TW201507861A - Method for producing laminate and laminate - Google Patents

Abstract

A method for producing a laminate (21) which is provided with a substrate (11), a light-transmitting support plate (12) that supports the substrate (11), and a first separation layer (15) that is arranged between the substrate (11) and the support plate (12) and is altered in properties by means of absorption of light that is irradiated thereon through the support plate (12). The first separation layer (15) is formed by plasma processing using a reaction gas that contains a fluorine compound and an organic compound having an unsaturated bond.

Description

Method for manufacturing laminate and laminate

The present invention relates to a method for producing a laminate in which a substrate and a support are laminated, and a laminate.

With the high functionality of mobile phones, digital AV devices, and IC cards, the semiconductor wafers (hereinafter referred to as wafers) mounted are miniaturized and thinned, and they are integrated into the package. The demand is increasing. For example, in an integrated circuit in which a single packaged complex wafer represented by CSP (Chip Size Package) or MCP (Multi Chip Package) is required, it is required to be thinned. In order to achieve high integration of the wafer in the package, the thickness of the wafer needs to be thinned to a range of 25 to 150 μm.

However, since the semiconductor wafer (hereinafter referred to as a wafer) to be a wafer substrate is thinned by grinding, the strength thereof is weak, and the wafer is likely to be cracked or warped. Further, since it is difficult to automatically transfer a wafer having a weakened strength by flaking, it is necessary to carry out manual transfer, which is cumbersome to operate.

Therefore, the development of a glass or hard will be called a support plate A wafer operating system (WHS) in which a board made of plastic is bonded to a wafer to be ground to maintain wafer strength while preventing cracking and wafer warpage. Since the wafer strength can be maintained by the wafer operating system, the transport of the thinned semiconductor wafer can be automated.

A method of manufacturing a semiconductor wafer as a separation support after bonding a support to a semiconductor wafer and processing the semiconductor wafer is known as the method described in Patent Document 1. In the method described in Patent Document 1, the light-transmitting support and the semiconductor wafer are bonded through the photothermal conversion layer and the adhesive layer provided on the support side, and the semiconductor wafer is processed, and the self-supporting body side is processed. The radiant energy is irradiated to decompose the photothermal conversion layer, and the semiconductor wafer is separated from the support.

Further, in the method described in Patent Document 2, the support layer is separated from the semiconductor wafer by dissolving and removing the separation layer formed on the back surface of the support plate using an acid or an alkaline solution.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-64040 (published on February 26, 2004)

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2007-188967 (published on July 26, 2007)

In the technique of Patent Document 2, high-density plasma is generated in order to form a separation layer. When a high-density plasma is used in the formation of the separation layer, it is necessary to complicate the structure of the plasma generation apparatus in order to increase the size of the laminated substrate. Therefore, it is difficult to enlarge the substrate using the high-density plasma. On the other hand, when a low-density plasma is used for the formation of the separation layer, there is a problem that a separation layer which is deteriorated by absorbing light cannot be formed.

The present invention has been made in view of the above problems, and an object thereof is to provide a laminate including a separation layer which can increase the size of a laminated substrate.

In order to solve the above problems, a method for producing a laminate according to the present invention includes a substrate, a support for supporting light transmittance of the substrate, and a substrate provided between the substrate and the support, and absorbing and transmitting the support A method for producing a laminate of a first separation layer which is deteriorated by light irradiated by a body, characterized in that the first step is formed by plasma treatment using a reaction gas containing an organic compound having an unsaturated bond and a fluorine compound A first separation layer forming step of the separation layer.

Further, the laminate system of the present invention includes a substrate, a light transmissive support that supports the substrate, and is disposed between the substrate and the support, and is deteriorated by absorbing light irradiated through the support. The laminate of the first separation layer is characterized in that the first separation layer is formed by plasma treatment using a reaction gas containing an organic compound having an unsaturated bond and a fluorine compound.

The present invention has an effect of providing a laminate having a separation layer capable of increasing the size of a laminated substrate.

11‧‧‧Substrate

12‧‧‧Support plate (support)

13‧‧‧Next layer

14‧‧‧Second separation layer

15‧‧‧First separation layer

20,21‧‧‧Layer

100‧‧‧ Plasma processing unit

101‧‧‧Reaction room

102‧‧‧ parallel plate electrode

103‧‧‧ stage

111‧‧‧Containing containers for organic compounds

112‧‧‧Liquid main flow controller

113‧‧‧ gasifier

114‧‧‧Fluorine compound pressure tank

115‧‧‧Main flow controller

116,116a,116b‧‧‧Pipe

Fig. 1 is a schematic view showing the outline of a manufacturing method according to an embodiment of the present invention.

Fig. 2 is a schematic view showing the steps of manufacturing the first separation layer included in the production method according to the embodiment of the present invention.

Fig. 3 is a schematic view showing the outline of a laminate according to an embodiment of the present invention.

Fig. 4 is a schematic view showing the outline of a laminate according to another embodiment of the present invention.

<Method of Manufacturing Laminated Body>

The method for producing a laminate according to the present invention includes a substrate, a support for supporting light transmittance of the substrate, and a light provided between the substrate and the support by absorbing light irradiated through the support. A method for producing a laminate of a deteriorated first separation layer, characterized in that the first separation of the first separation layer is formed by plasma treatment using a reaction gas containing an organic compound having an unsaturated bond and a fluorine compound Layer shape Into the steps.

Thereby, not only the case of using a high-density plasma, but also a case where a low-density plasma is used, a separation layer which is deteriorated by absorbing light can be formed. Thereby, the enlargement of the plasma generating apparatus becomes easy. Therefore, it is possible to manufacture a laminate including a separation layer which can increase the size of the laminated substrate.

Further, the method for producing a laminate according to the present invention may further comprise a second separation layer forming step of forming a second separation layer which is deteriorated by absorbing light irradiated through the support.

According to this, the first separation layer and the second separation layer are formed on the support. Therefore, the laminate can have both the advantages of the first separation layer having good chemical resistance in various drug treatments, and the advantages of the second separation layer which is appropriately deteriorated by irradiation light. For example, when the first separation layer is present on the second separation layer, the first separation layer can be utilized to prevent deterioration of the second separation layer due to drug treatment. When the second separation layer is present on the first separation layer, the function of the separation layer can be ensured by the first separation layer even if the second separation layer is deteriorated by the drug treatment. Further, since the first separation layer and the second separation layer can be appropriately deteriorated by the light irradiated through the support, the substrate can be easily separated from the laminate.

Further, in the method for producing a laminate of the present invention, when the first separation layer and the second separation layer are formed, the order of the first separation layer forming step and the second separation layer forming step is not limited. That is, the method of manufacturing the laminate of the present invention may also be that the first separation layer is formed on the support by the first separation layer forming step, and then the second separation layer forming step is performed as the second separation layer by the second separation layer forming step. form. Moreover, the step may be formed by the second separation layer A second separation layer is formed on the support, and then the first separation layer forming step is used as an embodiment for forming the first separation layer.

Lamination of an embodiment of the present invention using Figures 1-4 The manufacturing method of the body will be described. Fig. 1 is a schematic view showing the outline of a method for producing the laminate 20 of the present embodiment. Further, the embodiment shown in Fig. 1 is an embodiment in which the first separation layer 15 is formed after the second separation layer 14 is formed.

As shown in Fig. 1, the manufacturer of the laminate of the present embodiment The method includes forming an adhesive layer forming step of the adhesive layer 13 on the substrate 11 ((1) to (2) of FIG. 1), and forming a second separation layer of the second separation layer 14 on the support plate (support) 12 Step ((3) to (4) of FIG. 1), after the second separation layer forming step, forming a first separation layer forming step of the first separation layer 15 ((4) to (5) of FIG. 1), and The bonding step of the substrate 11 and the support plate 12 is bonded through the second separation layer 14, the first separation layer 15, and the subsequent layer 13 ((6) of FIG. 1).

Here, the manufacturer of the laminate of one embodiment of the present invention The method includes a light-transmitting support plate (support) 12 having a substrate 11 and a support substrate 11, and is disposed between the substrate 11 and the support plate 12, and is deteriorated by absorbing light irradiated through the support plate 12. A method of manufacturing the laminate 20 of the first separation layer 15 comprising performing a plasma treatment using a reaction gas containing an organic compound having an unsaturated bond and a fluorine compound, thereby forming a first separation layer of the first separation layer 15 step.

[substrate]

The substrate 11 is supported by the support plate 12 and is provided for processes such as thinning and mounting. In the present embodiment, the substrate 11 is a wafer. However, the substrate 11 included in the laminate 20 of the present invention is not limited to a wafer, and any substrate such as a thin film substrate or a flexible substrate may be used. Further, the surface of the substrate 11 on the side of the adhesive layer 13 may have a fine structure of an electronic component such as a circuit.

In one embodiment, as shown in (1) to (2) of FIG. 1, an adhesive layer 13 for bonding the support plate 12 is formed on the substrate 11 (step of forming a layer).

(following layer)

Next, the layer 13 is such that the substrate 11 is attached to the support plate 12 and the first separation layer 15 . Further, the bonding layer 13 may also protect the surface of the covering substrate 11.

Next, the method of forming the layer 13 may be performed by applying an adhesive to the substrate 11, or attaching an adhesive tape having both surfaces coated with an adhesive to the substrate 11. The coating method of the adhesive is not particularly limited, and examples thereof include a coating method by a spin coating method, a dipping method, a roll doctor method, a doctor blade method, a spray method, and a slit die method. Further, after applying the adhesive, it may be dried by heating.

The thickness of the layer may be appropriately set according to the type of the substrate 11 and the support plate 12 to be attached, the treatment to be applied to the substrate 11 after attachment, and the like, but it is preferably in the range of 10 to 150 μm, more preferably 15 Within the range of ~100μm.

Moreover, it may be 2 mm or less from the peripheral end of the substrate, preferably The width of the range of 0.5 mm or more and 0.8 mm or less removes the peripheral end portion of the adhesive layer 13 on the substrate 11. When the peripheral end portion is removed, the film thickness of the subsequent layer 13 may be, for example, about 50 μm. Thereby, the laminate formation step can be appropriately suppressed, and the layer 13 is oozing out from the laminate 20.

As the adhesive, various adhesives known in the art such as acrylic, novolak, naphthoquinone, hydrocarbon, polyimide, or elastomer can be used as an adhesive constituting the adhesive layer 13 of the present invention. . Hereinafter, the composition of the resin contained in the adhesive layer 13 in the present embodiment will be described.

The resin contained in the adhesive layer 13 may be, for example, a hydrocarbon resin, an acrylic-styrene resin, a maleimide resin, an elastomer resin, or the like, or a combination thereof. .

The glass transition temperature (Tg) of the subsequent agent varies depending on the type or molecular weight of the above-mentioned resin and the formulation of a plasticizer to the adhesive. The type or molecular weight of the resin contained in the above-mentioned adhesive can be appropriately selected depending on the type of the substrate and the support, but the Tg of the resin used in the adhesive is preferably in the range of -60 ° C to 200 ° C, more preferably - Within the range of 25 ° C or more and 150 ° C or less. The adhesion of the adhesive layer 13 can be appropriately reduced by not requiring excessive energy during cooling in the range of -25 ° C or more and 150 ° C or less. Further, the Tg of the subsequent layer 13 can also be adjusted by appropriately blending a plasticizer or a resin having a low degree of polymerization.

The glass transition temperature (Tg) can be measured using, for example, a conventional differential scanning calorimetry device (DSC).

(hydrocarbon resin)

The hydrocarbon resin has a hydrocarbon skeleton and a resin obtained by polymerizing a monomer composition. The hydrocarbon resin is exemplified by a cycloolefin polymer (hereinafter sometimes referred to as "resin (A)"), and at least one selected from the group consisting of a terpene resin, a rosin resin, and a petroleum resin (hereinafter sometimes also It is called "resin (B)"), etc., but it is not limited to these.

The resin (A) may be a resin obtained by polymerizing a monomer component containing a cycloolefin monomer. Specific examples thereof include a ring-opening (co)polymer containing a monomer component of a cycloolefin monomer, and a resin obtained by subjecting a monomer component containing a cycloolefin monomer to addition (co)polymerization.

The cycloolefin-based monomer contained in the monomer component constituting the resin (A) is, for example, a bicyclic ring such as norbornene or norbornadiene, or a tricyclic ring such as dicyclopentadiene or dihydroxypentadiene. a tetracyclic ring such as tetracyclododecene, a pentacyclic ring such as a cyclopentadiene terpolymer, a heptacyclic ring such as tetracyclopentadiene, or an alkyl group of the polycyclic ring (methyl or ethyl) Substituent, propyl, butyl, etc., substituted, alkenyl (vinyl or the like), substituted alkylene (ethylene, etc.), aryl (phenyl, tolyl, naphthyl, etc.), etc. . Preferably, the norbornene-based monomer selected from the group consisting of norbornene, tetracyclododecene, or the alkyl substituents.

The monomer component constituting the resin (A) may further contain another monomer copolymerizable with the above cycloolefin-based monomer, and preferably contains, for example, an olefin monomer. The olefin monomer is exemplified by, for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, α-olefin, and the like. The olefin monomer may be linear or branched.

Moreover, as a monomer component constituting the resin (A), it is highly resistant. From the viewpoint of heat (low thermal decomposition, thermal weight reduction), a cycloolefin monomer is preferred. The ratio of the cycloolefin monomer to the entire monomer component constituting the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more. Further, the ratio of the cycloolefin monomer to the entire monomer component constituting the resin (A) is not particularly limited, but is preferably 80 mol% from the viewpoint of solubility and stability over time in the solution. Hereinafter, it is preferably 70 mol% or less.

Further, as a monomer component constituting the resin (A), it may be contained There are linear or branched chain olefin monomers. The ratio of the olefin monomer to the entire monomer component constituting the resin (A) is preferably from 10 to 90 mol%, more preferably from 20 to 85 mol%, from the viewpoint of solubility and flexibility. Better 30% to 80%.

In addition, when the resin (A) is a resin obtained by polymerizing a monomer component composed of a cycloolefin monomer and an olefin monomer, for example, when a resin having no polar group is used, gas generation at a high temperature is suppressed. The language is better.

The polymerization method, polymerization conditions, and the like in the case of polymerizing the monomer component are not particularly limited, and may be appropriately set according to a usual method.

Commercial products which can be used as the resin (A) are, for example, "TOPAS" manufactured by Polyplastic Co., Ltd., "APEL" manufactured by Mitsui Chemicals Co., Ltd., "ZEONOR" and "ZEONEX" manufactured by Japan ZEON Co., Ltd. "ARTON" manufactured by JSR Co., Ltd., etc.

The glass transition point (Tg) of the resin (A) is preferably 60 ° C or higher, preferably 70 ° C or higher. Resin (A) glass transfer point is 60 ° C In the above, the softening of the subsequent layer when the laminate is exposed to a high temperature environment can be further suppressed.

The resin (B) is at least one selected from the group consisting of terpene resins, rosin resins, and petroleum resins. Specifically, the terpene-based resin is exemplified by a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, a hydrogenated terpene phenol resin, and the like. The rosin-based resin is exemplified by, for example, rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized pine ester, polymerized rosin ester, modified rosin, and the like. Petroleum resins are listed, for example, as aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, coumarins.茚 petroleum resin, etc. Among these, a hydrogenated terpene resin or a hydrogenated petroleum resin is preferred.

The softening point of the resin (B) is not particularly limited, and is preferably from 80 to 160 °C. When the softening point of the resin (B) is 80 ° C or more, the softening of the laminate when it is exposed to a high temperature environment can be suppressed, and the subsequent defects are not caused. On the other hand, when the softening point of the resin (B) is 160 ° C or less, the peeling speed at the time of peeling the laminate is good.

The weight average molecular weight of the resin (B) is not particularly limited, but is preferably from 300 to 3,000. When the weight average molecular weight of the resin (B) is 300 or more, the heat resistance is sufficient, and the amount of degassing in a high temperature environment is small. On the other hand, when the weight average molecular weight of the resin (B) is 3,000 or less, the peeling speed at the time of peeling the laminate is good. Further, the weight average molecular weight of the resin (B) of the present embodiment means a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

Further, a mixed resin (A) and a resin (B) may be used. The person is a resin. By mixing, heat resistance and peeling speed are improved. For example, when the mixing ratio of the resin (A) and the resin (B) is (A): (B) = 80: 20 to 55: 45 (mass ratio), the peeling speed, the heat resistance in a high temperature environment, and the flexibility Excellent is better.

(acrylic-styrene resin)

Examples of the acrylic-styrene-based resin include a resin obtained by polymerizing a derivative of styrene or styrene, a (meth) acrylate, or the like as a monomer.

The (meth) acrylate is exemplified by, for example, an alkyl (meth)acrylate formed of a chain structure, a (meth) acrylate having an aliphatic ring, and a (meth) acrylate having an aromatic ring. The alkyl (meth)acrylate formed by the chain structure is exemplified by an acrylic long-chain alkyl ester having an alkyl group having 15 to 20 carbon atoms, an acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms, and the like. The acrylic long-chain alkyl ester is exemplified by an alkyl group of n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl or the like. Alkyl methacrylate. Further, the alkyl group may also be branched.

The acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms is exemplified by a conventional acrylic alkyl ester used in the conventional acrylic adhesive. For example, the alkyl group is a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylhexyl group, an isooctyl group, an isodecyl group, an isodecyl group, a dodecyl group, a lauryl group, a tridecyl group, or the like. Alkyl ester of acrylic acid or methacrylic acid.

(meth) acrylate having an aliphatic ring, listed as Cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, (methyl) Tricyclodecyl acrylate, tetracyclododecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, etc., but more preferably isobornyl methacrylate or dicyclopentanyl (meth)acrylate .

The (meth) acrylate having an aromatic ring is not particularly limited, and examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group, and a phenoxy group. Methyl, phenoxyethyl and the like. Further, the aromatic ring may have a chain or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferred.

(Malay ylide resin)

The maleic imine resin is exemplified by, for example, N-methyl maleimide, N-ethyl maleimide, N-n-propyl maleimide, N- as a monomer. Isopropyl maleimide, N-n-butyl maleimide, N-isobutyl maleimide, N-second butyl maleimide, N-t-butyl horse醯imine, N-n-pentylmaleimide, N-n-hexylmaleimide, N-n-heptylmaleimide, N-n-octylmaleimide, N- An alkyl-containing maleimine, N-cyclopropyl maleimide, N-cyclobutyl malayan, etc., such as lauryl maleimide, N-stearyl amidine, and the like. An aliphatic hydrocarbon group such as an amine, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide or the like Indomethacin, N-phenylmaleimide, N-m-methylphenylmaleimide, N- A resin obtained by polymerization of an aromatic maleic imine or the like having an aryl group such as o-methylphenylmaleimide or N-p-methylphenylmaleimide.

For example, a resin having a cyclic olefin oligomer having a repeating unit represented by the following chemical formula (1) and a copolymer represented by the following chemical formula (2) as a binder component can be used.

(In the chemical formula (2), n is an integer of 0 or 1 to 3).

As the cycloolefin oligomer, APL 8008T, APL 8009T, and APL 6013T (all manufactured by Mitsui Chemicals, Inc.) and the like can be used.

(elastomer)

The elastomer preferably contains a styrene unit as a constituent unit of the main chain, and the "styrene unit" may have a substituent. The substituent is exemplified by, for example, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an ethoxy group, a carboxyl group and the like. Further, the content of the styrene unit is preferably in the range of 14% by weight or more and 50% by weight or less. Further, the weight average molecular weight of the elastomer is preferably in the range of 10,000 or more and 200,000 or less.

If the content of styrene unit is 14% by weight or more, 50 weight When the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less, the amount of the elastomer is easily dissolved in the hydrocarbon solvent described later, so that the adhesive layer can be removed more easily and quickly. Further, by setting the content of the styrene unit and the weight average molecular weight within the above range, the resist solvent (for example, PGMEA, PGME, etc.) exposed when the wafer is subjected to the resist lithography step is exhibited. Excellent resistance to acids (hydrofluoric acid, etc.), alkalis (TMAH), etc.

Further, the above (meth) acrylate may be further mixed in the elastomer.

Further, the content of the styrene unit is more preferably 17% by weight or more, and still more preferably 40% by weight or less.

The weight average molecular weight is preferably in the range of 20,000 or more, and more preferably in the range of 150,000 or less.

When the elastomer is contained in a range of 14% by weight or more and 50% by weight or less, and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less, various elastomers can be used. For example, polystyrene-poly(ethylene/propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block can be used. Copolymer (SBS), styrene-butadiene-butene-styrene block copolymer (SBBS), and such hydrides, styrene-ethylene-butylene-styrene block copolymer (SEBS) , styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene-propylene-styrene The block copolymer (SEEPS) and the styrene block are reaction-crosslinked type styrene-ethylene-ethylene-propylene-styrene block copolymer (Septon V9461 (manufactured by KURARAY Co., Ltd.)), and the styrene block is a reaction. Content and weight average of styrene units of a crosslinked styrene-ethylene-butylene-styrene block copolymer (Septon V9827 (manufactured by KURARAY Co., Ltd.) having a reactive polystyrene-based hard block) The molecular weight is within the above range.

Further, the elastomer is more preferably a hydride. In the case of a hydride, the stability to heat is improved, and deterioration such as decomposition or polymerization is less likely to occur. Further, it is also preferable from the viewpoints of solubility in a hydrocarbon solvent and resistance to a solvent.

Further, it is more preferable that the elastomer is a block polymer of styrene at both ends. This is because it exhibits higher heat resistance by capping styrene having high thermal stability at both ends.

More specifically, the elastomer is more preferably a hydride of a block copolymer of styrene and a conjugated diene. Improve the stability to heat, and it is not easy to cause deterioration of decomposition or polymerization. Further, higher heat resistance is exhibited by blocking styrene having high thermal stability at both ends. Further, it is more preferable from the viewpoints of solubility in a hydrocarbon solvent and resistance to a solvent.

Commercial products which can be used as the elastomer contained in the adhesive composition of the present invention are, for example, "Septon (trade name)" manufactured by KURARAY Co., Ltd., and "HYBRAR (trade name)" manufactured by KURARAY Co., Ltd. "TUFTEC (trade name)" manufactured by Asahi Kasei Co., Ltd., manufactured by JSR Co., Ltd. "DYNARON (trade name)" and so on.

The elastomer content contained in the adhesive composition of the present invention For example, the total amount of the adhesive composition is 100 parts by weight, preferably 50 parts by weight or more and 90 parts by weight or less, more preferably 60 parts by weight or more and 99 parts by weight or less, and most preferably 70%. It is in the range of the weight part or more and 95 parts by weight or less. By being in these ranges, the wafer and the support can be appropriately bonded while maintaining heat resistance.

Further, the elastomer may be mixed in a plurality of types. That is, the present invention The adhesive composition may also contain a plurality of elastomers. As long as at least one of the plurality of elastomers contains a styrene unit as a constituent unit of the main chain. Further, the content of at least one of the plurality of elastomers is in the range of 14% by weight or more and 50% by weight or less, or the weight average molecular weight is in the range of 10,000 or more and 200,000 or less. It is the scope of the invention. Further, when a plurality of elastomers are contained in the adhesive composition of the present invention, the content of the styrene unit may be adjusted to the above range as a result of mixing. For example, Septon 4033 of Septon (trade name) manufactured by Kuraray Co., Ltd. and Septon 2063 of Septon (trade name) having a styrene unit content of 13% by weight are mixed at a weight ratio of 1:1 by weight. The styrene content is 21 to 22% by weight based on the total amount of the elastomer contained in the adhesive composition, and therefore it is 14% by weight or more. Further, for example, when the styrene unit is 10% by weight or 60% by weight in a weight ratio of 1 to 1, it is 35% by weight, which is within the above range. The present invention is only required to be in this form. Further, it is preferable that all of the plurality of elastomers contained in the adhesive composition of the present invention are all or more The range includes styrene units and is a weight average molecular weight within the above range.

Further, it is preferred to use a photocurable resin (for example, UV curing) The adhesive layer is formed of a resin other than the resin. This is because the photocurable resin may remain as a residue on the periphery of the micro unevenness of the substrate 11 after the adhesive layer 8 is peeled off or removed. In particular, it is preferred to use a binder which can be dissolved in a specific solvent as a material constituting the adhesive layer 13. This is because the physical force of the substrate 11 is not required to be removed by dissolving the adhesive layer 13 in a solvent. When the adhesive layer 13 is removed, the strength is lowered and removed from the substrate 11, and the adhesive layer 13 can be easily removed without breaking or deforming the substrate 11.

(diluted solvent)

The diluent solvent for forming the second separation layer and the subsequent layer may, for example, be a linear chain such as hexane, heptane, octane, decane, methyl octane, decane, undecane, dodecane or tridecane. a hydrocarbon, a branched hydrocarbon having 4 to 15 carbon atoms, for example, a cyclic hydrocarbon such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene or tetrahydronaphthalene, p-menthane or o-menthane. , m-menthane, diphenyl menthane, 1,4-deuterate, 1,8-deuterate, borneol, norbornane, decane, thujane, decane, longene ( Longifolene), geraniol, nerol, linalool, citral, Citronellol, menthol, isomenthol, neomenthol, alpha-pine Oleohydrin, β-terpineol, γ-terpineol, terpineol-1-ol, terpineol-4-ol, dihydroterpineol acetate, 1,4-alcohol (cineol) 1,8-nonyl oleyl alcohol, borneol, carvone, ionone, thujone, camphor, d-limonene, 1-limonene, dipentane Terpenes such as olefins; lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentanone, methyl isoamyl ketone, 2-heptanone, etc. Ketones; polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetic acid a compound having an ester bond such as an ester, or an ether bond such as a monomethyl ether of a compound having the ester bond, a monoether ether such as monoethyl ether, monopropyl ether or monobutyl ether or a monophenyl ether. a derivative of a polyhydric alcohol of a compound or the like (in which propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred); a cyclic ether such as dioxane, or a lactate Ester, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxylate Propionate B An ester such as an ester; an aromatic organic solvent such as anisole, ethylbenzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether or butylphenyl ether.

(other ingredients)

The adhesive constituting the adhesive layer may further contain other substances having a miscibility within a range not impairing the essential characteristics. For example, various conventional additives such as an additive resin, a plasticizer, an auxiliary agent, a stabilizer, a colorant, a thermal polymerization inhibitor, and a surfactant for improving the performance of the adhesive can be further used.

[support]

The support plate (support) 12 means a support for supporting the substrate 11, and has light transparency. Therefore, when light is irradiated from the outside of the laminate 20 toward the support plate 12, the light reaches the second separation layer 14 and the first separation layer 15 through the support plate 12. Further, the support plate 12 does not necessarily have to transmit all of the light, and it is only necessary to transmit light that should be absorbed by the second separation layer 14 and the first separation layer 15 (having a specific wavelength).

The support plate 12 is a support substrate 11 and may have a necessary strength for preventing damage or deformation of the substrate 11 when the substrate 11 is thinned, transported, or mounted. From the above viewpoints, the support plate 12 is exemplified by glass, enamel, or acrylic resin.

[first separation layer]

The first separation layer 15 means a layer formed of a material which is deteriorated by absorbing light irradiated through the support plate 12. Further, the first separation layer 15 is formed by a separation layer forming step of performing plasma treatment using a reaction gas containing an organic compound having an unsaturated bond and a fluorine compound. In one embodiment, the first separation layer 15 is provided to cover the second separation layer 14 formed on the support plate 12.

In the present specification, the term "deterioration" of the first separation layer 15 means a state in which the first separation layer 15 is broken by receiving a small external force, or a state in which the adhesion between the first separation layer 15 and the contact layer is lowered. The first separation by the deterioration of the first separation layer 15 generated by the absorption of light Layer 15 loses its strength or adhesion prior to exposure to light.

Moreover, the deterioration of the first separation layer 15 may be due to absorption of light. Energy-induced (heat-generating or non-heat-generating) decomposition, cross-linking, stereo configuration change, or functional group dissociation (and, in addition, the separation layer hardens, degassing, shrinking, or expanding). The deterioration of the first separation layer 15 is caused by the absorption of light by the material constituting the first separation layer 15. Therefore, the type of deterioration of the first separation layer 15 may vary depending on the kind of the material constituting the first separation layer 15.

The light for tempering the first separation layer 15 and irradiating the first separation layer 15 may also be irradiated by a laser. Examples of the laser that emits light that is irradiated to the first separation layer 15 are a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, or a fiber laser, and a pigment laser. Such as liquid laser, CO ₂ laser, excimer laser, Ar laser, He-Ne laser and other gas lasers, semiconductor lasers, free electron laser and other laser light, or non-laser light. The laser light that emits the light irradiated to the first separation layer 15 can be appropriately selected depending on the material constituting the first separation layer 15, and it is only necessary to select a laser that can illuminate the light of the wavelength constituting the material of the first separation layer 15.

[First separation layer forming step]

The first separation layer forming step included in the method for producing a laminate of the present invention is a step of forming a first separation layer by performing a plasma treatment using a reaction gas containing an organic compound having an unsaturated bond and a fluorine compound.

(reaction gas)

The inventors of the present application have independently studied the formation of a separation layer of a laminate treated by plasma, and found that laminating can be formed by using a liquid compound in a liquid state at a normal temperature and a fluorine compound as a reaction gas. The separation layer of the substrate is enlarged.

In the method for producing a laminate according to the present embodiment, the reaction gas used for forming the first separation layer preferably contains an organic compound having an unsaturated bond and a fluorine compound.

The organic compound may be an unsaturated bond as long as it has an unsaturated bond, and examples thereof include an alkene, a cycloolefin, an alkyne, and an aromatic compound. Here, the olefin can be exemplified by, for example, 1,2-butadiene, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 3-methyl-1,2-butyl Diene, isoprene, and the like. Further, examples of the cycloolefin include 1,3-hexadiene, 1,4-hexadiene, cyclopentadiene, and 1,5-cyclooctadiene. Further, the alkyne may, for example, be acetylene or the like. Further, examples of the aromatic compound include benzene, toluene, xylene, and styrene. Further, if it has an unsaturated bond, an organic compound having, for example, an ether bond, an ester bond, and a xenon bond can be used. The organic compound having an ether bond and/or a oxime bond may, for example, be 1-methoxy-3-(trimethyldecyloxy)-1,3-butadiene, and 2-trimethyldecyloxy group. -1,3-butadiene and the like. Further, examples of the organic compound having an ester bond include, for example, ethyl 2,3-butadienoate. Further, these organic compounds may be used in combination of two or more kinds. By using these organic compounds as a reaction gas for plasma treatment, an unsaturated bond can be introduced into the first separation layer 15. Thereby, the first separation layer 15 which is deteriorated by absorbing light can be formed not only in the high-density plasma but also in the low-density plasma.

Here, the organic compound is preferably an alkene or a cycloolefin. Alkene or ring Alkene has a structure that is not easily disintegrated by low-density plasma. Therefore, since the reaction gas contains an olefin or a cycloolefin, the olefin or the cycloolefin in the plasma treatment can be appropriately polymerized without excessively disintegrating. Further, an unsaturated bond can be introduced into the first separation layer 15 formed by the plasma treatment. Therefore, by using an olefin or a cycloolefin as an organic compound, the first separation layer 15 which is deteriorated by absorbing light can be preferably formed.

Further, the unsaturated bond of the organic compound is preferably two or more. Thereby, a first separation layer which is more suitable for absorbing light can be formed.

Further, the boiling point of the organic compound is preferably in the range of 30 ° C or more and 100 ° C or less, more preferably in the range of 30 ° C or more and 60 ° C or less, and more preferably in the range of 40 ° C or more and 50 ° C or less. When the boiling point of the organic compound is in the range of 30 ° C or more and 100 ° C or less, an organic compound can be suitably used as the reaction gas in the conditions for plasma treatment.

Examples of the fluorine compound contained in the reaction gas used in the method for producing a laminate of the present embodiment include fluorocarbon, carbon tetrafluoride (CF ₄ ), nitrogen trifluoride (NF ₃ ), and sulfur hexafluoride ( SF ₆ ) and so on. The fluorocarbon may, for example, be C ₄ F ₈ or the like. By containing a fluorine compound in the reaction gas, the brittleness of the first separation layer 15 can be improved, and the chemical resistance of the first separation layer 15 can be improved. Here, the fluorine compound is preferably sulfur hexafluoride (SF ₆ ). By containing sulfur hexafluoride (SF ₆ ) in the reaction gas, the brittleness of the first separation layer can be further improved, and the first separation layer having good chemical resistance can be preferably formed.

(plasma processing)

The plasma processing apparatus used for the plasma treatment is not particularly limited, and a conventional plasma processing apparatus can be used.

The electrode provided in the plasma processing apparatus is not particularly limited. For example, a double coil antenna, a single coil antenna, or a parallel plate electrode can be used, but by using a parallel plate electrode, the surface area of the first separation layer formed on the support can be made larger, and as a result, the diameter can be used more. The large substrate is made of a laminate.

The shape of the reaction chamber of the plasma processing device is not particularly limited. The system may be of a hemispherical shape or may have other shapes such as a cylindrical shape. The size of the reaction chamber may be appropriately selected depending on the substrate size of the object to be processed. Further, the material of the reaction chamber can be appropriately selected from conventional materials which do not interfere with the plasma treatment and the formation of the first separation layer.

The plasma generated in the plasma processing device has a basis for application Inductively coupled plasma (CCP: Conductive Coupled Plasma) generated by high-frequency power generated by coil electrodes or parallel plate electrodes, and inductive coupling caused by induced electric field due to high-frequency current flowing to the coil electrode ICP (Inductive Coupled Plasma).

In the present embodiment, the plasma treatment of the first separation layer forming step is preferably performed by low-density plasma treatment. Here, the low-density plasma system means a plasma having an ion density of 1 × 10 ¹⁰ cm ^-3 or less, and means a plasma of a capacitively coupled body. By using low-density plasma treatment as the plasma treatment of the first separation layer forming step, it becomes easy to increase the size of the plasma processing apparatus. Therefore, the surface area of the first separation layer formed on the support can be made larger. Therefore, it is possible to increase the size of the laminated substrate.

The first separation layer forming step included in the method for producing a laminate according to an embodiment of the present invention will be described in more detail with reference to Fig. 2 . Fig. 2 is a schematic view showing the steps of manufacturing the first separation layer included in the production method according to an embodiment of the present invention.

As shown in FIG. 2, the plasma processing apparatus 100 used in the first separation layer forming step included in the method for producing a laminate of the present embodiment includes a pair of parallel plate electrodes 102 and a mounting support plate 12 in the reaction chamber 101. The configuration of the stage 103. Here, the plasma processing apparatus 100 is connected to the container 111 in which the organic compound has been stored by the liquid main flow controller 112 and the vaporizer 113 via the pipe 116a, and passes through the main flow controller through the pipe 116b. In the manner of 115, it is connected to the fluorine compound pressure tank 114. Further, the pipes 116a and 116b are joined to the pipe 116.

The reaction chamber 101 is used for plasma treatment to form the first separation layer 15 from the reaction gas. Further, in the reaction chamber 101, the pressure in the reaction chamber 101 can be adjusted by a vacuum pump (not shown).

A pair of parallel plate electrodes 102 are disposed in the reaction chamber 101, and plasma is generated using a reaction gas by applying high frequency power.

The stage 103 is provided with one of a pair of parallel plate electrodes 102, and the support plate 12 can be placed.

The container 111 stores the organic compound used in the reaction gas, and is pressurized by nitrogen, and the organic compound is supplied to the liquid main flow controller 112 through the pipe 116a.

Liquid main flow controller 112 is for adjusting the flow of organic compounds The amount of the device adjusts the flow rate of the organic compound supplied to the gasifier 113 through the pipe 116a.

The fluorine compound pressure tank 114 is a pressure tank for storing a fluorine compound used in the reaction gas, and the fluorine gas is supplied to the main flow controller 115 through the pipe 116b.

The main flow controller 115 is a device for adjusting the flow rate of the fluorine gas, and the flow rate of the supplied fluorine gas is adjusted through the pipe 116b.

The pipe 116a and the pipe 116b are joined to the pipe 116. Here, by heating the pipe 116, liquefaction of the reaction gas can be prevented.

As shown in FIG. 2, in the first separation layer forming step, the support plate 12 is placed in the reaction chamber 101 on the stage 103 including one of the pair of parallel plate electrodes 102. Here, a preheating step of preheating the support plate 12 in the reaction chamber 101 may also be performed.

Further, in the pretreatment, the surface of the support plate 12 can also be cleaned by containing oxygen in the pretreatment gas.

In the first separation layer forming step, the reaction gas which becomes the first separation layer 15 is supplied into the reaction chamber 101, and the first separation layer 15 is formed on the support plate 12 by plasma treatment. Here, the organic compound contained in the reaction gas is supplied from the vessel 111, and the flow rate is adjusted by the liquid main flow controller 112 to be vaporized by the gasifier 113. Further, the fluorine compound is supplied from the fluorine compound pressure tank 114, and the flow rate is adjusted by the main flow controller 115. Subsequently, the vaporized organic compound and the fluorine compound are mixed in the pipe 116, and supplied to the reaction chamber 101 while being heated.

By controlling the liquid main flow controller 112 and the main flow The device 115 adjusts the flow rate of the organic compound and the fluorine gas, and adjusts the volume ratio of the organic compound to the fluorine compound contained in the reaction gas. For example, when the volume ratio of the organic compound to the fluorine compound is from 6:4 to 9:1, a first separation layer which is not brittle and has good chemical resistance can be formed. Further, a first separation layer which can be preferably removed by the cleaning liquid after the light is transmitted through the support plate can be formed. Further, the volume ratio of the organic compound to the fluorine compound may be adjusted during the first separation layer forming step.

Further, one or more inert gases such as nitrogen, helium, and argon, and an additive gas such as hydrogen or oxygen may be added to the reaction gas.

The target temperature in the reaction chamber 101 is not particularly limited, and a known temperature can be used, but it is preferably in the range of 100 ° C or more and 300 ° C or less, preferably in the range of 200 ° C or more and 250 ° C or less. By setting the temperature in the reaction chamber to this range, the plasma treatment can be preferably performed.

The thickness of the first separation layer 15 formed in the first separation layer forming step is not particularly limited as long as it is sufficient to sufficiently absorb the film thickness of the light to be used, but is preferably in the range of, for example, 0.5 μm or more and 2.0 μm or less. The film thickness in the film is preferably in the range of 1.0 μm or more and 1.5 μm or less. The formation time of the first separation layer 15 in the first separation layer forming step may be set according to the film thickness formed.

[Second separation layer forming step]

In one embodiment, the method for producing a laminate according to the present invention further includes a second separation layer forming step of forming a second separation layer which is deteriorated by absorbing light irradiated through the support.

Thereby, when the laminate is subjected to the desired treatment, one side can be By the separation layer, the second separation layer is prevented from being deteriorated by various drug treatments, and a laminate which can appropriately deteriorate the second separation layer and the separation layer by the light irradiated through the support is produced.

Using FIG. 1, a second embodiment is included in an embodiment of the present invention. The separation layer forming step will be described.

As shown in (3) to (4) of Fig. 1, the laminate of the present invention The second separation layer forming step included in the manufacturing method is a step of forming the second separation layer 14 which is deteriorated by absorbing light irradiated through the support plate 12 before the separation layer forming step.

In one embodiment, as shown in (3) to (4) of FIG. 1 , A second separation layer 14 is formed on the support plate 12. Subsequently, as shown in (4) to (5) of FIG. 1, the first separation layer 15 is formed on the second separation layer 14 by the first separation layer forming step. Accordingly, the second separation layer 14 and the first separation layer 15 are formed on the support plate 12.

(second separation layer)

The second separation layer 14 is a layer formed of a material which is deteriorated by absorbing light irradiated through the support plate 12. In one embodiment, the second separation layer 14 is coated on the first separation layer 15 in the first separation layer forming step.

In the present specification, the term "deterioration" in the second separation layer 14 means the same phenomenon as "deterioration" in the first separation layer 15.

Further, the laser that emits the light irradiated to the second separation layer 14 may be appropriately selected depending on the material constituting the second separation layer 14, as long as the irradiation is selected It is sufficient that the laser of the wavelength of the material constituting the second separation layer 14 is deteriorated.

The second separation layer 14 is disposed on the surface of the support plate 12 on the side of the substrate 13 to which the substrate 11 is bonded.

The thickness of the second separation layer 14 is preferably in the range of, for example, 0.05 μm or more and 50 μm or less, more preferably in the range of 0.3 μm or more and 1 μm or less. If the thickness of the second separation layer 14 is limited to a range of 0.05 μm or more and 50 μm or less, the second separation layer 14 can be desirably deteriorated by irradiation with light for a short period of time and irradiation with low-energy light. Further, the thickness of the second separation layer 14 is preferably limited to the range of 1 μm or less from the viewpoint of productivity.

Further, in the laminate 20, another layer may be further formed between the second separation layer 14 and the support plate 12. In this case, the other layers may be formed of a material that transmits light. Accordingly, the light is prevented from entering the second separation layer 14, and a layer having a preferable property or the like to the laminate 20 can be appropriately added. Depending on the type of material constituting the second separation layer 14, the wavelength of light that can be used is also different. Therefore, the material constituting the other layer does not need to transmit all of the light, and can be appropriately selected from materials which can transmit light of a wavelength at which the material constituting the second separation layer 14 is deteriorated.

Further, the second separation layer 14 is preferably formed only of a material having a structure capable of absorbing light, but may be formed by adding a material having a structure capable of absorbing light within a range not impairing the essential characteristics of the present invention. Two separate layers 14. Further, the surface of the second separation layer 14 on the side opposite to the adhesion layer 13 is preferably flat (no unevenness is formed), whereby the second portion can be easily performed. The separation layer 14 is formed and can be uniformly attached when attached.

The second separation layer 14 may constitute a second separation layer as shown below The material of 14 is formed into a film shape in advance and bonded to the support plate 12, and the material constituting the second separation layer 14 is also applied to the support plate 12 and cured into a film shape. The method of applying the material constituting the second separation layer 14 to the support plate 12 can be appropriately selected by a conventional method known in the art of chemical vapor deposition (CVD) deposition or the like depending on the kind of the material constituting the second separation layer 14. .

The second separation layer 14 may also be degraded by absorption of light irradiated from the laser. That is, the light that is irradiated to the second separation layer 14 in order to deteriorate the second separation layer 14 may be a self-laser irradiator. Examples of the laser that emits light that is irradiated to the second separation layer 14 are a solid laser such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, or a fiber laser, and a pigment laser. Such as liquid laser, CO ₂ laser, excimer laser, Ar laser, He-Ne laser and other gas lasers, semiconductor lasers, free electron laser and other laser light, or non-laser light. The laser light that emits the light irradiated to the second separation layer 14 may be appropriately selected depending on the material constituting the second separation layer 14, as long as the laser of the wavelength of the light constituting the second separation layer 14 is irradiated.

(fluorocarbon)

The second separation layer 14 may also be composed of fluorocarbon. The second separation layer 14 is made of fluorocarbon and is deteriorated by absorption of light, and as a result, the strength or adhesion before receiving light irradiation is lost. Therefore, by accepting a little external force (for example, The second separation layer 14 can be broken by pulling the support plate 12 up, etc., so that the support plate 12 and the substrate 11 can be easily separated.

Further, from the viewpoint of the above, the fluorocarbon constituting the second separation layer 14 can be preferably formed into a film by a plasma CVD method. Further, the fluorocarbon includes C _x F _y (perfluorocarbon) and C _x H _y F _z (x, y, and z are integers), but is not limited thereto, and may be, for example, CHF ₃ , CH ₂ F ₂ , or C. ₂ H ₂ F ₂ , C ₄ F ₈ , C ₂ F ₆ , C ₅ F ₈ and the like. Further, as the fluorocarbon for constituting the second separation layer 14, an inert gas such as nitrogen, helium or argon, a hydrocarbon such as an alkene or an olefin, or oxygen, carbon dioxide or hydrogen may be added as needed. Further, a plurality of such gases may be mixed and used (a mixed gas of fluorocarbon, hydrogen, and nitrogen). Further, the second separation layer 14 may be composed of a single fluorocarbon or two or more fluorocarbons.

Fluorocarbon absorbs wavelengths with an intrinsic range with its type Light. The fluorocarbon can be preferably deteriorated by irradiating the second separation layer with light of a wavelength in the range of absorption of the fluorocarbon used in the second separation layer 14. Further, the light absorption rate in the second separation layer 14 is preferably 80% or more.

As the light irradiated to the second separation layer 14, as long as it corresponds to the wavelength at which fluorocarbon can be absorbed, for example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, a fiber laser is suitably used. Liquid lasers such as solid-state lasers, pigment lasers, CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers, gas lasers, semiconductor lasers, free electron lasers, etc., or Non-laser light can be. The wavelength at which the fluorocarbon can be deteriorated is not limited thereto, and for example, a range of 600 nm or less can be used.

(polymers having a light absorbing structure in a repeating unit)

The second separation layer 14 may also contain a polymer having a structure having light absorbability in its repeating unit. The polymer is degraded by exposure to light. The deterioration of the polymer is produced by absorbing the irradiated light by the above configuration. As a result of the deterioration of the polymer of the second separation layer 14, the strength or adhesion before the light irradiation is lost. Therefore, the second separation layer 14 can be broken by applying a small external force (for example, pulling up the support plate 12, etc.), and the support plate 12 and the substrate 11 can be easily separated.

The above structure having light absorptivity absorbs light and chemically changes the polymer containing the structure as a repeating unit. The structure is an atomic group containing a conjugated π-electron system formed, for example, by a substituted or unsubstituted benzene ring, a condensed ring or a heterocyclic ring. More specifically, the structure may be a cardo structure, or a benzophenone structure present on the side chain of the above polymer, a diphenylarylene structure, a diphenylanthracene structure (diphenylanthracene structure), two Phenyl structure or diphenylamine structure.

When the above structure exists in the side chain of the above polymer, the structure can be represented by the following formula.

(wherein R is each independently alkyl, aryl, halogen, hydroxy, keto, fluorenylene, fluorenyl or N(R ¹ )(R ² ) (here, R ¹ and R ^{2 are} each independently hydrogen Atom or an alkyl group having 1 to 5 carbon atoms, Z may be absent, or is CO-, -SO ₂ -, -SO- or -NH-, and n is 0 or an integer of 1 to 5).

Further, the polymer includes, for example, a repeating unit represented by any one of (a) to (d), or a structure represented by (e) or containing (f) in its main chain.

(wherein l is an integer of 1 or more, m is an integer of 0 or 1 to 2, and X is any one of the formulas shown in the above-mentioned "Chemical 2" in (a) to (e), Any one of the formulas represented by the above "Chemical 2", or absent, Y ₁ and Y _{2 are} each independently -CO- or SO ₂ -, and l is preferably an integer of 10 or less).

Examples of the benzene ring, the condensed ring and the heterocyclic ring represented by the above "Chemical 2" are listed as For example, phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted hydrazine, hydrazine, substituted hydrazine, acridine, substituted acridine, azobenzene, Substituted azobenzene, fluorime, substituted fluorescamine, fluorimon, substituted fluorimon, carbazole, substituted carbazole, N-alkylcarbazole, dibenzofuran, substituted dibenzofuran , Philippine, substituted phenanthrene, anthracene and substituted 芘. When the exemplified substituent further has a substitution, the substituent is selected from, for example, an alkyl group, an aryl group, a halogen atom, an alkoxy group, a nitro group, an aldehyde group, a cyano group, a decylamine group, a dialkylamino group, a sulfonamide, An imine, a carboxylic acid, a carboxylic acid ester, a sulfonic acid, a sulfonate, an alkylamino group, and an arylamine group.

In the substituent represented by the above "Chemical 2", as the fifth substituent having two phenyl groups, and Z is -SO ₂ -, exemplified by bis(2,4-dihydroxyphenyl)fluorene , bis(3,4-dihydroxyphenyl)fluorene, bis(3,5-dihydroxyphenyl)fluorene, bis(3,6-dihydroxyphenyl)fluorene, bis(4-hydroxyphenyl)fluorene, Bis(3-hydroxyphenyl)fluorene, bis(2-hydroxyphenyl)fluorene, and bis(3,5-dimethyl-4-hydroxyphenyl)hydrazine.

Among the substituents shown in the above "Chemical 2", as having two The fifth substituent of the phenyl group and the case where Z is -SO- are exemplified by bis(2,3-dihydroxyphenyl)anthracene and bis(5-chloro-2,3-dihydroxyphenyl)arene. , bis(2,4-dihydroxyphenyl)arylene, bis(2,4-dihydroxy-6-methylphenyl)anthracene, bis(5-chloro-2,4-dihydroxyphenyl) Anthraquinone, bis(2,5-dihydroxyphenyl)arylene, bis(3,4-dihydroxyphenyl)anthracene, bis(3,5-dihydroxyphenyl)anthracene, bis(2,3, 4-trihydroxyphenyl)arylene, bis(2,3,4-trihydroxy-6-methylphenyl)-arylene, bis(5-chloro-2,3,4-trihydroxybenzene Amidino, bis(2,4,6-trihydroxyphenyl)arylene, and bis(5-chloro-2,4,6-trihydroxyphenyl) anthracene.

Among the substituents shown in the above "Chemical 2", as having two The fifth substituent of the phenyl group, and the case where Z is -C(=O)-, is exemplified by 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2 , 2',4,4'-tetrahydroxybenzophenone, 2,2',5,6'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxyl 4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,6-di Hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-amino-2'-hydroxybenzophenone, 4- Dimethylamino-2'-hydroxybenzophenone, 4-diethylamino-2'-hydroxybenzophenone, 4-dimethylamino-4'-methoxy-2'-hydroxydiphenyl Methyl ketone, 4-dimethylamino-2', 4'-dihydroxybenzophenone, and 4-dimethylamino-3',4'-dihydroxybenzophenone, and the like.

When the above structure is present in the side chain of the above polymer, The ratio of the repeating unit of the structure to the above polymer is such that the light transmittance of the second separation layer 14 is in the range of 0.001% or more and 10% or less. When the polymer is prepared so that the ratio is limited to the range, the second separation layer 14 can sufficiently absorb light and can be deteriorated reliably and rapidly. That is, the support plate 12 can be easily removed from the laminate 20, and the necessary light irradiation time for the removal can be shortened.

The above structure can be absorbed according to the choice of its kind. The wavelength of the light. For example, the wavelength of the light absorbable by the above configuration is more preferably in the range of 100 nm or more and 2000 nm or less. In this range, the wavelength of the light absorbable by the above structure is a shorter wavelength side, for example, 100 nm or more. And within the range of 500 nm or less. For example, the above configuration can preferably deteriorate the polymer containing the structure by absorbing ultraviolet light having a wavelength in the range of about 300 nm or more and 370 nm or less.

The above-mentioned configuration absorbs light from, for example, a high pressure mercury lamp ( Wavelength: 254 nm or more and 436 nm or less), KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), F2 excimer laser (wavelength: 157 nm), XeCl laser (wavelength: 308 nm) XeF laser (wavelength: 351 nm) or solid-state UV laser (wavelength: 355 nm), or g line (wavelength: 436 nm), h line (wavelength: 405 nm) or i line (wavelength: 365 nm).

The second separation layer 14 described above contains the above structure as a heavy The polymer of the complex unit, but the second separation layer 14 may further contain components other than the above polymers. The component is exemplified by a filler, a plasticizer, and a component which can improve the peelability of the support plate 12. These components are suitably selected from conventional materials or materials which do not interfere with the absorption of light by the above-described structure, and the deterioration of the polymer or which promote the absorption and deterioration.

(inorganic matter)

The second separation layer 14 may also be composed of an inorganic material. The second separation layer 14 is made of an inorganic substance and can be deteriorated by absorbing light, and as a result, the strength or adhesion before receiving light irradiation is lost. Therefore, by applying a little external force (for example, pulling up the support plate 12, etc.), the second separation layer 14 can be broken, and the support plate 12 can be easily separated from the substrate 11.

The inorganic material may be formed by absorbing light, and for example, one or more inorganic substances selected from the group consisting of a metal, a metal compound, and carbon may be suitably used. The metal compound means a compound containing a metal atom, and for example, it may be a metal oxide or a metal nitride. The inorganic material is not limited, and may be, for example, selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon. One or more inorganic substances. Further, carbon is also a concept that may include carbon isotopes, and may be, for example, diamond, fullerene, diamond-like carbon, carbon nanotubes, or the like.

The above inorganic substance absorbs light having a wavelength of an intrinsic range depending on the kind thereof. By irradiating the second separation layer with wavelength light of a range absorbed by the inorganic substance used in the second separation layer 14, the inorganic substance can be appropriately deteriorated.

As the light to be irradiated to the second separation layer 14 made of an inorganic material, as long as it corresponds to the wavelength at which the inorganic substance can absorb, for example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, or an LD laser is suitably used. Solid-state lasers such as fiber lasers, liquid lasers such as pigment lasers, CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers, gas lasers, semiconductor lasers, free electron lasers, etc. Laser light, or non-laser light.

The second separation layer 14 made of an inorganic material can be formed on the support plate 12 by a conventional technique such as sputtering, chemical vapor deposition (CVD), electroplating, plasma CVD, or spin coating. The thickness of the second separation layer 14 made of an inorganic material is not particularly limited as long as it is sufficient to sufficiently absorb the film thickness of the light to be used, but is preferably a film thickness in the range of, for example, 0.05 μm or more and 10 μm or less. Moreover, the second separation layer 14 may be formed in advance. An adhesive is applied to both surfaces or one surface of an inorganic film (for example, a metal film) made of an inorganic material, and is bonded to the support plate 12 and the substrate 11.

Further, when a metal film is used as the second separation layer 14, depending on the film quality of the second separation layer 14, the type of the laser light source, and the laser output, it is possible to cause reflection of the laser or charge the film. Therefore, it is preferable to provide such countermeasures by providing the antireflection film or the antistatic film on the upper or lower side of the second separation layer 14 or on one side thereof.

(a compound having an infrared absorbing structure)

The second separation layer 14 can also be formed by a compound having an infrared absorbing structure. This compound is degraded by absorption of infrared rays. The second separation layer 14 loses strength or adhesion before receiving infrared radiation as a result of deterioration of the compound. Therefore, the second separation layer 14 can be broken by applying a small external force (for example, pulling up the support body, etc.), and the support plate 12 can be easily separated from the substrate 11.

The compound having a structure having infrared absorbing property or a structure containing infrared absorbing property may be, for example, an alkane, an ene (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulative polyene (cumulene) ), cyclic formula, alkyne (monosubstituted, disubstituted), monocyclic aromatic (benzene, monosubstituted, disubstituted, trisubstituted), alcohols and phenols (free OH, intramolecular hydrogen bonds, intermolecular hydrogen bonds) , saturated secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane cyclic ether, peroxide ether , ketones, dialkylcarbonyls, aromatic carbonyls, enols of 1,3-diketones, o-hydroxyaryl ketones, dialkyl aldehydes, aromatic aldehydes, carbonic acid (dimers, carbonate anions), Acid esters, acetates, conjugated esters, non-conjugated esters, aromatic esters, lactones (β-, γ-, δ-), aliphatic hydrochlorides, aromatic hydrochlorides, anhydrides (conjugated, Non-conjugated, cyclic, acyclic), primary guanamine, secondary guanamine, indoleamine, primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic) Tertiary amine (aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carboxy quinone imine, aliphatic isonitrile, aromatic isonitrile , isocyanate, thiocyanate, aliphatic isothiocyanate, aromatic isothiocyanate, aliphatic nitro compound, aromatic nitro compound, nitroamine, nitrosamine, nitrate , nitrite, nitroso bond (aliphatic, aromatic, monomeric, dimer), thiol and thiophene and sulfur compounds such as thiol, thiocarbonyl, hydrazine, hydrazine, sulfonium chloride, first grade Sulfonamide, secondary sulfonamide, sulfate, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), PA ² bond (A ² is H, C or O), Or Ti-O bond.

The structure including the above carbon-halogen bond is exemplified by, for example, -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF ₂ -, -CF ₃ , -CH=CF ₂ , -CF=CF ₂ , fluorination. An aryl group, an aryl chloride group, and the like.

The structure containing the Si—Al ¹ bond is exemplified by SiH, SiH ₂ , SiH ₃ , Si—CH ₃ , Si—CH ₂ —, Si—C ₆ H ₅ , SiO—aliphatic, Si—OCH ₃ , Si—. OCH ₂ CH ₃ , Si-OC ₆ H ₅ , Si-O-Si, Si-OH, SiF, SiF ₂ , and SiF ₃ , and the like. The structure containing the Si-A ¹ bond is preferably a naphthene skeleton and a sesquiterpene skeleton.

The structure containing the above PA ² bond is exemplified by PH, PH ₂ , P-CH ₃ , P-CH ₂ -, PC ₆ H ₅ , A ³ ₃ -PO (A ³ is aliphatic or aromatic), (A ⁴ O) _3- PO (A ⁴ is an alkyl group), P-OCH ₃ , P-OCH ₂ CH ₃ , P-OC ₆ H ₅ , POP, P-OH, and O=P-OH.

The above structure can be absorbed according to the choice of its kind The infrared wavelength of the wavelength of the range. Specifically, the wavelength of the infrared ray absorbable by the above structure is, for example, in the range of 1 μm or more and 20 μm or less, and can be better absorbed in the range of 2 μm or more and 15 μm or less. Further, when the above structure is a Si—O bond, a Si—C bond, and a Ti—O bond, it may be in the range of 9 μm or more and 11 μm or less. Moreover, the wavelength of the infrared light absorbable by each structure can be easily understood by those skilled in the art. For example, the absorption band in each configuration can be referred to the non-patent literature: SILVERSTEIN. BASSLER. MORRILL, "Identification of Organic Compound Spectra (5th Edition) - MS, IR, NMR, and UV -" (published in 1992), pp. 146 - 151.

The second separation layer 14 is formed by infrared absorption The compound having a structure as described above is not particularly limited as long as it is a compound having the above-described structure, and is soluble in a solvent to be coated and can form a solid layer to be cured. However, in order to effectively deteriorate the compound in the second separation layer 14 and to facilitate separation of the support plate 12 from the substrate 11, it is preferred to increase the absorption of infrared rays in the second separation layer 14, that is, to the second. When the separation layer 14 is irradiated with infrared rays, the infrared transmittance is low. Specifically, it is preferred that the infrared transmittance in the second separation layer 14 is less than 90%, and the infrared transmittance is better than 80%.

If an example is given, it has a naphthenic skeleton. As the compound, for example, a resin of a repeating unit represented by the following chemical formula (3) and a copolymer of a repeating unit represented by the following chemical formula (4), or a repeating unit represented by the following chemical formula (3) and an acrylic compound-based compound can be used. The resin of the copolymer of the repeating unit.

(In the chemical formula (4), R ³ is hydrogen, an alkyl group having 10 or less carbon atoms, or an alkoxy group having 10 or less carbon atoms).

Among them, the compound having a oxoxane skeleton is preferably a copolymer of a repeating unit represented by the above formula (3) and a copolymer of a repeating unit represented by the following chemical formula (5): tert-butylstyrene (TBST)-dimethyl Further, the oxyalkylene copolymer further preferably comprises a TBST-dimethyloxane copolymer having a repeating unit represented by the above formula (3) and a repeating unit represented by the following chemical formula (5) in a range of 1;

Further, a compound having a sesquiterpene oxide skeleton can be used as an example A resin which is a copolymer of a repeating unit represented by the following chemical formula (6) and a repeating unit represented by the following chemical formula (7).

(In the chemical formula (6), R ⁴ is hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms, and in the chemical formula (7), R ⁵ is an alkyl group having 1 or more and 10 or less carbon atoms or a phenyl group).

In addition to the compound having a sesquioxane skeleton, it is also possible to use, as appropriate, JP-A-2007-258663 (published on October 4, 2007), and JP-A-2010-120901 (2010) Various sesquiterpene oxides disclosed in Japanese Laid-Open Patent Publication No. 2009-263316 (published on Nov. 12, 2009) and JP-A-2009-263596 (published on Nov. 12, 2009). Resin.

Among them, as a compound having a sesquiterpene oxide skeleton The copolymer of the repeating unit represented by the following chemical formula (8) and the repeating unit represented by the following chemical formula (9), and more preferably 7:3, the repeating unit represented by the following chemical formula (8) and the following chemical formula ( 9) A copolymer representing the repeating unit.

The polymer having a sesquiterpene skeleton has a random structure, a step structure, and a cage structure, and may have any structure.

Further, examples of the compound containing a Ti-O bond are, for example, (i) tetra-isopropoxide titanium oxide, tetra-n-butyltin oxide, ruthenium (2-ethylhexyloxy) titanium, and isopropyl isobutyloxide octanediol. Isoalkoxide titanium, (ii) di-isopropoxy. Chelating titanium such as bis(ethylmercaptoacetone) titanium and propane dioxytitanium bis(ethylacetoxyacetate), (iii) iC ₃ H ₇ O-[-Ti(OiC ₃ H ₇ ) ₂ -O-] _n -iC ₃ H ₇ , and nC ₄ H ₉ O-[-Ti(OnC ₄ H ₉ ) ₂ -O-] _n -nC ₄ H ₉ etc. Titanium polymer, (iv) tri- N-butoxytitanium monostearate, titanium stearate, diisopropoxy titanium diisostearate, and (2-n-butoxycarbonylbenzylideneoxy) tributyl titanate Titanium, (v) di-n-butoxy. A water-soluble titanium compound such as bis(triethanolamine) titanium or the like.

Among them, the compound containing a Ti-O bond is preferably a di-n-butoxy group. Bis(triethanolamine)titanium (Ti(OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N(C ₂ H ₄ OH) ₂ ] ₂ ).

The second separation layer 14 contains a compound having an infrared absorbing structure, but the second separation layer 14 may further contain components other than the above compounds. The component is exemplified by a filler, a plasticizer, and a component which can improve the peelability of the support plate 12. These components may be appropriately selected from conventional materials or materials which are not hindered by the infrared absorption of the above structure and the deterioration of the compound, or which promote the absorption and deterioration.

(infrared absorbing material)

The second separation layer 14 may also contain an infrared absorbing material. The second separation layer 14 is composed of an infrared absorbing material, and can be deteriorated by absorbing light, and as a result, the strength or adhesion before receiving light irradiation is lost. Therefore, the second separation layer 14 can be broken by applying a small external force (for example, pulling up the support plate 12, etc.), and the support plate 12 and the substrate 11 can be easily separated.

The infrared ray absorbing material may be configured to be deteriorated by absorbing infrared rays, and for example, carbon black, iron particles or aluminum particles can be preferably used. The infrared absorbing material absorbs light having a wavelength of an intrinsic range depending on its kind. The infrared absorbing material can be preferably deteriorated by irradiating the second separation layer 14 with light of a wavelength in a range absorbed by the infrared absorbing material used in the second separation layer 14.

(other steps)

Finally, as shown in FIG. 1 (6), the substrate 11 and the support plate 12 are bonded to each other by laminating the adhesive layer 13 provided on the substrate 11 and the first separation layer 15 provided on the support plate 12. (Fitting step). Thereby, the laminate 20 including the second separation layer 14 and the first separation layer 15 can be manufactured. Subsequently, the laminate 20 is subjected to a thinning step of the substrate 11 to perform the desired treatment.

Laminate

A lamination system according to an embodiment includes a substrate, a support for supporting light transmittance of the substrate, and a first separation which is provided between the substrate and the support and which is deteriorated by absorbing light irradiated through the support In the laminate of the layers, the first separation layer is formed by plasma treatment using a reaction gas containing an organic compound having an unsaturated bond and a fluorine compound.

According to the above configuration, the laminate of one embodiment has the first separation layer which can increase the size of the laminated substrate. Further, it has a first separation layer having good chemical resistance.

Moreover, the method for producing a laminate of the present invention further includes a second separation layer forming step of forming a second separation layer which is deteriorated by absorbing light irradiated through the support.

Further, the laminate of the present invention may further comprise a second separation layer.

According to the above configuration, the lamination system of one embodiment is supported A first separation layer and a second separation layer are formed on the body. Here, the first separation layer is provided with chemical resistance in various drug treatments, and the second separation layer has good separability after irradiation with light. For example, when the first separation layer is present on the second separation layer, the first separation layer can be utilized to prevent the second separation layer from being deteriorated by the drug treatment. When the second separation layer is present on the first separation layer, even if the second separation layer is deteriorated by the drug treatment, the function of using the first separation layer as the separation layer can be ensured. Further, since the separation layer can be appropriately irradiated by irradiating light to the separation layer through the support, the substrate can be easily separated from the laminate.

Substrate, support body, first separation layer, second separation layer The description is based on the above-mentioned "manufacturing method of the laminate". Moreover, when both the first separation layer and the second separation layer are formed on the laminate, the first separation layer may be formed on the support, and the second separation layer may be formed on the first separation layer. It may also be an embodiment in which a second separation layer is formed on the support and a first separation layer is formed on the second separation layer.

An embodiment of the laminate of the present invention will be described using FIG. 3. The construction of the laminate 20. This is a laminate produced by an embodiment of the method for producing a laminate of the present invention shown in Fig. 1.

As shown in FIG. 3, a laminate of an embodiment of the present invention 20: a support plate (support) 12 having a light transmittance of the substrate 11 and the support substrate 11, and a first separation between the substrate 11 and the support plate 12 by absorbing the light irradiated through the support plate 12 Layer 15, and the first separation layer 15 is obtained by using an organic compound containing an unsaturated bond The reaction gas of the fluorine compound is formed by slurry treatment.

Moreover, on the support plate 12, the first separation layer 15 is formed Before, the second separation layer 14 separated by absorbing light irradiated through the support plate 12 is formed.

The laminate 20 is formed by laminating the substrate 11, the subsequent layer 13, the second separation layer 14, the first separation layer 15, and the support plate 12 in this order. That is, the substrate 11 is supported on the support plate 12 through the adhesive layer 13, the second separation layer 14, and the first separation layer 15. Therefore, when the substrate 11 in the laminate 20 is ground to a desired thickness by a grinding machine, it is possible to prevent the substrate 11 from being damaged due to excessive stress. Moreover, a desired circuit component can be formed by using a photoresist for the surface of the substrate 11 ground to a desired thinness. In these processes, the laminate 20 is exposed to various drugs.

As shown in FIG. 3, the laminate 20 is formed on the second separation layer 14 to form the first separation layer 15. Here, since the first separation layer 15 is formed by plasma treatment using a reaction gas containing an organic compound having an unsaturated bond and a fluorine compound, the chemical resistance is good. Therefore, in the desired treatment using the drug, the second separation layer 14 can be protected from the influence of the drug by the first separation layer 15. According to this, the second separation layer 14 can be prevented from being invaded by the medicine, and the separation of the support plate 12 from the laminate 20 during the desired treatment can be prevented. Further, after the desired treatment, the second separation layer 14 and the first separation layer 15 are irradiated with light through the support plate 12, whereby the support plate 12 can be appropriately separated from the laminate 20.

The structure of the laminate 21 of another embodiment of the laminate of the present invention will be described with reference to Fig. 4 . Figure 4 is a view showing another embodiment of the present invention A schematic view of the laminate 21. Here, in the embodiment of the method for producing the laminate of the present invention shown in Fig. 1, the laminate 21 is a laminate in which the second separation layer forming step of (3) to (4) of Fig. 1 is omitted.

As shown in FIG. 4, the laminate of another embodiment of the present invention A support plate (support) 12 having a light transmittance of the substrate 11 and the support substrate 11 and a first separation between the substrate 11 and the support plate 12 by absorbing the light irradiated through the support plate 12 The layer 15 and the first separation layer 15 are formed by plasma treatment using a reaction gas containing an organic compound having an unsaturated bond and a fluorine compound.

The laminate 21 is based on the substrate 11, the subsequent layer 13, and the first portion. The layer 15 and the support plate 12 are laminated in this order. In the laminate 21, the first separation layer 15 is formed by plasma treatment using a reaction gas containing an organic compound having an unsaturated bond and a fluorine compound. Therefore, even if the plasma treatment is performed using the low-density plasma in the first separation layer forming step, the laminate 21 may be provided with the first separation layer 15 which is deteriorated by absorbing light. In other words, the laminate 21 can be suitably produced by using a low-density plasma processing apparatus having a parallel plate electrode which is easy to increase in size. Therefore, the laminate 21 can be manufactured using a larger substrate than a substrate used in the manufacture of a general semiconductor wafer or the like. Therefore, the amount of semiconductor wafers available from one laminate can be increased.

(Other embodiments)

Any of the first separation layer and the second separation layer included in one embodiment of the present invention may be formed first. Therefore, the laminate of the present invention The embodiment is not limited to the embodiment in which only the first separation layer is formed, and the first separation layer is formed after the second separation layer is formed. Other embodiments may be exemplified by first forming the first separation layer 15 on the support plate 12 by the first separation layer forming step, and then forming the laminate of the second separation layer 14 by the second separation layer forming step.

According to the above configuration, the laminate can be provided in various medicines. The advantages of the first separation layer 15 which is good in chemical resistance and the advantages of the second separation layer 14 which can be appropriately deteriorated by light can be used. That is, when the laminate is subjected to a desired treatment, even if one of the second separation layers 14 is partially deteriorated by various drug treatments, since the first separation layer 15 is formed, the support plate 12 can be prevented from being separated from the laminate. Further, since the first separation layer and the second separation layer can be appropriately deteriorated by the light irradiated through the support, the substrate can be easily separated from the laminate.

The present invention is not limited to the above embodiments, and can be applied for Various modifications are possible within the scope of the patent range, and embodiments of the technical means that can be appropriately combined in different embodiments are also included in the technical scope of the present invention.

[Examples] [Evaluation of separation of support plates]

As the examples 1 to 3, laminates in which the separation layers of the respective embodiments were formed were produced. The laminate was produced using the support sheets of Examples 1 to 3, and the separation property of the support sheets was evaluated. The contents of the respective embodiments are as follows.

Example 1: Support plate for forming only isoprene film (first separation layer)

Example 2: forming a isoprene film (first separation layer) on a support plate, and subsequently forming a support plate of a fluorocarbon film (second separation layer) on the first separation layer

Embodiment 3: forming a fluorocarbon film (second separation layer) on a support plate, and subsequently forming a support plate of a isoprene film (first separation layer) on the second separation layer

Further, the support system forming the separation layer used a 12-inch glass support plate having a thickness of 700 μm.

(formation of the first separation layer)

The lamination system of Examples 1 to 3 formed the first separation layer as follows. The conditions for producing the reaction chamber of the laminate having the parallel plate electrodes were adjusted so that the output power of the high-frequency power source was 1.0 kW, the pressure was 67 Pa, and the film formation temperature was 220 °C. In the reaction chamber, first, isoprene was adjusted to a flow rate of 200 sccm, and supplied as a reaction gas and subjected to plasma treatment by a plasma CVD method. Subsequently, the plasma treatment was not interrupted, and isoprene was adjusted to a flow rate of 100 sccm, sulfur hexafluoride (SF ₆ ) was adjusted to a flow rate of 100 sccm, and isoprene and hexafluoride were supplied by a supply of 1:1. The reaction gas of sulfur (SF ₆ ) is subjected to plasma treatment by plasma CVD. Thereby, a first separation layer (film thickness: 0.5 μm) formed of isoprene and sulfur hexafluoride (SF ₆ ) was formed.

(formation of the second separation layer)

The laminate system of Examples 2 and 3 was prepared as follows. The conditions of the reaction chamber were adjusted to a pressure of 70 Pa, a high frequency power of 2,800 W, and a film formation temperature of 240 °C. In the reaction chamber, a fluorocarbon film (film thickness: 0.5 μm) of the second separation layer was formed by a CVD method in which C ₄ F _{8 was} supplied as a reaction gas at a flow rate of 400 sccm.

(production of laminate)

Next, a laminate was produced using a support plate on which the above separation layer was formed. TZNR (registered trademark)-A3007t (manufactured by Tokyo Ohka Kogyo Co., Ltd.) of the adhesive composition was spin-coated on a 12-inch wafer, and heated at 100 ° C, 160 ° C, and 200 ° C for 3 minutes to form a film. Layer (film thickness 50 μm). Next, the laminate was bonded to the support plate for 3 minutes under vacuum at a temperature of 220 ° C and 4000 Kg to form a laminate.

(separation of the support plate)

The laminate produced under the above production conditions was treated as follows, and it was evaluated whether or not the support plate was separated from the wafer.

A pulsed laser having a wavelength of 532 nm is irradiated from the support plate side of the laminate toward the first separation layer. The laser conditions are an irradiation speed of 6,500 mm/sec, a pulse frequency of 40 kHz, an irradiation pitch of 180 μm, and an irradiation range of 309mm.

(result)

In the first embodiment, it was confirmed that the laminate having the first separation layer formed by plasma treatment using a reaction gas containing isoprene and sulfur hexafluoride (SF ₆ ) can be self-illuminated by irradiation. The laminate suitably separates the support plates. Further, in Examples 2 and 3, it was confirmed that the support plate can be appropriately separated from the laminate by irradiation of light. Thereby, it was confirmed that any of the first separation layer and the second separation layer was formed on the support plate, and the support plate can be appropriately separated from the laminate by the irradiation light.

[Evaluation of NMP tolerance of separation layer]

The support plate on which the separation layer was formed under the same conditions as in Examples 1 to 3 was immersed in N-methyl-2-pyrrolidone (NMP) for 5 minutes to evaluate NMP resistance. Further, as Comparative Example 1, the same evaluation was carried out for the support plate in which only the fluorocarbon film (film thickness: 0.5 μm) was formed under the same conditions as those of the second separation layer.

(result)

The first separation layer of the support plate of Example 1 was not swollen after being immersed in NMP for 5 minutes. Further, in the first separation layer of Example 1, the separation layer was sprayed with water after immersion in NMP, and no peeling occurred. The first separation layer of the support plate of Example 2 was not swollen, and only the second separation layer was swollen, and when water was sprayed, one of the second separation layers was partially peeled off. Further, in the support plate of Example 3, since the second separation layer was covered by the first separation layer, no swelling or peeling was observed in the first and second separation layers. On the other hand, the separation layer of Comparative Example 1 was immersed in NMP for 5 minutes and then swollen. Moreover, the separation layer of Comparative Example 1 When the water is sprayed, one of the separation layers is partially peeled off.

From the results of these, it was confirmed that the first separation layer formed by plasma treatment using a reaction gas containing isoprene and sulfur hexafluoride (SF ₆ ) was used in any of Examples 1 to 3. The solvent resistance to NMP is good. Therefore, there is provided a laminate having a first separation layer formed by plasma treatment using a reaction gas containing isoprene and sulfur hexafluoride (SF ₆ ), compared to a layer having a separation layer only having a fluorocarbon film. The combination prevents swelling of the separation layer by NMP and prevents separation of the support plates. Further, in the laminate produced by using the support plate of Example 2, although the second separation layer was swollen by NMP, it was judged that the separation of the support plate from the laminate was prevented because the first separation layer was not deteriorated.

[Industrial availability]

The method for producing a laminate of the present invention and the laminate can be widely used in, for example, a manufacturing step of a miniaturized semiconductor device.

11‧‧‧Substrate

12‧‧‧Support plate (support)

13‧‧‧Next layer

14‧‧‧Second separation layer

15‧‧‧First separation layer

20‧‧‧Layer

Claims (11)

A method for producing a laminate comprising: a substrate; a support for supporting light transmittance of the substrate; and a substrate disposed between the substrate and the support, and being deteriorated by absorbing light irradiated through the support A method for producing a laminate of a first separation layer, characterized in that the first separation of the first separation layer is formed by plasma treatment using a reaction gas containing an organic compound having an unsaturated bond and a fluorine compound Layer formation step. The method for producing a laminate according to claim 1, wherein the organic compound is an olefin or a cycloolefin. The method for producing a laminate according to claim 1, wherein the organic compound has a boiling point of 30 ° C or more and 100 ° C or less. The method for producing a laminate according to claim 1, wherein the fluorine compound is sulfur hexafluoride (SF ₆ ). The method for producing a laminate according to claim 1, wherein the volume ratio of the organic compound to the fluorine compound is from 6:4 to 9:1. The method for producing a laminate according to claim 1, wherein the plasma treatment of the separation layer forming step is a low-density plasma treatment. The method for producing a laminate according to any one of claims 1 to 6, further comprising: a second separation layer forming step of forming a second separation layer which is deteriorated by absorbing light irradiated through the support. The method of producing a laminate according to claim 7, wherein the second separation layer is composed of a fluorocarbon. a laminate comprising a substrate and supporting the substrate a light-transmissive support and a laminate of a first separation layer which is disposed between the substrate and the support and which is deteriorated by light transmitted through the support, the first separation layer is borrowed It is formed by plasma treatment using a reaction gas containing an organic compound having an unsaturated bond and a fluorine compound. The laminate according to claim 9, wherein the support further forms a second separation layer which is deteriorated by absorbing light irradiated through the support. The laminate of claim 10, wherein the second separation layer is composed of a fluorocarbon.