JP2928787B2 - Thermoplastic polyester resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermoplastic polyester resin composition in which deterioration in color tone and deterioration in physical properties during heating are prevented, and in particular, a long-chain dialkyl acid phosphate compound is added. The present invention relates to a thermoplastic polyester resin composition in which deterioration in color tone and deterioration in physical properties during heating are prevented.

[Conventional technology and its problems]

Thermoplastic polyester resins such as polyethylene terephthalate and polybutylene terephthalate are used as films, molded articles, fibers, etc. because of their high strength and excellent heat resistance and weather resistance. The polymer blend of a plastic polyester resin and a polycarbonate resin has a high heat distortion temperature and a high impact strength, so that its use is rapidly expanding.

Since these thermoplastic polyester resins have a large decrease in physical properties upon heating, various antioxidants such as phenolic antioxidants and organic phosphite compounds have been added. When an antioxidant was added, there was a drawback that coloring due to heating was remarkable.

JP-B-38-7244 proposes to add a monoalkyl acid phosphate compound in order to improve the dyeability of a polyester resin.
No. 0, JP-B-44-32307 proposes to add various acid phosphate metal salts for the same purpose, and JP-A-54-58754 discloses a superior amount of polycarbonate resin and polyester resin. It has been proposed to improve the thermal coloring and impact strength by adding a metal salt of acid phosphate to the blend of the above. However, even when these compounds are added, the effect of preventing deterioration of physical properties over time due to heating can be prevented. Was scarcely recognized, and the effect of preventing coloring by heating was insufficient.

[Means for solving the problem]

In view of the present situation, the present inventors have prevented the deterioration of physical properties during heating of the thermoplastic polyester resin, and, as a result of intensive studies to find an additive capable of preventing coloring,
Thermoplastic polyester resin, or a polymer blend 10 of a thermoplastic polyester resin and a polycarbonate resin containing at least 10% by weight of the thermoplastic polyester resin
With respect to 0 parts by weight, at least one kind of the long-chain dialkyl acid phosphate compound represented by the following general formula (I) is used.
By adding 1 to 5 parts by weight, it has been found that physical properties during heating can be prevented and coloration can be improved.
The present invention has been completed.

(In the formula, R represents an alkyl group having 12 to 22 carbon atoms.) Hereinafter, the present invention having the above gist will be described in more detail.

In the long-chain dialkyl acid phosphate compound represented by the general formula (I), the number of carbon atoms represented by R is 12
Examples of the alkyl group of -22 include dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and the like.

The long-chain dialkyl acid phosphate compound represented by the above general formula (I) can be prepared by, for example, a method of hydrolyzing a corresponding trialkyl phosphate, a method of reacting phosphorus oxychloride with a corresponding alkanol and then hydrolyzing the compound. It can be easily synthesized by a well-known method such as a method of reacting phosphorus oxide with a corresponding alkanol.

Further, for example, a long-chain alkyl acid phosphate compound synthesized by a method of reacting phosphorus pentoxide with a corresponding alkanol is generally obtained as a mixture of a monoalkyl diacid phosphate and a dialkyl acid phosphate. The separation operation for separating the two is complicated, and the monoalkyldiaside phosphate compound contained in the mixture not only does not adversely affect the object of the present invention, but also as described in JP-B-38-7244. Since the effect of improving the dyeability of a thermoplastic polyester resin can also be expected, in the present invention, these alkyl acid phosphate mixtures can be used as they are.

The amount of the long-chain dialkyl acid phosphate compound represented by the general formula (I) is 0.001 to 5, more preferably 0.005 to 100 parts by weight of the thermoplastic polyester resin.
１1 part by weight.

If the amount is less than 0.001 part by weight, it is insufficient to achieve the intended purpose. If the amount is more than 5 parts by weight, the effect is not further improved, and other physical properties are adversely affected. Can be considered.

The thermoplastic polyester resin used in the present invention,
It is a linear saturated polyester obtained by using terephthalic acid or an ester-forming derivative thereof as an acid component, and using a glycol having 2 to 10 carbon atoms or an ester-forming derivative thereof as a glycol component, such as polyethylene terephthalate and polypropylene terephthalate. ,
Examples thereof include polybutylene terephthalate, polyhexamethylene terephthalate, poly (cyclohexane-1,4-dimethylene) terephthalate, and polyneobenthylene terephthalate, and a mutual blend thereof, for example, polyethylene terephthalate and polybutylene terephthalate. It may be a polymer alloy.

In addition, the thermoplastic polyester resin used in the present invention may contain a part of terephthalic acid and / or glycol as another copolymer component, for example, isophthalic acid, phthalic acid, tetrabromophthalic acid, tetrabromoterephthalic acid, and methyl isophthalic acid. , 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,4'-diphenyldicarboxylic acid, 4,4'-diphenoxy Aromatic dicarboxylic acids such as ethanedicarboxylic acid; succinic acid, adipic acid,
Aliphatic or alicyclic dicarboxylic acids such as sebacic acid, azelaic acid, decanedicarboxylic acid and cyclohexanedicarboxylic acid; polyoxyalkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol; hydroquinone and resorcinol , 2,2
-Bis (4-hydroxyphenyl) propane, bis (4
Bisphenols such as -hydroxyphenyl) sulfone;
Ether diols obtained by adding ethylene oxide to bisphenols; may be replaced with oxycarboxylic acids such as ε-oxycaproic acid, hydroxybenzoic acid, hydroxyethoxybenzoic acid, etc., and the proportion of these copolymer components is It is preferably about 20 mol% or less, especially 10% or less of the total carboxylic acid component.

Further, these thermoplastic polyesters may include, in addition to branched components, for example, trivalent or tetravalent carboxylic acids such as tricarballylic acid, trimesic acid, trimellitic acid, and pyromellitic acid, and / or glycerin, trimethylolpropane, and pentaerythritol. 1 mol% of polyhydric alcohol such as
Below, more preferably 0.5 mol% or less may be copolymerized.

The above-mentioned thermoplastic polyester can be produced by an ordinary production method such as a solution polymerization reaction or a method combining this with a solid-phase polymerization reaction, and a commercially available product can be used.

In the present invention, the polycarbonate resin used by being blended with the thermoplastic polyester resin is one or more homo- or copolycarbonates selected from bisphenol A, a nucleus alkyl derivative or a nucleus halogenated derivative thereof. A branched polycarbonate resin in which a part is replaced with a triphenol compound may be used.

Further, the thermoplastic polyester resin of the present invention or a blend of a thermoplastic polyester resin and a polycarbonate resin, a small proportion of another thermoplastic resin for the purpose of improving heat shrinkage, improving impact strength, etc. Is also good.
Such other thermoplastic resins include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene
Examples thereof include a / 4-methylpentene copolymer, an ethylene / butene-1 copolymer, an ethylene / glycidyl methacrylate copolymer, an ethylene / vinyl acetate / glycidyl methacrylate copolymer, and a maleic anhydride-modified product thereof.

The thermoplastic polyester-based resin composition of the present invention may also contain other commonly used additives.

Among these additives, phenolic antioxidants, antioxidants such as phosphite or phosphonite antioxidants, and thioether antioxidants have a large effect of improving the thermal stability of the thermoplastic polyester resin, In addition, when the compound is used in combination with the long-chain dialkyl acid phosphate compound of the present invention, it is particularly preferable because the deterioration in physical properties during heating can be further improved.

Examples of the phenolic antioxidant include, for example, 2,6-
Ditertiary dibutyl-p-cresol, 2,6-diphenyl-
4-octadecyloxyphenol, stearyl (3,5-
Di-tert-butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethyleneglycolbis [(3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-di-tert-butyl-4- Hydroxyphenyl) propionamide], 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′- Chiridenbisu (6-tert-butyl--m- cresol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2 '
-Ethylidenebis (4-sec-butyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl- 4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl ) Isocyanurate, 1,3,5
Tris (3,5-di-tert-butyl-4-hydroxylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6 -Trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-
(Hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-
(Acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-
{Β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-
Tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-
5-methylphenyl) propionate].

Among these phenolic antioxidants, in particular, β
A derivative of-(3,5-dialkyl-4-hydroxyphenyl) propionic acid and 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene The effect is large and preferable.

Examples of the phosphite or phosphonite antioxidants include, for example, trisnonylphenyl phosphite,
Tris (2,4-di-tert-butylphenyl) phosphite,
Tris [2-tert-butyl-4- (3-tert-butyl-4-
[Hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, didecyl monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite Phyte, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6
Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tetra (C _12-15 alkyl) - bisphenol A diphosphite, tetra (tridecyl)-4,4'-n
-Butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3
-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,
4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like.

Examples of the thioether-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl, and β-alkyl mercapto of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). And propionates.

The addition amount of these antioxidants is 0.001 to 5 parts by weight, particularly preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin. Further, as the antioxidant, a phenolic antioxidant or a phosphite or phosphonite antioxidant is particularly preferable. Generally, a phenolic, phosphite or phosphonite, phenol / phosphite or phosphonite, Antioxidant components are used alone or in combination of two or more, such as phenol / thioether, phenol / phosphite or phosphonite / thioether.

In addition, the inorganic filler is compounded as a reinforcing agent for the thermoplastic polyester resin or as an electrical, thermal and other property modifier, but the present invention relates to a case where such an inorganic filler is compounded. It is also effective.

As the inorganic filler used in the thermoplastic polyester resin, for example, glass fiber, asbestos, carbon fiber, potassium titanate fiber, steel fiber, ceramic fiber, fibrous material such as boron whisker fiber, asbestos, mica, silica, Examples include powdery, granular or plate-like inorganic fillers such as talc, calcium carbonate, glass beads, glass flakes, clay and wollastonite.

Among these modifiers, particularly, when glass fiber is used, the mechanical strength and heat resistance are greatly improved,
This is preferable because the effect of significantly reducing the molding shrinkage is obtained.

The glass fiber is not particularly limited as long as it is generally used for reinforcing a resin. For example, long fiber type (glass roving), short fiber chopped strand, milled fiber, and the like can be used. The glass fibers may be treated with a sizing agent (eg, polyvinyl acetate, polyester sizing agent, etc.), a coupling agent (eg, a silane compound, a borane compound, etc.), and other surface treatment agents. Furthermore, it may be covered with a thermoplastic resin, a thermosetting resin, or the like. The long fiber type glass fiber is usually used after being cut to a desired length before or after blending with a resin.

The amount of the inorganic filler used is 5 to 100 parts by weight based on 100 parts by weight of the thermoplastic polyester resin.

In addition, if necessary, the thermoplastic polyester resin composition of the present invention contains a nucleating agent, a flame retardant, a release agent, a lubricant, an ultraviolet absorber, an epoxy compound, a coloring agent, an antistatic agent, a foaming agent, and the like. Can be added.

〔Example〕

Next, the present invention will be specifically described with reference to examples. However, the invention is not limited by these examples.

Example 1 A chopped strand glass fiber 3 mm in fiber length 3 mm was added to 70 parts by weight of polyethylene terephthalate having [η] of 0.72.
0 parts by weight, 0.5 parts by weight of talc and 0.2 parts by weight of the sample compound were blended and uniformly mixed in a V-type blender for 5 minutes. The mixture was extruded at a cylinder temperature of 270 ° C. to form a pellet, and then the pellet was injection-molded under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 140 ° C., and a molding cycle of 60 seconds. Created a dumbbell.

The dumbbell test piece was placed in an oven at 160 ° C., and after 500 hours, the yellowness was measured with a Hunter colorimeter, and the Izod impact strength (kg · cm / cm ² ) was measured.

 Table 1 shows the results.

Example 2 In order to see the effect of the combined use of the acid phosphate compound of the present invention and a phenolic antioxidant and / or a phosphite antioxidant, 0.2 parts by weight of a mono / di mixed stearyl acid phosphate and 0.2 part of an antioxidant were used. A test piece was prepared in the same manner as in Example 1 except that parts by weight were used, and a similar test was performed.

 Table 2 shows the results.

Example 3 30 parts by weight of 6 mm long chopped strand glass fiber, 30 parts by weight of glass frame (48 mesh), 15 parts by weight of decabromodiphenyl ether, 10 parts by weight of antimony trioxide were added to 100 parts by weight of polybutylene terephthalate having [η] of 0.75.
Parts by weight, 12 parts by weight of polycarbonate resin, 0.1 part by weight of tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, bis (2,6-di-tert-butyl-4-) (Methylphenyl) pentaerythritol diphosphite (0.2 part by weight) and a sample compound (0.3 part by weight) were added, and the mixture was uniformly mixed with a blender.
The mixture was extruded to form pellets, and the pellets were injection-molded at a cylinder temperature of 250 ° C. to prepare ASTM-1 dumbbells.

The dumbbell test piece was placed in an oven at 180 ° C., and the tensile strength after heating for a predetermined time was measured, compared with the tensile strength of the unheated test piece, and the result was determined as the tensile strength retention.

In addition, the tensile strength after the resin was retained in the cylinder of the molding machine set at 260 ° C. for 30 minutes was measured, and the same was compared with the tensile strength of the above-mentioned unheated test piece. Asked.

 Table 3 shows the results.

Example 4 75 parts by weight of polybutylene terephthalate having [η] of 0.75, 25 parts by weight of a polycarbonate resin, 0.5 parts by weight of tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane and 0.5 part by weight of the sample compound was uniformly mixed with a blender and then extruded to form a pellet.

The pellets were placed in an injection molding machine with a cylinder temperature of 260 ° C, injection-molded without retention and after 20 minutes of residence, ASTM
No.-1 dumbbell was made.

The tensile strength (kg · cm / cm) at 23 ° C. of the unretained test piece and the test piece after the retention were compared, and the result was obtained as a tensile strength retention. The color difference (ΔE) between the unretained test piece and the retained test piece was measured.

 Table 4 shows the results.

Example 5 20 parts by weight of polybutylene terephthalate having [η] of 0.75, 80 parts by weight of a polycarbonate resin, 0.2 parts by weight of bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and sample compound 0.3 The parts by weight were uniformly mixed with a blender and then extruded to form pellets.

The pellets were placed in an injection molding machine with a cylinder temperature of 300 ° C, injection-molded without retention and after 20 minutes of residence.
No.-1 dumbbell was made.

The tensile strength (kg · cm / cm) at 23 ° C. of the unretained test piece and the test piece after the retention were compared, and the result was obtained as a tensile strength retention. The color difference (ΔE) between the unretained test piece and the retained test piece was measured.

 The results are shown in Table-5.

[Effects of the Invention] As is clear from the results of the above Examples, the dialkyl acid phosphate compound of the present invention improves the colorability and heat resistance of a thermoplastic polyester resin and a blend of a thermoplastic polyester resin and a polycarbonate resin. The effect is remarkably excellent.

On the other hand, monoalkyl acid phosphate compounds or metal salts of alkyl acid phosphate hardly have these effects, and it is clear that the effects of the present invention are extremely specific.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-50-4147 (JP, A) JP-A-62-218451 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 67/00-67/08 C08L 69/00 C08K 3/00-13/08

Claims (1)

(57) [Claims] (1) To 100 parts by weight of a thermoplastic polyester resin or a polymer blend of a thermoplastic polyester resin containing 10% by weight or more of a thermoplastic polyester resin and a polycarbonate resin, (a) the following general formula (A) At least one of the phosphate compounds represented by I)
A thermoplastic polyester resin composition comprising 0.001 to 5 parts by weight. _{(R-O) 2 P (} = O) -OH (I) ( wherein, R represents an alkyl group having 12 to 22 carbon atoms.)