JPH11349740A - Colored synthetic resin composition for injection molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject colored synthetic resin composition excellent in process stability, high in the rigidity of the molded product and little in deformation by including a crystalline high-molecular compound, specific compound and specific coloring agent. SOLUTION: This composition is obtained by including (A) 100 pts.wt. of crystalline high-molecular compound, (B) 0.005 to 5 pts.wt. of the compound of formula I (R<1> and R<2> are each an 1-3C alkyl; (n) is 1 or 2; and M is an alkali metal when (n) is 1 and an alkaline earth metal or =Al-OH when (n) is 2) and (C) 0.02 to 20 pts.wt. of coloring agent selected from the group consisting of iron oxide-based pigment, azo-based pigment and phthalocyanine-based pigment. The component A is pref. exemplified by a polyolefin-based resin. The component B is obtained by e.g. reacting phosphorus trichloride with a 2,2'-methylene bisphenol derivative, hydrolyzing it for obtaining a cyclic acidic phosphoric acid ester and reacting it with a metal hydride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored synthetic resin composition used for the production of injection molded articles, and more particularly, to suppress the shrinkage and deformation of molded articles after injection molding and improve the productivity of the molded articles. And a colored synthetic resin composition.

[0002]

2. Description of the Related Art Synthetic resins such as polyethylene, polypropylene, polybutene-1, polyethylene terephthalate, and polyamide have the disadvantage that the crystallization rate after heat molding is low and the molding cycle becomes long. In addition, there is a disadvantage that the rigidity of the molded product is low due to insufficient crystallization. Further, when a coloring agent is added to color the resin, the shrinkage after heat molding is increased, and there is a disadvantage that the molded product is deformed along the resin.

[0003] These drawbacks are derived from the crystallinity of the polymer material, and it is known that it can be improved by increasing the crystallization temperature of the polymer material and rapidly generating fine crystals. For this purpose, a crystallization agent (crystal nucleating agent or crystallization accelerator) has been added, and it is known that a molding cycle can be shortened, and that rigidity and transparency are increased.

As the above-mentioned nucleating agent or crystallization accelerator, for example, metal salts of carboxylic acids such as sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate, and sodium bis (4-tert-butylphenyl) phosphate Acid phosphate metal salts such as sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate; polyhydric alcohol derivatives such as dibenzylidene sorbitol and bis (methylbenzylidene) sorbitol; I was Among these compounds, metal salts of alkylidene bisphenol cyclic phosphates described in JP-A-58-1736 and JP-A-59-184252 have particularly large effects and have been widely used.

However, synthetic resin compositions containing these compounds have improved molding cycleability, rigidity and transparency, but have insufficient effects on deformation. Further, in a synthetic resin composition in which a specific pigment is blended as a colorant, the effect of the crystallization agent may be sufficiently exhibited or the effect may be insufficient depending on the type of the crystallization agent contained. Was.

Accordingly, an object of the present invention is to provide a colored synthetic resin composition for injection molding which has excellent processing stability, high rigidity of a molded product, and extremely small deformation.

[0007]

The present inventors have conducted intensive studies and as a result, have found that a colored synthetic resin composition using a specific phosphate compound as a crystallization agent can achieve the above object. I learned.

According to the present invention, 0.005 to 5 parts by weight of a compound represented by the following general formula (I) is added to 100 parts by weight of a crystalline polymer compound; An object of the present invention is to provide a colored synthetic resin composition for injection molding obtained by adding 0.02 to 20 parts by weight of a coloring agent selected from iron oxide pigments, azo pigments and phthalocyanine pigments.

[0009]

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[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the colored synthetic resin composition for injection molding of the present invention will be described in detail.

The compound represented by the general formula (I) used in the colored synthetic resin composition for injection molding of the present invention is used as a crystallization agent. Examples of the alkyl group having 1 to 8 carbon atoms represented by R1 and R2 in the general formula (I) include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl,
Isobutyl, amyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, tertiary octyl, 2-ethylhexyl and the like. Examples of the alkali metal atom represented by M include sodium, potassium, and lithium, and examples of the alkaline earth metal atom include magnesium and calcium.

Specific examples of the compound represented by the above general formula (I) include the following compound Nos. 3 to 8: 1
To 6 and the like. However, the present invention is not limited at all by the following exemplified compounds.

[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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The compound represented by the above general formula (I) is obtained by, for example, reacting phosphorus trichloride with a 2,2'-methylenebisphenol derivative, hydrolyzing it to form a cyclic acidic phosphate, and then adding water. React with metal hydroxide such as sodium oxide. Next, after being filtered and dried, it is pulverized, if necessary, to produce the compound as a crystallization agent.

The amount of the compound represented by the above general formula (I) is 0.1 to 100 parts by weight of the crystalline polymer compound.
005 to 5 parts by weight, preferably 0.01 to 3 parts by weight. If the amount is less than 0.005 parts by weight, the effect is not exhibited, and if it exceeds 5 parts by weight, no further effect is obtained.

The crystalline polymer compound used in the colored synthetic resin composition for injection molding of the present invention includes, for example,
(1) α-olefin polymers such as low-density polyethylene, linear low-density polyethylene, high-density polyethylene, polypropylene, polybutene-1, poly-3-methylbutene, ethylene / propylene block or random copolymer, (2) Examples include thermoplastic linear polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyhexamethylene terephthalate; and (3) linear polyamides such as polyphenylene sulfide and polycaprolactone, and polyhexamethylene adipamide.

Among the above crystalline polymers, polyolefin resins such as crystalline α-olefin polymers, especially polypropylene, ethylene / propylene copolymers, and these propylene polymers and other α
-Polypropylene resins such as mixtures with olefin polymers are preferred.

The crystalline polymer compound has a molecular weight, a molecular weight distribution, a melt flow index, a ratio of an insoluble component in a solvent such as hexane, a stereoregularity, for example, a pentad fraction of isotactic and a triad of syndiotactic. It can be used irrespective of the degree of the fraction, the type of catalyst used for the polymerization of the Ziegler-Natta catalyst, the metallocene catalyst, or the like, and the presence or absence of a catalyst removal step. JP-A-37-152, JP-A-63-90552, and JP-A-63-210152
JP-A-63-213547 and JP-A-63-243
Nos. 150, 63-243152, 63-
260943, 63-260944, 63-264650, JP-A-1-178541, 2-49047, 2-102242, 2-251548, 2- 279746
And JP-A-3-195751 can also be suitably used.

The colorant used in the colored synthetic resin composition for injection molding of the present invention is selected from iron oxide pigments, azo pigments and phthalocyanine pigments. Examples of the iron oxide pigments include iron black, red iron oxide, and zinc ferrite pigment. As azo pigments,
For example, azo lake pigments such as Lake Red C and Brilliant Carmine 6B, benzimidazolone pigments such as Hosta Palm Yellow, Nova Palm Red, PV Bordeaux, and PV Fast Brown; Pigment, PV Fast Yellow HG, and Chromophthal Yellow GR. Examples of the phthalocyanine pigment include phthalocyanine blue and phthalocyanine green. These colorants are compatible with the desired color and crystalline polymer compound, heat and light resistance, cost,
It is appropriately selected and used depending on the degree of toxicity.

The colorant is added in an amount of 0.02 to 20 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the crystalline polymer compound. When the added amount is 0.02
If the amount is less than parts by weight, almost no coloring occurs, and 2
When the amount exceeds 0 parts by weight, the physical properties of the resin composition are significantly reduced.

When imparting further stability to the colored synthetic resin composition for injection molding of the present invention, additives such as general-purpose antioxidants, ultraviolet absorbers and hindered amine light stabilizers are added as necessary. be able to.

Particularly preferred examples of these additives include phenol-based, sulfur-based, phosphorus-based antioxidants, ultraviolet absorbers, and hindered amine light stabilizers.

The phenolic antioxidants include, for example, 2,6-di-tert-butyl-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, thiodiethylene glycol bis [(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) butylic acid] glycol ester, 4,4'-butylidenebis (6-tert-butyl-m-cresol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), , 2'-ethylidenebis (4-sec-butyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl Tributyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert. Tributylbenzyl) isocyanurate,
1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)
-2,4,6-trimethylbenzene, 1,3,5-
[(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-{(3-
Tert-butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] 2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4- Hydroxy-5-
Methylphenyl) propionate].

The sulfur-based antioxidants include, for example, dilauryl thiodipropionate, dimyristyl,
And dialkylthiodipropionates such as distearyl and β-alkylmercaptopropionates of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate).

Examples of the phosphorus-based antioxidants include trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, and tris [2-tert-butyl-4- (3- Tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite Phyte, distearylpentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2
6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-diphenyl) (Tert-butylphenyl) -2-ethylhexyl phosphite, 2,2 ′
-Methylenebis (4,6-di-tert-butylphenyl) -2
-Octadecylphosphite, 2,2'-ethylidenebis (4,6-ditertbutylphenyl) fluorophosphite, tetra (tridecyl) isopropylidenediphenol 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, tris (2-[(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-6 -Oxy] ethyl) amine, 2,2-bis (4
-[(2,4,8,10-tetrakis-tert-butylbenzo [d, f] [1,3,2] dioxaphosphepin-6
-Yl) oxy] phenyl) propane;
In particular, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4 , 6-ditert-butylphenyl) -2-ethylhexyl phosphite,
Those having a melting point of 40 ° C. or higher, such as tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, are preferred because they have little effect on the softening point of the crystalline polymer compound.

Examples of the ultraviolet absorber include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-
2-hydroxybenzophenones such as 4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole,
(2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole,
-(2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4 -Third octyl-6
2- (2-hydroxyphenyl) benzotriazoles such as -benzotriazole) phenol and polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole; phenyl salicylate, resorcinol monobenzoate Benzoates such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2 Substituted oxanilides such as' -ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-
and cyanoacrylates such as β, β-diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Examples of the hindered amine light stabilizer include, for example, 2,2,6,6-tetramethyl-4-
Piperidyl benzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide,
1-[(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-di-tert-butyl-4- (Hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) sebacate, bis (1,2,2,6)
6-pentamethyl-4-piperidyl) -2-butyl-2
-(3,5-di-tert-butyl-4-hydroxybenzyl)
Malonate, N, N-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl)
Butanetetracarboxylate, tetra (1,2,2,2)
6,6-pentamethyl-4-piperidylbutanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis (1,2,2,6 , 6-Pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-)
Piperidyloxycarbonyloxy) butylcarbonyloxy {ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2-} tris (1,2 , 2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxydiethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,1
2-tetrakis [4,6-bis {N- (2,2,6,6
-Tetramethyl-4-piperidyl) butylamino}-
1,3,5-triazin-2-yl] -1,5,8,1
2-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6, -tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dicyclo-s- Triazine / N, N-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N′-bis (2
2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensate.

In addition, if necessary, the colored synthetic resin composition for injection molding of the present invention may contain in advance a heavy metal deactivator, an alkali metal, alkaline earth metal or zinc metal soap, hydrotalcite, nonionic surfactant. Agents, cationic surfactants, anionic surfactants, antistatic agents composed of amphoteric surfactants, flame retardants such as halogen-based, phosphorus-based or metal oxides, lubricants such as ethylenebisalkylamide, processing aids , Fillers and the like.

Examples of molded articles obtained by injection molding the composition of the present invention include exterior parts such as bumpers, automobile resin parts such as various interior parts such as dashboards and instrument panels, refrigerators, washing machines, and vacuum cleaners. And household goods such as tableware, buckets and bathing goods, and miscellaneous goods such as toys.

[0035]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited by the following examples.

Example 1 and Comparative Example 1 Polypropylene ("Profax650" manufactured by Montell Corporation)
1 ") 100 parts by weight, tetrakis [methylene-3-
(3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane 0.05 part by weight, tris (2,4
0.05 parts by weight of (-di-tert-butylphenyl) phosphite, 0.1 part by weight of a crystallization agent shown in Table 1 below, and 2 parts by weight of a pigment were mixed to obtain a synthetic resin composition. This composition was applied to an in-line injection molding machine (cylinder temperature 230
C.) and injection molding was performed at a mold temperature of 60 ° C. using a mold for a disk-shaped molded product having a thickness of 1.8 mm and a diameter of 100 mm to obtain a test piece. After the test piece was left at room temperature for 24 hours, the maximum warpage was measured based on JIS K6911, and ASTM D-747-63 was used to examine the rigidity.
Was used to measure the flexural modulus. The results are shown in Table 1 below. In Table 1, No. 1-9, 1-1
0, 1-14, 1-15, 1-19, and 1-20 are Examples, and Nos. 1-1 to 1-8, 1-11 to 1-13,
1-16 to 1-18 are comparative examples. Comparative Compound 1 is sodium benzoate, and Comparative Compound 2 is
Sodium bis (4-tert-butylphenyl) phosphate (the same applies hereinafter).

[0037]

[Table 1]

Example 2 and Comparative Example 2 Polypropylene ("Profax650" manufactured by Montell Corporation)
1 ") 100 parts by weight, tetrakis [methylene-3-
(3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane 0.05 part by weight, tris (2,4
0.05 parts by weight of di-tert-butylphenyl) phosphite, 0.05 parts by weight of lithium myristate, 0.1 part by weight of a crystallization agent shown in Table 2 below, and 2 parts by weight of a pigment were mixed, and a synthetic resin was obtained. A composition was obtained. Using this composition, a test piece was prepared in the same manner as in Example 1, and the maximum warpage and flexural modulus were measured. The results are shown in Table 2 below.
In addition, in [Table 2], No. 2-6 to 2-8, 2-10 to 2-
12, 2-14 to 2-16 are examples, and No. 2-
1-2-5, 2-9, and 2-13 are comparative examples.

[0039]

[Table 2]

Example 3 and Comparative Example 3 100 parts by weight of high-density polyethylene (“HIZEX” manufactured by Mitsui Petrochemical Co., Ltd.), 0.3 parts by weight of distearylthiodipropionate, tetrakis [methylene-3- (3,3)
0.1 part by weight of 5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 0.1 part by weight of a crystallization agent shown in Table 3 below, and 2 parts by weight of a pigment were mixed to prepare a synthetic resin composition. Obtained. Using this composition, a test piece was prepared in the same manner as in Example 1, and the maximum warpage and flexural modulus were measured. The results are shown in Table 3 below. In addition, [Table 3]
Medium, No. 3-9, 3-10, 3-14, 3-15, 3-
19 and 3-20 are Examples, and Nos. 3-1 to 3-
8, 3-11 to 13-13 and 3-16 to 3-18 are comparative examples.

[0041]

[Table 3]

[0042]

The colored synthetic resin composition for injection molding of the present invention can provide a molded article having a small warp after heat molding and a high rigidity regardless of the kind of the coloring agent contained.

Claims (4)

[Claims] 1. A compound represented by the following general formula (I): 0.005 to 100 parts by weight of a crystalline polymer compound
A colored synthetic resin composition for injection molding, wherein the composition contains 0.02 to 20 parts by weight of a coloring agent selected from iron oxide pigments, azo pigments and phthalocyanine pigments. Embedded image 2. The colored synthetic resin composition for injection molding according to claim 1, wherein the crystalline polymer compound is a polyolefin resin. 3. The colored synthetic resin composition for injection molding according to claim 1, wherein the colorant is an iron oxide pigment. 4. The colored synthetic resin composition for injection molding according to claim 1, wherein the colorant is a phthalocyanine pigment.