JP6022878B2 - Laminate manufacturing method and separation layer forming apparatus - Google Patents

Description

  The present invention relates to a method for manufacturing a laminate in which a substrate and a support are laminated, and a separation layer forming apparatus.

  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 decreases due to the thinning of the wafer substrate, a circuit is formed on the wafer substrate while automatically supporting the substrate while the support is bonded to the wafer substrate to prevent damage to the thinned wafer substrate. Etc. are mounted. Then, after the manufacturing process, the wafer substrate is separated from the support. Therefore, it is preferable that the wafer substrate and the support are firmly bonded during the manufacturing process, but it is preferable that the wafer substrate can be smoothly separated from the support after the manufacturing process.

  When the wafer substrate and the support are firmly bonded, depending on the adhesive material, it is difficult to separate the support from the wafer substrate without damaging the structure mounted on the wafer substrate. Therefore, it is an extremely difficult temporary fixing technology that realizes strong adhesion between the wafer substrate and the support 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 after the semiconductor wafer is processed, the support side The photothermal conversion layer is decomposed by irradiating radiant energy from the substrate to separate the semiconductor wafer from the support.

  In addition, in the laminate described in Patent Document 2, the material constituting the photoelectric conversion layer is a thermally decomposable resin having a functional group capable of self-crosslinking by heat treatment in the molecule, or heat that can be cross-linked by ultraviolet or visible light. The chemical resistance of the photoelectric conversion layer is improved by blending a degradable resin or a precursor thereof.

Japanese Patent Laying-Open No. 2005-159155 (released on June 16, 2005) JP 2004-64040 A (published February 26, 2004) JP 9-50897 A (published February 18, 1997)

  According to the knowledge of the present inventors, when a separation layer is formed on a support and various treatments are performed on a laminate in which a wafer is bonded to the separation layer, depending on the chemicals used in the treatment, There may be a case where the separation layer is partially denatured and peeled off from the support.

  For example, when the laminate is exposed to a stripping solution containing a polar solvent (for example, a stripping solution containing an aprotic solvent such as N-methyl-2-pyrrolidone) at a high temperature and for a long time in a resist stripping step or the like, The stripping solution may permeate from the edge end surface of the laminate, and the separation layer may be peeled off from the support at the portion.

  As described above, if the separation layer is peeled off during the process, the wafer is cracked, cracked, or uneven, and the process cannot proceed.

  The present invention has been made in view of such problems. When a separation layer is formed on a support and a desired structure is applied to a laminate in which a wafer is bonded to the separation layer, the separation is performed. In order to suppress the peeling of the layer from the support, the main object is to provide a method for producing a laminate excellent in chemical resistance and a separation layer forming apparatus used therefor.

  In order to solve the above-described problems, a manufacturing method according to the present invention includes a substrate, a light-transmitting support that supports the substrate, and the substrate and the support. A method of manufacturing a laminate including a separation layer that is altered by absorbing irradiated light, wherein the support is positioned vertically below the exhaust hole in a reaction chamber having an exhaust hole. A separation layer forming step of forming the separation layer on the support by plasma CVD is included.

  In addition, the separation layer forming apparatus according to the present invention forms a separation layer on a light-transmitting support by a plasma CVD method, wherein the separation layer is altered by absorbing light irradiated through the support. An apparatus comprising: a reaction chamber having an exhaust hole; and a mounting table for mounting the support in the reaction chamber, wherein the exhaust hole is 1 mm or more with respect to the mounting table. It is characterized by being arranged vertically upward.

  ADVANTAGE OF THE INVENTION According to this invention, it can be excellent in chemical resistance and can provide the laminated body which can suppress suitably that a separated layer peels from a support body when performing a desired process with respect to a laminated body.

It is a figure which shows typically each process of the manufacturing method of the laminated body which concerns on one Embodiment of this invention. (A) shows sectional drawing and its partial enlarged view which show the laminated body which concerns on one Embodiment of this invention, (b) shows sectional drawing which shows the laminated body which concerns on a prior art, and its partial enlarged view. (A) is sectional drawing which shows the example of 1 structure of the separation layer manufacturing apparatus used in the separation layer formation process in this embodiment, (b) is a figure which shows the positional relationship of the exhaust hole and a support body. (A) is sectional drawing which shows the reference structural example of a separated layer manufacturing apparatus, (b) is a figure which shows the positional relationship of the exhaust hole and a support body.

<Method for producing laminate>
A manufacturing method according to an embodiment of the present invention will be described with reference to FIGS. 1 and 2. FIG. 1 is a diagram schematically showing each step of the method for manufacturing a laminate according to the present embodiment. Moreover, (a) of FIG. 2 shows sectional drawing which shows the laminated body 1 which concerns on this embodiment, and its partial enlarged view. FIG. 2B shows a cross-sectional view and a partially enlarged view showing the laminate 2 according to the prior art.

  A laminate 1 manufactured by the method for manufacturing a laminate according to the present embodiment includes a support 12, a surface treatment film 14, a separation layer 15, an adhesive layer 13, and a substrate 11 stacked in this order (see FIG. 2). (See (a)). As shown in FIG. 1, the manufacturing method of the laminated body which concerns on this embodiment is the surface treatment process ((1) of FIG. 1) which hydrophobizes the surface in which the separation layer of the support body 12 is provided, and after a surface treatment process, A separation layer forming step (FIG. 1 (2)) for forming the separation layer 15 on the support 12, an adhesive layer forming step ((3) in FIG. 1) for forming the adhesive layer 13 on the substrate 11, and the substrate 11 And the support 12 are included in a lamination process in which the adhesive layer 13 and the separation layer 15 are bonded together. However, the surface treatment step can be omitted. In that case, the surface treatment film 14 is not formed.

[Surface treatment process]
The surface treatment step in the method for manufacturing a laminate according to the present embodiment is a step of hydrophobizing the surface on which at least the separation layer 15 of the light-transmissive support 12 that supports the substrate 11 is provided and has a hydrophilic surface. is there.

  In the conventional manufacturing method of a laminated body, when using the support body which consists of glass as the support body 12, the contact angle of the water with respect to the surface of this support body 12 takes a low value of 10-20 degrees or less. In particular, the contact angle of water with the surface of the support 12 made of glass subjected to oxygen plasma treatment takes a lower value of 0 to 5 °. In contrast, the material used for the separation layer 15 is hydrophobic. The inventors of the present invention pay attention to this point and have found that this is one factor causing the breakage of the separation layer in the laminate. Then, the present inventors provide a hydrophobic surface treatment film 14 by surface-treating the support 1 made of hydrophilic glass by a surface treatment process, and thereby improve the affinity between the support 12 and the separation layer 15. It has been found that by increasing, the adverse effect on the support 1 due to the separation of the separation layer 15 can be reduced.

  That is, by increasing the affinity between the support 12 and the separation layer 15, the separation layer 15 is prevented from peeling off from the support 12 when a desired treatment such as a chemical treatment is performed on the laminate 1. be able to.

  In addition, since the chemical resistance of the material of the separation layer 15 itself is not improved, an effect that the residue of the separation layer 15 attached on the support 12 after the separation process of the support 12 can be easily washed. Play. That is, the laminate according to the present invention can achieve the conflicting benefits of maintaining the ease of cleaning the separation layer while eliminating breakage of the separation layer due to chemicals. This is an effect that cannot be achieved by a method of improving the chemical resistance of the separation layer (photothermal conversion layer) itself as in the conventional laminate.

  In the surface treatment step, the surface is preferably hydrophobized so that the contact angle of water with the surface is 50 ° or more. Thereby, the affinity between the support 12 and the separation layer 15 can be sufficiently improved.

(Support)
The support 12 is a support that supports the substrate 11 and has light transmittance. Therefore, when light is irradiated from the outside of the laminated body 10 toward the support body 12, the light passes through the support body 12 and reaches the separation layer 15. Further, the support 12 does not necessarily need to transmit all the light, and it is sufficient that the support 12 can transmit the light to be absorbed by the separation layer 15 (having a predetermined wavelength).

  The support 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 12 include those made of glass, silicon, and acrylic resin.

  In addition, the support body 12 consists of a hydrophilic substance, for example, when using what consists of glass, the contact angle of the water with respect to the surface of this support body 12 takes a low value of 10-20 degrees or less. In particular, the contact angle of water with the surface of the support 12 made of glass subjected to oxygen plasma treatment takes a lower value of 0 to 5 °.

  The surface treatment agent for forming the surface treatment film 14 is not particularly limited as long as the surface of the support 12 can be hydrophobized. For example, a silylating agent, a polymer coating agent, and the like can be used, and particularly preferably. Hexamethyldisilazane can be used. Each surface treatment agent will be described below.

(Silylating agent)
The silylating agent used in the surface treatment agent in the surface treatment step according to the present invention is not particularly limited, and any conventionally known silylating agent can be used. As such a silylating agent, for example, a silylating agent having a substituent represented by the following general formula (1) can be used.

(In the general formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a nitrogen-containing group or an organic group, provided that they are included in R ¹ , R ² and R ^3. (The total number of carbon atoms is one or more.)
More specifically, as the silylating agent having a substituent represented by the general formula (1), silylating agents represented by the following general formulas (2) to (8) can be used.

(In the general formula (2), R ¹ , R ² and R ³ are the same as in the general formula (1), R ⁴ represents a hydrogen atom or a saturated or unsaturated alkyl group, and R ⁵ represents Represents a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an acetyl group, or a saturated or unsaturated heterocycloalkyl group, and R ⁴ and R ⁵ are saturated with a nitrogen atom bonded to each other. Or an unsaturated heterocycloalkyl group may be formed.)

(In the general formula (3), R ¹ , R ² and R ³ are the same as in the general formula (1), R ⁶ represents a hydrogen atom, a methyl group, a trimethylsilyl group, or a dimethylsilyl group, R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an organic group, provided that the total number of carbon atoms contained in R ⁷ , R ⁸ and R ⁹ is 1 or more.

(In the general formula (4), R ¹ , R ² and R ³ are the same as those in the general formula (1), and X represents O, CHR ²² , CHOR ²² , CR ²² R ²² , or NR ²³ . R ¹⁰ and R ²² each independently represent a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a trialkylsilyl group, a trialkylsiloxy group, an alkoxy group, a phenyl group, a phenylethyl group, or Represents an acetyl group, and R ²³ represents a hydrogen atom, an alkyl group, or a trialkylsilyl group.)

(In the general formula (5), R ¹ , R ² and R ³ are the same as in the general formula (1), R ⁶ is the same as in the general formula (3), and R ¹¹ is hydrogen. Represents an atom, a saturated or unsaturated alkyl group, a trifluoromethyl group, or a trialkylsilylamino group.)

(In the general formula (6), R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group, or a trialkylsilyl group, and at least one of R ¹² and R ¹³ represents a trialkylsilyl group. )

(In the general formula (7), R ¹⁴ represents a trialkylsilyl group, and R ¹⁵ and R ¹⁶ each independently represents a hydrogen atom or an organic group.)

(In the general formula (8), R ¹ , R ² and R ³ are the same as in the general formula (1), R ¹⁷ represents an organic group, and R ¹⁸ is not present or present. , —SiR ²⁴ R ²⁵ R ²⁶ , R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom, a halogen atom, a nitrogen-containing group or an organic group, and any one of R ²⁴ , R ^{25 and} R ²⁶ One may combine with any one of R ¹ , R ² or R ³ via a nitrogen atom to form an imino group.)
Examples of the silylating agent represented by the above formula (2) include N, N-dimethylaminotrimethylsilane, N, N-dimethylaminodimethylsilane, N, N-dimethylaminomonomethylsilane, N, N-diethylaminotrimethylsilane, t-butylaminotrimethylsilane, allylaminotrimethylsilane, trimethylsilylacetamide, N, N-dimethylaminodimethylvinylsilane, N, N-dimethylaminodimethylpropylsilane, N, N-dimethylaminodimethyloctylsilane, N, N- Examples thereof include dimethylaminodimethylphenylethylsilane, N, N-dimethylaminodimethylphenylsilane, N, N-dimethylaminodimethyl-t-butylsilane, N, N-dimethylaminotriethylsilane, and trimethylsilanamine.

  As the silylating agent represented by the above formula (3), hexamethyldisilazane (HMDS), N-methylhexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-dimethyldi Silazane, 1,2-di-N-octyltetramethyldisilazane, 1,2-divinyltetramethyldisilazane, heptamethyldisilazane, nonamethyltrisilazane, tris (dimethylsilyl) amine, tris (trimethylsilyl) amine, penta Examples thereof include methylethyl disilazane, pentamethylvinyl disilazane, pentamethylpropyl disilazane, pentamethylphenylethyl disilazane, pentamethyl-t-butyldisilazane, pentamethylphenyl disilazane, and trimethyltriethyldisilazane.

  Examples of the silylating agent represented by the above formula (4) include trimethylsilyl acetate, dimethylsilyl acetate, monomethylsilyl acetate, trimethylsilylpropionate, trimethylsilylbutyrate, trimethylsilyloxy-3-penten-2-one, and the like.

  Examples of the silylating agent represented by the above formula (5) include bis (trimethylsilyl) urea, N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide and the like.

  Examples of the compound represented by the above formula (6) include bis (trimethylsilyl) trifluoroacetamide and the like, and examples of the compound represented by the above formula (7) include 2-trimethylsiloxypent-2-ene-4- ON etc. are mentioned. Examples of the compound represented by the above formula (8) include 1,2-bis (dimethylchlorosilyl) ethane, t-butyldimethylchlorosilane, 2,2,5,5-tetramethyl-2,5-disila-1- And azacyclopentane.

  Moreover, a cyclic silazane compound can also be used as a silylating agent. As this cyclic silazane compound, 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane, 2,2,6,6-tetramethyl-2,6-disila-1-aza Cyclic disilazane compounds such as cyclohexane, cyclic trisilazane compounds such as 2,2,4,4,6,6-hexamethylcyclotrisilazane, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane, And cyclic tetrasilazane compounds such as 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane.

  The silylating agents exemplified above can be used alone or in admixture of two or more.

  A silylated heterocyclic compound can also be added to the silylating agent. The silylated heterocyclic compound can promote the silylation of the surface of the support 12 by the silylating agent (for example, hexamethyldisilazane (HMDS)) by catalytic action. Further, the surface of the support 12 can be highly hydrophobized by the catalytic action.

  The silylated heterocyclic compound used for the surface treatment agent in the surface treatment step is a compound having a structure in which a heterocyclic group is bonded to a silyl group. Examples of such a compound include compounds represented by the following general formula (9).

(In the above general formula (9), R ¹⁹ , R ²⁰ and R ²¹ each independently represents a hydrogen atom or an organic group, provided that at least one of R ¹⁹ , R ²⁰ and R ²¹ represents an organic group. A represents a heterocyclic group, which may have a substituent.
The silylated heterocyclic compound is preferably a silylated nitrogen-containing heterocyclic compound in which A in the general formula (9) has a nitrogen atom. The silylated heterocyclic compound is preferably a compound in which A in the general formula (1) has aromaticity. When A in the general formula (9) has aromaticity, the hydrophobicity of the surface of the support 12 treated with the surface treatment agent can be increased.

  In addition, the silylated heterocyclic compound is particularly preferable from the viewpoint of availability and that the surface of the support 12 can be provided with a large hydrophobicity, in which A in the general formula (9) is an aromatic ring having a nitrogen atom. . Examples of such silylated heterocyclic compounds include silylated imidazole compounds and silylated triazole compounds.

  Examples of the silylated heterocyclic compound used in the surface treatment agent include monomethylsilylimidazole, dimethylsilylimidazole, trimethylsilylimidazole, monomethylsilyltriazole, dimethylsilyltriazole, trimethylsilyltriazole and the like. These silylated heterocyclic compounds can be used alone or in admixture of two or more.

  The solvent is not particularly limited as long as it can dissolve the silylating agent and the silylated heterocyclic compound, and a conventionally known solvent can be used.

  Specifically, sulfoxides such as dimethylsulfoxide; sulfones such as dimethylsulfone, diethylsulfone, bis (2-hydroxyethyl) sulfone, tetramethylenesulfone; N, N-dimethylformamide, N-methylformamide, N, N -Amides such as dimethylacetamide, N-methylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-hydroxymethyl-2 -Lactams such as pyrrolidone and N-hydroxyethyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidi Non-imidazolidinones such as dimethyl glycol, dimethyl Dialkyl glycol ethers such as glycol, dimethyl triglycol, methyl ethyl diglycol and diethyl glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono- n-propyl ether , Propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (Poly) alkylene glycol monoalkyl ethers such as monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (Poly) alkylene glycol monoalkyl ether acetates such as dimethyl ether, diethyl ether, methyl ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Other ethers; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; 2-hydroxy-2-methylpropion Acid ethyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxyprop Methyl onate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate , Ethyl acetate, acetic acid-n-propyl, acetic acid-i-propyl, acetic acid-n-butyl, acetic acid-i-butyl, formic acid-n-pentyl, acetic acid-i-pentyl, propionic acid-n-butyl, ethyl butyrate, Others such as n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate Esters: Lactones such as β-propyrolactone, γ-butyrolactone, δ-pentyrolactone, p- Pentane, diphenyl-menthane, limonene, terpinene, bornane, norbornane, terpenes such as pinane; and the like. These solvents can be used alone or in admixture of two or more.

  In addition, when using disilazane as a surface treating agent, it is preferable to use a 5- or 6-membered lactone compound as a solvent. Among these, at least one selected from the group consisting of γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-hexanolactone and γ-hexanolactone is preferable. These solvents can be used alone or in combination of two or more. Among the solvent components listed above, γ-butyrolactone is particularly preferably used in terms of industrial availability.

  When the surface treatment agent contains a solvent, it is practically preferable that the total concentration of the silylating agent and the silylated heterocyclic compound contained in the surface treatment agent is 0.1% by mass or more.

  The surface treatment step using a silylating agent is a step of treating the surface of the support 12 by exposing the surface treatment agent to the surface of the support 12.

  As a method for exposing the surface treatment agent to the surface of the support 12, a conventionally known method can be used without particular limitation. For example, the surface treatment agent is vaporized to form a vapor, and the vapor is used as the surface of the support 12. And a method of bringing the surface treatment agent into contact with the surface of the support 12 by a spin coating method, a dipping method, or the like. By such an operation, the affinity of the separation layer 15 for the support 12 can be improved by silylating the surface of the support 12 and forming the hydrophobic surface treatment film 14 on the support 12.

(Polymer coating)
Moreover, in order to form the surface treatment film | membrane 14 provided between the support body 12 and the separation layer 15 as a surface treatment agent used in the surface treatment process of this embodiment, a mass average molecular weight is 1,000-50,000. A polymer coating containing an epoxy resin may be used.

  The “epoxy resin” includes a relatively low molecular weight polymer (prepolymer) having two or more epoxy groups in one molecule, and a thermosetting resin generated by a ring-opening reaction of the epoxy group.

  The epoxy resin (hereinafter referred to as “component (G)”) has a mass average molecular weight of 1,000 to 50,000, preferably 2,000 to 40,000, and 3,000 to 30,000. Is more preferable, and 3,000 to 20,000 is most preferable.

  When the weight average molecular weight of the component (G) is in the above range, a surface-treated film that is well bonded to the support can be formed, and the affinity with the support 12 is excellent.

  When the mass average molecular weight is not less than the lower limit, the crosslinking efficiency with the support 12 is increased, and the support 12 and the surface treatment film are firmly bonded. Further, when a solution obtained by dissolving the component (G) in an organic solvent is used as the surface treatment agent, the solution has an appropriate viscosity, and the solution can be easily applied uniformly on the support 12. On the other hand, by being below the upper limit, an increase in the viscosity of the solution is suppressed, and it becomes easy to uniformly apply the solution on the support.

  In the above, “mass average molecular weight” indicates a value in terms of polystyrene conversion by gel permeation chromatography. Hereinafter, the mass average molecular weight may be expressed as Mw.

  As the component (G), an epoxy resin having an unopened epoxy group is preferable because the surface of the support 12 is hydrophobized. For example, an epoxy group represented by the following general formula (g0-1) is a polymer. A compound in which the carbon atom of the epoxy group forms part of the main chain in the middle of the main chain of the compound; the epoxy group represented by the following general formula (g0-2) is a side chain of the polymer compound In which the epoxy group represented by the following general formula (g0-2) forms the terminal of the main chain of the polymer compound; the epoxy represented by the following general formula (g0-3) The group contained in the side chain of the polymer compound, the epoxy group represented by the following general formula (g0-3) forming the terminal of the main chain of the polymer compound; the following general formula (g0 -4) is contained in the side chain of the polymer compound The epoxy group represented by the following general formula (g0-4) forms the terminal of the main chain of the polymer compound; the epoxy group represented by the following general formula (g0-5) is the polymer compound The thing contained in the side chain, the thing in which the epoxy group represented by the following general formula (g0-5) forms the terminal of the principal chain of a high molecular compound, etc. are mentioned.

Wherein R ⁶³ and R ⁶⁴ are each independently a hydrogen atom or an alkyl group. R ^{66 to} R ⁶⁸ are each independently a hydrogen atom or an alkyl group. R ^66a , R ^69a and R ^69b are each Independently a hydrogen atom or an alkyl group, g4 is an integer of 1-20, and g5 is an integer of 1-20.)
In the above formula (g0-1), R ⁶³ and R ⁶⁴ are each independently a hydrogen atom or an alkyl group. The alkyl group for R ⁶³ and R ⁶⁴ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Of these, R ⁶³ and R ⁶⁴ are each preferably a hydrogen atom or a methyl group.

In the above formula (g0-2), R ^{66 to} R ⁶⁸ are each independently a hydrogen atom or an alkyl group. The alkyl group for R ^{66 to} R ⁶⁸ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Among these, R ⁶⁶ is preferably a hydrogen atom or a methyl group; R ^{67 to} R ⁶⁸ are each preferably a hydrogen atom or a methyl group, and particularly preferably all are hydrogen atoms.

In the above formula (g0-3), R ^66a , R ^69a and R ^69b are each independently a hydrogen atom or an alkyl group. The alkyl group in R ^66a , R ^69a and R ^69b is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. Among these, R ^66a is preferably a hydrogen atom or a methyl group; R ^69a and R ^69b are each preferably a hydrogen atom or a methyl group, and particularly preferably both are hydrogen atoms.

  g4 is an integer of 1 to 20, preferably 1 to 5, more preferably 1 or 2, and most preferably 2.

  g5 is an integer of 1 to 20, preferably 1 to 5, more preferably 1 or 2, and most preferably 1.

  Among the above, the epoxy group represented by the general formula (g0-1) is present in the middle of the main chain of the polymer compound, and the carbon atom of the epoxy group forms part of the main chain. An epoxy group represented by the general formula (g0-2) is contained in the side chain of the polymer compound, and an epoxy group represented by the general formula (g0-3) is contained in the side chain of the polymer compound. And those having an epoxy group represented by the general formula (g0-4) in the side chain of the polymer compound are preferred.

  More preferable examples of the component (G) include those having a repeating structure of the structural unit (g1) containing an epoxy group.

  Those having this repeating structure are preferably in the range of 1,000 to 50,000 because the affinity between the support 12 and the separation layer 15 is improved.

  The structural unit (g1) containing an epoxy group is not particularly limited, and examples thereof include a structural unit composed of an organic group containing an epoxy group, and a carbon atom of the epoxy group forming part of the main chain.

  Other structural units (g1) include a structural unit derived from hydroxystyrene, a structural unit derived from an acrylate ester, or a structural unit having a cyclic main chain (hereinafter referred to as “main-chain cyclic structural unit”). Among these, a structural unit derived from an acrylate ester is preferable.

  Here, in the present specification and claims, the “structural unit derived from hydroxystyrene” means a structural unit formed by cleavage of an ethylenic double bond of hydroxystyrene.

  “Hydroxystyrene” is a concept that includes hydroxystyrene and those in which the hydrogen atom at the α-position of hydroxystyrene is substituted with another substituent such as an alkyl group, and derivatives thereof. Note that the α-position (α-position carbon atom) of a structural unit derived from hydroxystyrene means a carbon atom to which a benzene ring is bonded, unless otherwise specified.

  Specific examples of the alkyl group as a substituent at the α-position in hydroxystyrene include an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , T-butyl groups, pentyl groups, isopentyl groups, neopentyl groups, and the like, and linear or branched alkyl groups.

  “A structural unit derived from an acrylate ester” means a structural unit formed by cleavage of an ethylenic double bond of an acrylate ester.

  In the present specification, the “main chain cyclic structural unit” has a monocyclic or polycyclic ring structure, and at least one, preferably two or more carbon atoms on the ring of the ring structure. A structural unit constituting the main chain.

  “Acrylic acid esters” include those in which a hydrogen atom is bonded to the carbon atom at the α-position, and those in which a substituent (atom or group other than a hydrogen atom) is bonded to the carbon atom in the α-position. Include concepts. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms and a halogenated alkyl group having 1 to 5 carbon atoms. Note that the α-position (α-position carbon atom) of a structural unit derived from an acrylate ester means a carbon atom to which a carbonyl group is bonded, unless otherwise specified.

  In the acrylic ester, the alkyl group having 1 to 5 carbon atoms as the substituent at the α-position, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl And a lower linear or branched alkyl group such as a group, a pentyl group, an isopentyl group and a neopentyl group.

  Further, as the halogenated alkyl group having 1 to 5 carbon atoms, specifically, a part or all of the hydrogen atoms in the above-mentioned “alkyl group having 1 to 5 carbon atoms as a substituent at the α-position” are substituted with halogen atoms Group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable.

  The α-position of the acrylate ester is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. Are more preferably an alkyl group or a fluorinated alkyl group having 1 to 5 carbon atoms, and most preferably a hydrogen atom or a methyl group in terms of industrial availability.

  As the structural unit (g1), for example, structural units represented by the following general formulas (g1-1) to (g1-4) are disclosed in paragraphs [0012] to [0042] of JP-A-2003-076012. And a structural unit derived from the compound.

  Especially, since it is excellent in the effect which hydrophobizes the surface of the support body 12, it contains at least 1 type selected from the group which consists of a structural unit represented by the following general formula (g1-1)-(g1-4). Is preferred.

(In the formula, R ⁶¹ and R ⁶² each independently represent a divalent hydrocarbon group which may have a substituent, and R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom or an alkyl group. R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, R ⁶⁵ is a divalent hydrocarbon group which may have a substituent, and R ⁶⁶ R ⁶⁸ is each independently a hydrogen atom or an alkyl group, R ^65a is a divalent hydrocarbon group which may have a substituent, and R ^66a , R ^69a and R ^69b are each independently A hydrogen atom or an alkyl group, g4 is an integer of 1 to 20, and g5 is an integer of 1 to 20. R ^65b is a divalent hydrocarbon group which may have a substituent.
In the above formula (g1-1), R ⁶¹ and R ⁶² are each independently a divalent hydrocarbon group which may have a substituent.

  The term “having a substituent” for the hydrocarbon group means that part or all of the hydrogen atoms in the hydrocarbon group are substituted with groups or atoms other than hydrogen atoms.

In R ⁶¹ or R ⁶² , the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

  “Aliphatic hydrocarbon group” means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

Specific examples of the aliphatic hydrocarbon group for R ⁶¹ or R ⁶² include a linear or branched aliphatic hydrocarbon group, and an aliphatic hydrocarbon group containing a ring in the structure thereof.

  The linear or branched aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, still more preferably 1 to 5, and most preferably 1 to 2.

As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.

As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 -CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH ₂ CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - - CH 2 CH (CH 3) CH 2 alkyltetramethylene groups such as; -CH (CH _{3 ) CH 2 CH 2 CH 2 -} , - CH 2 CH (CH 3) CH 2 CH 2 Alkyl alkylene group such as an alkyl tetramethylene group, etc. and the like. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

  The linear or branched aliphatic hydrocarbon group (hereinafter referred to as “chain aliphatic hydrocarbon group”) may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms, and an oxygen atom (═O).

  Examples of the aliphatic hydrocarbon group containing a ring in the structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing two or more hydrogen atoms from an aliphatic hydrocarbon ring), and the cyclic aliphatic hydrocarbon group described above. And a group that is bonded to the terminal of the chained aliphatic hydrocarbon group or intervenes in the middle of the chained aliphatic hydrocarbon group.

  The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.

  The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. As the monocyclic group, a group in which two or more hydrogen atoms are removed from a monocycloalkane having 3 to 6 carbon atoms is preferable, and examples of the monocycloalkane include cyclopentane and cyclohexane. As the polycyclic group, a group in which two or more hydrogen atoms have been removed from a polycycloalkane having 7 to 12 carbon atoms is preferable. Specific examples of the polycycloalkane include adamantane, norbornane, isobornane, and tricyclodecane. And tetracyclododecane.

  The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms, and an oxygen atom (= O).

Examples of the aromatic hydrocarbon group in R ⁶¹ or R ⁶² include monovalent aromatic groups such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. A divalent aromatic hydrocarbon group obtained by further removing one hydrogen atom from the nucleus of the aromatic hydrocarbon of the hydrocarbon group; a part of carbon atoms constituting the ring of the divalent aromatic hydrocarbon group is an oxygen atom , Aromatic hydrocarbon groups substituted with heteroatoms such as sulfur atoms and nitrogen atoms; benzyl groups, phenethyl groups, 1-naphthylmethyl groups, 2-naphthylmethyl groups, 1-naphthylethyl groups, 2-naphthylethyl groups, etc. And an aromatic hydrocarbon group obtained by further removing one hydrogen atom from the nucleus of the aromatic hydrocarbon.

  The aromatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).

R ⁶¹ or R ⁶² is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group. preferable.

In the above formula ^{(g1-1), R 63} and ^{R 64} are each independently hydrogen atom or an alkyl group.

The alkyl group in R ⁶³ and R ⁶⁴ is the same as described in the above formula (g0-1).

Of these, R ⁶³ and R ⁶⁴ are each preferably a hydrogen atom or a methyl group.

  In said formula (g1-2), R is a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group.

  The alkyl group or halogenated alkyl group of R is the same as the alkyl group having 1 to 5 carbon atoms or the halogenated alkyl group having 1 to 5 carbon atoms which may be bonded to the α-position of the acrylate ester.

  Among these, R is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, particularly preferably a hydrogen atom or a methyl group.

In the above formula (g1-2), R ⁶⁵ is a divalent hydrocarbon group which may have a substituent, and examples thereof include those similar to R ⁶¹ and R ⁶² in the above formula (g1-1). A linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is most preferable.

In the above formula (g1-2), R ^{66 to} R ⁶⁸ are each independently a hydrogen atom or an alkyl group. The alkyl group in R ^{66 to} R ⁶⁸ is the same as described in the above formula (g0-2).

Among these, R ^{66 to} R ⁶⁸ are each preferably a hydrogen atom or a methyl group.

In the above formula (g1-3), R ^65a is a divalent hydrocarbon group which may have a substituent, and examples thereof include those similar to R ⁶⁵ in the above formula (g1-2). A chain aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group is most preferable.

In the above formula (g1-3), R ^66a , R ^69a and R ^69b are each independently a hydrogen atom or an alkyl group. The alkyl group in R ^66a , R ^69a and R ^69b is the same as that described in the above formula (g0-3). Among these, R ^{66 to} R ⁶⁸ are each preferably a hydrogen atom or a methyl group.

  g4 and g5 are both the same as in the above formula (g0-3).

In the above formula (g1-4), R ^65b is a divalent hydrocarbon group which may have a substituent, and examples thereof include those similar to R ⁶⁵ in the above formula (g1-2). A chain aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group is most preferable.

  Specific examples of the structural units represented by the general formulas (g1-1) to (g1-4) are shown below.

  In the following formulas, Rα represents a hydrogen atom, a methyl group or a trifluoromethyl group.

  In the component (G), one type of structural unit (g1) may be used alone, or two or more types may be used in combination.

  Among these, as the component (G), a component having a structural unit represented by the above formula (g1-1), a structure represented by the above formula (g1-2) or the formula (g1-3) Those having units are preferred.

  When the structural unit represented by the formula (g1-1) is used, the component (G) is a polymer (homopolymer) composed of one type of repeating structural unit represented by the formula (g1-1). Preferably there is.

  When the structural unit represented by the above formula (g1-2) or formula (g1-3) is used, the component (G) is composed of the structural unit represented by the formula (g1-2) and the other units described below. A copolymer (copolymer) having a structural unit; a copolymer (copolymer) having a structural unit represented by the formula (g1-3) and other structural units described later; the formula (g1-2) A copolymer having a structural unit represented by formula (g1-3) and a structural unit represented by formula (g1-3); a structural unit represented by formula (g1-2); It is preferable that it is a copolymer (copolymer) which has the structural unit represented by -3) and the other structural unit mentioned later.

  In the component (G), the proportion of the structural unit (g1) is preferably 10 mol% or more, more preferably 20 mol% or more, based on the total of all the structural units constituting the component (G). 30 mol% or more is more preferable, 35 mol% or more is particularly preferable, and 100 mol% may be used.

  When the proportion of the structural unit (g1) is at least the lower limit value, the crosslinking efficiency with the support 12 is increased and the affinity with the separation layer 15 is further increased.

  When the component (G) is a copolymer (copolymer), the proportion of the structural unit (g1) is preferably 10 to 80 mol% with respect to the total of all the structural units constituting the component (G). More preferably, it is 20-80 mol%, and it is further more preferable that it is 30-80 mol%.

  When the proportion of the structural unit (g1) is within the above range, the crosslinking efficiency with the support 12 is increased, and the affinity between the support 12 and the separation layer 15 is further increased.

  The component (G) may have other structural units (g2) other than the structural unit (g1) as necessary as long as the hydrophobic effect on the surface of the support 12 is not impaired.

  The other structural unit (g2) is not particularly limited, and a structural unit derived from a compound copolymerizable with the compound that derives the structural unit (g1) is preferable.

  Specific examples of the other structural unit (g2) include, for example, a structural unit derived from acrylic acid and a structural unit derived from methacrylic acid (hereinafter collectively referred to as “structural unit (g21)”). A structural unit derived from an alkyl acrylate such as methyl acrylate or ethyl acrylate (preferably the alkyl having 1 to 5 carbon atoms) (hereinafter referred to as “structural unit (g22)”); methacrylic acid A structural unit derived from alkyl methacrylate such as methyl or ethyl methacrylate (preferably having 1 to 5 carbon atoms of the alkyl) (hereinafter referred to as “structural unit (g23)”); 1) The structural units (a1) to (a4) and the like in the description of the component are preferable. Among the structural units (a1) to (a4), since the separation layer 15 can be further prevented from peeling from the support 12, the structural units (a1), (a2), and (a4) are more preferable, and the structural unit ( a4) is more preferred.

  In the component (G), one type of structural unit (g2) may be used alone, or two or more types may be used in combination.

  In the component (G), the proportion of the structural unit (g2) is preferably 1 to 30 mol%, and preferably 5 to 25 mol%, based on the total of all the structural units constituting the component (G). More preferably, it is 10-20 mol%, and it is still more preferable.

  When the proportion of the structural unit (g2) is within the above range, the affinity between the support 12 and the separation layer 15 is maintained well.

  In the surface treatment agent, as the component (G), one type may be used alone, or two or more types may be used in combination.

  In the present invention, the component (G) is preferably, for example, a polymer (homopolymer) composed of repeating structural units (g1) or a copolymer (copolymer) having structural units (g1) and structural units (g2). It is mentioned as a thing.

  Specific examples of such a copolymer (copolymer) include a copolymer having a structural unit (g1) and a structural unit (g21).

  As this (G) component, the epoxy resin which has the following structural units is especially preferable.

(In the formula, g6 and g7 are each independently an integer of 1 to 5.)
The epoxy resin represented by the formula (G-1) is a homopolymer composed of repeating structural units represented by the formula (G-1).

  In the above formula, g6 and g7 are each independently preferably 1 or 2, more preferably 1, and particularly preferably both g6 and g7 are 1.

(In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and a plurality of R may be the same or different. G8 is 1) An integer of ˜5, and R ^β is an alkyl group.)
In the above formula, R is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, particularly preferably a hydrogen atom or a methyl group.

  g8 is preferably 1 or 2, and more preferably 1.

  R1 is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

(In the formula, R is the same as above, and a plurality of R may be the same or different. G8 is the same as above. G9 is an integer of 1 to 5, and g4 and g5 are Each is the same as above.)
In the above formula, R is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, particularly preferably a hydrogen atom or a methyl group.

  g8 is preferably 1 or 2, and more preferably 1.

  g9 is preferably 1 or 2, and more preferably 1.

  g4 is preferably 1 or 2, and more preferably 2.

  g5 is preferably 1 or 2, and more preferably 1.

  The polymer (homopolymer) or copolymer (copolymer) having a repeating structure of the structural unit (g1) is a monomer derived from a desired structural unit, such as azobisisobutyronitrile (AIBN), dimethyl azobisisobutyrate. It can obtain by making it superpose | polymerize by well-known radical polymerization etc. which used radical polymerization initiators, such as.

  The dispersity (Mw / Mn) of the component (G) is preferably 1.0 to 6.5, more preferably 1.5 to 6, and most preferably 1.5 to 5. “Mn” represents a number average molecular weight.

  In the surface treatment agent, the content of the component (G) is preferably 0.010 to 0.050% by mass, more preferably 0.010 to 0.040% by mass, and 0.015 to 0%. More preferably, it is 0.035 mass%.

  When the content of the component (G) is equal to or higher than the lower limit, the affinity between the support 12 and the separation layer 15 becomes higher. Further, when a solution obtained by dissolving the component (G) in an organic solvent is used as the surface treatment agent, the solution has an appropriate viscosity, and it becomes easy to uniformly apply the solution on the support. On the other hand, when the amount is not more than the upper limit, an increase in the viscosity of the solution is suppressed, and the solution can be easily applied uniformly on the support.

  The surface treatment agent may contain other components other than the component (G).

  Examples of other components include organic solvents and surfactants.

  Any organic solvent may be used as long as it can dissolve the component (G) to form a uniform solution, and examples thereof include those used as organic solvents for general chemical amplification resist compositions. .

  Examples of the organic solvent include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; ethylene glycol, diethylene glycol, propylene glycol, di- Polyhydric alcohols such as propylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, the polyhydric alcohols or compounds having the ester bond Monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Derivatives of polyhydric alcohols such as compounds having an ether bond such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred among them; cyclic ethers such as dioxane; , Methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc .; anisole, ethyl benzyl ether, cresyl methyl Ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, cymene, mesitile And aromatic organic solvents and the like.

  An organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixed solvent.

  The form of the surface treatment agent is not particularly limited as long as it contains the (G) component and can form a surface treatment film. For example, the surface treatment agent is used as a solution obtained by dissolving the (G) component in an organic solvent. It may be used as a sheet-like product obtained by drying the solution.

  Suitable examples of the epoxy resin contained in the surface treatment agent include those having a repeating structure of the structural unit (g1) because the affinity between the support 12 and the separation layer 15 becomes better. What the ratio of the said structural unit (g1) is 10 mol% or more with respect to the sum total of all the structural units which comprise this epoxy resin is preferable.

  Moreover, as a suitable thing in the said structural unit (g1), since the affinity of the support body 12 and the separation layer 15 becomes especially favorable, it is the said General formula (g1-1)-(g1-4). Examples thereof include at least one selected from the group consisting of the structural units represented.

  The method for forming the surface treatment film on the support using the surface treatment agent is not particularly limited, and a conventionally known method can be used.

  For example, when a solution ((G) component solution) obtained by dissolving the (G) component in an organic solvent is used as the surface treating agent, a conventionally known method using the spinner or the like on the support 12 with the (G) component solution. It is possible to form a surface treatment film by applying and baking, and volatilizing the organic solvent.

  The baking temperature in the baking treatment is preferably 80 to 400 ° C, more preferably 180 to 300 ° C, the baking treatment time is preferably 15 to 120 seconds, and more preferably 30 to 90 seconds. preferable.

  When the epoxy resin used for the surface treatment agent has the structural unit represented by the general formula (g1-1), the baking temperature is preferably 150 to 300 ° C, and preferably 180 to 300 ° C. Is more preferable.

  The epoxy resin used for the surface treatment agent is represented by the structural unit represented by the general formula (g1-2), the structural unit represented by the general formula (g1-3), or the general formula (g1-4). When it has a structural unit, the baking temperature is preferably 85 to 350 ° C, and more preferably 120 to 300 ° C.

  When any of the above baking temperatures is within the above range, the surface of the support 12 can be particularly preferably hydrophobized.

  The thickness of the surface treatment film is preferably 0.01 to 3.5 nm, more preferably 0.3 to 2.5 nm. By setting the thickness of the surface treatment film within the above range, the surface of the support 12 can be sufficiently hydrophobized and the affinity between the support 12 and the separation layer 15 can be further increased.

[Separation layer forming step]
In the separation layer forming step in the laminate manufacturing method according to the present embodiment, the separation layer 15 is formed on the hydrophobized surface treatment film 14 on the surface of the support 12 surface-treated in the surface treatment step. Is a step of forming.

(Separation layer)
The separation layer 15 is a layer formed of a material that changes quality by absorbing light irradiated through the support 12. In the present specification, the “deterioration” of the separation layer 15 is a phenomenon in which the separation layer 15 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 15 is reduced. means. As a result of the alteration of the separation layer 15 caused by absorbing light, the separation layer 15 loses its strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support 12), the separation layer 15 is broken, and the support 12 and the substrate 11 can be easily separated.

  Further, the alteration of the separation layer 15 is caused by decomposition (exothermic or non-exothermic), cross-linking, configuration change or dissociation of functional groups (and curing of the separation layer and degassing caused by these). , Contraction or expansion) and the like. The alteration of the separation layer 15 occurs as a result of light absorption by the material constituting the separation layer 15. Therefore, the type of alteration of the separation layer 15 can be changed according to the type of material constituting the separation layer 15.

  The separation layer 15 is provided on the surface of the support 12 on the side where the substrate 11 is bonded via the adhesive layer 13. That is, the separation layer 15 is provided between the surface treatment film 14 and the adhesive layer 13.

  For example, the thickness of the separation layer 15 is more preferably 0.05 to 50 μm, and further preferably 0.3 to 1 μm. If the thickness of the separation layer 15 is within the range of 0.05 to 50 μm, desired alteration can be caused in the separation layer 15 by short-time light irradiation and low-energy light irradiation. The thickness of the separation layer 15 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 15 and the support 12. In this case, the other layer should just be comprised from the material which permeate | transmits light. Thereby, a layer imparting preferable properties to the stacked body 10 can be appropriately added without hindering the incidence of light on the separation layer 15. The wavelength of light that can be used varies depending on the type of material constituting the separation layer 15. 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 15.

  In addition, the separation layer 15 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 of the present invention are not impaired. May be added to form the separation layer 15. In addition, it is preferable that the surface of the separation layer 15 facing the adhesive layer 13 is flat (unevenness is not formed), so that the separation layer 15 can be easily formed and even when pasted. It becomes possible to paste on.

  As the separation layer 15, a material that forms the separation layer 15 as described below may be used by bonding it to the support 12 in advance, or the separation layer 15 may be formed on the support 12. You may use what applied the material and solidified in the film form. The method of applying the material constituting the separation layer 15 on the support 12 is appropriately selected from conventionally known methods such as deposition by a chemical vapor deposition (CVD) method according to the type of material constituting the separation layer 15. can do.

The separation layer 15 may be altered by absorbing light emitted from the laser. In other words, the light irradiated to the separation layer 15 in order to change the quality of the separation layer 15 may be emitted from a laser. Examples of lasers that emit light to irradiate the separation layer 15 include solid lasers such as YAG lasers, Libby lasers, glass lasers, YVO ₄ lasers, LD lasers, fiber lasers, liquid lasers such as dye lasers, CO ₂ lasers, and excimers. Examples thereof include a gas laser such as a laser, an Ar laser, and a He—Ne laser, a laser beam such as a semiconductor laser and a free electron laser, or a non-laser beam. The laser that emits light for irradiating the separation layer 15 can be appropriately selected according to the material constituting the separation layer 15 and irradiates light having a wavelength that can alter the material constituting the separation layer 15. The laser to be selected may be selected.

(Fluorocarbon)
The separation layer 15 may be made of a fluorocarbon. Since the separation layer 15 is composed of fluorocarbon, the separation layer 15 is altered by absorbing light. As a result, the separation layer 15 loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support 12), the separation layer 15 is broken, and the support 12 and the substrate 11 can be easily separated.

Moreover, from one viewpoint, the fluorocarbon constituting the separation layer 15 can be suitably formed by a plasma CVD method. In addition, fluorocarbon includes CxFy (perfluorocarbon) and CxHyFz (x, y, and z are integers), but is not limited thereto, for example, CHF ₃ , 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, 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 15 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 15 may be composed of a single kind of fluorocarbon, or may be composed of two or more kinds 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 in a range that is absorbed by the fluorocarbon used in the separation layer 15, the fluorocarbon can be suitably altered. The light absorption rate in the separation layer 15 is preferably 80% or more.

As light to irradiate the separation layer 15, depending on the wavelength that can be absorbed by the fluorocarbon, for example, YAG laser, Libby laser, glass laser, YVO ₄ laser, LD laser, liquid laser such as fiber laser, liquid laser such as dye laser, etc. 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.

(Polymer containing light-absorbing structure in its repeating unit)
The separation layer 15 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 15 has lost its strength or adhesion 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 12), the separation layer 15 is broken, and the support 12 and the substrate 11 can be easily separated.

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

(In the formula, each R ³⁰ is independently an alkyl group, aryl group, halogen, hydroxyl group, ketone group, sulfoxide group, sulfone group or N (R ³¹ ) (R ³² ) (where R ³¹ and R ³² is each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), Z is absent or is —CO—, —SO ₂ —, —SO— or —NH—, k Is 0 or an integer of 1 to 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.

(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 18” in (a) to (e)). Yes, in (f), any of the formulas shown above for “Chemical Formula 18” or absent, and Y1 and Y2 are each independently —CO— or SO ₂ —, preferably 1 Is an integer of 10 or less.)
Examples of the benzene ring, condensed ring and heterocyclic ring shown in the above “chemical formula 18” 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, alkylamino and arylamino.

Among the substituents represented by the above “chemical formula 18”, as an example of the fifth substituent having two phenyl groups and Z is —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.

  Of the substituents represented by the above “Chemical Formula 18”, the fifth substituent having two phenyl groups, and Z is —SO—, includes 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-methylphenol) ) -Sulfoxide, bis (5-chloro-2,3,4-trihydroxyphenyl) sulfoxide, bis (2,4,6-trihydroxyphenyl) sulfoxide, bis (5-chloro-2,4,6-tri) Hydroxyphenyl) sulfoxide and the like.

  Among the substituents represented by the above “Chemical Formula 18”, 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-di Tylamino-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 15 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 15 can sufficiently absorb light and can be reliably and rapidly altered. That is, it is easy to remove the support 12 from the laminate 10, and the light irradiation time 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.

  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 F2 excimer laser (wavelength: 157 nm), or XeCl. Light emitted from 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 15 described above contains a polymer containing the above structure as a repeating unit, the separation layer 15 may further contain components other than the polymer. Examples of the component include a filler, a plasticizer, and a component that can improve the peelability of the support 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 15 may be made of an inorganic material. The separation layer 15 is made of an inorganic material and is altered by absorbing light. As a result, the separation layer 15 loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support 12), the separation layer 15 is broken, and the support 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, can use 1 or more types of inorganic substances selected from the group which consists of a metal, a metal compound, and carbon suitably. The metal compound refers to a compound containing a metal atom, and can be, for example, a metal oxide or a metal nitride. Exemplary of such inorganic 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 is absorbed by the inorganic material used for the separation layer 15, the inorganic material can be suitably altered.

The light applied to the separation layer 15 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 15 made of an inorganic material can be formed on the support 12 by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, or spin coating. The thickness of the separation layer 15 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 sides or one side of an inorganic film (for example, a metal film) made of an inorganic material constituting the separation layer 15 and attached to the support 12 and the substrate 11.

  When a metal film is used as the separation layer 15, laser reflection or charging of the film may occur depending on conditions such as the film quality of the separation layer 15, the type of laser light source, and laser output. Therefore, it is preferable to take measures against them by providing an antireflection film or an antistatic film on the upper and lower sides of the separation layer 15 or on either one of them.

(Compound having infrared absorbing structure)
The separation layer 15 may be formed of a compound having an infrared absorbing structure. The compound is altered by absorbing infrared rays. The separation layer 15 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), the separation layer 15 is broken and the support 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 and 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, 1,3-diketone enol, o-hydroxy aryl ketone, dialkyl aldehyde, aromatic aldehyde, carboxylic acid (dimer Carboxylate anion), formate ester, acetate 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, Acid ester, nitrite ester, nitroso bond (aliphatic, aromatic, monomer, dimer), mercaptan and sulfur compounds such as thiophenol and thiolic acid, thiocarbonyl group, sulfoxide, sulfone, sulfonyl chloride, primary Secondary sulfonamide, secondary sulfonamide, sulfate ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), P-A 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.

As a structure including the Si-A1 _{bonds, 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 , SiF _{3 and the} like. As a structure including a Si—A ¹ bond, it is particularly preferable to form a siloxane skeleton and a silsesquioxane skeleton.

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— P—O (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 are 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 15, 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 15 and facilitate separation of the support 12 and the substrate 11, the absorption of infrared rays in the separation layer 15 is large, that is, the separation layer 15 is irradiated with infrared rays. It is preferable that the infrared transmittance is low. Specifically, the infrared transmittance in the separation layer 15 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 (10) and a repeating unit represented by the following chemical formula (11), or A resin that is a copolymer of a repeating unit represented by the following chemical formula (10) and a repeating unit derived from an acrylic compound can be used.

(In the chemical formula (11), R ⁴¹ 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, t-butylstyrene (TBST) -dimethylsiloxane copolymer, which is a copolymer of the repeating unit represented by the chemical formula (10) and the repeating unit represented by the following chemical formula (12), is used. A polymer is more preferable, and a TBST-dimethylsiloxane copolymer containing a repeating unit represented by the above formula (10) and a repeating unit represented by the following chemical formula (12) at 1: 1 is further preferable.

  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 (13) and a repeating unit represented by the following chemical formula (14) can be used. .

(In the chemical formula (13), R ⁴² is hydrogen or an alkyl group having 1 to 10 carbon atoms, and in the chemical formula (14), R ⁴³ is an alkyl group having 1 to 10 carbon atoms, or a phenyl group. Is)
As other compounds having a silsesquioxane skeleton, Patent Document 4: JP 2007-258663 A (published October 4, 2007), Patent Document 5: JP 2010-120901 A (2010). Published on June 3, 2009), Patent Document 6: JP 2009-263316 A (published on November 12, 2009) and Patent Document 7: JP 2009-263596 A (published on November 12, 2009). Each disclosed silsesquioxane resin can be suitably used.

  Among these, as the compound having a silsesquioxane skeleton, a repeating unit represented by the following chemical formula (15) and a copolymer of a repeating unit represented by the following chemical formula (16) are more preferable. A copolymer containing the repeating unit represented by the following chemical formula (16) and 7: 3 is more preferable.

  The polymer having a silsesquioxane skeleton may have a random structure, a ladder structure, and a cage structure, but 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. (Ii) chelating titanium such as di-i-propoxy bis (acetylacetonato) titanium, and propanedioxytitanium bis (ethylacetoacetate); (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- propoxy Titanium diisostearate and acylate titanium such as (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium; (v) water-soluble titanium compounds such as di-n-butoxy-bis (triethanolaminato) titanium Is 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 15 described above contains a compound having an infrared absorbing structure, the separation layer 15 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 12. These components are appropriately selected from conventionally known substances or materials that do not prevent or promote the absorption of infrared rays by the above structure and the alteration of the compound.

(Infrared absorbing material)
The separation layer 15 may contain an infrared absorbing material. The separation layer 15 is configured to contain an infrared absorbing material, so that the separation layer 15 is altered by absorbing light, and as a result, loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support 12), the separation layer 15 is broken, and the support 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 15 with light having a wavelength in a range that is absorbed by the infrared absorbing material used for the separation layer 15, the infrared absorbing material can be suitably altered.

(Separation layer production equipment)
FIG. 3A is a cross-sectional view showing a configuration example of the separation layer manufacturing apparatus 100 used in the separation layer forming step in the present embodiment, and FIG. 3B shows the positional relationship between the exhaust holes and the support. FIG. The method for forming the separation layer 15 may be selected as appropriate according to the material constituting the separation layer 15, and in particular, as shown in FIG. 3, the support 12 is evacuated in a reaction chamber 102 having an exhaust hole 109. It is preferable to form the separation layer 15 on the support 12 by a plasma CVD method in a state vertically below the hole 109. Thereby, as shown to (a) of FIG. 2, the laminated body 1 by which the homogeneous thin thin layer 15 without the fine unevenness | corrugation was formed in the surface can be provided. In this specification, “the state in which the support 12 is positioned vertically below the exhaust hole 109” refers to the state in which the upper surface of the support 12 is positioned vertically below the vertical bottom of the exhaust hole 109. Point to.

  Thereby, as shown to (a) of FIG. 2, in the separated layer 15 of the laminated body 1 which concerns on this embodiment, compared with the laminated body 2 which concerns on a prior art as shown to (b) of FIG. The part exposed to the outside of 1 can be reduced. Therefore, the separation layer 15 becomes difficult to be altered by chemical treatment. As a result, the separation layer 15 can be prevented from peeling from the support 12 when a desired treatment is performed on the laminate 1.

  In addition, since the chemical resistance of the material of the separation layer 15 itself is not improved, an effect that the residue of the separation layer 15 attached on the support 12 after the separation process of the support 12 can be easily washed. Play. That is, the laminate according to the present invention can achieve the conflicting benefits of maintaining the ease of cleaning the separation layer while eliminating breakage of the separation layer due to chemicals. This is an effect that cannot be achieved by a method of improving the chemical resistance of the separation layer (photothermal conversion layer) itself as in the conventional laminate.

  The above will be described in more detail. 4A is a cross-sectional view showing a reference configuration example of the separation layer manufacturing apparatus, and FIG. 4B is a view showing the positional relationship between the exhaust holes and the support. In the separation layer manufacturing apparatus 100 ′ shown in FIG. 4A, as shown in FIG. 4B, the exhaust hole 109 is at the same height as the support 12 that is the object to be processed. When such a separation layer manufacturing apparatus 100 ′ is used, as shown in FIG. 2B, the separation layer 15 is formed thick at the end of the support 12 and further to the end face of the support 12. A film is formed. Moreover, since the solidified product of the active species in the plasma rides on the separation layer 15, fine irregularities are formed on the surface of the separation layer 15, and it is difficult to form a uniform separation layer 15. For this reason, the separation layer 15 in the laminate 2 has a wider surface exposed to the outside of the laminate 2, and as a result, the separation layer 15 formed up to the end face of the support 12 by the chemical treatment for the laminate 2. There is a problem that the support 12 is peeled off from the laminate 2 in various processes after the change. In the plasma CVD apparatus according to the related art described in Patent Document 3, the exhaust hole is provided vertically below the support that is the object to be processed, but the same problem occurs.

  Here, the present inventors paid attention to the airflow in the reaction chamber of the separation layer forming apparatus, and intensively studied the influence of changes in the shape and position of each member of the apparatus on the airflow in the reaction chamber. As a result, it has been found that the position of the exhaust hole in the reaction chamber of the separation layer forming apparatus greatly affects the flow of active species generated by the plasma above the surface of the support 12. Then, when the separation layer 15 is formed using the separation layer forming apparatus 100 in which the lowermost vertical part of the exhaust hole 109 is provided vertically apart from the upper surface of the support 12 as shown in FIG. As shown in FIG. 2A, the separation layer 15 is formed with a uniform thickness from the end of the support 12 to the center of the support 12, and the separation layer 15 is also formed on the end surface of the support 12. Reduced. In addition, a homogeneous separation layer 15 having no fine irregularities on the surface was formed. Thereby, the chemical resistance of the laminated body 1 was able to be improved. In particular, it is found that when the surface treatment step described above is performed on the support 12 and the separation layer 15 is formed using the reaction chamber described above, the chemical resistance of the laminate 1 is significantly improved. It was.

  As shown in FIG. 3, the separation layer manufacturing apparatus 100 includes a base 101, a mounting table / lower electrode 103, an exhaust ring 104, a quartz chamber body 105, a quartz chamber upper part 106, and a top plate so as to surround the reaction chamber 102. 108, and an exhaust hole 109 is provided in the exhaust ring 104.

  The base 101 is a support portion that supports members constituting the side wall of the reaction chamber 102. That is, the exhaust ring 104, the quartz chamber body 105, the quartz chamber upper part 106, and the top plate 108 overlap with the base 101 in this order. The exhaust ring 104 is provided with an exhaust hole 109 for exhausting gas from the reaction chamber 102. The quartz chamber body 105 and the quartz chamber upper portion 106 are made of quartz and constitute the side wall of the reaction chamber 102. The quartz chamber body 105 has a cylindrical shape, and the quartz chamber upper portion 106 has a bottom shape, and forms a bell jar structure as a whole. In addition, the said shape is an example and the shape of the separation layer forming apparatus 100 which concerns on this embodiment is not limited to this.

  A coiled upper electrode is provided outside the upper quartz chamber 106. The upper electrode is electrically connected to a high frequency power source. A top plate 108 is placed on the top of the quartz chamber upper portion 106. The top plate 108 is provided with a gas supply port for supplying a gas such as a reaction gas to the reaction chamber 102.

  Further, an opening is provided vertically below the base 101, and a mounting table / lower electrode 103 is attached so as to close the opening. The mounting table / lower electrode (mounting table) 103 functions as a mounting table for mounting the support 12 and also functions as a lower electrode for applying a voltage between the upper electrode and the mounting table. The mounting table / lower electrode 103 is made of, for example, a conductor such as an aluminum alloy and is grounded.

  It is preferable that the diameter of the inner circumference of the quartz chamber body 105 is longer than the height from the upper surface of the mounting table / lower electrode 103 to the bottom surface of the top plate 108.

  Then, a reaction gas, which is a material for forming the separation layer 15, is introduced into the reaction chamber 102 from the gas supply port, and a voltage is applied between the upper electrode and the lower electrode to generate plasma, thereby generating plasma. The separation layer 15 is formed by the active species generated together.

  Here, as shown in FIG. 3B, the exhaust hole 109 is disposed so as to be positioned 1 mm or more vertically above the mounting table / lower electrode 103. Note that the exhaust hole 109 is located 1 mm or more vertically above the mounting table / lower electrode 103. The vertical lowest part of the exhaust hole 109 is 1 mm or more perpendicular to the upper surface of the mounting table / lower electrode 103. It means to be located above. Here, the thickness of the support 12 that is usually used is about 0.7 mm. For this reason, the upper surface of the support 12 placed on the mounting table / lower electrode 103 (the separation layer 15 is formed) by disposing the exhaust hole 109 vertically above the mounting table / lower electrode 103 by 1 mm or more. Can be maintained so as to be positioned vertically below the exhaust hole 109 (the lowermost part).

  Thus, by installing the exhaust hole 109 vertically above the mounting table and lower electrode 103 by 1 mm or more, the upper surface of the support 15 that is the object to be processed (the surface on which the separation layer 15 is formed) It is located vertically below the exhaust hole 109 (the lowermost part). Accordingly, it is possible to suppress the plasma sucked into the exhaust hole 109 during the separation layer forming step from staying at the end portion and the end surface of the support 15. Moreover, it is possible to suppress the solidified product of active species in the plasma sucked into the exhaust hole 109 from being deposited on the separation layer 15.

  Due to these effects, the separation layer 15 formed by the separation layer forming apparatus 100 is formed with a uniform thickness from the end of the support 12 to the center of the support 12, and the end surface of the support 12. The formation of the separation layer 15 is also reduced. In addition, a homogeneous separation layer 15 having no fine irregularities on the surface can be formed.

  In the separation layer forming step, the uniform formation of the separation layer 15 is achieved by disposing the exhaust holes 109 vertically above the surface of the support 12 on which the separation layer 15 is formed. Therefore, in the application, when forming the separation layer 15 or a deposition layer of other materials on the thinner support 12 or other base material, the position is lower than 1 mm with respect to the mounting table / lower electrode 103. It should be considered that even if the exhaust hole 109 is arranged, the effect of the present invention can be produced if the surface of the support 12 or other base material is located vertically below the exhaust hole 109.

  In one embodiment, an insulating ring (insulating member: not shown) may be provided vertically below the exhaust hole 109 in the inner wall of the reaction chamber 102 (inner wall of the exhaust ring 104). The insulating ring can prevent the plasma from concentrating around the inner wall of the reaction chamber 102 when the inner wall of the reaction chamber 102 is made of metal. Thereby, a more uniform separation layer 15 can be formed. However, it is not necessary to provide an insulating ring.

  In addition, the horizontal distance between the exhaust hole 109 and the support 12 is preferably 1 mm or more. This is because even when the distance between the exhaust hole 109 and the support 12 is set to 1 mm or more in the horizontal direction, the air flow in the reaction chamber is controlled and the homogeneous separation layer 15 is easily formed. Therefore, it is preferable that the exhaust hole 109 is located outside by 1 mm or more from the end surface of the mounting table / lower electrode 103. Thereby, the position of the exhaust hole 109 can be reliably separated from the support 12 by 1 mm or more in the horizontal direction.

  The reaction gas may be appropriately selected according to the separation layer 15 to be formed. For example, in one embodiment, a gas containing at least one of a fluorocarbon gas and a hydrocarbon gas can be used. By performing the plasma CVD method using at least one of a fluorocarbon gas and a hydrocarbon gas as a reaction gas, the separation layer 15 can be suitably formed.

Examples of the fluorocarbon gas include CxFy and CxHyFz (x, y and z are natural numbers), and more specifically, CHF ₃ , 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 are exemplified, but not limited thereto. Examples of the hydrocarbon gas include alkanes such as CH ₄ , alkenes such as ethylene, and alkynes such as acetylene.

  One or more kinds of inert gases such as nitrogen, helium and argon, hydrocarbon gases such as alkanes, alkenes and alkynes, fluorocarbon gases, hydrogen and oxygen may be added to the reaction gas. The addition amount of the additive gas is not particularly limited. For example, when hydrogen is added, it is not limited to this, but it may be added at a rate of 5% or more and 20% or less with respect to the entire gas. preferable. Further, oxygen is not limited to this, but it is preferable to add a very small amount or not.

  The reaction gas may contain a fluorocarbon gas as a main component. In this case, a hydrocarbon gas may be contained as an additive gas. The content of the additive gas with respect to the entire raw material gas is preferably 5% or more and 20% or less, for example. Conversely, when the reaction gas is mainly composed of a hydrocarbon gas, it is preferable to contain a fluorocarbon gas as an additive gas. Note that the main component means a gas having the largest content (volume%) in the gas supplied to the reaction chamber 102. Further, by adding an appropriate amount of an inert gas, the reaction gas can be suitably stirred to form the separation layer 15 uniformly.

  The flow rate of the reaction gas and the pressure in the reaction chamber 102 are not particularly limited, and may be set to various conditions. The reaction gas is preferably supplied from a gas supply port provided in the top plate 108 and exhausted from the exhaust hole 109 by a pump or the like.

  The target temperature in the reaction chamber 102 at the time of performing the plasma CVD method is not particularly limited, and a known temperature can be used, but it is more preferably in a range of 100 ° C. or more and 300 ° C. or less, 200 ° C. or more, A range of 250 ° C. or lower is particularly preferable. By setting the temperature in the reaction chamber 102 in such a range, the plasma CVD method can be suitably executed.

  The high frequency power applied to the upper electrode provided in the quartz chamber upper portion 106 is not limited to this, but is preferably set to be larger than the power causing the mode jump. In general, capacitively coupled plasma (E-mode plasma) is generated when the plasma density is low, and inductively coupled plasma (H-mode plasma) is generally generated when the plasma density is high. The transition from the E mode to the H mode depends on the dielectric electric field, and when the dielectric electric field exceeds a certain value, the capacitive coupling is switched to the inductive coupling. This phenomenon is generally called “mode jump” or “density jump”. That is, plasma generated at a power lower than that causing mode jump is E-mode plasma, and plasma generated at a power higher than power causing mode jump is H-mode plasma (for example, Japanese Patent No. 3852655, Japanese Patent No. 4272654, etc.) checking). Thereby, a high-quality separation layer 15 can be formed.

[Adhesive layer forming step]
The adhesive layer forming step in the laminate manufacturing method according to the present embodiment is a step of forming the adhesive layer 13 on the substrate 11.

(substrate)
The substrate 11 is subjected to processes such as thinning and mounting while being supported by the support 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.

(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 substrate 11 fixed to the support plate 12 and covering 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 lowered 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, polyimide, and elastomer are adhesives that constitute the adhesive layer 13 according to the present embodiment. It can be used. 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, elastomer resins, and combinations thereof. It is done.

(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, a cycloolefin polymer (hereinafter sometimes referred to as “resin (A)”), and at least one resin selected from the group consisting of a terpene resin, a rosin resin and a petroleum resin (hereinafter referred to as “the 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 alkyl (methyl, ethyl, propyl, butyl, etc.) substituted polyalkenyls, alkenyl (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 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 Co., Ltd., “APEL” manufactured by Mitsui Chemicals, Inc., “ZEONOR” and “ZEONEX” manufactured by Zeon Corporation. 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 higher, softening of the adhesive layer can be further suppressed when the 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 layer can be prevented from being softened when the laminate is 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 less, the peeling rate when peeling the 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 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). It is preferable because of excellent resistance and flexibility.

(Acrylic-styrene resin)
Examples of the acryl-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, Nt-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, etc. Maleimide having an aliphatic hydrocarbon group such as maleimide having an alkyl group, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide, etc. N- phenylmaleimide, N-m-methylphenyl maleimide, N-o-methylphenyl maleimide, N-p-methyl resin obtained by polymerizing an aromatic maleimides such as having an aryl group of phenyl maleimide, and the like.

  For example, a cycloolefin copolymer, which is a copolymer of a repeating unit represented by the following chemical formula (17) and a repeating unit represented by the following chemical formula (18), can be used as the adhesive component resin.

(In chemical formula (18), n is 0 or an integer of 1-3.)
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 A compound having an ester bond such as a monomethyl ether, a monoethyl ether, a monopro of the polyhydric alcohol or the compound having an ester bond. Derivatives of polyhydric alcohols such as compounds having an ether bond such as monoalkyl ether such as pill ether and monobutyl ether or monophenyl ether (in these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME ); Preferably cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, Esters such as ethyl ethoxypropionate; fragrances such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetol, butyl phenyl ether It can be exemplified system organic solvent.

(Elastomer)
The elastomer preferably contains a styrene unit as a constituent unit of the main chain. The elastomer used as the adhesive preferably has a styrene unit content in the range of 14% by weight to 50% by weight. Furthermore, the elastomer preferably has a weight average molecular weight in the range of 10,000 to 200,000.

  Examples of the elastomer include polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), and styrene-butadiene-butylene-styrene block. Copolymer (SBBS), ethylene-propylene terpolymer (EPT), hydrogenated products thereof, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) ) (SEPS) and styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS).

(Other ingredients)
The adhesive material may further contain other miscible substances as long as the essential characteristics of the present invention are not impaired. For example, various conventional additives such as additional resins, plasticizers, adhesion aids, stabilizers, colorants, antioxidants and surfactants for improving the performance of the adhesive can be further used. .

[Lamination process]
A lamination process means the process of laminating | stacking the board | substrate 11 and the support body 12 through the contact bonding layer 13 so that the separation layer 15 may be provided between the board | substrate 11 and the support body 12. FIG.

  As a specific method of the laminating process, as shown in FIG. 1, the surface of the substrate 11 on which the adhesive layer 13 is formed and the surface of the support 12 on which the separation layer 15 is formed are bonded together under vacuum. The process of laminating | stacking by baking and crimping | bonding is mentioned.

  In the laminate according to the present invention, the substrate and the support are laminated via an adhesive layer so that a separation layer is provided between the substrate and the support, and at least the separation layer in the support is provided. The order of the steps is not particularly limited as long as the surface to be formed is made hydrophobic by the surface treatment step.

  As described above, the laminate 1 according to this embodiment can be manufactured. The laminate 1 has a support body (i) in which at least the surface on which the separation layer 15 is provided in the support body 12 having a hydrophilic surface is hydrophobized (the surface treatment film 14 is provided on the surface). 12 and the separation layer 15 are improved, and (ii) in a reaction chamber having exhaust holes, the support 12 is supported by the plasma CVD method in a state vertically below the exhaust holes. By forming the separation layer 15 on the body 12, it is possible to form a uniform and thin separation layer 15 without fine irregularities on the surface. Thereby, the laminated body 1 with improved chemical resistance can be provided.

  In addition, when the support 12 on which the separation layer 15 is formed is stored in the cassette, the problem that the separation layer 15 formed on the end surface of the support 12 contaminates the cassette is also a problem with the laminate according to this embodiment. Can be resolved.

  In addition, although it is preferable that the laminated body which concerns on this embodiment is equipped with both the structures of said (i) and (ii), it may be provided only with either one. Moreover, the manufacturing method of the laminated body which concerns on this embodiment is (iii) the process of hydrophobizing the surface in which the separation layer 15 is provided in the support body 12 where the surface is hydrophilic, and (iv) the reaction which has an exhaust hole. It is preferable to include both of the steps of forming the separation layer 15 on the support 12 by the plasma CVD method with the support 12 positioned vertically below the exhaust hole in the room. It may include only one of them.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

[Example 1]
Hexamethyldisilane (HMDS) is used as a silylating agent for the surface treatment process, and this is set in a HMDS treatment unit of a resist coating apparatus SK-W80A (manufactured by Dainippon Screen Mfg. Co., Ltd.), and a vapor at 80 ° C. for 10 minutes. Surface treatment of the support (12-inch glass substrate, thickness 700 μm) was performed under heating conditions (surface treatment step).

  The surface-treated support is installed in the reaction chamber of the CVD apparatus in which the position of the exhaust hole is set so that the surface of the support is 16.5 mm vertically upward and 8.0 mm horizontally. did.

Under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2800 W, and a film forming temperature of 240 ° C., the above-described fluorocarbon film (thickness 0.5 μm) as a separation layer is supported by the CVD method using C ₄ F ₈ as a reaction gas It formed on the surface which surface-treated the body (separation layer formation process).

  Next, a hydrocarbon-based adhesive composition “TZNR-A3007” (manufactured by Tokyo Ohka Kogyo Co., Ltd.) in an amount that becomes a thickness of 50 μm after baking on a 725 μm-thick semiconductor wafer (12-inch silicon wafer) substrate. ) Was applied. Then, each of 90 ° C., 160 ° C. and 220 ° C. was baked stepwise for 15 minutes to form an adhesive layer on the semiconductor wafer substrate (adhesive layer forming step). And it laminated | stacked with the support body which formed the separation layer for 3 minutes on 220 degreeC and 4000 kg conditions under vacuum, and was set as the laminated body (lamination process).

(Chemical resistance evaluation)
The wafer was ground to 40 μm, and chemical resistance was evaluated using NMP (N-methyl-2-pyrrolidone) as a stripping solution. After immersing the above laminate for 10 minutes in NMP heated to 60 ° C., it was evaluated whether there was a defect such as peeling by visual inspection and observation of the edge portion from the glass side and the substrate side by a microscope.

(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. Then, it was evaluated whether there was any defect such as peeling by visual inspection and observation of the edge portion from the glass side and the substrate side with a microscope.

  In the laminated body of Example 1, both the chemical resistance evaluation and the heat treatment evaluation were satisfactory.

[Example 2]
As a polymer coating for the surface treatment process, COUT200 (epoxy polymer coating, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is applied on a support, baked at 240 ° C. for 60 seconds, and then dried. A surface treatment film having a thickness of 220 nm was formed.

  The surface-treated support is installed in the reaction chamber of the CVD apparatus in which the position of the exhaust hole is set so that the surface of the support is 16.5 mm vertically upward and 8.0 mm horizontally. did.

Under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2800 W, and a film forming temperature of 240 ° C., the above-described fluorocarbon film (thickness 0.5 μm) as a separation layer is supported by the CVD method using C ₄ F ₈ as a reaction gas It formed on the surface which surface-treated the body (separation layer formation process).

  Next, a hydrocarbon-based adhesive composition “TZNR-A3007” (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied on a semiconductor wafer substrate having a thickness of 725 μm so as to have a thickness of 50 μm after baking. Then, each of 90 ° C., 160 ° C. and 220 ° C. was baked stepwise for 15 minutes to form an adhesive layer on the semiconductor wafer substrate (adhesive layer forming step). And it laminated | stacked with the support body which formed the separation layer for 3 minutes on 220 degreeC and 4000 kg conditions under vacuum, and was set as the laminated body (lamination process).

(Chemical resistance evaluation)
The wafer was ground to 40 μm, and chemical resistance was evaluated using NMP (N-methyl-2-pyrrolidone) as a stripping solution. After immersing the above laminate for 10 minutes in NMP heated to 60 ° C., it was evaluated whether there was a defect such as peeling by visual inspection and observation of the edge portion from the glass side and the substrate side by a microscope.

(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. Then, it was evaluated for defects such as peeling by visual inspection and observation of the edge portion from the glass side and the substrate side with a microscope.

  In the laminate of Example 2, there was no problem in both chemical resistance evaluation and heat treatment evaluation.

  The present invention can be suitably used, for example, in the field of manufacturing miniaturized semiconductor devices.

DESCRIPTION OF SYMBOLS 1 Laminated body 2 Laminated body 11 Board | substrate 12 Support body 13 Adhesive layer 14 Surface treatment film 15 Separation layer 100 Separation layer formation apparatus 101 Base 102 Reaction chamber 103 Mounting stand and lower electrode (mounting stand)
104 Exhaust ring 105 Quartz chamber body 106 Quartz chamber upper part 108 Top plate 109 Exhaust hole

Claims (7)

A substrate, a light-transmitting support that supports the substrate, and a separation layer that is provided between the substrate and the support and changes quality by absorbing light irradiated through the support. A method for producing a laminate,
A separation layer forming step of forming the separation layer on the support by a plasma CVD method in a state where the support is positioned vertically below the exhaust hole in a reaction chamber having an exhaust hole ;
The reaction chamber is of a bell jar type as a whole, and the exhaust hole is provided in an exhaust ring constituting the inner wall of the reaction chamber, and a gas supply port is provided at the top of the inner wall of the reaction chamber. A method for producing a laminate, characterized by comprising: In the reaction chamber, a mounting table for mounting the support is provided,
The method for manufacturing a laminate according to claim 1, wherein the exhaust hole is disposed vertically above the mounting table by 1 mm or more.   The method for manufacturing a laminate according to claim 1, wherein an insulating member is provided vertically below the exhaust hole in the inner wall of the reaction chamber.   The method for producing a laminate according to any one of claims 1 to 3, wherein a distance in a horizontal direction between the exhaust hole and the support is 1 mm or more.   5. The method according to claim 1, wherein in the separation layer forming step, the separation layer is formed by a plasma CVD method using a reaction gas containing at least one of a hydrocarbon gas and a fluorocarbon gas. The manufacturing method of the laminated body as described in any one. A separation layer forming apparatus for forming, on a light transmissive support, a separation layer that is altered by absorbing light irradiated through the support by a plasma CVD method,
A reaction chamber having an exhaust hole;
A mounting table for mounting the support in the reaction chamber,
The exhaust hole is arranged 1 mm or more vertically above the mounting table ,
The reaction chamber is of a bell jar type as a whole, and the exhaust hole is provided in an exhaust ring constituting the inner wall of the reaction chamber, and a gas supply port is provided at the top of the inner wall of the reaction chamber. An apparatus for forming a separation layer.   The separation layer forming apparatus according to claim 6, wherein an insulating member is further provided vertically below the exhaust hole in the inner wall of the reaction chamber.

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