WO2022113415A1 - Stratifié - Google Patents

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Publication number
WO2022113415A1
WO2022113415A1 PCT/JP2021/025411 JP2021025411W WO2022113415A1 WO 2022113415 A1 WO2022113415 A1 WO 2022113415A1 JP 2021025411 W JP2021025411 W JP 2021025411W WO 2022113415 A1 WO2022113415 A1 WO 2022113415A1
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Prior art keywords
film
polymer film
easily peelable
layer
inorganic substrate
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PCT/JP2021/025411
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English (en)
Japanese (ja)
Inventor
桂也 ▲徳▼田
哲雄 奥山
直樹 渡辺
正幸 横山
治美 米虫
伝一朗 水口
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東洋紡株式会社
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Priority to JP2022536542A priority Critical patent/JPWO2022113415A1/ja
Publication of WO2022113415A1 publication Critical patent/WO2022113415A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides

Definitions

  • the present invention relates to a laminated body.
  • the laminated body is often exposed to a high temperature.
  • a process in a temperature range of about 200 ° C. to 600 ° C. is required.
  • a temperature of about 200 to 300 ° C. may be applied to the film, and further, in order to heat and dehydrogenate the amorphous silicon to obtain low temperature polysilicon, the temperature is about 450 ° C. to 600 ° C. Heating may be required.
  • the polymer film constituting the laminated body is required to have heat resistance, but as a practical matter, the polymer film that can withstand practical use in such a high temperature range is limited.
  • Adhesive it is generally conceivable to use an adhesive or an adhesive for bonding the polymer film to the support, but at that time, the bonding surface between the polymer film and the support (that is, the adhesive for bonding) Adhesive) is also required to have heat resistance.
  • ordinary adhesives and adhesives for bonding do not have sufficient heat resistance, bonding with an adhesive or adhesive cannot be applied when the formation temperature of the functional element is high.
  • the inorganic substrate is made of polyimide before or during device formation by interposing a layer containing a silane coupling agent (hereinafter, also referred to as a silane coupling agent layer) between the inorganic substrate and the polyimide film.
  • a silane coupling agent layer a layer containing a silane coupling agent (hereinafter, also referred to as a silane coupling agent layer) between the inorganic substrate and the polyimide film.
  • the silane coupling agent physically or chemically intervenes between the inorganic substrate and the polyimide film to enhance the initial adhesive force between the two. Further, by using the silane coupling agent, it is suppressed that the adhesive force between the two is increased by the heat at the time of forming the device.
  • the present inventors may obtain a silane coupling agent layer (inorganic substrate) depending on the type of the polymer film. We have found a problem that the peelability of silane may not be sufficient.
  • the present inventors conducted further diligent research. As a result, if an easily peelable layer having a specific composition is provided between the polymer film and the silane coupling agent layer, surprisingly, regardless of the type of the polymer film, it is easy to easily perform after device formation. It has been found that the inorganic substrate can be peeled off from the polymer film. Further, if the easily peelable layer itself having a specific composition is used as a film for forming a device, the inorganic substrate can be easily peeled off from the easily peelable layer (film for forming a device) after the device is formed. I found. From the above, the present invention has been completed.
  • the present invention provides the following. (1) An inorganic substrate, a silane coupling agent layer, and an easily peelable layer are provided in this order.
  • the easily peelable layer is a laminate characterized by having a biphenyltetracarboxylic acid dianhydride and a structural unit derived from diaminobenzanilide.
  • the inorganic substrate can be easily attached to the easily peelable layer (device) after the device is formed. It can be peeled off from the forming film). Further, when the heat-resistant polymer film is further provided on the easily peelable layer, the heat-resistant polymer film and the silane coupling agent layer have the easily peelable layer, so that the heat resistance is high. Regardless of the type of the molecular film (film for forming the device), the inorganic substrate can be easily peeled off from the heat-resistant polymer film after the device is formed. This is clear from the results of the examples.
  • the easily peelable layer has a structural unit derived from biphenyltetracarboxylic acid dianhydride and diaminobenzanilide, so that the structural unit is highly oriented when it is made into a sheet, and the peeling is performed. It is speculated that cleavage is more likely to occur.
  • the 90 ° peel strength between the easily peelable layer and the inorganic substrate after heating at 450 ° C. for 1 hour is preferably 0.3 N / cm or less.
  • the inorganic substrate is easily peeled from the easy peel layer after the device is formed on the easy peel layer.
  • the 90 ° initial peel strength between the easily peelable layer and the inorganic substrate is 0.03 N / cm or more.
  • the 90 ° initial peel strength is 0.03 N / cm or more, it is possible to prevent the easy peel layer from peeling from the inorganic substrate before or during the formation of the device on the easy peel layer.
  • the easily peelable layer is present between the heat-resistant polymer film and the silane coupling agent layer. Therefore, the heat-resistant polymer film (for device formation) is formed. Regardless of the type of film), the inorganic substrate can be easily peeled off from the heat-resistant polymer film after the device is formed.
  • the 90 ° peel strength between the heat-resistant polymer film and the inorganic substrate after heating at 450 ° C. for 1 hour is preferably 0.3 N / cm or less.
  • the 90 ° peel strength is 0.3 N / cm or less, the inorganic substrate and the heat-resistant polymer film are easily peeled off after the device is formed.
  • the 90 ° initial peel strength between the heat-resistant polymer film and the inorganic substrate is preferably 0.03 N / cm or more.
  • the 90 ° initial peel strength is 0.03 N / cm or more, it is possible to prevent the heat-resistant polymer film from peeling from the inorganic substrate before or during device formation.
  • the present invention it is possible to provide a laminate capable of easily peeling an inorganic substrate from a film for forming a device after forming the device.
  • the laminated body according to this embodiment is An inorganic substrate, a silane coupling agent layer, and an easily peelable layer are provided in this order.
  • the easily peelable layer has a biphenyltetracarboxylic acid dianhydride and a structural unit derived from diaminobenzanilide.
  • the laminate has an easily peelable layer on the silane coupling agent layer
  • the easily peelable layer itself is used as a film for forming a device
  • the inorganic substrate can be easily peeled off (device formation) after the device is formed. It is possible to peel off from the film).
  • the heat-resistant polymer film is further provided on the easily peelable layer
  • the heat-resistant polymer film and the silane coupling agent layer have the easily peelable layer, so that the heat resistance is high.
  • the inorganic substrate can be easily peeled off from the heat-resistant polymer film after the device is formed.
  • the 90 ° peel strength between the easily peelable layer and the inorganic substrate after heating at 450 ° C. for 1 hour is preferably 0.3 N / cm or less, and more preferably 0.29 N / cm. Below, it is more preferably 0.28 N / cm or less.
  • the 90 ° peel strength is preferably 0.03 N / cm or more, more preferably 0.05 N / cm or more, and further preferably 0.07 N / cm or more. When the 90 ° peel strength is 0.3 N / cm or less, the inorganic substrate and the easily peelable layer are easily peeled off after the device is formed.
  • the 90 ° peel strength is such that a structure having a biphenyltetracarboxylic acid dianhydride and a structural unit derived from diaminobenzanilide is adopted as the structure of the easy peel layer, and conditions for forming a sheet (particularly). , Imidization conditions).
  • the measurement conditions for the 90 ° peel strength are according to the method described in the examples.
  • the 90 ° initial peel strength between the easily peelable layer and the inorganic substrate of the laminated body is preferably 0.03 N / cm or more, more preferably 0.05 N / cm or more, still more preferably 0.07 N. / Cm or more.
  • the 90 ° initial peel strength is preferably 0.3 N / cm or less, more preferably 0.29 N / cm or less, and further preferably 0.28 N / cm or less.
  • the 90 ° initial peel strength is 0.03 N / cm or more, it is possible to prevent the easy peel layer from peeling from the inorganic substrate before or during device formation. Further, when the 90 ° initial peel strength is 0.3 N / cm or less, the inorganic substrate and the easily peelable layer are easily peeled off after the device is formed.
  • the 90 ° initial peel strength is determined by adopting a structure having a biphenyltetracarboxylic acid dianhydride and a structural unit derived from diaminobenzanilide as the structure of the easy peel layer, and conditions for forming a sheet (the conditions for forming a sheet). In particular, it can be controlled by the imidization condition).
  • the measurement conditions for the 90 ° initial peel strength are the same as the measurement conditions for the 90 ° peel strength.
  • the 90 ° initial peel strength refers to the 90 ° peel strength between the inorganic substrate and the easy peeling layer after the laminated body is heat-treated at 100 ° C. for 10 minutes in an atmospheric atmosphere.
  • the laminated body further includes a heat-resistant polymer film on the easily peelable layer.
  • the easily peelable layer is present between the heat-resistant polymer film and the silane coupling agent layer. Therefore, the heat-resistant polymer film (for device formation) is formed. Regardless of the type of film), the inorganic substrate can be easily peeled off from the heat-resistant polymer film after the device is formed.
  • the 90 ° peel strength between the heat-resistant polymer film and the inorganic substrate after heating at 450 ° C. for 1 hour is 0.3 N / cm or less. , More preferably 0.29 N / cm or less, still more preferably 0.28 N / cm or less.
  • the 90 ° peel strength is preferably 0.03 N / cm or more, more preferably 0.05 N / cm or more, and further preferably 0.07 N / cm or more.
  • the 90 ° peel strength is such that a structure having a biphenyltetracarboxylic acid dianhydride and a structural unit derived from diaminobenzanilide is adopted as the structure of the easy peel layer, and conditions for forming a sheet (particularly). , Imidization conditions).
  • the measurement conditions for the 90 ° peel strength are according to the method described in the examples.
  • the laminate preferably has a 90 ° initial peel strength between the heat-resistant polymer film and the inorganic substrate of 0.03 N / cm or more, more preferably 0.05 N / cm. It is cm or more, more preferably 0.07 N / cm or more.
  • the 90 ° initial peel strength is preferably 0.3 N / cm or less, more preferably 0.29 N / cm or less, and further preferably 0.28 N / cm or less.
  • the 90 ° initial peel strength is 0.03 N / cm or more, it is possible to prevent the heat-resistant polymer film from peeling from the inorganic substrate before or during device formation.
  • the 90 ° initial peel strength is determined by adopting a structure having a biphenyltetracarboxylic acid dianhydride and a structural unit derived from diaminobenzanilide as the structure of the easy peel layer, and conditions for forming a sheet (the conditions for forming a sheet).
  • the measurement conditions for the 90 ° initial peel strength are the same as the measurement conditions for the 90 ° peel strength.
  • the 90 ° initial peel strength refers to the 90 ° peel strength between the inorganic substrate and the heat-resistant polymer film after the laminated body is heat-treated at 100 ° C. for 10 minutes in an atmospheric atmosphere.
  • the easily peelable layer is a polyimide film having a structural unit derived from biphenyltetracarboxylic acid dianhydride and diaminobenzanilide.
  • a polyimide film is a green film (hereinafter referred to as a green film) in which a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent is applied to a support for producing a polyimide film and dried.
  • a polyamic acid polyimide precursor
  • precursor film polyamic acid film
  • the green film is heat-treated at high temperature to perform a dehydration ring closure reaction on or in a state of being peeled off from the support for producing a polyimide film. It can be obtained by.
  • the green film refers to a polyamic acid film containing a solvent and having self-supporting properties.
  • the solvent content of the green film is not particularly limited as long as it has self-supporting property, but is preferably 1% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more. Yes, more preferably 20% by mass or more, and particularly preferably 30% by mass or more. Further, it is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and particularly preferably 50% by mass or less.
  • a polyimide solution obtained by a dehydration ring closure reaction between diamines and tetracarboxylic acids in a solvent is applied to a support for producing a polyimide film, dried, and contains, for example, 1 to 50% by mass of a solvent. It can also be obtained by treating a polyimide film containing a solvent of 1 to 50% by mass at a high temperature and drying it on a support for producing a polyimide film or in a state of being peeled off from the support.
  • diaminobenzanilide is used as the diamines for obtaining the easily peelable layer.
  • diaminobenzanilide 4,4'-diaminobenzanilide (hereinafter, also referred to as DABAN) is preferable.
  • the content of the diaminobenzanilide is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass when the total diamine component is 100% by mass. % Or more, particularly preferably 100% by mass.
  • the diamines other than the diaminobenzanilide are not particularly limited, and aromatic diamines, aliphatic diamines, alicyclic diamines and the like usually used for polyimide synthesis can be used. More preferably, diamines used in the heat-resistant polymer film described later can be used.
  • biphenyltetracarboxylic acid dianhydride is used as the tetracarboxylic acids for obtaining the easily peelable layer.
  • the biphenyltetracarboxylic acid dianhydride 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride (hereinafter, also referred to as BPDA) is preferable. More preferably, tetracarboxylic acids used in the heat-resistant polymer film described later can be used.
  • the content of the biphenyltetracarboxylic acid dianhydride is preferably 80% by mass or more, more preferably 90% by mass or more, when the total tetracarboxylic acid component is 100% by mass. , More preferably 95% by mass or more, and particularly preferably 100% by mass.
  • the tetracarboxylic acids other than the biphenyltetracarboxylic acid dianhydride are not particularly limited, and aromatic tetracarboxylic acids (including the acid anhydride thereof) and aliphatic tetracarboxylic acids (the acid anhydride thereof) usually used for polyimide synthesis are not particularly limited. (Including the substance), alicyclic tetracarboxylic acids (including the acid anhydride thereof) can be used. When these are acid anhydrides, the number of anhydride structures in the molecule may be one or two, but those having two anhydride structures (dianhydride) are preferable. good.
  • the easily peelable layer uses diaminobenzanilide as the diamines for obtaining the easily peelable layer and biphenyltetracarboxylic acid dianhydride as the tetracarboxylic acids
  • the easily peelable layer is biphenyltetra. It will have a structural unit derived from carboxylic acid dianhydride and diaminobenzanilide.
  • the easily peelable layer preferably has a structural unit derived from BPDA and DABAN.
  • the total structural units contained in the easily peelable layer are 100% by mass
  • the total of the structural units derived from BPDA and DABAN is preferably 80% by mass or more, more preferably 90% by mass or more. It is more preferably 95% by mass or more, and particularly preferably 100% by mass.
  • the easily peelable layer may contain a composition other than BPDA and polyimide having a structural unit derived from DABAN.
  • the content of the polyimide (BPDA and the polyimide having a structural unit derived from DABAN) contained in the easily peelable layer is preferably 80% by mass or more, more preferably 90% by mass or more, and further. It is preferably 95% by mass or more, and may be 100% by mass.
  • the composition other than BPDA and polyimide having a structural unit derived from DABAN is not particularly limited as long as it does not contradict the gist of the present invention.
  • the easily peelable layer preferably has a melting point of 250 ° C. or higher, more preferably 300 ° C. or higher, and even more preferably 400 ° C. or higher. When the melting point is 250 ° C. or higher, the heat resistance is more excellent. Further, the easily peelable layer preferably has a glass transition temperature of 200 ° C. or higher, more preferably 320 ° C. or higher, and further preferably 380 ° C. or higher. When the glass transition temperature is 200 ° C. or higher, the heat resistance is more excellent. In the present specification, the melting point and the glass transition temperature are determined by differential thermal analysis (DSC). When the melting point exceeds 500 ° C., it is determined whether or not the melting point has been reached by visually observing the thermal deformation behavior when heated at the corresponding temperature.
  • DSC differential thermal analysis
  • the easily peelable layer is a polyamic acid (polyimide precursor) solution obtained by reacting biphenyltetracarboxylic acid dianhydride (tetracarboxylic acids) and diaminobenzanilide (diamines) in a solvent. Is applied to a support for producing a polyimide film and dried to obtain a green film (also referred to as “polyimide acid film”), and the green film is heated at a high temperature on the support for producing a polyimide film or in a state of being peeled off from the support. It is obtained by heat treatment to carry out a dehydration ring closure reaction.
  • polyimide precursor polyamic acid (polyimide precursor) solution obtained by reacting biphenyltetracarboxylic acid dianhydride (tetracarboxylic acids) and diaminobenzanilide (diamines) in a solvent.
  • a polyimide solution obtained by a dehydration ring closure reaction with biphenyltetracarboxylic acid dianhydride (tetracarboxylic acids) and diaminobenzanilide (diamines) in a solvent is used as a support for producing a polyimide film. It is coated and dried to form a polyimide film containing, for example, 1 to 50% by mass of a solvent, and further, a polyimide containing 1 to 50% by mass of a solvent on a support for producing a polyimide film or in a state of being peeled off from the support. It can also be obtained by treating the film at a high temperature and drying it.
  • the solvent used when polymerizing biphenyltetracarboxylic acid dianhydride and diaminobenzanilide to obtain polyamic acid is not particularly limited as long as it dissolves both the raw material monomer and the produced polyamic acid.
  • Polar organic solvents are preferred, for example N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethyl.
  • Examples thereof include phosphoric amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, and halogenated phenols.
  • N-methyl-2-pyrrolidone and N, N-dimethylacetamide are preferably applied.
  • These solvents can be used alone or in admixture.
  • the amount of the solvent used may be an amount sufficient to dissolve the monomer as a raw material, and the specific amount used is such that the mass of the monomer in the solution in which the monomer is dissolved is usually 5 to 40% by mass.
  • the amount is preferably 10 to 20% by mass.
  • the polyamic acid can be produced by a known production method. That is, one or more kinds of tetracarboxylic acid anhydrous components (including biphenyltetracarboxylic acid dianhydride) and one or more kinds of diamine components (including diaminobenzanilide) which are raw materials are used. , Polymerize in the solvent to obtain a polyamic acid solution.
  • the reaction apparatus is preferably equipped with a temperature adjusting device for controlling the reaction temperature, and the reaction temperature is preferably 0 ° C. or higher and 80 ° C. or lower, and further 15 ° C. or higher and 60 ° C. or lower is the reverse of polymerization. It is preferable because it suppresses the hydrolysis of the polyamic acid, which is a reaction, and the viscosity of the polyamic acid tends to increase.
  • an imidization catalyst, inorganic fine particles, or the like may be added to the polyamic acid solution.
  • a tertiary amine As the tertiary amine, a heterocyclic tertiary amine is preferable. Preferred specific examples of the heterocyclic tertiary amine include pyridine, 2,5-diethylpyridine, picoline, quinoline, isoquinoline and the like.
  • the amount of the imidization catalyst used is preferably 0.01 to 2.00 equivalents, more preferably 0.02 to 1.20 equivalents, relative to the reaction site of the polyamic acid (polyimide precursor). When the amount of the imidization catalyst used is 0.01 equivalent or more, the effect of the catalyst can be sufficiently obtained. Further, when the amount of the imidization catalyst used is 2.00 equivalents or less, the proportion of the catalyst not involved in the reaction can be reduced, which is preferable in terms of cost.
  • the inorganic fine particles include inorganic oxide powders such as fine-grained silicon dioxide (silica) powder and aluminum oxide powder; and inorganic salt powders such as fine-grained calcium carbonate powder and calcium phosphate powder. If the inorganic fine particles are present as coarse particles, they may cause defects in the next and subsequent steps. Therefore, it is preferable that the inorganic fine particles are uniformly dispersed in the polyamic acid solution. ..
  • the reduced viscosity ( ⁇ sp / C) of the polyamic acid solution or the polyimide solution is preferably 0.1 or more, more preferably 1 or more, and further preferably 2 or more. Further, it is preferably 5 or less, more preferably 4.5 or less, and further preferably 4 or less.
  • the drying temperature is preferably 70 to 130 ° C., more preferably 80. It is about 125 ° C., more preferably 85 to 120 ° C.
  • the drying temperature is preferably 70 to 130 ° C. or lower. It is about 125 ° C., more preferably 85 to 120 ° C.
  • the drying time is preferably 5 to 90 minutes, more preferably 15 to 80 minutes, although it depends on the drying temperature.
  • the drying time is preferably 5 to 90 minutes, more preferably 15 to 80 minutes, although it depends on the drying temperature.
  • By setting the drying time to 90 minutes or less it is possible to suppress a decrease in molecular weight and brittleness of the film. Further, by setting the drying time to 5 minutes or more, it is possible to suppress deterioration of handleability due to insufficient drying.
  • Conventionally known drying devices can be applied, and examples thereof include hot air, hot nitrogen, far infrared rays, and high frequency induction heating.
  • the number of steps is preferably 2 or more, and more preferably 3 or more.
  • the number of steps is preferably 10 or less, more preferably 5 or less.
  • the number of steps is too large, a temperature range in which a reverse reaction is likely to occur is used, and the mechanical properties of the obtained polyimide film may deteriorate. Therefore, by setting the number of steps to 10 or less, it is possible to suppress deterioration of the mechanical properties of the obtained polyimide film.
  • imidization heat treatment
  • the temperature and time in each step are set from the following viewpoints.
  • First step By preferably removing the residual solvent, the thickness unevenness of the film is reduced.
  • 1st to 2nd steps Imidization and tension control are performed with a certain amount of solvent remaining to achieve high orientation. Also, avoid temperature ranges where reverse reactions are likely to occur.
  • the imidization is completed and the terminals produced by the reverse reaction are recombined.
  • the imidization temperature of the first step is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 180 ° C. or higher, because the thickness unevenness of the film can be reduced by removing the residual solvent. It is preferably 185 ° C. or higher, and particularly preferably 190 ° C. or higher.
  • the imidization temperature of the first step is preferably 220 ° C. or lower, more preferably 210 ° C. or lower.
  • the imidization time of the first step is preferably 1 minute or longer, more preferably 2 minutes or longer.
  • the imidization time of the first step is preferably 10 minutes or less, more preferably 5 minutes or less.
  • the imidization reaction (heat treatment) of the second step is performed.
  • the imidization temperature of the second step is preferably 220 ° C. or higher, more preferably 230 ° C. or higher, and further preferably 240 ° C. or higher.
  • the imidization temperature in the second step is preferably 280 ° C. or lower, more preferably 270 ° C. or lower.
  • the imidization time of the second step is preferably 1 minute or longer, more preferably 2 minutes or longer.
  • the imidization time of the second step is preferably 10 minutes or less, more preferably 5 minutes or less.
  • the imidization reaction (heat treatment) of the third step is performed.
  • the imidization temperature in the third step is preferably more than 280 ° C, more preferably 290 ° C or higher, and even more preferably 295 ° C or higher.
  • the imidization temperature in the third step is preferably less than 480 ° C, more preferably 400 ° C or lower, still more preferably 350 ° C or lower, because the thickness unevenness of the film can be reduced. be.
  • the imidization time of the third step is preferably 2 minutes or more, more preferably 4 minutes or more.
  • the imidization time of the third step is preferably 20 minutes or less, more preferably 10 minutes or less.
  • Imidization heat treatment
  • a pin tenter or a clip a clip
  • tension in the width direction and the longitudinal direction of the film it is preferable to make the tension in the width direction and the longitudinal direction of the film as uniform as possible.
  • both ends of the film are pressed with a brush so that the pins are evenly pierced into the film.
  • the brush is preferably a rigid and heat-resistant fibrous brush, and a high-strength and high elastic modulus monofilament can be adopted.
  • the easily peelable layer is preferably manufactured via a green film of polyamic acid. That is, by imidizing the grease film, a release sheet having more excellent peelability and heat resistance can be obtained.
  • the easily peelable layer is usually preferably a non-stretched sheet, but may be a uniaxially or biaxially stretched sheet.
  • the non-stretched sheet means a film obtained by tenter stretching, roll stretching, inflation stretching, or the like without intentionally applying a mechanical external force in the surface expansion direction of the film.
  • the thickness of the easily peelable layer when used by laminating with a polymer film is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and further preferably 1 ⁇ m or less.
  • the lower limit of the thickness of the easily peelable layer is not particularly limited, but is substantially 0.01 ⁇ m or more.
  • the easily peelable layer is 5 ⁇ m or less, it is possible to suppress the occurrence of warpage due to the difference in CTE and mechanical properties with the polymer film.
  • the thickness of the easily peelable layer is preferably 3 ⁇ m or more, more preferably 11 ⁇ m or more, still more preferably 13 ⁇ m.
  • the above is more preferably 15 ⁇ m or more.
  • the upper limit of the thickness of the easily peelable layer is not particularly limited, but is preferably 250 ⁇ m or less, more preferably 150 ⁇ m or less, still more preferably 90 ⁇ m or less for use as a flexible electronic device.
  • the average CTE of the easily peelable layer between 30 ° C. and 300 ° C. is preferably ⁇ 5 ppm / ° C. to + 20 ppm / ° C., more preferably ⁇ 5 ppm / ° C. to + 15 ppm / ° C., and even more preferably 1 ppm. It is from / ° C to + 10 ppm / ° C.
  • the CTE is within the above range, the difference in the coefficient of linear expansion from that of a general support (inorganic substrate) can be kept small, and the easily peelable layer and the inorganic substrate can be peeled off even when subjected to a heat application process. It can be avoided.
  • the CTE difference from the polymer film is small, so that warpage can be suppressed.
  • CTE is a factor that represents reversible expansion and contraction with respect to temperature.
  • the CTE of the easily peelable layer is a value measured for a single film film having the same composition as the easily peelable layer, and is an average of the CTE in the flow direction (MD direction) and the CTE in the width direction (TD direction) of the coating. Point to a value.
  • the heat shrinkage of the easily peelable layer between 30 ° C. and 500 ° C. is preferably ⁇ 0.9%, more preferably ⁇ 0.6%.
  • the heat shrinkage rate is a factor that represents irreversible expansion and contraction with respect to temperature.
  • the heat shrinkage rate of the easily peelable layer is determined by measuring a single-layer film having the same composition as the easily peelable layer.
  • the heat-resistant polymer is a polymer having a melting point of 400 ° C. or higher, preferably 500 ° C. or higher, and a glass transition temperature of 250 ° C. or higher, preferably 320 ° C. or higher, more preferably 380 ° C. or higher. ..
  • the melting point and the glass transition temperature are determined by differential thermal analysis (DSC). When the melting point exceeds 500 ° C., it may be determined whether or not the melting point has been reached by observing and observing the thermal deformation behavior when heated at the corresponding temperature.
  • the heat-resistant polymer film includes polyimide resins such as polyimide, polyamideimide, polyetherimide, and fluorinated polyimide (for example, aromatic polyimide resin and alicyclic polyimide resin); polyethylene. , Polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate and other copolymerized polyesters (eg, fully aromatic polyesters, semi-aromatic polyesters); copolymerized (meth) acrylates typified by polymethylmethacrylate; polycarbonate.
  • polyimide resins such as polyimide, polyamideimide, polyetherimide, and fluorinated polyimide (for example, aromatic polyimide resin and alicyclic polyimide resin)
  • polyethylene Polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate and other copolymerized polyesters (eg, fully aromatic polyesters, semi-
  • Polyimide; Polysulphon; Polyethersulphon; Polyetherketone; Cellulose acetate; Cellulite nitrate; Aromatic polyamide; Polyvinyl chloride; Polyphenol; Polyallylate; Polyphenylene sulfide; Polyphenylene oxide; Polystyrene and other films can be exemplified.
  • the polymer film is premised on being used in a process involving a heat treatment of 450 ° C. or higher, the polymer films exemplified are limited to those that can be actually applied.
  • a film using a so-called super engineering plastic is preferable, and more specifically, an aromatic polyimide film, an aromatic amide film, an aromatic amide imide film, an aromatic benzoxazole film, and an fragrance.
  • an aromatic polyimide film an aromatic amide film, an aromatic amide imide film, an aromatic benzoxazole film, and an fragrance.
  • examples thereof include group benzothiazole film and aromatic benzoimidazole film.
  • a polyimide-based resin film is a green film (hereinafter referred to as a green film) in which a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent is applied to a support for producing a polyimide film and dried.
  • a polyamic acid (polyimide precursor) solution obtained by reacting diamines and tetracarboxylic acids in a solvent is applied to a support for producing a polyimide film and dried.
  • polyamic acid film It is also referred to as "polyamic acid film", and is obtained by subjecting a green film to a high-temperature heat treatment on a support for producing a polyimide film or in a state of being peeled off from the support to carry out a dehydration ring closure reaction.
  • the application of the polyamic acid (polyimide precursor) solution is, for example, application of a conventionally known solution such as spin coating, doctor blade, applicator, comma coater, screen printing method, slit coating, reverse coating, dip coating, curtain coating, and slit die coating. Means can be used as appropriate.
  • the diamines constituting the polyamic acid are not particularly limited, and aromatic diamines, aliphatic diamines, alicyclic diamines and the like usually used for polyimide synthesis can be used. From the viewpoint of heat resistance, aromatic diamines are preferable, and among aromatic diamines, aromatic diamines having a benzoxazole structure are more preferable. When aromatic diamines having a benzoxazole structure are used, it is possible to develop high elastic modulus, low coefficient of thermal expansion, and low linear expansion coefficient as well as high heat resistance.
  • the diamines may be used alone or in combination of two or more.
  • the aromatic diamines having a benzoxazole structure are not particularly limited, and are, for example, 5-amino-2- (p-aminophenyl) benzoxazole, 6-amino-2- (p-aminophenyl) benzoxazole, 5 -Amino-2- (m-aminophenyl) benzoxazole, 6-amino-2- (m-aminophenyl) benzoxazole, 2,2'-p-phenylenebis (5-aminobenzoxazole), 2,2' -P-Phenylenebis (6-aminobenzoxazole), 1- (5-aminobenzoxazole) -4- (6-aminobenzoxazolo) benzene, 2,6- (4,4'-diaminodiphenyl) benzo [1,2-d: 5,4-d'] bisoxazole, 2,6- (4,4-diaminodiphenyl) benzo [1,2-d: 4,5
  • aromatic diamines other than the above-mentioned aromatic diamines having a benzoxazole structure examples include 2,2'-dimethyl-4,4'-diaminobiphenyl and 1,4-bis [2- (4-aminophenyl).
  • a halogen atom an alkyl group or an alkoxyl group having 1 to 3 carbon atoms, a cyano group, or a part or all of a hydrogen atom of an alkyl group or an alkoxyl group having 1 to 3 carbon atoms substituted with a halogen atom.
  • aliphatic diamines examples include 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,8-diaminootan and the like.
  • alicyclic diamines examples include 1,4-diaminocyclohexane, 4,4'-methylenebis (2,6-dimethylcyclohexylamine) and the like.
  • the total amount of diamines (aliphatic diamines and alicyclic diamines) other than aromatic diamines is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less of all diamines. Is. In other words, the aromatic diamines are preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more of all diamines.
  • tetracarboxylic acids constituting the polyamic acid examples include aromatic tetracarboxylic acids (including its acid anhydride), aliphatic tetracarboxylic acids (including its acid anhydride) and alicyclic tetracarboxylic acids usually used for polyimide synthesis. Acids (including its acid anhydride) can be used. Among them, aromatic tetracarboxylic acid anhydrides and alicyclic tetracarboxylic acid anhydrides are preferable, aromatic tetracarboxylic acid anhydrides are more preferable from the viewpoint of heat resistance, and alicyclics are more preferable from the viewpoint of light transmission. Group tetracarboxylic acids are more preferred.
  • the number of anhydride structures in the molecule may be one or two, but those having two anhydride structures (dianhydride) are preferable. good.
  • the tetracarboxylic acids may be used alone or in combination of two or more.
  • Examples of the alicyclic tetracarboxylic acid include cyclobutanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 3,3', 4,4'-bicyclohexyltetracarboxylic acid and the like.
  • Examples include carboxylic acids and their acid anhydrides.
  • dianhydrides having two anhydride structures eg, cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 3,3', 4,4 '-Bicyclohexyltetracarboxylic acid dianhydride, etc. is suitable.
  • the alicyclic tetracarboxylic acids may be used alone or in combination of two or more.
  • the alicyclic tetracarboxylic acids are preferably, for example, 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more of all tetracarboxylic acids.
  • aromatic tetracarboxylic acids are not particularly limited, but are preferably pyromellitic acid residues (that is, those having a structure derived from pyromellitic acid), and more preferably an acid anhydride thereof.
  • aromatic tetracarboxylic acids include pyromellitic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, 3.
  • aromatic tetracarboxylic acids are preferably, for example, 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more of all tetracarboxylic acids.
  • the thickness of the polymer film is preferably 3 ⁇ m or more, more preferably 11 ⁇ m or more, further preferably 24 ⁇ m or more, and even more preferably 45 ⁇ m or more.
  • the upper limit of the thickness of the polymer film is not particularly limited, but is preferably 250 ⁇ m or less, more preferably 150 ⁇ m or less, still more preferably 90 ⁇ m or less for use as a flexible electronic device.
  • the average CTE of the polymer film between 30 ° C. and 300 ° C. is preferably ⁇ 5 ppm / ° C. to + 20 ppm / ° C., more preferably ⁇ 5 ppm / ° C. to + 15 ppm / ° C., still more preferably 1 ppm. It is from / ° C to + 10 ppm / ° C.
  • the CTE is within the above range, the difference in the coefficient of linear expansion from the general support (inorganic substrate) can be kept small, and the polymer film and the inorganic substrate are peeled off even when subjected to the heat application process. It can be avoided.
  • CTE is a factor that represents reversible expansion and contraction with respect to temperature.
  • the CTE of the polymer film refers to the average value of the CTE in the flow direction (MD direction) and the CTE in the width direction (TD direction) of the polymer film.
  • the method for measuring CTE of the polymer film is as described in Examples.
  • the thermal shrinkage of the polymer film between 30 ° C. and 500 ° C. is preferably ⁇ 0.9%, more preferably ⁇ 0.6%.
  • the heat shrinkage rate is a factor that represents irreversible expansion and contraction with respect to temperature.
  • the tensile breaking strength of the polymer film is preferably 60 MPa or more, more preferably 120 MPa or more, and further preferably 240 MPa or more.
  • the upper limit of the tensile breaking strength is not particularly limited, but is practically less than about 1000 MPa.
  • the tensile breaking strength of the polymer film refers to the average value of the tensile breaking strength in the flow direction (MD direction) and the tensile breaking strength in the width direction (TD direction) of the polymer film.
  • the method for measuring the tensile breaking strength of the polymer film is as described in Examples.
  • the tensile elongation at break of the polymer film is preferably 1% or more, more preferably 5% or more, still more preferably 20% or more. When the tensile elongation at break is 1% or more, the handleability is excellent.
  • the tensile elongation at break of the polymer film refers to the average value of the tensile elongation at break in the flow direction (MD direction) and the tensile elongation at break in the width direction (TD direction) of the polymer film.
  • MD direction flow direction
  • TD direction width direction
  • the tensile elastic modulus of the polymer film is preferably 3 GPa or more, more preferably 6 GPa or more, and further preferably 8 GPa or more.
  • the tensile elastic modulus is preferably 20 GPa or less, more preferably 12 GPa or less, and further preferably 10 GPa or less.
  • the polymer film can be used as a flexible film.
  • the tensile elastic modulus of the polymer film refers to the average value of the tensile elastic modulus in the flow direction (MD direction) and the tensile elastic modulus in the width direction (TD direction) of the polymer film.
  • the method for measuring the tensile elastic modulus of the polymer film is as described in Examples.
  • the thickness unevenness of the polymer film is preferably 20% or less, more preferably 12% or less, still more preferably 7% or less, and particularly preferably 4% or less. When the thickness spot exceeds 20%, it tends to be difficult to apply to a narrow part.
  • the polymer film is preferably obtained in the form of being wound as a long polymer film having a width of 300 mm or more and a length of 10 m or more at the time of its manufacture, and has a roll-like height wound around a winding core.
  • the one in the form of a molecular film is more preferable.
  • a lubricant (particle) having a particle size of about 10 to 1000 nm is added / contained in the polymer film in an amount of about 0.03 to 3% by mass. Therefore, it is preferable to impart fine irregularities to the surface of the polymer film to ensure slipperiness.
  • the inorganic substrate may be a plate-shaped substrate that can be used as a substrate made of an inorganic substance.
  • a glass plate, a ceramic plate, a semiconductor wafer, a metal or the like, and these glass plates and ceramic plates are used.
  • the semiconductor wafer and the composite of the metal include those in which these are laminated, those in which they are dispersed, and those in which these fibers are contained.
  • the glass plate examples include quartz glass, high silicate glass (96% silica), soda lime glass, lead glass, aluminoborosilicate glass, borosilicate glass (Pylex (registered trademark)), borosilicate glass (non-alkali), and the like. Includes borosilicate glass (microsheet), aluminosilicate glass and the like. Among these, those having a coefficient of linear expansion of 5 ppm / K or less are desirable, and if they are commercially available products, “Corning (registered trademark) 7059” and “Corning (registered trademark) 1737” manufactured by Corning Inc., which are glass for liquid crystal, are used. "EAGLE”, "AN100” manufactured by Asahi Glass Co., Ltd., “OA10” manufactured by Nippon Electric Glass Co., Ltd., “AF32” manufactured by SCHOTT Co., Ltd., etc. are desirable.
  • the semiconductor wafer is not particularly limited, but is limited to silicon wafer, germanium, silicon-germanium, gallium-arsenic, aluminum-gallium-indium, nitrogen-phosphorus-arsenide-antimony, SiC, InP (indium phosphorus), InGaAs, GaInNAs, and the like. Wafers such as LT, LN, ZnO (zinc oxide), CdTe (cadmium telluride), and ZnSe (zinc selenide) can be mentioned. Among them, the wafer preferably used is a silicon wafer, and particularly preferably a mirror-polished silicon wafer having a size of 8 inches or more.
  • the metal includes single element metals such as W, Mo, Pt, Fe, Ni, and Au, alloys such as inconel, monel, mnemonic, carbon copper, Fe—Ni-based invar alloy, and superinvar alloy. Further, a multilayer metal plate formed by adding another metal layer or a ceramic layer to these metals is also included. In this case, if the overall coefficient of linear expansion (CTE) with the additional layer is low, Cu, Al, or the like is also used for the main metal layer. The metal used as the additional metal layer is limited as long as it has properties such as strong adhesion to the polymer film, no diffusion, and good chemical resistance and heat resistance. Although not, Cr, Ni, TiN, Mo-containing Cu and the like are preferable examples.
  • the flat surface portion of the inorganic substrate is sufficiently flat.
  • the PV value of the surface roughness is 50 nm or less, more preferably 20 nm or less, and further preferably 5 nm or less. If it is coarser than this, the peel strength between the polymer film layer and the inorganic substrate may be insufficient.
  • the thickness of the inorganic substrate is not particularly limited, but from the viewpoint of handleability, a thickness of 10 mm or less is preferable, 3 mm or less is more preferable, and 1.3 mm or less is further preferable.
  • the lower limit of the thickness is not particularly limited, but is preferably 0.07 mm or more, more preferably 0.15 mm or more, still more preferably 0.3 mm or more.
  • Silane coupling agent layer A silane coupling agent layer containing a silane coupling agent is provided on the inorganic substrate.
  • the silane coupling agent physically or chemically intervenes between the inorganic substrate and the easily peelable layer, and has an effect of enhancing the adhesive force between the inorganic substrate and the easily peelable layer.
  • the coupling agent is not particularly limited, but a silane coupling agent having an amino group or an epoxy group is preferable.
  • Preferred specific examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (.
  • the silane coupling agent includes n-propyltrimethoxysilane, butyltrichlorosilane, 2-cyanoethyltriethoxysilane, cyclohexyltrichlorosilane, decyltrichlorosilane, diacetoxydimethylsilane, diethoxydimethylsilane, and dimethoxy.
  • a silane coupling agent having one silicon atom in one molecule is particularly preferable, and for example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N- 2- (Aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Examples thereof include propylmethyldiethoxysilane, 3-glycidoxypropyltrie
  • the coupling agent includes 1-mercapto-2-propanol, 3-mercaptopropionate methyl, 3-mercapto-2-butanol, 3-mercaptopropionate butyl, 3- (dimethoxymethylsilyl)-.
  • a method for forming the silane coupling agent layer a method of applying a silane coupling agent solution to the inorganic substrate, a vapor deposition method, or the like can be used.
  • the silane coupling agent layer may be formed on the surface of the easily peelable layer.
  • a spin coating method As a method of applying the silane coupling agent solution, a spin coating method, a curtain coating method, a dip coating method, a slit die coating method, a gravure coating method, a bar, using a solution obtained by diluting the silane coupling agent with a solvent such as alcohol is used.
  • Conventionally known solution coating means such as a coating method, a comma coating method, an applicator method, a screen printing method, and a spray coating method can be appropriately used.
  • the silane coupling agent layer can also be formed by a vapor deposition method, and specifically, the inorganic substrate is formed by exposing the inorganic substrate to the vapor of the silane coupling agent, that is, the silane coupling agent in a substantially gaseous state. ..
  • the vapor of the silane coupling agent can be obtained by heating the silane coupling agent in a liquid state to a temperature from 40 ° C. to about the boiling point of the silane coupling agent.
  • the boiling point of the silane coupling agent varies depending on the chemical structure, but is generally in the range of 100 to 250 ° C. However, heating at 200 ° C. or higher is not preferable because it may cause a side reaction on the organic group side of the silane coupling agent.
  • the environment for heating the silane coupling agent may be any of pressure, normal pressure, and reduced pressure, but in the case of promoting vaporization of the silane coupling agent, normal pressure or reduced pressure is preferable. Since many silane coupling agents are flammable liquids, it is preferable to carry out the vaporization work in a closed container, preferably after replacing the inside of the container with an inert gas.
  • the time for exposing the inorganic substrate to the silane coupling agent is not particularly limited, but is preferably 20 hours or less, more preferably 60 minutes or less, still more preferably 15 minutes or less, and most preferably 1 minute or less.
  • the temperature of the inorganic substrate during exposure of the inorganic substrate to the silane coupling agent is an appropriate temperature between -50 ° C and 200 ° C depending on the type of the silane coupling agent and the desired thickness of the silane coupling agent layer. It is preferable to control the temperature.
  • the film thickness of the silane coupling agent layer is extremely thin compared to the inorganic substrate, the easily peelable layer, the polymer film, etc., and is negligible from the viewpoint of mechanical design. In principle. At a minimum, a thickness on the order of a single molecular layer is sufficient. Generally, it is less than 400 nm, preferably 200 nm or less, more preferably 100 nm or less, more preferably 50 nm or less, still more preferably 10 nm or less in practical use. However, in the calculated region of 5 nm or less, the silane coupling agent layer may exist in a cluster shape rather than as a uniform coating film.
  • the film thickness of the silane coupling agent layer can be calculated from the ellipsometry method or the concentration and coating amount of the silane coupling agent solution at the time of coating.
  • Step A to form a silane coupling agent layer on an inorganic substrate to obtain a first laminate
  • Step B to prepare the easily peelable layer
  • It has at least a step C of forming the easily peelable layer on the first laminated body.
  • the step B is a step of preparing a second laminated body in which the easily peelable layer and the heat-resistant polymer film are laminated.
  • the step C may be a step of laminating the first laminated body and the second laminated body.
  • step A a silane coupling agent layer is formed on the inorganic substrate to obtain a first laminated body. Since the details of the method of forming the silane coupling agent layer on the inorganic substrate have already been described, the description thereof is omitted here.
  • step B an easily peelable layer is prepared. Since the method of preparing the easily peelable layer as a single substance has already been described, the description thereof is omitted here.
  • the step B may be a step of preparing a second laminated body in which the easily peelable layer and the heat-resistant polymer film are laminated.
  • a method for preparing the second laminate first, an easily peelable layer (polyamic acid film) before imidization is prepared, and then a polyamic acid for forming a polymer film is formed on the easily peelable layer before imidization.
  • the solution is applied and dried to form a polymer film (polyamic acid film) before imidization, and finally, imidization (heat treatment) is performed to make the easily peelable layer before imidization and the height before imidization.
  • imidization heat treatment
  • a method of imidizing the molecular film together to obtain a second laminated body in which the easily peelable layer and the heat-resistant polymer film are laminated can be mentioned.
  • the polyamic acid solution for forming the easily peelable layer is applied on the surface coated with the polyamic acid solution without drying (in the solution state).
  • a polyamic acid solution for forming a polymer film is applied, and both are dried to make the easily peelable layer before imidization and the polymer film before imidization laminated, and finally imidization (heating). Treatment) to imidize both the easy-release layer before imidization and the polymer film before imidization to obtain a second laminated body in which the easy-release layer and the heat-resistant polymer film are laminated. Can be mentioned.
  • step C the first laminated body and the easily peelable layer are bonded together.
  • the step C may be a step of laminating the first laminated body and the second laminated body. Specifically, the silane coupling agent layer formed on the inorganic substrate and the easily peelable layer or the second laminated body are pressed and bonded as a bonding surface.
  • the pressurization treatment may be performed, for example, in an atmospheric pressure atmosphere or in a vacuum while heating a press, a laminate, a roll laminate, or the like.
  • a method of pressurizing and heating in a flexible bag can also be applied. From the viewpoint of improving productivity and reducing the processing cost brought about by high productivity, pressing or roll laminating in an air atmosphere is preferable, and a method using rolls (roll laminating or the like) is particularly preferable.
  • the pressure is preferably 1 MPa to 20 MPa, more preferably 3 MPa to 10 MPa.
  • the temperature when pressurization and heating are performed at the same time is preferably 80 ° C. to 300 ° C., more preferably 100 ° C. to 250 ° C.
  • the polymer film is a polyimide film, if the temperature is too high, the polyimide film may be damaged, and if the temperature is too low, the adhesion tends to be weakened.
  • Examples of the process of simultaneously heating and pressurizing include high temperature roll laminating.
  • the temperature is high within the above range.
  • the heating / pressurizing time is preferably 1 to 60 seconds, more preferably 1 to 30 seconds.
  • the pressurization treatment can be performed in an atmospheric pressure atmosphere as described above, but it is preferable to perform the pressure treatment under vacuum in order to obtain a stable peel strength on the entire surface.
  • the degree of vacuum is sufficient with the degree of vacuum by a normal oil rotary pump, and about 10 Torr or less is sufficient.
  • a device that can be used for pressure treatment for example, "11FD” manufactured by Imoto Seisakusho can be used for pressing in a vacuum, and a roll-type film laminator in a vacuum or after vacuuming.
  • a film laminator that applies pressure to the entire surface of the glass at once with a thin rubber film
  • "MVLP" manufactured by Meiki Seisakusho can be used.
  • the pressurization process can be performed separately for the pressurization process and the heating process. In this case, only the pressurization process may be performed and the heating process may not be performed.
  • the pressurizing process is separated into a pressurizing process and a heating process, the polymer film and the inorganic substrate are added at a relatively low temperature (for example, a temperature of less than 120 ° C., more preferably 95 ° C. or lower). It is preferable to secure close contact between the two by applying pressure (preferably about 0.2 to 50 MPa).
  • the heating process is performed, the heating process is performed at a relatively high temperature (for example, 100 ° C.
  • the heating time is preferably 1 minute to 120 minutes, more preferably 5 minutes to 90 minutes.
  • the method for producing a laminate according to the present invention is not limited to this example.
  • a polyamic acid solution for forming an easily peelable layer is applied on the silane coupling agent layer, dried, and further, if necessary, high. Examples thereof include a method in which a polyamic acid solution for forming a molecular film is applied, dried, and then imidized to obtain a laminate.
  • an electronic device is formed on the polymer film of the laminate using existing equipment and processes for manufacturing electronic devices, and the polymer film or the easily peelable layer is peeled off from the laminate.
  • Flexible electronic devices can be made.
  • an electronic device is a wiring board having a single-sided, double-sided, or multi-layered structure for electrical wiring, an electronic circuit including active elements such as transistors and diodes, and passive devices such as resistors, capacitors, and inductors, and others.
  • Sensor elements that sense pressure, temperature, light, humidity, etc., biosensor elements, light emitting elements, liquid crystal displays, electrophoretic displays, self-luminous displays and other image display elements, wireless and wired communication elements, arithmetic elements, storage elements, MEMS element, solar cell, thin film, etc.
  • a device is formed on a polymer film or an easily peelable layer of a laminate produced by the above-mentioned method, and then the polymer film is peeled off from the inorganic substrate.
  • the method of peeling the polymer film or the easily peelable layer with the device from the inorganic substrate is not particularly limited, but the method of winding from the end with a tweezers or the like, making a cut in the polymer film, and applying an adhesive tape to one side of the cut portion.
  • a method of winding from the tape portion after sticking, a method of vacuum-adsorbing one side of the cut portion of the polymer film or the easily peelable layer, and then winding from that portion can be adopted.
  • the cut portion of the polymer film or the easily peelable layer is bent with a small curvature, stress is applied to the device at that portion and the device may be destroyed. Therefore, the curvature is as large as possible.
  • a method of making a cut in the polymer film or the easily peelable layer a method of cutting the polymer film or the easily peelable layer with a cutting tool such as a cutting tool, or a polymer film by relatively scanning a laser and a laminate.
  • a method of cutting the easily peelable layer a method of cutting the polymer film or the easily peelable layer by relatively scanning the water jet and the laminate, or a polymer film or a polymer film while slightly cutting to the glass layer by a semiconductor chip dicing device.
  • a method of cutting the easily peelable layer but the method is not particularly limited.
  • the flexible electronic device to be peeled off is the backplane of the display device
  • N- Colloidal silica is a dispersion of dimethylacetamide (DMAc) and colloidal silica (lubricant) dispersed in dimethylacetamide ("Snowtex (registered trademark) DMAC-ST-ZL” manufactured by Nissan Chemical Industries, Ltd.).
  • DMAc dimethylacetamide
  • Snowtex colloidal silica
  • ⁇ Preparation Example 2 Preparation of Polyamic Acid Solution 2> After nitrogen substitution in the reaction vessel equipped with a nitrogen introduction tube, a reflux tube and a stirring rod, 11.36 parts by mass of 4,4'-diaminobenzanilide (DABAN) and 11.32 parts by mass of 2,2' -A dispersion consisting of bis (trifluoromethyl) benzidine (TFMB), 21.1 parts by mass of N, N-dimethylacetamide (DMAc), and colloidal silica (lubricant) dispersed in dimethylacetamide (manufactured by Nissan Chemical Industries, Ltd.).
  • DABAN 4,4'-diaminobenzanilide
  • TFMB bis (trifluoromethyl) benzidine
  • DMAc N-dimethylacetamide
  • colloidal silica lubricant
  • ⁇ Preparation Example 3 Preparation of Polyamic Acid Solution 3> A container equipped with a nitrogen introduction tube, a thermometer and a stirring rod was replaced with nitrogen, and then 4,4'-diaminodiphenyl ether (ODA) was added. Next, DMAc was added to completely dissolve it, and then pyrolimetic acid anhydride (PMDA) was added to polymerize ODA and PMDA as monomers in DMAc at a molar ratio of 1/1, and the monomer charging concentration was 15. The mixture was adjusted to be mass% and stirred at 25 ° C. for 5 hours to obtain a brown viscous polyamic acid solution 3. The reduced viscosity ( ⁇ sp / C) was 2.1 dl / g.
  • ODA 4,4'-diaminodiphenyl ether
  • ⁇ Preparation Example 4 Preparation of Polyamic Acid Solution 4> After nitrogen substitution in the reaction vessel equipped with a nitrogen introduction tube, a reflux tube and a stirring rod, 22.72 parts by mass of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 21.1 parts by mass were added. N, N-dimethylacetamide (DMAc) and a dispersion obtained by dispersing colloidal silica (lubricant) in dimethylacetamide (“Snowtex (registered trademark) DMAC-ST-ZL” manufactured by Nissan Chemical Industries, Ltd.) are used as silica ( Lubricants) were added so that the total amount of polymer solids in the polyamic acid solution was 0.4% by mass, and the mixture was completely dissolved.
  • DMAc N-dimethylacetamide
  • lubricant colloidal silica
  • DMAC-ST-ZL dimethylacetamide
  • CBDA 1,2,3,4-cyclobutanetetracarboxylic acid unihydrate
  • ⁇ Preparation Example 5 Preparation of Polyimide Solution 1> While introducing nitrogen gas into a reaction vessel equipped with a nitrogen introduction tube, a Dean Stark tube and a reflux tube, a thermometer, and a stirring rod, 19.86 parts by mass of 4,4'-diaminodiphenyl sulfone (4,4') was introduced. -DDS), 4.97 parts by mass of 3,3'-diaminodiphenyl sulfone (3,3'-DDS) and 80 parts by mass of gamma butyrolactone (GBL) were added.
  • GBL gamma butyrolactone
  • ⁇ Manufacturing Example 1 Manufacture of Polyimide Film F1>
  • the polyamic acid solution 1 was coated on the non-slip material surface of the polyethylene terephthalate film A4100 (support manufactured by Toyobo Co., Ltd.) by adjusting the final film thickness to 15 ⁇ m using a comma coater.
  • the polyethylene terephthalate film A4100 passed through a hot air furnace, was wound up, and was dried at 100 ° C. for 10 minutes at this time.
  • the self-supporting polyamic acid film (green film) is peeled off from the support, passed through a pin tenter having a pin sheet on which pins are arranged, and the film end is gripped by inserting it into the pins, and the film does not break.
  • the pin sheet spacing is adjusted and transported so that unnecessary slack does not occur, and the film is heated at 200 ° C for 3 minutes, 250 ° C for 3 minutes, and 300 ° C for 6 minutes to carry out the imidization reaction. I made it progress.
  • the film was cooled to room temperature in 2 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain 500 m of a polyimide film F1 having a width of 450 mm.
  • ⁇ Manufacturing Example 3 Manufacture of Polyimide Film F3>
  • the polyamic acid solution 1 was coated on the non-slip material surface of the polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd.) by adjusting the final film thickness to 0.5 ⁇ m using a comma coater.
  • the polyethylene terephthalate film A4100 passed through the hot air furnace and was wound up, and at this time, it was dried at 100 ° C. for 10 minutes.
  • the polyamic acid solution 3 obtained in Production Example 3 was applied onto the dried product of the polyamic acid solution 1 so that the final film thickness was 15 ⁇ m. This was dried at 100 ° C. for 10 minutes. After drying, the self-supporting polyamic acid film is peeled off from the support, passed through a pin tenter having a pin sheet on which the pins are arranged, and the film end is gripped by inserting it into the pins so that the film does not break and The pin sheet spacing was adjusted so as not to cause unnecessary slack, and the film was transported, and heated at 200 ° C. for 3 minutes, 250 ° C. for 3 minutes, and 400 ° C.
  • the film was cooled to room temperature in 2 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain 100 m of a polyimide film F3 having a width of 450 mm.
  • ⁇ Manufacturing Example 5 Manufacture of Polyimide Film F5> The same as in Production Example 3 except that the polyimide solution 1 was used instead of the polyamic acid solution 3 and the heat treatment after gripping with a pin sheet was set to 200 ° C. for 3 minutes, 250 ° C. for 2 minutes, and 320 ° C. for 3 minutes. A polyimide film F5 was obtained in an amount of 100 m.
  • ⁇ Manufacturing Example 7 Manufacture of Polyimide Film F7>
  • the polyamic acid solution 1 obtained in Production Example 1 was applied to the non-slip material surface of the polyethylene terephthalate film A4100 (manufactured by Toyo Spinning Co., Ltd.) using a comma coater so that the final film thickness was 0.5 ⁇ m.
  • the polyamic acid solution 3 obtained in Production Example 3 was applied onto the polyamic acid solution 1 with a die coater so that the final film thickness was 15 ⁇ m. This was dried at 110 ° C. for 10 minutes.
  • the polyamic acid film that has obtained self-support after drying is peeled off from the A4100 film that has been used as a support, passed through a pin tenter having a pin sheet on which pins are arranged, and the film end is gripped by inserting it into the pins, and the film does not break.
  • the pin sheet spacing is adjusted and transported so that unnecessary slack does not occur, and the film is heated at 200 ° C for 3 minutes, 250 ° C for 3 minutes, and 400 ° C for 6 minutes to carry out the imidization reaction. I made it progress.
  • the film was cooled to room temperature in 2 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain 100 m of a polyimide film F7 having a width of 450 mm.
  • ⁇ Manufacturing Example 10 Manufacture of Polyimide Film F10>
  • the polyamic acid solution 1 was changed to the polyimide acid solution 1, and the heat treatment after gripping with the pin sheet was the same as in Production Example 1 except that the heat treatment was performed at 200 ° C. for 3 minutes, 250 ° C. for 2 minutes, and 320 ° C. for 3 minutes.
  • a polyimide film F10 was obtained in an amount of 100 m.
  • a glass substrate was prepared.
  • the glass substrate is 0.7 mm thick OA10G glass (manufactured by NEG) cut into a size of 100 mm ⁇ 100 mm.
  • the glass substrate used was washed with pure water, dried, and then irradiated with a UV / O3 irradiator (SKR1102N- 03 manufactured by LAN Technical) for 1 minute to dry wash.
  • a silane coupling agent layer was formed on the glass substrate. The method of applying the silane coupling agent to the glass substrate was carried out using the experimental apparatus shown in FIG. FIG.
  • the experimental apparatus includes a processing chamber (chamber) 6 connected to a gas introduction port 2, an exhaust port 8, and a chemical liquid tank (silane coupling agent tank) 3.
  • the chemical liquid tank (silane coupling agent tank) 3 is filled with a silane coupling agent, and the temperature is controlled by a hot water tank (water bath) 4 provided with a heater 5.
  • a gas introduction port 12 is connected to the chemical liquid tank (silane coupling agent tank) 3, and gas can be introduced from the outside. The gas flow rate is adjusted by the flow meter 1 connected to the gas introduction port 12.
  • the vaporized silane coupling agent in the chemical liquid tank 3 is extruded into the treatment chamber 6, and the silane coupling agent layer is placed on the glass substrate 7 arranged in the treatment chamber 6.
  • Adheres as. 150 g of 3-aminopropyltrimethoxysilane (silane coupling agent Shin-Etsu Chemical KBM903) was placed in a chemical solution tank 3 having a capacity of 1 L, and the outer water bath was warmed to 41 ° C. Then, the steam that came out was sent to the chamber together with clean dry air.
  • the gas flow rate was 25 L / min
  • the substrate temperature was 23 ° C.
  • the exposure time of the glass substrate was 5 minutes.
  • the temperature of the clean dry air was 23 ° C. and the humidity was 1.2% RH. Since the exhaust is connected to the negative pressure exhaust port, it is confirmed by the differential pressure gauge that the chamber has a negative pressure of about 10 Pa.
  • the polyimide film F1 was bonded onto the silane coupling agent layer to obtain a laminate according to Example 1.
  • the polyimide film F2 was bonded onto the silane coupling agent layer to obtain a laminate according to Example 2.
  • the polyimide film F9 was laminated on the silane coupling agent layer to obtain a laminate according to Comparative Example 1.
  • the polyimide film F10 was laminated on the silane coupling agent layer to obtain a laminate according to Comparative Example 2.
  • the polyimide film F11 was laminated on the silane coupling agent layer to obtain a laminate according to Comparative Example 3.
  • the size of the polyimide film to be bonded was 70 mm ⁇ 70 mm.
  • a laminator manufactured by MCK was used for bonding, and the bonding conditions were compressed air pressure: 0.6 MPa, temperature: 23 ° C., humidity: 55% RH, and laminating speed: 50 mm / sec.
  • the polyimide film F1 in Example 1 and the polyimide film F2 in Example 2 correspond to the easily peelable layer in the present invention.
  • Example 3 The laminates according to Examples 3 to 8 were obtained by the same method as the method for producing the laminates according to Examples 1, 2 and Comparative Examples 1, 2 and 3.
  • Example 3 the polyimide film F3 was bonded onto the silane coupling agent layer to obtain a laminate according to Example 3.
  • Example 4 the polyimide film F4 was bonded onto the silane coupling agent layer to obtain a laminate according to Example 4.
  • Example 5 the polyimide film F5 was bonded onto the silane coupling agent layer to obtain a laminate according to Example 5.
  • Example 6 the polyimide film F6 was bonded onto the silane coupling agent layer to obtain a laminate according to Example 6.
  • Example 7 the polyimide film F7 was bonded onto the silane coupling agent layer to obtain a laminate according to Example 7. Further, in Example 8, the polyimide film F8 was bonded onto the silane coupling agent layer to obtain a laminate according to Example 8.
  • the bonding was performed by using a polyimide surface made of a polyamic acid solution 1 or 2 of a two-layered polyimide film as a bonding surface with a silane coupling agent layer.
  • the layer formed from the polyamic acid solution 1 corresponds to the easily peelable layer of the present invention
  • the layer formed from the polyamic acid solution 3 corresponds to the polymer film of the present invention. do.
  • the layer formed from the polyamic acid solution 2 corresponds to the easily peelable layer of the present invention
  • the layer formed from the polyamic acid solution 3 corresponds to the polymer film of the present invention.
  • the layer formed from the polyimide solution 1 corresponds to the easily peelable layer of the present invention
  • the layer formed from the polyimide solution 1 corresponds to the polymer film of the present invention.
  • the layer formed from the polyamic acid solution 4 corresponds to the polymer film of the present invention. do.
  • the layer formed from the polyamic acid solution 1 corresponds to the easily peelable layer of the present invention
  • the layer formed from the polyamic acid solution 3 corresponds to the polymer film of the present invention. do.
  • the layer formed from the polyamic acid solution 2 corresponds to the easily peelable layer of the present invention
  • the layer formed from the polyamic acid solution 3 corresponds to the polymer film of the present invention. do.
  • the laminate obtained by producing the above laminate was heat-treated at 100 ° C. for 10 minutes in an atmospheric atmosphere. Then, the 90 ° initial peel strength between the inorganic substrate (glass substrate or silicon wafer) and the polyimide film was measured. The results are shown in Table 1.
  • the measurement conditions for the 90 ° initial peel strength are as follows. Peel the film at a 90 ° angle to the inorganic substrate. Measure 5 times and use the average value as the measured value. Measuring device; Shimadzu Autograph AG-IS Measurement temperature; room temperature (25 ° C) Peeling speed; 100 mm / min Atmosphere; Atmosphere measurement sample width; 2.5 cm

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  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Stratifié comprenant un substrat inorganique, une couche d'agent de couplage silane et une couche facilement pelable dans cet ordre. La couche facilement pelable possède une unité structurelle dérivée de dianhydride d'acide biphényltétracarboxylique et de diaminobenzanilide.
PCT/JP2021/025411 2020-11-27 2021-07-06 Stratifié WO2022113415A1 (fr)

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JP2000319421A (ja) * 1999-05-12 2000-11-21 Kanegafuchi Chem Ind Co Ltd ポリイミドフィルム
WO2005084948A1 (fr) * 2004-03-04 2005-09-15 Toray Industries, Inc. Film laminé en résine thermo-résistante, film multicouches avec couche métallique et dispositif semi-conducteur
JP2006068986A (ja) * 2004-09-01 2006-03-16 Toray Ind Inc 多層ポリイミドフィルム及びこれを用いた金属層付き積層フィルム
US20080214777A1 (en) * 2005-08-02 2008-09-04 Srs Technologies Heteropolymeric Polyimide Polymer Compositions
JP2009172941A (ja) * 2008-01-28 2009-08-06 Toray Ind Inc 金属層付き積層フィルムおよびこれを用いたフレキシブルプリント回路基板
CN102816431A (zh) * 2012-08-30 2012-12-12 江西先材纳米纤维科技有限公司 一种超细纤维多孔膜及其制备方法和应用
JP2013222520A (ja) * 2012-04-13 2013-10-28 Toray Ind Inc カラーフィルター層を有する有機エレクトロルミネッセンス表示装置
JP2019203117A (ja) * 2018-05-16 2019-11-28 東レ株式会社 ポリイミド前駆体樹脂組成物、ポリイミド樹脂組成物およびその膜状物、それを含む積層体、ならびにフレキシブルデバイス
JP2020500111A (ja) * 2017-01-31 2020-01-09 エルジー・ケム・リミテッド 可撓性基板製造用の積層体及びそれを用いた可撓性基板の製造方法
JP2020125466A (ja) * 2019-01-31 2020-08-20 Ｊｘｔｇエネルギー株式会社 ポリイミドアロイ、ポリイミドアロイ前駆体樹脂組成物、ポリイミドアロイ前駆体樹脂溶液、及び、ポリイミドアロイの製造方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000319421A (ja) * 1999-05-12 2000-11-21 Kanegafuchi Chem Ind Co Ltd ポリイミドフィルム
WO2005084948A1 (fr) * 2004-03-04 2005-09-15 Toray Industries, Inc. Film laminé en résine thermo-résistante, film multicouches avec couche métallique et dispositif semi-conducteur
JP2006068986A (ja) * 2004-09-01 2006-03-16 Toray Ind Inc 多層ポリイミドフィルム及びこれを用いた金属層付き積層フィルム
US20080214777A1 (en) * 2005-08-02 2008-09-04 Srs Technologies Heteropolymeric Polyimide Polymer Compositions
JP2009172941A (ja) * 2008-01-28 2009-08-06 Toray Ind Inc 金属層付き積層フィルムおよびこれを用いたフレキシブルプリント回路基板
JP2013222520A (ja) * 2012-04-13 2013-10-28 Toray Ind Inc カラーフィルター層を有する有機エレクトロルミネッセンス表示装置
CN102816431A (zh) * 2012-08-30 2012-12-12 江西先材纳米纤维科技有限公司 一种超细纤维多孔膜及其制备方法和应用
JP2020500111A (ja) * 2017-01-31 2020-01-09 エルジー・ケム・リミテッド 可撓性基板製造用の積層体及びそれを用いた可撓性基板の製造方法
JP2019203117A (ja) * 2018-05-16 2019-11-28 東レ株式会社 ポリイミド前駆体樹脂組成物、ポリイミド樹脂組成物およびその膜状物、それを含む積層体、ならびにフレキシブルデバイス
JP2020125466A (ja) * 2019-01-31 2020-08-20 Ｊｘｔｇエネルギー株式会社 ポリイミドアロイ、ポリイミドアロイ前駆体樹脂組成物、ポリイミドアロイ前駆体樹脂溶液、及び、ポリイミドアロイの製造方法

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