TW201736145A - Method for producing laminate, and utilization thereof - Google Patents

Abstract

To provide a new method for producing a laminate which has high heat resistance and can successfully peel a substrate formed of a polyimide resin, and to provide a related technique thereof. A method for producing a laminate 10 includes: a hydrolysis step of hydrolyzing a part of an imide bond of a polyimide resin forming a substrate 1; an adhesive layer formation step of forming an adhesive layer 3 containing a polyamic acid having a structural unit represented by formula (1) on a support plate 2; and a sticking step of sticking the substrate 1 and the support plate 2 through the adhesive layer 3. In formula (1), Ris a tetravalent C2-11 aromatic group; Ris a C2-50 aromatic group which may contain a divalent nitrogen atom and the like; and n is equal to or greater than 1.

Description

Manufacturing method of laminate, and utilization thereof

The present invention relates to a method of producing a laminate and use thereof.

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

For example, Patent Document 1 describes a polymer film laminated substrate in which a film is formed continuously or discontinuously on at least one side of at least one side of an inorganic substrate, on the film. A polymer film laminated substrate obtained by continuously or discontinuously forming a decane coupling agent layer and further laminating a polymer film layer on a decane coupling agent layer.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. 2014-237270 (published on Dec. 18, 2014)

However, as in the case of the polymer film laminated substrate described in Patent Document 1, the substrate having the high heat resistance and the substrate formed of the polyimide resin can be smoothly peeled off from the support regardless of whether or not the film is provided. A method of manufacturing a combination can be useful in forming various circuits on the substrate.

The present invention has been made in view of the above problems, and an object of the invention is to provide a novel method for producing a novel laminate which has high heat resistance and can be smoothly peeled off from a substrate formed of a polyimide resin. technology.

In order to solve the above problems, a method for producing a laminate according to an embodiment of the present invention is a laminate in which a substrate formed of a polyimide resin and a support supporting the substrate are laminated by an adhesive layer. The method comprising: a hydrolysis step of partially hydrolyzing one of the quinone imine bonds present in one of the two planar portions of the substrate; and forming an underlayer formation step on the support An adhesive layer formed of a polyamic acid represented by the formula (1),

(In the above formula (1), R ¹ is a tetravalent organic group, and is an aromatic group, an aliphatic group or an alicyclic group having 2 or more and 11 or less carbon atoms; and R ² is a divalent organic group; The group may include an atom selected from a 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 is an aromatic group having 2 or more and 50 or less carbon atoms. Or an aliphatic group or an alicyclic group; n is 1 or more; and the adhesion step is such that the planar portion of the yttrium imine bond is hydrolyzed to face the support, and the substrate is formed by the adhesive layer Adhered to and heated with the above support.

Further, a laminate according to an embodiment of the present invention is a laminate obtained by laminating a substrate formed of a polyimide resin and a support supporting the substrate by an adhesive layer, and is characterized by having a laminate An amine group having an amine group which is an amine group of a polyimine resin present in a plane portion of the substrate opposite to the support, and an amine group having a carboxyl group as defined in the above-mentioned substrate a carboxyl group of a polyamic acid represented by the following formula (1);

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

According to the present invention, it is possible to obtain a novel method for producing a novel laminate which is provided with a high heat resistance and which can be smoothly peeled off from a substrate formed of a polyimide resin, and the related art effects.

1‧‧‧Substrate

2‧‧‧Support plate (support)

3‧‧‧Next layer

10‧‧‧Layer

Fig. 1 is a view for explaining an outline of a method for producing a laminate, a laminate, and a method for treating a substrate according to an embodiment of the present invention.

<Method of Manufacturing Laminated Body>

Hereinafter, a method of producing a laminate according to an embodiment will be described in more detail.

As shown in Fig. 1(a), the method for producing a laminate according to the present embodiment includes a hydrolysis step of hydrolyzing a flat portion of a substrate 1 formed of a polyimide resin (Fig. 1(a) and (Fig. 1(a) and b)), forming an adhesive layer forming step of the bonding layer 3 on the support plate (support) 2 ((c) and (d) of FIG. 1), and bonding the substrate 1 with the bonding layer 3 The bonding step of the support plate 2 is adhered and heated ((e) of Fig. 1).

Further, if the hydrolysis step (Fig. 1 (b)) and the subsequent layer formation step (Fig. 1 (d)) are before the pasting step (Fig. 1 (e)), they may be performed simultaneously or may be performed first. Someone.

[hydrolysis step]

As shown in (a) and (b) of FIG. 1, in the hydrolysis step, a part of the quinone bond which is present in the plane portion of the substrate 1 formed through the polyimide resin is hydrolyzed to cause cracking. An amine group and a carboxyl group are formed. These amine groups and carboxyl groups are present at the end of the molecular chain in the cracked polyimine resin.

(b) of FIG. 1 is a view for explaining an outline of a hydrolysis step included in the method for producing a laminate of the present embodiment. As shown in FIG. 1(b), in the method for producing a laminate according to the present embodiment, in the hydrolysis step, for example, it is filled with a treatment containing an alkali compound and water. The substrate 1 is immersed in the liquid treatment tank 50 to hydrolyze the polyimide resin on the surface of the substrate 1.

The immersion conditions in the treatment liquid are appropriately designed depending on the type of the polyimide resin to be formed on the substrate 1, the type or concentration of the treatment liquid, and the like, and are not particularly limited. For example, it can be in the range of 20 ° C or higher and 50 ° C or lower. Under the temperature conditions, the immersion treatment may be performed for a period of time of 1 minute or longer and 10 minutes or shorter. Thereby, an amine group can be formed in the planar portion of the substrate 1, and it is also possible to prevent the substrate 1 from being dissolved and the film thickness from being changed due to excessive hydrolysis of the polyimide substrate.

In the hydrolysis step, the substrate 1 is immersed in the treatment liquid, and after the hydrazine bond present in the plane portion of the substrate 1 is hydrolyzed, the substrate 1 is lifted from the treatment tank 50 and washed with water. Thereafter, the substrate 1 is heated at a temperature of 90 ° C to 100 ° C for 5 minutes to 20 minutes to remove moisture from the substrate 1 .

(substrate 1)

As shown in FIG. 1( a ), the substrate 1 is formed of a polyimide resin which is formed in a film shape in advance, and typically a substrate such as a film substrate or a flexible substrate is used. In the state in which the substrate 1 is laminated to the laminate 10, a wiring or the like is formed by performing various steps, and a structure such as an integrated circuit is mounted.

The substrate 1 is a film of a polyimide resin having a thickness of about 10 μm to 100 μm, and may be, for example, a substrate which is stretch-molded by a biaxial stretching method or the like. Further, the size of the film substrate is not particularly limited, but the embodiment is In the method for producing a laminate, a film substrate having a shape of a plan view of, for example, a rectangular A3 size (that is, 297 mm × 420 mm) is used.

The polyimine resin used for forming the substrate 1 is not particularly limited as long as it is versatile, and more preferably a heat-resistant polyimide resin. The polyimine resin is an aromatic polyimine resin obtained by polymerizing an aromatic acid dianhydride and an aromatic diamine, and polymerizing an alicyclic acid dianhydride and an alicyclic diamine. The obtained alicyclic polyimine resin, and a semi-aromatic polyimide resin having both an aromatic structure and an alicyclic structure. Further, as the polyimine resin, a pigment or the like may be blended as needed.

(treatment liquid)

The treatment liquid is hydrolyzed by hydrazide bonds present on the surface of the substrate 1 formed through the polyimide resin to form an amine group. The treatment liquid contains an organic base compound and water, and more preferably further contains a water-soluble organic solvent.

In the treatment liquid, the concentration of the organic alkali compound can be appropriately designed depending on the type of the organic base compound, and is not limited, but is preferably in the range of 1% by weight or more and 25% by weight or less, more preferably 1% by weight or more, or 10%. In the range of % by weight or less, it is preferably in the range of 2% by weight or more and 5% by weight or less. Further, as for the solvent for dissolving the organic base compound, the ratio of water to the water-soluble organic solvent is preferably in the range of from 9:1 to 1:9, more preferably in the range of from 8:2 to 3:7. As such, by using a treatment liquid containing an organic base compound, water, and a water-soluble organic solvent, The quinone imine bond present on the surface of the substrate 1 can be uniformly hydrolyzed. Therefore, the peel strength of the substrate 1 in the laminate 10 can be made uniform.

The organic base compound is preferably a nitrogen-containing organic compound, and a quaternary ammonium hydroxide can be more preferably used. Examples of the fourth-order ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, and dimethyldiethylate. Ammonium hydroxide, methyltriethylammonium hydroxide, methyltripropylammonium hydroxide, methyltributylammonium hydroxide, benzyltrimethylammonium hydroxide, and (2-hydroxyethyl)trimethyl As the ammonium hydroxide or the like, tetramethylammonium hydroxide is preferably used. These organic base compounds may be used in combination of two or more kinds.

As described above, from the viewpoint of suppressing excessive hydrolysis of the polyimide resin in the substrate 1 and appropriately hydrolyzing the quinone bond in the surface layer of the substrate 1, the circuit will be formed by a photolithography step or the like. The organic alkali compound used is effective for the treatment liquid of the substrate 1.

The treatment liquid preferably further contains a water-soluble organic solvent. Thereby, the polyimine resin can be uniformly hydrolyzed on the surface of the substrate 1. Suitable examples of the water-soluble organic solvent include alcohols, polyhydric alcohols and derivatives thereof, anthraquinones, anthraquinones, decylamines, indoleamines, lactones, imidazolinones, and Alkanolamines, more preferably alcohols.

Examples of the alcohols include methanol, ethanol, n-propanol, and isopropyl alcohol. Examples of the polyols and derivatives thereof include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoacetate, and ethylene glycol monomethyl ether. Acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol monomethyl ether, diethylene glycol single Ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, glycerol, 1,2-butanediol, 1,3-butanediol , and, 2,3-butanediol and the like. Examples of the anthracene include dimethyl anthracene, and the like, and examples of the anthracene include dimethyl hydrazine, diethyl hydrazine, bis(2-hydroxyethyl) fluorene, and cyclobutyl hydrazine ( Tetramethylene sulfone) and the like. Examples of the guanamines include N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, and N. , N-diethylacetamide and the like. Examples of the indoleamines include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, and N-hydroxyethyl-2-pyrrolidone. . Examples of the lactones include β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, and ε-caprolactone. Examples of the imidazolinones include 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-diisopropyl-2- Imidazolinone and the like. Examples of the alkanolamines include monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, and N,N-diethylethanolamine. N,N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, and triiso Propanolamine and the like. Further, the hydrophilic organic solvent may be used in combination of two or more kinds.

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

[Next layer formation step]

As shown in FIG. 1(d), in the subsequent layer forming step, an adhesive containing polyamic acid is applied onto the support plate 2, and the support layer 2 is heated to form the adhesive layer 3.

Examples of the method of applying the adhesive to the support plate 2 include spin coating, dipping, roller blade, spray coating, and slit coating.

The thickness of the layer 3 may be appropriately set according to the type of the substrate 1 and the support plate 2 as the adhesive member, the treatment of the substrate 1 after the adhesion, and the like, but it is preferably in the range of 1 nm to 1 μm, more preferably Within the range of 1 nm to 200 nm.

In the layer forming step, the support sheet 2 coated with the adhesive is heated at a temperature of 150 ° C or more and 220 ° C or less for 1 minute to 10 minutes, preferably 3 minutes to 5 minutes, thereby removing the aggregation of the adhesive. The solvent and water contained in the amine acid. Thus, in the subsequent step (for example, including [other steps] in the specification of the present invention), when the laminate 10 is heated, the evaporation of the solvent and water remaining in the adhesive layer 3 can be prevented on the substrate 1 and A gap is created between the support plates 2.

(support plate 2)

The support plate (support) 2 is a support for supporting the substrate 1 ((c) of Fig. 1). The support plate 2 is adhered to the substrate 1 by the adhesive layer 3. The support plate 2 may have strength necessary for preventing damage or deformation of the substrate 1 during the process of transporting the substrate 1 and mounting the circuit or the like on the substrate 1, and may be supported by glass or crucible. Board and so on.

Further, in the method for producing a laminate of the present embodiment, a glass support plate having the same A3 size as the substrate 1 is used. In the method for producing a laminate according to the present embodiment, the adhesive layer 3 can be formed in a uniform thickness on the flat portion of the large-sized support plate 2. Therefore, the adhesion to the adhesive layer 3 can be uniformly increased over the entire surface of the planar portion of the substrate 1. As such, the use of the large support plate 2 for processing the large substrate 1 is also one of the advantages of the method for manufacturing the laminate of the present embodiment.

(Next layer 3)

Next, the layer 3 is a layer comprising a polyamic acid having a constituent unit represented by the following formula (1).

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

Polyacyl acid represented by the above formula (1) can be said to The tetracarboxylic dianhydride component and the diamine component are reacted in a solvent (organic solvent) to synthesize.

The amount of the tetracarboxylic dianhydride component and the diamine component used in the synthesis of the polyamic acid is not particularly limited, but it is preferably 0.50 to 1.50 moles per 1 mole of the tetracarboxylic dianhydride component. The diamine component is more preferably a 0.60 mole to 1.30 mole diamine component, and particularly preferably a 0.70 mole to 1.20 mole diamine component.

The amount of the solvent used in the synthesis of the polyamic acid is not particularly limited as long as it does not impair the object of the present invention. In a typical case, the amount of the solvent used is preferably from 20 parts by mass to 2,000 parts by mass, more preferably 100 parts by mass, per 100 parts by mass of the total amount of the tetracarboxylic dianhydride component and the amount of the diamine component. ~1500 parts by mass, preferably 150 parts by mass to 1000 parts by mass.

The solvent (organic solvent) can be appropriately selected from the solvents conventionally used in the synthesis of polyamic acid. Examples of such a solvent include an aprotic polar solvent, and examples of the aprotic polar solvent include an anthracene, an anthracene, an guanamine, and the like, which are described in one of the above (water-soluble organic solvents). Indoleamines, lactones, and imidazolinones. Among these aprotic polar solvents, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), dimethylacetamidine are more preferably used as a solvent for the adhesive. Amine (DMAC), hexamethylphosphoniumamine, and 1,3-dimethyl-2-imidazolidinone.

The temperature at the time of reacting the tetracarboxylic dianhydride component with the diamine component is not particularly limited as long as the reaction proceeds satisfactorily. Typical situation The reaction temperature of 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 reaction time of the tetracarboxylic dianhydride component and the diamine component varies depending on the reaction temperature. Typically, it is preferably from 1 hour to 50 hours, more preferably from 2 hours to 40 hours, and most preferably 5 hours. ~30 hours.

(tetracarboxylic dianhydride component)

The tetracarboxylic dianhydride component which is a synthetic raw material of polylysine is not particularly limited as long as it can react with the diamine component to form polyamic acid. The tetracarboxylic dianhydride component can be suitably selected from the conventional tetracarboxylic dianhydride used as a synthetic raw material of poly-proline. The tetracarboxylic dianhydride component may be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride. The tetracarboxylic dianhydride component is preferably an aromatic tetracarboxylic dianhydride from the viewpoint of heat resistance of the formed adhesive layer 3. Further, the tetracarboxylic dianhydride component may be used in combination of two or more kinds.

Specific examples of suitable aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic acid Anhydride, etc. Among the aromatic tetracarboxylic dianhydrides, pyromellitic dianhydride is more preferably used. Further, 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)

For the diamine component which is a synthetic raw material of polylysine, as long as it can pass It is not particularly limited as long as it is reacted with a tetracarboxylic dianhydride component to form polyamic acid. The diamine component can be appropriately selected from the conventional diamine used as a synthetic raw material of polyamic acid. The diamine component may be either an aromatic diamine or an aliphatic diamine. The diamine component is more preferably an aromatic diamine from the viewpoint of heat resistance of the formed adhesive layer 3. Two or more types of diamine components can be used in combination.

Specific examples of suitable aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminobiphenyl, and 4,4'-di. Amino-2,2'-bis(trifluoromethyl)biphenyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-di Aminodiphenyl hydrazine, 4,4'-diaminodiphenyl hydrazine, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylmethane, 4,4'-diamine Diphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-double (4-Aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-( 4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)anthracene, 9,9-bis(4- Amino-3-methylphenyl)anthracene, and 4,4'-[1,4-phenylphenylbis(1-methylethane-1,1-diyl)]diphenylamine. Among these aromatic diamines, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene and 4,4'-diaminodiphenyl are more preferably used in terms of price and availability. ether.

(other ingredients)

For the synthesis of poly-proline, in addition to the tetracarboxylic dianhydride component, two Other than the amine component and the solvent, a polymerization accelerator and a dicarboxylic acid dianhydride may be contained as other components.

As the polymerization accelerator, for example, imidazole, benzimidazole, or 4-hydroxypyridine can be suitably used, but is not limited thereto.

Further, in the case of synthesizing polyamic acid, tetracarboxylic dianhydride and dicarboxylic anhydride can be used at the same time. When these carboxylic anhydrides are used at the same time, the properties of the produced polyglycolic acid may be further improved. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyl endomethylenetetrahydrogen. Phthalic anhydride, chlorobridge anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, and the like.

Further, by adjusting the concentration of the polyamic acid to 1% by weight or more and 10% by weight or less by using the aprotic polar solvent described above, an adhesive for forming the adhesive layer 3 can be obtained. As the aprotic polar solvent used in the adhesive, for example, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), and dimethylacetamide are preferably used. (DMAC), etc.

[Paste step]

In the pasting step, the plane portion which is hydrolyzed by the quinone bond is opposed to the support plate 2, and the substrate 2 is adhered to the substrate 1 by the adhesion layer 3.

The adhesion step may be carried out, for example, by heating, lamination, roll lamination, or the like. In the pasting step, for example, the substrate 1 and the support plate 2 are superposed by the adhesive layer 3, and the use can be carried out through a commercial route. The laminating machine device obtained by the diameter is heated and pasted at a temperature of about 40 ° C to 100 ° C. Here, the pressure applied to the laminate 10 by the laminator apparatus may be appropriately adjusted according to the mechanical strength of the support plate 2, the size of the laminate, and the like. Further, the pasting step may be carried out under any conditions of atmospheric pressure or under reduced pressure. Further, when the adhesion step is carried out under atmospheric pressure, it is more preferable to carry out the humidity in an environment in which the substrate 1 does not absorb moisture.

[other steps]

In the subsequent step 10 of the bonding step, a circuit or the like can be formed on the substrate 1 by a photolithography method, a plasma chemical vapor deposition method (plasma CVD method) or the like in the subsequent step. In the step of forming a circuit or the like on the substrate 1, the dehydrogenation of the amorphous germanium deposited on the substrate by the plasma CVD method, and the polycrystallization of the germanium layer formed by dehydrogenation may be performed. . In the above step, the laminate 10 is supplied to a temperature condition in a range of 200 ° C or more and 400 ° C or less under a reduced pressure atmosphere or an inert gas atmosphere such as nitrogen or argon.

Thereby, the amine group formed on the substrate 1 can be appropriately condensed with the carboxyl group present in the adhesive layer 3, and a guanamine bond can be formed between the substrate 1 and the adhesive layer 3. In addition, the laminate 10 may be heated under the temperature conditions of 200 ° C or higher and 400 ° C or lower after the adhesion step to form the polyamine acid forming the adhesion layer 3 .醯imination. Thereby, the adhesion between the adhesive layer 3 and the support plate 2 can be improved. In addition, it is possible to prevent a gap from being generated between the substrate 1 and the support plate 2. because However, the laminate 10 can be subjected to a high temperature treatment process.

Further, examples of the electronic device that can be formed on the substrate 1 after the bonding step include an active device, an electronic circuit, and other components. For example, the active element includes a wiring board, a transistor, a diode, and the like which are responsible for the electric wiring. Examples of the electronic circuit include a passive device such as a resistor, a capacitor, and an inductor. Further, examples of other elements include sensor elements such as sensor elements, light-emitting elements, liquid crystal display, electrophoretic display, and self-luminous display, which are inductive temperature, light, and humidity, and communication elements using wireless or wired, Computing elements, memory elements, MEMS elements, solar cells, thin film transistors, and the like.

[Layer 10]

The laminate 10 is a substrate 1 which has been previously formed into a film shape via a polyimide resin, and a support layer 2 of the support substrate 1 is formed by a bonding layer 3 comprising a polyamic acid represented by the above formula (1). Laminating the formed laminate, and having a sulfhydryl bond formed by condensation with a carboxyl group of a polyamic acid via an amine group derived from the substrate and opposite to the support Polyimide resin in the flat portion. In other words, the laminate of one embodiment of the present invention is a laminate 10 produced by the method for producing a laminate according to an embodiment of the present invention.

Thus, the laminate 10 is different from the laminate obtained by forming an adhesive layer using an acrylic resin. For example, when the laminate 10 is treated under high temperature conditions of about 350 ° C, generation of gas due to thermal decomposition of the adhesive layer 3 can be prevented. Therefore, when heating, it can be prevented from being on the substrate 1 and the support plate 2 A gap is created between them. Further, the laminate 10 is different from, for example, a laminate in which a substrate and a support are laminated using a coupling agent such as an amino decane, and the adhesion between the adhesive layer 3 and the support sheet 2 in the laminate is appropriately adjusted. Therefore, the substrate 1 can be favorably peeled off from the support sheet 2 together with the polyimide layer which is polyimideized.

[Layer for forming a laminate]

The kit for forming a laminate according to an embodiment of the present invention includes the treatment liquid used in the hydrolysis step included in the method for producing the laminate according to the embodiment of the present invention, and the treatment liquid used in the step of forming the adhesive layer. Follow-up agent.

According to the above configuration, a method for producing a laminate according to an embodiment of the present invention can be suitably carried out. Therefore, the kit for manufacturing the laminate of the present embodiment is also within the scope of the invention.

<Processing method of substrate>

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

The method for processing a substrate according to the present embodiment includes a method for producing a laminate according to an embodiment of the present invention, a step of forming a laminate ((a) to (e) of FIG. 1), and peeling off the substrate 1 from the laminate 10. The stripping step ((f) and (g) of Figure 1). Further, the step of forming the laminate is the same as the method of manufacturing the laminate according to the above-described embodiment, and thus the description thereof will be omitted. Also, for the lamination shown in (e) of Fig. 1 In the body 10, various wirings and the like are formed on the substrate 1 before the peeling step, and a structure such as an integrated circuit is mounted.

[Peeling step]

The method for peeling the substrate 1 from the laminate 10 may be appropriately selected depending on the type of the substrate 1 and the type of circuit formed on the substrate 1. For example, as shown in FIG. 1(f), in the peeling step, the support plate 2 in the laminate 10 is adsorbed and fixed to the mounting table, for example, and one side of the substrate 1 is lifted while one side of the substrate 1 is fixed. , and slowly stripped. Examples of the method of fixing one side of the substrate in the laminate 10 include a method of sandwiching a tape by a tweezers or the like, a method of adhering the tape, and a method of adsorbing and fixing by the adsorption portion. Moreover, the laminated body 10 may be laminated in such a manner that one of the edge portions of the substrate 1 is exposed from the support plate 2 in advance, and then the substrate 1 is lifted by sandwiching the portion and lifting the substrate 1.

In the peeling step, before the substrate 1 is peeled off, the substrate 1 may be cut out in a predetermined size, and the slit may be cut out in the substrate 1 in advance. As a method for cutting a slit in the substrate 1, for example, a method in which a laser is scanned relative to the substrate 1 to cut a slit; a water jet is relatively scanned with respect to the substrate 1 Thus, a method of cutting out the slit, a method of cutting out the slit by using a cutting device of the semiconductor wafer, and the like.

Further, in the peeling step, the angle between the plane portion of the substrate 1 and the plane portion of the support plate 2 opposed to each other is not limited to that of FIG. (f) is approximately 90° as shown. The angle between the substrate 1 and the support plate 2 in the peeling step takes into consideration the tension applied due to the stretching of the substrate 1 and the stress applied due to the bending of the circuit formed on the substrate 1, etc., so that the substrate 1 and the circuit If it is not damaged, it can be adjusted appropriately.

With respect to the laminate 10, the peel strength of the layer 3 with respect to the support plate 2 is moderately adjusted. More specifically, regarding the peeling strength of the adhesive layer 3 with respect to the support sheet 2, for example, at a peeling speed of 0.75 cm/sec, the peel strength of the substrate 1 is about 30 g/cm to 80 g/cm, more preferably 30 g. /cm~50g/cm or so. Therefore, as shown in FIG. 1(g), in the peeling step, the integrated substrate 1 and the adhesive layer 3 can be smoothly peeled off from the interface between the adhesive layer 3 and the support plate 2. Therefore, it is possible to prevent the circuit or the like mounted on the substrate 1 from being damaged by the force applied when the substrate 1 is peeled off.

Further, 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 taken up by the roll to be peeled off.

<Method for Producing Laminate of Other Embodiments>

The method for producing a laminate according to an embodiment of the present invention is not limited to the above embodiment. For example, in the method for producing a laminate according to another embodiment, in the hydrolysis step, only one surface on the side opposite to the subsequent layer 3 is subjected to a hydrolysis step among the two planar portions in the substrate 1.

In the hydrolysis step included in the method for producing a laminate according to the embodiment, for example, a protective film of a PET film, a PEN film, an olefin film, a polyimide film, or the like with an adhesive attached thereto is adhered to one of the substrates 1 The flat portion is processed to perform hydrolysis treatment only on one planar portion of the substrate 1. Of course, with this configuration, the adhesion between the substrate 1 and the adhesive layer 3 can be appropriately improved.

Further, in the method for producing a laminate according to still another embodiment, for example, polylysine may be produced by dissolving a tetracarboxylic dianhydride component and a diamine component in a solvent, and coating the obtained solution. It is placed on the support plate 2 and the support plate 2 is heated. Thereby, the adhesive layer 3 containing polyamic acid can be formed on the support plate 2. Therefore, the method for producing a laminate according to an embodiment of the present invention can be suitably carried out.

Further, in the method for producing a laminate according to still another embodiment, for example, in the hydrolysis step, the polyimine resin of the substrate 1 may be hydrolyzed and cracked by vacuum plasma treatment or UV ozone treatment. In this configuration, an amine group can also be formed on the plane portion of the substrate 1.

<Laminate of Other Embodiments>

In the laminate of the present invention, the amine group derived from the polyimide resin forming the substrate is not limited to the amine group obtained by cracking the quinone bond by hydrolysis. That is, in the case of an amine group derived from a diamine component used in the synthesis of a polyimide resin, the source of the amine group of the substrate is not limited. In this configuration, the amine group which is present in the planar portion of the substrate and the carboxyl group of the polyamic acid contained in the adhesive layer may be condensed to form a guanamine bond.

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

[Examples] [Evaluation of heat resistance and peeling of laminates]

The laminate of Example 1 and the laminates of Comparative Examples 1 and 2 were produced, and each laminate was evaluated for heat resistance and evaluation of peelability.

(Example 1)

First, in Example 1, as a binder containing poly-proline, Pyre-ML (registered trademark) RC-5019 (poly(pyrenetetracarboxylic dianhydride) was prepared by NMP so that the concentration of the resin became 2% by weight. -co-4,4'-diaminodiphenyl ether (methine acid solution; NMP solution, concentration: 15.0% by weight to 16.0% by weight, manufactured by Sigma-Aldrich Co., Ltd.). Next, the adhesive containing polyamic acid was applied to a 10 cm square glass support by spin coating, and heated at 170 ° C for 3 minutes to form an adhesive layer having a thickness of 200 nm on the glass support. (Next layer formation step).

Further, tetramethylammonium hydroxide (TMAH) was dissolved in a mixed liquid having a weight ratio of water to ethanol of 6:4 so as to have a concentration of 4.5% by weight to prepare a treatment liquid. A 10 cm square PI (polyimine) film substrate was immersed in a treatment liquid at 23 ° C for 3 minutes (product name: polyimine film Kapton H type, thickness: 50 μm, DU) After PONT-TORAY Co., Ltd., it was lifted, washed with water, and drained, and then dried at 90 ° C for 5 minutes to remove water (hydrolysis step).

Then, a laminate apparatus VA-700 (manufactured by Dacheng Laminator Co., Ltd.) set to a temperature of 80 ° C and a laminating machine conveying speed of 1.0 m/min was used to form a PI film substrate after hydrolysis treatment. The glass support of the subsequent layer is pasted by the adhesive layer (adhesion step).

(Comparative Example 1)

Next, as a laminate of Comparative Example 1, a poly(acrylic acid) solution (having an average molecular weight of ~100,000, an aqueous solution, a concentration of 35 wt%, manufactured by Sigma-Aldrich Co., Ltd.) was diluted with water so that the concentration of the polyacrylic acid was 4% by weight. The coating method was applied to the same glass support as the glass support used in Example 1. Next, the glass support was heated at 100 ° C for 3 minutes to form an adhesive layer having a thickness of 200 nm. Further, under the same conditions as in Example 1, the PI film substrate was subjected to hydrolysis treatment and dried by heating. Thereafter, the PI film substrate and the glass support were adhered under the same conditions as in Example 1. Thus, the laminate of Comparative Example 1 was produced.

(Comparative Example 2)

Next, as a laminate of Comparative Example 2, 3-aminopropyltriethoxysilane (APTES, coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.) was applied by the spin coating method to the same glass support as used in Example 1. Glass support on. Next, the glass support was heated at 170 ° C for 3 minutes. Further, under the same conditions as in Example 1, the PI film substrate was subjected to hydrolysis treatment and dried by heating. Thereafter, the PI film substrate and the glass support were adhered under the same conditions as in Example 1. Thus, the laminate of Comparative Example 2 was produced.

The composition of the laminate of Example 1 and the laminate of Comparative Examples 1 and 2 is shown in Table 1 below.

[Evaluation of heat resistance and peelability]

Next, the laminate of Example 1 and the laminate of Comparative Examples 1 and 2 were evaluated for peelability. The evaluation conditions of heat resistance and peelability are as follows.

(heat resistance)

The laminates prepared in the above-mentioned production were placed in a vertical baking oven TS8000MB (manufactured by Tokyo Ohka Kogyo Co., Ltd.), and heated under a nitrogen atmosphere at 350 ° C for 1 hour to carry out heat resistance. Evaluation. In the state after the heating, whether or not a void was generated between the PI film substrate and the glass support was evaluated by visual observation, the laminate having no voids was evaluated as "○", and the laminate in which the void was generated was evaluated as "X". The evaluation results of the heat resistance are shown in Table 1 below.

(peelability)

For the evaluation of the peelability, for each laminate after the heat resistance evaluation, Cutting a slit having a size of 1 cm × 9 cm on the PI film substrate laminated on the glass support, and holding the laminate at a horizontal position, holding one end of the portion of the PI film substrate cut out of the slit, The peel strength at the time of lifting up to the vertical direction at a speed of 0.75 cm/sec was evaluated. Further, a tensile compression tester SV-55C-2H (manufactured by Ikuta Seisakusho Co., Ltd.) was used for the measurement of the peel strength. The results of the evaluation of the peelability are shown in Table 1 below.

[result]

With respect to the laminate of Example 1, no occurrence of voids was observed even under heating conditions of 350 ° C for 1 hour. Further, in the laminate of Example 1, the peel strength of the PI film substrate was 45 to 47 g/cm, and the PI film substrate was smoothly peeled off without being damaged. Further, the adhesive layer is peeled off from the glass support body integrally with the PI film substrate.

On the other hand, in the laminate of Comparative Example 1, it was confirmed between the PI film substrate and the glass support in the evaluation of heat resistance. Void (×). Further, in the laminate of Comparative Example 1, the PI film substrate was immediately peeled off, and the peel strength was not measured.

In the laminate of Comparative Example 2, voids (○) were not produced, but as a result, the peel strength of the PI film substrate was high, and a structure such as an integrated circuit which can be formed on the PI film substrate during peeling may occur. damaged.

From the above results, it was confirmed that the PI film substrate was subjected to hydrolysis treatment and adhered to the glass support by using polyamic acid, whereby heat resistance was improved, and the PI film substrate was smoothly peeled off.

[Industrial availability]

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

1‧‧‧Substrate

2‧‧‧Support plate (support)

3‧‧‧Next layer

10‧‧‧Layer

50‧‧‧Processing tank

Claims (10)

A method for producing a laminate, which is a method for producing a laminate obtained by laminating a substrate made of a polyimide resin and a support for supporting the substrate by an adhesive layer, comprising: hydrolysis a step of partially hydrolyzing one of the quinone imine bonds present in one of the two planar portions of the substrate; and forming a composition comprising the following formula (1) on the support by forming an adhesive layer forming step a layer of polylysine made up of a unit; (In the above formula (1), R ¹ is a tetravalent organic group, an aromatic group, an aliphatic group or an alicyclic group having 2 or more and 11 or less carbon atoms; and R ² is a divalent organic group; In addition to a carbon atom and a hydrogen atom, an atom selected from a group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen may be contained, and an aromatic group or an aliphatic group having 2 or more and 50 or less carbon atoms may be contained. Or an alicyclic group, n is 1 or more; and a bonding step of adhering the substrate and the support to the support by the adhesive layer so that the flat portion in which the quinone bond is hydrolyzed faces the support. The method for producing a laminate according to claim 1, wherein R ¹ in the constituent unit represented by the above formula (1) is a tetravalent aromatic group, and R ² is selected from a phenyl group and a divalent phenyl group. At least one of the group consisting of an ether group and a divalent benzophenone group. The method for producing a laminate according to claim 1 or 2, wherein in the hydrolysis step, the quinone bond is hydrolyzed via a treatment liquid containing an organic base compound and water. The method for producing a laminate according to claim 3, wherein the organic base compound is a 4-stage ammonium hydroxide. The method for producing a laminate according to claim 3 or 4, wherein the treatment liquid further contains a water-soluble organic solvent. A method for processing a substrate, comprising: a laminate forming step of producing a laminate by a method for producing a laminate according to any one of claims 1 to 5; and a peeling step, after the step of forming the laminate, The substrate is peeled off from the laminate. A laminate obtained by laminating a substrate formed of a polyimide resin and a support supporting the substrate by an adhesive layer, and having an amine group derived from the following a guanamine bond of a carboxyl group, wherein the amine group is an amine group of a polyimine resin present in a plane portion of the substrate opposite to the support, and the carboxyl group is a constituent unit represented by the following formula (1) The carboxyl group of the polyglycolic acid, In the above formula (1), R ¹ is a tetravalent organic group, and is an aromatic group, an aliphatic group or an alicyclic group having 2 or more and 11 or less carbon atoms; and R ² is a divalent organic group. In addition to the carbon atom and the hydrogen atom, the atom may be an atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen, and is an aromatic group having 2 or more and 50 or less carbon atoms. An aliphatic group or an alicyclic group; N is 1 or more. The laminate of claim 7, wherein R ¹ in the structural unit represented by the above formula (1) is a tetravalent aromatic group, and R ² is selected from a phenylene group, a divalent phenyl ether group, and At least one group of the divalent benzophenone groups. A kit for forming a laminate, which is a kit for forming a laminate for use in a method for producing a laminate according to claim 3 or 4, comprising: an organic base compound, and a water base The treatment liquid and the binder comprising the polyamine acid having the constituent unit represented by the above formula (1) and an organic solvent. a kit for forming a laminate according to claim 9, wherein the above The treatment liquid further contains a water-soluble organic solvent.