TW201410832A - Laminate and laminate manufacturing method - Google Patents

Abstract

The purpose of this invention is to inhibit the wafer peeling and protect a separation layer during the treatment of interest on a laminate. The solving means is the laminate of this invention, which is formed by lamination, in the order below, a substrate (11), an adhesion layer (13), a separation layer (14) which changes its property after the light absorption, and a support board (12). On the surface of the separation layer (14) not adhered to the support board (12), a protection layer (15) is further provided which at least covers the surface not overlapping the adhesion layer (13).

Description

Laminated body and method of manufacturing the same

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

In recent years, electronic devices such as IC cards and mobile phones have been required to be thinner, smaller, and lighter. In order to meet these requirements, thin semiconductor wafers must also be used for assembled semiconductor wafers. Therefore, the thickness (film thickness) of the wafer substrate of the semiconductor wafer substrate is currently 125 μm to 150 μm, but the wafer used in the next generation is considered to be 25 μm to 50 μm. Therefore, in order to obtain the wafer substrate having the above film thickness, the thinning step of the wafer substrate is indispensable.

Since the strength of the wafer substrate is reduced due to thinning, the wafer substrate is mounted on the wafer substrate while the wafer substrate and the support plate are bonded together in the manufacturing process in order to prevent the wafer substrate from being damaged. A structure such as a circuit. Moreover, after the manufacturing process, the wafer substrate is separated from the support plate. Therefore, in the manufacturing process, it is preferable to firmly follow the wafer substrate and the support plate, but it is preferable to smoothly separate the wafer substrate from the support plate after the manufacturing process.

When the wafer substrate and the support plate are firmly adhered to each other, the structure mounted on the wafer substrate can be prevented from being broken by the bonding material, but it is difficult to separate the support plate from the wafer substrate. Therefore, it is required to develop a very difficult pseudo-fixing technique in which a wafer substrate and a support plate can be firmly adhered to in a manufacturing process, and the components mounted on the wafer substrate can be broken and separated after the manufacturing process.

As a method of manufacturing a semiconductor wafer in which a semiconductor wafer is bonded to a semiconductor wafer and a semiconductor wafer is processed and a support is separated, a method as disclosed in Patent Document 1 is known. In the method described in Patent Document 1, the light-transmitting support and the semiconductor wafer are bonded to each other via a photothermal conversion layer and an adhesive layer provided on the support side, and the semiconductor wafer is processed by the support. The side illuminates the radiant energy to decompose the photothermal conversion layer, thereby separating the semiconductor wafer from the support.

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2005-159155 (published on June 16, 2005)

When various processes are performed on a laminate in which a substrate such as a wafer and a support are bonded to each other through a separation layer to be separated later, the separation layer is deteriorated by a drug or the like during the treatment, resulting in a process leading to the process. The problem of stripping.

For example, in the resist stripping step or the like, in particular, when the laminate is exposed to the peeling liquid at a high temperature, the end surface of the end portion of the laminate is impregnated with the stripping liquid to cause the wafer to peel off.

If the film is peeled off during the process, cracks, cracks, irregularities, and the like are generated on the wafer, so that it is not possible to proceed to the next step.

The present invention has been made in view of such a problem, and is intended to provide a laminate in which a separation layer is protected in order to suppress wafer peeling when a laminate is desired.

In order to solve the above problems, the laminate of the present invention is characterized in that a substrate, an adhesive layer, a separation layer which is deteriorated by absorption of light, and a support are laminated in this order, and the surface of the separation layer is not bonded to the support. Further, a protective layer covering at least the surface not overlapping the above-mentioned subsequent layer is further provided.

Further, a method for producing a laminate according to the present invention includes a step of forming a separation layer formed on a support and deteriorating by absorbing light, and forming an adhesive layer on the substrate or the separation layer. a forming step; a lamination step of laminating in the order of the substrate, the adhesive layer, the separation layer, and the support; and, before the laminating step, further comprising a protective layer forming step, wherein the protective layer forming step is When laminating in the laminating step, at least the cover and the adhesive layer are not heavy on the surface of the separation layer and not in the surface adjacent to the support. The protective layer of the stack.

According to the present invention, when the laminate is subjected to a desired treatment, since the separation layer is protected, the effect of wafer peeling can be suppressed.

10‧‧‧Layer

11‧‧‧Substrate

12‧‧‧Support plate (support)

13‧‧‧Next layer

14‧‧‧Separation layer

15‧‧‧Protective layer

Fig. 1 is a view showing the structure of a laminate 10 according to an embodiment of the laminate of the present invention.

Fig. 2 is a view showing an embodiment of a method for producing a laminate of the present invention.

<Layer>

The laminate 10 of the present invention will be described with reference to Fig. 1 by taking the laminate 10 of one embodiment as an example. Fig. 1 is a structural view showing a laminate 10 of an embodiment of the laminate of the present invention.

The laminate 10 is formed by laminating the substrate 11, the subsequent layer 13, the separation layer 14 which is degraded by absorption of light, and the support plate (support) 12, and is on the surface of the separation layer 14 and is not in contact with the support plate. Among them, the protective layer 15 covering at least the surface not overlapping the adhesive layer 13 is further provided.

Since the protective layer 15 covers at least the overlap with the adhesive layer 13 In the surface of the separation layer 14, in the manufacturing process of the substrate 11, even when various processes such as a photoresist stripping step are performed, the separation layer 14 is protected from a drug such as a peeling liquid used for the treatment or the like, or a high temperature. The heat of the environment. Therefore, even when the laminate 10 is subjected to a desired treatment, since the separation layer 14 is protected, peeling of the substrate 11 can be suppressed.

[substrate]

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

[support plate]

The support plate 12 is a support for supporting the substrate 11, and has light transparency. Therefore, when light is irradiated from the outer surface 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 have to penetrate all of the light as long as the light which the separation layer 14 should absorb (having a predetermined wavelength) can pass.

The support plate 12 is a support substrate 11 and may have a required strength to prevent the substrate 11 from being damaged or deformed during the process of thinning, transporting, or mounting the substrate 11. From the above viewpoints, examples of the support plate 12 include those made of glass, enamel, and acrylic resin.

[separation layer]

The separation layer 14 is a layer formed of a material which is deteriorated by absorbing light irradiated through the support plate 12. In the present specification, the "deterioration" of the separation layer 14 means a state in which the separation layer 14 can be broken only by a slight external force, or a state in which the adhesion force between the separation layer 14 and the contact layer is lowered. As a result of the deterioration of the separation layer 14 due to absorption of light, the separation layer 14 loses strength or adhesion before being irradiated with light. Therefore, by applying a little external force (for example, lifting the support plate 12 or the like), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

Further, the deterioration of the separation layer 14 may be a decomposition (cross-linking, a change in a stereo configuration, or a dissociation of a functional group due to the energy of the absorbed light (heating or non-heating) (and, along with the separation layer) Hardening, degassing, shrinking or expanding). The modification of the separation layer 14 is produced as a result of light absorption by the material constituting the separation layer 14. Therefore, the metamorphic type of the separation layer 14 can be varied depending on the kind of the material constituting the separation layer 14.

The separation layer 14 is provided on the support plate 12 via the adhesive layer 13 and the substrate 11 is subjected to the surface on the bonding side. 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 preferably 0.05 to 50 μm, more preferably 0.3 to 1 μm. When the thickness of the separation layer 14 is set in the range of 0.05 to 50 μm, the separation layer 14 can be deformed by a short-time light irradiation and low-energy light irradiation. Further, the thickness of the separation layer 14 is particularly preferably in the range of 1 μm or less from the viewpoint of productivity.

Further, in the laminate 10, another layer may be formed between the separation layer 14 and the support plate 12. At this time, the other layers need only be composed of a material that can penetrate light. Thereby, it is possible to appropriately add a layer which can impart the preferable properties and the like of the laminate 10 without hindering the incidence of light on the separation layer 14. Depending on the type of material constituting the separation layer 14, the wavelengths of light that can be used are also different. Therefore, the materials constituting the other layers are not necessarily all those which can penetrate the light, and may be selected from materials which can penetrate light of a wavelength at which the material constituting the separation layer 14 is deteriorated.

Further, the separation layer 14 is preferably formed of a material having a structure that absorbs light, but may be formed by adding a material having no structure for absorbing light, within a range not impairing the essential characteristics of the present invention. Layer 14. Further, it is preferable that the surface of the separation layer 14 and the opposite side of the adhesive layer 13 are flat (no unevenness is formed), whereby the formation of the separation layer 14 can be easily performed, and evenly attached even when attached. Attached.

The separation layer 14 may be formed by laminating a material constituting the separation layer 14 as follows, and then bonding it to the support plate 12, or applying the material constituting the separation layer 14 to the support plate 12 and curing it. Film-like. The method of applying the material constituting the separation layer 14 to the support plate 12 is preferably a conventionally known method selected from the group consisting of chemical vapor deposition (CVD) deposition, etc., depending on the type of material constituting the separation layer 14.

The separation layer 14 may also be degraded by absorbing light irradiated by the laser. That is, the light system that irradiates the separation layer 14 in order to degrade the separation layer 14 may be irradiated by a laser. Examples of the laser light that emits the light that illuminates the separation layer 14 include solid lasers such as YAG lasers, ruby lasers, glass lasers, YVO ₄ lasers, LD lasers, and fiber lasers. Laser lasers such as liquid lasers, CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers, semiconductor lasers, free electron lasers, etc., or non-laser light. The laser light that emits the light that illuminates the separation layer 14 can be appropriately selected in accordance with the material constituting the separation layer 14, and a laser that can illuminate the wavelength light that can temper the material constituting the separation layer 14 can be selected.

<Polymer having a light absorbing structure in its repeating unit>

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

The above structure having light absorbability is a chemical structure which absorbs light and deteriorates a polymer containing the structure as a repeating unit. This structure is, for example, a group containing a conjugated π-electron system composed of a substituted or unsubstituted benzene ring, a condensed ring or a heterocyclic ring. In more detail, the configuration may be a cardo structure, or a benzophenone structure present on the side chain of the above polymer, a diphenyl fluorene structure, a diphenyl fluorene structure (diphenyl fluorene) Construction), diphenyl structure or diphenylamine structure.

When the above structure is a 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 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 an integer of 0 or 1 to 5.

Further, the polymer may, for example, contain a repeating unit represented by any one of (a) to (d) in the following formula, or may be represented by (e) or contain (f) in its main chain. Construction.

In the formula, 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 above-mentioned "Chemical 1" in (a) to (e), and is (f) Either or none of the above-mentioned "Chemical Formula 1", 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, the condensed ring and the hetero ring shown in the above "Chemical Formula 1" include a phenyl group, a substituted phenyl group, a benzyl group, a substituted benzyl group, a naphthalene group, a substituted naphthalene group, an anthracene group, a substituted fluorene group, and a fluorene group.醌, substituted anthracene, acridine, substituted acridine, azobenzene, substituted azobenzene, Fluorime, substituted Fluorime, Fluorimone, substituted Fluorimone, carbazole, substituted carbazole, N-alkylcarbazole, dibenzofuran Substituting dibenzofuran, phenanthrene, substituted phenanthrene, anthracene and substituted anthracene. When the exemplified substituent is substituted, the substituent may be selected from For example, alkyl, aryl, halogen atom, alkoxy group, nitro group, aldehyde group, cyano group, decylamino group, dialkylamino group, sulfonamide, quinone imine, carboxyl group, carboxyl ester, sulfonic acid, sulfonate An acid ester, an alkylamino group and an arylamine group.

Examples of the substituent represented by the above "Chemical Formula 1" include a fifth substituent of two phenyl groups and Z is -SO ₂ -, and examples thereof include bis(2,4-dihydroxyphenyl). Anthraquinone, bis(3,4-dihydroxyphenyl)anthracene, bis(3,5-dihydroxyphenyl)anthracene, bis(3,6-dihydroxyphenyl)anthracene, bis(4-hydroxyphenyl)anthracene , bis(3-hydroxyphenyl)fluorene, bis(2-hydroxyphenyl)fluorene, and bis(3,5-dimethyl-4-hydroxyphenyl)hydrazine.

Examples of the substituent represented by the above "Chemical Formula 1" include a fifth substituent of two phenyl groups and Z is -SO-, and examples thereof include bis(2,3-dihydroxyphenyl). Azulene, bis(5-chloro-2,3-dihydroxyphenyl)arylene, bis(2,4-dihydroxyphenyl)anthracene, bis(2,4-dihydroxy-6-methylphenyl) Anthraquinone, bis(5-chloro-2,4-dihydroxyphenyl)arylene, bis(2,5-dihydroxyphenyl)anthracene, bis(3,4-dihydroxyphenyl)anthracene, Bis(3,5-dihydroxyphenyl)anthracene, bis(2,3,4-trihydroxyphenyl)anthracene, bis(2,3,4-trihydroxy-6-methylphenyl)- Bismuth, bis(5-chloro-2,3,4-trihydroxyphenyl)arylene, bis(2,4,6-trihydroxyphenyl)arylene, bis(5-chloro-2,4,6- Trishydroxyphenyl) anthracene and the like.

In the case where the substituent represented by the above "Chemical Formula 1" has a fifth substituent of two phenyl groups and Z is -C(=O)-, examples thereof include 2,4-dihydroxy group Benzene, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2',5,6'-tetrahydroxybenzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone Ketone, 2-hydroxy-4-dodecylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,6-dihydroxy-4-methoxybenzophenone Ketone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-amino-2'-hydroxybenzophenone, 4-dimethylamino-2'-hydroxyl Benzophenone, 4-diethylamino-2'-hydroxybenzophenone, 4-dimethylamino-4'-methoxy-2'-hydroxybenzophenone, 4-dimethyl Amino-2',4'-dihydroxybenzophenone, and 4-dimethylamino-3',4'-dihydroxybenzophenone and the like.

When the above structure is present in the side chain of the polymer, the ratio of the repeating unit containing the above structure to the polymer is such that the light transmittance of the separation layer 14 is in the range of 0.001 to 10%. If the polymer is prepared so that the ratio is within this range, the separation layer 14 can sufficiently absorb light and deteriorate qualitatively and rapidly. That is, the support plate 12 can be easily removed from the laminate 10, and the light irradiation time necessary for the removal can be shortened.

The above configuration absorbs light having a wavelength of a desired range depending on the type of the selection. For example, the wavelength of the light absorbable by the above structure is preferably from 100 to 2000 nm. In this range, the wavelength of the light absorbable by the above configuration is the shorter wavelength side, for example, 100 to 500 nm. For example, the above configuration preferably deteriorates the polymer containing the structure by absorbing ultraviolet light having a wavelength of about 300 to 370 nm.

The light absorbing structure of the above configuration 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), and an F ₂ excimer laser (wavelength: 157 nm), XeCl laser (308 nm), XeF laser (wavelength: 351 nm) or solid UV laser (wavelength: 355 nm), or g-line (wavelength: 436 nm), h-line (wavelength: 405 nm) or i line (wavelength: 365 nm) and the like.

The separation layer 14 contains a polymer having the above-described structure as a repeating unit, but the separation layer 14 may contain components other than the above polymer. Examples of the component include a filler, a plasticizer, and a component which can improve the peelability of the support sheet 12. These components may be suitably selected from materials or materials which are not known to hinder or promote the absorption of light and the deterioration of the polymer by the above-mentioned structure.

(inorganic matter)

The separation layer 14 is also made of an inorganic substance. The separation layer 14 is made of an inorganic substance and can be deteriorated by light absorption and reception, and as a result, the strength or adhesion before the light irradiation is lost. Therefore, by applying a little external force (for example, lifting the support plate 12 or the like), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

The inorganic material may be formed by absorbing light, and for example, an inorganic substance 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 may be, for example, a metal oxide or a metal nitride. Examples of such inorganic substances are not limited thereto, 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 inorganic substances of one or more types in which carbon is grouped. Furthermore, carbon refers to the concept of carbon allotropes, such as diamonds, fullerenes, diamond-like carbons, carbon nanotubes, and the like.

The inorganic substance absorbs light having a wavelength of an intrinsic range depending on the type thereof. The inorganic substance can be suitably deteriorated by irradiating the separation layer with light of a wavelength range which can be absorbed by the inorganic substance used in the separation layer 14.

As the light for irradiating the separation layer 14 composed of an inorganic substance, for example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, a fiber laser or the like is preferably used in consideration of the wavelength at which the inorganic substance can be absorbed. Laser lasers such as solid lasers, pigment lasers, CO ₂ lasers, excimer lasers, Ar lasers, He-Ne lasers, semiconductor lasers, free electron lasers, etc. Or non-laser light.

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

Further, when a metal film is used as the separation layer 14, the reflection of the laser or the charging of the film may be caused depending on the film quality of the separation layer 14, the type of the laser light source, and the laser output. Therefore, it is preferable to take measures such as providing an antireflection film or an antistatic film on the upper or lower side of the separation layer 14.

<Compound having an infrared absorbing structure>

The separation layer 14 may also be formed of a compound having an infrared absorbing structure. This compound is degraded by absorption of infrared rays. As a result of the deterioration of the compound, the separation layer 14 loses strength or adhesion before being irradiated with infrared rays. Therefore, by applying a little external force (for example, lifting the support plate 12 or the like), the separation layer 14 is broken and the support plate 12 and the substrate 11 can be easily separated.

As the compound having an infrared absorbing structure or containing an infrared absorbing structure, for example, it may be an alkane or an alkene (ethylene, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, alkene, or cyclic). , alkyne (monosubstituted, disubstituted), monocyclic aromatic (benzene, monosubstituted, disubstituted, trisubstituted), alcohol and phenol (free OH, intramolecular hydrogen bonding, intermolecular hydrogen bonding, saturated second stage , saturated third stage, unsaturated second stage, unsaturated third stage), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane ring ether, peroxide ether, ketone, Dialkylcarbonyl, aromatic carbonyl, 1,3-diketone ethanol, o-hydroxyaryl ketone, dialkyl aldehyde, aromatic aldehyde, carboxyl (dimer, carboxyl anion), formic acid ester, acetic acid Esters, conjugated esters, non-conjugated esters, aromatic esters, lactones (β-, γ-, δ-), aliphatic acid chlorides, aromatic acid chlorides, acid anhydrides (conjugated, non-conjugated, cyclic , acyclic, first-grade guanamine, second-grade guanamine, indoleamine, first-grade amine (aliphatic, aromatic), secondary amine (aliphatic, aromatic) Tertiary amine (aliphatic, aromatic), first-grade amine salt, second-grade amine salt, tertiary amine salt, ammonium ion, aliphatic nitrile, aromatic nitrile, carbodiimide, aliphatic Nitrile, aromatic isonitrile, isocyanate, thiocyanate, aliphatic isothiocyanate, aromatic isothiocyanate, aliphatic nitro compound, aromatic nitro compound, nitroamine, nitrosamine , nitrates, nitrites, nitroso bonds (aliphatic, aromatic, monomeric, dimer), sulfur compounds such as thiols and thiophenols and thiol acids, thiocarbonyls, hydrazine, hydrazine, chlorine Sulfonyl, first-stage sulfonamide, second-stage 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 a Ti-O bond.

Examples of the structure containing the carbon-halogen bond include, for example, -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF ₂ -, -CF ₃ , -CH=CF ₂ , -CF=CF _{2 .} , fluorinated aryl, and aryl chloride.

Examples of the structure including the Si—Al ¹ bond include SiH, SiH ₂ , SiH ₃ , Si—CH ₃ , Si—CH ₂ —, Si—C ₆ H ₅ , SiO aliphatic, and Si—OCH ₃ . Si—OCH ₂ CH ₃ , Si—OC ₆ H ₅ , Si—O—Si, Si—OH, SiF, SiF ₂ , and SiF ₃ . As the structure including the Si-A ¹ bond, it is particularly preferable to form a siloxane chain and a sesquiterpene skeleton.

Examples of the structure including the above PA ² bond include PH, PH ₂ , P-CH ₃ , P-CH ₂ -, PC ₆ H ₅ , and 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 absorbs infrared rays having a wavelength of a desired range depending on the type of the selection. Specifically, the wavelength of the infrared ray absorbable by the above structure is, for example, in the range of 1 μm to 20 μm, which is suitable for absorption. Within the range of 2 μm to 15 μm. 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 to 11 μm. Moreover, the wavelength of the infrared light that each structure can absorb can be easily understood by the industry. For example, as the absorption band in each structure, reference can be made to the non-patent literature: SILVERSTEIN‧BASSLER‧MORRILL "Spectral Measurement Identification of Organic Compounds (5th Edition) - Combination of MS, IR, NMR, UV-" (1992) Issued on pages 146 to 151.

The compound having an infrared absorbing structure used for the formation of the separation layer 14 is not particularly limited as long as it is soluble in the solvent to be coated and can be solidified to form a solid layer. By. However, in order to effectively deteriorate the compound in the separation layer 14, and the support plate 12 and the substrate 11 can be easily separated, the infrared absorption in the separation layer 14 is large, that is, the infrared ray is worn when the separation layer 14 is irradiated with infrared rays. The permeability is preferably low. Specifically, it is preferable that the transmittance of infrared rays of the separation layer 14 is less than 90%, and the transmittance of infrared rays is preferably less than 80%.

As an example of the compound having a oxoxane skeleton, for example, a resin of a repeating unit represented by the following chemical formula (1) and a copolymer of a repeating unit represented by the following chemical formula (2), or A resin of a repeating unit represented by the chemical formula (1) and a copolymer derived from a repeating unit of an acrylic compound.

(In the chemical formula (2), R ₁ is hydrogen, an alkyl group having 10 or less carbon atoms, and an alkoxy group having 10 or less carbon atoms)

In the above, as a compound having a oxoxane skeleton, a tert-butyl styrene (TBST)-two copolymer of a repeating unit represented by the above chemical formula (1) and a repeating unit represented by the following chemical formula (3) The methyl methoxy olefin copolymer is preferably a TBST-dimethyl siloxane copolymer containing the repeating unit represented by the above formula (1) and the repeating unit represented by the following chemical formula (3) in a ratio of 1:1. For better.

In addition, as the compound having a sesquiterpene oxide skeleton, for example, a resin of 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.

(In the chemical formula (4), R ₂ is hydrogen or an alkyl group having 1 or more and 10 or less carbon atoms, and in the chemical formula (5), R ₃ is an alkyl group having 1 or more and 10 or less carbon atoms or a phenyl group)

As a compound having a sesquiterpene oxyalkylene skeleton, Patent Document 3: JP-A-2007-258663 (published on October 4, 2007), and Patent Document 4: JP-A-2010- 120901 Japanese Patent Publication No. 2009-263316 (published on Nov. 12, 2009) and Patent Document 6: JP-A-2009-263596 (2009-11) Each sesquiterpene oxide resin disclosed in the publication of the month of the month.

In addition, the compound having a sesquiterpene oxide skeleton is preferably a copolymer of the repeating unit represented by the following chemical formula (6) and a repeating unit represented by the following chemical formula (7), and is contained in a ratio of 7:3. The copolymer of the repeating unit represented by the chemical formula (6) and the repeating unit represented by the following chemical formula (7) is more preferable.

The polymer having a sesquiterpene skeleton may be a random structure, a ladder structure or a cage structure, or may have any structure.

Further, examples of the compound containing a Ti-O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, iridium (2-ethylhexyloxy)titanium, and Titanium alkoxide such as titanium-i-propoxyoctyl glycolate, (ii) titanium di-i-propoxy bis(ethylmercaptopyruvate), and propane dioxy titanium bis (ethyl ethyl Chelating titanium, such as hydrazine acetate, (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 such as titanium polymer, (iv) tri-n-butoxy titanium monostearate, titanium stearate, di-i- a titanium oxytitanium diisostearate, and a titanium oxide such as (2-n-butoxycarbonylbenzyloxy) tributoxytitanium or the like, (v) di-n-butoxy bis ( A water-soluble titanium compound such as triethanolamine) titanium or the like.

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

The separation layer 14 contains a compound having an infrared absorbing structure, but the separation layer 14 may further contain components other than the above compounds. Examples of the component include a filler, a plasticizer, and a component which can improve the peelability of the support sheet 12. These components may be suitably selected from materials or materials which are not known to hinder or promote the infrared absorption due to the above structure and the deterioration of the compound.

(fluorocarbon)

The separation layer 14 can be made of fluorocarbon. The separation layer 14 is made of fluorocarbon and can be deteriorated by absorbing light, and as a result, the strength or adhesion before being irradiated with light is lost. Therefore, by applying a little external force (for example, lifting the support plate 12 or the like), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

Further, from another point of view, the fluorocarbon constituting the separation layer 14 can be suitably formed by a plasma CVD method. Further, the fluorocarbon system 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 or CH ₂ F _{2 .} 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 used to constitute the separation layer 14, an inert gas such as nitrogen, helium or argon, a hydrocarbon such as an alkene or an alkene, and oxygen, carbon dioxide or hydrogen may be added as necessary. Further, these gases may be mixed and used in combination (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 fluorocarbons.

Fluorocarbon absorbs light having a wavelength within an intrinsic range depending on its kind. The fluorocarbon can be suitably deteriorated by irradiating the separation layer with light of a range wavelength which can be absorbed by the fluorocarbon used in the separation layer 14. Further, the light absorptivity in the separation layer 14 is preferably 80% or more.

As the light irradiated to the separation layer 14, depending on the wavelength at which fluorocarbon can be absorbed, for example, 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 is suitably used, Laser light, non-laser light such as liquid laser, CO ₂ laser, excimer laser, Ar laser, He-Ne laser, etc., laser laser, semiconductor laser, etc. Just fine. 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.

(infrared absorbing material)

The separation layer 14 may also contain an infrared absorbing material. The separation layer 14 is formed by containing an infrared absorbing material, and can be deteriorated by absorbing light, and as a result, the strength or adhesion before being irradiated with light is lost. Therefore, by applying a little external force (for example, lifting the support plate 12 or the like), the separation layer 14 is broken, and the support plate 12 and the substrate 11 can be easily separated.

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

[Next layer]

Next, the layer 13 is configured to cover the surface of the substrate 11 while the substrate 11 is subsequently fixed to the support plate 12. Therefore, in the processing or transport of the substrate 11 , it is necessary to maintain the adhesion and strength of the substrate 11 to be fixed to the support plate 12 and the surface to be protected by the substrate 11 . On the other hand, when the fixing of the substrate 11 to the support plate 12 becomes unnecessary, it is necessary to be easily peeled off or removed from the substrate 11.

Therefore, the adhesive layer 13 is composed of an adhesive which is generally strong in adhesion, which is improved in adhesion by a certain treatment, or which is soluble in a specific solvent. The thickness of the layer 13 is preferably, for example, 1 to 200 μm, more preferably 10 to 150 μm. Next, the layer 13 can be formed by applying a material as described below to the substrate 11 by a conventionally known method such as spin coating.

As the adhesive, various adhesives known in the art such as acrylic, phenolic, naphthoquinone, hydrocarbon, or polyimine 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 to be contained in the adhesive layer 13 may be, for example, a hydrocarbon resin, an acrylic-styrene resin, a maleic imine resin, or the like, or a combination thereof.

(hydrocarbon resin)

The hydrocarbon resin is a resin having a hydrocarbon skeleton and polymerizing the monomer composition. Examples of the hydrocarbon resin include a cycloolefin polymer (hereinafter also referred to as "resin (A)"), and at least one selected from the group consisting of terpene resins, rosin resins, and petroleum resins. The resin (hereinafter also referred to as "resin (B)") or the like is not limited thereto.

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 type monomer, and a resin obtained by addition (co)polymerization of a monomer component containing a cycloolefin type monomer.

Examples of the cycloolefin-based monomer to be contained in the monomer component constituting the resin (A) include a bicyclic ring such as norbornene and norbornadiene, dicyclopentadiene, dihydroxypentadiene, and the like. a tetracyclic ring such as a tricyclic ring or a tetracyclododecene, a pentacyclic ring such as a cyclopentadiene terpolymer, a heptacyclic ring such as tetracyclopentadiene or an alkyl group of such a polycyclic ring ( Substituents such as methyl, ethyl, propyl or butyl, substituted by alkenyl (vinyl or the like), substituted by alkylene (such as ethane), or aryl (phenyl, tolyl, naphthyl, etc.) ) Substitutes, etc. Among these, a decene-based monomer selected from the group consisting of norbornene, tetracyclododecene, or an alkyl-substituted product thereof is particularly preferred.

The monomer component constituting the resin (A) may also contain the above The other monomer copolymerized with the cycloolefin monomer is preferably, for example, an olefin monomer. Examples of the olefin monomer include ethylene, propylene, 1-butene, isobutylene, 1-hexene, and α-olefin. The olefin monomer may be linear or branched.

Further, the monomer component constituting the resin (A) is preferably a cycloolefin monomer from the viewpoint of high heat resistance (low thermal decomposition and thermogravimetric reduction). 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. In addition, the ratio of the cycloolefin monomer to the entire monomer component constituting the resin (A) is not particularly limited, and is preferably 80 mol% or less from the viewpoint of solubility and stability over time in the solution. 70 mol% or less is preferred.

Further, the monomer component constituting the resin (A) may contain a linear or branched olefin monomer. 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. 80% of the moles is better.

In addition, the resin (A) is, for example, a resin obtained by polymerizing a monomer component composed of a cycloolefin monomer and an olefin monomer, and a resin having no polar group can suppress generation of gas at a high temperature. good.

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.

A commercially available product which can be used as the resin (A), for example, "TOPAS" manufactured by Polyplastics Co., Ltd., and manufactured by Mitsui Chemicals Co., Ltd. "APEL", "ZEONOR" and "ZEONEX" manufactured by Zeon Corporation of Japan, and "ARTON" manufactured by JSR Corporation.

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 more, the softening of the adhesive layer when the adhesive laminate is exposed to a high temperature environment can be further suppressed.

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-based resin include a terpene resin, a terpene phenol resin, a denatured terpene resin, a hydrogenated terpene resin, and a hydrogenated terpene phenol resin. Examples of the rosin-based resin include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and denatured rosin. Examples of the petroleum resin include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, denatured petroleum resins, alicyclic petroleum resins, and xanthones and hydrazine petroleum resins. 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 80 to 160 °C. When the softening point of the resin (B) is at least 80 ° C, the softening of the adhesive laminate when exposed to a high temperature environment can be further suppressed, and no defects are caused. On the other hand, when the softening point of the resin (B) is 160 ° C or lower, the peeling speed at the time of peeling off the adhesive laminate is good.

The molecular weight of the resin (B) is not particularly limited, and is preferably from 300 to 3,000. When the 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 also small. On the other hand, when the molecular weight of the resin (B) is 3,000 or less, the release agent is peeled off. The peeling speed at the time of the laminate is good. Further, the 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, as the resin, a resin (A) and a resin (B) may be used in combination. By mixing, heat resistance and peeling speed are all good. For example, as a mixing ratio of the resin (A) and the resin (B), (A): (B) = 80: 20 to 55: 45 (mass ratio) is excellent in heat resistance and flexibility at a peeling speed and a high temperature environment. Therefore, it is better.

(block copolymer)

The block copolymer which can comprise the adhesive layer which consists of the laminated body of this invention is a polymer which couple|bonds the block site which the two or more monomer unit continuously couples, and is also called a block copolymer.

As the block copolymer, various block copolymers can be used, and for example, styrene-isobutylene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), benzene can be used. Ethylene-butadiene-butene-styrene block copolymer (SBBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (Styrene-isobutylene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), and the like.

The block copolymer which can constitute the adhesive layer provided in the laminate of the present invention may also bond at least one functional group-containing atomic group. Such a block copolymer can be made, for example, by using a denaturant for a known block copolymer. The functional group-containing atomic group is obtained by bonding at least one.

The functional group-containing atomic group means an atomic group containing one or more functional groups. The functional group contained in the atomic group containing a functional group in the present invention may, for example, be an amine group, an acid anhydride group (preferably an anhydrous maleic acid group), an oxime imido group, an amino carboxylate group or an epoxy group. And a mercapto group, a hydroxyl group, a carboxyl group, a decyl alcohol group, and an alkoxyalkyl group (the alkoxy group is preferably a carbon number of 1 to 6). In the present invention, the block copolymer is an elastomer and has a functional group that generates polarity. In the present invention, the flexibility and adhesion of the adhesive composition can be improved by containing a block copolymer having at least one functional group-containing atomic group.

The block copolymer is preferably a diblock copolymer or a triblock copolymer, and a triblock copolymer is preferred. Further, a diblock copolymer and a triblock copolymer may also be used in combination. Thereby, the loss coefficient (tan σ) at 220 ° C of the adhesive layer formed using the adhesive composition can be made into an optimum value of 1.1 or less.

Further, the block copolymer is preferably a styrene group, and more preferably a styrene group at both ends of the main chain. This is because high heat resistance can be exhibited by blocking styrene blocks having high thermal stability at both ends.

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

Further, the weight average molecular weight of the block copolymer is preferably 50,000 or more and 150,000 or less, more preferably 60,000 or more and 120,000 or less. Thereby, the storage modulus (G') at 220 ° C of the adhesive layer formed using the adhesive composition can be made into an optimum value of 1 × 10 ⁵ Pa or less.

In addition, when 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 solubility in the hydrocarbon solvent is excellent. Therefore, it is better. Thereby, when the adhesive layer formed by the adhesive composition is removed, the hydrocarbon-based solvent can be easily and quickly removed.

Further, the block copolymer is preferably a hydride. If it is a hydride, the stability to heat is further improved, and it is not easy to cause deterioration of decomposition or polymerization. Further, it is also preferable from the viewpoints of solubility in a hydrocarbon solvent and resistance to a photoresist solvent.

Further, the block copolymer is preferably one having a glass transition point of 23 ° C or less. The block copolymer can have an Young's modulus at 23 ° C of an adhesive layer formed using the adhesive composition as an optimum value of 0.1 GPa or more by containing a unit having a glass transition point of 23 ° C or less.

The block copolymer may also be a mixture of plural types. That is, the adhesive composition of the present invention may also comprise a plurality of types of block copolymers. It is preferred that at least one of the plurality of types of block copolymers contains a styrene group. Further, in at least one of the plurality of types of block copolymers, the styryl group content is in the range of 10% by weight or more and 65% by weight or less, and at least one of the plurality of kinds of block copolymers, the weight average molecular weight If it is in the range of 50,000 or more and 150,000 or less, it is the scope of the present invention. Further, the adhesive composition of the present invention comprises a plurality of blocks In the case of the copolymer, the mixing result and the content of the styrene group can be adjusted to the above range.

(acrylic-styrene resin)

The acrylic-styrene-based resin may, for example, be a resin obtained by polymerizing a monomer such as styrene or styrene and a (meth) acrylate.

Examples of the (meth) acrylate include (meth)acrylic acid alkyl ester composed of a chain structure, (meth) acrylate having an aliphatic ring, and (meth)acrylic acid having an aromatic ring. ester. Examples of the alkyl (meth)acrylate composed of a chain structure include an acrylic long-chain alkyl ester having an alkyl group having 15 to 20 carbon atoms, and an acrylic acid having an alkyl group having 1 to 14 carbon atoms. Alkyl esters and the like. As the acrylic long-chain alkyl ester, an alkyl group is an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-n-19 group, and an n-tetradecyl group. An alkyl ester of acrylic acid or methacrylic acid. Still, the alkyl group may also be branched.

The acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms may, for example, be a known acrylic alkyl ester used in an existing acrylic adhesive. For example, an alkyl group is composed of 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 thirteen group, or the like. An alkyl ester of acrylic acid or methacrylic acid.

Examples of the (meth) acrylate having an aliphatic ring include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, and hydrazine. (meth) propylene Acid ester, isodecyl (meth) acrylate, tricyclodecyl (meth) acrylate, tetracyclododecyl (meth) acrylate, dicyclopentyl (meth) acrylate, etc. Mercapto methacrylate and dicyclopentyl (meth) acrylate are preferred.

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 fluorenyl group, a biphenyl group, a naphthyl group, and a fluorenyl group. , phenoxymethyl, 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)

Examples of the maleic imine-based resin include, for example, N-methyl maleimide, N-ethyl maleimide, and Nn-propyl maleimide as monomers. N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec-butylmaleimide, N-tert-butyl Maleidin, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-lauryl horse An alkylene-containing maleimide, N-cyclopropylmaleimide, N-cyclobutylmaleimide, etc., such as imine, N-stearic acid, maleimide, etc. An aliphatic hydrocarbon group such as N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide, etc.醯imine, N-phenylmaleimide, Nm-methylphenylmaleimide, No-methylphenylmaleimide, Np-methylphenylmaleimide A resin obtained by polymerizing an aromatic maleic imine or the like having an aryl group.

For example, a cyclic olefin copolymer of a copolymer represented by the following chemical formula (8) and a repeating unit represented by the following chemical formula (9) may be used as a resin.

(In the chemical formula (9), n is an integer of 0 or 1 to 3).

As such a cyclic olefin copolymer, for example, APL 8008T, APL 8009T, and APL 6013T (all manufactured by Mitsui Chemicals, Inc.) and the like can be used.

Further, it is preferable to form the adhesive layer 13 using a resin other than a photocurable resin (for example, a UV curable resin). On the other hand, after the photocurable resin is peeled off or removed from the adhesive layer 13, the residue may remain as a residue around the minute unevenness of the substrate 11. In particular, it is preferred to use a binder which is soluble in a specific solvent as the material constituting the adhesive layer 13. On the other hand, since the physical force can be applied to the substrate 11, the adhesive layer 13 can be removed by dissolving it in a solvent. When the adhesive layer 13 is removed, the adhesive layer 13 can be easily removed without breaking or deforming the substrate 11 from the substrate 11 having reduced strength.

Examples of the diluent solvent for forming the separation layer and the subsequent layer include hexane, heptane, octane, decane, methyl octane, decane, undecane, dodecane, tridecane, and the like. a linear hydrocarbon, a branched hydrocarbon having 3 to 15 carbon atoms, p-menthane, o-menthane, m-menthane, diphenylmethane, 1,4-decanediol, 1,8- Decylene glycol, decane, norbornane, decane, oxane, calane, longene, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, new Menthol, α-terpineol, β-terpineol, γ-terpineol, terpinene-1-ol, terpinene-4-ol, dihydroethylene rosin acetate, 1,4-anthracene oil a terpene solvent such as phenol, 1,8-nonyl phenol, decyl alcohol, humulone, citricone, thuja ketone, camphor, d-pinene, 1-decene, fennel, etc.; γ-butyl Lactones such as lactones; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-amyl ketone, methyl isoamyl ketone, 2-heptanone; Polyols such as alcohol, diethylene glycol, propylene glycol, dipropylene glycol, etc.; ethylene glycol monoacetate, diethylene glycol monoacetate a compound having an ester bond such as propylene glycol monoacetate or dipropylene glycol monoacetate; a monomethyl ether, a monoethyl ether, a monopropyl ether or a monobutyl group of the aforementioned polyol or a compound having the above ester bond; a derivative of a polyhydric alcohol such as a monoalkyl ether or a monophenyl ether or the like having an ether bond, etc. (such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl Ethyl ether (PGME) is preferred; dioxane-like cyclic ethers, or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate Ester, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate, etc.; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl Ether, dibenzyl An aromatic organic solvent such as ether, phenethyl ether or butylphenyl ether, or a condensed polycyclic hydrocarbon.

The condensed polycyclic hydrocarbon means a hydrocarbon in which two or more monocyclic rings can be supplied to each other in a condensed ring of the respective rings, and it is preferred to use two monocyclic condensed hydrocarbons.

As such a hydrocarbon, a combination of a 5-member ring and a 6-member ring, or a combination of two 6-member rings may be mentioned. Examples of the hydrocarbon in which a 5-membered ring and a 6-membered ring are combined include hydrazine, pentene, indoline, and tetrahydroanthracene. Examples of the hydrocarbon having two 6-membered rings are combined, and examples thereof include naphthalene and tetrahydrogen. Terenain and decalin.

〔The protective layer〕

The protective layer 15 is on the surface of the separation layer 14 and does not cover at least the surface that is not overlapped with the adhesive layer 13 among the faces of the support plate 12. The protective layer 15 protects the separation layer 14 from a high-temperature and long-time drug treatment such as a photoresist stripping treatment (photoresist stripping step), or a heat treatment step at a high temperature (for example, 260 ° C) thereafter. The resulting separation layer 14 is deteriorated.

The surface of the separation layer 14 covered by the protective layer 15 may be any surface that is included on the surface of the separation layer 14 and that is not overlapped with the adhesion layer 13 in at least the surface of the support sheet 12.

That is, in the present embodiment, the protective layer 15 may cover the surface of the separation layer 14 and not overlap the surface of the support layer 12 with the adhesion layer 13. However, the protective layer of the laminate of the present invention is not It is limited to such a form, and it is also possible to cover only the surface which is not overlapped with the subsequent layer on the surface of the separation layer and the surface which is not in contact with the support. In any of the configurations, since at least the surface of the separation layer and the surface which is not adjacent to the support (support plate) are covered with at least the surface which is not overlapped with the adhesion layer, the separation layer can be protected from the photoresist peeling treatment or the like. The deterioration caused by high temperature and long-term drug treatment.

The material for forming the protective layer 15 can be appropriately selected for the treatment to be performed by the laminate 10. That is, it is preferable to select a material which is resistant to the drug used in the treatment and the environment in which the treatment is performed. For example, if the laminate 10 is supplied to a high temperature and long time photoresist peeling step, it is sufficient to select resistance to the stripping liquid used in the step.

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

When the protective layer 15 is formed of an adhesive, the adhesive may be the same composition as the adhesive constituting the adhesive layer 13. As the above-mentioned adhesive agent constituting the adhesive layer 13, as described above, since the chemical resistance to the peeling liquid or the like is selected, if the protective layer 15 is formed by the above-described adhesive, the separation layer 14 can be favorably protected.

Further, the adhesive constituting the protective layer 15 is also a composition different from the adhesive constituting the adhesive layer 13. However, even if such an adhesive is used, it is more preferable as an adhesive which is a candidate for the adhesive constituting the adhesive layer 13. As the above-mentioned adhesive agent constituting the adhesive layer 13, as described above, it is possible to form a protective layer 15 by using an adhesive which is a candidate for the above-mentioned adhesive, since it is preferable to have a chemical resistance to a peeling liquid or the like. Protective separation layer 14.

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 plural types. The description of the block copolymer and the cycloolefin polymer is based on the description of each component carried out in the above-mentioned subsequent layer 13.

The thickness of the film of the protective layer 15 is preferably, for example, 1 to 10 μm. By the thickness of the film of the protective layer 15 being 1 μm or more, the protective layer 15 can be favorably subjected to high-temperature and long-time treatment of various chemicals. The thickness of the film of the protective layer 15 is preferably 10 μm or less, and the substrate 11 can be well separated in the step of separating the substrate 11 from the laminate.

<Method of Manufacturing Laminated Body>

Next, a method of manufacturing the laminate of the present invention will be described using FIG. Fig. 2 is a view showing an embodiment of a method for producing a laminate of the present invention.

As described above, the protective layer provided in the laminate of the present invention may be on the surface of the separation layer and may not include at least a surface which is not overlapped with the subsequent layer, and may be, for example, in the separation layer. The surface is not covered with the surface of the support layer, and the surface overlapping the adhesion layer may be covered on the surface of the separation layer, and the surface not overlapped with the adhesion layer may be covered only on the surface of the separation layer. In the form, as shown in the laminate 10, the case where the surface of the separation layer is produced and the surface which is not overlapped with the support body is also covered with the surface of the adhesion layer is described.

One embodiment of the method for producing a laminate of the present invention The method includes the steps of: forming a separation layer on the support plate 12 to form a separation layer 14 which is deteriorated by absorbing light; forming an adhesion layer on the substrate 11 to form an adhesion layer 13; and the substrate 11, the adhesion layer 13, the separation layer 14, and the support The laminating step of laminating the sheets 12; and further including laminating in the laminating step before the laminating step, on the surface of the separating layer 14 and not in the vicinity of the supporting plate 12 A protective layer 15 forming step of forming a protective layer covering at least the surface not overlapping the adhesive layer 13 is formed.

[Separation layer forming step]

The separation layer forming step refers to a step of forming a separation layer 14 which is deteriorated by absorption of 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 can be mentioned.

[Next layer formation step]

The layer forming step is followed by forming an adhesive layer 13 on the substrate 11. As shown in FIG. 2, an adhesive containing the hydrocarbon-based resin as a main component and dissolved in a solvent is spin-coated on the substrate 11. Further, an example in which the adhesive layer is cured by stepwise baking and the adhesive layer is cured to form the adhesive layer 13 is exemplified. Further, the adhesive layer forming step in the method for producing a laminate of the present invention may be carried out by forming an adhesive layer on the substrate or on the separation layer. That is, the adhesive layer 13 may be formed on the substrate 11 as in the present embodiment, or an adhesive layer may be formed on the separation layer. When the form of the adhesion layer is formed on the separation layer, in the surface of the separation layer and not in contact with the support layer, the adhesion layer is not formed. The protective layer described later may be formed on the exposed surface.

[Protective layer forming step]

The protective layer forming step means that the protective layer 15 covering at least the surface not overlapping the adhesive layer 13 is formed on the surface of the separation layer 14 and not in the subsequent surface of the support layer 12 when laminating in the laminating step. step. As shown in Fig. 2, a protective agent containing a block copolymer or a hydrocarbon resin as a main component and dissolved in a solvent is spin-coated on the separation layer 14 formed on the support plate 12. Thereafter, the step of forming the protective layer 15 by curing the protective agent by raising the temperature and performing the stepwise baking is an example. Further, the protective layer 15 can also be formed by forming an adhesive used for the adhesive layer 13.

[Lamination step]

The laminating step refers to a step of laminating in the order of the substrate 11, the subsequent layer 13, the separation layer 14, and the support plate 12. As a specific method of the laminating step, as shown in FIG. 2, the surface on which the protective layer 15 is formed on the substrate 11 and the surface of the support plate 12 on which the adhesive layer 13 is formed are bonded together, and under vacuum A method of laking and pressing to laminate.

Further, the method for producing the laminate of the present invention is not particularly limited as long as it is laminated in the order of the substrate, the adhesive layer, the separation layer, and the support, and the protective layer is at least a portion that does not overlap the separation layer and the adhesion layer. The order of the steps.

[Examples] [Example 1] (modulation of the composition of the adhesive)

"TOPAS (trade name) 8007X10, cyclic olefin copolymer, Mw = 95,000, Mw / Mn = 1.9, norbornene: ethylene = 35:65 (mr ratio)", manufactured by Polyplastics Co., Ltd., which is an adhesive resin. The parts by weight are dissolved in 800 parts by weight of decalin in the main solvent. Then, a butyl acetate solution containing a thermal polymerization inhibitor was added in an amount of 1 part by weight of the thermal polymerization inhibitor and 20 parts by weight of butyl acetate, based on 100 parts by weight of the adhesive resin. Thereby, an adhesive composition is obtained.

(Process)

The fluorocarbon film (thickness: 1 μm) of the separation layer was formed on the support by a CVD method using C ₄ F ₈ as a reaction gas under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2,500 W, and a film formation temperature of 240 ° C. (12-inch glass substrate, thickness: 700 μm) (separation layer forming step), the above-mentioned adhesive composition was applied thereon, and baked at 220 ° C for 3 minutes to form a protective layer having a film thickness of 3 μm (protective layer forming step) . The above-mentioned adhesive composition was spin-coated on a 12-inch wafer to 280 parts by weight of the above-mentioned adhesive composition, and heated at 100 ° C, 160 ° C, and 200 ° C for 3 minutes to form an adhesive layer (film thickness: 50 μm) (subsequent layer formation). Step), bonding to a glass support was carried out for 3 minutes under vacuum at 220 ° C and 4000 Kg to form a laminate (laminating step).

(drug resistance evaluation)

The wafer was ground to 40 μm, and the evaluation of the chemical resistance of various stripping liquids and organic solvents was carried out. For the stripping liquid, NMP (N-methyl-2-pyrrolidone), DMSO (dimethyl sulfonium), and Stripper 104 and Stripper 106 of the stripping liquid manufactured by Tokyo Chemical Industry Co., Ltd. are used (all are trade names). ). The evaluation conditions are shown in Table 1. In addition, the visual inspection was performed visually, and the end of the end portion was observed from the glass side and the substrate side by the microscope, and those having no peeling or the like were rated as "○", and those having problems were evaluated as "x".

The laminate of this example was subjected to a high-temperature, long-time peeling liquid immersion test, and the results did not cause any problems.

(heat treatment evaluation)

The laminate after the evaluation of the chemical resistance was heat-treated in an N ₂ atmosphere at 260 ° C for 30 minutes. Then, the visual inspection was performed visually, and the result of observing the end portion from the glass side and the substrate side by the microscope was evaluated as "○" in the case of no peeling, and as "X" in the case of a problem.

(separation evaluation)

The laminate after the evaluation of the heat treatment described above was irradiated with a laser beam having a wavelength of 532 nm from the side of the laminate support body toward the separation layer. As a result, those who can be separated from the support are rated as "○", and those who cannot be separated are rated as "X".

[Examples 2 to 13 and Comparative Examples 1 to 4]

Except that the adhesive resin applied to the support (glass) and the adhesive resin applied to the substrate (wafer) were changed, and the film thicknesses thereof were as shown in Table 1 below, the other methods were carried out in the same manner as in Example 1. The same operation and similar evaluation of chemical resistance and the like. The results are shown in Table 1.

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

APEL8008T (manufactured by Mitsui Chemicals, Inc.): cyclododecene: ethylene = 20:80 (mole 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 denaturation, styrene content 28% by weight, molecular weight 67000

TOPAS6017 (made by Polyplastics Co., Ltd.): decene: ethylene = 58:42 (mole ratio), molecular weight 82,000

Further, in Comparative Examples 1 to 4, as a result of evaluation of chemical resistance, in the peeling liquid immersion test at a high temperature and for a long period of time, all of them were peeled off, and irregularities were generated on the crucible. Further, the wafer was broken after the heat treatment step in the N ₂ environment at 260 ° C, and the glass could not be separated.

[Example 14]

A fluorocarbon film (thickness: 1 μm) was formed on a 12-inch glass under the same conditions as in Example 1 by plasma CVD, and the same electrode composition as in Example 1 was dropped from the end of the wafer to 3 mm. Spin coating at the same time. Thereafter, heating was carried out under the same conditions as in Example 1 to confirm that the film thickness was 3 μm. The subsequent processes were carried out in the same manner as in Example 1 and evaluated. As a result, it was confirmed that there was no resistance caused by the stripping solution and the organic solvent. The question of character.

[Industrial Applicability]

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

10‧‧‧Layer

11‧‧‧Substrate

12‧‧‧Support plate (support)

13‧‧‧Next layer

14‧‧‧Separation layer

15‧‧‧Protective layer

Claims (8)

A laminate characterized in that a substrate, an adhesive layer, a separation layer which is deteriorated by absorption of light, and a support are laminated in this order, and on the surface of the separation layer and not in contact with the support body, A protective layer covering at least a surface that is not overlapped with the above-described subsequent layer is provided. The laminate according to claim 1, wherein the protective layer is selected from the group consisting of a block copolymer and a cycloolefin polymer. The laminate according to claim 1 or 2, wherein the protective layer is on a surface of the separation layer and not in contact with the support, and covers a surface overlapping the laminate. The laminate according to claim 1 or 2, wherein the protective layer is a surface which is on the surface of the separation layer and which is not in contact with the support, and covers only a surface which is not overlapped with the subsequent layer. The laminate according to any one of claims 1 to 4, wherein the protective layer is composed of an adhesive. The laminate according to claim 5, wherein the adhesive constituting the protective layer is the same as the adhesive constituting the adhesive layer. The laminate of claim 5, wherein the adhesive constituting the protective layer and the adhesive constituting the adhesive layer are different compositions. A method for producing a laminate comprising: a separation layer forming step of forming a separation layer which is deteriorated by absorbing light on a support; a subsequent layer formation step of forming an adhesion layer on the substrate or the separation layer, a laminating step of laminating in accordance with the substrate, the adhesive layer, the separation layer, and the support; and further comprising a protective layer forming step before the laminating step; the protective layer forming step is performed in the laminating step When laminating them, a protective layer covering at least the surface not overlapping the above-mentioned subsequent layer is formed on the surface of the separation layer and not in contact with the support.