JP6611325B2 - Laminate manufacturing method and use thereof - Google Patents

Description

  The present invention relates to a method for manufacturing a laminate and use thereof.

  Polyimide resins are widely used as flexible substrates used in electronic devices such as flat panel displays and touch panels.

  For example, in Patent Document 1, a thin film is formed continuously or discontinuously on a part of at least one surface of an inorganic substrate, a silane coupling agent layer is formed continuously or discontinuously on the thin film, and a silane coupling agent layer is further formed. A polymer film laminated substrate having a polymer film layer laminated thereon is described.

JP 2014-237270 A (released on December 18, 2014)

  However, like the polymer film laminated substrate described in Patent Document 1, a laminated body having high heat resistance and capable of successfully peeling a substrate formed of a polyimide resin from a support regardless of the presence or absence of a thin film. This manufacturing method is useful because various circuits can be formed on the substrate.

  The present invention has been made in view of the above problems, and its purpose is to provide a novel laminate manufacturing method that has high heat resistance and can successfully peel off a substrate formed of a polyimide resin. And it is providing the related technique.

  In order to solve the above-described problems, a method for manufacturing a laminate according to an embodiment of the present invention includes a laminate in which a substrate made of polyimide resin and a support that supports the substrate are laminated via an adhesive layer. And a structural unit represented by the following formula (1): a hydrolysis step of hydrolyzing a part of an imide bond present in one of the two planar portions of the substrate;

(In the above formula (1), R ¹ is a tetravalent organic group, which is an aromatic group, aliphatic group or alicyclic group having 2 or more and 11 or less carbon atoms, and R ² is 2 A valent organic group, which may contain, in addition to carbon and hydrogen atoms, an atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen, having 2 or more carbon atoms, An adhesive layer forming step of forming an adhesive layer comprising a polyamic acid having 50 or less aromatic group, aliphatic group, or alicyclic group, and n is 1 or more on the support, Including a pasting step of pasting and heating the substrate and the support through the adhesive layer so that the planar portion hydrolyzed from the imide bond faces the support. It is characterized by.

  The laminate according to an embodiment of the present invention is a laminate formed by laminating a substrate made of polyimide resin and a support that supports the substrate via an adhesive layer, and the support on the substrate. Amino group possessed by the polyimide resin present in the plane portion facing the body, and a structural unit represented by the following formula (1)

(In the above formula (1), R ¹ is a tetravalent organic group, which is an aromatic group, aliphatic group or alicyclic group having 2 or more and 11 or less carbon atoms, and R ² is 2 A valent organic group, which may contain, in addition to carbon and hydrogen atoms, an atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen, having 2 or more carbon atoms, It is characterized by having an amide bond derived from a carboxyl group of a polyamic acid having 50 or less aromatic group, aliphatic group or alicyclic group, and n is 1 or more) Yes.

  Advantageous Effects of Invention According to the present invention, there is an effect that it is possible to provide a novel laminate manufacturing method that has high heat resistance and can successfully peel a substrate formed of a polyimide resin, and a related technique. .

It is a figure explaining the outline of the manufacturing method of a laminated body which concerns on one Embodiment of this invention, a laminated body, and the processing method of a board | substrate.

<Method for producing laminate>
Hereinafter, the manufacturing method of the laminated body which concerns on one Embodiment is demonstrated in detail.

  As shown in FIG. 1 (a), the laminate manufacturing method according to this embodiment is a hydrolysis step (FIG. 1 (a)) in which a hydrolysis process is performed on a planar portion of a substrate 1 formed of a polyimide resin. And (b)), an adhesive layer forming step ((c) and (d) in FIG. 1) for forming the adhesive layer 3 on the support plate (support) 2, and the substrate 1 and the support plate 2 are bonded to each other. 3 and a pasting step ((e) of FIG. 1) of pasting and heating.

  In addition, if a hydrolysis process ((b) of FIG. 1) and an adhesive layer formation process ((d) of FIG. 1) are before a sticking process ((e) of FIG. 1), they may be performed simultaneously. Well, either may be done first.

[Hydrolysis step]
As shown in FIGS. 1 (a) and (b), in the hydrolysis step, a part of the imide bond existing in the planar portion of the substrate 1 formed of polyimide resin is hydrolyzed to cleave it, and amino Groups and carboxyl groups are formed. These amino groups and carboxyl groups are present at the ends of molecular chains in the cleaved polyimide resin.

  (B) of FIG. 1 is a figure explaining the outline of the hydrolysis process which the manufacturing method of the laminated body which concerns on this embodiment is included. As shown in FIG. 1B, in the method for manufacturing a laminate according to the present embodiment, in the hydrolysis step, for example, a substrate is disposed on a treatment rod 50 filled with a treatment liquid containing an alkali compound and water. By immersing 1, the polyimide resin on the surface of the substrate 1 is hydrolyzed.

  The immersion condition in the treatment liquid is not limited as long as it is appropriately designed depending on the type of polyimide resin forming the substrate 1 and the kind and concentration of the treatment liquid. For example, the temperature condition in the range of 20 ° C. or more and 50 ° C. or less In this case, the immersion treatment may be performed for a time within the range of 1 minute or more and 10 minutes or less. Thereby, it can prevent that the board | substrate 1 melt | dissolves and a film thickness changes because a polyimide substrate is hydrolyzed excessively, forming an amino group in the plane part of the board | substrate 1. FIG.

  In the hydrolysis step, the substrate 1 is immersed in the treatment liquid to hydrolyze the imide bond present on the planar portion of the substrate 1, and then the substrate 1 is lifted from the treatment basket 50 and washed with water. Thereafter, the substrate 1 is heated at 90 to 100 ° C. for 5 to 20 minutes to remove moisture from the substrate 1.

(Substrate 1)
As shown to (a) of FIG. 1, the board | substrate 1 is formed from the polyimide resin previously formed in the film form, and is typically used as a film board | substrate, a flexible substrate, etc. In the state where the substrate 1 is stacked on the stacked body 10, various processes are performed to form wiring and the like, and a structure such as an integrated circuit is mounted.

  The substrate 1 is a polyimide resin film having a thickness of about 10 μm to 100 μm, and may be stretched and formed by a biaxial stretching method or the like, for example. The size of the film substrate is not particularly limited, but in the method for manufacturing a laminate according to the present embodiment, a film substrate having an A3 size (that is, 297 mm × 420 mm) having a rectangular shape in a top view is used.

  If the polyimide resin used for forming the board | substrate 1 is used widely, the kind will not be limited, but it is more preferable that it is what has heat resistance. Polyimide resins include aromatic polyimide resins obtained by polymerizing aromatic dianhydrides and aromatic diamines, and alicyclic rings obtained by polymerizing alicyclic acid dianhydrides and alicyclic diamines. And a semi-aromatic polyimide resin having both an aromatic structure and an alicyclic structure. Moreover, a pigment etc. may be mix | blended with the polyimide resin as needed.

(Processing liquid)
The treatment liquid cleaves an imide bond existing on the surface of the substrate 1 formed of a polyimide resin by hydrolysis to form an amino group. The treatment liquid contains an organic alkali compound and water, and more preferably contains a water-soluble organic solvent.

  In the treatment liquid, the concentration of the organic alkali compound may be appropriately designed according to the type of the organic alkali compound, and is not limited, but may be in the range of 1 wt% or more and 25 wt% or less. Preferably, it is in the range of 1% by weight or more and 10% by weight or less, more preferably in the range of 2% by weight or more and 5% by weight or less. The solvent for dissolving the organic alkali compound preferably has a ratio of water to the water-soluble organic solvent in the range of 9: 1 to 1: 9, preferably in the range of 8: 2 to 3: 7. It is more preferable. Thus, by using a treatment liquid containing an organic alkali compound, water, and a water-soluble organic solvent, imide bonds existing on the surface of the substrate 1 can be uniformly hydrolyzed. For this reason, the peeling strength of the board | substrate 1 in the laminated body 10 can be made uniform.

  The organic alkali compound is preferably a nitrogen-containing organic compound, and a quaternary ammonium hydroxide can be more preferably used. Quaternary ammonium hydroxide includes tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, dimethyldiethylammonium hydroxide, Examples thereof include methyltriethylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, benzyltrimethylammonium hydroxide, and (2-hydroxyethyl) trimethylammonium hydroxide. Tetramethyl Most preferably, ammonium hydroxide is used. These organic alkali compounds may be used in combination of two or more.

  Thus, using the organic alkali compound used when forming a circuit by a photolithography process or the like as the treatment liquid for the substrate 1 suppresses excessive hydrolysis of the polyimide resin on the substrate 1, This is effective from the viewpoint that the imide bond can be suitably hydrolyzed on the surface layer of the substrate 1.

  The treatment liquid preferably further contains a water-soluble organic solvent. Thereby, the polyimide resin can be hydrolyzed uniformly on the surface of the substrate 1. Preferable examples of the water-soluble organic solvent include alcohols, polyhydric alcohols and derivatives thereof, sulfoxides, sulfones, amides, lactams, lactones, imidazolidinones, and alkanolamines. It is more preferable to use alcohols.

  Examples of alcohols include methanol, ethanol, n-propanol, and i-propanol. Examples of polyhydric alcohols and derivatives thereof include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol , Diethylene glycol monoacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether , Glycerine, 1,2-butylene glycol, 1,3-butylene glycol and, may be mentioned 2,3-butylene glycol. Examples of the sulfoxides include dimethyl sulfoxide, and examples of the sulfones include dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, and tetramethylene sulfone. Examples of amides include N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetamide, and N, N-diethylacetamide. Examples of the lactams include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone. Examples of lactones include β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone. Examples of imidazolidinones include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2-imidazolidinone. . Examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, 2- (2-aminoethoxy) ethanol, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanol. Examples include amine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine. In addition, you may use a hydrophilic organic solvent in mixture of 2 or more types.

  Further, the treatment liquid may contain a surfactant or the like as necessary.

[Adhesive layer forming step]
As shown in FIG. 1D, in the adhesive layer forming step, an adhesive containing polyamic acid is applied onto the support plate 2 and the support plate 2 is heated to form the adhesive layer 3.

  Examples of the method of applying the adhesive on the support plate 2 include spin coating, dipping, roller blades, spray coating, slit coating, and the like.

  The thickness of the adhesive layer 3 may be set as appropriate according to the types of the substrate 1 and the support plate 2 to be attached, the treatment applied to the substrate 1 after being attached, etc., but in the range of 1 nm to 1 μm. Is preferably within the range of 1 nm to 200 nm.

  In the adhesive layer forming step, the support plate 2 to which the adhesive is applied is heated at a temperature of 150 ° C. or higher and 220 ° C. or lower for 1 minute to 10 minutes, preferably 3 minutes to 5 minutes. Remove the solvent and water contained in the acid. Thereby, in a later process (for example, including [other processes] in the present specification), when the laminate 10 is heated, the solvent and water remaining in the adhesive layer 3 evaporate, whereby the substrate 1 and Generation of voids between the support plate 2 and the support plate 2 can be prevented.

(Support plate 2)
The support plate (support) 2 is a support that supports the substrate 1 ((c) in FIG. 1). The support plate 2 is attached to the substrate 1 through the adhesive layer 3. The support plate 2 only needs to have a strength necessary to prevent breakage or deformation of the substrate 1 during the process of transporting the substrate 1 and mounting a circuit or the like on the substrate 1, and is made of glass or silicon. A support plate or the like can be used.

  In addition, in the manufacturing method of the laminated body which concerns on this embodiment, the glass support plate of the same A3 size as the board | substrate 1 is used. In the manufacturing method of the laminated body which concerns on this embodiment, the contact bonding layer 3 can be formed in the flat part of such a large sized support plate 2 with uniform thickness. For this reason, the adhesiveness with respect to the contact bonding layer 3 can be uniformly improved in the whole surface of the plane part of the board | substrate 1. FIG. Thus, it is also one of the advantages of the manufacturing method of the laminated body which concerns on this embodiment that the large sized board | substrate 1 can be processed using the large sized support plate 2. FIG.

(Adhesive layer 3)
The adhesive layer 3 is a layer containing a polyamic acid having a structural unit represented by the following formula (1).

Here, in the formula (1), R ¹ is a tetravalent organic group, and is an aromatic group, aliphatic group, or alicyclic group having 2 to 11 carbon atoms, and R ² is A divalent organic group, which may contain an atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen in addition to a carbon atom and a hydrogen atom, and has 2 or more carbon atoms , 50 or less aromatic group, aliphatic group, or alicyclic group, and n is 1 or more.

  The polyamic acid represented by the above formula (1) can be synthesized by reacting a tetracarboxylic dianhydride component and a diamine component described below in a solvent (organic solvent).

  Although the usage-amount of a tetracarboxylic dianhydride component and a diamine component at the time of synthesize | combining a polyamic acid is not specifically limited, A diamine component is 0.50 mol-1. It is preferable to use 50 mol, more preferably 0.60 mol to 1.30 mol, and particularly preferably 0.70 mol to 1.20 mol.

  The amount of the solvent used when synthesizing the polyamic acid is not particularly limited as long as the object of the present invention is not impaired. Typically, the amount of the solvent used is preferably 20 parts by mass to 2000 parts by mass, and 100 parts by mass to 1500 parts by mass with respect to 100 parts by mass in total of the amount of the tetracarboxylic dianhydride component and the amount of the diamine component. Mass parts are more preferable, and 150 to 1000 parts by mass are most preferable.

  The solvent (organic solvent) can be appropriately selected from solvents conventionally used for the synthesis of polyamic acid. Examples of such a solvent include an aprotic polar solvent. Examples of the aprotic polar solvent include sulfoxides, sulfones, and the like described in the above-mentioned column (Water-soluble organic solvent). Examples include amides, lactams, lactones, and imidazolidinones. Among these aprotic polar solvents, N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), dimethylacetamide (DMAC), hexamethylphosphoramide, and 1,3-dimethyl- It is more preferable to use 2-imidazolidinone or the like as a solvent for the adhesive.

  The temperature at which the tetracarboxylic dianhydride component and the diamine component are reacted is not particularly limited as long as the reaction proceeds well. Typically, the reaction temperature between the tetracarboxylic dianhydride component and the diamine component is preferably -5 ° C to 150 ° C, more preferably 0 ° C to 120 ° C, and most preferably 0 ° C to 70 ° C. The time for reacting the tetracarboxylic dianhydride component and the diamine component varies depending on the reaction temperature, but is typically 1 hour to 50 hours, more preferably 2 hours to 40 hours, more preferably 5 hours to 30 hours is most preferred.

(Tetracarboxylic dianhydride component)
The tetracarboxylic dianhydride component that is a raw material for synthesizing the polyamic acid is not particularly limited as long as it can form a polyamic acid by reacting with the diamine component. The tetracarboxylic dianhydride component can be appropriately selected from tetracarboxylic dianhydrides conventionally used as raw materials for synthesizing polyamic acids. The tetracarboxylic dianhydride component may be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride. From the viewpoint of heat resistance of the adhesive layer 3 to be formed, the tetracarboxylic dianhydride component is preferably an aromatic tetracarboxylic dianhydride. In addition, you may use a tetracarboxylic dianhydride component in combination of 2 or more types.

  Preferable specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic An acid dianhydride etc. can be mentioned. Of these aromatic tetracarboxylic dianhydrides, it is more preferable to use pyromellitic dianhydride. Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and 1 2,4,5-cyclohexanetetracarboxylic dianhydride and the like.

(Diamine component)
The diamine component used as the raw material for synthesizing the polyamic acid is not particularly limited as long as it can form the polyamic acid by reacting with the tetracarboxylic dianhydride component. The diamine component can be appropriately selected from diamines conventionally used as a raw material for synthesizing polyamic acid. The diamine component may be an aromatic diamine or an aliphatic diamine. From the viewpoint of heat resistance of the adhesive layer 3 to be formed, the diamine component is more preferably an aromatic diamine. Two or more diamine components may be used in combination.

  Preferable specific examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis ( Trifluoromethyl) biphenyl, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, 4 , 4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-aminophenoxy) benzene, 1,3-bis (3-aminophenyl) Noxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2- Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) fluorene, 9,9 -Bis (4-amino-3-methylphenyl) fluorene, 4,4 '-[1,4-phenylenebis (1-methylethane-1,1-diyl)] dianiline and the like can be mentioned. Among these aromatic diamines, it is more preferable to use p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether in view of price and availability.

(Other ingredients)
In the synthesis of the polyamic acid, in addition to the tetracarboxylic dianhydride component, the diamine component, and the solvent, a polymerization accelerator and a dicarboxylic dianhydride may be included as other components.

  As the polymerization accelerator, for example, imidazole, benzimidazole, and 4-hydroxypyridine can be preferably used, but are not limited thereto.

  In addition, when synthesizing polyamic acid, tetracarboxylic dianhydride and dicarboxylic anhydride may be used in combination. When these carboxylic acid anhydrides are used in combination, the properties of the resulting polyamic acid may be further improved. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, chlorendic anhydride, methyl tetrahydro Examples thereof include phthalic anhydride, glutaric anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride and the like.

  In addition, the adhesive agent for forming the contact bonding layer 3 can be obtained by adjusting the density | concentration of a polyamic acid within the range of 1 weight% or more and 10 weight% or less with the above-mentioned aprotic polar solvent. . As the aprotic polar solvent used for the adhesive, for example, N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), dimethylacetamide (DMAC) and the like are preferably used.

[Attaching process]
In the pasting step, the substrate 1 and the support plate 2 are pasted via the adhesive layer 3 so that the plane portion hydrolyzed from the imide bond faces the support plate 2.

  The pasting step may be performed while heating, for example, by pressing, laminating, roll laminating, or the like. In the pasting step, for example, the substrate 1 and the support plate 2 are overlapped via the adhesive layer 3 and heated using a commercially available laminator device or the like under a temperature condition of about 40 ° C. to 100 ° C., paste. Here, the pressure applied to the laminated body 10 by the laminator device may be appropriately adjusted according to the mechanical strength of the support plate 2, the size of the laminated body, and the like. Moreover, what is necessary is just to perform a sticking process on either conditions of atmospheric pressure conditions or pressure reduction conditions. In addition, when performing a sticking process on atmospheric pressure conditions, it is more preferable to carry out in the environment which adjusted humidity so that the board | substrate 1 may not absorb moisture.

[Other processes]
In the laminated body 10 formed in the attaching step, a circuit or the like is formed on the substrate 1 by photolithography, plasma enhanced chemical vapor deposition (plasma CVD method), or the like in the subsequent steps. In such a process of forming a circuit or the like on the substrate 1, dehydrogenation of amorphous silicon deposited on the substrate by the plasma CVD method and polycrystallization of the silicon layer formed by dehydrogenation are also performed. Done. In these steps, the laminate 10 is subjected to a temperature condition within a range of 200 to 400 ° C. under a reduced pressure environment or an inert gas environment such as nitrogen or argon.

  Thereby, the amino group formed on the substrate 1 and the carboxyl group present on the adhesive layer 3 can be suitably condensed, and an amide bond can be formed between the substrate 1 and the adhesive layer 3. In addition, the polyamic acid forming the adhesive layer 3 may be imidized by heating the laminate 10 under a temperature condition in the range of 200 to 400 ° C. after the pasting step and before the peeling step. it can. Thereby, the adhesiveness of the contact bonding layer 3 and the support plate 2 can be improved. In addition, voids can be prevented from being generated between the substrate 1 and the support plate 2. Therefore, the laminated body 10 can be adapted to a high temperature treatment process.

  Note that examples of the electronic device formed on the substrate 1 after the attaching step include an active element, an electronic circuit, and other elements. For example, the active element can include a wiring board, a transistor, and a diode that carry electric wiring, and the electronic circuit can include a passive device such as a resistor, a capacitor, and an inductor. As other elements, sensor elements for sensing temperature, light, humidity, etc., light emitting elements, liquid crystal displays, electrophoretic displays, self-luminous display and other image display elements, wireless and wired communication elements, arithmetic elements, memory Examples include an element, a MEMS element, a solar cell, and a thin film transistor.

[Laminate 10]
The laminate 10 includes a substrate 1 formed in advance in a film shape with a polyimide resin and a support plate 2 that supports the substrate 1 via an adhesive layer 3 containing polyamic acid represented by the above formula (1). A laminate obtained by laminating an amide bond formed by condensation of an amino group derived from a polyimide resin present in a plane portion facing the support in the substrate and a carboxyl group possessed by a polyamic acid. Have. That is, the laminate according to one embodiment of the present invention is typically the laminate 10 manufactured by the method for manufacturing a laminate according to one embodiment of the present invention.

  Thereby, the laminated body 10 is different from the laminated body in which the adhesive layer is formed using the acrylic resin. For example, when the laminated body 10 is processed under a high temperature condition of about 350 ° C., the adhesive layer 3 is thermally decomposed. It is possible to prevent the generation of gas. For this reason, it can prevent that a void generate | occur | produces between the board | substrate 1 and the support plate 2 when it heats. Moreover, the laminated body 10 is different from the laminated body which laminated | stacked the board | substrate and the support body using coupling agents, such as aminosilane, for example, and the adhesiveness of the contact bonding layer 3 and the support plate 2 in a laminated body adjusts moderately. Has been. For this reason, it is possible to peel the substrate 1 from the support plate 2 together with the adhesive layer 3 made of polyimide.

[Laminated body formation kit]
A kit for forming a laminate according to an embodiment of the present invention is used in a treatment liquid used in a hydrolysis step included in a method for manufacturing a laminate according to an embodiment of the present invention and an adhesive layer forming step. With adhesive.

  According to said structure, the manufacturing method of the laminated body which concerns on one Embodiment of this invention can be performed suitably. Therefore, the laminate manufacturing kit according to the present embodiment is also within the scope of the present invention.

<Substrate processing method>
Hereinafter, a substrate processing method according to an embodiment of the present invention will be described in more detail.

  The substrate processing method according to the present embodiment includes a layered body forming step ((a) to (e) of FIG. 1) in which the method for manufacturing a layered body according to one embodiment of the present invention is performed, and the layered body 10 to the substrate. 1 and the peeling process ((f) and (g) in FIG. 1). In addition, about the laminated body formation process, since it is the same as the manufacturing method of the laminated body which concerns on one above-mentioned embodiment, the description is abbreviate | omitted. Note that in the laminate 10 shown in FIG. 1E, various wirings and the like are formed on the substrate 1 and a structure such as an integrated circuit is mounted before the peeling process.

[Peeling process]
A method for peeling the substrate 1 from the stacked body 10 may be appropriately selected according to the type of the substrate 1 and the type of the circuit formed on the substrate 1. For example, as shown in FIG. 1 (f), in the peeling step, the support plate 2 in the stacked body 10 is fixed to one side of the substrate 1 by, for example, adsorbing and fixing the support plate 2 to the mounting table. By gradually lifting, peel off. Examples of the method for fixing one side of the substrate in the laminated body 10 include a method of sandwiching with a tweezers, a method of sticking an adhesive tape, a method of fixing by suction using a suction part, and the like. The laminated body 10 may be laminated such that a part of the peripheral portion of the substrate 1 protrudes from the support plate 2, and the substrate 1 may be peeled by lifting the substrate 1 while sandwiching the part. .

  In the peeling step, before the substrate 1 is peeled off, the substrate 1 may be cut in advance so that the substrate 1 can be peeled off at a predetermined size. As a method for making a cut in the substrate 1, for example, a method in which a laser beam is scanned relative to the substrate 1, or a water jet is scanned relative to the substrate 1. Examples thereof include a method of making a cut and a method of making a cut by a semiconductor chip dicing apparatus.

  In the peeling step, the angle between the planar portion of the substrate 1 and the planar portion of the support plate 2 facing each other is not limited to approximately 90 ° as shown in FIG. In the peeling process, the angle between the substrate 1 and the support plate 2 takes into account the tension applied when the substrate 1 is pulled and the stress applied when the circuit or the like formed on the substrate 1 is bent. The substrate 1 and the circuit may be adjusted as appropriate so as not to be damaged.

  In the laminate 10, the peel strength of the adhesive layer 3 with respect to the support plate 2 is appropriately adjusted. More specifically, the peel strength of the adhesive layer 3 with respect to the support plate 2 is, for example, a peel strength of the substrate 1 of about 30 g / cm to 80 g / cm at a peel rate condition of 0.75 cm / sec. Preferably, it is about 30 g / cm-50 g / cm. For this reason, as shown in FIG. 1G, the integrated substrate 1 and adhesive layer 3 can be successfully peeled at the interface between the adhesive layer 3 and the support plate 2 in the peeling step. Therefore, it is possible to prevent a circuit or the like mounted on the substrate 1 from being damaged by a force applied when the substrate 1 is peeled off.

  In addition, in the peeling step, one side of the substrate 1 may be fixed to a roll having a large curvature, and the substrate 1 may be wound up by the roll.

<The manufacturing method of the laminated body which concerns on another embodiment>
The manufacturing method of the laminated body which concerns on one Embodiment of this invention is not limited to said embodiment. For example, in the manufacturing method of the laminated body which concerns on another embodiment, in a hydrolysis process, a hydrolysis process is performed only to one surface of the side which opposes the contact bonding layer 3 among the two plane parts in the board | substrate 1. FIG.

  In the hydrolysis step included in the method for producing a laminate according to one embodiment, for example, a protective film such as a PET film with a pressure-sensitive adhesive, a PEN film, an olefin film, a polyimide film, By attaching to the substrate and performing the treatment, only one planar portion of the substrate 1 is hydrolyzed. It goes without saying that even with this configuration, the adhesion between the substrate 1 and the adhesive layer 3 can be appropriately increased.

  Moreover, in the manufacturing method of the laminated body which concerns on another embodiment, for example, polyamic acid apply | coats the solution which melt | dissolved the tetracarboxylic dianhydride component and the diamine component on the support plate 2, and the said It may be generated by heating the support plate 2. As a result, the adhesive layer 3 containing polyamic acid can be formed on the support plate 2. Therefore, the manufacturing method of the laminated body which concerns on one Embodiment of this invention can be implemented suitably.

  Moreover, in the manufacturing method of the laminated body which concerns on another embodiment, you may hydrolyze and cleave the polyimide resin of the board | substrate 1 by a vacuum plasma process or UV ozone process in a hydrolysis process, for example. Also in this configuration, an amino group can be formed on the planar portion of the substrate 1.

<Laminated body according to another embodiment>
In the laminate according to the present invention, the amino group derived from the polyimide resin forming the substrate is not limited to that obtained by cleaving the imide bond by hydrolysis. That is, the origin of the amino group which a board | substrate has will not be limited if it is an amino group derived from the diamine component used when synthesize | combining a polyimide resin. This is also because in this configuration, an amide bond that condenses the amino group present in the planar portion of the substrate and the carboxyl group of the polyamic acid contained in the adhesive layer can be formed.

  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.

[Evaluation of heat resistance and peelability of laminate]
The laminated body of Example 1 and the laminated body of Comparative Examples 1-2 were produced, and heat resistance evaluation and peelability evaluation were performed about each laminated body.

Example 1
First, for Example 1, as an adhesive containing polyamic acid, Pyre-ML (registered trademark) RC-5019 (poly (pyromellitic dianhydride-co-4,4′-oxydianiline) amic acid solution; An NMP solution (concentration: 15.0 to 16.0 wt%, manufactured by Sigma-Aldrich) was diluted with NMP so that the resin concentration was 2 wt%. Next, this adhesive agent containing polyamic acid is applied to a 10 cm square glass support by spin coating, and heated at 170 ° C. for 3 minutes, whereby a 200 nm thick adhesive layer is formed on the glass support. Was formed (adhesive layer forming step).

  Further, a treatment liquid was prepared by dissolving tetramethylammonium hydroxide (TMAH) in a mixed solution having a weight ratio of 6: 4 with water and ethanol so that the concentration became 4.5% by weight. After immersing a 10 cm square PI (polyimide) film substrate (product name: polyimide film Kapton H type, thickness: 50 μm, manufactured by Toray DuPont) at 23 ° C. for 3 minutes in the prepared treatment solution Then, after lifting, washing and draining, it was dried at 90 ° C. for 5 minutes to remove water (hydrolysis step).

  Subsequently, a laminator apparatus in which the PI film substrate after the hydrolysis treatment and the glass support on which the adhesive layer is formed are set to a temperature of 80 ° C. and a laminator feed rate of 1.0 m / min through the adhesive layer. It stuck using VA-700 (made by Taisei Laminator Co., Ltd.) (sticking process).

(Comparative Example 1)
Next, as the laminate of Comparative Example 1, a poly (acrylic acid) solution (average molecular weight ~ 100,000, aqueous solution, concentration 35 wt%, manufactured by Sigma-Aldrich), and polyacrylic acid concentration becomes 4 wt%. The solution was diluted with water as described above, and applied to the same glass support as that used in Example 1 by spin coating. Subsequently, the glass support was heated at 100 ° C. for 3 minutes to form an adhesive layer having a thickness of 200 nm. Further, the PI film substrate was hydrolyzed under the same conditions as in Example 1 and dried by heating. Thereafter, a PI film substrate and a glass support were bonded under the same conditions as in Example 1. Thereby, the laminated body of the comparative example 1 was produced.

(Comparative Example 2)
Subsequently, as a laminate of Comparative Example 2, 3-aminopropyltriethoxysilane (APTES, coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to the same glass support used in Example 1 by spin coating. . Subsequently, the glass support was heated at 170 ° C. for 3 minutes. Further, the PI film substrate was hydrolyzed under the same conditions as in Example 1 and dried by heating. Thereafter, a PI film substrate and a glass support were attached under the same conditions as in Example 1. Thereby, the laminated body of the comparative example 2 was produced.

  In the following Table 1, the structure of the laminated body of Example 1 and the laminated body of Comparative Examples 1-2 is shown.

[Evaluation of heat resistance and peelability]
Subsequently, peelability was evaluated about the laminated body of Example 1, and the laminated body of Comparative Examples 1-2. The evaluation conditions for heat resistance and peelability are as follows.

(Heat-resistant)
Evaluation of heat resistance is performed by placing each laminate in a vertical baking furnace TS8000MB (manufactured by Tokyo Ohka Kogyo Co., Ltd.) and heating it under conditions of 350 ° C. and 1 hour in a nitrogen environment. It was. In the state after heating, visually, whether or not voids are generated between the PI film substrate and the glass support is evaluated, and the laminate in which no voids are generated is evaluated as “◯”. The laminated body in which the occurrence of was evaluated as "x". The evaluation results of heat resistance are shown in Table 1 below.

(Peelability)
For the evaluation of peelability, for each laminated body after the heat resistance evaluation, the PI film substrate laminated on the glass support was cut into a size of 1 cm × 9 cm, and the laminated body was fixed horizontally. One end in the length direction of the cut portion was gripped, and the peel strength when it was lifted upward at a speed of 0.75 cm / second in the vertical direction was evaluated. In addition, the tensile strength tester SV-55C-2H (made by Imada Seisakusho) was used for the measurement of peeling strength. The evaluation results of peelability are shown in Table 1 below.

〔result〕
In the laminate of Example 1, no voids were observed even at 350 ° C. for 1 hour. Further, the laminate of Example 1 had a peel strength of the PI film substrate of 45 to 47 g / cm, and could be peeled off successfully without damaging the PI film substrate. The adhesive layer was integrated with the PI film substrate and peeled off from the glass support.

  On the other hand, in the laminated body of Comparative Example 1, voids were observed between the PI film substrate and the glass support (×) in the heat resistance evaluation. In the laminate of Comparative Example 1, the PI film substrate was peeled off immediately, and the peel strength could not be measured.

  In the laminate of Comparative Example 2, there is no generation of voids (◯), but the peel strength of the PI film substrate is high, and there is a concern that structures such as integrated circuits that can be formed on the PI film substrate at the time of peeling are damaged. As a result.

  Based on the above results, it is possible to confirm that the PI film substrate has high heat resistance and can be peeled off successfully by hydrolyzing the PI film substrate and affixing it to the glass support using polyamic acid. It was.

  The present invention can be suitably used, for example, in a manufacturing process of a miniaturized semiconductor device.

1 Substrate 2 Support plate (support)
3 Adhesive layer 10 Laminate

Claims (8)

A method for producing a laminate comprising a substrate made of a polyimide resin and a support for supporting the substrate via an adhesive layer,
A hydrolysis step of hydrolyzing a part of the imide bond present in one of the two planar portions of the substrate;
The structural unit shown in the following formula (1)

(In the above formula (1), R ¹ is a tetravalent organic group, and is an aromatic group, aliphatic group, or alicyclic group having 2 to 11 carbon atoms,
R ² is a divalent organic group, and may contain an atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen in addition to a carbon atom and a hydrogen atom. Is an aromatic group, aliphatic group, or alicyclic group of 2 or more and 50 or less,
n is 1 or more)
Forming an adhesive layer comprising a polyamic acid having an adhesive layer on the support, and
Including a pasting step of pasting the substrate and the support through the adhesive layer such that the planar portion hydrolyzed from the imide bond faces the support. A method for manufacturing a laminate. R ¹ in the structural unit represented by the formula (1) is a tetravalent aromatic group, and R ² is at least selected from the group consisting of a phenylene group, a divalent diphenyl ether group, and a divalent benzophenone group. It is one group, The manufacturing method of the laminated body of Claim 1 characterized by the above-mentioned.   The method for producing a laminate according to claim 1 or 2, wherein in the hydrolysis step, the imide bond is hydrolyzed by a treatment liquid containing an organic alkali compound and water.   The said organic alkali compound is a quaternary ammonium hydroxide, The manufacturing method of the laminated body of Claim 3 characterized by the above-mentioned.   The method for producing a laminate according to claim 3 or 4, wherein the treatment liquid further contains a water-soluble organic solvent. The laminated body formation process which manufactures a laminated body with the manufacturing method of the laminated body of any one of Claims 1-5,
And a peeling step of peeling the substrate from the laminated body after the laminated body forming step. A kit for forming a laminate used in the method for producing a laminate according to claim 3 or 4,
The treatment liquid comprising an organic alkali compound and water;
A laminate-forming kit comprising: a polyamic acid comprising the structural unit represented by the above formula (1); and an adhesive comprising an organic solvent. The said process liquid contains the water-soluble organic solvent further, The formation kit of the laminated body of Claim 7 characterized by the above-mentioned.

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