JP6006569B2 - Laminate and method for producing laminate - Google Patents

Description

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

  In recent years, electronic devices such as IC cards and mobile phones have been required to be thinner, smaller, and lighter. In order to satisfy these requirements, a thin semiconductor chip must be used as a semiconductor chip to be incorporated. For this reason, the thickness (film thickness) of the wafer substrate on which the semiconductor chip is based is currently 125 μm to 150 μm, but it is said that it must be 25 μm to 50 μm for the next generation chip. Therefore, in order to obtain a wafer substrate having the above film thickness, a wafer substrate thinning step is indispensable.

  Since the strength of the wafer substrate is reduced due to the thin plate, in order to prevent damage to the thinned wafer substrate, a circuit is placed on the wafer substrate while automatically supporting the support plate on the wafer substrate during the manufacturing process. Etc. are mounted. Then, after the manufacturing process, the wafer substrate is separated from the support plate. Therefore, it is preferable that the wafer substrate and the support plate are firmly bonded during the manufacturing process, but it is preferable that the wafer substrate can be smoothly separated from the support plate after the manufacturing process.

  When the wafer substrate and the support plate are firmly bonded, depending on the adhesive material, it is difficult to separate the support plate from the wafer substrate without damaging the structure mounted on the wafer substrate. Therefore, it is a very difficult temporary fixing technology that realizes strong adhesion between the wafer substrate and the support plate during the manufacturing process and separates the elements mounted on the wafer substrate without damaging them after the manufacturing process. Development is required.

  As a method for manufacturing a semiconductor chip in which a support is bonded to a semiconductor wafer, the semiconductor wafer is processed, and then the support is separated, a method described in Patent Document 1 is known. In the method described in Patent Document 1, a light-transmitting support and a semiconductor wafer are bonded together via a photothermal conversion layer and an adhesive layer provided on the support, and the semiconductor wafer is processed and then supported. By irradiating radiation energy from the body side, the photothermal conversion layer is decomposed, and the semiconductor wafer is separated from the support.

Japanese Patent Laying-Open No. 2005-159155 (released on June 16, 2005)

  When various processes are performed on a laminate in which a base material such as a wafer and a support are bonded to each other via a separation layer for later separation, the separation layer is caused by chemicals or the like during the process. If the quality changes, there will be a problem of peeling off during the process.

  For example, in a resist stripping process or the like, when the laminate is exposed to a stripping solution particularly at a high temperature, the stripping solution penetrates from the edge end surface of the laminate and the wafer is peeled off.

  If it is peeled off in the middle of processing, the wafer is cracked, cracked, or uneven, and cannot proceed to the next step.

  The present invention has been made in view of such problems, and in order to suppress separation of the wafer when a desired treatment is performed on the laminate, a laminate in which the separation layer is protected is provided. The purpose is to provide.

  In order to solve the above problems, a laminate according to the present invention comprises a substrate, an adhesive layer, a separation layer that is altered by absorbing light, and a support, which are laminated in this order. And a protective layer that covers at least a surface that does not overlap with the adhesive layer among the surfaces that are not bonded to the support.

  Moreover, the manufacturing method of the laminated body which concerns on this invention forms the separated layer formation process which forms the separated layer which changes in quality by absorbing light on a support body, and forms an contact bonding layer on a board | substrate or the said separated layer. An adhesive layer forming step, a laminating step of laminating the substrate, the adhesive layer, the separation layer, and the support in this order, and a surface of the separation layer that adheres to the support. A protective layer forming step of forming a protective layer that covers at least a surface that does not overlap with the adhesive layer when being laminated in the laminating step is included before the laminating step.

  According to the present invention, since the separation layer is protected when a desired treatment is performed on the laminate, it is possible to suppress the peeling of the wafer.

It is a figure which shows the structure of the laminated body 10 which concerns on one Embodiment of the laminated body of this invention. It is a figure which concerns on one Embodiment of the manufacturing method of the laminated body of this invention.

<Laminated body>
A laminated body according to the present invention will be described with reference to FIG. 1 using a laminated body 10 according to an embodiment as an example. FIG. 1 is a diagram showing a structure of a laminate 10 according to an embodiment of the laminate of the present invention.

  The laminated body 10 is formed by laminating a substrate 11, an adhesive layer 13, a separation layer 14 that is altered by absorbing light, and a support plate (support) 12 in this order. And a protective layer 15 that covers at least a surface that does not overlap with the adhesive layer 13 among the surfaces that are not bonded to the support plate.

  Since the protective layer 15 covers at least the surface of the separation layer 14 that does not overlap with the adhesive layer 13, the separation layer 14 can be used even when various processes such as a resist stripping process are performed in the manufacturing process of the substrate 11. It is protected from chemicals such as stripping solution used in processing and heat from high temperature environment. Therefore, even when a desired treatment is performed on the stacked body 10, the separation layer 14 is protected, so that the substrate 11 can be prevented from peeling off.

〔substrate〕
The substrate 11 is subjected to processes such as thinning and mounting while being supported by the support plate 12. In the present embodiment, the substrate 11 is a wafer, but the substrate included in the laminate according to the present invention is not limited to a wafer, and any substrate such as a thin film substrate or a flexible substrate can be employed. Further, a fine structure of an electronic element such as an electric circuit may be formed on the surface of the substrate 11 on the adhesive layer 13 side.

[Support plate]
The support plate 12 is a support body that supports the substrate 11 and has optical transparency. Therefore, when light is irradiated from the outside of the laminated body 10 toward the support plate 12, the light passes through the support plate 12 and reaches the separation layer 14. Further, the support plate 12 does not necessarily need to transmit all the light, and it is sufficient if the support plate 12 can transmit the light to be absorbed by the separation layer 14 (having a predetermined wavelength).

  The support plate 12 supports the substrate 11 and may have a strength necessary for preventing the substrate 11 from being damaged or deformed during processes such as thinning, transporting, and mounting of the substrate 11. From the above viewpoint, examples of the support plate 12 include those made of glass, silicon, and acrylic resin.

(Separation layer)
The separation layer 14 is a layer formed of a material that changes quality by absorbing light irradiated through the support plate 12. In the present specification, the “deterioration” of the separation layer 14 is a phenomenon in which the separation layer 14 can be broken by receiving a slight external force, or a state in which the adhesive force with the layer in contact with the separation layer 14 is reduced. means. As a result of the alteration of the separation layer 14 caused by absorbing light, the separation layer 14 loses its strength or adhesion prior to receiving light irradiation. Therefore, by applying a slight external force (for example, lifting the support plate 12), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

  Further, the alteration of the separation layer 14 includes decomposition (exothermic or non-exothermic), cross-linking, configuration change or dissociation of functional groups (and curing of the separation layer accompanying these, degassing). , Contraction or expansion) and the like. The alteration of the separation layer 14 occurs as a result of light absorption by the material constituting the separation layer 14. Therefore, the type of alteration of the separation layer 14 can be changed according to the type of material constituting the separation layer 14.

  The separation layer 14 is provided on the surface of the support plate 12 on the side where the substrate 11 is bonded via the adhesive layer 13. That is, the separation layer 14 is provided between the support plate 12 and the adhesive layer 13.

  The thickness of the separation layer 14 is more preferably, for example, 0.05 to 50 μm, and further preferably 0.3 to 1 μm. If the thickness of the separation layer 14 is within the range of 0.05 to 50 μm, desired alteration can be caused in the separation layer 14 by short-time light irradiation and low-energy light irradiation. The thickness of the separation layer 14 is particularly preferably within a range of 1 μm or less from the viewpoint of productivity.

  In the laminate 10, another layer may be further formed between the separation layer 14 and the support plate 12. In this case, the other layer should just be comprised from the material which permeate | transmits light. Accordingly, a layer imparting preferable properties to the stacked body 10 can be appropriately added without hindering the incidence of light on the separation layer 14. The wavelength of light that can be used varies depending on the type of material constituting the separation layer 14. Therefore, the material constituting the other layer does not need to transmit all light, and can be appropriately selected from materials capable of transmitting light having a wavelength that can alter the material constituting the separation layer 14.

  In addition, the separation layer 14 is preferably formed only from a material having a structure that absorbs light, but the material does not have a structure that absorbs light as long as the essential characteristics in the present invention are not impaired. May be added to form the separation layer 14. Further, it is preferable that the surface of the separation layer 14 on the side facing the adhesive layer 13 is flat (unevenness is not formed), whereby the separation layer 14 can be easily formed, and even when pasted. It becomes possible to paste on.

  As the separation layer 14, a material that forms the separation layer 14 as described below may be used by bonding it to the support plate 12 in advance, or the separation layer 14 may be formed on the support plate 12. You may use what applied the material and solidified in the film form. The method of applying the material constituting the separation layer 14 on the support plate 12 is appropriately selected from conventionally known methods such as chemical vapor deposition (CVD) deposition according to the type of material constituting the separation layer 14. can do.

The separation layer 14 may be altered by absorbing light irradiated from the laser. That is, the light applied to the separation layer 14 to alter the separation layer 14 may be light emitted from a laser. Examples of lasers that emit light to irradiate the separation layer 14 include YAG lasers, Libby lasers, glass lasers, YVO ₄ lasers, LD lasers, liquid lasers such as fiber lasers, liquid lasers such as dye lasers, CO ₂ lasers, and excimers. Examples thereof include gas lasers such as lasers, Ar lasers, and He—Ne lasers, laser beams such as semiconductor lasers and free electron lasers, and non-laser beams. The laser that emits light to irradiate the separation layer 14 can be appropriately selected according to the material constituting the separation layer 14 and irradiates light having a wavelength that can alter the material constituting the separation layer 14. The laser to be selected may be selected.

(Polymer containing light absorbing structure in its repeating unit)
The separation layer 14 may contain a polymer containing a light-absorbing structure in its repeating unit. The polymer is altered by irradiation with light. The alteration of the polymer occurs when the structure absorbs the irradiated light. The separation layer 14 loses its strength or adhesiveness before being irradiated with light as a result of the alteration of the polymer. Therefore, by applying a slight external force (for example, lifting the support plate 12), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

  The structure having light absorption is a chemical structure that absorbs light and alters the polymer containing the structure as a repeating unit. The structure is an atomic group including a conjugated π electron system composed of, for example, a substituted or unsubstituted benzene ring, condensed ring, or heterocyclic ring. More specifically, the structure may be a cardo structure or a benzophenone structure, diphenyl sulfoxide structure, diphenyl sulfone structure (bisphenyl sulfone structure), diphenyl structure or diphenylamine structure present in the side chain of the polymer.

  When the structure is present in the side chain of the polymer, the structure can be represented by the following formula:

式中、Ｒはそれぞれ独立して、アルキル基、アリール基、ハロゲン、水酸基、ケトン基、スルホキシド基、スルホン基又はＮ（Ｒ_１）（Ｒ_２）であり（ここで、Ｒ_１及びＲ_２はそれぞれ独立して、水素原子又は炭素数１〜５のアルキル基である）、Ｚは、存在しないか、又は−ＣＯ−、−ＳＯ_２−、−ＳＯ−もしくは−ＮＨ−であり、ｎは０又は１〜５の整数である。

In the formula, each R is independently an alkyl group, aryl group, halogen, hydroxyl group, ketone group, sulfoxide group, sulfone group, or N (R ₁ ) (R ₂ ) (where R ₁ and R ₂ are Each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), Z is absent or —CO—, —SO ₂ —, —SO— or —NH—, and n is 0 Or it is an integer of 1-5.

  In addition, the polymer includes, for example, a repeating unit represented by any one of (a) to (d) among the following formulas, represented by (e), or represented by (f) Contains structure in its main chain.

式中、ｌは１以上の整数であり、ｍは０又は１〜２の整数であり、Ｘは、（ａ）〜（ｅ）において上記の“化１”に示した式のいずれかであり、（ｆ）において上記の“化１”に示した式のいずれかであるか、又は存在せず、Ｙ_１及びＹ_２はそれぞれ独立して、−ＣＯ−又は−ＳＯ_２−である。ｌは好ましくは１０以下の整数である。

In the formula, l is an integer of 1 or more, m is 0 or an integer of 1 to 2, and X is any one of the formulas shown in the above “Chemical Formula 1” in (a) to (e). , (F) is any one of the formulas shown in the above “Chemical Formula 1” or does not exist, and Y ₁ and Y ₂ are each independently —CO— or —SO ₂ —. l is preferably an integer of 10 or less.

  Examples of the benzene ring, condensed ring and heterocyclic ring shown in the above “chemical formula 1” include phenyl, substituted phenyl, benzyl, substituted benzyl, naphthalene, substituted naphthalene, anthracene, substituted anthracene, anthraquinone, substituted anthraquinone, acridine, substituted Examples include acridine, azobenzene, substituted azobenzene, fluoride, substituted fluoride, fluoride, substituted fluoride, carbazole, substituted carbazole, N-alkylcarbazole, dibenzofuran, substituted dibenzofuran, phenanthrene, substituted phenanthrene, pyrene, and substituted pyrene. When the exemplified substituent has a substituent, the substituent is, for example, alkyl, aryl, halogen atom, alkoxy, nitro, aldehyde, cyano, amide, dialkylamino, sulfonamide, imide, carboxylic acid, carboxylic acid Selected from esters, sulfonic acids, sulfonate esters, alkylaminos and arylaminos.

Of the substituents represented by “Chemical Formula 1” above, as an example of the fifth substituent having two phenyl groups and Z being —SO ₂ —, bis (2, 4-dihydroxyphenyl) sulfone, bis (3,4-dihydroxyphenyl) sulfone, bis (3,5-dihydroxyphenyl) sulfone, bis (3,6-dihydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis (3-hydroxyphenyl) sulfone, bis (2-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone and the like can be mentioned.

  Of the substituents represented by “Chemical Formula 1” above, as an example of the fifth substituent having two phenyl groups and Z being —SO—, bis (2,3 -Dihydroxyphenyl) sulfoxide, bis (5-chloro-2,3-dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxyphenyl) sulfoxide, bis (2,4-dihydroxy-6-methylphenyl) sulfoxide, bis (5 -Chloro-2,4-dihydroxyphenyl) sulfoxide, bis (2,5-dihydroxyphenyl) sulfoxide, bis (3,4-dihydroxyphenyl) sulfoxide, bis (3,5-dihydroxyphenyl) sulfoxide, bis (2,3 , 4-Trihydroxyphenyl) sulfoxide, bis (2,3,4-trihydroxy-6-methylpheny ) -Sulfoxide, bis (5-chloro-2,3,4-trihydroxyphenyl) sulfoxide, bis (2,4,6-trihydroxyphenyl) sulfoxide, bis (5-chloro-2,4,6-trihydroxy) Phenyl) sulfoxide and the like.

  Among the substituents represented by the above “Chemical Formula 1”, the fifth substituent having two phenyl groups and Z is —C (═O) — , 4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 5,6'-tetrahydroxybenzophenone, 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,6-dihydroxy-4-methoxybenzophenone, 2,2 ' -Dihydroxy-4,4'-dimethoxybenzophenone, 4-amino-2'-hydroxybenzophenone, 4-dimethyl Ruamino-2'-hydroxybenzophenone, 4-diethylamino-2'-hydroxybenzophenone, 4-dimethylamino-4'-methoxy-2'-hydroxybenzophenone, 4-dimethylamino-2 ', 4'-dihydroxybenzophenone, and 4 -Dimethylamino-3 ', 4'-dihydroxybenzophenone and the like.

  When the structure is present in the side chain of the polymer, the proportion of the repeating unit containing the structure in the polymer is such that the light transmittance of the separation layer 14 is 0.001 to 10%. It is in the range. If the polymer is prepared so that the ratio falls within such a range, the separation layer 14 can sufficiently absorb light and can be surely and rapidly altered. That is, it is easy to remove the support plate 12 from the stacked body 10, and the irradiation time of light necessary for the removal can be shortened.

  The said structure can absorb the light which has a wavelength of a desired range by selection of the kind. For example, the wavelength of light that can be absorbed by the above structure is more preferably 100 to 2000 nm. Within this range, the wavelength of light that can be absorbed by the structure is on the shorter wavelength side, for example, 100 to 500 nm. For example, the structure can alter the polymer containing the structure by absorbing ultraviolet light, preferably having a wavelength of about 300-370 nm.

The light that can be absorbed by the above structure is, for example, a high-pressure mercury lamp (wavelength: 254 nm to 436 nm), a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), an F ₂ excimer laser (wavelength: 157 nm), Light emitted from XeCl laser (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) ) Etc.

  Although the separation layer 14 described above contains a polymer containing the above structure as a repeating unit, the separation layer 14 may further contain a component other than the polymer. Examples of the component include a filler, a plasticizer, and a component that can improve the peelability of the support plate 12. These components are appropriately selected from conventionally known substances or materials that do not hinder or promote the absorption of light by the above structure and the alteration of the polymer.

(Inorganic)
The separation layer 14 may be made of an inorganic material. The separation layer 14 is composed of an inorganic substance, and is thereby altered by absorbing light. As a result, the separation layer 14 loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support plate 12), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

The said inorganic substance should just be the structure which changes in quality by absorbing light, for example, 1 or more types of inorganic substances selected from the group which consists of a metal, a metal compound, and carbon can be used conveniently. The metal compound refers to a compound containing a metal atom, and can be, for example, a metal oxide or a metal nitride. Examples of such inorganic materials include, but are not limited to, gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO ₂ , SiN, Si ₃ N ₄ , TiN, and carbon. One or more inorganic substances selected from the group consisting of: Carbon is a concept that may include an allotrope of carbon, for example, diamond, fullerene, diamond-like carbon, carbon nanotube, and the like.

  The inorganic material absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength within a range that the inorganic material used for the separation layer 14 absorbs, the inorganic material can be suitably altered.

The light applied to the separation layer 14 made of an inorganic material may be, for example, a solid-state laser such as a YAG laser, Libby laser, glass laser, YVO ₄ laser, LD laser, or fiber laser, or a dye laser depending on the wavelength that the inorganic material can absorb. For example, a liquid laser such as a CO ₂ laser, an excimer laser, an Ar laser, a He—Ne laser, or a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be used as appropriate.

  The separation layer 14 made of an inorganic material can be formed on the support plate 12 by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, or spin coating. The thickness of the separation layer 14 made of an inorganic material is not particularly limited as long as it is a film thickness that can sufficiently absorb the light to be used. For example, a film thickness of 0.05 to 10 μm is more preferable. Alternatively, an adhesive may be applied in advance to both surfaces or one surface of an inorganic film (for example, a metal film) made of an inorganic material constituting the separation layer 14 and attached to the support plate 12 and the substrate 11.

  When a metal film is used as the separation layer 14, laser reflection or charging of the film may occur depending on conditions such as the film quality of the separation layer 14, the type of laser light source, and laser output. Therefore, it is preferable to take such measures by providing an antireflection film or an antistatic film on the upper and lower sides of the separation layer 14 or one of them.

(Compound having infrared absorbing structure)
The separation layer 14 may be formed of a compound having an infrared absorbing structure. The compound is altered by absorbing infrared rays. The separation layer 14 has lost its strength or adhesiveness before being irradiated with infrared rays as a result of the alteration of the compound. Therefore, by applying a slight external force (for example, lifting the support plate), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

Examples of the compound having an infrared absorptive structure or a compound having an infrared absorptive structure include alkanes, alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulene, ring Formula), alkyne (monosubstituted, disubstituted), monocyclic aromatic (benzene, monosubstituted, disubstituted, trisubstituted), alcohol and phenols (free OH, intramolecular hydrogen bond, intermolecular hydrogen bond, saturated Secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane ether, peroxide ether, ketone, dialkylcarbonyl, aromatic Carbonyl, enol of 1,3-diketone, o-hydroxy aryl ketone, dialkyl aldehyde, aromatic aldehyde, carboxylic acid (dimer, Bonic acid anion), formic acid ester, acetic acid ester, conjugated ester, non-conjugated ester, aromatic ester, lactone (β-, γ-, δ-), aliphatic acid chloride, aromatic acid chloride, acid anhydride ( Conjugated, non-conjugated, cyclic, acyclic), primary amide, secondary amide, lactam, primary amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic), secondary Tertiary amine (aliphatic, aromatic), primary amine salt, secondary amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide, aliphatic isonitrile, aromatic isonitrile, Isocyanate ester, thiocyanate ester, aliphatic isothiocyanate ester, aromatic isothiocyanate ester, aliphatic nitro compound, aromatic nitro compound, nitroamine, nitrosamine, nitric acid Steal, nitrite, nitroso bond (aliphatic, aromatic, monomer, dimer), sulfur compounds such as mercaptan and thiophenol and thiolic acid, thiocarbonyl group, sulfoxide, sulfone, sulfonyl chloride, primary Sulfonamide, secondary sulfonamide, sulfate ester, 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 bonds.

As a structure containing halogen bond, for _{example, -CH 2 Cl, -CH 2 Br} , -CH 2 I, -CF 2 - - the _{carbon, - CF 3, -CH = CF} 2, -CF = CF 2, fluoride Aryl chloride, and aryl chloride.

Examples of the structure including the Si—A ¹ bond include 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 the like SiF _3. As a structure including a Si—A ¹ bond, a siloxane skeleton and a silsesquioxane skeleton are particularly preferably formed.

Examples of the structure containing the P—A ² bond include PH, PH ₂ , P—CH ₃ , P—CH ₂ —, P—C ₆ H ₅ , A ³ ₃ —PO— (A ³ is aliphatic or aromatic. _{^{family), (A 4 O) 3}} -P-O (A 4 _{alkyl), P-OCH 3, P} -OCH 2 CH 3, P-OC 6 H 5, P-O-P, P-OH, and O = P-OH and the like can be mentioned.

  The said structure can absorb the infrared rays which have the wavelength of a desired range by selection of the kind. Specifically, the wavelength of infrared rays that can be absorbed by the above structure is, for example, in the range of 1 μm to 20 μm, and more preferably in the range of 2 μm to 15 μm. Further, when the structure is a Si—O bond, a Si—C bond, and a Ti—O bond, it can be in the range of 9 μm to 11 μm. In addition, those skilled in the art can easily understand the infrared wavelength that can be absorbed by each structure. For example, as an absorption band in each structure, Non-Patent Document: SILVERSTEIN / BASSLER / MORRILL, “Identification method by spectrum of organic compound (5th edition) —Combination of MS, IR, NMR and UV” (published in 1992) The description on page 146 to page 151 can be referred to.

  As a compound having an infrared-absorbing structure used for forming the separation layer 14, among the compounds having the structure as described above, it can be dissolved in a solvent for coating and solidified to form a solid layer. As long as it is possible, there is no particular limitation. However, in order to effectively alter the compound in the separation layer 14 and facilitate separation of the support plate 12 and the substrate 11, the absorption of infrared rays in the separation layer 14 is large, that is, the separation layer 14 is irradiated with infrared rays. It is preferable that the infrared transmittance is low. Specifically, the infrared transmittance in the separation layer 14 is preferably lower than 90%, and the infrared transmittance is more preferably lower than 80%.

  For example, as the compound having a siloxane skeleton, for example, a resin that is a copolymer of a repeating unit represented by the following chemical formula (1) and a repeating unit represented by the following chemical formula (2), or A resin that is a copolymer of a repeating unit represented by the following chemical formula (1) and a repeating unit derived from an acrylic compound can be used.

（化学式（２）中、Ｒ_１は、水素、炭素数１０以下のアルキル基、炭素数１０以下のアルコキシ基である）
中でも、シロキサン骨格を有する化合物としては、上記化学式（１）で表される繰り返し単位及び下記化学式（３）で表される繰り返し単位の共重合体であるｔｅｒｔ−ブチルスチレン（ＴＢＳＴ）−ジメチルシロキサン共重合体がより好ましく、上記式（１）で表される繰り返し単位及び下記化学式（３）で表される繰り返し単位を１：１で含む、ＴＢＳＴ−ジメチルシロキサン共重合体がさらに好ましい。

(In the chemical formula (2), R ₁ is hydrogen, an alkyl group having 10 or less carbon atoms, or an alkoxy group having 10 or less carbon atoms)
Among them, as a compound having a siloxane skeleton, a copolymer of tert-butylstyrene (TBST) -dimethylsiloxane which is a copolymer of a repeating unit represented by the above chemical formula (1) and a repeating unit represented by the following chemical formula (3). A polymer is more preferable, and a TBST-dimethylsiloxane copolymer containing a repeating unit represented by the above formula (1) and a repeating unit represented by the following chemical formula (3) in a ratio of 1: 1 is further preferable.

また、シルセスキオキサン骨格を有する化合物としては、例えば、下記化学式（４）で表される繰り返し単位及び下記化学式（５）で表される繰り返し単位の共重合体である樹脂を用いることができる。

Moreover, as the compound having a silsesquioxane skeleton, for example, a resin that is a copolymer of a repeating unit represented by the following chemical formula (4) and a repeating unit represented by the following chemical formula (5) can be used. .

（化学式（４）中、Ｒ_２は、水素又は炭素数１以上、１０以下のアルキル基であり、化学式（５）中、Ｒ_３は、炭素数１以上、１０以下のアルキル基、又はフェニル基である）
シルセスキオキサン骨格を有する化合物としては、このほかにも、特許文献３：特開２００７−２５８６６３号公報（２００７年１０月４日公開）、特許文献４：特開２０１０−１２０９０１号公報（２０１０年６月３日公開）、特許文献５：特開２００９−２６３３１６号公報（２００９年１１月１２日公開）及び特許文献６：特開２００９−２６３５９６号公報（２００９年１１月１２日公開）において開示されている各シルセスキオキサン樹脂を好適に利用できる。

(In chemical formula (4), R ₂ is hydrogen or an alkyl group having 1 to 10 carbon atoms, and in chemical formula (5), R ₃ is an alkyl group having 1 to 10 carbon atoms, or a phenyl group. Is)
Other compounds having a silsesquioxane skeleton include Patent Document 3: Japanese Patent Laid-Open No. 2007-258663 (published on October 4, 2007), Patent Document 4: Japanese Patent Laid-Open No. 2010-120901 (2010). Published on June 3, 2009), Patent Document 5: JP 2009-263316 A (published on November 12, 2009) and Patent Document 6: JP 2009-263596 A (published on November 12, 2009). Each disclosed silsesquioxane resin can be suitably used.

  Among them, as the compound having a silsesquioxane skeleton, a repeating unit represented by the following chemical formula (6) and a copolymer of a repeating unit represented by the following chemical formula (7) are more preferable. More preferably, the copolymer contains a repeating unit represented by the following chemical formula (7) and a repeating unit represented by the following chemical formula (7) at 7: 3.

シルセスキオキサン骨格を有する重合体としては、ランダム構造、ラダー構造、及び籠型構造があり得るが、何れの構造であってもよい。

The polymer having a silsesquioxane skeleton may have a random structure, a ladder structure, and a cage structure, and any structure may be used.

Examples of the compound containing a Ti-O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, and titanium-i-propoxyoctylene glycolate. alkoxy titanium such as, (ii) di -i- propoxy bis (acetylacetonato) titanium, and propane di oxytitanium bis (ethylacetoacetate) chelate titanium such _{as, (iii) i-C 3} H 7 O - [- _{Ti (O-i-C 3} H 7) 2 -O-] n -i-C 3 H 7, and _{n-C 4 H 9 O -} [- Ti (O-n-C 4 H 9) 2 -O - _titanium polymers such as _{n -n-C 4 H 9,} (iv) tri -n- butoxy titanium monostearate, titanium stearate, di -i- Puropokishichi Diisostearate, acylate titanium such as (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium, (v) water-soluble titanium compounds such as di-n-butoxy-bis (triethanolaminato) titanium, etc. Can be mentioned.

Among them, as a compound containing a Ti—O bond, di-n-butoxy bis (triethanolaminato) titanium (Ti (OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N (C ₂ H ₄ OH) ₂ ] ₂ ) is preferred.

  Although the separation layer 14 described above contains a compound having an infrared absorbing structure, the separation layer 14 may further contain a component other than the above compound. Examples of the component include a filler, a plasticizer, and a component that can improve the peelability of the support plate 12. These components are appropriately selected from conventionally known substances or materials that do not interfere with or promote infrared absorption by the above structure and alteration of the compound.

(Fluorocarbon)
The separation layer 14 may be made of a fluorocarbon. Since the separation layer 14 is composed of fluorocarbon, the separation layer 14 is altered by absorbing light. As a result, the separation layer 14 loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support plate 12), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

From one viewpoint, the fluorocarbon constituting the separation layer 14 can be suitably formed by a plasma CVD method. In addition, fluorocarbon includes C _x F _y (perfluorocarbon) and C _x H _y F _z (x, y, and z are integers), but is not limited to these, for example, CHF ₃ , CH ₂ F ₂ , C ₂ It can be H ₂ F ₂ , C ₄ F ₈ , C ₂ F ₆ , C ₅ F ₈ or the like. Further, an inert gas such as nitrogen, helium, and argon, a hydrocarbon such as alkane and alkene, and oxygen, carbon dioxide, and hydrogen are added to the fluorocarbon used for constituting the separation layer 14 as necessary. May be. Further, a mixture of these gases may be used (a mixed gas of fluorocarbon, hydrogen, nitrogen, etc.). Further, the separation layer 14 may be composed of a single type of fluorocarbon, or may be composed of two or more types of fluorocarbon.

  The fluorocarbon absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength within a range that is absorbed by the fluorocarbon used in the separation layer 14, the fluorocarbon can be suitably altered. The light absorption rate in the separation layer 14 is preferably 80% or more.

As light to irradiate the separation layer 14, for example, a liquid laser such as a solid laser such as a YAG laser, Libby laser, glass laser, YVO ₄ laser, LD laser, or fiber laser, or a dye laser, depending on the wavelength that can be absorbed by the fluorocarbon. A gas laser such as a CO ₂ laser, an excimer laser, an Ar laser, or a He—Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be used as appropriate. The wavelength at which the fluorocarbon can be altered is not limited to this, but for example, a wavelength in the range of 600 nm or less can be used.

(Infrared absorbing material)
The separation layer 14 may contain an infrared absorbing material. The separation layer 14 is configured to contain an infrared absorbing material, so that the separation layer 14 is altered by absorbing light. As a result, the strength or adhesiveness before receiving the light irradiation is lost. Therefore, by applying a slight external force (for example, lifting the support plate 12), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

  The infrared absorbing material only needs to have a structure that is altered by absorbing infrared rays. For example, carbon black, iron particles, or aluminum particles can be suitably used. The infrared absorbing material absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer 14 with light having a wavelength in a range that is absorbed by the infrared absorbing material used for the separation layer 14, the infrared absorbing material can be suitably altered.

[Adhesive layer]
The adhesive layer 13 is configured to cover and protect the surface of the substrate 11 at the same time as the substrate 11 is adhesively fixed to the support plate 12. Therefore, the adhesive layer needs to have adhesiveness and strength for maintaining the fixing of the substrate 11 to the support plate 12 and the covering of the surface to be protected of the substrate 11 when the substrate 11 is processed or transported. . On the other hand, when it becomes unnecessary to fix the substrate 11 to the support plate 12, it needs to be easily peeled or removed from the substrate 11.

  Therefore, the adhesive layer 13 usually has strong adhesiveness, and the adhesive layer 13 is constituted by an adhesive whose adhesiveness is reduced by some treatment or has solubility in a specific solvent. The thickness of the adhesive layer 13 is more preferably, for example, 1 to 200 μm, and further preferably 10 to 150 μm. The adhesive layer 13 can be formed by applying an adhesive material as described below onto the substrate 11 by a conventionally known method such as spin coating.

  As the adhesive, for example, various adhesives known in the art such as acrylic, novolak, naphthoxan, hydrocarbon, and polyimide can be used as the adhesive constituting the adhesive layer 13 according to the present invention. is there. Below, the composition of resin which the contact bonding layer 13 in this Embodiment contains is demonstrated.

  The resin contained in the adhesive layer 13 is not particularly limited as long as it has adhesiveness, and examples thereof include hydrocarbon resins, acrylic-styrene resins, maleimide resins, and combinations thereof.

(Hydrocarbon resin)
The hydrocarbon resin is a resin that has a hydrocarbon skeleton and is obtained by polymerizing a monomer composition. As the hydrocarbon resin, cycloolefin polymer (hereinafter sometimes referred to as “resin (A)”), and at least one resin selected from the group consisting of terpene resin, rosin resin and petroleum resin (hereinafter referred to as “resin (A)”). Resin (B) ”), and the like, but is not limited thereto.

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

  Examples of the cycloolefin monomer contained in the monomer component constituting the resin (A) include bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and dihydroxypentadiene, and tetracyclododecene. Tetracycles, pentacycles such as cyclopentadiene trimer, heptacycles such as tetracyclopentadiene, or polycyclic alkyl (methyl, ethyl, propyl, butyl, etc.) substituted alkenyls (vinyl, etc.) Examples include substituted, alkylidene (such as ethylidene) substituted, aryl (such as phenyl, tolyl, naphthyl) substituted, and the like. Among these, norbornene-based monomers selected from the group consisting of norbornene, tetracyclododecene, and alkyl-substituted products thereof are particularly preferable.

  The monomer component constituting the resin (A) may contain another monomer copolymerizable with the above-described cycloolefin-based monomer, and preferably contains, for example, an alkene monomer. Examples of the alkene monomer include ethylene, propylene, 1-butene, isobutene, 1-hexene, and α-olefin. The alkene monomer may be linear or branched.

  Moreover, it is preferable from a viewpoint of high heat resistance (low thermal decomposition and thermal weight reduction property) to contain a cycloolefin monomer as a monomer component which comprises resin (A). The ratio of the cycloolefin monomer to the whole monomer component constituting the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more. preferable. Further, the ratio of the cycloolefin monomer to the whole monomer component constituting the resin (A) is not particularly limited, but is preferably 80 mol% or less from the viewpoint of solubility and stability over time in a solution, More preferably, it is 70 mol% or less.

  Moreover, you may contain a linear or branched alkene monomer as a monomer component which comprises resin (A). The ratio of the alkene monomer to the whole monomer component constituting the resin (A) is preferably 10 to 90 mol%, more preferably 20 to 85 mol% from the viewpoint of solubility and flexibility. 30 to 80 mol% is more preferable.

  The resin (A) is a resin having no polar group, such as a resin obtained by polymerizing a monomer component composed of a cycloolefin monomer and an alkene monomer, at high temperatures. It is preferable for suppressing generation of gas.

  The polymerization method and polymerization conditions for polymerizing the monomer components are not particularly limited and may be appropriately set according to a conventional method.

  Examples of commercially available products that can be used as the resin (A) include “TOPAS” manufactured by Polyplastics, “APEL” manufactured by Mitsui Chemicals, “ZEONOR” and “ZEONEX” manufactured by Nippon Zeon, and JSR “ARTON” made by the manufacturer can be mentioned.

  The glass transition point (Tg) of the resin (A) is preferably 60 ° C. or higher, and particularly preferably 70 ° C. or higher. When the glass transition point of the resin (A) is 60 ° C. or higher, softening of the adhesive layer can be further suppressed when the adhesive laminate is exposed to a high temperature environment.

  The resin (B) is at least one resin selected from the group consisting of terpene resins, rosin resins and petroleum resins. Specifically, examples of the terpene resin include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, hydrogenated terpene phenol resins, and the like. Examples of the rosin resin include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and modified rosin. Examples of petroleum resins include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, coumarone-indene petroleum resins, and the like. Among these, hydrogenated terpene resins and hydrogenated petroleum resins are more preferable.

  Although the softening point of resin (B) is not specifically limited, It is preferable that it is 80-160 degreeC. When the softening point of the resin (B) is 80 ° C. or higher, the adhesive laminate can be suppressed from being softened when exposed to a high temperature environment, and adhesion failure does not occur. On the other hand, when the softening point of the resin (B) is 160 ° C. or lower, the peeling rate when peeling the adhesive laminate is good.

  Although the molecular weight of resin (B) is not specifically limited, It is preferable that it is 300-3000. When the molecular weight of the resin (B) is 300 or more, the heat resistance is sufficient, and the degassing amount is reduced under a high temperature environment. On the other hand, when the molecular weight of the resin (B) is 3000 or less, the peeling rate when peeling the adhesive laminate is good. In addition, the molecular weight of resin (B) in this embodiment means the molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

  In addition, you may use what mixed resin (A) and resin (B) as resin. By mixing, heat resistance and peeling speed are improved. For example, the mixing ratio of the resin (A) and the resin (B) is (A) :( B) = 80: 20 to 55:45 (mass ratio). Since it is excellent in tolerance and flexibility, it is preferable.

(Block copolymer)
The block copolymer that can constitute the adhesive layer included in the laminate according to the present invention is a polymer in which two or more block sites in which monomer units are continuously bonded are bonded, and may be referred to as a block copolymer.

  Various block copolymers can be used as the block copolymer. For example, styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene. Styrene block copolymer (SBBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene-propylene -Styrene block copolymer (SEEPS) etc. can be used.

  At least one functional group-containing atomic group may be bonded to the block copolymer that can constitute the adhesive layer included in the laminate according to the present invention. Such a block copolymer can be obtained, for example, by bonding at least one functional group-containing atomic group to a known block copolymer using a modifier.

  The functional group-containing atomic group is an atomic group containing one or more functional groups. Examples of the functional group contained in the functional group-containing atomic group in the present invention include an amino group, an acid anhydride group (preferably a maleic anhydride group), an imide group, a urethane group, an epoxy group, an imino group, a hydroxyl group, a carboxyl group, Examples include silanol groups and alkoxysilane groups (the alkoxy groups preferably have 1 to 6 carbon atoms). In the present invention, the block copolymer is an elastomer and has a functional group that brings about polarity. In this invention, the softness | flexibility and adhesiveness of an adhesive composition improve by containing the block copolymer which has an at least 1 functional group containing atomic group.

  The block copolymer is preferably a diblock copolymer or a triblock copolymer, and more preferably a triblock copolymer. A diblock copolymer and a triblock copolymer may be used in combination. Thereby, the loss count (tanσ) at 220 ° C. of the adhesive layer formed using the adhesive composition can be set to an optimal value of 1.1 or less.

  The block copolymer preferably contains a styrene group, and more preferably both ends of the main chain are styrene groups. This is because styrene having high thermal stability is blocked at both ends, thereby exhibiting higher heat resistance.

  The styrene group content of the block copolymer is preferably 10% by weight or more and 65% by weight or less, and more preferably 13% by weight or more and 45% by weight or less. Thereby, the Young's modulus at 23 degreeC of the contact bonding layer formed using the adhesive composition can be made into the optimal value of 0.1 GPa or more.

Furthermore, the weight average molecular weight of the block copolymer is preferably 50,000 or more and 150,000 or less, and more preferably 60,000 or more and 120,000 or less. Thereby, the storage elastic modulus (G ') at 220 degreeC of the contact bonding layer formed using the adhesive composition can be made into the optimal value of 1 * 10 < ⁵ > Pa or less.

  Further, if the styrene group content of the block copolymer is 13% by weight or more and 50% by weight or less, and the weight average molecular weight of the block copolymer is 50,000 or more and 150,000 or less, the hydrocarbon solvent It is more preferable because of its excellent solubility in water. Thereby, when removing the contact bonding layer formed with this adhesive composition, it can remove easily and rapidly using a hydrocarbon-type solvent.

  Furthermore, the block copolymer is more preferably a hydrogenated product. If it is a hydrogenated product, the stability to heat is further improved, and degradation such as decomposition and polymerization hardly occurs. Moreover, it is more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents.

  Moreover, it is preferable that the block copolymer contains the unit whose glass transition point is 23 degrees C or less. When the block copolymer contains units having a glass transition point of 23 ° C. or lower, the Young's modulus at 23 ° C. of the adhesive layer formed using the adhesive composition is set to an optimal value of 0.1 GPa or higher. can do.

  A plurality of types of block copolymers may be mixed. That is, the adhesive composition according to the present invention may include a plurality of types of block copolymers. It is preferable that at least one of the plurality of types of block copolymers contains a styrene group. Furthermore, if at least one of the plurality of types of block copolymers has a styrene group content in the range of 10 wt% or more and 65 wt% or less, at least one of the plurality of types of block copolymers. If the weight average molecular weight in the range is 50,000 or more and 150,000 or less, it is within the scope of the present invention. Moreover, in the adhesive composition which concerns on this invention, when several types of block copolymers are included, as a result of mixing, you may adjust so that content of a styrene group may become said range.

(Acrylic-styrene resin)
Examples of the acrylic-styrene resin include a resin obtained by polymerization using styrene or a styrene derivative and (meth) acrylic acid ester as monomers.

  Examples of the (meth) acrylic acid ester include a (meth) acrylic acid alkyl ester having a chain structure, a (meth) acrylic acid ester having an aliphatic ring, and a (meth) acrylic acid ester having an aromatic ring. . Examples of the (meth) acrylic acid alkyl ester having a chain structure include an acrylic long-chain alkyl ester having an alkyl group having 15 to 20 carbon atoms and an acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms. . As acrylic long-chain alkyl esters, acrylic or methacrylic acid whose alkyl group is n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. Examples include alkyl esters. The alkyl group may be branched.

  Examples of the acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms include known acrylic alkyl esters used in existing acrylic adhesives. For example, an alkyl group of acrylic acid or methacrylic acid in which the alkyl group is a methyl group, ethyl group, propyl group, butyl group, 2-ethylhexyl group, isooctyl group, isononyl group, isodecyl group, dodecyl group, lauryl group, tridecyl group, etc. Examples include esters.

  Examples of (meth) acrylic acid ester having an aliphatic ring include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl. (Meth) acrylate, tetracyclododecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate and the like can be mentioned, and isobornyl methacrylate and dicyclopentanyl (meth) acrylate are more preferable.

  The (meth) acrylic acid ester having an aromatic ring is not particularly limited. Examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, and an anthracenyl group. A phenoxymethyl group, a phenoxyethyl group, and the like. The aromatic ring may have a chain or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferable.

(Maleimide resin)
Examples of maleimide resins include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec as monomers. -Butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, etc. Males having an aliphatic hydrocarbon group such as maleimide having an alkyl group, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide Resin obtained by polymerizing aromatic maleimide having an aryl group such as imide, N-phenylmaleimide, Nm-methylphenylmaleimide, N-o-methylphenylmaleimide, Np-methylphenylmaleimide, etc. It is done.

  For example, a cycloolefin copolymer which is a copolymer of a repeating unit represented by the following chemical formula (8) and a repeating unit represented by the following chemical formula (9) can be used as the resin of the adhesive component.

（化学式（９）中、ｎは０又は１〜３の整数である）
このようなシクロオレフィンコポリマーとしては、ＡＰＬ ８００８Ｔ、ＡＰＬ ８００９Ｔ、及びＡＰＬ ６０１３Ｔ（全て三井化学社製）などを使用できる。

(In the chemical formula (9), n is 0 or an integer of 1 to 3)
As such cycloolefin copolymer, APL 8008T, APL 8009T, APL 6013T (all manufactured by Mitsui Chemicals, Inc.) and the like can be used.

  Note that the adhesive layer 13 is preferably formed using a resin other than a photocurable resin (for example, a UV curable resin). This is because the photocurable resin may remain as a residue around the minute irregularities of the substrate 11 after the adhesive layer 13 is peeled or removed. In particular, an adhesive that dissolves in a specific solvent is preferable as a material constituting the adhesive layer 13. This is because the adhesive layer 13 can be removed by dissolving it in a solvent without applying physical force to the substrate 11. Even when the adhesive layer 13 is removed, the adhesive layer 13 can be easily removed without damaging or deforming the substrate 11 even from the substrate 11 having a reduced strength.

  As a diluting solvent for forming the separation layer and the adhesive layer described above, for example, hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, tridecane and the like linear hydrocarbons, carbon number 3 to 15 Branched hydrocarbons of the following: p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpin, bornane, norbornane, pinane, tsujang, kalan, longifolene, geraniol, nerol, Linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, Borneo Terpene solvents such as ru, carvone, ionone, thuyon, camphor, d-limonene, l-limonene, dipentene; lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl Ketones such as isopentyl ketone and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetate Compounds having an ester bond such as monomethyl ether, monoethyl ether, monopropyl of the polyhydric alcohols or the compound having an ester bond Derivatives of polyhydric alcohols such as ethers, monoalkyl ethers such as monobutyl ether or compounds having an ether bond such as monophenyl ether (in these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) Preferred); cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxy Esters such as ethyl propionate; aromatics such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether It may be mentioned solvent, the condensed polycyclic hydrocarbons.

  The condensed polycyclic hydrocarbon is a condensed ring hydrocarbon in which two or more monocycles supply only one side of each ring to each other, and is a hydrocarbon obtained by condensing two monocycles. It is preferable to use it.

  Such hydrocarbons include combinations of 5-membered and 6-membered rings, or combinations of two 6-membered rings. Examples of hydrocarbons combining 5-membered and 6-membered rings include indene, pentalene, indane, tetrahydroindene and the like. Examples of hydrocarbons combining two 6-membered rings include naphthalene, tetrahydronaphthalene ( Tetralin) and decahydronaphthalene (decalin).

[Protective layer]
The protective layer 15 covers at least the surface of the separation layer 14 that is not bonded to the support plate 12 and that does not overlap with the adhesive layer 13. The protective layer 15 is formed so that the separation layer 14 is not deteriorated by, for example, a high-temperature and long-time chemical treatment such as a resist stripping process (resist stripping process) or a heat treatment process performed at a high temperature (for example, 260 ° C.). Can be protected.

  The surface of the separation layer 14 covered by the protective layer 15 only needs to include at least the surface that does not overlap with the adhesive layer 13 among the surfaces of the separation layer 14 that are not bonded to the support plate 12.

  That is, in the present embodiment, the protective layer 15 also covers the surface of the separation layer 14 that does not adhere to the support plate 12 and overlaps the adhesive layer 13. However, the protective layer provided in the laminate according to the present invention is not limited to such a form, and only the surface that is the surface of the separation layer and is not bonded to the support is not overlapped with the adhesive layer. It may be covered. Regardless of the configuration, at least the surface of the separation layer that is not bonded to the support (support plate) covers at least the surface that does not overlap the adhesive layer. The separation layer can be protected from being altered by high-temperature and long-time chemical treatment.

  The material for forming the protective layer 15 can be appropriately selected according to the treatment performed on the stacked body 10. That is, a material having resistance to the chemical used in the treatment and the environment in which the treatment is performed may be appropriately selected. For example, if the laminate 10 is subjected to a high-temperature and long-time resist stripping step, a material having resistance to the stripping solution used in the step may be selected.

  Specific examples of the material for forming the protective layer 15 include an adhesive. This is because the adhesiveness with the adhesive layer 13 can be improved.

  When the protective layer 15 is composed of an adhesive, the adhesive may have the same composition as the adhesive that constitutes the adhesive layer 13. As described above, the adhesive constituting the adhesive layer 13 is selected from those having chemical resistance to the stripping solution, etc. Therefore, if the protective layer 15 is formed with such an adhesive, the separation layer 14 can be satisfactorily formed. Can be protected.

  Further, the adhesive constituting the protective layer 15 may have a composition different from that of the adhesive constituting the adhesive layer 13. However, even such an adhesive is more preferably an adhesive that is a candidate for an adhesive constituting the adhesive layer 13. As described above, the adhesive constituting the adhesive layer 13 can be selected from those having chemical resistance to the stripping solution, etc. Therefore, if the protective layer 15 is formed with such an adhesive candidate, it is good In addition, the separation layer 14 can be protected.

  Specific examples of the material constituting the protective layer 15 include a block copolymer and a cycloolefin polymer. These may be used alone or in combination of two or more. The description of the block copolymer and the cycloolefin-based polymer is in accordance with the description of each component performed in the adhesive layer 13 described above.

  The thickness of the protective layer 15 is preferably 1 to 10 μm, for example. When the thickness of the protective layer 15 is 1 μm or more, the protective layer 15 can withstand various chemical treatments at a high temperature for a long time. When the thickness of the protective layer 15 is 10 μm or less, the substrate 11 can be satisfactorily separated in the step of separating the substrate 11 from the laminate.

<Method for producing laminate>
Next, the manufacturing method of the laminated body which concerns on this invention is demonstrated using FIG. FIG. 2 is a diagram showing an embodiment of a method for producing a laminate according to the present invention.

  As described above, the protective layer included in the laminate according to the present invention only needs to include at least the surface that is not superposed on the adhesive layer among the surfaces that are the surfaces of the separation layer and are not adhered to the support. Of the surface of the separation layer that is not bonded to the support, the surface overlapping the adhesion layer may also be covered, or the surface of the separation layer and the support However, in the present embodiment, the surface of the separation layer that is not bonded to the adhesive layer and is not bonded to the support as in the laminate 10 may be covered. A description will be given of the case of manufacturing a non-covered surface that also covers the surface overlapping the adhesive layer.

  In one embodiment of the method for manufacturing a laminate according to the present invention, a separation layer forming step for forming a separation layer 14 that is altered by absorbing light on a support plate 12 and an adhesive layer 13 on a substrate 11 are formed. An adhesive layer forming step, a substrate 11, an adhesive layer 13, a separation layer 14, and a laminating step for laminating the support plate 12 in this order, the surface of the separation layer 14 being bonded to the support plate 12. A protective layer forming step of forming a protective layer 15 that covers at least a surface that does not overlap with the adhesive layer 13 when being laminated in the laminating step is included before the laminating step.

[Separation layer forming step]
The separation layer forming step is a step of forming a separation layer 14 that is altered by absorbing light on the support plate 12 as shown in FIG. As a specific method of the separation layer forming step, for example, when the separation layer 14 is formed of fluorocarbon, a method using a plasma CVD method may be mentioned.

[Adhesive layer forming step]
In the adhesive layer forming step, the adhesive layer 13 is formed on the substrate 11. As shown in FIG. 2, an adhesive prepared by using the above-described hydrocarbon-based resin as a main component and dissolved in a solvent is spin-coated on the substrate 11. And the process which solidifies an adhesive agent by baking in steps, raising temperature, and forms the contact bonding layer 13 is mentioned as an example. In addition, what is necessary is just to form an contact bonding layer on a board | substrate or a separated layer in the contact bonding layer formation process in the manufacturing method of the laminated body which concerns on this invention. That is, the adhesive layer 13 may be formed on the substrate 11 as in the present embodiment, or the adhesive layer may be formed on the separation layer. In the form of forming the adhesive layer on the separation layer, a protective layer described later may be formed on the surface of the separation layer that is not in contact with the support layer and is exposed without the adhesion layer being formed. .

[Protective layer forming step]
The protective layer forming step is to form a protective layer 15 that covers at least the surface of the separation layer 14 that is not bonded to the support plate 12 and that is not bonded to the support plate 12 when stacked in the stacking step. It is a process to do. As shown in FIG. 2, on the separation layer 14 formed on the support plate 12, the above-mentioned block copolymer or hydrocarbon resin as a main component is spin-coated with a protective agent dissolved in a solvent. And the process which solidifies a protective agent by baking in steps, raising temperature, and forms the protective layer 15 is mentioned as an example. The protective layer 15 can also be formed by an adhesive used for forming the adhesive layer 13.

[Lamination process]
The lamination process is a process of laminating the substrate 11, the adhesive layer 13, the separation layer 14, and the support plate 12 in this order. As a specific method of the laminating process, as shown in FIG. 2, the surface of the substrate 11 on which the protective layer 15 is formed and the surface of the support plate 12 on which the adhesive layer 13 is formed are bonded together under vacuum. A method of laminating by baking and pressure bonding is mentioned.

  In the method for manufacturing a laminate according to the present invention, the substrate, the adhesive layer, the separation layer, and the support are laminated in this order, and the protective layer can at least protect a portion where the separation layer and the adhesion layer do not overlap. If possible, the order of the steps is not particularly limited.

[Example 1]
(Preparation of adhesive composition)
“TOPAS (trade name) 8007 × 10, cycloolefin copolymer, Mw = 95,000, Mw / Mn = 1.9, norbornene: ethylene = 35: 65 (molar ratio)” 100 weight, manufactured by Polyplastics as an adhesive resin A part was dissolved in 800 parts by weight of decahydronaphthalene as a main solvent. Next, a butyl acetate solution containing a thermal polymerization inhibitor was added to 100 parts by weight of the adhesive resin so that the thermal polymerization inhibitor was 1 part by weight and the butyl acetate was 20 parts by weight. In this way, an adhesive composition was obtained.

(Process) A fluorocarbon film (thickness 1 μm) as a separation layer is supported by a CVD method using C ₄ F ₈ as a reaction gas under conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2500 W, and a film forming temperature of 240 ° C. Formed on a body (12-inch glass substrate, thickness 700 μm) (separation layer forming step), coated with the above adhesive composition, and baked at 220 ° C. for 3 minutes to protect the film thickness of 3 μm A layer was formed (protective layer forming step). A 12-inch silicon wafer was spin-coated with the above adhesive composition having a main solvent of 280 parts by weight, and heated at 100 ° C., 160 ° C., and 200 ° C. for 3 minutes each to form an adhesive layer (film thickness 50 μm) (Adhesive layer forming step) Under a vacuum of 220 ° C. and 4000 kg for 3 minutes, the laminate was laminated with a glass support (lamination step).

(Chemical resistance evaluation)
The wafer was ground to 40 μm and evaluated for chemical resistance with various stripping solutions and organic solvents. As the stripping solution, NMP (N-methyl-2-pyrrolidone), DMSO (dimethyl sulfoxide), and Stripper 104 and Stripper 106 (both trade names), which are stripping solutions manufactured by Tokyo Ohka Kogyo Co., Ltd., were used. The evaluation conditions are shown in Table 1. Further, the appearance was visually inspected, and the edge portion was observed from the glass side and the substrate side with a microscope. As a result, “◯” indicates that there is no defect such as peeling, and “X” indicates that there is a defect.

  In the laminated body of the present Example, all the results in the high temperature and long time stripping solution immersion test were obtained.

(Evaluation of heat treatment)
Each of the laminated bodies after the chemical resistance evaluation described above was subjected to heat treatment for 30 minutes in an N ₂ environment at 260 ° C. Thereafter, the appearance was visually inspected, and the edge portion was observed from the glass side and the substrate side with a microscope. As a result, “◯” indicates that there is no defect such as peeling, and “X” indicates that there is a defect.

(Separation evaluation)
A laser having a wavelength of 532 nm was irradiated from the support side of the laminate toward the separation layer for each of the laminates after the heat treatment evaluation described above. As a result, the case where the support could be separated was designated as “◯”, and the case where the support was not separated was designated as “x”.

[Examples 2 to 13, Comparative Examples 1 to 4]
The same operation as in Example 1 was performed except that the adhesive resin applied to the support (glass), the adhesive resin applied to the substrate (wafer), and the film thickness thereof were changed to those shown in Table 1 below. Similarly, chemical resistance and the like were evaluated. The results are shown in Table 1.

なお、表１中のＡＰＥＬ８００８Ｔ、Ｓｅｐｔｏｎ２００４、ＨＧ２５２、ＴＯＰＡＳ６０１７の詳細は次の通りである。

The details of APEL8008T, Septon2004, HG252, and TOPAS6017 in Table 1 are as follows.

APEL8008T (Mitsui Chemicals): cyclododecene: ethylene = 20: 80 (molar ratio), molecular weight 100,000
Septon 2004 (manufactured by Kuraray Co., Ltd.): SEPS: polystyrene-poly (ethylene / propylene) block) -polystyrene, styrene content 18% by weight, molecular weight 94,000
HG252 (manufactured by Kuraray Co., Ltd.): SEEPS-OH: polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene terminal hydroxyl group modification, styrene content 28% by weight, molecular weight 67000
TOPAS6017 (manufactured by Polyplastics): norbornene: ethylene = 58: 42 (molar ratio), molecular weight 82,000
Moreover, in Comparative Examples 1-4, as a result of evaluating chemical resistance, peeling occurred in the high-temperature, long-time stripping solution immersion test, and unevenness occurred in silicon. Furthermore, after the heat treatment step in a N ₂ environment at 260 ° C., the wafer was cracked, and it was impossible to separate the glass.

Example 14
A fluorocarbon film is formed on 12-inch glass by the plasma CVD method under the same conditions as in Example 1 (thickness: 1 μm), and the same adhesive composition as in Example 1 is dropped on the wafer edge 3 mm from the edge of the wafer. Spin applied. Then, it heated on the same conditions as Example 1, and confirmed the film thickness of 3 micrometers. The subsequent processes were performed in the same manner as in Example 1 and evaluated. As a result, it was confirmed that there was no problem in chemical resistance due to the stripping solution and the organic solvent.

  The stacked body and the manufacturing method of the stacked body according to the present invention can be suitably used, for example, in a manufacturing process of a miniaturized semiconductor device.

10 Laminated body 11 Substrate 12 Support plate (support)
13 Adhesive layer 14 Separation layer 15 Protective layer

Claims (11)

A substrate, an adhesive layer, a separation layer that is altered by absorbing light, and a support are laminated in this order,
Of the surface of the separation layer that is not bonded to the support, further comprising a protective layer that covers at least the surface that does not overlap with the adhesive layer ,
Materials for forming the protective layer are styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-ethylene-butylene- It is one kind selected from the group consisting of styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS). Laminated body. A substrate, an adhesive layer, a separation layer that is altered by absorbing light, and a support are laminated in this order,
Of the surface of the separation layer that is not bonded to the support, further comprising a protective layer that covers at least the surface that does not overlap with the adhesive layer,
The material forming the protective layer and the material forming the adhesive layer are respectively styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block. Copolymer (SBBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), and A laminate comprising one type selected from the group consisting of cycloolefin polymers.   The said protective layer covers the surface which overlaps with the said contact bonding layer among the surfaces which are the surfaces of the said separation layer, and are not adhere | attached on the said support body, The 1 or 2 characterized by the above-mentioned. The laminated body as described in.   The said protective layer is a surface of the said separation layer, and covers only the surface which has not overlapped with the said contact bonding layer among the surfaces which are not adhere | attached on the said support body, The characterized by the above-mentioned. The laminated body as described in.   The said protective layer is comprised with an adhesive agent, The laminated body in any one of Claims 1-4 characterized by the above-mentioned. The adhesive constituting the adhesive layer includes styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS), and styrene-ethylene-butylene. -One type selected from the group consisting of styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS). The laminate according to claim 1.   The laminated body according to claim 5 or 6, wherein the adhesive constituting the protective layer has the same composition as the adhesive constituting the adhesive layer.   The laminate according to claim 5 or 6, wherein the adhesive constituting the protective layer has a composition different from that of the adhesive constituting the adhesive layer. A separation layer forming step of forming a separation layer which is altered by absorbing light on the support;
An adhesive layer forming step of forming an adhesive layer on the substrate or on the separation layer;
A laminating step of laminating the substrate, the adhesive layer, the separation layer, and the support in this order,
A protective layer forming step of forming a protective layer that covers at least a surface that does not overlap with the adhesive layer when being laminated in the laminating step among the surfaces of the separation layer that are not bonded to the support; Furthermore, only including in front of the lamination process,
Materials for forming the protective layer are styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-ethylene-butylene- It is one kind selected from the group consisting of styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS). A method for manufacturing a laminate. The adhesive constituting the adhesive layer includes styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS), and styrene-ethylene-butylene. -One type selected from the group consisting of styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS). The manufacturing method of the laminated body of Claim 9. A separation layer forming step of forming a separation layer which is altered by absorbing light on the support;
An adhesive layer forming step of forming an adhesive layer on the substrate or on the separation layer;
A laminating step of laminating the substrate, the adhesive layer, the separation layer, and the support in this order,
A protective layer forming step of forming a protective layer that covers at least a surface that does not overlap with the adhesive layer when being laminated in the laminating step among the surfaces of the separation layer that are not bonded to the support; Further including before the lamination step,
The material forming the protective layer and the material forming the adhesive layer are respectively styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block. Copolymer (SBBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), and A method for producing a laminate, which is one type selected from the group consisting of cycloolefin polymers.

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