JP5064673B2 - Polyarylate resin composition - Google Patents

Description

  The present invention relates to a polyarylate-based resin composition excellent in flame retardancy and chemical resistance in addition to heat resistance and transparency.

  Polyarylate represented by an aromatic polyester composed of 2,2-bis (4-hydroxyphenyl) propane and terephthalic acid and / or isophthalic acid (hereinafter sometimes abbreviated as PAR) has high heat resistance, It is used in various fields as a resin excellent in transparency, mechanical strength and dimensional stability. In addition, resin compositions alloyed with other polyester resins such as polyethylene terephthalate (hereinafter abbreviated as PET) for the purpose of improving moldability, chemical resistance and weather resistance have also expanded their fields of use. Yes.

  However, the resin composition of PAR and PET is improved in molding processability and chemical resistance as compared with PAR alone, but the thermal characteristics and impact resistance are reduced. In addition, handling such as preliminary drying becomes extremely difficult. Moreover, when impact resistance falls, it will become easy to crack etc. in a molded article, and a problem will remain in practical performance.

  In order to solve these problems, in Patent Document 1, a polyester resin (hereinafter sometimes abbreviated as PCTA) composed of an aromatic dicarboxylic acid and 1,4-cyclohexanedimethanol is alloyed with PAR. Proposed. However, this alloy has insufficient flame retardancy and is limited to applications in the electrical and electronic fields.

As a technique for imparting flame retardancy to PAR, Patent Document 2 describes blending a halogenated carbonate compound. Although this method can improve the flame retardancy while maintaining transparency, the chemical resistance becomes insufficient and the use is still limited.
JP 2002-302596 A JP 2002-80713 A

  The present invention solves the above-mentioned problems and maintains excellent performance such as heat resistance, molding processability and transparency inherent in the PAR / PCTA resin composition, while having excellent flame resistance and chemical resistance. It is a technical problem to provide an arylate resin composition.

  As a result of diligent research to solve the above-mentioned problems, the present inventor has found that the above-mentioned problems can be solved by blending a specific resin and a compound with a resin composition mainly composed of PAR. The invention has been reached.

That is, the present invention relates to a polyarylate resin (A1), a polycarbonate resin (A2), a polyester resin (B) mainly composed of a terephthalic acid component and a 1,4-cyclohexanedimethanol component, brominated diphenylethane (C) and The gist is a polyarylate-based resin composition comprising a phosphate compound (D), wherein the mass ratio of each component satisfies the following formulas (1) to (4).
(1): (A1) / (A2) = 100 / 0-10 / 90
(2): {(A1) + (A2)} / (B) = 10/90 to 90/10
(3): (C) / {(A1) + (A2) + (B)} = 5 / 100-30 / 100
(4): (D) / {(A1) + (A2) + (B)} = 0.01 / 100 to 0.3 / 100

  According to the present invention, a polyarylate system having excellent flame retardancy and chemical resistance while maintaining the heat resistance, molding processability, transparency and the like that a conventional PAR / PCTA resin composition has. A resin composition is provided, and this resin composition has an extremely high industrial utility value including automotive outer plate applications and electronic device component applications.

  Hereinafter, the present invention will be described in detail.

  The polyarylate-based resin composition of the present invention comprises a PAR resin (A1), a polycarbonate resin (A2), a polyester resin (B) mainly composed of a terephthalic acid component and a 1,4-cyclohexanedimethanol component, brominated diphenylethane. (C) and a phosphate compound (D).

  First, the PAR resin (A1) referred to in the present invention is a resin having an aromatic dicarboxylic acid residue and a bisphenol residue as repeating units.

  The raw materials for introducing bisphenol residues are bisphenols. Specific examples thereof include 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy-3,5-dimethylphenyl). ) Propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenylsulfone, 4 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane and the like.

  These compounds may be used alone or in combination of two or more. In particular, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as BA) is preferred, and it is economically optimal to use this compound alone.

  On the other hand, as raw materials for introducing an aromatic dicarboxylic acid residue into the PAR resin (A1), terephthalic acid, isophthalic acid, phthalic anhydride, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, Examples include diphenic acid, 4,4′-dicarboxydiphenyl ether, bis (p-carboxyphenyl) alkane, 4,4′-dicarboxydiphenyl sulfone, and among them, terephthalic acid and isophthalic acid are economically preferable.

  In the present invention, a polyarylate resin composition obtained by mixing and using both is particularly preferable in terms of melt processability and mechanical properties. The mixing ratio (terephthalic acid / isophthalic acid) can be arbitrarily selected, but is preferably in the range of 90/10 to 10/90 in terms of molar fraction, more preferably 70/30 to 30/70, The optimum is 50/50. Even if the mixing mole fraction of terephthalic acid is less than 10 mol% or more than 90 mol%, the interfacial polymerization method may not achieve a sufficient degree of polymerization.

  The PAR resin (A1) usually has an intrinsic viscosity of 0.4 to 1.0, preferably 0.4 to 0.8, and optimally 0.5 to 0.7 from the balance between mechanical properties and fluidity. Are preferred.

  In the present invention, as the PAR resin, for example, a commercially available U polymer (trademark) (U-100) manufactured by Unitika Co., Ltd. or a powder manufactured by the same company can be used.

  Next, the polycarbonate resin (A2) referred to in the present invention is a polycarbonate ester having bisphenol residues and carbonate residues as repeating units. Examples of the raw material for introducing the bisphenol residue unit include BA, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and 2,2-bis (4-hydroxy-3,5- Dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4 , 4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1, 1-bis (4-hydroxyphenyl) decane, 1,3- or 1,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 4,4'-dithiodi Phenol, 4,4'-dihydro Shi-3,3'-dichloro-diphenyl ether, 4,4-dihydroxy-2,5-dihydroxydiphenyl ether, and the like. In addition, diphenols described in US Pat. Nos. 2,999,835, 3,028,365, 3,334,154 and 4,131,575 can be used.

  These may be used alone or in combination of two or more. In particular, as described above, BA is preferable, and it is economically optimal to use this compound alone. Examples of the raw material for introducing the carbonate residue include phosgene and diphenyl carbonate.

  The polycarbonate resin (A2) preferably has an intrinsic viscosity of 0.3 to 0.7. As such a polycarbonate resin (A2), Caliber (trademark) (200-30, 200-13, 200, manufactured by Sumitomo Dow) -3), Panlite (trademark) (L-1250, L1225LL) manufactured by Teijin Chemicals Ltd., Lexan (trademark) (5221C) manufactured by Japan GE, and the like.

  The mixing ratio of the PAR resin (A1) and the polycarbonate resin (A2) can be selected according to the required heat resistance and moldability (fluidity) performance, and the polycarbonate resin (A2) May not be used. Usually, the mass ratio (PAR resin (A1) / polycarbonate resin (A2)) is 100/0 to 10/90, preferably 100/0 to 20/80, as in the formula (1). The PAR resin (A1) and the polycarbonate resin (A2) may be used in combination of two or more.

  Next, the polyester resin (B) referred to in the present invention is a polyester using terephthalic acid as a main dicarboxylic acid component and 1,4-cyclohexanedimethanol as a main diol component.

  In the polyester resin (B), the dicarboxylic acid component preferably contains a terephthalic acid component in an amount of 80 mol% or more, and most preferably 90 mol% or more. Examples of acid components other than terephthalic acid include, for example, isophthalic acid, phthalic anhydride, 1,4-cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenic acid, and esters of alkyls having 1 to 3 carbon atoms. And alkylesterified products having 1 to 3 carbon atoms of terephthalic acid and mixtures thereof.

  The polyester resin (B) preferably contains 70 mol% or more of 1,4-cyclohexanedimethanol as a diol component. If this component is less than 70 mol%, sufficient impact resistance performance may not be obtained or the heat resistance may be lowered.

  Examples of diol components other than 1,4-cyclohexanedimethanol include ethylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,4 butanediol. 1,5-pentanediol, 1,6-hexanediol, 3-methyl, 1,5-pentanediol, polytetramethylene glycol and mixtures thereof. As another particularly preferred diol component, ethylene glycol is used alone.

  The polyester resin (B) has an intrinsic viscosity of 0.5 to 1.2, preferably 0.6 to 1.0, from the viewpoint of mechanical properties and molding processability.

  Examples of the polyester resin (B) include commercially available Cermix (trademark) 6671 manufactured by Eastman Chemical Co., Durastar (trademark) DS2000, company Easter (trademark) DN003, and the like. Moreover, you may use a polyester resin (B) in combination of 2 or more types.

  The blending ratio of PAR resin (A1), polycarbonate resin (A2), and polyester resin (B) is as shown in the above formula (2) from the viewpoint of simultaneous molding processability, heat resistance, and chemical resistance of the resin composition. The mass ratio {(A1 + A2) / B} needs to be in the range of 10/90 to 90/10, preferably 15/85 to 85/15. When the mass ratio of the total (A1 + A2) of the PAR resin (A1) and the polycarbonate resin (A2) is less than 10%, the heat resistance and the impact strength are significantly reduced, and conversely, when the mass ratio exceeds 90%, Since the fluidity of the resin is lowered, the molding processability is deteriorated and the chemical resistance is also significantly lowered.

  Next, brominated diphenylethane (C) referred to in the present invention is prepared by reacting diphenylethane with bromine chloride, and has a bromine content of 60% to 90% and a melting point of 200 ° C. or higher. Is the body.

  The brominated diphenylethane (C) content needs to be 5 to 30 parts by mass, preferably 7 to 25 parts by mass with respect to 100 parts by mass of the total polymer components as in the formula (3). . When the content is less than 5 parts by mass, the effect of providing flame retardancy is low. On the other hand, when the content is more than 30 parts by mass, the mechanical strength and chemical resistance are significantly reduced.

  Examples of brominated diphenylethane (C) include SAYTEX (trademark) 8010 manufactured by ALBEMARLE.

  Furthermore, the phosphate compound (D) referred to in the present invention is a compound represented by the following general formula (a).

In the above formula (a), the same or different R ¹ and R ² are selected from a hydrogen atom, an alkyl group having 1 to 24 carbon atoms (preferably 2 to 18 and more preferably 4 to 18), or an alkenyl group. Group. If either R ¹ or R ² is an alkyl group or alkenyl group having 25 or more carbon atoms, discoloration of the resin composition during molding may not be suppressed. R ¹ is preferably hydrogen or the same alkyl group or alkenyl group as R ² . Examples of the alkyl group or alkenyl group having 1 to 24 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group Hexyl group, octyl group, 2-ethylhexyl group, lauryl group, myristyl group, stearyl group, oleyl group, behenyl group, tetracosyl group and the like.

  Examples of preferred phosphate compound (D) include, for example, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate and the like. Among these specific examples, butyl acid phosphate, 2-ethylhexyl acid phosphate and oleyl acid phosphate can be exemplified as preferred compounds. Two or more phosphate compounds may be used in combination.

  The phosphate compound (D) needs to be 0.01 to 0.3 parts by mass, preferably 0.03 to 0.2 parts by mass, with respect to 100 parts by mass of all polymer components as in the above-described formula (4). When the content is less than 0.01 part by mass, the effect of preventing discoloration during molding does not appear practically, and the transparency tends to be slightly lowered, which is not preferable in terms of design. Moreover, when content exceeds 0.3 mass part, discoloration will occur and transparency will fall.

  The polyarylate-based resin composition of the present invention may contain various additives such as a crosslinking agent, a bluing agent, a release agent, an antistatic agent, and a lubricant as long as the effects of the present invention are not significantly impaired.

  The polyarylate-based resin composition of the present invention comprises (A1), (B), (C) and (D), or (A1), (A2), (B), (C) and (D). The materials are mixed so as to satisfy the above formulas (1) to (4). As a mixing method, the materials may be simply dry blended or may be prepared by melting and kneading. However, from the viewpoint of ease of handling at the time of molding, the resin composition is preferably a kneaded material in the form of pellets.

  The polyarylate resin composition of the present invention can be easily processed into a sheet form by injection molding or extrusion molding, or a molded product can be obtained, but these products are heat resistant inherent in the PAR / PCTA resin composition. It has excellent flame retardancy and chemical resistance while maintaining performance such as property, moldability and transparency.

EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited only to an Example. In addition, the raw material used in the Example and the evaluation method of a physical property are as follows.
(1) PAR resin (A1): U-Powder manufactured by Unitika (Intrinsic viscosity 0.5)
(2) Polycarbonate resin (A2): Caliber (trademark) 200-30 manufactured by Sumitomo Dow, intrinsic viscosity 0.5)
(3) Polyester resin (B): Thermix 6761 (trademark) manufactured by Eastman Chemical Co., Ltd. (Intrinsic viscosity 0.9, monomer usage ratio: terephthalic acid / isophthalic acid / 1,4 cyclohexanedimethanol = 95/5/100 ( Molar ratio))
(4) Brominated diphenylethane (C): SAYTEX (trademark) manufactured by ALBEMARLE
8010
(5) Phosphate compound (D): JP-504 (alkyl acid phosphate) manufactured by Johoku Chemical Co., Ltd.
(6) Brominated carbonate compound: Teijin Kasei Fireguard (trademark) F
G-8500
2. Evaluation Method (1) Intrinsic Viscosity The intrinsic viscosity was determined from the solution viscosity measured at a temperature of 20 ° C. using an equal mixture of phenol and ethane tetrachloride as a solvent.
(2) Compounding properties Using a resin kneading apparatus (Toshiba Machine Co., Ltd. TEM-37BS), blending was carried out with each compounding, followed by compounding at a cylinder set temperature of 280 to 300 ° C. to obtain pellets. Evaluation was made as follows, and ◎ and ○ were accepted.

Less than 5 strand breaks / hour;
5 times / hour or more, less than 10 times /
10 times / hour or more; ×
(3) Bar flow measurement The resin composition pellets are formed into a bar shape with a thickness of 2 mm and a width of 20 mm using an injection molding machine (IS-100E-3S manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 300 ° C. and a flow tip pressure of 100 MPa. Injection molding was performed in the mold, and the moldability was evaluated by the length. Evaluation was made as follows, and ◎ and ○ were accepted.

Bar flow length is 200mm or more.
100mm or more, less than 200mm; ○
Less than 100 mm; ×
(4) DTUL
According to ASTM D648, the load was measured at 0.45 MPa. As a test piece, a resin composition pellet was molded at a resin temperature of 300 ° C. using an injection molding machine (IS-100E-3S manufactured by Toshiba Machine Co., Ltd.). This physical property measurement test piece was left at room temperature for one day or more and then subjected to measurement. Evaluation was made as follows, and ◎ and ○ were accepted.

DTUL value is 90 ℃ or higher;
70 ℃ or more, less than 90 ℃; ○
<70 ° C; ×
(5) Tensile strength
Measured according to ASTM D638. As a test piece, a resin composition pellet was molded at a resin temperature of 280 ° C. using an injection molding machine (IS-100E-3S manufactured by Toshiba Machine Co., Ltd.).

This physical property measurement test piece was left for 1 day or more at room temperature and then subjected to measurement. As evaluation judgment, 55 MPa or more was set as the pass.
(6) Elongation
Measured according to ASTM D638. As a test piece, a resin composition pellet was molded at a resin temperature of 280 ° C. using an injection molding machine (IS-100E-3S manufactured by Toshiba Machine Co., Ltd.). This physical property measurement test piece was left at room temperature for one day or more and then subjected to measurement. As an evaluation judgment, 40% or more was accepted.
(7) Flame resistance
Measured according to UL94V test method. As a test piece, a resin composition pellet was molded at a resin temperature of 280 ° C. using an injection molding machine (IS-100E-3S manufactured by Toshiba Machine Co., Ltd.). As evaluation judgment, V-2 or more is preferable.
(8) Mechanical oil resistance The test piece was immersed in Yushiroken CE50, and the surface state was observed. Evaluation was made as follows, and ◎ and ○ were accepted.

No change; ◎
Devitrification, micro cracks; ○
Crack generation ×
(9) Transparency An injection molding machine (IS-100E-3S manufactured by Toshiba Machine Co., Ltd.) was used to mold a sample plate with a resin temperature of 280 ° C and a thickness of 2 mm, and a color tone measurement device (Nippon Denshoku SZ-Σ80 type measurement) Measured in accordance with JIS K7103. Evaluation was made as follows, and ◎ and ○ were accepted.

Transparency is 80% or more; ◎
Less than 80%, 60% or more
Less than 60%
(Example 1)
60 parts by mass of PAR resin (A1), 40 parts by mass of polyester resin (B), 5 parts by mass of brominated diphenylethane (C) and 0.06 parts by mass of phosphate compound (D) were used using a continuous quantitative supply device manufactured by Kubota. Then, it was supplied to the main supply port of the same direction twin screw extruder (TEM-37BS manufactured by Toshiba Machine Co., Ltd.). Perform melt-kneading at a resin temperature of 290 ° C and a discharge rate of 25 kg / h, immerse the resin composition taken in a strand form from the nozzle in a water bath, solidify by cooling, cut with a pelletizer, and then dry with hot air at 100 ° C for 12 hours. Thus, pellets of the resin composition were obtained.

Next, the obtained resin composition pellets were molded at a resin temperature of 280 ° C. using an injection molding machine (TOSHIKI MACHINE Co., Ltd. IS-100E-3S) to produce physical property measurement test pieces, sample plates, and test plates. Various evaluation tests were conducted.
(Examples 2 to 8)
As shown in Table 1, melt-kneading was performed in the same manner as in Example 1 except that the amounts of the resin and the compound were changed to obtain pellets of the resin composition. Evaluation was performed in the same manner as in Example 1 using this pellet.

The evaluation results of Examples 1 to 8 are also shown in Table 1.
(Comparative Examples 1-8)
As shown in Table 2, melt-kneading was performed in the same manner as in Example 1 except that the amounts of the resin and the compound were changed to obtain pellets of the resin composition. Evaluation was performed in the same manner as in Example 1 using this pellet.

  Table 2 summarizes the evaluation results of Comparative Examples 1 to 8.

The resin compositions obtained in Examples 1 to 8 had no particular problem with respect to the compound property and could be pelletized well.

  Moreover, when the obtained pellets were evaluated, there was no problem in moldability in all compositions, and the tensile strength was 55 MPa or more, and the transparency of the molded product was good with a light transmittance of 60% or more. Further, the flame retardancy was as good as V-2 or more, and the machine oil resistance was also good.

  On the other hand, in Comparative Example 1, the brominated diphenylethane (C) was inferior in flame retardancy because it was outside the lower limit of the range of the present invention. Moreover, since the brominated diphenylethane (C) was outside the upper limit of the range of the present invention in Comparative Example 2, the elongation was less than 30% and the mechanical properties were inferior.

  Next, since the comparative example 3 did not mix | blend the phosphate compound (D), yellow discoloration occurred and transparency fell. Further, in Comparative Example 4, since the phosphate compound (D) deviated from the upper limit of the range of the present invention, black discoloration occurred and transparency was lowered.

  Further, in Comparative Example 5, since the polyester resin (B) deviated from the upper limit of the range of the present invention, the value of DTUL was less than 70 ° C. and the heat resistance was poor.

  In Comparative Example 6, since the PAR resin (A1) deviated from the upper limit of the range of the present invention, the bar flow length as the moldability evaluation was less than 100 mm, and the moldability was inferior.

  In Comparative Example 7, a brominated carbonate compound was used as a flame retardant, but the surface was cracked in the mechanical oil resistance test, and the chemical resistance was poor.

In Comparative Example 8, the ratio of the PAR resin (A1) to the polycarbonate (A2) was inferior in chemical resistance because it deviated from the lower limit of the range of the present invention.

Claims (1)

From polyarylate resin (A1), polycarbonate resin (A2), polyester resin (B) containing terephthalic acid component and 1,4-cyclohexanedimethanol component as main components, brominated diphenylethane (C) and phosphate compound (D) The mass ratio of each component satisfies the following formulas (1) to (4): a polyarylate-based resin composition.
(1): (A1) / (A2) = 100 / 0-10 / 90
(2): {(A1) + (A2)} / (B) = 10/90 to 90/10
(3): (C) / {(A1) + (A2) + (B)} = 5 / 100-30 / 100
(4): (D) / {(A1) + (A2) + (B)} = 0.01 / 100 to 0.3 / 100