JP5864926B2 - LAMINATE, SEPARATING METHOD, AND MANUFACTURING METHOD - Google Patents

Description

  The present invention relates to a laminate, a method for separating the laminate, a method for producing the laminate, and a method for producing various apparatuses using the laminate.

  Patent Document 1 describes a laminate for peeling a substrate to be ground such as a silicon wafer fixed on a support from the support.

  Patent Document 2 describes a photothermal conversion layer precursor for forming a laminate containing a photothermal conversion layer in which a substrate to be ground is fixed on a support.

JP 2004-64040 A (February 26, 2004) JP 2009-155652 A (released on July 16, 2009)

  In recent years, with the widespread use of portable devices such as mobile personal computers, smartphones, and electronic paper, the need for light and unbreakable displays is increasing. Conventionally, a glass substrate has been used for a display, but a film substrate is used instead of a glass substrate in accordance with the needs of a lightweight and hard-to-break display.

  In the display manufacturing process, the substrate is automatically conveyed. However, since the film substrate is thinner than the conventional glass substrate, it is difficult to automatically convey the film substrate in the same manner as the glass substrate. For this reason, in the manufacturing process using a film substrate, the laminated body which bonded together support plates, such as glass, to the film substrate is produced previously, and a film substrate is automatically conveyed in the state of a laminated body.

  During the manufacturing process, structures such as electric circuits and display elements are mounted on the film substrate while automatically transporting the film substrate bonded to the support plate. Then, after the manufacturing process, the film substrate is separated from the support plate. Therefore, it is preferable that the film substrate and the support plate are firmly bonded during the manufacturing process, but it is preferable that the film substrate can be smoothly separated from the support plate after the manufacturing process.

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

  The present invention has been made in view of the above problems, and its purpose is to provide a laminate of a substrate and a support plate that is firmly bonded during the manufacturing process and can be easily separated after the manufacturing process. And providing a method for separating the laminate, a method for producing the laminate, and a method for producing various apparatuses using the laminate.

  In order to solve the above problems, a laminate according to the present invention includes a light-transmitting support, an organic material layer containing an organic material supported by the support, the support, and the organic material layer. And a separation layer that changes in quality by absorbing light irradiated through the support.

  Further, the separation method according to the present invention is a separation method for separating the support from the organic material layer in the laminate, wherein the separation layer is irradiated with light through the support, and the separation layer is separated. It is characterized in that it includes a light irradiation process for altering the quality.

  Furthermore, the method for producing a laminate according to the present invention is a method for producing the laminate, including an organic material layer forming step of forming the organic material layer on the separation layer, and forming the organic material layer. In the step, an organic material layer is formed by laminating a layer made of the organic substance on the separation layer via an adhesive layer, or applying and drying a solution containing the organic substance on the separation layer. It is characterized by that.

  The display film manufacturing method according to the present invention includes a preparation step of preparing the laminate, a mounting step of mounting a display element on the organic material layer in the laminate, and the display element being mounted. The laminate includes a light irradiation step of irradiating the separation layer with light through the support to alter the separation layer, and a separation step of separating the support from the organic material layer. It is a feature.

  Furthermore, the manufacturing method of the solar cell according to the present invention includes a preparation step of preparing the laminate, a mounting step of mounting a solar cell element on the organic material layer in the laminate, and the solar cell element being mounted. The laminated body includes a light irradiation step of irradiating the separation layer with light through the support to alter the separation layer, and a separation step of separating the support from the organic material layer. It is characterized by that.

  The sensor manufacturing method according to the present invention includes a preparation step of preparing the laminate, a mounting step of mounting a sensor element on the organic material layer in the laminate, and a laminate in which the sensor element is mounted. In the body, the method includes a light irradiation step of irradiating the separation layer with light through the support to alter the separation layer, and a separation step of separating the support from the organic material layer. It is said.

  Furthermore, in the method for manufacturing a light emitting device according to the present invention, a preparation step of preparing the laminate, a mounting step of mounting a light emitting element on the organic material layer in the laminate, and the light emitting device are mounted. The laminate includes a light irradiation step of irradiating the separation layer with light through the support to alter the separation layer, and a separation step of separating the support from the organic material layer. It is said.

  The image scanner manufacturing method according to the present invention includes a preparation step of preparing the laminate, a mounting step of mounting a scanner element on the organic material layer in the laminate, and the scanner element being mounted. The laminate includes a light irradiation step of irradiating the separation layer with light through the support to alter the separation layer, and a separation step of separating the support from the organic material layer. It is said.

  The laminate according to the present invention is provided between a light transmissive support, an organic material layer containing an organic material supported by the support, and the support and the organic material layer. Since it has a separation layer that changes quality by absorbing light irradiated through the support, the support and the organic material layer that are firmly bonded during the manufacturing process can be easily separated after the manufacturing process. Is possible.

It is a figure which shows the manufacturing method of the laminated body which concerns on one Embodiment of this invention, and the separation method of a support plate. It is a figure which shows the isolation | separation process of a support plate.

[Laminate]
An embodiment of a laminate according to the present invention will be described below with reference to FIGS. FIG. 1 is a view showing a laminate manufacturing method and a support plate separation method according to an embodiment of the present invention, and FIG. 2 is a view showing a support plate separation step. As shown in FIGS. 1 and 2, the laminate 1 is provided between a support plate (support) 12, an organic material layer 11 supported by the support plate, and between the support plate 12 and the organic material layer 11. And a separation layer 16. Further, the laminate 1 may include an adhesive layer 14 between the organic material layer 11 and the support plate 12.

  The laminate 1 is formed by laminating an organic material layer 11, an adhesive layer 14, a separation layer 16, and a support plate 12 in this order. The organic material layer 11 is formed on the support plate 12 via the adhesion layer 14 and the separation layer 16. It is temporarily fixed.

(Organic material layer 11)
The organic material layer 11 is a flexible layer containing an organic material, and is used as a film substrate, a flexible substrate, or the like. Since the organic material layer 11 is more flexible than a glass substrate or the like, it is lightweight and difficult to break, and therefore can be suitably used as a film material for displays, solar cells, lighting devices, pressure sensors, image scanners, and the like.

  The organic material contained in the organic material layer 11 is a polymer. The organic material layer 11 may be a film in which the organic material containing the organic material described above is formed in advance. Alternatively, the organic material layer 11 may be formed by applying a liquid or the like of an organic material on the separation layer 16 and solidifying it into a film. May be. The organic substance contained in the organic material layer 11 can be appropriately selected according to the use of the organic material layer 11. The layer thickness of the organic material layer 11 can also be selected as appropriate according to the application of the organic material layer 11.

  Examples of the polymer used in the form of a film include polyester (for example, PET or polyethylene naphthalate), polyacrylate (for example, polymethyl methacrylate), polycarbonate, polypropylene, high-density or low-density polyethylene, polysulfone, and polyethersulfone. , Polyurethanes, polyamides, polyvinyl butyral, polyvinyl chloride, polyvinylidene difluoride, polyethylene sulfide and cyclic olefin polymers (eg, TOPAS® and Zeon Chemicals from Topas Advanced Polymers). Thermoplastic film cellulose such as ZEONOR (registered trademark) manufactured by (Zeon Chemicals, LP) Conductors, as well as polyimides, and flexible plastic materials including thermoset films such as polyimide benzoxazole and polybenzoxazole is.

  In addition, as a material for solidifying into a film by applying a liquid of an organic material, polyether ether ketone (PEEK) (for example, VICTREX (registered trademark)) and polyether imide (PEI) (for example, Ultem) (Registered trademark)).

(Support plate 12)
The support plate 12 is a support that supports the organic material layer 11 and has light transmittance. This is intended to reach the separation layer 16 through the support plate 12 when the light is irradiated from the outside of the stacked body 1. Therefore, the support plate 12 does not necessarily need to transmit all the light, and only needs to be able to transmit the light to be absorbed by the separation layer 16 (having a desired wavelength).

  The support plate 12 is configured to support the organic material layer 11. Therefore, the support plate 12 only needs to have a strength necessary for preventing damage or deformation of the organic material layer 11 in the case of mounting an element or the like on the organic material layer 11 or transporting the organic material layer 11.

  From the above viewpoint, examples of the support plate 12 include those made of glass, silicon, and acrylic. However, any support plate 12 can be adopted as long as it can achieve the above-described purpose. When the support plate 12 is a silicon plate, infrared rays having a wavelength of 2 μm or more can be transmitted.

(Separation layer 16)
The separation layer 16 is altered by absorbing light irradiated through the support plate 12. In the present specification, the “deterioration” of the separation layer 16 means a phenomenon in which the separation layer 16 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 16 is reduced. means. Further, the alteration of the separation layer 16 includes decomposition (exothermic or non-exothermic), cross-linking, configuration change or dissociation of functional groups due to absorbed light energy (and curing of the separation layer and degassing associated therewith). , Contraction or expansion) and the like. The alteration of the separation layer 16 occurs as a result of light absorption by the material constituting the separation layer 16. Therefore, the type of alteration of the separation layer 16 can be changed according to the type of material constituting the separation layer 16.

  The separation layer 16 is provided on the surface of the support plate 12 on the side where the organic material layer 11 is bonded via the adhesive layer 14. That is, the separation layer 16 is provided between the support plate 12 and the adhesive layer 14. Therefore, the light irradiated to the separation layer 16 through the support plate 12 can be prevented from reaching the organic material layer 11. For example, when a fine structure to be protected is formed on the surface in contact with the adhesive layer 14 in the organic material layer 11, such a fine structure can be prevented from being adversely affected by light irradiation.

  For example, the thickness of the separation layer 16 is more preferably 0.1 to 50 μm, and further preferably 0.1 to 10 μm. If the thickness of the separation layer 16 is within a range of 0.1 to 50 μm, the separation layer 16 can be altered as desired by irradiation with light for a short time and irradiation with low energy light.

  In the laminate 1, another layer may be further formed between the separation layer 16 and the support plate 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 1 can be appropriately added without hindering the incidence of light on the separation layer 16. The wavelength of light that can be used differs depending on the type of material constituting the separation layer 16. 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 16.

  Further, by selecting a material having a light-absorbing structure as a material constituting the adhesive layer 14, the adhesive layer 14 and the separation layer 16 can be formed as the same layer. Furthermore, the separation layer 16 is preferably formed only from a material having a structure that absorbs light. However, the material that 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 16. Moreover, it is preferable that the surface of the separation layer 16 on the side facing the adhesive layer 14 is flat (unevenness is not formed), so that the separation layer 16 can be easily formed and even when pasted. It becomes possible to paste on.

  As the separation layer 16, a material that forms the separation layer 16 as described below may be used by bonding it to the support plate 12 in advance, or the separation layer 16 may be formed on the support plate 12. You may use what applied the material and solidified in the film form. The method of applying the material constituting the separation layer 16 on the support plate 12 can be appropriately selected from conventionally known methods according to the type of material constituting the separation layer 16.

The separation layer 16 may be altered by absorbing light emitted from the laser. In other words, the light irradiated to the separation layer 16 in order to change the quality of the separation layer 16 may be emitted from a laser. Examples of lasers that emit light to irradiate the separation layer 16 include YAG lasers, Libby lasers, glass lasers, YVO ₄ lasers, LD lasers, liquid lasers such as fiber lasers, liquid lasers such as dye lasers, CO ₂ lasers, and excimers. Examples thereof include gas lasers such as lasers, Ar lasers, and He—Ne lasers, laser beams such as semiconductor lasers and free electron lasers, and non-laser beams. The laser that emits light to irradiate the separation layer 16 can be appropriately selected according to the material constituting the separation layer 16 and irradiates light having a wavelength that can alter the material constituting the separation layer 16. The laser to be selected may be selected.

<Polymer containing light absorbing structure in its repeating unit>
The separation layer 16 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 16 loses its strength or adhesiveness before being irradiated with light as a result of the alteration of the polymer. Therefore, by applying a slight external force (for example, lifting the support plate 12), the separation layer 16 is broken, and the support plate 12 and the organic material layer 11 can be easily separated.

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

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

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

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

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

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

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

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

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

  When the structure is present in the side chain of the polymer, the proportion of the repeating unit containing the structure in the polymer is such that the light transmittance of the separation layer 16 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 16 can sufficiently absorb light and can be reliably and rapidly altered. That is, it is easy to remove the support plate 12 from the laminate 1, 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.

  The light that can be absorbed by the above structure is, for example, a high-pressure mercury lamp (wavelength: 254 nm to 436 nm), a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), an 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 16 described above contains a polymer containing the above structure as a repeating unit, the separation layer 16 may further contain a component other than the polymer. Examples of the component include a filler, a plasticizer, and a component that can improve the peelability of the support plate 12. These components are appropriately selected from conventionally known substances or materials that do not hinder or promote the absorption of light by the above structure and the alteration of the polymer.

<Inorganic material>
The separation layer 16 may be made of an inorganic material. The separation layer 16 is composed of an inorganic substance, and is thereby altered by absorbing light. As a result, the separation layer 16 loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support plate 12 or the like), the separation layer 16 is broken, and the support plate 12 and the organic material layer 11 can be easily separated.

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

  The inorganic material absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength within a range that is absorbed by the inorganic material used for the separation layer 16, the inorganic material can be suitably altered.

The light applied to the separation layer 16 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 16 made of an inorganic material can be formed on the support plate 12 by a known technique such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, or spin coating. The thickness of the separation layer 16 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 0.1 to 10 μm is more preferable. Alternatively, an adhesive may be applied in advance to both surfaces or one surface of an inorganic film (for example, a metal film) made of an inorganic material constituting the separation layer 16 and attached to the support plate 12 and the organic material layer 11.

  When a metal film is used as the separation layer 16, laser reflection or charging of the film may occur depending on conditions such as the film quality of the separation layer 16, the type of laser light source, and laser output. Therefore, it is preferable to take such measures by providing an antireflection film or an antistatic film on the upper and lower sides of the separation layer 16 or one of them.

<Compound having infrared absorbing structure>
The separation layer 16 may be formed of a compound having an infrared absorbing structure. The compound is altered by absorbing infrared rays. The separation layer 16 loses its strength or adhesiveness before being irradiated with infrared rays as a result of the alteration of the compound. Therefore, by applying a slight external force (for example, lifting the support plate), the separation layer 16 is broken and the support plate 12 and the organic material layer 11 can be easily separated.

Examples of the compound having an infrared absorptive structure or an infrared absorptive structure include alkanes, alkenes (vinyl, trans, cis, vinylidene, trisubstituted, tetrasubstituted, conjugated, cumulene, ring Formula), alkyne (monosubstituted, disubstituted), monocyclic aromatic (benzene, monosubstituted, disubstituted, trisubstituted), alcohol and phenols (free OH, intramolecular hydrogen bond, intermolecular hydrogen bond, saturated Secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetal, ketal, aliphatic ether, aromatic ether, vinyl ether, oxirane ether, peroxide ether, ketone, dialkylcarbonyl, aromatic Carbonyl, 1,3-diketone enol, o-hydroxy aryl ketone, dialkyl aldehyde, aromatic aldehyde, carboxylic acid (dimer, Rubonic acid 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, glass Esters, nitrites, nitroso bonds (aliphatic, aromatic, monomer, dimer), sulfur compounds such as mercaptans and thiophenol and thiolic acid, thiocarbonyl groups, sulfoxides, sulfones, sulfonyl chlorides, primary Sulfonamide, secondary sulfonamide, sulfate ester, carbon-halogen bond, Si-A ¹ bond (A ¹ is H, C, O or halogen), PA ² bond (A ² is H, C or O), or Ti—O bonds.

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

Examples of the structure including the Si—A ¹ bond include SiH, SiH ₂ , SiH ₃ , Si—CH ₃ , Si—CH ₂ —, Si—C ₆ H ₅ , SiO aliphatic, Si—OCH ₃ , Si—OCH. _{2 CH 3, Si-OC 6} H 5, Si-O-Si, Si-OH, SiF, SiF 2, and the like SiF _3. As a structure including a Si—A ¹ bond, a siloxane skeleton and a silsesquioxane skeleton are particularly preferably formed.

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

  The said structure can absorb the infrared rays which have the wavelength of a desired range by selection of the kind. For example, 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 the range of 2 μm to 15 μm can be more suitably absorbed. 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 literature: 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 16, 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 16 and facilitate separation of the support plate 12 and the organic material layer 11, infrared absorption in the separation layer 16 is large. It is preferable that the infrared transmittance when irradiated with is low. Specifically, the infrared transmittance in the separation layer 16 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 formula (1) and a repeating unit represented by the following formula (2), or A resin that is a copolymer of a repeating unit represented by the following formula (1) and a repeating unit derived from an acrylic compound can be used.

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

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

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

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

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

Examples of the compound containing a Ti—O bond include (i) tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2-ethylhexyloxy) titanium, and titanium-i-propoxyoctylene glycolate. Chelating titanium such as (ii) 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- propoxytitanium diisopropyl Examples include sostearate and acylate titanium such as (2-n-butoxycarbonylbenzoyloxy) tributoxytitanium, and (v) water-soluble titanium compounds such as di-n-butoxy bis (triethanolaminato) titanium.

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 16 described above contains a compound having an infrared-absorbing structure, the separation layer 16 may further contain a component other than the above compound. Examples of the component include a filler, a plasticizer, and a component that can improve the peelability of the support plate 12. These components are appropriately selected from conventionally known substances or materials that do not interfere with or promote infrared absorption by the above structure and alteration of the compound.

<Fluorocarbon>
The separation layer 16 may be made of a fluorocarbon. Since the separation layer 16 is composed of fluorocarbon, the separation layer 16 is altered by absorbing light. As a result, the separation layer 16 loses strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, lifting the support plate 12), the separation layer 16 is broken, and the support plate 12 and the organic material layer 11 can be easily separated.

From one viewpoint, the fluorocarbon constituting the separation layer 16 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 H ₂ F, C ₂ F ₆ , C ₅ F _{8 and the} like. In addition, an inert gas such as nitrogen, helium, or argon, a hydrocarbon such as oxygen, alkane, or alkene, and carbon dioxide or hydrogen are added to the fluorocarbon used to configure the separation layer 16 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 16 may be composed of a single type of fluorocarbon, or may be composed of two or more types of fluorocarbon.

  The fluorocarbon absorbs light having a wavelength in a specific range depending on the type. By irradiating the separation layer with light having a wavelength within a range that is absorbed by the fluorocarbon used in the separation layer 16, the fluorocarbon can be suitably altered. In addition, it is preferable that the light absorption rate in the separation layer 16 is 80% or more.

The light applied to the separation layer 16 is, for example, a solid laser such as a YAG laser, Libby laser, glass laser, YVO4 laser, LD laser, or fiber laser, or a liquid laser such as a dye laser, depending on the wavelength that can be absorbed by the fluorocarbon. A gas laser such as a CO ₂ laser, an excimer laser, an Ar laser, or a He—Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be used as appropriate. The wavelength at which the fluorocarbon can be altered is not limited to this, but for example, a wavelength in the range of 600 nm or less can be used.

<Infrared absorbing material>
The separation layer 16 may contain an infrared absorbing material. The separation layer 16 is configured to contain an infrared absorbing material, so that the separation layer 16 is altered by absorbing light, and as a result, the strength or adhesiveness before receiving the light irradiation is lost. Therefore, by applying a slight external force (for example, lifting the support plate 12 or the like), the separation layer 16 is broken, and the support plate 12 and the organic material layer 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 16 with light having a wavelength in a range that is absorbed by the infrared absorbing material used for the separation layer 16, the infrared absorbing material can be suitably altered.

(Adhesive layer 14)
The adhesive layer 14 is configured to adhere and fix the organic material layer 11 to the support plate 12 and simultaneously cover and protect the surface of the organic material layer 11. Therefore, the adhesive layer has adhesiveness and strength for maintaining the fixing of the organic material layer 11 to the support plate 12 and the covering of the surface to be protected of the organic material layer 11 when the organic material layer 11 is processed or transported. Need to be. On the other hand, when it becomes unnecessary to fix the organic material layer 11 to the support plate 12, it needs to be easily peeled off or removed from the organic material layer 11.

  Therefore, the adhesive layer 14 usually has strong adhesiveness, and the adhesive layer 14 is composed of an adhesive whose adhesiveness is reduced by some treatment or has solubility in a specific solvent. As the adhesive, for example, various adhesives known in the art such as acrylic, novolak, naphthoxan, hydrocarbon, and polyimide can be used as the adhesive constituting the adhesive layer 14 according to the present invention. is there. Below, the composition of resin which the contact bonding layer 14 in this Embodiment contains is demonstrated.

  The resin contained in the adhesive layer 14 may be any resin having adhesiveness, and examples thereof include hydrocarbon resins, acrylic-styrene resins, maleimide resins, and the like, or combinations thereof.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

<Maleimide resin>
Examples of maleimide resins include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec as monomers. -Butylmaleimide, N-te
Maleimides having alkyl groups such as rt-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide and other maleimides having an aliphatic hydrocarbon group, N-phenylmaleimide, Examples thereof include resins obtained by polymerizing an aromatic maleimide having an aryl group, such as Nm-methylphenylmaleimide, N-o-methylphenylmaleimide, and Np-methylphenylmaleimide.

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

(In formula (9), n is 0 or an integer of 1 to 3)
In addition, as such a 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 14 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 organic material layer 11 after the adhesive layer 14 is peeled or removed. In particular, an adhesive that dissolves in a specific solvent is preferable as a material constituting the adhesive layer 14. This is because the adhesive layer 14 can be removed by dissolving it in a solvent without applying physical force to the organic material layer 11. When removing the adhesive layer 14, the adhesive layer 14 can be easily removed without damaging or deforming the organic material layer 11 even from the organic material layer 11 with 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-terpine, bornane, norbornane, pinane, tsujang, kalan, longifolene, geraniol, nerol, Linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, Borneo Terpene solvents such as ru, carvone, ionone, thuyon, camphor, d-limonene, l-limonene, dipentene; lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl Ketones such as isopentyl ketone and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetate Compounds having an ester bond such as monomethyl ether, monoethyl ether, monopropyl of the polyhydric alcohols or the compound having an ester bond Derivatives of polyhydric alcohols such as ethers, monoalkyl ethers such as monobutyl ether or compounds having an ether bond such as monophenyl ether (in these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) Preferred); cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxy Esters such as ethyl propionate; aromatics such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether Mention may be made of a solvent or the like.

[Method for separating laminates]
The separation method according to the present invention is a separation method for separating the support plate 12 from the organic material layer 11 in the laminate 1, and the separation layer 16 is irradiated with light through the support plate 12 to alter the separation layer 16. Including a light irradiation step. An embodiment of the separation method according to the present invention will be described below with reference to FIGS.

  As shown in FIG. 1, after the processing of the organic material layer 11 such as mounting various structures such as elements on the organic material layer 11 is finished, the light from the laser is applied to the laminated body 1 from the surface on the support plate 12 side. Irradiation (light irradiation step) ((4) laser irradiation in FIG. 1). When irradiated with light from the laser ((1) laser irradiation in FIG. 2), the separation layer 16 is altered ((2) alteration in the separation layer in FIG. 2). Here, the description will be made assuming that the alteration is decomposition of a compound contained in the separation layer 16.

  Next, the support plate 12 is peeled from the organic material layer 11 ((5) peeling step in FIG. 1). The strength of the altered separation layer 16 is significantly reduced. Therefore, for example, when the support plate 12 is pulled up by applying a slight external force, the separation layer 16 is easily broken and the support plate 12 is peeled from the laminate 1 ((3) Support plate peeling in FIG. 2). .

  The remaining adhesive layer 14 is sprayed with a solvent to remove the adhesive layer 14 on the organic material layer 11 ((6) cleaning in FIG. 1). Here, the separation layer 16 may remain on the adhesive layer 14 after the support plate 12 is peeled off. If only a small amount of the separation layer 16 remains attached, the solvent for dissolving the adhesive layer 14 may be sprayed as described above. However, before that, a solvent for dissolving the material of the separation layer 16 may be sprayed.

  As described above, since the laminate 1 includes the separation layer 16 as described above, the support plate 12 can be easily peeled from the organic material layer 11 by light irradiation.

  Note that the light irradiation is not necessarily performed on the entire region of the separation layer 16. Even if a region irradiated with light and a region not irradiated are mixed, if the strength of the separation layer 16 as a whole is sufficiently reduced, the support plate is lifted by applying a slight external force to separate the layers. The layer 16 can be easily broken and the support plate 12 can be peeled from the laminate 1.

  The ratio and positional relationship between the light-irradiated region and the non-irradiated region vary depending on the type of compound forming the separation layer 16, the thickness of the separation layer, the intensity of the light to be irradiated, etc. The conditions can be set as appropriate without requiring the above test. As described above, since the support plate can be separated even when only a part of the separation layer 16 is irradiated with light, the total irradiation time of light applied to the stacked body 1 can be shortened. The time required for processing can be shortened.

[Method for producing laminate]
The laminate manufacturing method according to the present invention is a method for manufacturing the above-described laminate, and includes an organic material layer forming step of forming the organic material layer 11 on the separation layer 16. The organic material layer 11 is formed by laminating a layer made of an organic substance on the separation layer 16 via the adhesive layer 14 or by applying a solution containing the organic substance on the separation layer 16 and drying it. One embodiment of a method for producing a laminate according to the present invention will be described below with reference to FIGS.

  As shown in FIG. 1, first, an adhesive 13 is spin-coated on the surface of the organic material layer 11 formed of a desired material that faces the surface on which a structure such as an element is mounted in a later step. ((1) Adhesive application in FIG. 1). For example, the adhesive 13 is applied to the organic material layer 11 in a state dissolved in a solvent. And the adhesive agent 13 is solidified by baking in steps while raising the temperature, and the adhesive layer 14 is formed.

  On the other hand, the separation layer 16 is formed on one surface of the support plate 12. In the present embodiment, as the material for forming the separation layer 16, the separation layer material 15 containing a polymer containing a light-absorbing structure in its repeating unit is used. Such separation layer material 15 is dissolved in a solvent and spin-coated ((2) Formation of separation layer in FIG. 1). Then, by evaporating the solvent, it is solidified to form the separation layer 16.

  Next, the support plate 12 is brought into contact with the organic material layer 11 so that the adhesive layer 14 formed on one surface of the organic material layer 11 and the separation layer 16 formed on one surface of the support plate 12 are in surface contact. Paste ((3) Separation layer support plate attachment in FIG. 1). Here, the adhesive layer 14 and the separating layer 16 are attached by bringing the separating layer 16 into contact with the adhesive layer 14 and applying pressure in a vacuum at 200 ° C.

  As described above, as shown in FIG. 2, it is possible to manufacture a laminate 1 in which the organic material layer 11, the adhesive layer 14, the separation layer 16, and the support plate 12 are laminated in this order.

  Alternatively, the material constituting the organic material layer 11 may be applied on the separation layer 16, and the organic material layer 11 may be formed on the separation layer 16 without using the adhesive layer 14. Note that the material may contain an adhesive material.

  Alternatively, the laminate 1 may be manufactured by sequentially applying and drying the materials constituting the adhesive layer 14 and the organic material layer 11 on the separation layer 16 formed on the support plate 12.

  According to the state of the organic material layer 11 (surface unevenness, strength, etc.), the material of the adhesive layer 14, the material of the separation layer 16, the material of the support plate 12, and the like, As a method for attaching the adhesive layer 14 and the separation layer 16, a suitable one is appropriately selected from various conventionally known methods.

[Manufacturing methods of various devices]
(Display film)
The display film manufacturing method according to the present invention includes a preparation step for preparing the laminate 1 described above, a mounting step for mounting a display element on the organic material layer 11 in the laminate 1, and the display element is mounted. The laminated body 1 includes a light irradiation process in which the separation layer 16 is irradiated with light through the support plate 12 to alter the separation layer 16 and a separation process in which the support plate 12 is separated from the organic material layer 11. Therefore, a display film can be more easily manufactured by using the laminated body 1 including the organic material layer 11 formed of a material suitable for a display film, for example, containing polyimide or the like.

  That is, during the process of mounting the display element on the organic material layer 11, the organic material layer 11 is firmly bonded to the support plate 12, so that the organic material layer 11 can be easily processed and transported. On the other hand, after the process, the organic material layer 11 and the support plate 12 can be easily separated. Therefore, a display film can be easily manufactured without damaging the display element mounted on the organic material layer 11. In addition, in this specification, the display element is intended for various elements or structures mounted on a display film, and not only for display elements but also for transistors, organic EL materials, color filters, liquid crystals, and electronic paper. Materials etc. are also included.

(Solar cell)
The method for manufacturing a solar cell according to the present invention includes a preparation step for preparing the laminate 1 described above, a mounting step for mounting the solar cell element on the organic material layer 11 in the laminate 1, and the solar cell element being mounted. The laminated body 1 includes a light irradiation step of irradiating the separation layer 16 with light through the support plate 12 to alter the separation layer 16 and a separation step of separating the support plate 12 from the organic material layer 11. To do. Therefore, a solar cell can be more easily manufactured by using the laminated body 1 including the organic material layer 11 formed of a material suitable for the solar cell.

  That is, during the process of mounting the solar cell element on the organic material layer 11, the organic material layer 11 is firmly bonded to the support plate 12, so that the organic material layer 11 can be easily processed and transported. On the other hand, after the process, the organic material layer 11 and the support plate 12 can be easily separated. Therefore, a solar cell can be easily manufactured without damaging the solar cell element mounted on the organic material layer 11. In addition, in this specification, the solar cell element intends various elements or structures mounted on the solar cell, and includes a photoelectric conversion element and the like.

(Sensor)
The method for manufacturing a sensor according to the present invention includes a preparation step for preparing the laminate 1 described above, a mounting step for mounting the sensor element on the organic material layer 11 in the laminate 1, and a laminate in which the sensor element is mounted. The body 1 includes a light irradiation process in which the separation layer 16 is irradiated with light through the support plate 12 to alter the separation layer 16 and a separation process in which the support plate 12 is separated from the organic material layer 11. Therefore, the sensor can be manufactured more easily by using the laminate 1 including the organic material layer 11 formed of a material suitable for the sensor.

  That is, during the process of mounting the sensor element on the organic material layer 11, the organic material layer 11 is firmly adhered to the support plate 12, so that the organic material layer 11 can be easily processed and transported. On the other hand, after the process, the organic material layer 11 and the support plate 12 can be easily separated. Therefore, the sensor can be easily manufactured without damaging the sensor element mounted on the organic material layer 11. In addition, in this specification, the sensor element intends various elements or structures mounted on the sensor. For example, when the sensor to be manufactured is a pressure sensor, a piezoelectric conversion element or the like is included.

(Light emitting device)
The manufacturing method of the light-emitting device according to the present invention includes a preparation step for preparing the laminate 1 described above, a mounting step for mounting the light-emitting element on the organic material layer 11 in the laminate 1, and the light-emitting device is mounted. The laminated body 1 includes a light irradiation process in which the separation layer 16 is irradiated with light through the support plate 12 to alter the separation layer 16 and a separation process in which the support plate 12 is separated from the organic material layer 11. Therefore, the light emitting device can be more easily manufactured by using the stacked body 1 including the organic material layer 11 formed of a material suitable for the light emitting device.

  That is, during the process of mounting the light emitting element on the organic material layer 11, the organic material layer 11 is firmly adhered to the support plate 12, so that the organic material layer 11 can be easily processed and transported. On the other hand, after the process, the organic material layer 11 and the support plate 12 can be easily separated. Therefore, the light emitting device can be easily manufactured without damaging the light emitting element mounted on the organic material layer 11. Note that in this specification, the light-emitting element is intended for various elements or structures mounted on a light-emitting device, and examples thereof include elements such as LEDs, semiconductor lasers, and organic ELs.

(Image scanner)
An image scanner manufacturing method according to the present invention includes a preparation step for preparing the laminate 1 described above, a mounting step for mounting a scanner element on the organic material layer 11 in the laminate 1, and the scanner element is mounted. The laminated body 1 includes a light irradiation process in which the separation layer 16 is irradiated with light through the support plate 12 to alter the separation layer 16 and a separation process in which the support plate 12 is separated from the organic material layer 11. Therefore, an image scanner can be manufactured more easily by using the laminate 1 including the organic material layer 11 formed of a material suitable for an image scanner.

  That is, during the process of mounting the scanner element on the organic material layer 11, the organic material layer 11 is firmly bonded to the support plate 12, so that the organic material layer 11 can be easily processed and transported. On the other hand, after the process, the organic material layer 11 and the support plate 12 can be easily separated. Therefore, the image scanner can be easily manufactured without damaging the scanner element mounted on the organic material layer 11. In this specification, the scanner element is intended for various elements or structures mounted on an image scanner, and includes an electro-optic conversion element and the like.

  Examples will be shown below, and the embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail. Further, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and the present invention is also applied to the embodiments obtained by appropriately combining the disclosed technical means. It is included in the technical scope of the invention. Moreover, all the literatures described in this specification are used as reference.

[Example 1]
A laminate was produced as follows and the separability was evaluated.

(Membrane formation of separation layer)
In a plasma CVD apparatus, a fluorocarbon film was formed on a plate-like inflexible support plate having a thickness of 0.7 mm by using CHF ₃ gas. Thereby, a separation layer having a thickness of 1 μm was formed on the support plate.

(Production of laminate)
Next, a polyimide film (product name: Kapton H type, manufactured by Toray DuPont) having a thickness of 50 μm is prepared as an organic material layer, and the adhesive layer has a thickness of 10 μm after baking on the polyimide film. A quantity of hydrocarbon-based adhesive was applied. Then, at 90 ° C., 160 ° C., and 220 ° C., an adhesive layer was formed on the polyimide film by baking stepwise for 10 to 20 minutes. The separation layer and the adhesive layer were bonded to each other at 200 ° C. so as to face each other.

(Evaluation of separability)
It was evaluated whether the support plate could be separated from the organic material layer after the following treatment was applied to the laminate produced as described above.

  The laminate obtained as described above was cured in nitrogen gas at 250 ° C. for 1 hour, assuming the thermal history of the display film manufacturing process. Thereafter, a green laser having a wavelength of 532 nm was irradiated from the support plate side of the laminate toward the separation layer. Specifically, a laser beam of 532 nm having a beam shape of 60 μm, an irradiation pitch of 120 μm, an average output of 0.6 W, and a feed rate of 3000 mm / sec is irradiated to two places on the laminate at a pulse frequency of 30 kHz and 50 kHz. did. The number of laser scans was one.

  As a result, the separation layer was altered by receiving laser irradiation, and the support plate was easily separated from the organic material layer simply by lifting the support plate. Further, when the surface of the support plate and the adhesive layer was visually observed after the support plate was separated, no residue was found except that a black powder with a modified fluorocarbon was seen on the adhesive layer.

  As described above, by forming the separation layer of the laminate with fluorocarbon, the separation layer was altered by laser irradiation, and the organic material layer could be separated from the support plate very easily.

[Examples 2 to 5]
About each of Examples 2-5, the material which comprises a separation layer, the film thickness of a separation layer, the film forming method of a separation layer, the wavelength of the light source used in a separation process, and light irradiation conditions were shown in the following tables. Regarding the points other than those shown in the table, a laminate was produced in the same manner as in Example 1 described above. As in Example 1, this laminate was irradiated with laser from the support plate side. As a result, the separation layer was altered and the organic material layer could be separated from the support plate very easily.

  Table 1 shows the configurations of the laminates of Examples 1 to 5, the processing conditions, and the evaluation results of the separability.

  As the resin 1 of Example 2, tert-butylstyrene (Mw = 8000, m: n = 1: 1) having a siloxane skeleton represented by the following formula was used.

  Further, as the resin 2 of Example 3, a resin (Mw = 4000, Mw / Mn = 3.3) having a cardo structure represented by the following formula in its repeating unit was used.

  The composition of the resin 3 of Example 5 is as follows.

  Resin (A-1) in the above composition was synthesized as follows.

  First, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 100 mg of 2,6-di-tert-butyl-4-methylphenol, and 72.0 g of acrylic acid Was heated and dissolved at 90 to 100 ° C. while blowing air at a rate of 25 ml / min. Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, the solution gradually became transparent and viscous, but stirring was continued as it was. During this time, the acid value was measured, and heating and stirring were continued until the acid value was less than 1.0 mgKOH / g. It took 12 hours for the acid value to reach the target value. Then, it cooled to room temperature and obtained the bisphenol fluorene type epoxy acrylate represented by the following formula (a-4) which is a colorless and transparent solid.

  Next, after adding 600 g of 3-methoxybutyl acetate to 307.0 g of the bisphenolfluorene-type epoxy acrylate thus obtained and dissolving, 80.5 g of benzophenone tetracarboxylic dianhydride and 1 g of tetraethylammonium bromide. The mixture was gradually heated to react at 110 to 115 ° C. for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed, reacted at 90 ° C. for 6 hours, and a resin having a cardo structure as a repeating unit ( A-1) was obtained. The disappearance of the acid anhydride group was confirmed by IR spectrum.

  Moreover, 3-methoxybutyl acetate / cyclohexanenon = 2/1 was used as the mixed solvent of Example 5.

Example 6
(Preparation of separation layer)
The same treatment as in Example 1 was performed to form a separation layer on the support plate.

(Preparation of organic material solution)
Polyetherimide (product name: Ultem, manufactured by SABIC Innovative Plastics Japan Co., Ltd.) was dissolved in N-methylpyrrolidone so as to have a solid content concentration of 20 wt% to obtain an organic material solution.

(Production of laminate)
The organic material solution was applied onto the separation layer formed on the support plate so that the organic material layer had a thickness of 30 μm after drying. And it baked step by step for 10-20 minutes in each of 90 degreeC, 160 degreeC, and 220 degreeC, and produced the laminated body.

(Evaluation of separability)
The produced laminate was irradiated with laser in the same manner as in Example 1 to alter the separation layer. As a result, the organic material layer could be separated from the support plate very easily. In addition, after the support plate was separated, the surfaces of the support plate and the organic material layer were visually observed, and there was no residue except that a small amount of black powder with altered fluorocarbon was seen on the organic material layer. .

Example 7
(Preparation of separation layer)
The same treatment as in Example 1 was performed to form a separation layer on the support plate.

(Preparation of organic material solution)
Polyvinyl butyral (product name: ESREC B BM2, manufactured by Sekisui Chemical Co., Ltd.) was dissolved in cyclohexanone so that the solid content concentration was 20 wt% to obtain an organic material solution.

(Production of laminate)
The organic material solution was applied onto the separation layer formed on the support plate so that the organic material layer had a thickness of 30 μm after drying. And it baked at 160 degreeC for 10 minute (s), and produced the laminated body.

(Separability evaluation)
The produced laminate was irradiated with laser in the same manner as in Example 1 to alter the separation layer. As a result, the organic material layer could be separated from the support plate very easily. In addition, after the support plate was separated, the surfaces of the support plate and the organic material layer were visually observed, and there was no residue except that a small amount of black powder with altered fluorocarbon was seen on the organic material layer. .

[Comparative Example]
Although an attempt was made to physically peel off the laminate produced in the same manner as in Example 1 without irradiating a laser, the support plate and the organic material layer could not be separated.

  ADVANTAGE OF THE INVENTION According to this invention, the temporarily fixed laminated body used at the time of manufacture of various products can be provided.

1 Laminate 11 Organic Material Layer 12 Support Plate 14 Adhesive Layer 16 Separation Layer

Claims (18)

A light transmissive support;
An organic material layer containing an organic material supported by the support;
A separation layer that is provided between the support and the organic material layer, and is altered by absorbing light irradiated through the support; and
An adhesive layer is provided between the organic material layer and the separation layer,
The said organic material layer is a flexible plastic material previously formed in the film form used for the flexible substrate in which an element is mounted, The laminated body characterized by the above-mentioned.   The laminate according to claim 1, wherein the support is made of glass or silicon.   The laminate according to claim 1 or 2, wherein the separation layer is altered by absorbing light irradiated from a laser.   The laminate according to any one of claims 1 to 3, wherein the separation layer contains a polymer containing a light-absorbing structure in its repeating unit.   The laminate according to any one of claims 1 to 3, wherein the separation layer is made of an inorganic substance.   The laminate according to any one of claims 1 to 3, wherein the separation layer is formed of a compound having an infrared absorbing structure.   The laminate according to any one of claims 1 to 3, wherein the separation layer is made of fluorocarbon.   The laminate according to any one of claims 1 to 3, wherein the separation layer contains an infrared absorbing substance.   The laminate according to claim 8, wherein the infrared absorbing material is made of carbon black, iron particles, or aluminum particles. A light transmissive support;
An organic material layer containing an organic material supported by the support;
A laminate comprising a separation layer made of a fluorocarbon which is provided between the support and the organic material layer and which is altered by absorbing light irradiated through the support. body. A separation method for separating the support from the organic material layer in the laminate according to any one of claims 1 to 10,
A separation method comprising a light irradiation step of irradiating the separation layer with light through the support to alter the separation layer. A method for producing the laminate according to claim 10 , comprising:
Including an organic material layer forming step of forming the organic material layer on the separation layer,
In the organic material layer forming step,
An organic material layer is formed by laminating a layer made of the organic substance on the separation layer via an adhesive layer, or applying and drying a solution containing the organic substance on the separation layer. A method for manufacturing a laminate. A method for producing the laminate according to any one of claims 1 to 9,
Including an organic material layer forming step of forming the organic material layer on the separation layer,
In the organic material layer forming step,
A method for producing a laminate, wherein an organic material layer is formed by laminating a layer made of the organic material on the separation layer via an adhesive layer. A preparation step of preparing the laminate according to any one of claims 1 to 10,
A mounting process for mounting a display element on the organic material layer in the laminate,
In the laminate in which the display element is mounted, a light irradiation step of irradiating the separation layer with light through the support to alter the separation layer;
And a separation step of separating the support from the organic material layer. A preparation step of preparing the laminate according to any one of claims 1 to 10,
A mounting step of mounting a solar cell element on the organic material layer in the laminate,
In the laminated body on which the solar cell element is mounted, a light irradiation step of irradiating the separation layer with light through the support to alter the separation layer; and
And a separation step of separating the support from the organic material layer. A preparation step of preparing the laminate according to any one of claims 1 to 10,
A mounting step of mounting a sensor element on the organic material layer in the laminate,
In the laminated body in which the sensor element is mounted, a light irradiation step of irradiating the separation layer with light through the support to alter the separation layer; and
And a separation step of separating the support from the organic material layer. A preparation step of preparing the laminate according to any one of claims 1 to 10,
A mounting step of mounting a light emitting element on the organic material layer in the laminate;
In the laminated body on which the light emitting element is mounted, a light irradiation step of altering the separation layer by irradiating the separation layer with light through the support;
And a separation step of separating the support from the organic material layer. A preparation step of preparing the laminate according to any one of claims 1 to 10,
A mounting process for mounting a scanner element on the organic material layer in the laminate,
In the laminated body on which the scanner element is mounted, a light irradiation step of changing the quality of the separation layer by irradiating the separation layer with light through the support;
And a separation step of separating the support from the organic material layer.

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