JP2015174908A - Varnish and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a varnish improved in solution stability and coatability using a polyarylate resin having excellent solubility in a non-halogen-based solvent and increased heat resistance.SOLUTION: A varnish is formed by dissolving a polyarylate resin in an organic solvent. A glass-transition temperature of the polyarylate resin is equal to or greater than 200°C but less than 320°C. The polyarylate resin at least contains the general formula (I). [W is a single bond, an oxygen atom, a sulfur atom, an alkylene group, or the like; Ar is a phenylene group, a biphenylene group, or the like; and Rto Rare each a hydrogen atom, a halogen atom, or the like.]

Description

  The present invention relates to a varnish comprising a polyarylate resin.

  Polyarylate resin is excellent in heat resistance, excellent in mechanical strength and dimensional accuracy represented by impact resistance, and is amorphous and transparent, so it is widely used in fields such as electric / electronics, automobiles and machinery. ing. Many products made of polyarylate resin are molded products processed in a molten state, such as extrusion molding and injection molding, but films cast by dissolving in a solvent or metals, glass, resin, wood, etc. Application to a substrate as a coating has become popular.

  Regarding such films and coatings made of polyarylate resin, for example, Patent Document 1 discloses a casting method using a solution in which polyarylate resin made of bisphenol A, terephthalic acid and isophthalic acid is dissolved in a halogen-based organic solvent. To form a film is disclosed. Patent Document 2 discloses a coating agent obtained by dissolving a polyarylate resin composed of bisphenol A, terephthalic acid, isophthalic acid and orthophthalic acid in a non-halogen organic solvent.

JP-A-8-269214 JP 2013-18943 A

However, regarding the polyarylate resin, the present inventors have found that there are the following problems with respect to the film and film obtained using the coating agent described in Patent Document 1 or 2.
In the film as described in Patent Document 1, the polyarylate resin to be used is obtained by dissolving in a halogen-based organic solvent such as methylene chloride or chloroform, and pouring and drying. In recent years, the use of such halogen-based organic solvents has been avoided because of concerns about the effects on the environment and the human body. By the way, the polyarylate resin has poor solubility in a non-halogen organic solvent, and it is difficult to obtain a stable resin solution. Therefore, when obtaining a fluent film, it has been difficult to use an organic solvent with reduced environmental load.
On the other hand, in the fields of electric / electronics and automobiles, in recent years, there has been a demand for weight reduction and thickness reduction. As a result, parts that require heat resistance have been required to have higher heat resistance.
Against this background, improvement in heat resistance is also demanded for polyarylate resins as coatings and films used in the above fields. The polyarylate resin described in Patent Document 2 has improved solvent solubility and is easy to form a film or film, but has insufficient heat resistance.

  An object of the present invention is to provide a varnish using a polyarylate resin having improved heat resistance, and having improved coatability and solution stability.

The inventor of the present invention has reached the present invention as a result of intensive studies to solve such problems.
That is, the gist of the present invention is as follows.
(1) A varnish obtained by dissolving a polyarylate resin in an organic solvent, wherein the glass transition temperature of the polyarylate resin is 200 ° C. or higher and lower than 320 ° C.
(2) The polyarylate resin contains a structure represented by the following general formulas (I) and (II), and the molar ratio thereof is 0.10 ≦ {(I) / [(I) + (II)]} ≦ The varnish of (1) that satisfies the range of 0.90.
[In general formula (I), W is a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkylidene group, a halo-substituted alkylene group, a carbonyl group, a sulfonyl group, a carboxyl alkylene group, a carboxyl alkylidene group, an alkoxycarbonylalkylene group, Selected from the group consisting of alkoxycarbonylalkylidene group, fluorene group, isatin group, phthalimidine group, alkylsilanediyl group, dialkylsilanediyl group, Ar is phenylene group, biphenylene group, naphthylene group, oxydiphenylene group, carbon number 3 Selected from the group consisting of ˜7 cyclic hydrocarbon groups, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a C 1-20 aliphatic hydrocarbon group, a carbon number 1-20 alicyclic hydrocarbon groups, C1-C20 aromatic hydrocarbon groups, B group, selected from the group consisting of halogenated alkyl groups. ]
[In the general formula (II), Ar is selected from the group consisting of a phenylene group, a biphenylene group, a naphthylene group, an oxydiphenylene group, and a cyclic hydrocarbon group having 3 to 7 carbon atoms; R ¹¹ , R ¹² , R ¹³ , And R ¹⁴ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon having 1 to 20 carbon atoms. R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic group having 1 to 20 carbon atoms. It is chosen from the group which consists of a hydrocarbon group, a C1-C20 aromatic hydrocarbon group, and a halogenated alkyl group, and k is an integer of 2-12. ]
(3) The organic solvent is at least one selected from halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, amide compounds, ether compounds, ketone compounds, and aromatic hydrocarbons not containing a halogen group (1) or Varnish of (2).
(4) The varnish of (1)-(3) whose solid content concentration is 1-40 mass%.
(5) The method for producing a varnish according to (1) to (4), wherein polyarylate resin particles of 100 μm or less are mixed and dissolved in an organic solvent.
(6) A film formed by applying the varnish of (1) to (4) to a substrate.
(7) A film formed from the varnish of (1) to (4).

According to the present invention, it is possible to obtain a varnish that uses a polyarylate resin with improved heat resistance and that has improved coatability and solution stability.
Since the coating film and film obtained from such a varnish are excellent in heat resistance and mechanical properties, they can be suitably used in various applications.

  The polyarylate resin used in the present invention is an aromatic dicarboxylic acid or a derivative thereof and a bisphenol or a derivative thereof, and an aromatic having a structure represented by the following general formulas (I) and (II) as a structural unit. It is a polyester polymer and is produced by methods such as solution polymerization, melt polymerization, and interfacial polymerization.

In general formula (I), W is a single bond, oxygen atom, sulfur atom, alkylene group, alkylidene group, halo-substituted alkylene group, carbonyl group, sulfonyl group, carboxyl alkylene group, carboxyl alkylidene group, alkoxycarbonylalkylene group, alkoxy. Carbonylalkylidene group, fluorene group, isatin group, phthalimidine group, alkylsilanediyl group, dialkylsilanediyl group, Ar is selected from the group consisting of phenylene group, biphenylene group, naphthylene group, oxydiphenylene group, 3 to 3 carbon atoms Selected from the group consisting of 7 cyclic hydrocarbon groups, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom. -20 alicyclic hydrocarbon group, C1-C20 aromatic hydrocarbon group, nitro Group, selected from the group consisting of halogenated alkyl groups.

Among these, W is preferably a single bond, a sulfur atom, an alkylene group or an alkylidene group in that it has good solubility and is excellent in the effect of improving heat resistance when used in combination with the following general formula (II). , Ar is preferably a phenylene group, and R ¹ , R ² , R ³ and R ⁴ are preferably each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, It is especially preferable that it is 1-4 aliphatic hydrocarbon groups.

  Examples of the bisphenol component for introducing a bisphenol residue into the structure represented by the general formula (I) include 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,2 -Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'- Dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 9,9-bis (4- Droxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, N-phenyl-3,3-bis (4-hydroxyphenyl) phthalimidine, N-methyl-3,3-bis ( 4-hydroxyphenyl) phthalimidine and the like. These compounds may be used alone or in combination of two or more. Among the above, from the viewpoints of solubility and heat resistance, 2-bis (4-hydroxyphenyl) propane (BPA), 2,2-bis (4-hydroxy-3-methylphenyl) propane (BPC), 2, 2-bis (3,5-dimethyl-4-hydroxyphenyl) propane (TMBPA) can be preferably used.

In general formula (II), Ar is selected from the group consisting of a phenylene group, a biphenylene group, a naphthylene group, an oxydiphenylene group, and a cyclic hydrocarbon group having 3 to 7 carbon atoms, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, Selected from the group consisting of a nitro group and a halogenated alkyl group, and R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic hydrocarbon having 1 to 20 carbon atoms. Selected from the group consisting of a group, an aromatic hydrocarbon group having 1 to 20 carbon atoms, and a halogenated alkyl group, and k is an integer of 2 to 12.

Among them, when used in combination with the following general formula (I), Ar is preferably a phenylene group from the viewpoint of having good solubility and a high effect of increasing the glass transition temperature. It is particularly preferred to use the acid in equimolar amounts. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms. Is particularly preferred. R ¹⁵ and R ¹⁶ are preferably each independently a hydrogen atom or a methyl group, and k is preferably 5.

  Examples of the bisphenol component for introducing a bisphenol residue into the structure represented by the general formula (II) include 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxy-3). , 5-dimethylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxy-3) , 5-dimethylphenyl) cyclopentane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, Examples thereof include 1-bis (4-hydroxyphenyl) -3,3,5-triethylcyclohexane. These compounds may be used alone or in combination of two or more. Among these, from the viewpoints of solubility and heat resistance, 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BPTMC) and 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane can be preferably used.

  Examples of the aromatic dicarboxylic acid component for introducing an aromatic dicarboxylic acid residue into the structure represented by the general formulas (I) and (II) include terephthalic acid, isophthalic acid, phthalic acid, chlorophthalic acid, nitrophthalic acid, , 5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, methyl terephthalic acid, 4,4'-biphenyldicarboxylic acid, 2,2'-biphenyl Dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-diphenylmethane dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 4,4′-diphenylisopropylidenedicarboxylic acid, 1,2-bis (4- Carboxyphenoxy) ethane, 5-sodium sulfoisophthalic acid, etc. It is. Among these, terephthalic acid and isophthalic acid are preferable, and it is particularly preferable to use a mixture of both from the viewpoint of solubility in a solvent. In that case, the mixing ratio is arbitrarily in the range of (terephthalic acid / isophthalic acid) = 100/0 to 0/100 (mol%), preferably 80/20 to 10/90 (mol%), more preferably If the range is 60/40 to 25/75 (mol%), the resulting polyarylate resin has excellent solubility.

  Moreover, you may use aliphatic dicarboxylic acids in the range which does not impair the characteristic and effect of this invention. The aliphatic dicarboxylic acids are not particularly limited, and examples thereof include dicarboxymethylcyclohexane, cyclohexanedicarboxylic acid, adipic acid, sebacic acid, glutaric acid, and dodecanedioic acid.

  As the polyarylate resin, aliphatic glycols and dihydroxybenzene may be used as long as the characteristics and effects of the present invention are not impaired. Aliphatic glycols are not particularly limited, but ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, nonanediol, decanediol, cyclohexanedimethanol, ethylene oxide adducts of bisphenol A, and propylene oxide adducts thereof Examples of dihydroxybenzenes such as ethylene oxide adducts of bisphenol S, hydroquinone, resorcinol, and catechol.

In the polyarylate resin used in the present invention, the molar ratio of the structures represented by the general formulas (I) and (II) preferably satisfies the following formula.
0.10 ≦ {(I) / [(I) + (II)]} ≦ 0.90

  The molar ratio is more preferably 0.15 to 0.85, and further preferably 0.20 to 0.80. When the molar ratio exceeds 0.90, the solubility of the polyarylate resin to be used in the organic solvent becomes insufficient, and the heat resistance of the polyarylate resin becomes inferior. When the molar ratio is less than 0.10, the heat resistance is sufficient, but the solubility in an organic solvent is insufficient.

  The polyarylate resin used in the present invention is a resin solution having a concentration of 1 g / dl dissolved in a 60/40 (mass ratio) mixture of phenol / 1,1,2,2-tetrachloroethane at a temperature of 25 ° C. The inherent viscosity in is preferably 0.40 to 1.20 dl / g, and more preferably 0.45 to 1.00 dl / g. Inherent viscosity is an index of molecular weight. In the present invention, when the inherent viscosity of the polyarylate resin used is less than 0.40 dl / g, the mechanical properties as a polymer are inferior. If the inherent viscosity exceeds 1.20 dl / g, the viscosity of the varnish is increased when the polyarylate resin to be used is dissolved in an organic solvent, and workability is deteriorated.

  In order to keep the inherent viscosity of the polyarylate resin, that is, the molecular weight within a predetermined range, the method of adjusting the molecular weight by controlling the reaction rate by adjusting the polymerization time, the blending of monomer of aromatic dicarboxylic acid component or dihydric phenol component A method of adjusting the molecular weight by polymerizing with a slight excess of any of the components, alcohols or phenols having only one reactive functional group in the molecule, or end-capping agents with carboxylic acids And a method of adjusting the molecular weight by adding together with the monomer. Among these, the method of adding a terminal blocking agent is preferable because the molecular weight can be easily controlled.

  Examples of the end-capping agent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, pentanol, hexanol, dodecyl alcohol, stearyl alcohol, benzyl alcohol, phenethyl alcohol, phenol, cresol and the like. , 2,6-xylenol, 2,4-xylenol, p-tert-butylphenol, cumylphenol and other phenols, benzoic acid, methylbenzoic acid, naphthoic acid, acetic acid, propionic acid, butyric acid, oleic acid, stearic acid And the like, or derivatives thereof.

  The polyarylate resin used in the present invention has a glass transition temperature of 200 ° C. or higher and lower than 320 ° C., preferably 210 ° C. or higher and lower than 310 ° C., more preferably 220 ° C. or higher and lower than 300 ° C., more preferably 230 ° C. or higher. More preferably, it is less than 290 degreeC.

  To the polyarylate resin used in the present invention, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a thioether-based antioxidant, a phosphorus-based antioxidant, or the like may be added as long as the characteristics are not impaired. .

  The polyarylate resin used in the present invention can be used as a varnish by dissolving in an organic solvent. The solid content concentration at the time of dissolution can be arbitrarily determined.

  In the present invention, the polyarylate resin used has a molar ratio of the structures represented by the general formulas (I) and (II) of 0.10 ≦ {(I) / [(I) + (II)]} ≦ 0. By polymerizing to 90 to obtain a polyarylate resin, the solubility in an organic solvent is particularly excellent. Such polyarylate resins can be suitably dissolved in organic solvents such as halogenated hydrocarbons, halogenated aromatic hydrocarbons, amide compounds, ether compounds, ketone compounds and aromatic hydrocarbons, and the resulting varnish This also improves the stability.

  In the varnish of the present invention, the judgment of the superiority or inferiority of the solubility of the polyarylate resin to be used in the organic solvent should be confirmed, for example, by whether or not it completely dissolves at a solid content concentration of 10% by mass or more at room temperature (23 ° C.). Can do. In general, depending on the structural unit, the polyarylate resin can be dissolved only in a specific organic solvent, or the solubility in the solvent is low, or although it dissolves, it gels in a few days after dissolution, sometimes in several hours, etc. There is a problem of poor stability. In the varnish of the present invention, even when any of the organic solvents listed above is used, those that dissolve only at a solid content concentration of less than 10% by mass or gel during dissolution do not have solubility. Judge.

  In the present invention, the method for producing the varnish is not particularly limited. For example, after the polyarylate resin is pulverized to a size of 100 μm or less, the obtained fine particles are mixed with an organic solvent, and stirred and dissolved as necessary. Is preferred. As a method of mixing the polyarylate resin with the organic solvent, a method in which a predetermined amount of the organic solvent and the polyarylate resin are placed in a container and maintained as a mixed liquid while being maintained at a constant temperature, and the mixed liquid is stirred with a stirrer, or the container The method of sealing and shaking is mentioned. The time required from the start of dissolution until the entire amount is dissolved is affected not only by the solubility of the polyarylate resin but also by the dissolution method, but preferably the conditions allow the entire amount to be dissolved within 24 hours, more preferably within 5 hours. Is preferable from the viewpoint of workability. During the dissolution, the state of the mixed solution is observed in a timely manner, and if any insoluble matter (precipitation), turbidity, and gelation are not observed, it can be confirmed that the solution is completely dissolved. At this time, depending on the size and fine structure of the polyarylate resin particles, it may take time to dissolve. In such a case, the polyarylate resin is pulverized so that the average particle size is 100 μm or less, and then the dissolution is performed. By dissolving by the method, workability can be improved.

  The organic solvent used for the dissolution is at least one organic solvent selected from halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, amide compounds, ether compounds, ketone compounds, and aromatic hydrocarbons. The organic solvent to be used is not particularly limited as long as the polyarylate resin can be dissolved into a varnish, and is preferably selected according to the process suitability for using the varnish.

  Specific examples of the halogenated aliphatic hydrocarbon include, for example, dichloromethane, chloroform, chloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, dibromomethane, and tribromo. Methane, bromoethane, 1,2-dibromoethane, 1-bromopropane and the like can be mentioned.

  Specific examples of the halogenated aromatic hydrocarbon include chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene and the like.

  Specific examples of the amide compound include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like.

  Specific examples of the ether compound include 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran and the like.

  Specific examples of the ketone compound include cyclopentanone and cyclohexanone.

  Specific examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like.

The polyarylate resin used in the present invention can be made into a varnish by dissolving in the organic solvent. In addition, when setting it as a varnish, in order to provide desired performance, you may melt | dissolve resin other than polyarylate resin within the range of the performance required by this invention. Examples of other resins include polycarbonate, polystyrene, polyester, acrylic resin, polyphenylene ether, polysulfone, polyethersulfone, and polyetherimide. Various additives such as an antioxidant, a flame retardant, an ultraviolet absorber, a fluidity modifier, and a fine particle inorganic filler may be mixed and used.

  The solid content concentration of the varnish obtained in the present invention is preferably 1 to 40% by mass, and more preferably 5 to 35% by mass.

  The method of using the varnish is not particularly limited, but a method of forming a film on a substrate such as resin or metal by coating, a method of obtaining a film by removing only the film formed on the substrate, drum, or belt, fibrous A method of impregnating a varnish into a reinforcing material and evaporating the solvent to form a composite material generally called a prepreg, forming a coating film on a substrate such as a resin or metal, and before evaporating the solvent, Examples thereof include a method of using a base material such as resin or metal as a bonding adhesive.

  Although the drying method of a varnish is not specifically limited, In order to remove a solvent efficiently, heat drying is preferable.

  Thus, since the film and film obtained from the varnish are excellent in heat resistance and mechanical properties, they can be applied to various applications. For example, in applications where heat resistance and mechanical properties are required in automotive parts, electrical / electronic parts, coatings are formed on metal parts and other resin parts, or as a single film, as a display, substrate, insulating layer, etc. Can be used. Moreover, after apply | coating a varnish to a 1st base material, a 2nd base material is laminated | stacked and it can integrate by heating and can also be set as a laminated body.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited only to these Examples.

1. Evaluation method (1) Inherent viscosity (ηinh)
Using a mixed solution of phenol / 1,1,2,2-tetrachloroethane = 60/40 (mass ratio) as a solvent, the relative viscosity (ηrel) was measured under the conditions of a concentration of 1 g / dl and a temperature of 25 ° C. From the obtained relative viscosity, the inherent viscosity was calculated from the following formula.
ηinh (dl / g) = Ln (ηrel) / c (c: concentration)

(2) Glass transition temperature Using a differential scanning calorimeter (Diamond DSC manufactured by PerkinElmer), the glass was heated from 30 ° C. to 400 ° C. at a heating rate of 10 ° C./min. The onset temperature of the discontinuous change derived from the transition temperature was defined as the glass transition temperature.

(3) Solubility Seal a total of 30 g of resin and organic solvent weighed to a prescribed concentration in a glass screw cap bottle with an internal volume of 50 ml, and use a mix rotor at a room temperature of 23 ° C. and a screw cap bottle at 70 rpm. Rotated. Rotation was stopped 24 hours after the start of rotation. Thereafter, the resin solution in the screw cap bottle was visually observed, and the solubility was evaluated according to the following criteria. As organic solvents, chloroform, chlorobenzene, N-methyl-2-pyrrolidone (hereinafter referred to as NMP), 1,3-dioxolane, cyclohexanone and toluene are used so as to have respective concentrations of 10, 20, and 30% by mass. A resin solution was prepared.
◯: Completely dissolved and transparent.
Δ: Cloudy.
X: There was insoluble matter.

(4) Solution stability For each resin solution whose solubility was evaluated in (3), the screw cap bottle whose rotation was stopped was allowed to stand at room temperature of 23 ° C. for 48 hours. Thereafter, the resin solution in the screw cap bottle was visually observed, and the solution stability was evaluated according to the following criteria.
○: Transparency was maintained and the viscosity was not increased. Δ: Cloudy and slightly thickened. However, it had fluidity.
X: Gelled. There was no fluidity.

(5) Coating property The polyarylate resin obtained in the Examples described later was dissolved in chloroform so that the solid content concentration was 20% by mass to obtain a varnish. The resulting varnish was dried at 150 ° C. after forming a coating film on a polyethylene terephthalate film substrate using an applicator so that the thickness after drying was 100 μm, to obtain a polyarylate resin film. The obtained polyarylate resin film was evaluated according to the following criteria. In addition, the coating property was not evaluated for (3) using chloroform with a solid content concentration of 20% by mass and a solubility of x.
A: The film surface is smooth, the thickness is uniform, and it is transparent.
Δ: The smoothness is slightly inferior.
X: It became cloudy.

Example 1
In a reaction vessel having an internal volume of 100 L equipped with a water cooling jacket and a stirrer, 850 g of sodium hydroxide was dissolved in 30 L of ion exchange water, and then 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as BPA) 3 0.000 mol, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter BPTMC) 3.00 mol and p-tertbutylphenol (hereinafter PTBP) 0.30 mol were dissolved.
In a separate container, 3.08 mol of terephthalic acid dichloride (hereinafter TPC) and 3.08 mol of isophthalic acid dichloride (hereinafter IPC) were dissolved in 18 L of dichloromethane.
After adjusting each solution to 20 ° C., 15 g of a 50% aqueous solution of benzyltrimethylammonium chloride was added to the reaction vessel in which the aqueous solution was stirred, and the entire amount of the dichloromethane solution was added, and stirring was continued for 6 hours. After that, the stirrer was stopped.
After standing separation, the aqueous phase was extracted, and 20 g of acetic acid was added to the remaining dichloromethane phase. Thereafter, 30 L of ion-exchanged water was added, stirred for 20 minutes, and allowed to stand again to extract the aqueous phase. This washing operation was repeated until the aqueous phase became neutral, and then the dichloromethane phase was poured into 50 ° C. warm water in a container equipped with a homomixer to evaporate the methylene chloride to obtain a powdered polyarylate. .

  The powdery polyarylate was dehydrated and then dried at 130 ° C. under reduced pressure for 24 hours using a vacuum dryer to obtain a polyarylate resin. The inherent viscosity of this resin was 0.52 dl / g, no crystallization and melting peak was observed by DSC measurement, and the glass transition temperature was 225 ° C. Furthermore, the obtained polyarylate resin was classified so that the average particle size was 100 μm or less.

  Using the obtained polyarylate resin, solubility, solution stability, and coatability were evaluated. The results are shown in Table 1.

Examples 2-7
A polyarylate resin was produced and evaluated in the same manner as in Example 1 except that the blending ratios of BPA, BPTMC, PTBP, TPC and IPC were changed to those shown in Tables 2 and 3. The results are shown in Tables 1 and 2.

Example 8
Using the same apparatus as in Example 1, 850 g of sodium hydroxide was dissolved in 30 L of ion exchange water, and then 3.00 mol of 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter BPC), BPTMC 3.00 mol and PTBP 0.30 mol were dissolved. In a separate container, 3.08 mol of TPC and 3.08 mol of IPC were dissolved in 18 L of dichloromethane.
After adjusting each solution to 20 ° C., 15 g of a 50% aqueous solution of benzyltrimethylammonium chloride was added to the reaction vessel in which the aqueous solution was stirred, and the entire amount of the dichloromethane solution was added, and stirring was continued for 6 hours. After that, the stirrer was stopped. Thereafter, a polyarylate resin was obtained by the same operation as in Example 1, and various evaluations were performed. The results are shown in Table 2.

Example 9
Using the same apparatus as in Example 1, 850 g of sodium hydroxide was dissolved in 30 L of ion-exchanged water, then 3.00 mol of BPA, 3.00 mol of 1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter referred to as BPZ), And PTBP 0.30 mol was melt | dissolved. In a separate container, 3.08 mol of TPC and 3.08 mol of IPC were dissolved in 18 L of dichloromethane.
After adjusting each solution to 20 ° C., 15 g of a 50% aqueous solution of benzyltrimethylammonium chloride was added to the reaction vessel in which the aqueous solution was stirred, and the entire amount of the dichloromethane solution was added, and stirring was continued for 6 hours. After that, the stirrer was stopped. Thereafter, a polyarylate resin was obtained by the same operation as in Example 1, and various evaluations were performed. The results are shown in Table 2.

Example 10
Using the same apparatus as in Example 1, 850 g of sodium hydroxide was dissolved in 30 L of ion exchange water, and then 3.00 mol of BPA, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane (hereinafter referred to as DMBPC). 3.00 mol and PTBP 0.30 mol were dissolved. In a separate container, 3.08 mol of TPC and 3.08 mol of IPC were dissolved in 18 L of dichloromethane.
After adjusting each solution to 20 ° C., 15 g of a 50% aqueous solution of benzyltrimethylammonium chloride was added to the reaction vessel in which the aqueous solution was stirred, and the entire amount of the dichloromethane solution was added, and stirring was continued for 6 hours. After that, the stirrer was stopped. Thereafter, a polyarylate resin was obtained by the same operation as in Example 1, and various evaluations were performed. The results are shown in Table 2.

Comparative Examples 1-5
A polyarylate resin was obtained in the same manner as in Example 1 except that the blending ratios of BPA, BPC, BPTMC, BPZ, PTBP, TPC, and IPC were changed to those shown in Table 3, and various evaluations were performed. The results are shown in Table 3.

Comparative Example 6
Various evaluations were performed using a polycarbonate resin (Iupilon S-3000 manufactured by Mitsubishi Engineering Plastics) instead of the polyarylate resin. The results are shown in Table 4.
In addition, about evaluation of coating property, the varnish melt | dissolved with the solid content density | concentration of 10 mass% was obtained and evaluated. The drying temperature was 120 ° C.

  Examples 1 to 10 The varnishes obtained had excellent solubility in various organic solvents and solution stability because a polyarylate resin having a predetermined structure was used. A film obtained from such a varnish had improved heat resistance, a smooth film surface, a uniform thickness, and was transparent.

  In Comparative Examples 1 to 4, since the polyarylate resin having a predetermined structure was not used, the polyarylate resin was dissolved in a specific organic solvent only at a relatively low concentration, and the solution stability was inferior.

  In Comparative Example 5, the solubility and solution stability were excellent, but the polyarylate resin having a predetermined structure was not used, and thus the required heat resistance of the polyarylate resin was not obtained.

In Comparative Example 6, since a heat-resistant resin other than the polyarylate resin was used, it had no solubility and solution stability except for a specific halogen-based solvent. Only an opaque film was obtained with the varnish used.

Claims (7)

  A varnish obtained by dissolving a polyarylate resin in an organic solvent, wherein the glass transition temperature of the polyarylate resin is 200 ° C. or higher and lower than 320 ° C. The polyarylate resin has a structure represented by the following general formulas (I) and (II), and the molar ratio thereof is 0.10 ≦ {(I) / [(I) + (II)]} ≦ 0.90 The varnish according to claim 1 satisfying the following range.
[In general formula (I), W is a single bond, an oxygen atom, a sulfur atom, an alkylene group, an alkylidene group, a halo-substituted alkylene group, a carbonyl group, a sulfonyl group, a carboxyl alkylene group, a carboxyl alkylidene group, an alkoxycarbonylalkylene group, Selected from the group consisting of alkoxycarbonylalkylidene group, fluorene group, isatin group, phthalimidine group, alkylsilanediyl group, dialkylsilanediyl group, Ar is phenylene group, biphenylene group, naphthylene group, oxydiphenylene group, carbon number 3 Selected from the group consisting of ˜7 cyclic hydrocarbon groups, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a C 1-20 aliphatic hydrocarbon group, a carbon number 1-20 alicyclic hydrocarbon groups, C1-C20 aromatic hydrocarbon groups, B group, selected from the group consisting of halogenated alkyl groups. ]
[In the general formula (II), Ar is selected from the group consisting of a phenylene group, a biphenylene group, a naphthylene group, an oxydiphenylene group, and a cyclic hydrocarbon group having 3 to 7 carbon atoms; R ¹¹ , R ¹² , R ¹³ , And R ¹⁴ are each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon having 1 to 20 carbon atoms. R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic group having 1 to 20 carbon atoms. It is chosen from the group which consists of a hydrocarbon group, a C1-C20 aromatic hydrocarbon group, and a halogenated alkyl group, and k is an integer of 2-12. ]   The organic solvent is at least one selected from a halogenated aliphatic hydrocarbon, a halogenated aromatic hydrocarbon, an amide compound, an ether compound, a ketone compound, and an aromatic hydrocarbon not containing a halogen group. varnish.   The varnish according to any one of claims 1 to 3, wherein the solid content concentration is 1 to 40% by mass.   The method for producing a varnish according to claim 1, wherein polyarylate resin particles of 100 μm or less are mixed and dissolved in an organic solvent.   The film formed by apply | coating the varnish in any one of Claims 1-4 to a base material. The film formed from the varnish in any one of Claims 1-4.