JP3017324B2 - Crystalline synthetic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crystalline synthetic resin composition having improved transparency, and more particularly, to a method in which a crystalline synthetic resin is compounded with a specific ammonium salt of an organic phosphate or an organic ammonium salt. The present invention relates to a crystalline synthetic resin composition having improved transparency.

[0002]

2. Description of the Related Art Crystalline synthetic resins such as polyethylene, polypropylene, polybutene-1, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, and polyamide have a low crystallization rate after heat molding. There were drawbacks that the molding cycleability was low, the mold temperature had to be lowered, and shrinkage due to crystallization after heat molding. Also,
These crystalline synthetic resins have disadvantages of insufficient strength and poor transparency because large crystals are generated.

[0003] All of these disadvantages are derived from the crystallinity of the synthetic resin, and are known to be eliminated if the crystallization temperature of the synthetic resin can be increased and fine crystals can be rapidly formed. I have.

It is known to add a nucleating agent or a crystallization accelerator for this purpose.
A metal salt of a carboxylic acid such as aluminum tertiary butyl benzoate, sodium adipate, sodium bis (4-
Tert-butylphenyl) phosphate, sodium-2,
2'-methylenebis (4,6-di-tert-butylphenyl)
Acidic phosphate metal salts such as phosphates and polyhydric alcohol derivatives such as dibenzylsorbitol and bis (4-methylbenzylidene) sorbidol have been used.

[0005] Among these compounds, JP-A-58-1
No. 736, JP-A-59-184252, and the like, metal salts of cyclic phosphoric acid esters of alkylidene bisphenols have a large effect and are widely used.

However, the effects of these compounds are still insufficient in some cases, and a method using a combination of an aluminum salt of 4-tert-butylbenzoic acid and an alkali metal salt or zinc salt of a higher aliphatic carboxylic acid (particularly). 62-26
No. 3244, JP-A-63-125551) or a method of using a metal salt of an aliphatic carboxylic acid with an organic phosphate compound (JP-A-3-79649, JP-A-3-81368) and the like are proposed. However, it was not enough yet, and practical improvement was strongly demanded.

[0007]

Means for Solving the Problems In view of the present situation, the present inventors have made various studies and found that by adding an ammonium salt or an organic ammonium salt of a specific organic phosphate to a crystalline synthetic resin. The present inventors have found that the transparency of the synthetic resin is greatly improved and the mechanical strength is increased, and the present invention has been achieved.

[0008] That is, the present invention relates to a crystalline synthetic resin 10
0 parts by weight of at least one of an ammonium salt or an organic ammonium salt of an organic phosphoric acid ester represented by the following general formulas 2 (the same as the chemical formula 1) represented by formulas (I) and (II): An object of the present invention is to provide a crystalline synthetic resin composition in which parts by weight are blended.

[0009]

Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom,
An alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,
Represents an aryl group or an aralkyl group, x is a direct bond,
A represents an alkylene group or an alkylidene group; A represents an ammonium ion or an organic ammonium ion;
And n represent 1 to 6, respectively. )

Hereinafter, the crystalline synthetic resin composition of the present invention will be described in detail.

[0011] R ₁ in the compound represented by the general formula which is added to improve the transparency of the synthetic resin used in the present invention (I) and _{(II), R 2, R} 3, R 4 and R ₅ Examples of the alkyl group represented by, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tertiary amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, Tertiary octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl groups and the like.

The cycloalkyl group includes cyclopentyl, cyclohexyl, cyclooctyl and the like, and the aryl group includes phenyl, methylphenyl, ethylphenyl, butylphenyl, hydroxyphenyl, methoxyphenyl and chlorophenyl. Can be Examples of the aralkyl group include benzyl, α-methylbenzyl, cumyl and the like.

Further, the alkylene group represented by x in the general formula (I) includes methylene, ethylene, propylene,
Butylene groups and the like, and as the alkylidene group,
Examples include ethylidene, isopropylidene, butylidene, hexylidene, octylidene, and cyclohexylidene groups.

The organic amine compounds constituting the organic ammonium salts represented by the general formulas (I) and (II) include, for example, methylamine, ethylamine, diethylamine, triethylamine, propylamine, 2-aminopropane, Propylamine, butylamine, isobutylamine, tert-butylamine, dipropylamine,
Diisobutylamine, disecondary butylamine, pentylamine, 2-aminopentane, hexylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, hexadecylamine, Octadecylamine, oleylamine, coconutamine, benzylamine, dibenzylamine, phenylethylamine, 3-methoxypropylamine, piperidine, pipecoline, N-aminopropyl pipecoline, morpholine, rupetidine, aniline, toluidine, xylidine, ethylaniline, pyridine , Picoline, ethylpyridine, lutidine, methylethylpyridine, 3-aminotriazine, aminotetrazole and other monoamine compounds, ethylenediamine , Propylene diamine, butylene diamine, hexamethylene diamine, diethylene triamine, dipropylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexamethylene tetramine, phenyl diamine,
Piperazine, pyrazine, aminoethylpyridine, N,
N'-bisaminoethyl-ethylenediamine, N, N '
-Bisaminoethyl-hexamethylenediamine, N,
N'-bisaminopropyl-ethylenediamine, N,
N′-bisaminopropyl-hexamethylenediamine,
Tris (2-aminoethyl) amine, tris (3-aminopropyl) amine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, octamethylenediamine, decamethylenediamine, undeca Methylenediamine, 3,9-bis (aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 4-oxa-1,7-diaminopentane, 4,7-dioxa-1, 10-diaminodecane, 4,8-dioxa-6,6-dimethyl-1,11
-Diaminoundecane, m-xylylenediamine, 1,
6,11-triaminoundecane, 4-aminomethyl-
And polyvalent amines such as 1,8-diaminooctane.

Accordingly, the compounds represented by the general formulas (I) and (II) used in the present invention include, for example, ammonium salts or organic ammonium salts of organic phosphates represented by the following chemical formulas (3) to (10). Salt (No. 1 ~
No. 8 compound).

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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These ammonium salts of organic phosphoric acid esters or organic ammonium salts can be easily produced, for example, by subjecting an acidic organic phosphoric acid ester and a corresponding amine compound to a heat reaction in a solvent.

Synthesis example2,2'-methylenebis (4,6-di-tert-butylphenyl
B) Lauryl ammonium salt of acidic phosphate ester (N
o. Synthesis of 1) 2,2'-methylenebis (4,6-di-tert-butylphenyl
B) 4.9 g (0.01 mol) of acidic phosphoric acid ester and
1.9 g (0.01 mol) of ethyl laurylamine
After heating and dissolving in 100 ml of alcohol, keep it for 1 hour.
Carry. The solvent was removed under reduced pressure at 60 ° C.
The color solid was filtered off and dried to obtain the desired product. This one is
Point 249 ° C. and 3000 cm in infrared absorption spectrum^-1
In NH_Three ⁺Showed broad absorption.

The amount of the ammonium salt or organic ammonium salt of these organic phosphates is determined by the amount of the synthetic resin 1
It is 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, based on 00 parts by weight.

The crystalline synthetic resin composition of the present invention further comprises a metal salt of an organic carboxylic acid, a hydrotalcite compound,
By blending a metal compound such as a zeolite compound, the transparency and physical properties are further greatly improved.

As the metal constituting the above metal compound,
Examples include metal atoms of Group I or Group II of the periodic table, for example, lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc and the like.
Group metals and Group IIa metals such as magnesium, calcium, barium are preferred.

The organic carboxylic acids constituting the metal salts of organic carboxylic acids include acetic acid, propionic acid, butyric acid,
Lactic acid, stearyl lactic acid, octylic acid, isooctylic acid,
Aliphatic carboxylic acids such as 2-ethylhexyl acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, 12-hydroxystearic acid, phenylstearic acid, behenic acid and montanic acid , Cyclopentanecarboxylic acid, methylcyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 2,2-dimethylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-octylcyclohexane Alicyclic carboxylic acids such as carboxylic acid, 4-phenylcyclohexanecarboxylic acid, cyclohexenecarboxylic acid and 4-butylcyclohexenecarboxylic acid, benzoic acid, toluic acid, xylyl acid, ethylbenzoic acid, 4- Tert-butylbenzoic acid, and aromatic carboxylic acids such as salicylic acid and the like.

These metal compounds are preferably added in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the synthetic resin.

Examples of the crystalline synthetic resin having improved transparency in the present invention include α-olefin polymers such as polyethylene, polypropylene, polybutene-1, and poly-3-methylbutene, polyethylene terephthalate, and polyhexamethylene terephthalate. And linear polyamides such as thermoplastic linear polyesters, polycaprolactone, polyhexamethylene adipamide, and polyphenylene sulfide.

In the present invention, the method of adding each component is not particularly limited, and a commonly used method can be applied as it is. That is, a method of dry blending the crystalline synthetic resin powder or pellets with the additive powder and performing extrusion molding, injection molding, or the like can be used.

Further, the crystalline synthetic resin composition of the present invention comprises:
It can be used for various molded articles, fibers, biaxially stretched films, sheets and the like.

The crystalline synthetic resin composition of the present invention may contain, if necessary, a phenolic antioxidant, an organic phosphorus-containing compound such as an organic phosphite, a thioether antioxidant, an ultraviolet absorber or a hindered amine compound. Such oxidative stability and light stability can be further improved by adding a light stabilizer such as.

The phenolic antioxidants usable in the present invention 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], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-
Di-tert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butyl) Phenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-tert-butyl-m-cresol), 2,2′-ethylidenebis (4,6-ditertbutylphenol),
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-ditert-butyl-4-hydroxybenzyl) 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-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5
5] undecane-bis [β- (3-tert-butyl-4-hydroxy-5-butylphenyl) propionate], triethylene glycol bis [β- (3-tert-butyl-4
-Hydroxy-5-methylphenyl) propionate]
And so on.

The amount of these phenolic antioxidants to be added is preferably 0.00 to 100 parts by weight of the synthetic resin.
It is 1 to 5 parts by weight, more preferably 0.01 to 3 parts by weight.

Examples of the organic phosphorus-containing compound include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tridecyl phosphite, and di (tridecyl) pentaerythritol diphosphite. , Distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,
4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
-1,1,3-tris (3-tert-butyl-4-hydroxy-5-methylphenyl) butanetriphosphite,
2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, 2,2'-methylene bis (4,6-di-tert-butylphenyl) octadecyl phosphite, 2,2'-methylene bis (4 , 6-Ditert-butylphenyl) fluorophosphite, tetrakis (2,
4-di-tert-butylphenyl) biphenylenediphosphonite and the like.

The amount of the organic phosphorus-containing compound to be added is preferably from 0.001 to 5 based on 100 parts by weight of the synthetic resin.
Parts by weight, more preferably 0.01 to 3 parts by weight.

Examples of the above thioether antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecylmercaptopropionate). Β-alkylmercaptopropionates of polyols such as acrylates).

The addition amount of these thioether-based antioxidants is preferably 0.00
It is 1 to 5 parts by weight, more preferably 0.05 to 3 parts by weight.

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

The amount of these ultraviolet absorbers is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the synthetic resin.

The light stabilizers such as the above hindered amine compounds include, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,2
6,6-pentamethyl-4-piperidyl stearate,
2,2,6,6-tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4) -Piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetrates (1,2,2
2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl)-
1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3 ′, 5′-di-tert-butyl-
4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-
Piperidinol / diethyl succinate polycondensate, 1,6-
Bis (2,2,6,6-tetraethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-
Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-chloro-6-morpholino-
s-Triazine polycondensate, 1,6-bis (2,2,6,
6-tetramethyl-4-piperidylamino) hexane /
Hindered amine compounds such as 2,4-chloro-6-tert-octylamino-s-triazine polycondensate are exemplified.

The amount of these light stabilizers added depends on the amount of the synthetic resin 1
The amount is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 00 parts by weight.

In addition, if necessary, the crystalline synthetic resin composition of the present invention may contain other nucleating materials such as aluminum-p-tert-butylbenzoate, dibenzylidenesorbitol, bis (4-methylbenzylidene) sorbitol and the like. Agents, metal soaps, pigments, dyes, fillers, foaming agents, flame retardants, antistatic agents, lubricants, processing aids, and the like may be added.

The crystalline synthetic resin composition of the present invention can be molded by a conventionally known method such as injection molding, extrusion molding or blow molding, and is not limited by the molding method or its form.

Further, the crystalline synthetic resin composition of the present invention comprises
After the molding, the surface characteristics can be improved by performing a known treatment such as a low-temperature plasma treatment.

[0048]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited in any way by these examples.

Example 1 Polyethylene terephthalate 100 having an intrinsic viscosity of 0.66
After sufficiently mixing 0.25 parts by weight of the ammonium phosphate salt and 0.25 parts by weight of lithium stearate shown in the following Table 1 with respect to parts by weight, pellets were prepared using a twin-screw extruder. Put the pellet in a differential calorimeter
/ Min, and the crystallization temperature during the heating was measured.

After melting at 280 ° C. for 10 minutes,
The crystallization temperature when the temperature was decreased at a rate of ° C./min was measured, and the ratio H / of the height H of the endothermic peak at the time of the temperature decrease to the width W at H / 2 was measured.
W was determined. The results are shown in Table 1 below.

As the crystallization temperature at the time of raising the temperature is lower, a molded article having a higher degree of crystallinity can be obtained when molded with a low-temperature mold.
The higher the crystallization temperature at the time of temperature decrease and the larger the H / W, the higher the crystallization speed.

[0052]

[Table 1]

Example 2 100 parts by weight of a propylene random copolymer, 0.2 parts by weight of 2,6-di-tert-butyl-4-methylphenol, stearyl-β- (3,5-di-tert-butyl-4-methyl) 0.1 part by weight of (hydroxyphenyl) propionate, 0.15 part by weight of an ammonium salt of an organic phosphoric acid ester (No. 3 compound) and 0.1 part by weight of a metal compound shown in the following Table 2 were sufficiently mixed by a mixer. , Temperature 230 ℃, rotation speed 20rp
Pellets were prepared using an extruder under the conditions of m 2. The pellets were molded at 250 ° C. and a mold temperature of 60 ° C. by an injection molding machine to prepare a test piece having a thickness of 1 mm. The haze value (haze value) of this test piece was measured according to the method of ASTM D-1003.

Further, this pellet was used as a differential scanning calorimeter (D
Using SC), after melting at 230 ° C. for 3 minutes, the peak temperature of the maximum peak when the temperature was lowered at 5 ° C./min was measured and defined as the crystallization temperature. The results are shown in Table 2 below.

[0055]

[Table 2]

Example 3 100 parts by weight of a polypropylene homopolymer, 0.1 part by weight of tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane,
0.05 parts by weight of calcium stearate and the following Table 3
After dry blending the ammonium phosphate salt shown in
Pellets were made with an extruder. Using this pellet, 25
A test piece having a thickness of 1 mm was prepared by injection molding at 0 ° C. The test piece was tested for Izod impact strength at 20 ° C (kg · cm / c
m ² ) was determined, and the results are shown in Table 3 below.

[0057]

[Table 3]

Example 4 0.1 part by weight of ammonium phosphate shown in the following Table 4 was dry blended with 100 parts by weight of nylon-66 resin, and a 3.5 oz. In-line screw type injection molding machine (cylinder) was used. Temperature 220 ° C, 240 ° C, 240 ° C, 2
35 ° C), molded product thickness 10mm, diameter 100mm
Was injection molded at a mold temperature of 80 ° C.

When the injection time is 14 seconds, the intermediate time is 4 seconds, and the cooling time is sequentially shortened from 50 seconds, and 30 shots are molded. When it is difficult to release from the mold or when warping or sinking occurs in the molded product. The cooling time was measured. The shorter the cooling time, the shorter the molding cycle,
Preferred for processing operations. The results are shown in Table 4 below.

[0060]

[Table 4]

As shown in each of the examples, the ammonium salt or organic ammonium salt of the organic phosphoric ester according to the present invention has an excellent effect of greatly improving the transparency and mechanical strength of the crystalline synthetic resin. It is clear that.
It is also apparent that the effect of the ammonium salt or the organic ammonium salt of the organic phosphoric acid ester according to the present invention can be further greatly improved by using a metal compound such as a metal salt of an organic carboxylic acid.

[0062]

The crystalline synthetic resin composition of the present invention has excellent transparency and high mechanical strength.

Claims (2)

(57) [Claims] 1. An ammonium phosphate or an organic ammonium salt of an organic phosphate represented by the following general formula (I) or (II) in 100 parts by weight of a crystalline synthetic resin. A crystalline synthetic resin composition containing from 0.01 to 10 parts by weight. Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom,
An alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,
Represents an aryl group or an aralkyl group, x is a direct bond,
A represents an alkylene group or an alkylidene group; A represents an ammonium ion or an organic ammonium ion;
And n represent 1 to 6, respectively. ) A metal salt of wherein further organic carboxylic acid, the formation
0.01 to 10 parts by weight based on 100 parts by weight of the crystalline synthetic resin
2. The crystalline synthetic resin composition according to claim 1, wherein the composition is mixed.