JP2007009015A - Polyarylate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which has improved retention stability, when molded, while maintaining the heat resistance, moldability, transparency and the like of conventional PAR/PCTA-based resin compositions. <P>SOLUTION: This resin composition comprising a polyarylate resin (A1), a polycarbonate resin (A2), a polyester resin (B) produced from terephthalic acid component and 1,4-cyclohexanedimethanol component as main components, a phenoxy resin (C), and a phosphate compound (D), wherein the mass ratios of the components satisfy all of the following expressions. (1): (A1)/(A2)=100/0 to 10/90, (2): ä(A1)+(A2)}/(B)=20/80 to 80/20, (3): (C)/ä(A1)+(A2)+(B)}=0.2/100 to 10/100, (4): (D)/ä(A1)+(A2)+(B)}=0.01/100 to 0.3/100. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyarylate resin composition that is excellent in heat resistance, transparency, and chemical resistance, and has improved residence stability during molding.

  So-called polyarylate (hereinafter abbreviated as PAR) represented by an aromatic polyester composed of a 2,2-bis (4-hydroxyphenyl) propane component and a phthalic acid component is widely known as an engineer plastic. PAR is used in various fields as a resin having high heat resistance and excellent 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. .

  However, although the resin composition of PAR and PET is improved in molding processability and chemical resistance as compared with the PAR alone, the thermal characteristics and impact resistance are lowered.

  In order to solve these problems, Patent Document 1 proposes a resin composition in which a polyester resin (hereinafter abbreviated as PCTA) composed of an aromatic dicarboxylic acid and 1,4-cyclohexanedimethanol is mixed with PAR. However, this resin composition has insufficient residence stability at the time of molding. In particular, if the residence time at the time of molding is long, the resin composition is deteriorated and the mechanical properties are not satisfactory.

In order to improve the retention stability of the polyester resin, a heat stabilizer (antioxidant) is generally used. However, the effect of the PAR / PCTA alloyed resin composition is low, which is not satisfactory.
JP 2002-302596 A

  In view of the above circumstances, an object of the present invention is to improve the retention stability during molding in a conventional PAR / PCTA-based resin composition.

  As a result of intensive studies to solve the above problems, the present inventors have found that the problems can be solved by blending a specific resin and compound with a resin composition comprising PAR, and completed the present invention. It was.

That is, the gist of the present invention is that a polyarylate resin (A1), a polycarbonate resin (A2), a polyester resin (B) having a terephthalic acid component and a 1,4-cyclohexanedimethanol component as main components, and a phenoxy resin (C). And a phosphate compound (D), and the mass ratio of each component satisfies the following formulas (1) to (4).
(1): (A1) / (A2) = 100/0 to 10/90
(2): {(A1) + (A2)} / (B) = 20/80 to 80/20
(3): (C) / {(A1) + (A2) + (B)} = 0.2 / 100 to 10/100
(4): (D) / {(A1) + (A2) + (B)} = 0.01 / 100 to 0.3 / 100

  According to the present invention, there is provided a resin composition having improved residence stability at the time of molding while maintaining the heat resistance, molding processability, transparency, etc., which a conventional PAR / PCTA resin composition has. The industrial utility value is extremely high, including applications such as automobile skins and electronic equipment parts.

  The PAR resin (A1) is a resin having an aromatic dicarboxylic acid residue and a bisphenol residue as repeating units.

  PAR 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-dimethyl). Phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, etc. . 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 economically preferable, and it is optimal to use the 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, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphene Examples include acid, 4,4′-dicarboxydiphenyl ether, bis (p-carboxyphenyl) alkane, 4,4′-dicarboxydiphenyl sulfone, and terephthalic acid and isophthalic acid are particularly 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 mixed mole fraction of terephthalic acid is less than 10 mol% or more than 90 mol%, it may be difficult to obtain a sufficient degree of polymerization by the interfacial polymerization method.

  The PAR resin (A1) has an intrinsic viscosity of 0.4 to 1.0, preferably 0.4 to 0.8, more preferably 0.5 to 0.7 from the viewpoint of mechanical properties and fluidity. Is desirable.

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

  The polycarbonate resin (A2) is a polycarbonate having a bisphenol residue and a carbonate residue 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- (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 4,4′-dithiodiphenol, 4,4′-dihydroxy-3,3′-dichlorodiphenyl 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, BA is preferable, and it is optimal to use the compound alone. Examples of the polycarbonate resin raw material for introducing the carbonate residue include phosgene and diphenyl carbonate.

  The intrinsic viscosity of the polycarbonate resin (A2) is preferably in the range of 0.3 to 0.7. As such a polycarbonate resin (A2), Caliber (registered trademark) (200-30, 200-13, manufactured by Sumitomo Dow) 200-3), Panlite (registered trademark) (L-1250, L1225LL) manufactured by Teijin Chemicals Ltd., Lexan (registered 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 at an appropriate ratio according to the required heat resistance and moldability (fluidity) requirements, and the polycarbonate resin (A2) is not used. Good. Usually, the mass ratio (PAR resin (A1) / polycarbonate resin (A2)) is 100/0 to 10/90, preferably 100/0 to 20/80. In addition, you may use PAR resin (A1) and polycarbonate resin (A2) in combination of 2 or more types, respectively.

  The polyester resin (B) mainly composed of a terephthalic acid component and a 1,4-cyclohexanedimethanol component (hereinafter simply referred to as “polyester resin (B)”) is preferably an all-alcohol component constituting the polyester. Among them, a polyester containing 70 mol% or more of 1,4-cyclohexanedimethanol. When this component is less than 70 mol%, sufficient impact resistance performance cannot be obtained, and the heat resistance tends to decrease. Examples of other diol components other than 1,4-cyclohexanedimethanol include ethylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1, Mention may be made of 5-pentanediol, 1,6-hexanediol, 3-methyl, 1,5-pentanediol, polytetramethylene glycol and mixtures thereof. Particularly preferred other diol components are those using ethylene glycol alone.

  Moreover, as a dicarboxylic acid component of a polyester resin (B), it is preferable to contain a terephthalic acid component 80 mol% or more, and it is especially preferable to contain 90 mol% or more. As an acid component other than terephthalic acid, for example, isophthalic acid, phthalic acid, 1,4-cyclohexanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenic acid, and esterified products of alkyl having 1 to 3 carbon atoms thereof, Mention may be made of alkylesters having 1 to 3 carbon atoms of terephthalic acid and mixtures thereof.

  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 (registered trademark) 6761 manufactured by Eastman Chemical Co., Durastar (registered trademark) DS2000 manufactured by the company, Easter (registered trademark) DN003 manufactured by the company, and the like. Moreover, you may use a polyester resin (B) in combination of 2 or more types.

  The blending ratio of the PAR resin (A1), the polycarbonate resin (A2), and the polyester resin (B) is the mass ratio {(A1 + A2) / B} from the viewpoint of molding processability, heat resistance, and chemical resistance of the resin composition. It is necessary to set it in the range of 20/80 to 80/20. When the mass ratio of the total {(A1) + (A2)} of the PAR resin (A1) and the polycarbonate resin (A2) is less than 20%, a decrease in heat resistance and a decrease in impact strength become significant. On the other hand, if it exceeds 80%, the fluidity of the resin is lowered, so that the moldability is remarkably deteriorated, and the chemical resistance is also lowered.

  Examples of the phenoxy resin (C) include polyhydroxy polyether resins produced from BA and epichlorohydrin, and those having a molecular weight (Mn) of 5000 to 20000 can be preferably used.

  The content of the phenoxy resin (C) needs to be 0.2 to 10 parts by mass with respect to 100 parts by mass of all the polymer components {(A1) + (A2) + (B)}, and preferably is 0.1. 5 to 8.0 parts by mass. If the content is less than 0.2 parts by mass, the effect of providing retention stability is low. If the content is more than 10 parts by mass, gelation occurs during processing, which hinders production.

  Commercially available phenoxy resins (C) include PACHEN (registered trademark) (PKHH) manufactured by Inchem Co., PAPHEN (registered trademark) ((PKHJ) manufactured by the same company, PAPHEN (registered trademark) ((PKHC) manufactured by the same company, manufactured by Epoxy Resin Co., Ltd.) Examples include Epicoat (registered trademark) (1256) and YP (YP-50) manufactured by Tohto Kasei Co., Ltd.

  The phosphate compound (D) referred to in the present invention is a compound represented by the following general formula (1).

In the formula, R ¹ and R ² are a hydrogen atom or a group selected from an alkyl group having 1 to 24 carbon atoms (preferably 2 to 18, more preferably 4 to 18) or an alkenyl group, and the same kind But it can be heterogeneous. 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.

  Examples of preferred phosphate compounds (D) include ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, oleyl acid phosphate, and tetracosyl acid phosphate. Among these specific examples, butyl acid phosphate, 2-ethylhexyl acid phosphate, and oleyl acid phosphate are preferable. Moreover, you may use a phosphate compound in combination of 2 or more types.

  The phosphate compound (D) needs to be 0.01 to 0.3 parts by mass, preferably 0.03 to 100 parts by mass with respect to 100 parts by mass of all polymer components {(A1) + (A2) + (B)}. 0.2 parts by mass. When the content is less than 0.01 parts by mass, the effect of preventing discoloration during molding is poor, and 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 further.

  The resin composition used in the present invention may contain various additives such as a bluing agent, a flame retardant, a release agent, an antistatic agent, and a lubricant as long as the effects of the present invention are not significantly impaired.

  The resin composition of the present invention is obtained by mixing the components (A1), (B), (C), (D) and, if necessary, (A2). As a mixing method, a pellet or powdery raw material may be simply dry blended, or a mixture obtained by melting and kneading may be pelletized. From the viewpoint of ease of handling during the molding process, a pellet-shaped kneaded product is preferable.

  The resin composition of the present invention can be easily processed into various molded products, sheets, films and the like by known molding methods such as injection molding and extrusion molding.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

1. Raw material (1) PAR resin (A1): Unitika U-polymer powder (intrinsic viscosity 0.5)
(2) Polycarbonate resin (A2): Caliber (registered trademark) 200-30 manufactured by Sumitomo Dow Co., Ltd. (Intrinsic viscosity 0.5)
(3) Polyester resin (B): Cermix (registered trademark) 6761 manufactured by Eastman Chemical Co., Ltd. (Intrinsic viscosity 0.9, monomer use ratio: terephthalic acid / isophthalic acid / 1,4 cyclohexanedimethanol = 95/5/100 (Molar ratio)
(4) Phenoxy resin (C): PAPHEN (registered trademark) (PKHH) manufactured by Inchem
(5) Phosphate compound (D): Johoku Chemical Co., Ltd. JP-504 (alkyl acid phosphate)

2. Evaluation methods

(1) Intrinsic viscosity: It was determined from the solution viscosity measured at a temperature of 20 ° C. using a mixture of equal mass of phenol and 1,1,2,2-tetrachloroethane as a solvent.

(2) Compound properties: Using a resin kneading apparatus (Toshiba Machine Co., Ltd. TEM-37BS), after blending each raw material, compounding was performed at a cylinder set temperature of 280 to 300 ° C. to obtain pellets. Evaluation judgment was made as follows, and ○ and Δ were regarded as acceptable.

Occurrence of strand breakage less than 5 times / hour; ○
Occurrence of strand breaks 5 times / hour or more and less than 10 times;
Occurrence of strand breakage 10 times / hour or more; ×

(3) Bar flow measurement: A resin composition pellet is a bar having 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. The mold was injection molded into a mold and the length was evaluated for moldability. Evaluation judgment was made as follows, and ○ and Δ were regarded as acceptable.

Bar flow length is 200mm or more; ○
Bar flow length is 100 mm or more and less than 200 mm;
Bar flow length is less than 100 mm; ×

(4) DTUL: Measured at a load of 0.45 MPa according to ASTM D648. The test piece formed the resin composition pellets 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 judgment was made as follows, and ○ and Δ were regarded as acceptable.

DTUL value is 100 ° C or higher;
DTUL value is 80 ° C or higher and lower than 100 ° C;
DTUL value is less than 80 ° C;

(5) Tensile strength: Measured according to ASTM D638. The test piece formed the resin composition pellets at a resin temperature of 280 ° C. using an injection molding machine (IS-100E-3S manufactured by Toshiba Machine Co., Ltd.). At this time, in order to evaluate the retention stability, the test piece when the injection molding cycle was 30 s was used as a control, and the test piece when the injection molding cycle was 100 s was also evaluated. 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, 55 MPa or more was accepted.

(6) Elongation: Measured according to ASTM D638. The test piece formed the resin composition pellets at a resin temperature of 280 ° C. using an injection molding machine (IS-100E-3S manufactured by Toshiba Machine Co., Ltd.). Under the present circumstances, the test piece was obtained like said (5) as residence stability evaluation. This physical property measurement test piece was left at room temperature for one day or more and then subjected to measurement.

  In addition, the retention stability was evaluated based on the following criteria based on the retention rate of the elongation of the test piece at 100 s using the test piece of the injection molding cycle 30 s as a control.

Retention elongation retention (100s / 30s) is 80% or more;
Residence elongation retention (100 s / 30 s) less than 80% 60% or more;
Residence elongation retention (100 s / 30 s) is less than 60%; ×

(7) Transparency: Using a injection molding machine (IS-100E-3S manufactured by Toshiba Machine Co., Ltd.), a 2 mm thick sample plate is molded at a resin temperature of 280 ° C., and a color tone measuring device (Nippon Denshoku SZ-Σ80 type) Measured based on JIS K7103 using a colorimeter. Evaluation judgment was made as follows, and ○ and Δ were regarded as acceptable.

Transparency is 80% or more; ○
Transparency is less than 80% and 60% or more;
Transparency is less than 60%; ×

Example 1
Using a continuous quantitative supply device manufactured by Kubota Corporation, 60 parts by mass of PAR resin (A1), 40 parts by mass of polyester resin (B), 0.4 parts by mass of phenoxy resin (C), and 0.06 parts by mass of phosphate compound (D) are used. Then, it was supplied to the main supply port of the same direction twin screw extruder (TEM-37BS manufactured by Toshiba Machine Co., Ltd.). Melt-knead at a resin temperature of 290 ° C and a discharge rate of 20 kg / h, soak and solidify the resin composition taken up in a strand form from a nozzle in a water bath, 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 IS-100E-3S), and a physical property measurement test piece, a sample plate, and a test plate were produced. Various evaluation tests were conducted.

Examples 2-7, Comparative Examples 1-7
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 7 are shown in Table 1, and the evaluation results of Comparative Examples 1 to 7 are shown in Table 2.

  The resin compositions of the present invention described in Examples 1 to 7 had no particular problem with respect to the compound property, and could be pelletized well. When the obtained pellets were evaluated, the tensile strength was 55 MPa or more, and at the same time, the retention elongation retention was 85% or more, which was excellent, and the retention stability was good. Further, the transparency of the molded product was good with a light transmittance of 60% or more.

  In Comparative Examples 1 and 2, since the phenoxy resin (C) was not blended, the rate of decrease in elongation was large, and it was found that residence deterioration occurred.

  In Comparative Example 3, conversely, the phenoxy resin (C) deviated from the upper limit of the range of the present invention, so that gelation occurred during compounding and pelletization was impossible.

  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.

  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 lower than 80 ° C. and the heat resistance was poor.

  In Comparative Example 6, since the total amount of the PAR resin (A1) and the polycarbonate resin (A2) deviated from the upper limit of the range of the present invention, the bar flow length, which is a moldability evaluation, was less than 100 mm, and the molding processability was poor. Met.

  In Comparative Example 7, since the phosphate compound (D) was not blended, yellow discoloration occurred and transparency was lowered.

Claims (1)

A polyarylate resin (A1), a polycarbonate resin (A2), a polyester resin (B) having a terephthalic acid component and a 1,4-cyclohexanedimethanol component as main components, a phenoxy resin (C), and a phosphate compound (D) The resin composition in which the mass ratio of each component satisfies all of the following formulas (1) to (4).
(1): (A1) / (A2) = 100/0 to 10/90
(2): {(A1) + (A2)} / (B) = 20/80 to 80/20
(3): (C) / {(A1) + (A2) + (B)} = 0.2 / 100 to 10/100
(4): (D) / {(A1) + (A2) + (B)} = 0.01 / 100 to 0.3 / 100