JPWO2012005346A1 - Polymer, method for producing the same, film and method for producing the same - Google Patents

Abstract

It has at least one structural unit (i) selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and is determined by gel permeation chromatography (GPC). A low molecular weight component having a polystyrene equivalent weight average molecular weight of 2.5 × 10 4 to 5.0 × 10 5 and a polystyrene equivalent molecular weight of 5.0 × 10 3 or less according to an integral molecular weight distribution curve measured by GPC. The polymer which the amount accounts for 5.0% or less with respect to the whole polymer.

Description

  The present invention relates to a polymer, a production method thereof, a film, and a production method thereof.

  In recent years, the development of information technology has been remarkable, and with the trend of information devices becoming lighter, thinner, and smaller, transparent resins are used for various applications as optical materials. Typical transparent resins include PMMA and polycarbonate. Although these PMMA and polycarbonate are excellent in transparency, they have a low glass transition temperature and insufficient heat resistance, so that they are difficult to use for applications requiring high heat resistance. On the other hand, with the advancement of technology, the use of engineering plastics has expanded, and a polymer having excellent heat resistance, mechanical strength, and transparency is required.

  Aromatic polyether obtained by reacting 9,9-bis (4-hydroxyphenyl) fluorene with 2,6-dihalogenated benzonitrile as a polymer having excellent heat resistance, mechanical strength and transparency (Patent Documents 1 and 2) have been proposed.

JP 2006-199746 A Japanese Patent Laid-Open No. 2-45526

  However, the film containing the aromatic polyether described in Patent Documents 1 and 2 may not have sufficient color resistance when heated.

  This invention is made | formed in view of such a problem, and it aims at providing the polymer and film which are excellent in coloring resistance, heat resistance, and light transmittance.

  As a result of intensive studies to solve the above problems, the present inventor found that the above problems can be solved by a polymer having a specific structural unit and molecular weight, and completed the present invention. That is, the present invention provides the following [1] to [13].

[1] having at least one structural unit (i) selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2):
The weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) is 2.5 × 10 ^{4 to} 5.0 × 10 ⁵ , and the molecular weight in terms of polystyrene is 5 based on the integral molecular weight distribution curve measured by GPC. The polymer which the quantity which the low molecular weight component which is 0.0 * 10 < ³ > or less occupies is 5.0% or less with respect to the whole polymer.

(In Formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.)

(In the formula (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO ₂ -Or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 And m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.)

  [2] The polymer further has at least one structural unit (ii) selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). The polymer according to [1].

(In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1 .)

(In the formula ^{(4), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f.)

[3] Step (a) of obtaining an alkali metal salt of component (B) by reacting component (B) containing a compound represented by the following formula (6) with an alkali metal compound, and after step (a) And a component (A) containing at least one compound selected from the group consisting of a compound represented by the following formula (5) and a compound represented by the following formula (7): Step (b) of reacting the alkali metal salt obtained in (1) with component (A)
The method for producing a polymer according to [1] or [2], comprising:

(In Formula (6), R < ¹ > -R < ⁴ > and ad are respectively independently synonymous with R < ¹ > -R < ⁴ > and said ad in said Formula (1), ^Ra is independently a hydrogen atom. And represents a methyl group, an ethyl group, an acetyl group, a methanesulfonyl group or a trifluoromethylsulfonyl group.)

(In formula (5), X independently represents a halogen atom.)

(In the formula ^{(7), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, X is independently the same as X in the formula (5), provided that when m is 0, R ⁷ is not a cyano group.

  [4] The method for producing a polymer according to [3], wherein the component (B) further contains a compound represented by the following formula (8).

(In Formula (8), R ⁵ , R ⁶ , Z, n, e and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in Formula (3); R ^a is independently synonymous with R ^a in the formula (6).

  [5] A resin composition comprising the polymer described in [1] or [2] or the polymer obtained by the production method described in [3] or [4].

  [6] A film comprising the polymer according to [1] or [2], or the polymer obtained by the production method according to [3] or [4].

  [7] A polymer having at least one structural unit (i) selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and JIS K7133 A film having a heat shrinkage rate of −0.1% to 0.1% at a heat treatment temperature of 220 ° C. for 60 minutes.

(In Formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.)

(In the formula (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO ₂ -Or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 And m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.)

  [8] The polymer further has at least one structural unit (ii) selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). The film according to [7].

(In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1 .)

(In the formula ^{(4), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f.)

[9] The film according to any one of [6] to [8], wherein a YI value (yellow index) at a thickness of 30 μm of the film is 3.0 or less.
[10] The YI value of a solution obtained by dissolving the film in N, N-dimethylacetamide (DMAc), wherein the concentration of the polymer is 10% by weight, is 32.0 or less. The film according to any one of [6] to [9].

  [11] The film according to any one of [6] to [10], wherein the total light transmittance according to a JIS K7105 transparency test method at a thickness of 30 μm is 85% or more.

  [12] The film according to any one of [6] to [11], wherein a glass transition temperature (Tg) determined by differential scanning calorimetry (DSC, heating rate 20 ° C./min) is 230 to 350 ° C.

[13] A method for producing the film according to any one of [6] to [12],
Applying a polymer composition containing the polymer and an organic solvent on a substrate to form a coating film;
And a step of baking the coating film at 210 to 350 ° C.

According to the present invention, it is possible to obtain a polymer and a film having low colorability, particularly low colorability even when exposed to high temperatures, and excellent heat resistance and light transmittance.
In addition, according to the present invention, a film having a smaller heat shrinkage rate can also be obtained.

  According to the method for producing a polymer and the method for producing a film of the present invention, the above-described polymer and film can be easily produced, respectively.

The polymer according to the present invention has at least one structural unit (i) selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2):
The weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) is 2.5 × 10 ^{4 to} 5.0 × 10 ⁵ , and the molecular weight in terms of polystyrene is 5 based on the integral molecular weight distribution curve measured by GPC. The amount occupied by the low molecular weight component of 0.0 × 10 ³ or less is 5.0% or less based on the entire polymer.

  The polymer having the structural unit (i) and a specific molecular weight and having a low molecular weight component is also referred to as “polymer (II)” hereinafter.

  The polymer (II) according to the present invention has the structural unit (i) and has few specific molecular weights and low molecular weight components. Therefore, the polymer (II) is excellent in coloring resistance, heat resistance, and light transmittance, and is particularly exposed to high temperatures. Even if it is a case, there is little coloring. Since the film containing the polymer (II) is excellent in coloring resistance, heat resistance and light transmittance, the polymer (II) is composed of a light guide plate, a polarizing plate, a display film, an optical disk film, a transparent conductive film, It can be suitably used as a raw material for a film such as a waveguide plate.

  The film according to the present invention contains a polymer having the structural unit (i), and has a thermal shrinkage rate of −0.1% to 0.1% in JIS K7133 (heat treatment temperature 220 ° C., 60 minutes). is there.

  Hereinafter, the polymer having the structural unit (i) is also referred to as “polymer (I)”.

  The film according to the present invention contains the polymer (I), has excellent heat resistance, and has a low thermal shrinkage rate. Therefore, even when exposed to a high temperature, the film has little shrinkage or expansion, and further has little coloration. Therefore, the film according to the present invention has little dimensional change even when exposed to a high temperature when, for example, an element or wiring is formed on the film, so that the stress generated in the formed element or wiring is small. For this reason, it can use suitably as films, such as a light-guide plate, a polarizing plate, a film for a display, a film for optical disks, a transparent conductive film, and a waveguide board.

  In addition, when it is desired to obtain a film excellent in coloration resistance, it is preferable to contain the polymer (II).

  The polymer (II) is a polymer in which the molecular weight of the polymer (I) and the amount of low molecular weight components are specified. As said polymer (I), polymer (II) is preferable.

  Hereinafter, the polymer (I) or the polymer (II) is also simply referred to as “polymer”.

<Polymer>
The polymer has a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (1)”) and a structural unit represented by the following formula (2) (hereinafter “structural unit (2)”). Or at least one structural unit (i) selected from the group consisting of: For this reason, the said polymer is excellent in coloring resistance, heat resistance, and light transmittance. Therefore, since the film containing the polymer can be subjected to a heat treatment such as high-temperature baking, it is possible to obtain a film that hardly undergoes thermal shrinkage at high temperatures.

In said formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently. a to d each independently represent an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

  The monovalent organic group having 1 to 12 carbon atoms includes a monovalent hydrocarbon group having 1 to 12 carbon atoms and 1 to 1 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. And 12 monovalent organic groups.

  Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and 6 to 12 carbon atoms. An aromatic hydrocarbon group etc. are mentioned.

  The linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferably a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and the linear or branched carbon group having 1 to 5 carbon atoms. A hydrogen group is more preferable.

  Preferable specific examples of the linear or branched hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and n-pentyl. Group, n-hexyl group and n-heptyl group.

  As said C3-C12 alicyclic hydrocarbon group, a C3-C8 alicyclic hydrocarbon group is preferable, and a C3-C4 alicyclic hydrocarbon group is more preferable.

  Preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group; cyclobutenyl group, cyclopentenyl group, and cyclohexenyl group. And the like. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

  Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group. The bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

  Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom include an organic group consisting of a hydrogen atom, a carbon atom and an oxygen atom, and among them, a total carbon consisting of an ether bond, a carbonyl group or an ester bond and a hydrocarbon group. Preferable examples include organic groups of formulas 1 to 12.

  Examples of the organic group having 1 to 12 carbon atoms having an ether bond include an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, an alkynyloxy group having 2 to 12 carbon atoms, and 6 to 12 carbon atoms. And an aryloxy group and an alkoxyalkyl group having 2 to 12 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, a cyclohexyloxy group, and a methoxymethyl group.

  Moreover, as a C1-C12 organic group which has a carbonyl group, a C2-C12 acyl group etc. can be mentioned. Specific examples include an acetyl group, a propionyl group, an isopropionyl group, and a benzoyl group.

  As a C1-C12 organic group which has an ester bond, a C2-C12 acyloxy group etc. are mentioned. Specific examples include an acetyloxy group, a propionyloxy group, an isopropionyloxy group, and a benzoyloxy group.

  Examples of the organic group having 1 to 12 carbon atoms including a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom and a nitrogen atom, and specifically, a cyano group, an imidazole group, a triazole group, a benzimidazole group and a benzine. A triazole group etc. are mentioned.

  Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom and a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom, an oxygen atom and a nitrogen atom. Specifically, an oxazole group, an oxadiazole group, Examples include a benzoxazole group and a benzoxadiazole group.

As R < ¹ > -R < ⁴ > in said Formula (1), a C1-C12 monovalent hydrocarbon group is preferable, a C6-C12 aromatic hydrocarbon group is more preferable, and a phenyl group is further more preferable.

In the formula (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO _2- or> C = O, R ⁷ and R ⁸ each independently represents a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group. g and h each independently represent an integer of 0 to 4, preferably 0.

  Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic group having 1 to 12 carbon atoms in the formula (1).

In the polymer, the molar ratio between the structural unit (1) and the structural unit (2) (however, the total of the structural unit (1) and the structural unit (2) is 100) is optical. From the viewpoint of properties, heat resistance and mechanical properties, the structural unit (1): structural unit (2) is preferably 50:50 to 100: 0, and the structural unit (1): structural unit (2) = 70: More preferably, it is 30-100: 0, and it is further more preferable that it is structural unit (1): structural unit (2) = 80: 20-100: 0.
Here, the mechanical properties refer to properties such as the tensile strength, breaking elongation and tensile elastic modulus of the polymer.

  The polymer further has at least one structural unit (ii) selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). Also good. It is preferable that the polymer has such a structural unit (ii) because the mechanical properties of the film containing the polymer are improved.

In the formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, and n represents 0 or 1. e and f each independently represent an integer of 0 to 4, preferably 0.

  Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic group having 1 to 12 carbon atoms in the formula (1).

  The divalent organic group having 1 to 12 carbon atoms includes a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom, and a nitrogen atom. A divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the above, and a divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. And halogenated organic groups.

  Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and Examples thereof include a bivalent aromatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a trimethylene group, an isopropylidene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group.

  Examples of the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkylene groups such as cyclopropylene group, cyclobutylene group, cyclopentylene group and cyclohexylene group; cyclobutenylene group, cyclopentenylene group and And cycloalkenylene groups such as a cyclohexenylene group. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

  Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenylene group, a naphthylene group, and a biphenylene group. The bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

  Examples of the divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms and a divalent halogenated fat having 3 to 12 carbon atoms. Examples thereof include a cyclic hydrocarbon group and a divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a difluoromethylene group, a dichloromethylene group, a tetrafluoroethylene group, a tetrachloroethylene group, a hexafluorotrimethylene group, and a hexachlorotrimethylene group. Group, hexafluoroisopropylidene group, hexachloroisopropylidene group and the like.

  As the divalent halogenated alicyclic hydrocarbon group having 3 to 12 carbon atoms, at least a part of the hydrogen atoms exemplified in the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is a fluorine atom. And a group substituted with a chlorine atom, a bromine atom or an iodine atom.

  As the divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms, at least a part of the hydrogen atoms exemplified in the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms is a fluorine atom, chlorine And a group substituted with an atom, a bromine atom or an iodine atom.

  The divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom is a hydrogen atom and a carbon atom, and an oxygen atom and / or a nitrogen atom. And a divalent organic group having 1 to 12 carbon atoms having an ether bond, a carbonyl group, an ester bond or an amide bond and a hydrocarbon group.

  The divalent halogenated organic group having 1 to 12 carbon atoms containing at least one kind of atom selected from the group consisting of oxygen atom and nitrogen atom is specifically selected from the group consisting of oxygen atom and nitrogen atom Examples include a group in which at least a part of the hydrogen atoms exemplified in the divalent organic group having 1 to 12 carbon atoms containing at least one atom is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. .

Z in the formula (3) is preferably a single bond, —O—, —SO ₂ —,> C═O or a divalent organic group having 1 to 12 carbon atoms, and a divalent organic group having 1 to 12 carbon atoms. A hydrocarbon group or a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms is more preferable, and the divalent hydrocarbon group having 1 to 12 carbon atoms may be a divalent alicyclic carbon atom having 3 to 12 carbon atoms. A hydrogen group is preferred.

In the formula (4), R ⁷ , R ⁸ , Y, m, g and h are each independently synonymous with R ⁷ , R ⁸ , Y, m, g and h in the formula (2), R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f. When m is 0, R ⁷ is not a cyano group.

  In the polymer, the molar ratio of the structural unit (i) to the structural unit (ii) (however, the sum of both ((i) + (ii)) is 100) has optical properties and heat resistance. And from the viewpoint of mechanical properties, (i) :( ii) = 50: 50 to 100: 0 is preferable, (i) :( ii) = 70: 30 to 100: 0 is more preferable, It is more preferable that (i) :( ii) = 80: 20 to 100: 0.

  The polymer preferably contains 70 mol% or more of the structural unit (i) and the structural unit (ii) in the total structural unit from the viewpoints of optical properties, heat resistance and mechanical properties, and 95 mol in the total structural unit. It is more preferable that it contains more than%.

<Polymer synthesis method>
Examples of the polymer include a compound represented by the following formula (5) (hereinafter also referred to as “compound (5)”) and a compound represented by the following formula (7) (hereinafter also referred to as “compound (7)”). .) Can be obtained by reacting a component (A) containing at least one compound selected from the group consisting of: and a component (B) containing a compound represented by the following formula (6).

  In said formula (5), X shows a halogen atom independently and a fluorine atom is preferable.

In the formula ^{(7), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, X is independently synonymous with X in the formula (5). However, when m is 0, R ⁷ is not a cyano group.

In the formula (6), R ^a independently represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, a methanesulfonyl group or a trifluoromethylsulfonyl group, and among them, a hydrogen atom is preferable. In the formula (6), R ¹ to R ⁴ and a~d have the same meanings as R ¹ to R ⁴ and a~d each independently the formula (1).

  Specific examples of the compound (5) include 2,6-difluorobenzonitrile, 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6-dichlorobenzonitrile, and 2,5-dichloro. Mention may be made of benzonitrile, 2,4-dichlorobenzonitrile and their reactive derivatives. In particular, 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferably used from the viewpoints of reactivity and economy. These compounds can be used in combination of two or more.

  Specific examples of the compound represented by the above formula (6) (hereinafter also referred to as “compound (6)”) include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3 -Phenyl-4-hydroxyphenyl) fluorene, 9,9-bis (3,5-diphenyl-4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9- Examples include bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, and reactive derivatives thereof. Among the above-mentioned compounds, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene are preferably used. These compounds can be used in combination of two or more.

  Specific examples of the compound (7) include 4,4′-difluorobenzophenone, 4,4′-difluorodiphenylsulfone, 2,4′-difluorobenzophenone, 2,4′-difluorodiphenylsulfone, 2,2 '-Difluorobenzophenone, 2,2'-difluorodiphenylsulfone, 3,3'-dinitro-4,4'-difluorobenzophenone, 3,3'-dinitro-4,4'-difluorodiphenylsulfone, 4,4'- Dichlorobenzophenone, 4,4'-dichlorodiphenylsulfone, 2,4'-dichlorobenzophenone, 2,4'-dichlorodiphenylsulfone, 2,2'-dichlorobenzophenone, 2,2'-dichlorodiphenylsulfone, 3,3 ' -Dinitro-4,4'-dichlorobenzophenone and 3,3'- And nitro-4,4'-dichloro diphenyl sulfone. Among these, 4,4′-difluorobenzophenone and 4,4′-difluorodiphenyl sulfone are preferable. These compounds can be used in combination of two or more.

  It is preferable that at least one compound selected from the group consisting of compound (5) and compound (7) is contained in 80 mol% to 100 mol% in 100 mol% of component (A), and 90 mol% to More preferably, it is contained at 100 mol%.

  Moreover, it is preferable that a component (B) contains the compound (henceforth "compound (8)") represented by following formula (8) as needed.

  Compound (6) is preferably contained in 50 mol% to 100 mol%, more preferably 80 mol% to 100 mol%, and more preferably 90 mol% in 100 mol% of component (B). More preferably, it is contained in an amount of ˜100 mol%.

In the formula (8), R ⁵ , R ⁶ , Z, n, e and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in the formula (3), R ^a is independently synonymous with R ^a in the formula (6).

  Examples of the compound (8) include hydroquinone, resorcinol, 2-phenylhydroquinone, 4,4′-biphenol, 3,3′-biphenol, 4,4′-dihydroxydiphenylsulfone, 3,3′-dihydroxydiphenylsulfone, 4 , 4′-dihydroxybenzophenone, 3,3′-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy) Phenyl) -1,1,1,3,3,3-hexafluoropropane and reactive derivatives thereof. These compounds can be used in combination of two or more.

  Among the above-mentioned compounds, resorcinol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy) Phenyl) -1,1,1,3,3,3-hexafluoropropane is preferred, and 4,4′-biphenol is suitably used from the viewpoint of reactivity and mechanical properties.

  More specifically, the polymer can be synthesized by the following method (I ′) or method (II ′). Among these, by using the method (I ′), there are few low molecular weight components having the structural unit (i), having a specific weight average molecular weight, and having a polystyrene-reduced molecular weight by GPC of a certain molecular weight or less. A polymer can be easily obtained.

  In the method (I ′), the component (B) and an alkali metal compound are reacted to obtain an alkali metal salt of the component (B), and the mixture after the step (a) and the component (A) And a step (b) of reacting the alkali metal salt obtained in step (a) with the component (A).

  Specifically, in step (a), an alkali metal salt such as compound (6) or compound (8) is obtained, and in step (b), a polymer having the structural unit (i) is obtained.

  In the steps (a) and (b), it is preferable to perform each reaction in the presence of an organic solvent.

  Method (II ′) is a method in which the reaction between component (B) and an alkali metal compound is carried out in the presence of component (A).

  In this method (II '), the alkali metal salt of component (B) reacts with component (A) to obtain the polymer.

  In the method (II ′), the reaction is preferably performed in the presence of an organic solvent.

  In the case of producing the polymer by the method (I ′) or the method (II ′), for example, the component (A) in the reaction system (component (A) + component (B) + amount of organic solvent) ) And the concentration of component (B) are preferably increased. Specifically, the sum of the concentrations of component (A) and component (B) before the start of the reaction is 20 wt% to 50 wt% with respect to 100 wt% of the total amount of component (A), component (B) and organic solvent. Is preferable, and it is more preferable that it is 24 wt%-35 wt%.

  Since the sum of the concentrations of component (A) and component (B) in the reaction system is in the above range, the molecular weight distribution is narrow and the proportion of low molecular weight components having a molecular weight of 5000 or less is small. Is obtained. For this reason, by using the polymer, it is possible to obtain a film having excellent light resistance, in particular, excellent light transmittance in which coloring due to heating is suppressed.

  Examples of the alkali metal compound used in the reaction include alkali metals such as lithium, potassium and sodium; alkali hydrides such as lithium hydride, potassium hydride and sodium hydride; lithium hydroxide, potassium hydroxide and sodium hydroxide And alkali metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate; alkali metal hydrogen carbonates such as lithium hydrogen carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate. These can be used alone or in combination of two or more.

In the alkali metal compound, the amount of metal atoms in the alkali metal compound is usually 1 to 3 times equivalent, preferably 1.1 to 2 times equivalent to all —O—R ^a in the component (B). Preferably it is used in an amount of 1.2 to 1.5 times equivalent.

  Examples of the organic solvent that can be used for the reaction include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyllactone, Sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, dialkoxybenzene (1 to 4 carbon atoms of alkoxy group) and trialkoxybenzene (1 to 4 carbon atoms of alkoxy group) ) Etc. can be used. Among these solvents, polar organic solvents having a high dielectric constant such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone, and dimethylsulfoxide are particularly preferably used.

  Further, in the reaction, a solvent azeotropic with water such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole and phenetole can be further used.

  The proportion of component (A) and component (B) used is preferably 45 mol% or more and 55 mol% or less when component (A) and component (B) are 100 mol% in total. More preferably 50 mol% to 52 mol%, still more preferably more than 50 mol% to 52 mol%, and component (B) is preferably 45 mol% to 55 mol%, more preferably 48 mol%. % Or more and 50 mol% or less, more preferably 48 mol% or more and less than 50 mol%.

  Moreover, reaction temperature becomes like this. Preferably it is 60-250 degreeC, More preferably, it is the range of 80-200 degreeC. The reaction time is preferably in the range of 15 minutes to 100 hours, more preferably 1 hour to 24 hours.

<Physical properties of polymer>
The polymer (I) was measured by using an HLC-8220 type GPC apparatus (column: TSKgel α-M, developing solvent: tetrahydrofuran (hereinafter also referred to as “THF”)) manufactured by TOSOH. Mw) is preferably 5,000 to 500,000, more preferably 15,000 to 400,000, and even more preferably 30,000 to 300,000.

The polymer (II) was measured using a TOSOH HLC-8220 GPC apparatus (column: SuperH2000 and SuperH4000, guard column: SuperH-L linked column, developing solvent: THF), weight average in terms of polystyrene. The molecular weight (Mw) is preferably 2.5 × 10 ^{4 to} 5.0 × 10 ⁵ , more preferably 5.0 × 10 ^{4 to} 4.0 × 10 ⁵ , more preferably 7.0 ×. 10 ^{4 to} 3.0 × 10 ⁵ .

Further, the polymer preferably has an amount (ratio) of a low molecular weight component having a polystyrene-equivalent molecular weight by GPC of 5.0 × 10 ³ or less, calculated from an integrated molecular weight distribution curve by GPC, It is 5.0% or less, more preferably 3.5% or less.

  When the molecular weight of the polymer and the distribution thereof are within the above ranges, the polymer is excellent in color resistance, particularly color resistance even when exposed to high temperatures. For this reason, the film containing polymer (II) is excellent in light transmittance, especially even when exposed to high temperatures.

In addition, the amount occupied by low molecular weight components having a molecular weight in terms of polystyrene of 5.0 × 10 ³ or less is, specifically, an HLC-8220 type GPC apparatus manufactured by TOSOH (column: SuperH2000 and SuperH4000, guard column: SuperH-L , Developing solvent: THF, detector: UV254 nm, flow rate: 0.6 ml / min), and the integrated value in the chromatogram of the components eluted before the elution time of the polystyrene standard sample having a molecular weight of 5.0 × 10 ³ It can be calculated by measuring the integrated value in the chromatogram of the components eluted after the elution time of the polystyrene standard sample having a molecular weight of 5.0 × 10 ³ .

  The polymer has a thermal decomposition temperature measured by thermogravimetric analysis (TGA) of preferably 400 ° C. or higher, more preferably 425 ° C. or higher, and further preferably 450 ° C. or higher.

<Film>
The film according to the present invention contains the polymer. For this reason, the film which concerns on this invention is excellent in coloring property, heat resistance, and light transmittance.

  Moreover, the film containing the polymer (II) is further excellent in heat-resistant colorability, heat resistance and light transmittance. Therefore, these films can be suitably used as films such as light guide plates, polarizing plates, display films, optical disk films, transparent conductive films, and waveguide plates.

<Film production method>
Although it does not restrict | limit especially as a manufacturing method of the film of this invention, The process of apply | coating the polymer composition containing the said polymer on a board | substrate, forming a coating film, and the process of removing an organic solvent from this coating film The method of including is mentioned.

  In addition, after the step of forming the coating film or after the step of removing the organic solvent, a step of baking the coating film or the coating film from which the organic solvent has been removed (hereinafter also referred to as “baking step”) is included. It is preferable. By including the step of firing, a film having the specific heat shrinkage rate can be obtained.

  The step of removing the organic solvent from the coating film can be performed simultaneously in the baking step, but it is preferable to perform the step of removing the organic solvent before the baking step. In addition, when baking the coating film peeled from the board | substrate, it is preferable to include the process of removing an organic solvent from a coating film previously, before peeling a coating film from a board | substrate.

  The polymer composition is not particularly limited as long as it is a composition containing the polymer. Specifically, the polymer obtained by the method (I ′) or (II ′) and an organic solvent are used. Can be used as they are. By using such a polymer composition, a film can be easily produced at a low cost.

The polymer composition is prepared by isolating (purifying) the polymer as a solid component from the mixture of the polymer obtained by the method (I ′) or (II ′) and an organic solvent, A polymer composition can also be prepared by re-dissolving in a solvent.
By using such a polymer composition, a film with less coloring and excellent light transmittance can be produced.

  The method for isolating (purifying) the polymer as a solid content can be performed, for example, by reprecipitation of the polymer in a poor solvent of the polymer such as methanol, followed by filtration and then drying under reduced pressure.

  As the organic solvent for dissolving the polymer, for example, methylene chloride, tetrahydrofuran, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and γ-butyrolactone are preferably used. From the viewpoints of properties and economy, methylene chloride, N, N-dimethylacetamide and N-methylpyrrolidone are preferably used. These solvents can be used alone or in combination of two or more.

  The polymer concentration in the polymer composition in which the polymer is dissolved is usually 5 to 40% by mass, preferably 7 to 25% by mass, although it depends on the molecular weight of the polymer used. When the concentration of the polymer in the polymer composition is within the above range, it is possible to form a film that can be thickened, hardly causes pinholes, and has excellent surface smoothness.

  The viscosity of the polymer composition is usually 2,000 to 100,000 mPa · s, preferably 3,000 to 50,000 mPa · s, although it depends on the molecular weight and concentration of the polymer used. When the viscosity of the polymer composition is in the above range, the composition is easily retained during film formation, and the thickness can be easily adjusted. Therefore, the film can be easily formed.

  The film of the present invention preferably consists essentially of the above polymer, but may contain additives such as an anti-aging agent depending on the desired application. By containing an anti-aging agent, the durability of the resulting film can be further improved.

  Preferred examples of the antiaging agent include hindered phenol compounds.

  Examples of hindered phenol compounds that can be used in the present invention include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) proonate], 1,6-hexanediol- Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -3,5-triazine, pentaerythritol tetrakis [3- (3,5-tert-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris [2-methyl-4- [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5- Di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and 3,9-bis [2- [3- ( 3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [ .5] undecane, and the like.

  When the anti-aging agent is blended in the polymer composition, the blending amount of the anti-aging agent is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the polymer.

  Examples of the method for forming the coating film by applying the polymer composition on a substrate include a roll coating method, a gravure coating method, a spin coating method, and a method using a doctor blade.

  Although the thickness of a coating film is not specifically limited, For example, it is 1-250 micrometers, Preferably it is 2-150 micrometers, More preferably, it is 5-125 micrometers.

  Examples of the substrate include a polyethylene terephthalate (PET) film and a SUS plate.

  In the method for producing the film, the method for removing the organic solvent from the coating film can be specifically performed by heating the coating film. The heating condition is not limited as long as the organic solvent can be removed from the coating film, and may be appropriately determined according to the substrate and the polymer. For example, the heating temperature is preferably 30 ° C to 300 ° C, and preferably 40 ° C to 250 ° C. It is more preferable that the temperature is 50 ° C to 230 ° C.

  The heating time is preferably 10 minutes to 8 hours. Note that heating may be performed in two or more stages. Specifically, after drying at a temperature of 30 to 80 ° C. for 10 minutes to 2 hours, heating is further performed at 100 to 250 ° C. for 10 minutes to 2 hours. Moreover, you may dry in nitrogen atmosphere or under reduced pressure as needed.

  Moreover, it is preferable to perform the said baking process at specific temperature, Preferably it is 210 to 350 degreeC, More preferably, it is 220 to 330 degreeC, More preferably, it is more preferable to bake at 230 to 320 degreeC. The firing time is preferably 10 minutes to 5 hours.

  The firing atmosphere is not particularly limited, but is preferably in the air or in an inert gas atmosphere, and particularly preferably in an inert gas atmosphere.

  Examples of the inert gas include nitrogen, argon, helium and the like from the viewpoint of colorability, and nitrogen is preferable.

  In the baking step, the coating film formed on the substrate may be baked together with the substrate, but the coating film formed on the substrate is peeled off from the substrate and then baked from the point that it is not affected by the properties of the substrate. It is preferable to do.

  The obtained film can be used after being peeled off from the substrate, or can be used as it is without being peeled depending on the kind of the substrate used and the purpose of the film.

<Physical properties of film>
The film of the present invention has a thermal shrinkage rate of −0.1 to 0.1%, preferably −0.05 to 0.05%, more preferably JIS K7133 (heat treatment temperature 220 ° C., 60 minutes). Is -0.03 to 0.03%.

The “heat shrinkage rate” is obtained by measuring in accordance with JIS K7133. Specifically, as a heat treatment, an accurate length is set in advance in a temperature-controlled room set at a predetermined temperature (220 ° C.). The film (100 mm × 100 mm) whose thickness was measured was put in a non-tensioned state, held for 60 minutes, then taken out, returned to room temperature, and the change in dimensions was read. From the length L ₀ before the heat treatment and the length L after the heat treatment, the thermal contraction rate is obtained by the following equation.
Thermal contraction rate = (L ₀ −L) × 100 / L ₀ (%)

  The film of the present invention preferably has a thermal shrinkage rate of −0.2 to 0.2%, more preferably when measured in the same manner as described above except that the temperature during heat treatment is changed to 240 ° C. Is -0.1 to 0.1%, more preferably -0.05 to 0.05%, and particularly preferably -0.03 to 0.03%.

  Such a film having a value of thermal shrinkage in the above range has little dimensional change even when exposed to a high temperature when forming an element or wiring on the film, for example. This is preferable because the amount of stress and displacement generated is small.

  Although the thickness of the film of this invention is suitably selected according to a desired use, Preferably it is 1-250 micrometers, More preferably, it is 2-150 micrometers, More preferably, it is 10-125 micrometers.

Further, the film of the present invention preferably has a glass transition temperature (Tg) measured at 230 ° C. to 350 ° C. using a Thermo Plus DSC8230 manufactured by Rigaku under a temperature rising rate of 20 ° C./min under nitrogen. It is more preferable that it is 250-300 degreeC.
The film of the present invention has excellent heat resistance by having such a glass transition temperature.

Moreover, when the film of this invention is 30 micrometers in thickness, it is preferable that the total light transmittance in a JIS K7105 transparency test method is 85% or more, and it is more preferable that it is 88% or more. The total light transmittance can be measured using a haze meter SC-3H (manufactured by Suga Test Instruments Co., Ltd.).
The film of the present invention has a particularly high light transmittance because the transmittance is in such a range.

  When the thickness of the film of the present invention is 30 μm, the YI value (yellow index) is preferably 3.0 or less, more preferably 2.5 or less, and 2.0 or less. Is more preferable. The YI value can be measured using an SM-T color measuring device manufactured by Suga Test Instruments Co., Ltd. When the YI value is in such a range, a film that is difficult to be colored can be obtained.

  Moreover, when the film of this invention is 30 micrometers in thickness, it is preferable that YI value after heating for 1 hour at 230 degreeC in air | atmosphere with a hot air dryer is 3.0 or less. It is more preferably 5 or less, and further preferably 2.0 or less. When the YI value is in such a range, a film that is difficult to be colored even at high temperatures can be obtained.

The film of the present invention is a solution obtained by dissolving the film in N, N-dimethylacetamide (DMAc), and the YI value of the solution having a polymer concentration of 10% by weight is 32.0 or less. It is preferable that
In particular,
The YI value of a solution obtained by drying the film of the present invention at 200 ° C. for 6 hours and then dissolving in DMAc, the concentration of the polymer being 10% by weight is 15.0 or less. Is preferable, and it is more preferable that it is 7.0 or less.

  In addition, a solution obtained by drying the film of the present invention at 200 ° C. for 6 hours and further drying at 270 ° C. for 1 hour and then dissolving in DMAc, wherein the concentration of the polymer is 10% by weight. The YI value of is preferably 32.0 or less, more preferably 30.0 or less, and even more preferably 20.0 or less.

  The YI values of the solutions were calculated by measuring the hues of these solutions with an ultraviolet-visible spectrophotometer (V-570 (manufactured by JASCO), C light source, viewing angle 10 degrees).

  When the YI value is in such a range, it is possible to obtain a film that is difficult to be colored, particularly difficult to be colored even at high temperatures. A light guide plate, a polarizing plate, a display film, an optical disk film, a transparent conductive film, It can be suitably used for a film such as a waveguide plate.

  The film of the present invention preferably has a refractive index of 1.55 to 1.75, more preferably 1.60 to 1.70 with respect to light having a wavelength of 633 nm. The refractive index can be measured using a prism coupler model 2010 (manufactured by Metricon).

  The film of the present invention preferably has a tensile strength of 50 to 200 MPa, and more preferably 80 to 150 MPa. The tensile strength can be measured using a tensile tester 5543 (manufactured by INSTRON).

  The film of the present invention preferably has an elongation at break of 5 to 100%. The elongation at break can be measured using a tensile tester 5543 (manufactured by INSTRON).

  The film of the present invention preferably has a tensile modulus of 2.5 to 4.0 GPa, more preferably 2.7 to 3.7 GPa. The tensile elastic modulus can be measured using a tensile tester 5543 (manufactured by INSTRON).

  The film of the present invention preferably has a humidity expansion coefficient of 15 ppm /% RH or less, more preferably 12 ppm /% RH or less. The humidity expansion coefficient can be measured using a TMA (SII Nanotechnology, TMA-SS6100) humidity control option. When the expansion coefficient of the film is in the above range, the light guide plate, polarizing plate, display film, optical disk film, transparent conductive film, waveguide plate, etc. indicate that the dimensional stability (environmental reliability) of the film is high. It can be used more suitably as a film.

  Moreover, the said polymer and polymer composition can be conveniently used as a polymer composition mainly used in order to manufacture the above-mentioned film.

  Hereinafter, the present invention will be specifically described by way of examples.

(1-1) Structural analysis The structural analysis of the polymers obtained in Examples 1-1 to 6 and Comparative Examples 1-1 to 1-4 described below was performed using IR (ATR method, FT-IR, 6700, manufactured by NICOLET) and NMR (ADVANCE 500 type, manufactured by BRUKAR) was used.

(1-2) Weight average molecular weight The weight average molecular weights of the polymers obtained in Examples 1-1 to 6 and Comparative Examples 1-1 to 1-4 described below were measured by an HLC-8220 GPC apparatus (column: TSKgelα-M manufactured by TOSOH). , Developing solvent: THF). Detector is RI, flow rate 0.6 ml / min, measured concentration 0.2% by weight, standard polystyrene conversion.

(1-3) Glass transition temperature (Tg)
The glass transition temperature of the film for evaluation obtained in the following Examples 1-1 to 6 and Comparative Examples 1-1 to 4 was evaluated using a Thermo Plus DSC8230 manufactured by Rigaku Corporation with a temperature increase rate of 20 ° C./min.

(1-3 ') Thermal decomposition temperature The thermal decomposition temperature of the polymer obtained in the following Examples 1-1 to 6 and Comparative Examples 1-1 to 4 was determined by thermogravimetric analysis (TGA: temperature increase rate in a nitrogen atmosphere). 10 ° C./min, 5% weight loss temperature).

(1-4) Mechanical strength Tensile strength, breaking elongation, and tensile elastic modulus at room temperature of the films for evaluation obtained in the following Examples 1-1 to 6 and Comparative Examples 1-1 to 4 were measured according to JIS K7127. , And measured using a tensile tester 5543 (manufactured by INSTRON).

(1-5) Optical Properties For the evaluation films obtained in the following Examples 1-1 to 6 and Comparative Examples 1-1 to 4, the total light transmittance and the YI value were measured according to the JIS K7105 transparency test method. . Specifically, the total light transmittance of the film was measured using a SC-3H type haze meter manufactured by Suga Test Instruments Co., Ltd., and the YI value (yellow index) was measured using a SM-T color measurement device manufactured by Suga Test Instruments Co., Ltd. (YI before heating).

  Furthermore, the YI value after heating the film for evaluation obtained in the following Examples 1-1 to 6 and Comparative Examples 1-1 to 4 in the air at 230 ° C. for 1 hour in a hot air dryer was subjected to a suga test. Measurement was performed using an SM-T color measuring device manufactured by Kikai Co., Ltd. (YI after heating).

  The refractive indexes of the films for evaluation obtained in the following Examples 1-1 to 6 and Comparative Examples 1-1 to 4 were measured using a prism coupler model 2010 (manufactured by Metricon). The refractive index was measured using a wavelength of 633 nm.

(1-6) Thermal Shrinkage Ratio The film for evaluation obtained in Examples 1-1 to 6 and Comparative Examples 1-1 to 1-4 described below was used in accordance with JIS K7133. Specifically, after putting a film (100 mm × 100 mm) whose exact length was measured in advance in a temperature-controlled room set at a predetermined temperature (220 ° C. or 240 ° C.) in a non-tensioned state and holding it for 60 minutes After taking out and returning to room temperature, the change in the dimensions was read. From the film length L ₀ before the heat treatment and the film length L after the heat treatment, the thermal shrinkage rate was obtained by the following formula.
Thermal contraction rate = (L ₀ −L) × 100 / L ₀ (%)

(1-7) Humidity expansion coefficient (CHE)
The humidity expansion coefficient of the films for evaluation obtained in the following Examples 1-1 to 6 and Comparative Examples 1-1 to 4 is TMA (TMA-SS6100 manufactured by SII Nanotechnology, with humidity control option, humidity condition: 40% Humidity changed from RH to 70% RH every 10% (tensile method: load 5 g), temperature maintained at 23 ° C. for 2 hours at each humidity, CHE calculated from slope, sample size 4 mm × 20 mm, thickness 30 μm, 10 mm between chucks ).

[Example 1-1]
Component (B): 125.65 g (0.250 mol) of 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene (hereinafter also referred to as “BPPFL”), potassium carbonate 41. 46 g (0.300 mol), 643 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 161 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask.

  Next, after the atmosphere in the flask was replaced with nitrogen, the obtained solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the solution was cooled to room temperature, then component (A): 34.95 g (0.251 mol) of 2,6-difluorobenzonitrile was added, and the temperature was gradually raised to 140 ° C. The reaction was carried out for 6 hours at the same temperature.

  After cooling to room temperature (25 ° C.), the purified salt was removed with filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (polymer) (yield 150.77 g, yield 100%).

Table 1 shows the physical properties of the obtained polymer. The obtained polymer was subjected to a structural analysis and a weight average molecular weight measurement. The results show that the characteristic absorption of the infrared absorption spectrum is 3035 cm ⁻¹ (CH stretching), 2229 cm ⁻¹ (CN), 1574 cm ⁻¹ , 1499 cm ⁻¹ (aromatic ring skeleton absorption), 1240 cm ⁻¹ (—O—). The weight average molecular weight was 94,000.

Next, the obtained polymer was redissolved in DMAc to obtain a polymer composition having a polymer concentration of 20% by mass. The polymer composition is applied onto a substrate made of polyethylene terephthalate (PET) using a doctor blade, dried at 70 ° C. for 30 minutes, and then dried at 100 ° C. for 30 minutes to form a film, and then a PET substrate. More peeled. Then, the film was fixed to a metal frame, and further, as a baking step, it was baked in the atmosphere at 230 ° C. for 2 hours to obtain an evaluation film having a thickness of 30 μm.
Table 1 shows the physical properties of the obtained film for evaluation.

[Example 1-2]
Component (B): Example except that 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene (hereinafter also referred to as “BPFL”) was used instead of BPPFL (0.250 mol). It carried out similarly to 1-1.
Table 1 shows the physical properties of the obtained polymer and the film for evaluation.

[Example 1-3]
In the firing step of Example 1-1, the same procedure as in Example 1-1 was performed except that the firing temperature was changed from 230 ° C. to 270 ° C. and the firing atmosphere was changed from the atmosphere to the nitrogen atmosphere.
Table 1 shows the physical properties of the obtained polymer and the film for evaluation.

[Example 1-4]
Component (B): 52.56 g (0.150 mol) of BPFL and 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane instead of BPPFL (0.250 mol) (Hereinafter also referred to as “Bis-F”.) The same operation as in Example 1-1 was performed except that 33.62 g (0.100 mol) was used.
Table 1 shows the physical properties of the obtained polymer and the film for evaluation.

[Example 1-5]
Component (B): Instead of BPPFL (0.250 mol), BPFL 78.92 g (0.225 mol) and 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter also referred to as “Bis-Z”) 6.72 g The same procedure as in Example 1-1 was performed except that (0.025 mol) was used.
Table 1 shows the physical properties of the obtained polymer and the film for evaluation.

[Example 1-6]
Component (B): 87.69 g (0.250 mol) of BPFL was used instead of BPPFL (0.250 mol), and component 4, (A): 4,4′- instead of 2,6-difluorobenzonitrile (0.251 mol) The same procedure as in Example 1-1 was performed except that 72.15 g (0.251 mol) of dichlorodiphenyl sulfone was used.
Table 1 shows the physical properties of the obtained polymer and the film for evaluation.

[Comparative Example 1-1]
The same procedure as in Example 1-1 was performed except that the firing temperature in the firing step of Example 1-1 was changed from 230 ° C. to 200 ° C., and the firing atmosphere was changed from the atmosphere to a nitrogen atmosphere.
Table 1 shows the physical properties of the obtained polymer and the film for evaluation.

[Comparative Example 1-2]
It carried out similarly to Example 1-2 except having changed the calcination temperature in the calcination process of Example 1-2 from 230 degreeC to 200 degreeC, and having changed the calcination atmosphere from air | atmosphere to nitrogen atmosphere.
Table 1 shows the physical properties of the obtained polymer and the film for evaluation.

[Comparative Example 1-3]
The same procedure as in Example 1-6 was performed except that the firing temperature in the firing step of Example 1-6 was changed from 230 ° C. to 200 ° C., and the firing atmosphere was changed from the atmosphere to a nitrogen atmosphere.
Table 1 shows the physical properties of the obtained polymer and the film for evaluation.

[Comparative Example 1-4]
Component (B): The same procedure as in Example 1-6 except that 46.55 g (0.250 mol) of 4,4′-dihydroxybiphenyl was used instead of 87.69 g (0.250 mol) of BPFL. The film baking step was changed to 200 ° C. because deformation of the film was observed at 230 ° C.
Table 1 shows the physical properties of the obtained polymer and the film for evaluation. The heat shrinkage ratio after heat treatment at 240 ° C. could not be measured because the evaluation film was not able to be measured by undulation.

(2-1) Structural analysis The structural analysis of the polymers obtained in the following Examples 2-1 to 6 and Comparative Examples 2-1 to 5 was performed by IR (ATR method, FT-IR, 6700, manufactured by NICOLET) and NMR (ADVANCE 500 type, manufactured by BRUKAR) was used.

(2-2) Weight average molecular weight The weight average molecular weights of the polymers obtained in Examples 2-1 to 6 and Comparative Examples 2-1 to 5 described below were measured by a TOSOH HLC-8220 GPC apparatus (columns: SuperH2000 and SuperH4000). , Guard column: column connected with SuperH-L, developing solvent: THF). Detector is UV, wavelength 254 nm, flow rate 0.6 ml / min, measured concentration 0.3% by weight, standard polystyrene conversion. The amount of the component having a polystyrene-equivalent molecular weight of 5.0 × 10 ³ or less by GPC relative to the whole polymer was calculated from an integral molecular weight distribution curve by GPC.

(2-3) Glass transition temperature (Tg)
The glass transition temperature of the film for evaluation obtained in the following Examples 2-1 to 6 and Comparative Examples 2-1 to 5 was measured using a Thermo Plus DSC8230 manufactured by Rigaku under a temperature rising rate of 20 ° C./min under nitrogen.

(2-4) Optical properties The films for evaluation obtained in Examples 2-1 to 6 and Comparative Examples 2-1 to 5 below, and the films after baking the films at 270 ° C. for 1 hour were used. The UV-visible spectrophotometer was used for the hue (YI value) of the solution dissolved in DMAc so that the concentration of the polymer obtained in Examples 2-1 to 6 and Comparative Examples 2-1 to 5 was 10% by weight. (Measured by JASCO Corporation Model No. V-570, C light source, viewing angle 10 degrees).
In addition, the total light transmittance according to the JIS K7105 transparency test method in the thickness of 30 μm of the film for evaluation obtained in the following Examples 2-1 to 6 and Comparative Examples 2-1 to 5 was measured using a haze meter SC-3H (Suga Test Machine). The measurement was performed using

[Example 2-1]
In a 3 L four-necked flask, component (B): 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene (hereinafter also referred to as “BPFL”), 41.46 g of potassium carbonate (0 300 mol), 490 g of DMAc and 122 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask.

  Next, after the atmosphere in the flask was replaced with nitrogen, the obtained solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the solution was cooled to room temperature, and then component (A): 34.95 g (0.251 mol) of 2,6-difluorobenzonitrile was added, and the temperature was gradually raised to 160 ° C. The reaction was continued for 6 hours at the same temperature.

  After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (polymer) (yield 112.55 g, yield 100%).

Table 1 shows the physical properties of the obtained polymer. The obtained polymer was subjected to a structural analysis and a weight average molecular weight measurement. The results show that the characteristic absorption of the infrared absorption spectrum is 3035 cm ⁻¹ (CH stretching), 2229 cm ⁻¹ (CN), 1574 cm ⁻¹ , 1499 cm ⁻¹ (aromatic ring skeleton absorption), 1240 cm ⁻¹ (—O—). )Met. Further, the proportion of the weight average molecular weight of 259,500 and the molecular weight of 5000 or less was 3.72%.

  Next, the obtained polymer was redissolved in DMAc to obtain a resin composition having a polymer concentration of 20% by mass. The resin composition is applied onto a substrate made of polyethylene terephthalate (PET) using a doctor blade, dried at 70 ° C. for 30 minutes, and then dried at 100 ° C. for 30 minutes to form a film. It peeled. Thereafter, the film was fixed to a metal frame and further dried at 200 ° C. for 6 hours to obtain an evaluation film having a thickness of 30 μm.

  The physical properties of the obtained film for evaluation are shown in Table 2.

[Example 2-2]
The same procedure as in Example 2-1 was performed except that 293 g of DMAc and 73 g of toluene were used instead of 490 g of DMAc and 122 g of toluene. Table 2 shows the physical properties of the obtained polymer and the film for evaluation.

[Example 2-3]
Instead of 87.60 g (0.250 mol) of BPFL, 78.84 g (0.225 mol) of BPFL and 6.71 g (0.025 mol) of 1,1-bis (4-hydroxyphenyl) cyclohexane (also referred to as BisZ) were used. Except for this, the same procedure as in Example 2-2 was performed. Table 2 shows the physical properties of the obtained polymer and the film for evaluation.

[Example 2-4]
Instead of 87.60 g (0.250 mol) of BPFL, 78.84 g (0.225 mol) of BPFL and 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (BisAF) The same procedure as in Example 2-2 was performed except that 8.41 g (0.025 mol) was used. Table 2 shows the physical properties of the obtained polymer and the film for evaluation.

[Example 2-5]
Instead of 34.95 g (0.251 mol) of 2,6-difluorobenzonitrile, 27.96 g (0.201 mol) of 2,6-difluorobenzonitrile and 10.91 g (0.050 mol) of 4,4′-difluorobenzophenone The procedure was the same as in Example 2-2 except that was used. Table 2 shows the physical properties of the obtained polymer and the film for evaluation.

[Example 2-6]
The same procedure as in Example 2-2 was performed except that 63.82 g (0.251 mol) of 4,4′-difluorodiphenylsulfone was used instead of 34.95 g (0.251 mol) of 2,6-difluorobenzonitrile. . Table 2 shows the physical properties of the obtained polymer and the film for evaluation.

[Comparative Example 2-1]
In a 3 L four-necked flask, component (B): 87.60 g (0.250 mol) of BPFL, component (A): 34.95 g (0.251 mol) of 2,6-difluorobenzonitrile, 41.46 g of potassium carbonate (0. 300 mol), 490 g of DMAc and 122 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask.

  Next, after the atmosphere in the flask was replaced with nitrogen, the obtained solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours. The subsequent step of obtaining a polymer and the step of obtaining an evaluation film were carried out in the same manner as in Example 2-1. Table 2 shows the physical properties of the obtained polymer and the film for evaluation.

[Comparative Example 2-2]
Component (B): BPFL 78.84 g (0.225 mol) and BisZ 6.71 g (0.025 mol), Component (A): 2,6-difluorobenzonitrile 34.95 g (0.251 mol), potassium carbonate 41.46 g ( 0.300 mol), DMAc 490 g and toluene 122 g were used, and the same procedure as in Comparative Example 2-1 was performed. Table 2 shows the physical properties of the obtained polymer and the film for evaluation.

[Comparative Example 2-3]
Component (B): BPFL 78.84 g (0.225 mol) and BisAF 8.41 g (0.025 mol), Component (A): 2,6-difluorobenzonitrile 34.95 g (0.251 mol), potassium carbonate 41.46 g ( 0.300 mol), DMAc 490 g and toluene 122 g were used, and the same procedure as in Comparative Example 2-1 was performed. Table 2 shows the physical properties of the obtained polymer and the film for evaluation.

[Comparative Example 2-4]
(A) component: 2,6-difluorobenzonitrile 27.96 g (0.201 mol) and 4,4′-difluorobenzophenone 10.91 g (0.050 mol), (B) component: BPFL 87.60 g (0.250 mol) , Except that 41.46 g (0.300 mol) of potassium carbonate, 490 g of DMAc and 122 g of toluene were used. Table 2 shows the physical properties of the obtained polymer and the film for evaluation.

[Comparative Example 2-5]
Component (A): 63.82 g (0.251 mol) of 4,4′-difluorodiphenylsulfone, Component (B): 87.60 g (0.250 mol) of BPFL, 41.46 g (0.300 mol) of potassium carbonate, 490 g of DMAc, and toluene It carried out similarly to the comparative example 2-1, except having used 122g. Table 2 shows the physical properties of the obtained polymer and the film for evaluation.

Claims (13)

Having at least one structural unit (i) selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2):
The weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) is 2.5 × 10 ^{4 to} 5.0 × 10 ⁵ , and the molecular weight in terms of polystyrene is 5 based on the integral molecular weight distribution curve measured by GPC. The polymer which the quantity which the low molecular weight component which is 0.0 * 10 < ³ > or less occupies is 5.0% or less with respect to the whole polymer.

(In Formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.)

(In the formula (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO ₂ -Or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 And m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.) The polymer further has at least one structural unit (ii) selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). The polymer described in 1.

(In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1 .)

(In the formula ^{(4), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f.) The step (a) of obtaining the alkali metal salt of the component (B) by reacting the component (B) containing the compound represented by the following formula (6) with an alkali metal compound, and the mixture after the step (a) And a component (A) containing at least one compound selected from the group consisting of a compound represented by the following formula (5) and a compound represented by the following formula (7), and obtained in step (a). A step (b) of reacting the obtained alkali metal salt with the component (A)
The manufacturing method of the polymer of Claim 1 or 2 containing these.

(In Formula (6), R < ¹ > -R < ⁴ > and ad are respectively independently synonymous with R < ¹ > -R < ⁴ > and said ad in said Formula (1), ^Ra is independently a hydrogen atom. And represents a methyl group, an ethyl group, an acetyl group, a methanesulfonyl group or a trifluoromethylsulfonyl group.)

(In formula (5), X independently represents a halogen atom.)

(In the formula ^{(7), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, X is independently the same as X in the formula (5), provided that when m is 0, R ⁷ is not a cyano group. The method for producing a polymer according to claim 3, wherein the component (B) further contains a compound represented by the following formula (8).

(In Formula (8), R ⁵ , R ⁶ , Z, n, e and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in Formula (3); R ^a is independently synonymous with R ^a in the formula (6).   A resin composition comprising the polymer according to claim 1 or 2, or the polymer obtained by the production method according to claim 3 or 4.   A film comprising the polymer according to claim 1 or 2 or the polymer obtained by the production method according to claim 3 or 4. A polymer having at least one structural unit (i) selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), and JIS K7133 (heat treatment temperature) A film having a thermal shrinkage rate of −0.1% to 0.1% at 220 ° C. for 60 minutes.

(In Formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.)

(In the formula (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO ₂ -Or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 And m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.) The polymer further has at least one structural unit (ii) selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). Film.

(In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1 .)

(In the formula ^{(4), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f.)   The film according to any one of claims 6 to 8, wherein a YI value (yellow index) at a thickness of 30 µm of the film is 3.0 or less.   The YI value of a solution obtained by dissolving the film in N, N-dimethylacetamide (DMAc) and having a concentration of the polymer of 10% by weight is 32.0 or less. The film of any one of -9.   The film according to any one of claims 6 to 10, wherein the total light transmittance according to a JIS K7105 transparency test method at a thickness of 30 µm is 85% or more.   The film of any one of Claims 6-11 whose glass transition temperature (Tg) by differential scanning calorimetry (DSC, temperature increase rate of 20 degree-C / min) is 230-350 degreeC. It is a method of manufacturing the film of any one of Claims 6-12,
Applying a polymer composition containing the polymer and an organic solvent on a substrate to form a coating film;
And a step of baking the coating film at 210 to 350 ° C.