dropped in 30 seconds, heated at 110 DEG C for 3 minutes using a hot plate, and further heated at 190 DEG C for 3 minutes to obtain a laminate B having an adhesive layer formed on the laminate A, A laminate E having an adhesive layer was obtained. The laminate B and the layered product E were pressed in a vacuum of 190 占 폚 under a pressure of 0.11 MPa for 3 minutes by a wafer bonder wafer bonding apparatus (Synapse V manufactured by Tokyo Electron Co., Ltd.) so that the adhesive layer side was in contact with the laminate, Sieve F was obtained. Subsequently, the side of the silicon wafer used previously of the layered product F was polished to a thickness of 35 mu m using a back grinder DFG8540 (Disco) to obtain a thin layered product G. With respect to the obtained laminate B, the arithmetic surface roughness (Ra) and the number of voids were measured in the same manner as described above, and found to be 1.1 μm and 1, respectively.

As is clear from the above table, it was found that cracks of the device wafer after thinning were suppressed in the laminate of the present invention. Particularly, when a crack occurs in the device wafer, a problem occurs in that the yield of the device chip due to breakage is lowered, but in the present invention, the technical value is high because the number of cracks is greatly reduced.

1:
11: adhesive layer
12: carrier substrate
15: Molding layer
60: device wafer
60a: Thinning device wafer
61: Device substrate
61a: Surface
61b :, 61b1:
62: circuit surface

Claims (15)

1. A laminated body having a device wafer having a circuit surface, a molding layer covering a surface of the circuit surface, and an adhesive layer located on a surface of the molding layer,
And wherein not more than one observed with an optical microscope from the direction perpendicular to the film surface, the number of more than the maximum length 30μm voids, the adhesive layer film surface 700cm ² per, 3 of the adhesive layer, wherein the roughness arithmetic average of the surface of the adhesive layer Ra Is Ra? 10.0 占 퐉. The method according to claim 1,
Wherein the component having a molecular weight of 1000 or less in the molding layer is 5 mass% or less. The method according to claim 1 or 2,
Wherein the molding layer is formed by baking a liquid molding material. The method according to claim 1 or 2,
Wherein the molding layer is formed by a solid compression molding material. The method according to claim 1 or 2,
Wherein the heat-shrinkage degree of the molding layer after the heat treatment is from 5 to 10% by mass when the temperature of the molding layer after the heat treatment is raised from 100 占 폚 to 200 占 폚 at 10 占 폚 / Laminates. The method of claim 5,
Wherein the molding layer covering the surface of the circuit surface is subjected to heat treatment at 100 ° C to 250 ° C and then an adhesive layer is provided. The method of claim 5,
Wherein a surface of the molding layer covering the surface of the circuit surface is cleaned with an organic solvent, and then an adhesive layer is provided. The method of claim 5,
Wherein a surface of the molding layer covering the surface of the circuit surface is subjected to an ashing treatment and then a temporary adhesive layer is provided. The method according to claim 1 or 2,
Heating the molding layer covering the surface of the circuit surface at 100 ° C to 250 ° C; cleaning the surface of the molding layer covering the surface of the circuit surface with an organic solvent; Wherein at least two of the ashing treatment of the surface of the molding layer on which the adhesive layer is formed are provided with an adhesive layer. The method of claim 8,
Wherein the ashing treatment is performed with oxygen plasma. The method according to claim 1 or 2,
Wherein the molding layer and the backing layer each independently comprise a resin. The method according to claim 1 or 2,
Wherein the adhesive layer has a carrier substrate on the side opposite to the side in contact with the molding layer. The method according to claim 1 or 2,
Wherein the thickness of the device wafer is 200 占 퐉 or less. The method according to claim 1 or 2,
Wherein the adhesive layer is in contact with the carrier substrate. 15. The method of claim 14,
Wherein the adhesive layer is one layer.

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