JP3510937B2 - Heat resistant polyester amide sulfide resin and composition thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel modified polyester resin having excellent heat resistance and impact resistance.

[0002]

2. Description of the Related Art Aromatic polyester resins, particularly polybutylene terephthalate resins, have a high degree of crystallization and a high rate of crystallization and are well balanced in heat resistance and mechanical strength. Due to its physical properties, it has been heavily used as an engineering plastic, but the recently required properties have also become more sophisticated. As one of the required properties, there is an improvement in heat resistance, and particularly when applied to the electric and electronic fields, higher heat resistance such as solder heat resistance is required, but at present, aromatic polyesters satisfying such requirements are required. No resin is provided.

[0003]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an aromatic polyester resin is melt-reacted with a specific amount of a bisoxazoline compound and a dithiol compound, and injection molding is performed. The inventors have found that a polyester amide sulfide resin having excellent heat resistance and extremely high heat resistance can be obtained, and completed the present invention. That is, the present invention is to blend 100 parts by weight of an aromatic polyester resin having an intrinsic viscosity of 0.5 or more and 1.5 or less with 2 to 29 parts by weight of a substantially equimolar mixture of a bisoxazoline compound and a dithiol compound, and melt the aromatic polyester resin. It is a heat-resistant polyester amide sulfide resin that is made to react under. In the present invention, the mechanism of development of heat resistance is considered as follows. That is, the bisoxazoline compound and the dithiol compound alternately react with each other to form a high-melting-point polymer compound, and at the same time, the heat-resistant unit is introduced into the polyester molecule by binding to the polyester terminal and forming a block copolymer. It is presumed that the amide sulfide block exerts the effect of the crystal nucleating agent and improves the crystallinity of the polyester, and the heat resistance is remarkably improved.

The present invention will be described in detail below. In the present invention, the aromatic polyester resin is a polyester resin containing aromatic carboxylic acid and its ester-forming derivative and glycols as main starting materials, and polyalkylene terephthalate resin such as polyethylene terephthalate resin and polybutylene terephthalate resin. Among them, polybutylene terephthalate resin is preferable in view of the balance of crystallinity, crystallization rate, heat resistance, mechanical strength and the like. A copolymerized aromatic polyester resin modified by copolymerization may be used depending on the purpose of use.
As the copolymerization component, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, aromatic dicarboxylic acids such as 4,4′-diphenyldicarboxylic acid and derivatives thereof, adipic acid,
Sebacic acid, aliphatic dicarboxylic acids such as succinic acid and derivatives thereof, trimesic acid, aromatic tricarboxylic acids such as trimellitic acid and derivatives thereof, hydroxybenzoic acid,
Aromatic hydroxycarboxylic acids and their derivatives such as hydroxynaphthoic acid, low molecular weight glycols such as ethylene glycol, propanediol, butenediol and hexanediol, high molecular weight glycols such as polyethylene oxide glycol and polybutylene oxide glycol, bisphenol A, bisphenol S , Aromatic diols such as 4,4′-hydroxydiphenyl and their ethylene oxide and propylene oxide adducts, and polyhydroxy compounds such as pentaerythritol. The amount of modification by the copolymerization component is limited to a range that does not significantly reduce heat resistance, and it is generally necessary that the main repeating unit is 70 mol% or more of the entire skeleton structure. The above polyester, the monomer raw material, and, using a polycondensation catalyst such as titanium tetrabutoxide, by applying the polycondensation method of the polyester that is generally performed,
It can be produced in the molten state, the solid state, or a combination of both. Further, in the present invention, it is necessary to select and use an aromatic polyester resin having an intrinsic viscosity of 0.5 or more and 1.5 or less. When the intrinsic viscosity of the raw material polyester is lower than 0.5, the mechanical properties such as impact resistance of the resulting resin are low, and when it is higher than 1.5, the fluidity at the time of molding becomes low, which is not preferable.

The bisoxazoline compound used as the starting material compound of the present invention is represented by the following general formula (1).

[0006]

[Chemical 1]

(R is an alkylene group, a substituted alkylene group,
A divalent organic group selected from an arylene group and a substituted arylene group, R ₁ and R ₂ are alkylene groups or substituted alkylene groups, preferably ethylene groups or propylene groups) represented by the general formula (1) Specific examples of the bisoxazoline compound include 2,2′-methylenebis (2-oxazoline),
2,2'-ethylenebis (2-oxazoline), 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-propylenebis (2-oxazoline), 2,2'-tetramethylene Bis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-p-phenylenebis (2
-Oxazoline), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4-dimethyl-2-oxazoline), 2,2'-p -Phenylene bis (4-phenyl-2-oxazoline), 2,
2'-m-phenylene bis (2-oxazoline), 2,2'-
m-phenylene bis (4-methyl-2-oxazoline), 2,2'-m-phenylene bis (4,4-dimethyl-2)
-Oxazoline), 2,2'-m-phenylenebis (4-phenyl-2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline), 2,2'-phenylbis (4-methyl- 2-oxazoline), 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4-ethyl-2-oxazoline),
2,2'-bis (4-phenyl-2-oxazoline) and the like can be mentioned. Such bisoxazoline compounds may be used alone or in combination of two or more kinds. Of these bisoxazoline compounds, the preferred one is R
Is an arylene group, more preferably a phenylene group. Particularly preferred are 2,2'-p-phenylenebis (2-oxazoline) and 2,2'-m-phenylenebis (2-oxazoline).

Next, the dithiol compound used in the present invention is represented by the general formula HS-R ₅ -SH (in the formula, R ₅ is an aliphatic hydrocarbon group which may have a heteroatom or a heteroatom. Represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent). Examples of the aliphatic hydrocarbon group of the aliphatic hydrocarbon group which may have a hetero atom include methylene, ethylene, propylene, butylene, hexamethylene, dodecyl methylene and the like alkylene groups having 1 to 15 carbon atoms. . Specific examples of the compound include ethylenedithiol and butylenedithiol. Further, examples of the aliphatic hydrocarbon group through a hetero atom include those having oxygen and the like as a hetero atom such as diethylene glycol residue and dibutylene glycol residue, and specific compounds include: Examples thereof include mercapto-substituted acyloxydithiol compounds such as ethylene glycol bisthioglycolate and butylene glycol bisthioglycolate. The aromatic hydrocarbon group of the aromatic hydrocarbon group which may have a hetero atom,
Examples thereof include arylene groups having 6 to 14 carbon atoms such as phenylene, tolylene, xylylene, biphenylene and naphthylene. Specific examples include o-dimercaptobenzene and m-
Dimercaptobenzene, p-dimercaptobenzene, o
-Dimercaptotoluene, m-dimercaptotoluene,
p-dimercaptotoluene, 2,4'-thiobisbenzenethiol, 4,4'-thiobisbenzenethiol and the like can be mentioned. In addition, examples of the aromatic hydrocarbon group through a hetero atom include bisphenylene ether, bisphenylenesulfonyl, bis (propoxyphenylpropane), and the like, and specific compounds include bis (4′-mercaptophenyl). ) Ether, 2,2′-bis (2-hydroxy-3-mercaptopropoxyphenylpropane) and the like.

The aromatic heterocyclic group which may have a substituent includes a 5-membered to 6-membered ring containing 1 to 4 hetero atoms (eg, nitrogen, sulfur, etc.). .
A 6-membered ring is preferable, and for example, a triazine group or a thiadiazole group is used. The triazine group may have a substituent, and examples of the substituent include a lower alkyl group such as methyl, ethyl, propyl and butyl, a phenyl group, a substituted aryl group such as alkylphenyl and aminophenyl, amino and alkylamino, Substituted amino groups such as dialkylamino and the like can be mentioned. Specific compounds include 6-dibutylamino-1,3,5-triazine-2,4-dithiol,
6-aminophenyl-1,3,5-triazine-2,4-dithiol, 2,5-dimercapto-1,2,4-thiadiazole and the like can be mentioned. These dithiol compounds may be used alone or in combination. Among the dithiol compounds, 4,4'-
Thiobisbenzenethiol, 6-dibutylamino-1,3,
5-triazine-2,4-dithiol and 6-aminophenyl-1,3,5-triazine-2,4-dithiol are preferably used.

When blending the bisoxazoline compound and the dithiol compound into the aromatic polyester, unless the molar numbers of the bisoxazoline compound and the dithiol compound are substantially equal to each other, a large amount of unreacted low molecular weight substance is left in the resin after the reaction. Therefore, it is necessary to be careful because it will remain in the product and deteriorate the physical properties. The term "substantially equimolar" as used herein means that the molar ratio of the bisoxazoline compound to the dithiol compound is in the range of 0.9 to 1.1, preferably 0.95 to 1.05.

Further, when this mixture is blended with an aromatic polyester resin and the mixture is melt-reacted, if the blending amount of the above equimolar mixture is less than 2 parts by weight with respect to 100 parts by weight of the aromatic polyester resin, the effect of exhibiting heat resistance is exhibited. Insufficient, 29
If the amount is more than the amount by weight, the crystallization of the polyester is hindered and the heat resistance is rather lowered, which is not preferable. The reaction speed of polyester and bisoxazoline compounds and dithiol compounds under melting is extremely fast, and the reaction is completed immediately if melt kneading at a temperature above these melting points, so a kneading device such as a melt polymerization reactor equipped with a stirrer or a Henschel mixer Alternatively, the thermoplastic elastomer can be produced by a uniaxial or biaxial extruder or the like. The order of mixing the respective components is not particularly limited, and an equimolar mixture of the bisoxazoline compound and the dithiol compound may be added to the molten polyester, or the bisoxazoline compound and the dithiol compound may be sequentially added.

The polyester amide sulfide resin of the present invention may be blended with various fibrous, powdery or plate-like inorganic and organic fillers depending on the purpose of use. As the fibrous filler, glass fiber, asbestos fiber, silica fiber, silica-alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and further stainless steel, aluminum, titanium Inorganic fibrous substances such as metal fibrous substances such as copper, copper and brass. A particularly representative fibrous filler is glass fiber. Incidentally, a high melting point organic fibrous substance such as a polyamide resin, a fluororesin, a polyester resin or an acrylic resin can also be used. On the other hand, as the particulate filler, carbon black, graphite, silica, quartz powder, glass beads, milled glass fiber, glass balloon, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, Silicates such as wollastonite,
Iron oxide, titanium oxide, zinc oxide, antimony trioxide, metal oxides such as alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, other ferrites, silicon carbide, Examples thereof include silicon nitride, boron nitride and various metal powders. Examples of the plate-like filler include mica, glass flakes, various metal foils and the like. Examples of organic fillers include heat-resistant and high-strength synthetic fibers such as aromatic polyester fibers, liquid crystalline polymer fibers, aromatic polyamide, and polyimide fibers. These inorganic and organic fillers can be used alone or in combination of two or more. The combined use of the fibrous filler and the powdery or plate-like filler is a preferable combination particularly in terms of mechanical strength, dimensional accuracy, electrical properties and the like. The content of the filler is 95% by weight or less, preferably 1 to 80% by weight, based on the total amount of the composition. When using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary. If necessary, an antioxidant,
Add additives such as UV absorbers, photoprotectors, phosphite stabilizers, peroxide decomposers, basic auxiliaries, nucleating agents, plasticizers, lubricants, antistatic agents, flame retardants, colorants, etc. Any amount can be added within the range that does not impair the physical properties of the invention.

[0013]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. Example 1 Polybutylene terephthalate (PBT: manufactured by Polyplastics Co., Ltd., “Duranex 2002”, intrinsic viscosity 1.0)
0) 100 parts by weight, 2,2'-p-phenylenebis (2-oxazoline) (PPBO) (manufactured by Takeda Pharmaceutical Co., Ltd.) 2.44 parts by weight, 4,
2.82 parts by weight of 4'-thiobisbenzenethiol (mercaptophenyl sulfide: MPS) was added using a single screw extruder.
The mixture was melt-kneaded at an extrusion temperature of 240 ° C to obtain pellets. The polymer obtained was subjected to ¹ H-NMR measurement using trifluoroacetic acid-d as a measurement solvent, and unreacted PPB was detected.
O and MPS were not observed, and it was confirmed that the composition was expected from the charged amount. Also, heating rate 10 ℃ / min
In addition to the melting peak of PBT crystal,
A melting peak was seen in the higher temperature region. MI is test temperature 23
It was determined at 5 ° C and a test load of 2.16 kg. In addition, as an index showing the crystallization rate of PBT, the cooling rate from the molten state is 10 ° C / min.
The difference between the crystallization peak temperature (Tc) and the melting peak temperature (Tm) of the PBT crystal part was determined. This (Tm-Tc)
Is smaller, the crystallization rate is higher. Further, various samples for measuring physical properties were obtained by injection molding using these pellets as raw materials, and physical properties were measured. The tensile strength and tensile elongation are based on JIS K6361, and the impact strength is Izod impact (JI
S K7110). In addition, the heat distortion temperature is JIS K7207.
The evaluation was made for each case of high load and low load. The results are shown in Table 1. Example 2 9.76 parts by weight of PPBO and 11.2 parts of MPS
A polymer was obtained in the same manner as in Example 1 except that the amount was 8 parts by weight, and the same evaluation was performed. The results are shown in Table 1. Example 3 A polymer was obtained in the same manner as in Example 1 except that 2,2′-m-phenylenebis (2-oxazoline) was used instead of PPBO, and the same evaluation was performed. The results are shown in Table 1. Comparative Example 1 Polybutylene terephthalate (PBT: manufactured by Polyplastics Co., Ltd., “Duranex 2002”, intrinsic viscosity 1.0)
For 0), the same evaluation as in Example 1 was performed. The results are shown in Table 1. Comparative Example 2 A polymer was obtained and evaluated in the same manner as in Example 1 except that polybutylene terephthalate having an intrinsic viscosity of 0.45 (manufactured by Polyplastics Co., Ltd.) was used. The results are shown in Table 1.

[0014]

[Table 1]

Example 4 When the same operation as in Example 1 was carried out to obtain a polymer, glass fibers (chopped strands) were added in an amount of 30 with respect to the total amount of the resin.
By adding parts by weight and melt-kneading, glass fiber reinforced resin composition pellets were obtained, and the same evaluation was performed. The results are shown in Table 2. Comparative Example 3 The same operation as in Example 4 was carried out in Comparative Example 1 to obtain glass fiber-reinforced PBT resin composition pellets, and the same evaluation was performed. The results are shown in Table 2.

[0016]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 63/00-63/91

Claims (6)

(57) [Claims] 1. To 2 to 29 parts by weight of a substantially equimolar mixture of a bisoxazoline compound and a dithiol compound is added to 100 parts by weight of an aromatic polyester resin having an intrinsic viscosity of 0.5 or more and 1.5 or less, and the aromatic polyester resin is melted. Heat-resistant polyester amide sulfide resin made by reacting with. 2. The heat-resistant polyester amide sulfide resin according to claim 1, wherein the aromatic polyester resin is a polyalkylene terephthalate resin. 3. The main skeleton of the polyalkylene terephthalate resin is polybutylene terephthalate.
The heat-resistant polyester amide sulfide resin described. 4. The heat-resistant polyester amide sulfide resin according to claim 1, wherein the bisoxazoline compound is phenylene bisoxazoline. 5. The heat-resistant polyester amide sulfide resin according to claim 1, and 95% by weight of a filler.
(To the total amount of the composition), a heat-resistant polyester amide sulfide resin composition 6. An electric / electronic component formed by molding the heat-resistant polyester amide sulfide resin according to claim 1 or a composition thereof.