JP6815025B2 - Polyarylate resin - Google Patents

Description

The present invention provides a polyarylate resin that can be molded at a relatively low temperature as compared with the conventional one, while maintaining the original heat resistance, transparency, and mechanical properties of the polyarylate resin.

Polyarylate resin, which is known as an engineering plastic, is used in a wide range of fields such as electrical and electronic applications, automobile applications, and mechanical applications because it has excellent heat resistance, transparency, and mechanical properties. In recent years, it has also been developed for optical applications such as optical fibers, optical lenses, liquid crystal panels, prisms, and optical disks.

However, since the polyarylate resin has a high melt viscosity, it is necessary to heat it at a high temperature of 300 ° C. or higher in order to develop melt fluidity, and it cannot be said that the polyarylate resin has high molding processability. Further, at high temperatures, there have been problems that transparency is impaired due to coloring and mechanical properties are deteriorated due to thermal deterioration.

In recent years, attempts have been made to add a fluidity modifier in order to improve moldability. For example, Patent Document 1 describes a method of adding an N-phenylmaleimide-styrene copolymer as a fluidity modifier. However, although the polyarylate resin of Patent Document 1 is improved in fluidity, there is a problem that the appearance of the surface is deteriorated due to the decomposition gas of the additive at high temperature.

Japanese Unexamined Patent Publication No. 2001-279575

The present invention solves the above problems, and provides a polyarylate resin that can be molded at a relatively low temperature as compared with the conventional one while maintaining the original heat resistance, transparency, and mechanical characteristics of the polyarylate resin. The purpose is.

As a result of diligent studies to solve the above problems, the present inventors have found that the above object can be achieved by containing a specific monovalent carboxylic acid residue at the terminal, and have reached the present invention. ..

That is, the gist of the present invention is as follows.
(1) A polyarylate resin containing a divalent phenol residue and an aromatic divalent carboxylic acid residue as main components and having a monovalent carboxylic acid residue represented by the following general formula (1) at the end (however, the number average molecular weight). Excludes polyarylate resins with a polystyrene equivalent of less than 10,000.)
(In formula (1), X represents a linear or branched alkyl group having 14 to 27 carbon atoms.)
(2) The polyarylate according to (1), wherein the monovalent carboxylic acid residue represented by the general formula (1) is 10.0 to 18.0 mol% with respect to the total aromatic divalent carboxylic acid residue. resin.
(3) The polyarylate resin according to (1) or (2), wherein the monovalent carboxylic acid residue represented by the general formula (1) is a stearic acid residue or an isostearic acid residue.
(4) The polyarylate resin according to any one of (1) to (3), wherein the divalent phenol residue is a divalent phenol residue represented by the following general formula (2).
(In formula (2), R1 and R2 independently represent a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an alkyl halide group or an aryl group. P and q are 0 or 1 to 8 When p and q are 0, Y represents a saturated or unsaturated chain or cyclic hydrocarbon group having 4 to 14 carbon atoms, and when p and q are 1 to 8, Y is. Represents a saturated or unsaturated chain or cyclic hydrocarbon group having 3 to 14 carbon atoms.)
(5) The polyarylate resin according to any one of (1) to (4), wherein the weight average molecular weight (Mw) of the polyarylate resin is 20000-90000 in terms of standard polystyrene.
(6) A film made of the polyarylate resin according to any one of (1) to (5).

According to the present invention, it is possible to provide a polyarylate resin that can be molded at a relatively low temperature as compared with the conventional one, while maintaining the original heat resistance, transparency, and mechanical properties of the polyarylate resin. The polyarylate resin of the present invention and a film made of the polyarylate resin of the present invention are difficult to be colored during molding, and can be suitably used particularly for optical applications such as optical fibers, optical lenses, liquid crystal panels, prisms, and optical disks.

The polyarylate resin of the present invention contains a specific monovalent carboxylic acid residue at the terminal, and contains a divalent phenol residue and an aromatic divalent carboxylic acid residue as main components. In the present invention, "mainly composed" means that the total of the divalent phenol residue and the aromatic divalent carboxylic acid residue is 70 mol% or more with respect to all the monomer residues.

Polyarylate resins of the present invention, the terminal, be contained monocarboxylic acid residues carbon atoms represented by the general formula (1) having a linear or branched long chain alkyl group of 14 to 27 is necessary. By containing the residue represented by the general formula (1), the glass transition temperature can be lowered while maintaining the mechanical characteristics, and the molding process at a relatively low temperature becomes possible.

In the general formula (1), X is independently, carbon atoms represents straight-chain or branched alkyl group 14 to 27. When the number of carbon atoms is less than 14 , the glass transition temperature of the obtained polyarylate resin becomes high, and sufficient molding processability cannot be obtained, which is not preferable. On the other hand, when the number of carbon atoms exceeds 27 , heat resistance and mechanical properties are significantly lowered, which is not preferable.

The monovalent carboxylic acid residue is introduced, for example, by using a monovalent carboxylic acid chloride as an end-capping agent in the interfacial polymerization method.

Examples of the monovalent carboxylic acid chloride giving a monovalent carboxylic acid residue represented by the general formula (1) include pentadecanoic acid chloride (15 carbon atoms), palmitic acid chloride (16 carbon atoms), and isopalmitate chloride (16 carbon atoms). 16 carbon atoms), margaric acid chloride (17 carbon atoms), stearic acid chloride (18 carbon atoms), isostearic acid chloride (15 carbon atoms), arachidic acid chloride (20 carbon atoms), behenic acid chloride (22 carbon atoms), Examples thereof include lignoceric acid chloride (24 carbon atoms), cerotic acid chloride (26 carbon atoms), and montanic acid chloride (28 carbon atoms). Among these, stearate chloride and isostearic acid chloride are preferable because they are industrially easily available and easily synthesized.

The content of the monovalent carboxylic acid residue represented by the general formula (1) is preferably 10.0 to 18.0 mol% with respect to the total divalent carboxylic acid component, and 13.0 to 16 More preferably, it is 0.0 mol%. When the content is less than 10.0 mol%, the glass transition temperature of the obtained polyarylate resin becomes high, and sufficient molding processability may not be obtained. On the other hand, if the content exceeds 18.0 mol%, the mechanical properties are significantly deteriorated, which is not preferable.

The polyarylate resin of the present invention may contain a monovalent carboxylic acid residue other than the residue represented by the general formula (1) as long as the effect of the present invention is not impaired. Examples of the monovalent carboxylic acid chloride giving the other monovalent carboxylic acid residue include benzoyl chloride, benzoic acid chloride, methanesulfonyl chloride, and phenylchloroformate. When another monovalent carboxylic acid residue is contained, the content thereof may be 5 mol% or less with respect to the monovalent carboxylic acid residue represented by the general formula (1) from the viewpoint of processability. It is preferably 3 mol% or less.

Examples of the divalent phenol that gives a divalent phenol residue include 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, and 1,1-bis. (4-Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 9,9 -Bis (3-methyl-4-hydroxyphenyl) fluorene, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 2,2-bis Examples thereof include (4-hydroxyphenyl) hexafluoropropane and 4,4'-(1-phenylethylidene) bisphenol.

Among these, a divalent phenol that gives a residue represented by the following general formula (2) is preferable because it is easily industrially available and easily synthesized.

In the general formula (2), R ¹ and R ² independently represent a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an alkyl halide group or an aryl group. p and q are 0 or 1-8, and when p and q are 0, Y represents a saturated or unsaturated chain or cyclic hydrocarbon group with 4-14 carbon atoms, p and q. When is 1 to 8, Y represents a saturated or unsaturated chain or cyclic hydrocarbon group having 3 to 14 carbon atoms.

The polyarylate resin of the present invention may contain a divalent alcohol residue other than the divalent phenol residue. Examples of the dihydric alcohol that gives the other dihydric alcohol residue include aliphatic diols such as ethylene glycol and propylene glycol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, and 1,2-cyclohexanediol. Such as alicyclic diols. When the other divalent alcohol residue is contained, the content thereof is preferably 10 mol% or less, preferably 5 mol% or less, based on the total divalent phenol residue from the viewpoint of mechanical properties. Is preferable.

Examples of the aromatic divalent carboxylic acid that gives an aromatic divalent carboxylic acid residue include phthalates such as terephthalic acid, isophthalic acid, and orthophthalic acid, 4,4'-biphenyldicarboxylic acid, and 2,2'-biphenyl. Biphenyldicarboxylic acids such as dicarboxylic acids, naphthalenedicarboxylic acids such as 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid, diphenyl ether-2,2'-dicarboxylic acid, diphenyl ether-2,3'-dicarboxylic acid , Diphenyl ether-2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenyl ether-3,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid and other diphenyl ether dicarboxylic acids.

The polyarylate resin of the present invention may contain a divalent carboxylic acid other than the aromatic divalent carboxylic acid residue. Examples of the divalent carboxylic acid giving the other divalent carboxylic acid residue include aliphatic dicarboxylic acids such as adipic acid and sebacic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1 , 2-Cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids. When the other divalent carboxylic acid residue is contained, the content thereof is preferably 10 mol% or less with respect to the total aromatic divalent carboxylic acid residue from the viewpoint of mechanical characteristics, and 5 mol. % Or less is preferable.

The weight average molecular weight of the polyarylate resin of the present invention is preferably 20000 to 90000 from the viewpoint of mechanical properties and molding processability. If the weight average molecular weight is less than 20000, the mechanical properties may be significantly reduced. On the other hand, when the weight average molecular weight exceeds 90,000, the melt viscosity may be too high and the molding processability may be lowered.

The glass transition temperature of the polyarylate resin of the present invention is preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and even more preferably 130 ° C. or lower.

Examples of the method for producing the polyarylate resin of the present invention include a method of reacting in an organic solvent such as an interfacial polymerization method and a solution polymerization method, and a method of reacting in a molten state such as melt polymerization. From the viewpoint of polymerizability and appearance of the obtained resin, it is preferable to use an interfacial polymerization method capable of reacting in an organic solvent, particularly at a low temperature.

As an interfacial polymerization method, for example, a solution (organic phase) in which a divalent carboxylic acid halide is dissolved in an organic solvent that is incompatible with water is mixed with an alkali containing a divalent phenol, a terminal sealant, an antioxidant and a polymerization catalyst. Examples thereof include a method of mixing with an aqueous solution (aqueous phase) and carrying out a polymerization reaction while stirring at a temperature of 50 ° C. or lower for 1 to 8 hours.

As the solvent used for the organic phase, for example, a solvent that is incompatible with water and dissolves polyarylate is preferable. Examples of such a solvent include methylene chloride and chloroform, and methylene chloride is preferable because it is easy to use in production.

Examples of the alkaline aqueous solution used for the aqueous phase include an aqueous solution of sodium hydroxide and potassium hydroxide.

Antioxidants are used to prevent the oxidation of divalent phenolic components. Examples of the antioxidant include sodium hydrosulfite, L-ascorbic acid, erythorbic acid, catechin, tocophenol, and butylhydroxyanisole. Of these, sodium hydrosulfite is preferable because it has excellent water solubility.

Examples of the polymerization catalyst include quaternary ammonium salts such as tri-n-butylbenzylammonium halide, tetra-n-butylammonium halide, trimethylbenzylammonium halide and triethylbenzylammonium halide, and tri-n-butylbenzylphosphonium halide. , Tetra-n-butylphosphonium halide, trimethylbenzylphosphonium halide, quaternary phosphonium salt such as triethylbenzylphosphonium halide and the like. Among them, tri-n-butylbenzylammonium halide, trimethylbenzylammonium halide, tetra-n-butylammonium halide, tri-n-butylbenzylphosphonium halide, and tetra can be obtained because a polymer having a high molecular weight and a low acid value can be obtained. -N-Butylphosphonium halide is preferred.

Examples of the organic solvent for dissolving the polyallylate resin include methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o. Examples thereof include -dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, toluene, benzene, xylene and tetrahydrofuran.

The polyarylate resin film can be obtained by processing the polyarylate resin by a method such as a casting method or a melt extrusion method. The casting method is a method in which a resin is dissolved in an organic solvent, the resin solution is applied to a base material, dried, and then peeled off from the base material to prepare a film. On the other hand, the melt extrusion method is a method in which a dried resin is put into an extruder, and the molten resin is extruded from a T-die or the like onto a cooling roll and wound up.

Examples of the organic solvent used in the casting method include methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, o. -Dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, toluene, benzene, xylene, tetrahydrofuran can be mentioned.

Examples of the base material include a PET film, a polyimide film, a glass plate, and a stainless steel plate. Examples of the coating method include wire bar coater coating, film applicator coating, brush coating, spray coating, gravure roll coating method, screen printing method, reverse roll coating method, lip coating, air knife coating method, curtain flow coating method, and the like. Immersion coating method can be mentioned.

The tensile breaking strength of the film obtained from the polyarylate resin of the present invention is preferably 50 MPa or more, more preferably 60 MPa or more, from the viewpoint of mechanical properties. Further, from the viewpoint of toughness, the tensile elongation at break is preferably 20% or more, and more preferably 30% or more. The tensile elastic modulus is preferably 1.2 GPa or more.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The physical properties of the polyarylate resin were measured by the following method.

(1) Resin composition The resin composition was determined from the peak area of each copolymer component by ¹ H-NMR analysis using a high-resolution nuclear magnetic resonance apparatus (LA-400 NMR manufactured by JEOL Ltd.) (resolution). : 400 MHz, solvent: mixed solvent with deuterated trifluoroacetic acid and deuterated tetrachloroethane in a volume ratio of 1/11, temperature: 50 ° C.).

(2) Number average molecular weight (Mn) and weight average molecular weight (Mw)
Using gel permeation chromatography (GPC), the number average molecular weight and weight average molecular weight in terms of standard polystyrene were measured under the following conditions.
Liquid feeder: Isocratic HPLC Pump 1515, manufactured by Waters
Detector: Refractometer Index 2414, manufactured by Waters
Column: Mixed-D (filled silica gel particle size 5 μm, tube length 300 mm, inner diameter 7.5 mm)
Solvent: Chloroform Flow rate: 1 mL / min Measurement temperature: 35 ° C

(3) Glass transition temperature (Tg)
Using 10 mg of polyarylate resin as a sample, the temperature is raised at a temperature rise rate of 10 ° C./min using a DSC (differential scanning calorimetry) device (DSC7 manufactured by Perkin Elmer), and the glass transition in the temperature rise curve. The intermediate value of the two bending point temperatures derived from the above was taken as the glass transition temperature.
If the glass transition temperature is 150 ° C. or lower, the molding process can be performed at a relatively low temperature, so that it can be judged that the molding processability is high.

(4) Tensile breaking strength, tensile elongation at breaking, tensile elastic modulus 90 to 85 parts by mass of chloroform was added to 10 to 15 parts by mass of polyarylate resin to obtain a resin solution. A coating film was formed on the PET film using the obtained resin solution. After air-drying at room temperature, the film was peeled off from the PET film and dried under reduced pressure at 150 ° C. for 24 hours to prepare a film having a thickness of 100 μm. The obtained film was used and measured under the following conditions in accordance with JIS K7127.
Test equipment: Model2020, manufactured by Intesco Co., Ltd.
Tensile rate: 50 mm / min Test environment: 23 ° C, 60% RH

Example 1
In a reaction vessel equipped with a stirrer, 100.00 parts by mass of 2,2-bis (3-methyl-4-hydroxyphenyl) propane (BisC) as a divalent phenol component and sodium hydroxide (NaOH) as an alkali 40. 56 parts by mass, 1.63 parts by mass of a 50% by mass aqueous solution of tri-n-butylbenzylammonium chloride (TBBAC) as a polymerization catalyst, 25.00 parts by mass of caustic sodium as an antioxidant, and 2500 parts by mass of water. Dissolved in (aqueous phase). Separately, in 2000 parts by mass of methylene chloride, 15.98 parts by mass of stearic acid chloride (Ste) as a monocarboxylic acid component, and isophthalic acid chloride / terephthalic acid chloride = 1/1 (mol) as a divalent carboxylic acid component. Ratio) 73.84 parts by mass of the mixture (MPC) dissolved (organic phase) (BizC: Ste: MPC: TBBAC: NaOH = 100.0: 13.0: 93.5: 0.7: 260.0 (BisC: Ste: MPC: TBBAC: NaOH = 100.0: 13.0: 93.5: 0.7: 260.0 ( (Molar ratio). The aqueous phase was stirred in advance, the organic phase was added to the aqueous phase under strong stirring, and polymerization was carried out at 15 ° C. for 2 hours by an interfacial polymerization method. After that, stirring was stopped. The aqueous phase and the organic phase were decanted and separated. After removing the aqueous phase, 500 parts by mass of methylene chloride, 3000 parts by mass of pure water and 10 parts by mass of acetic acid were added to stop the reaction, and the reaction was stopped at 15 ° C. for 30 minutes. After stirring, the organic phase was washed 10 times with pure water, and the organic phase was added to methanol to precipitate the polymer. The precipitated polymer was filtered and then vacuum dried at 165 ° C. for 24 hours. A polyarylate resin was obtained.
When the resin composition of the obtained polyarylate resin was analyzed, it was BisC: Ste: MPC = 100.0: 13.0: 93.5 (molar ratio), which was the same as the prepared composition.

Examples 2-8, Comparative Examples 1-3
As shown in Table 1, a polyarylate resin was obtained by performing the same operation as in Example 1 except that the resin composition was changed.

Table 1 shows the evaluation results of the polyarylate resins obtained in Examples 1 to 8 and Comparative Examples 1 to 3.

Since the polyarylate resins of Examples 1 to 8 contained a monovalent carboxylic acid residue represented by the general formula (1) at the end, the glass transition temperature was low and the molding processability was sufficient.

Since the polyarylate resin of Comparative Example 1 did not contain the monovalent carboxylic acid residue represented by the general formula (1) at the end, the glass transition temperature was high and the molding processability was insufficient.
Since the polyarylate resin of Comparative Example 2 had less than 14 carbon atoms in the alkyl group of the monovalent carboxylic acid residue, the glass transition temperature was high and the molding processability was insufficient.
The polyarylate resin of Comparative Example 3 had low mechanical properties because the number of carbon atoms of the alkyl group of the monovalent carboxylic acid residue exceeded 27 .

Claims (6)

A polyarylate resin containing a divalent phenol residue and an aromatic divalent carboxylic acid residue as main components and having a monovalent carboxylic acid residue represented by the following general formula (1) at the end (however, the number average molecular weight is converted to polystyrene). Excludes polyaromatic resins of less than 10,000.)
(In formula (1), X represents a linear or branched alkyl group having 14 to 27 carbon atoms.) The polyarylate resin according to claim 1, wherein the monovalent carboxylic acid residue represented by the general formula (1) is 10.0 to 18.0 mol% with respect to the total aromatic divalent carboxylic acid residue. The polyarylate resin according to claim 1 or 2, wherein the monovalent carboxylic acid residue represented by the general formula (1) is a stearic acid residue or an isostearic acid residue. The polyarylate resin according to any one of claims 1 to 3, wherein the divalent phenol residue is a divalent phenol residue represented by the following general formula (2).
(In formula (2), R1 and R2 independently represent a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an alkyl halide group or an aryl group. P and q are 0 or 1 to 8 When p and q are 0, Y represents a saturated or unsaturated chain or cyclic hydrocarbon group having 4 to 14 carbon atoms, and when p and q are 1 to 8, Y is. Represents a saturated or unsaturated chain or cyclic hydrocarbon group having 3 to 14 carbon atoms.) The polyarylate resin according to any one of claims 1 to 4, wherein the weight average molecular weight (Mw) of the polyarylate resin is 20000-90000 in terms of standard polystyrene. A film made of the polyarylate resin according to any one of claims 1 to 5.