JP3439262B2 - Film adhesive having improved properties at high temperature and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film adhesive which has both heat resistance and low-temperature processability and is excellent in adhesiveness to silicon substrates and metals suitable for electronic applications, especially semiconductor mounting materials, and a method for producing the same. It is a thing.

[0002]

2. Description of the Related Art In recent years, while semiconductor chips have become larger due to higher functionality and larger capacity, the size of the package has not changed from the conventional one due to restrictions on printed circuit design, demand for miniaturization of electronic equipment, or a rather small external shape. Is being requested. In response to this tendency, some new mounting methods have been proposed for high density and high density mounting of semiconductor chips. One is a COL that mounts a chip on a lead frame without a die pad proposed for memory devices.
(Chip-on-lead) structure and LOC (lead-on-chip) structure in which leads are mounted on a chip, which is a development of the structure. On the other hand, the logic element has a multi-layered lead frame structure in which a power source and a ground are provided in different frames, and a metal plate for heat dissipation is multilayered. According to these, it is possible to rationalize the wiring in the chip and wire bonding, to speed up the signal by shortening the wiring, to dissipate heat generated due to the increase in power consumption, and to reduce the element size.

In this new mounting mode, there are bonding interfaces of the same kind and different materials such as the semiconductor chip and the lead frame, the lead frame and the plate, and the lead frames, and the bonding reliability thereof has a great influence on the reliability of the element. . Not only the reliability of withstanding the process temperature at the time of assembling the element, but also the bonding reliability at the time of moisture absorption, heat and humidity. Further, the workability of bonding is also an important item.

Conventionally, a paste-like adhesive or a heat-resistant base material coated with an adhesive has been used for these adhesions. Epoxy resin-based, acrylic resin-based, and rubber-phenol resin-based thermosetting resins are used as adhesives, but there are many ionic impurities, heat curing requires high temperature and long time, and productivity is poor, heat curing It is hard to say that the requirements for a highly reliable adhesive such as a large amount of volatile components that contaminate leads and high hygroscopicity are satisfied, and no satisfactory material is found. There is a demand for the development of adhesives suitable for new mounting forms. One of such methods is a hot-melt type film adhesive using a polyimide resin (see JP-A-5-105850, 112760, 112761). A hot-melt type adhesive can be thermocompression-bonded to an adherend in a short time, and a heat-curing step after adhesion is not required, which is considered to greatly contribute to improvement in productivity and reliability. . However, since it is a hot-melt type, if the glass transition temperature of the adhesive resin is high, it takes a very high temperature for processing, and there is a great possibility that the adherend is thermally damaged. On the other hand, if the glass transition temperature is lowered in order to impart low-temperature processability, there is a problem that the heat resistance is lowered, and thus the reliability is lowered.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been earnestly studied in order to obtain a film adhesive which can be bonded at a low temperature in a short time and is excellent in heat resistance. As a result, an epoxy compound and the epoxy compound are added to a polyimide resin having a specific structure. The present inventors have found that the above problems can be solved by adding a compound having an active hydrogen group capable of reacting with the compound, and have reached the present invention.

[0006]

The present invention provides a polyimide resin 100 having a glass transition temperature of 350 ° C. or lower and soluble in an organic solvent.
An adhesive resin component mainly composed of 5 parts by weight, 5 to 100 parts by weight of an epoxy compound having at least two epoxy groups in one molecule, and 0.1 to 20 parts by weight of a compound having an active hydrogen group capable of reacting with the epoxy compound. The present invention relates to a heat-resistant film adhesive and a method for producing the same.

The component (A) polyimide resin, which is an essential component of the adhesive resin of the present invention, is 4,4'-oxydiphthalic acid dianhydride. From other acid components 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride and ethylene glycol bistrimellitic dianhydride One or two or more tetracarboxylic dianhydrides selected from the group can be used in combination within a range not exceeding 50 mol% of the acid component. The main amine components are the diaminosiloxane compound represented by the general formula (1) and 1,3-bis (3-aminophenoxy) benzene.

[0008]

[Chemical 1] (In the formula, R ₁ and R ₂ : a divalent aliphatic group or an aromatic group having 1 to 4 carbon atoms R ₃ , R ₄ , R ₅ and R ₆ : a monovalent aliphatic group or an aromatic group k : Integer of 1 to 20)

Other amine components include, for example, 1,4-bis (3
-Aminophenoxy) benzene, 1,4-bis (2- (4-aminophenyl) propyl) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2-bis (4- (4-aminophenoxy) ) Phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenoxy) hexafluoropropane, bis-4- (4-aminophenoxy) Phenyl sulfone, bis-4- (3-aminophenoxy) phenyl sulfone and the like can be used alone or in combination so long as they do not exceed 50 mol% of the diamine component.

Further, it is more preferable to use the diaminosiloxane compound in an amount of 5 to 50 mol% of the total amount of the diamine component. If it is less than 5 mol% of the total amount of the diamine component, the solubility in an organic solvent will decrease, and if it exceeds 50 mol%, the glass transition temperature will significantly decrease, causing a problem in heat resistance. Specifically as the siloxane compound represented by the general formula (1),
Α, ω-bis (3-aminopropyl) polydimethylsiloxane (APPS) represented by the following general formula (2) is preferable, and particularly when the value of k is 4 to 10, the glass transition temperature is
It is preferable in terms of adhesiveness and heat resistance. These siloxane compounds may be used alone or in combination of two or more. In particular, blending k = 1 with the above k = 4 to 10 is preferable for applications where importance is placed on adhesiveness.

[0011]

[Chemical 2] (In the formula, k: an integer of 1 to 20)

The equivalent ratio of the acid component and the amine component in the polycondensation reaction is an important factor that determines the molecular weight of the polyamic acid obtained. It is well known that there is a correlation between polymer molecular weight and physical properties, especially number average molecular weight and mechanical properties. The larger the number average molecular weight, the better the mechanical properties. Therefore, in order to obtain practically excellent strength, it is necessary that the polymer has a high molecular weight to some extent. In the present invention,
The equivalent ratio r of the acid component and the amine component is more preferably 0.900 ≤ r ≤ 1.060, and more preferably 0.975 ≤ r ≤ 1.025. However, r = [equivalent number of all acid components] / [equivalent number of all amine components]. r is 0.
If it is less than 900, the molecular weight is low and it becomes brittle, so the adhesive strength becomes weak. On the other hand, if it exceeds 1.06, unreacted carboxylic acid may be decarboxylated during heating to cause gas generation and foaming, which is not preferable.

In the present invention, addition of a dicarboxylic acid anhydride or a monoamine for controlling the molecular weight of the polyimide resin is not particularly hindered if the acid / amine molar ratio is within the above range.

The reaction between the tetracarboxylic dianhydride and the diamine is carried out by a known method in an aprotic polar solvent. The aprotic polar solvent is N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMA
C), N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), diglyme, cyclohexanone,
1,4-dioxane (1,4-DO) and the like. The aprotic polar solvent may be used alone or in combination of two or more. At this time, a non-polar solvent compatible with the aprotic polar solvent may be mixed and used. Aromatic hydrocarbons such as toluene, xylene and solvent naphtha are often used. The proportion of the non-polar solvent in the mixed solvent is preferably 30% by weight or less. This is because if the amount of the nonpolar solvent is 30% by weight or more, the solubility of the solvent may decrease and polyamic acid may precipitate. The reaction between the tetracarboxylic dianhydride and the diamine is carried out by dissolving the well-dried diamine component in the dehydrated and purified reaction solvent described above, and the ring closure rate is 98%, more preferably 99% or more of the well-dried tetracarboxylic dianhydride. Anhydrous is added to drive the reaction.

The polyamic acid solution thus obtained is subsequently heated to dehydration and cyclization in an organic solvent to give an imidized polyimide. Since the water generated by the imidization reaction interferes with the ring-closing reaction, an organic solvent that is not compatible with water is added to the system to azeotropically evaporate it and use a device such as a Dean-Stark tube to remove it from the system. To discharge. Dichlorobenzene is known as an organic solvent which is incompatible with water, but for electronics use, the aromatic hydrocarbon is preferably used since chlorine components may be mixed therein. Further, the use of compounds such as acetic anhydride, β-picoline and pyridine as a catalyst for the imidization reaction is not hindered.

In the present invention, the higher the degree of imide ring closure, the better, and if the imidization ratio is low, imidization occurs due to heat during use and water is generated, which is not preferable. Therefore, 95% or more, more preferably 98% or more. It is desirable that the imidization ratio of is achieved.

In the present invention, an epoxy compound or a compound having an active hydrogen group capable of reacting with the epoxy compound may be added to the obtained polyimide solution as it is, and a resin varnish may be prepared and coated on a support. It is preferable that the polyimide solution is put into a poor solvent to reprecipitate and precipitate the polyimide resin to remove unreacted monomers and to perform purification. A purified and dried polyimide resin, an epoxy compound, and a compound having an active hydrogen group capable of reacting with the epoxy compound are dissolved in an organic solvent to prepare a coating varnish. The solvent used at this time may be the same as the reaction solvent, but it is preferable to select a solvent having a low boiling point, preferably a boiling point of 200 ° C. or less, in consideration of workability in the coating and drying step. As a solvent of 200 ℃ or less, in the present invention, as a ketone solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, as an ether solvent, 1,4-dioxane, tetrahydrofuran, diglyme, as an amide solvent , N, N-dimethylformamide, N, N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

The component (B) epoxy compound used in the adhesive resin of the present invention is not particularly limited as long as it has at least two epoxy groups in one molecule, but it may be used as a solvent for the polyimide resin. Those having good solubility are preferred. Examples thereof include bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, phenol novolac type epoxy resin, and biphenyl type epoxy resin.

The compounding amount of the epoxy compound is the component (A).
5-100 parts by weight per 100 parts by weight of polyimide resin, especially 1
It is preferably in the range of 0 to 70 parts by weight. If it is less than 5 parts by weight, the effect of adding an uncured epoxy compound to lower the softening temperature of the resin composition and improving the low-temperature processability is unlikely to appear, and if it exceeds 100 parts by weight, the heat resistance of the polyimide resin is impaired. Absent.

Component (C) used in the adhesive resin of the present invention is a compound having an active hydrogen group capable of reacting with the epoxy compound, which is a polyimide resin of component (A) or component (B).
It is preferable that the compatibility with the epoxy compound and the solubility of the polyimide resin in the solvent are good. For example, resole,
Examples include novolak and amine compounds. The mixing ratio of the component (C) is 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polyimide resin of the component (A). If the amount is less than 0.1 parts by weight, it is difficult to control the resin flow when the elastic modulus of the resin at high temperature is reduced. If it exceeds 20 parts by weight, a gel is likely to be formed in a resin solution state, processability is impaired, and heat resistance of the resin composition is impaired, which is not preferable.

The heat-resistant resin composition of the present invention may contain a fine inorganic filler as long as the processability and heat resistance are not impaired.

If necessary, various additives such as a leveling agent, a leveling agent, and a defoaming agent can be added to the resin varnish for providing surface smoothness. Further, an aromatic hydrocarbon solvent can be used within a range in which the solvent is uniformly dissolved in order to control the evaporation rate of the solvent.

In the present invention, the resin varnish is used as a film adhesive, which is obtained by casting or coating a resin varnish. For example, a heat-resistant film base material is used as a support, and a film layer is similarly formed on one side or both sides thereof. To form a film adhesive with the support, rolls, metal sheets,
Form a film on a release sheet such as a polyester sheet with a flow coater, roll coater, etc.,
It can be obtained by a method such as heating, drying and peeling to obtain a film adhesive.

The heat-resistant film base material used in the present invention is that the polyimide resin film has a small coefficient of thermal expansion and is excellent in dimensional stability with respect to temperature changes, is flexible and easy to handle, and is made of the resin of the present invention. Is preferable because it has excellent adhesion. In particular, a polyimide resin having a glass transition temperature of 350 ° C or higher is excellent in workability and stability in the step of drying the coating varnish.

For coating and drying the resin varnish, an apparatus in which coating equipment such as a flow coater or roll coater and a hot air drying furnace are combined can be used. After coating the resin varnish on the support, the resin varnish is introduced into a hot air drying oven and dried at a temperature and an air volume sufficient to vaporize the solvent of the varnish.

The method of using the film adhesive of the present invention is not particularly limited, but the film adhesive can be used as an adhesive tape by thermocompression bonding with a heat block heated to a predetermined shape and heated. .

[0027]

[Function] The film adhesive of the present invention has a main acid component of 4,
4'-oxydiphthalic acid dianhydride, the main amine component of which is composed of a diaminosiloxane compound represented by general formula (1) and 1,3-bis (3-aminophenoxy) benzene, soluble in organic solvents And 5 to 100 parts by weight of an epoxy compound having at least two epoxy groups in one molecule and 100 parts by weight of a polyimide resin having a glass transition temperature of 350 ° C. or less, and an active hydrogen group capable of reacting with the epoxy compound. 0.1 to 20 parts by weight of a compound having the following is included as a main resin component. The apparent glass transition temperature of this resin is lower than the glass transition temperature of the main component polyimide resin, and the low temperature processability is improved. On the other hand, the adhesive strength in the temperature range higher than the glass transition temperature is higher than that of the polyimide resin, and the physical properties in the high temperature area are improved such that peeling is not observed even when a thermal shock such as IR reflow is applied. Although there is a part where the detailed mechanism for this unique phenomenon is not yet clear, a low molecular weight product obtained by reacting an epoxy compound and a compound having an active hydrogen group capable of reacting with the epoxy compound is a polyimide resin having a specific structure. On the other hand, it acts as a plasticizer and lowers the elastic modulus in a temperature range lower than the glass transition temperature of the polyimide resin, thus improving workability at low temperature such as adhesiveness and processability. On the other hand, in a temperature range higher than the glass transition temperature, it is considered that a three-dimensional network structure is formed by the applied heat and the fluidity of the polyimide resin is lowered, and thus the heat resistance of the polyimide resin is maintained or improved. By the above mechanism, both low temperature processability and heat resistance reliability at high temperature can be achieved. Further, it can be bonded in an extremely short time as compared with a thermosetting adhesive which involves a chemical reaction. By processing into a tape shape, the workability of bonding and the dimensional accuracy of the bonded portion can be made excellent. The present invention is described in detail below with reference to examples, but the present invention is not limited to these examples.

[0028]

【Example】

(Synthesis of Polyimide Resin PI-1) In a four-necked flask equipped with a dry nitrogen gas introduction tube, a cooler, a thermometer, and a stirrer,
Add 674 g of dehydrated and purified NMP, and stir vigorously for 10 minutes while flowing nitrogen gas. Next, 61.391 g (0.210 mol) of 1,3-bis (3-aminophenoxy) benzene (APB),
2,2-bis (4- (4-aminophenoxy) phenyl) propane (BAPP) 18.473 g (0.045 mol), α, ω-bis (3-aminopropyl) polydimethylsiloxane (APPS, formula (2)) 37.665 g (average molecular weight 837, 0.045 mol) is added, the system is heated to 60 ° C., and stirred until uniform. After uniform dissolution, the system was cooled to 5 ° C in an ice-water bath, and 93.067 g (0.300 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) was added as a powder over 15 minutes, and then for 3 hours. Stirring was continued. During this time, the flask was kept at 5 ° C.

Thereafter, the nitrogen gas introducing pipe and the cooler were removed,
A Dean-Stark tube filled with xylene was attached to the flask, and 168 g of xylene was added to the system. Instead of the oil bath, the system was heated to 175 ° C. and the water generated was removed from the system. After heating for 4 hours, generation of water from the system was not observed. After cooling, this reaction solution was poured into a large amount of methanol to precipitate a polyimide resin. After filtering the solids, 80
195.22 g (yield 92.7
%) Solid resin was obtained. When the infrared absorption spectrum was measured by the KBr tablet method, it was found to be 5.6
Absorption of μm was observed, but 6.06 μm derived from amide bond
It was confirmed that the resin was almost 100% imidized.

The polyimide resin thus obtained has a glass transition temperature of 151 ° C., a tensile elastic modulus of 211 kgf / mm ² , dimethylformamide (DMF), and 1,4-dioxane (1,4-
It was confirmed that it was well dissolved in DO).

(Synthesis of Polyimide Resins PI-2 and PI-3) PI-2 and PI-3 were obtained in the same manner as the synthesis of the polyimide resin PI-1. Table 1 shows the physical properties of the obtained polyimide resins PI-1, PI-2 and PI-3.

[0032]

[Table 1]

BTDA and APDS in the column of monomer are 3,
3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 1,
Represents 3-bis (3-aminopropyl) tetramethyldisiloxane (k = 1 in formula (2)).

S in the solubility column indicates that the compound is soluble in the corresponding solvent. The glass transition temperature was determined by DSC measurement. The tensile test was performed at room temperature and a tensile speed of 5 mm / min. Young's modulus was determined by a viscoelastic spectrometer.

(Example 1) (Preparation of coating varnish) 100 g of polyimide resin PI-1 and 355 g of DMF were placed in a glass flask and thoroughly stirred at room temperature to completely dissolve the polyimide. After uniform dissolution, bisphenol A type epoxy compound (Epicoat 8
28, 40 g of Yuka Shell Epoxy Co., Ltd. was added and stirred at room temperature for 2 hours. Then, after confirming that the resin was uniformly dissolved, 5.0 g of a resole resin (PR-50781, manufactured by Sumitomo Dures Co., Ltd.) was gradually added while stirring the system.
Subsequently, the mixture was stirred for 2 hours to prepare a heat resistant resin solution. The solution composition did not gel even after standing at room temperature for 5 days and remained in a uniform solution state.

(Production of Heat-Resistant Film Adhesive) The above-mentioned varnish was applied to one side of a polyimide film (trade name Upilex SGA, thickness 50 μm, Ube Industries, Ltd.) with a reverse roll coater to give an adhesive layer having a thickness of An adhesive tape of 30 μm was obtained. Drying temperature is up to 200 ° C and drying time is 15
It was a minute. A test piece was prepared by thermocompression-bonding this adhesive tape to a 42 alloy plate (heat-pressing for 2 seconds at 250 ° C., releasing pressure, and annealing for 30 seconds at 250 ° C. The pressure applied to the adhesive surface is the gauge pressure and the adhesive area. Calculation result from 4kgf / cm ²
Met. ), And the results of measuring 180 degree peel strength with a tensile tester are shown in Table 2. The adhesive strength was determined by measuring 180 degree peel strength at room temperature after treating with normal condition and pressure cooker (125 ° C., 48 hours, 100% saturation) (pulling speed 50 mm / min). On the fractured surface of the test piece, the adhesive resin layer was cohesively destroyed and no foaming was observed.

(Example 2) The above-mentioned varnish was applied to a biaxially stretched polyester film (trade name: Diamond foil, thickness 50 µm, manufactured by Mitsubishi Rayon Co., Ltd.) with a reverse roll coater, and after drying, peeled from the polyester film, 30 μm
A uniform monolayer film adhesive without a support of thickness was obtained.
Peeling was easy and there was no particular problem. 4 as in Example 1
Table 2 shows the results of adhesion to the plate of 2 alloy.

(Examples 3 to 5) In the same manner as in Examples 1 and 2, coating varnishes were prepared with the formulations shown in Table 2 to obtain film adhesives. Table 2 shows the obtained evaluation results.

[0039]

[Table 2]

S in the solubility column indicates that the compound is soluble in the corresponding solvent. The glass transition temperature was determined by DSC measurement. The tensile test was performed at room temperature and a tensile speed of 5 mm / min. Young's modulus was determined by a viscoelastic spectrometer. Regarding the component (B) epoxy compound used, YX
-4000H is a biphenyl type epoxy compound Epicoat YX-4000H, manufactured by Yuka Shell Epoxy Co., Ltd., EO
CN-1020 is a phenol novolac type epoxy compound EOCN-1020, manufactured by Nippon Kayaku Co., Ltd., respectively. Regarding the component (C) used, PR-507
81, 175, 53647 are manufactured by Sumitomo Dures Co., Ltd.

(Comparative Examples 1, 2, 3) Polyimide resin PI
-1, PI-2 and PI-3 were applied on one surface of a polyimide film (Upilex) to obtain a film adhesive. The adhesive strength with the 42 alloy plate was measured in the same manner as in the example, and the results are shown in Table 3.

(Comparative Example 4) Polyimide resin PI-1, 10
The adhesive strength of an adhesive tape obtained from a resin prepared only with 0 g and Epicoat 828, 20 g was measured in the same manner as in the example, and the results are shown in Table 3.

[0043]

[Table 3]

From the results shown in Tables 2 and 3, the adhesive strength of the film adhesives of the examples was slightly decreased even after the moisture absorption and heating, but the adhesive strength of the films of the comparative polyimide resin only was normal. Compared to the above, the value after heating by moisture absorption is significantly decreased. From the above, it is shown that the present invention can provide a film adhesive excellent in heat resistance and molding processability.

[0045]

According to the present invention, it is possible to provide a highly reliable film adhesive having both heat resistance and molding processability. Since it is soluble in a low boiling point solvent, it is possible to almost completely eliminate the residual solvent, and since it has already been imidized, a high temperature process for imidization is not required during processing and no water is generated. Since it can be used as a tack-free film, it is very effective when continuous workability and a clean environment are required. Therefore, it is industrially extremely useful as a material for electronics that requires high reliability and heat resistance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09J 179/08 C09J 179/08 (58) Fields investigated (Int.Cl. ⁷ , DB name) C09J 7/00 C08G 59/40 C08G 77/455 C09J 7/02 C09J 163/00 C09J 179/08

Claims (5)

(57) [Claims] 1. A main acid component (A) is 4,4′-oxydiphthalic dianhydride, and a main amine component is a diaminosiloxane compound represented by the general formula (1) and 1,3-bis.
Polyimide resin consisting of (3-aminophenoxy) benzene, soluble in organic solvents and having a glass transition temperature of 350 ° C or less 1
00 parts by weight, (B) 5 to 100 parts by weight of an epoxy compound having at least two epoxy groups in one molecule, and (C) a compound having an active hydrogen group capable of reacting with the epoxy compound.
A heat resistant film adhesive containing 0.1 to 20 parts by weight as a main component. [Chemical 1] (In the formula, R ₁ and R ₂ : a divalent aliphatic group or an aromatic group having 1 to 4 carbon atoms R ₃ , R ₄ , R ₅ and R ₆ : a monovalent aliphatic group or an aromatic group k : Integer of 1 to 20) 2. The heat-resistant film adhesive according to claim 1, wherein the component (A) is a polyimide resin containing the diaminosiloxane compound represented by the general formula (1) in an amount of 5 to 50 mol% of the total amount of the amine components. . 3. (A) The main acid component is 4,4′-oxydiphthalic dianhydride, and the main amine component is a diaminosiloxane compound represented by the general formula (1) and 1,3-bis.
Polyimide resin consisting of (3-aminophenoxy) benzene, soluble in organic solvents and having a glass transition temperature of 350 ° C or less 1
5 to 100 parts by weight of (B) an epoxy compound having at least two epoxy groups in one molecule, relative to 00 parts by weight,
(C) A solution of a heat-resistant resin composition containing 0.1 to 20 parts by weight of a compound having an active hydrogen group capable of reacting with the epoxy compound as a main component is cast on one side or both sides of a support. A method for producing a heat-resistant film adhesive characterized by the above. 4. The heat-resistant film adhesive according to claim 3, wherein the component (A) is a polyimide resin containing a diaminosiloxane compound represented by the general formula (1) in an amount of 5 to 50 mol% of the total amount of amine components. Manufacturing method. 5. The heat-resistant film adhesive according to claim 3, which is obtained by casting on a support using an organic solvent having a boiling point of 200 ° C. or lower, drying and peeling from the support. Production method.