JP2010254947A - Polyimide-based material, film and composition, and method of producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide-based material, and a film and a composition made of the polyimide-based material which are excellent in water resistance while maintaining heat resistance, and to provide a method for producing the film and the composition. <P>SOLUTION: The polyimide-based material is made of a polyamic acid and/or polyimide resin which is obtained by reacting at least one kind of acyl compound selected from a group consisting of diamine compounds (A) including the following (a-1), (a-2) components, aliphatic and/or alicyclic tetracarboxylic acid dianhydrides (B) and these reactive derivatives. Further, the film and the composition made of the polyimide-based material are disclosed and the method for producing the film and the composition. Therein, (a-1) is 10 to 60 mass% of silicone diamine having a number-average molecular weight calculated from the amine value, of 500 to 10,000, and (a-2) is 30 to 90 mass% (therein, the total amount of diamine compound is 100 mass%) of at least one kind of compound selected from aliphatic diamines and alicyclic diamines. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel polyimide-based material, a composition containing the material, a film made of the material, and a method for producing the film.

In general, wholly aromatic polyimides obtained by reacting aromatic tetracarboxylic dianhydrides with aromatic diamines are due to molecular rigidity, resonance stabilization of molecules, and strong chemical bonds. Excellent heat resistance, mechanical properties, electrical properties, oxidation resistance and hydrolysis resistance, and in fields such as electricity, batteries, automobiles, and aerospace industries, films, coating agents, molded parts, insulating materials As widely used as.
However, for example, wholly aromatic polyimide films represented by Kapton (trade name, registered trademark, manufactured by Toray DuPont) require a heat treatment at a high temperature to be formed into a film shape, so that the process load is high. Therefore, there is a problem that use as an optical material is limited. Specifically, the polyimide forming the film has low solubility in an organic solvent, and the film cannot be formed using the polyimide as it is. Therefore, after using the organic solvent solution of the polyamic acid which is the said precursor of the polyimide, and making it into a film-like coating film by the application | coating to a board | substrate, etc., this coating film is heat-processed at about 400 degreeC high temperature, It is necessary to imidize the polyamic acid therein to obtain a film made of polyimide.
In order to solve such problems, various types of polyimides have been proposed in which non-coloring properties and transparency are improved and solubility in an organic solvent is imparted to improve moldability. For example, Patent Document 1 proposes an all alicyclic polyimide resin composed of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and an alicyclic diamine.

JP 2005-15629 A

However, although all alicyclic polyimides described in Patent Document 1 are excellent in transparency, they have a problem that they are inferior in water resistance because of high imide group concentration and high water absorption.
Then, an object of this invention is to provide the film and composition which consist of a polyimide-type material which is excellent in water resistance, maintaining heat resistance, and this polyimide-type material, and its manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventor has (A) a silicone diamine having a specific number average molecular weight, and a diamine containing at least one compound selected from an aliphatic diamine and an alicyclic diamine in a specific ratio. A polyimide-based material comprising a polyamic acid and / or a polyimide resin obtained by reacting a compound with (B) an aliphatic and / or alicyclic tetracarboxylic dianhydride, and the object of the present invention We have found that this can be achieved and have completed the present invention.

That is, the present invention provides the following [1] to [8].
[1] (A) A diamine compound containing the following components (a-1) and (a-2), (B) an aliphatic and / or alicyclic tetracarboxylic dianhydride, and a reactive derivative thereof. A polyimide-based material comprising a polyamic acid and / or a polyimide resin obtained by reacting at least one acyl compound selected from the group.
(A-1) Silicone diamine having a number average molecular weight of 500 to 10,000 calculated by amine value 10 to 60% by mass
(A-2) 30 to 90% by mass of at least one compound selected from aliphatic diamines and alicyclic diamines
(However, the total amount of the diamine compound is 100% by mass.)
[2] The polyimide material according to [1], wherein the silicone diamine is a compound represented by the following formula (1).

（式中、複数あるＲ^１は、各々独立に、アルキル基、シクロアルキル基、またはアリール基、アルコキシ基を示し、複数あるＲ^２は、各々独立に、メチレン基、炭素数２〜１０のアルキレン基、またはフェニレン基を示し、ｎは１〜１００の整数を表す。）
［３］ アミン価により計算したシリコーンジアミンの数平均分子量が３，０００〜８，０００である、上記［１］または［２］に記載のポリイミド系材料。
［４］ 上記［１］〜［３］のいずれかに記載のポリイミド系材料、及び有機溶媒を含有するポリイミド系樹脂組成物。
［５］ 上記［１］〜［４］のいずれかに記載のポリイミド系材料からなるフィルム。
［６］ 光学部材用である上記［５］に記載のフィルム。
［７］ プリント配線用基板用である上記［５］に記載のフィルム。
［８］ 上記［５］〜［７］のいずれかに記載のフィルムの製造方法であって、上記（Ａ）シリコーンジアミンと上記（Ｂ）脂肪族及び／又は脂環族テトラカルボン酸二無水物とを反応させて得られるポリアミック酸及び／又はポリイミドと、有機溶媒とを含む溶液を、基板上に塗布して塗膜を形成する工程と、該塗膜から前記溶媒を蒸発させることにより除去してフィルムを得る工程とを含む、フィルムの製造方法。

(In the formula, a plurality of R ^{1 s} each independently represent an alkyl group, a cycloalkyl group, or an aryl group or an alkoxy group, and a plurality of R ^{2 s} each independently represent a methylene group or a C 2-10 alkylene) A group or a phenylene group, and n represents an integer of 1 to 100.)
[3] The polyimide material according to [1] or [2] above, wherein the number average molecular weight of the silicone diamine calculated based on the amine value is 3,000 to 8,000.
[4] A polyimide resin composition containing the polyimide material according to any one of [1] to [3] above and an organic solvent.
[5] A film comprising the polyimide material according to any one of [1] to [4].
[6] The film according to [5], which is for an optical member.
[7] The film according to [5], which is for a printed wiring board.
[8] The method for producing a film according to any one of [5] to [7], wherein (A) the silicone diamine and (B) the aliphatic and / or alicyclic tetracarboxylic dianhydride. A step of applying a solution containing polyamic acid and / or polyimide obtained by reacting with an organic solvent on a substrate to form a coating film, and removing the solvent from the coating film by evaporating the solvent. And obtaining a film.

The polyimide material comprising the polyamic acid and / or polyimide (hereinafter also referred to as “polyimide”) of the present invention comprises at least one compound selected from silicone diamine having a specific molecular weight, and aliphatic diamine and alicyclic diamine. A film and composition comprising a polyimide-based material having excellent heat resistance and water resistance because a diamine compound and aliphatic and / or alicyclic tetracarboxylic dianhydride contained at a specific ratio are reacted. You can get things.
Moreover, the polyimide of this invention has the outstanding solubility with respect to the organic solvent, and it can dissolve in an organic solvent as it is, and can form a film. In this case, an organic solvent solution containing the polyimide or the like is applied to a substrate or the like to form a coating film, and then heated at a temperature at which the solvent in the coating film evaporates. For example, an organic solvent solution containing polyamic acid Since it is not necessary to perform heat treatment at a high temperature exceeding 400 ° C. as in the case of thermal imidization using, a reduction in process load can be achieved. Moreover, when the polyimide of the present invention is cured and the solvent is removed, the amount of residual solvent in the cured product can be reduced.

The polyimide-based material of the present invention comprises (A) a specific molecular weight silicone diamine, and a diamine compound containing a specific proportion of at least one compound selected from an aliphatic diamine and an alicyclic diamine, and (B) an aliphatic and / or fat. A polyimide material comprising a polyamic acid and / or a polyimide resin obtained by reacting at least one acyl compound selected from the group consisting of a cyclic tetracarboxylic dianhydride and a reactive derivative thereof It is based on.
First, the diamine compound of the present invention will be described.
[(A) component]
The diamine compound used in the present invention includes the following components (a-1) and (a-2).
(A-1) Silicone diamine having a number average molecular weight of 500 to 10,000 calculated by amine value 10 to 60% by mass
(A-2) 30 to 90% by mass of at least one compound selected from aliphatic diamines and alicyclic diamines
(However, the total amount of the diamine compound is 100% by mass.)

  The component (a-1), which is a diamine compound used in the present invention, is a silicone diamine having a number average molecular weight of 500 to 10,000 calculated by an amine value. The silicone diamine is preferably a compound represented by the following formula (1).

（式中、複数あるＲ^１は、各々独立に、アルキル基、シクロアルキル基、またはアリール基、アルコキシ基を示し、Ｒ^２は、各々独立に、メチレン基、炭素数２〜１０のアルキレン基、またはフェニレン基を示し、ｎは１〜１００の整数を表す。）
式中、Ｒ^１としては、アルキル基、シクロアルキル基、またはアリール基、アルコキシ基が挙げられる。アルキル基としては、炭素数１〜１０のアルキル基であることが好ましく、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基等が挙げられる。シクロアルキル基としては、炭素数３〜１０のシクロアルキル基であることが好ましく、具体的には、シクロペンチル基、シクロヘキシル基等が挙げられる。アリール基としては、炭素数６〜１２のアリール基であることが好ましく、具体的には、フェニル基、トリル基、ナフチル基等が挙げられる。アルコキシ基としては、炭素数１〜１０のアルコキシ基であることが好ましく、メトキシ基、エトキシ基、プロポキシ基、イソプロピルオキシ基、ブトキシ基、フェノキシ基、アリルオキシ基、シクロヘキシルオキシ基等が挙げられる。
また、式中、Ｒ２としては、メチレン基、炭素数２〜１０のアルキレン基、またはフェニレン基が挙げられる。炭素数２〜１０のアルキレン基としては、ジメチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基等が挙げられる。
上記シリコーンジアミンとしては、耐熱性（高ガラス転移温度）及び耐水性に優れたポリアミック酸及び／又はポリイミドを得る観点から数平均分子量が１，０００〜９，０００であることが好ましく、３，０００〜８，０００であることがより好ましい。
具体的には、両末端アミノ変性メチルフェニルシリコーン（信越化学社製 Ｘ２２−１６６０Ｂ（数平均分子量４，４００），Ｘ２２−９４０９（数平均分子量１，３００））、両末端アミノ変性ジメチルシリコーン（信越化学社製 Ｘ２２−１６１Ａ（数平均分子量１，６００））、東レダウコーニング製 BY１６−８３５U（数平均分子量９００））などを挙げることができる。なお、ポリイミド等を合成する際、上記シリコーンジアミンは１種を単独であるいは２種以上を組み合わせて用いることができる。

(In the formula, a plurality of R ^{1 s} each independently represents an alkyl group, a cycloalkyl group, or an aryl group or an alkoxy group, and R ^{2 s} each independently represent a methylene group, an alkylene group having 2 to 10 carbon atoms, Alternatively, it represents a phenylene group, and n represents an integer of 1 to 100.)
In the formula, examples of R ¹ include an alkyl group, a cycloalkyl group, an aryl group, and an alkoxy group. The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, A hexyl group etc. are mentioned. The cycloalkyl group is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples include a cyclopentyl group and a cyclohexyl group. The aryl group is preferably an aryl group having 6 to 12 carbon atoms, and specific examples include a phenyl group, a tolyl group, and a naphthyl group. The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, an allyloxy group, and a cyclohexyloxy group.
In the formula, R2 includes a methylene group, an alkylene group having 2 to 10 carbon atoms, or a phenylene group. Examples of the alkylene group having 2 to 10 carbon atoms include dimethylene group, trimethylene group, tetramethylene group, pentamethylene group and hexamethylene group.
As said silicone diamine, it is preferable that a number average molecular weight is 1,000-9,000 from a viewpoint of obtaining the polyamic acid and / or polyimide which were excellent in heat resistance (high glass transition temperature) and water resistance, and 3,000. More preferably, it is -8,000.
Specifically, both terminal amino-modified methyl phenyl silicone (X22-1660B (number average molecular weight 4,400), X22-9409 (number average molecular weight 1,300) manufactured by Shin-Etsu Chemical Co., Ltd.), both terminal amino-modified dimethyl silicone (Shin-Etsu) X22-161A (number average molecular weight 1,600)) manufactured by Kagaku Co., and BY16-835U (number average molecular weight 900)) manufactured by Toray Dow Corning. In addition, when synthesize | combining a polyimide etc., the said silicone diamine can be used individually by 1 type or in combination of 2 or more types.

The component (a-2) which is a diamine compound used in the present invention is at least one compound selected from aliphatic diamines and alicyclic diamines (however, the component (a-1) is excluded). Specific examples of the aliphatic diamine and alicyclic diamine include, for example, 1,1-metaxylylenediamine, 1,2-ethylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, hepta. Aliphatic diamines such as methylene diamine, octamethylene diamine and nonamethylene diamine;
1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoin danylene dimethylene diamine, tricyclo [6.2.1.0 ^2.7 ] -undecylenedimethyl diamine, And alicyclic diamines such as 4,4′-methylenebis (cyclohexylamine) and 4,4′diaminocyclohexylmethane; and the like. These can be used alone or in combination of two or more.
Among these diamine compounds, aliphatic diamines and alicyclic diamines are preferably used from the viewpoint of obtaining a polyamic acid and / or polyimide excellent in transparency, and from the viewpoint of obtaining a polyamic acid and / or polyimide excellent in heat resistance. An alicyclic diamine is particularly preferably used.
Moreover, these diamine compounds may be used as they are, or may be used after re-reducing the commercially available products.

When the total amount of all diamine compounds is 100% by mass, the silicone diamine is preferably contained in an amount of 20 to 50% by mass, more preferably 25 to 50% by mass, and even more preferably 30 to 50% by mass. .
The at least one compound selected from the aliphatic diamine and the alicyclic diamine preferably includes 40 to 80% by mass, preferably 45 to 75% by mass, when the total amount of all diamine compounds is 100% by mass. More preferably, it is more preferable to include 50 to 70% by mass.

Next, the acyl compound (component (B)) for reacting with the diamine compound to give the polyimide material of the present invention will be described.
[Component (B)]
The acyl compound of the present invention is at least one acyl compound selected from the group consisting of aliphatic and / or alicyclic tetracarboxylic dianhydrides and reactive derivatives thereof.
Here, the reactive derivative is a compound that can be converted into an aliphatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic dianhydride, for example, an aliphatic tetracarboxylic dianhydride or an alicyclic tetra A compound having two carboxyl groups in place of the anhydride of carboxylic dianhydride, a compound in which one or both of the two carboxyl groups are esterified esters, or the two carboxyl groups An acid chloride in which one or both of them are chlorinated is preferably used.
Specific examples of the aliphatic tetracarboxylic dianhydride include, for example, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride, hexanetetracarboxylic dianhydride, heptanetetra Examples thereof include carboxylic dianhydrides.

Specific examples of the alicyclic tetracarboxylic dianhydride include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic Acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 , 2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1-cis-2-cis -3-trans-4-trans-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic Such dianhydride.
As said acyl compound, it is preferable to use alicyclic tetracarboxylic dianhydride or this reactive derivative from a viewpoint of obtaining the polyimide etc. which were especially excellent in heat resistance.
In addition, when synthesizing polyimide or the like, the acyl compounds can be used alone or in combination of two or more.

Next, the manufacturing method of the polyimide-type material of this invention and the manufacturing method of a film are demonstrated.
The method for producing a polyimide-based material of the present invention comprises a step (a) of preparing a solution containing a polyamic acid and an organic solvent by reacting the component (A) with the component (B), and the polyamic acid. And (b) a step of imidizing at least a part.
Moreover, the manufacturing method of the film of this invention apply | coats the solution containing the polyamic acid and / or polyimide obtained by making said (A) component and said (B) component react, and an organic solvent on a support substrate. And forming a coating film, and removing the solvent from the coating film by evaporating to obtain a film.
The manufacturing method of the film of this invention can include the pre-process which prepares the solution containing a polyamic acid and / or a polyimide, and the organic solvent. In this case, the method for producing a film of the present invention comprises a step of reacting the component (A) and the component (B) to prepare a solution containing a polyamic acid and / or polyimide and an organic solvent (for example, the above-mentioned Steps (a) and (b)), a step of forming a coating film by applying a solution containing the polyamic acid and / or polyimide and an organic solvent on a supporting substrate (Step (c)), and the coating film And removing the organic solvent by evaporation to obtain a film (step (d)).

[Step (a)]
Step (a) is a step of preparing a solution containing a polyamic acid and an organic solvent by reacting the component (A) with the component (B).
Specifically, after dissolving at least one (A) diamine compound in an organic solvent, at least one (B) acyl compound is added to the resulting solution, and the temperature is 0 to 100 ° C. The method of stirring for -60 hours is mentioned.
Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, N, N′-dimethylimidazolidinone, and tetramethyl. Aprotic polar solvents such as urea; phenolic solvents such as cresol, xylenol, and halogenated phenol; Of these, N-methyl-2-pyrrolidone and N, N-dimethylacetamide are preferable.
These solvents can be used alone or in combination of two or more.
In addition, it is preferable that the total amount of (A) diamine compound and (B) acyl compound in a reaction liquid is 5-30 mass% of the reaction liquid whole quantity.

  Here, the ratio of the (B) acyl compound to the (A) diamine compound is such that the acid anhydride group of the (B) component is 0.8 to 1 equivalent to 1 equivalent of the amino group or isocyanate group of the (A) component. A ratio of 1.2 equivalents is preferable, and a ratio of 1.0 to 1.1 equivalents is more preferable. If the value is less than 0.8 equivalent or more than 1.2 equivalent, the molecular weight may be low and it may be difficult to form a film.

The terminal of the polyamic acid and / or polyimide obtained by the above method is mainly a carboxylic acid anhydride. The end group of the polymer can be formed into a film as it is without being treated. Further, imidization treatment can be performed by adding a monofunctional aromatic amine typified by an aniline derivative.
The polyamic acid is an acid having a structure containing —CO—NH— and —CO—OH, which is generated by a reaction between an acid anhydride group and an amino group, or a derivative thereof (specifically, For example, it means -CO-NH- and -CO-OR (wherein R is an alkyl group or the like). The polyamic acid becomes a polyimide having a cyclic chemical structure (—CO—N—CO—) by dehydrating H of —CO—NH— and OH of —CO—OH by heating or the like.

[Step (b)]
Next, the obtained polyamic acid is imidized by dehydrating and cyclizing. As this method, a method using a dehydrating agent (chemical imidization), 160 ° C. to 350 ° C. (160 to 220 ° C. in a solution, cast In the case of a film, a method (thermal imidization) in which heat treatment is generally performed at a temperature of 300 ° C. or higher is used.
Examples of the dehydrating agent in chemical imidization include acid anhydrides such as acetic anhydride, propionic anhydride and benzoic anhydride, or corresponding acid chlorides, carbodiimide compounds such as dicyclohexylcarbodiimide, and the like. In addition, it is preferable to heat at the temperature of 60-120 degreeC in the case of chemical imidation.
In the case of thermal imidization, it is preferable to carry out while removing water generated by the dehydration reaction out of the system. At this time, water can be removed azeotropically using benzene, toluene, xylene or the like.
In the imidization, a base catalyst such as pyridine, isoquinoline, trimethylamine, triethylamine, N, N-dimethylaminopyridine, imidazole, 1-methylpiperidine, 1-methylpiperazine can be used as necessary. . The dehydrating agent or the base catalyst is preferably used in an amount of 0.1 to 8 moles per mole of the acyl compound.
As the imidization method, chemical imidization is preferable because imidization can be performed by heating at a lower temperature.
The imidization is performed so as to imidize at least a part of the polyamic acid, preferably 75 mol% or more, more preferably 80 mol% or more, and particularly preferably 85 mol% or more.
The obtained polyamic acid and / or a solution containing polyimide and an organic solvent can be used as it is, but after isolating polyimide or the like as a solid component, it can also be used by re-dissolving in an organic solvent. In addition, as an organic solvent which redissolves, the thing similar to the said organic solvent is mentioned. As a method for isolating polyimide and the like, a solution containing polyimide and an organic solvent is poured into a poor solvent for polyimide such as methanol and isopropyl ether to precipitate the polyimide, and the polyimide is solidified by filtration, washing, drying, etc. The method of separating as a minute is mentioned. By performing such an operation, it is possible to remove the dehydration catalyst (imidization catalyst) used in the imidization.

In the present invention, the ratio of polyimide is 85 mol% or more, preferably 90 mol% or more, particularly preferably 95 mol% or more, in the total 100 mol% of polyamic acid and polyimide. When the proportion of polyimide is less than 80 mol%, the water absorption rate of the film may increase or the durability may decrease.
The resulting polyamic acid and / or polyimide has a polystyrene-equivalent weight average molecular weight of 40,000 to 300,000, preferably 60,000 to 200,000.
The obtained polyamic acid and / or polyimide preferably has an imide group concentration of 2.0 to 4.5 mmol / g, assuming that the imidization rate is 100 mol%. It is more preferable that it is -4.0 mmol / g, and it is further more preferable that it is 3.0-3.6 mmol / g. When the obtained polyamic acid and / or polyimide satisfies the imide group concentration, a polyimide film particularly excellent in low water absorption can be obtained.

[Step (c)]
Step (c) is a step of forming a coating film by applying a solution containing polyamic acid and / or polyimide and an organic solvent on a support substrate.
Examples of the support substrate include a polyethylene terephthalate (PET) film and a SUS plate.
As a method for applying a solution containing polyimide or the like and an organic solvent on the support substrate, a roll coating method, a gravure coating method, a spin coating method, a method using a doctor blade, or the like can be used.
Although the thickness of a coating film is not specifically limited, For example, it is 1-250 micrometers.

[Step (d)]
Step (d) is a step of removing the organic solvent from the coating film by evaporation to obtain a film.
Specifically, the organic solvent in the coating film is evaporated and removed by heating the coating film.
The heating condition is not particularly limited as long as the organic solvent evaporates. For example, the heating condition is 60 to 250 ° C. for 1 to 5 hours. Heating may be performed in two stages. For example, after heating at 100 ° C. for 30 minutes, heating at 150 ° C. for 1 hour. Further, if necessary, drying may be performed under a nitrogen atmosphere or under reduced pressure.
In this step, it is sufficient if the organic solvent can be removed, and it is not necessary to perform imidization. Therefore, a film can be obtained at a lower temperature than in the prior art. Therefore, even if other members forming the optical member have low heat resistance, the film is removed by directly applying a solution containing the polyimide or the like and an organic solvent to the member and evaporating and removing the organic solvent. Can be formed.
The obtained film can be used as it is without being peeled off from the support substrate.

In the film of the present invention, the ratio of polyimide is 85 mol% or more, preferably 90 mol% or more, and particularly preferably 95 mol% or more in the total 100 mol% of polyamic acid and polyimide. If the proportion of polyimide is less than 85 mol%, the water absorption rate of the film may increase or the durability may decrease.
The film of the present invention has a thickness of 1 to 250 μm, preferably 5 to 200 μm. Moreover, when using the film of this invention as a base material, it is especially preferable that thickness is 10-150 micrometers.
The film of the present invention preferably has a glass transition temperature (Tg) of 200 ° C. or higher, and more preferably 250 ° C. or higher. By having such a glass transition temperature, excellent heat resistance can be obtained.
The film of the present invention preferably has a water absorption rate of 3.0% or less, more preferably 2.5% or less, and even more preferably 2.0% or less.

  The film of the present invention can be used for light emitting diode peripheral materials, solar cell peripheral materials, flat display peripheral materials, and electronic circuit peripheral materials. Specifically, it can be used for optical members such as heat-resistant transparent films and conductive transparent films. Moreover, as an electronic circuit peripheral material, it can also be used as a printed wiring board substrate, a flexible printed wiring board, a rigid printed wiring board, an optoelectronic printed wiring board, a COF (Chip on Film) board, a TAB ( A substrate for Tape Automated Bonding) can be given. When used as a printed wiring board, for example, a copper layer for wiring can be provided. Examples of a method for providing a copper layer on the film of the present invention include a laminating method and a metalizing method. In the case of the laminating method, for example, a printed wiring board provided with a copper layer can be produced by hot pressing a copper foil on the film of the present invention. In the case of the metalizing method, for example, after the surface modification is performed in order to develop the affinity of the film of the present invention with the metal, the Ni-based metal layer bonded to the polyimide by vapor deposition or sputtering is used. A seed layer necessary for wet electroplating is formed. And the board | substrate for printed wiring with which the copper layer was provided can be manufactured by providing the copper layer of a predetermined film thickness with a wet-plating method.

Moreover, the polyimide-type solution containing the polyimide etc. and organic solvent obtained by process (a), (b) is a light emitting diode peripheral material, a solar cell peripheral material, a flat display peripheral material, an electron as a polyimide-type resin composition. It can also be used as a circuit peripheral material. Specifically, it can be used as a sealant, a lens material, a printed wiring board forming material, and the like. For example, when used as a printed wiring board forming material, a printed wiring board can be manufactured by a casting method. Specifically, a printed wiring board provided with a copper layer can be produced by applying a heat treatment after applying the polyimide resin composition on a copper foil.
In addition, the said polyimide resin composition can use the organic solvent whose boiling point is 150 degrees C or less as a cosolvent. Examples of the organic solvent include methanol, ethanol, isopropanol, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane and the like.
These solvents can be used alone or in combination of two or more.
In addition, it is preferable that the density | concentration of the polyamic acid in a polyimide-type resin composition and / or a polyimide is 5-30 mass% of the reaction liquid whole quantity.

Hereinafter, the present invention will be specifically described by way of examples.
[Example 1]
In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, 5.46 g (26.0 mmol) of 4,4′-diaminodicyclohexylmethane and amino-modified methylphenylsilicone at both ends (manufactured by Shin-Etsu Chemical, X22-1660B, number average molecular weight 4,400) 3.53 g (0.8 mmol) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added and stirred until uniform. To the resulting solution, 6.00 g (26.8 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added at room temperature, and stirring was continued at that temperature for 24 hours to obtain a polyamic acid solution. .
To the obtained polyamic acid solution, 2.6 ml of N-methylpiperidine and 7.3 ml of acetic anhydride were added, followed by imidization by stirring at 75 ° C. for 4 hours. After cooling to room temperature, it was poured into a large amount of methanol, and the polymer was isolated by filtration. The obtained polymer was vacuum-dried overnight at 60 ° C. to obtain a white powder (yield 13.0 g, yield 92.6% by mass).
Subsequently, the obtained polymer was redissolved in N, N-dimethylacetamide (DMAc) to obtain a 20% by mass resin solution. The resin solution is applied onto a substrate made of polyethylene terephthalate (PET) using a doctor blade (100 μm gap), dried at 100 ° C. for 30 minutes, and then dried at 150 ° C. for 60 minutes to form a film. It peeled. Thereafter, the film was further dried at 150 ° C. under reduced pressure for 3 hours to obtain a film having a thickness of 20 μm.
The polymer was subjected to structural analysis by IR (KBr method). As a result, the characteristic absorption of the carbonyl group was 1776 cm ⁻¹ and 1704 cm ⁻¹ .
Moreover, about the said polymer, the weight average molecular weight, the glass transition temperature, the imidation rate, and the imide group density | concentration (theoretical value when it is assumed that the imidation rate is 100 mol%) were calculated | required by the following method.
Further, the water absorption of the obtained film was measured by the following method.
The results are shown in Table 1.

(1) Weight average molecular weight The weight average molecular weight was measured using an HLC-8020 GPC apparatus manufactured by TOSOH. As the solvent, N-methyl-2-pyrrolidone (NMP) to which lithium bromide and phosphoric acid were added was used, and the molecular weight in terms of polystyrene was determined at a measurement temperature of 40 ° C.
(2) Glass transition temperature (Tg)
Using a Rigaku 8230 type DSC measuring apparatus, the temperature elevation rate was 20 ° C./min.
(3) Imidization rate (ring closure rate)
The ring closure rate of the polyimide was measured using 1H-NMR. D-DMSO was used as a solvent. Peak integral value of N—H proton of unclosed amide group and peak integral value of proton of —CH _2- (methylene group) derived from alicyclic diamine, or peak integral of aromatic ring proton derived from aromatic diamine Calculated from the ratio of values.
(4) Imido group concentration Assuming that the imidization ratio is 100 mol%, the molecular weight of the repeating unit in the obtained polymer is obtained by (molecular weight of acyl compound) + (molecular weight of diamine) -2H ₂ O. . Since each of these repeating units contains two imide groups, the imide group concentration (theoretical value when it is assumed that the imidization rate is 100 mol%) was determined by the following formula.
[Imide group concentration] (unit: mmol / g) = 2 / {(molecular weight of acyl compound) + (molecular weight of diamine) -2H ₂ O} × 1000
(5) Water absorption rate Three pieces of the obtained film were cut into a size of 3 cm × 4 cm and dried at 180 ° C. for 8 hours under reduced pressure drying. After measuring the mass of the film, the film was immersed in distilled water at 25 ° C. for 24 hours. After immersion, water droplets on the film surface were wiped off, and the water absorption was calculated from the mass change before and after immersion.
(6) Residual solvent amount The obtained polymer was redissolved in THF (tetrahydrofuran) to obtain a 20 mass% resin solution. The resin solution is applied onto a substrate made of polyethylene terephthalate (PET) using a doctor blade (250 μm gap), dried at 70 ° C. for 30 minutes, and then dried at 150 ° C. for 60 minutes to form a film. It peeled. Thereafter, the film was further dried at 180 ° C. under reduced pressure for 1 hour to obtain a film having a thickness of 50 μm.
The obtained film was dissolved in d-DMSO and measured using 1H-NMR. The residual solvent amount (unit: wt / wt%) was calculated from the peak integrated value of protons in the polymer backbone and the peak integrated value of protons in THF.

[Example 2]
In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 5.15 g (24.5 mmol) of 4,4′-diaminodicyclohexylmethane and amino-modified methylphenylsilicone at both ends (manufactured by Shin-Etsu Chemical Co., Ltd., X22-1660B, number average molecular weight 4,400) 2.19 g (0.5 mmol) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added and stirred until uniform. To the resulting solution was added 7.65 g (25.0 mmol) of 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride at room temperature, and after addition, the mixture was stirred at 120 ° C. for 15 minutes to dissolve the precipitated salt. It was. Stirring was continued for 24 hours at the same temperature to obtain a polyamic acid solution.
To the obtained polyamic acid solution, 2.5 ml of N-methylpiperidine and 6.9 ml of acetic anhydride were added and stirred at 75 ° C. for 4 hours for imidization. After cooling to room temperature, it was poured into a large amount of methanol, and the polymer was isolated by filtration. The obtained polymer was vacuum-dried overnight at 60 ° C. to obtain a white powder (yield 13.1 g, yield 93.1% by mass).
Next, the obtained polymer was treated in the same manner as in Example 1 to obtain a film having a thickness of 20 μm.
The structural analysis of the obtained polymer was performed in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1774 cm ⁻¹ and 1701 cm ⁻¹ .
Further, various physical properties of the obtained polymer were evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 3]
In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 6.13 g (29.1 mmol) of 4,4′-diaminodicyclohexylmethane and diaminosilicone X22-1660B (number average molecular weight) manufactured by Shin-Etsu Chemical 4,400) 2.62 g (0.6 mmol) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added and stirred until uniform. To the obtained solution was added 6.25 g (29.7 mmol) of 1-cis-2-cis-3-trans-4-trans-cyclopentanetetracarboxylic dianhydride at room temperature, and the mixture was stirred at 120 ° C. for 15 minutes after the addition. The precipitated salt was dissolved. Stirring was continued for 24 hours at the same temperature to obtain a polyamic acid solution.
To the obtained polyamic acid solution, 2.9 ml of N-methylpiperidine and 8.3 ml of acetic anhydride were added, followed by imidization by stirring at 75 ° C. for 4 hours. After cooling to room temperature, it was poured into a large amount of methanol, and the polymer was isolated by filtration. The obtained polymer was vacuum-dried overnight at 60 ° C. to obtain a white powder (yield 12.7 g, yield 91.5% by mass).
Next, the obtained polymer was treated in the same manner as in Example 1 to obtain a film having a thickness of 20 μm.
The structural analysis of the obtained polymer was performed in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1772 cm ⁻¹ and 1703 cm ⁻¹ .
Further, various physical properties of the obtained polymer were evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 4]
A 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube was charged with 5.25 g (25.0 mmol) of 4,4′-diaminodicyclohexylmethane and amino-modified dimethyl silicone at both ends (X22 manufactured by Shin-Etsu Chemical Co., Ltd., X22). -9409, number average molecular weight 1,300) 1.71 g (1.3 mmol) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added and stirred until uniform. To the resulting solution was added 8.05 g (26.3 mmol) of 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride at room temperature, and after addition, the mixture was stirred at 120 ° C. for 15 minutes to dissolve the precipitated salt. It was. Stirring was continued for 24 hours at the same temperature to obtain a polyamic acid solution.
To the obtained polyamic acid solution, 2.5 ml of N-methylpiperidine and 7.0 ml of acetic anhydride were added, and the mixture was stirred at 75 ° C. for 4 hours for imidization. After cooling to room temperature, it was poured into a large amount of methanol, and the polymer was isolated by filtration. The obtained polymer was vacuum-dried overnight at 60 ° C. to obtain a white powder (yield 13.0 g, yield 92.6% by mass).
Next, the obtained polymer was treated in the same manner as in Example 1 to obtain a film having a thickness of 20 μm.
The structural analysis of the obtained polymer was performed in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1773 cm ⁻¹ and 1702 cm ⁻¹ .
Further, various physical properties of the obtained polymer were evaluated in the same manner as in Example 1. The results are shown in Table 1.
[Example 5]
In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 5.11 g (24.3 mmol) of 4,4′-diaminodicyclohexylmethane and amino-modified dimethyl silicone at both ends (X22 manufactured by Shin-Etsu Chemical Co., Ltd., X22) -161A, number average molecular weight 1,600) 2.05 g (1.3 mmol) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added and stirred until uniform. To the resulting solution was added 7.84 g (25.6 mmol) of 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride at room temperature, and after addition, the mixture was stirred at 120 ° C. for 15 minutes to dissolve the precipitated salt. It was. Stirring was continued for 24 hours at the same temperature to obtain a polyamic acid solution.
To the obtained polyamic acid solution, 2.4 ml of N-methylpiperidine and 6.9 ml of acetic anhydride were added, and the mixture was stirred at 75 ° C. for 4 hours for imidization. After cooling to room temperature, it was poured into a large amount of methanol, and the polymer was isolated by filtration. The obtained polymer was vacuum-dried overnight at 60 ° C. to obtain a white powder (yield 13.1 g, yield 93.3 mass%).
Next, the obtained polymer was treated in the same manner as in Example 1 to obtain a film having a thickness of 20 μm.
The structural analysis of the obtained polymer was performed in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1772 cm ⁻¹ and 1702 cm ⁻¹ .
Further, various physical properties of the obtained polymer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
7.26 g (34.5 mmol) of 4,4′-diaminodicyclohexylmethane was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added and stirred until uniform. To the resulting solution, 7.74 g (34.5 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added at room temperature, and after the addition, the mixture was stirred at 120 ° C. for 15 minutes to dissolve the precipitated salt. Stirring was continued for 24 hours at the same temperature to obtain a polyamic acid solution.
To the resulting polyamic acid solution, 3.5 ml of N-methylpiperidine and 9.8 ml of acetic anhydride were added, and the mixture was stirred at 75 ° C. for 3 hours for imidization. After cooling to room temperature, it was poured into a large amount of methanol, and the polymer was isolated by filtration. The obtained polymer was vacuum-dried overnight at 60 ° C. to obtain a white powder (yield 12.8 g, yield 93.1% by mass).
Next, the obtained polymer was treated in the same manner as in Example 1 to obtain a film having a thickness of 20 μm.
The structural analysis of the obtained polymer was performed in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1775 cm ⁻¹ and 1705 cm ⁻¹ .
Further, various physical properties of the obtained polymer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2]
As in Comparative Example 1, instead of 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 8.89 g (29.0 mmol) of 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride was added. Used, except that the amounts of 4,4′-diaminodicyclohexylmethane, N-methylpiperidine, and acetic anhydride were changed to 6.11 g (29.0 mmol), 2.9 ml, and 8.2 ml, respectively. In the same manner as in Example 1, a polymer composed of white powder (yield 13.2 g, yield 94.6% by mass) and a film were obtained.
The structural analysis of the obtained polymer was performed in the same manner as in Comparative Example 1. As a result, the characteristic absorption of the carbonyl group was 1773 cm ⁻¹ and 1701 cm ⁻¹ .
Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 1.

[Comparative Example 3]
To a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube, 7.50 g (35.7 mmol) of 4,4′-diaminodicyclohexylmethane was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added and stirred until uniform. To the obtained solution was added 1.50 g (35.7 mmol) of 1-cis-2-cis-3-trans-4-trans-cyclopentanetetracarboxylic dianhydride at room temperature, and the mixture was stirred at 120 ° C. for 15 minutes after the addition. The precipitated salt was dissolved. Stirring was continued for 24 hours at the same temperature to obtain a polyamic acid solution.
To the obtained polyamic acid solution, 2.5 ml of N-methylpiperidine and 6.8 ml of acetic anhydride were added, and the mixture was stirred at 75 ° C. for 3 hours for imidization. After cooling to room temperature, it was poured into a large amount of methanol, and the polymer was isolated by filtration. The obtained polymer was vacuum-dried overnight at 60 ° C. to obtain a white powder (yield 12.8 g, yield 93.5% by mass).
Next, the obtained polymer was treated in the same manner as in Example 1 to obtain a film having a thickness of 20 μm.
The structural analysis of the obtained polymer was performed in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1773 cm ⁻¹ and 1704 cm ⁻¹ (see FIG. 5).
Further, various physical properties of the obtained polymer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 4]
In a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and cooling tube, 3.44 g (16.3 mmol) of 4,4′-diaminodicyclohexylmethane and amino-modified dimethyl silicone at both ends (manufactured by Shin-Etsu Chemical, PAME) , Number average molecular weight 260) 4.25 g (16.3 mmol) was added. Next, after the atmosphere in the flask was replaced with nitrogen, 58 ml of N-methyl-2-pyrrolidone (hereinafter referred to as NMP) was added and stirred until uniform. To the resulting solution, 7.32 g (32.7 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added at room temperature, and after addition, the mixture was stirred at 120 ° C. for 15 minutes to dissolve the precipitated salt. Stirring was continued for 24 hours at the same temperature to obtain a polyamic acid solution.
To the obtained polyamic acid solution, 1.6 ml of N-methylpiperidine and 4.6 ml of acetic anhydride were added, and the mixture was stirred at 75 ° C. for 4 hours for imidization. After cooling to room temperature, it was poured into a large amount of methanol, and the polymer was isolated by filtration. The obtained polymer was vacuum-dried overnight at 60 ° C. to obtain a white powder (yield 12.5 g, yield 90.4% by mass).
Next, the obtained polymer was treated in the same manner as in Example 1 to obtain a film having a thickness of 20 μm.
The structural analysis of the obtained polymer was performed in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1777 cm ⁻¹ and 1708 cm ⁻¹ .
Further, various physical properties of the obtained polymer were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Claims (8)

(A) Selected from the group consisting of the following (a-1), a diamine compound containing the component (a-2), (B) an aliphatic and / or alicyclic tetracarboxylic dianhydride, and reactive derivatives thereof. A polyimide-based material comprising a polyamic acid and / or a polyimide resin, which is obtained by reacting at least one acyl compound.
(A-1) Silicone diamine having a number average molecular weight of 500 to 10,000 calculated by amine value 10 to 60% by mass
(A-2) 30 to 90% by mass of at least one compound selected from aliphatic diamines and alicyclic diamines
(However, the total amount of the diamine compound is 100% by mass.) The polyimide-type material of Claim 1 whose said silicone diamine is a compound represented by following formula (1).

(In the formula, a plurality of R ^{1 s} each independently represent an alkyl group, a cycloalkyl group, or an aryl group or an alkoxy group, and a plurality of R ^{2 s} each independently represent a methylene group or a C 2-10 alkylene) A group or a phenylene group, and n represents an integer of 1 to 100.)   The polyimide-based material according to claim 1 or 2, wherein the number average molecular weight of the silicone diamine calculated by the amine value is 3,000 to 8,000.   The polyimide-type resin composition containing the polyimide-type material in any one of Claims 1-3, and an organic solvent.   The film which consists of a polyimide-type material in any one of Claims 1-4.   The film according to claim 5, which is for an optical member.   The film according to claim 5, which is for a printed wiring board.   It is a manufacturing method of the film of any one of Claims 5-7, Comprising: Said (A) silicone diamine and said (B) aliphatic and / or alicyclic tetracarboxylic dianhydride are made to react. A solution containing polyamic acid and / or polyimide obtained in this manner and an organic solvent is applied on a substrate to form a coating film, and the solvent is removed from the coating film by evaporation to obtain a film. And a process for producing the film.