KR100258316B1 - Crystalline Synthetic Resin Composition - Google Patents

Abstract

The present invention, 100 parts by weight of the crystalline synthetic resin, (a) at least one selected from the group consisting of alkali metal carboxylate, alkali metal β-diketonate and alkali metal β-keto acetic acid ester salt 0.01 to 5 weight Part and (b) crystalline synthetic resin composition comprising at least 0.01 to 5 parts by weight of a cyclic organic phosphate ester basic polyvalent metal salt represented by the following general formula (I).

(Wherein R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₂ and R ₃ each represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M represents a group III or group of the periodic table) Represents a metal atom of group IV, X represents HO- when M represents a metal atom of group III of the periodic table, and 0 = or (HO) when M represents a metal atom of group IV of the periodic table _2- .)

Description

Crystalline Synthetic Resin Composition

The present invention relates to a crystalline synthetic resin composition, and more particularly, to a crystalline synthetic resin fired product having improved transparency, mechanical properties, and the like, obtained by mixing an alkali metal compound mole and a cyclic organic phosphate ester basic polyvalent metal salt with a synthetic resin. It is about.

Crystalline synthetic resins such as polyethylene, polypropylene, polybutene-1, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyamide, and the like have low molding cycle properties because the crystallization rate after hot melt molding is delayed, Moreover, there existed a fault which shrink | contracts by the crystallization progress after heat forming. In addition, these crystalline synthetic resins have disadvantages in that they have insufficient strength or inferior transparency because large crystals are produced.

These defects are all derived from the crystallinity of the synthetic resin and are known to be resolved if the crystallization temperature of the synthetic resin can be raised to rapidly produce fine crystals.

It is known to add a nucleating agent or a crystallization promoter for the purpose of eliminating the above-mentioned drawbacks, and conventionally, carboxylate metal salts such as 4-t-butyl benzoate aluminum salt and sodium adipic acid, sodium ratio (4-t- Acid phosphate ester metal salts such as butyl phenyl) phosphate, sodium-2,2'-methylene bis (4,6-di-t-butylphenyl) phosphate, dibenzylidene sorbitol, bis (4-methylbenzylidene) sorbitol, etc. Polyhydric alcohol derivatives.

Among these compounds, metal salts of cyclic phosphate esters of alkylidene bisphenols described in JP-A-58-1,736, JP-A-59-184,252 and the like are widely used.

In addition, attempts have been made to improve the effect by using these compounds and other metal compounds in combination. For example, Japanese Unexamined Patent Application Publication No. 63-69,853 discloses the prevention of stiffness deterioration when an aromatic alkali metal salt nucleating agent and an alkaline earth metal salt of carxyl acid such as calcium stearate are used in combination. For this purpose, Bangbi which uses hydrotalcite or the alkali metal salt of carboxylic acid instead of the alkaline earth metal salt of carboxylic acid is proposed. Japanese Unexamined-Japanese-Patent No. 1-129,050 and 1-129,051. The publication proposes a method of using a cyclic organic phosphate ester metal salt and a periodic table group II metal salt of an aliphatic carboxylic acid together, and Japanese Patent Laid-Open Nos. 3-79,649 and 3-81,368 disclose acidic organic compounds. Bangbi which uses together a phosphate ester compound and an aliphatic carboxylic acid metal salt is proposed. In addition, Japanese Patent Application Laid-Open No. 3-43,437 discloses an alkali metal, an alkaline earth metal or an aluminum group metal in order to prevent a decrease in pH in hydrothermal immersion after irradiation when a cyclic organic phosphate ester metal salt is used. A method of using a hydroxide together is proposed.

However, the improvement effect by these combinations is not yet satisfactory practically, In particular, further improvement is calculated | required from the viewpoint of transparency improvement of crystalline synthetic resin.

In addition, Japanese Patent Laid-Open Publication No. Hei 1-104,638, Hei 1-l04,639 and Hei 1-104,647 disclose aromatic diphosphate diamine to improve processability and heat resistance of high rigid propylene resin. Although the use of basic aluminum salt of ester is proposed, transparency improvement effect is hardly recognized when such a compound is used, and such a basic polyhydric metal salt compound is considered to be less effective in improving transparency of crystalline synthetic resin. It is becoming.

The present inventors made various studies in light of this phenomenon, and as a result, alkali metal salts of organic carboxylic acids, alkali metal salts of β-diketonates or alkali metal salts of β-ketoacetic acid esters, and cyclic organic phosphoric acid were added to crystalline synthetic resins. By adding ester basic divalent metal salt, the present inventors have found that the transparency of this resin is greatly improved and the mechanical strength is also increased.

That is, the invention is characterized by 100 parts by weight of the crystalline synthetic resin, at least one selected from the group consisting of (a) an alkali metal salt of carboxylic acid, an alkali metal salt of β-diketonate and an alkali metal salt of β-ketacetic acid ester. It is providing the crystalline synthetic resin composition which mix | blends 1-5 weight part and (b) 1 or more types 0.01-5 weight part of cyclic organic phosphate ester basic polyvalent metal salt represented by following General formula (I).

(Wherein R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₂ and R ³ each represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M represents a group III of the periodic table) Or a group IV metal atom, X represents HO- when M represents a metal atom of group III of the periodic table, and O = or (HO if M represents a metal atom of group IV of the periodic table ) _2- .)

In the crystalline synthetic resin composition of the present invention, transparency is improved, and physical properties such as mechanical strength are also improved.

As an alkali metal which comprises each alkali metal salt compound of the alkali metal salt of the carboxylic acid which is (a) component of the crystalline synthetic resin composition of this invention, the alkali metal salt of (beta) -diketonate, and the alkali metal salt of (beta) -keto acetate ester, Lithium, sodium, potassium and the like.

As carboxylic acid which comprises the alkali metal salt of the said carboxylic acid, for example, acetic acid, propionic acid, acrylic acid, octylic acid, isooctyl acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, summitinic acid, stearin Acid, oleic acid, ricinolic acid, 12-hydroxystearic acid, behenic acid, montanic acid, melic acid, β-dodecyl mercapto acetic acid, β-dodecyl mercaptopropionic acid, β-N-laurylaminopropionic acid, β-N Aliphatic monocarboxylic acids such as -methyl-N-lauroylaminopropionic acid, malonic acid, succinic acid, adipic acid, maleic acid, azelaic acid, sebacic acid, dodecanediic acid, tartaric acid, butanetricarboxylic acid, butanetetracarboxylic acid Aliphatic polyhydric carboxylic acids, such as acids, naphthenic acid, cyclopentanecarboxylic acid, 1-methylcyclopentanecarboxylic acid, 2-methylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1- Methylcyclohex Carboxylic acid, 4-methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4-octylcyclohexanecarboxylic acid, cyclohexenecarboxylic acid, 4- Alicyclic mono or polycarboxylic acids such as cyclohexene-1,2-dicarboxylic acid; Aromatic mono or polycarboxylic acids such as benzoic acid, toluic acid, xylic acid, ethyl benzoic acid, 4-t-butyl benzoic acid, salicylic acid, phthalic acid, trimellitic acid and pyromellitic acid.

As a beta-diketone compound which comprises the alkali metal salt of the said beta-diketonate, acetyl acetone, pivaloyl acetone, palmitoyl acetone, benzoyl acetone, pivaloyl benzoyl acetone, dibenzoyl methane etc. are mentioned, for example. have.

Moreover, as (beta) -keto acetate ester which comprises the alkali metal salt of the said (beta)-ketone acetate ester, For example, aceto ethyl acetate, aceto octyl acetate, aceto lauryl acetate, aceto acetate stearyl, benzoyl acetate, benzoyl acetate lauryl, etc. Can be mentioned.

Alkali metal salts, β-diketonate alkali metal salts or alkali metal salts of β-ketacetic acid esters of the carboxylic acid as the component (a) are the alkali metal and the carboxylic acid, β-diketone compound or β-ketoacetic acid ester, respectively. It is a salt with, and can be manufactured by a conventionally well-known method. Moreover, among each alkali metal salt compound of these (a) component, the alkali metal salt of aliphatic monocarboxylic acid, especially the lithium salt of aliphatic carboxylic acid, is preferable, and the aliphatic monocarboxylate of 8-20 carbon atoms is especially preferable. .

The addition amount of the alkali metal salt of carboxylic acid which is the said (a) component, the alkali metal salt of (beta) -digetonate, or the alkali metal salt of (beta) -keto acetate ester is 0.01-5 weight part with respect to 100 weight part of crystalline synthetic resins, In particular, 0.05 or 3 weight part is preferable.

Moreover, in the cyclic organic phosphate ester basic polyvalent metal salt represented by the said General formula (I) which is (b) component of the crystalline synthetic resin composition of this invention, it is a C1-C4 alkyl group represented by R <_1> . , Methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, and the like. Examples of the alkyl group having 1 to 12 carbon atoms represented by R ₂ or R ₃ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, amyl, t-amyl, hexyl, heptyl, octyl, isooctyl, t-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, t- Dodecyl and the like.

Moreover, as metal atoms of group III or group IV of the periodic table represented by M, aluminum, gallium, germanium, tin, titanium, zirconium, etc. are mentioned, Especially aluminum is preferable.

Therefore, as a cyclic organic phosphate ester basic polyvalent metal salt represented by the said General formula (I), the following compound (compound No. 1-the compound No. 6) is mentioned, for example.

[Compound 1]

[Compound 2]

[Compound 3]

[Compound 4]

[Compound 5]

[Compound 6]

The cyclic organic phosphate ester basic polyvalent metal salt is, for example, a method of reacting an alkali metal salt of an acidic cyclic organic phosphate ester with a polyvalent metal halide or an oxidized polyvalent metal halide, and then hydrolyzing as necessary, acidic It can manufacture easily by the method etc. which make a cyclic organic phosphate ester and a polyvalent metal alkoxide react, and then hydrolyze as needed.

Although the specific example of manufacture of the said cyclic organophosphorous ssener basic polyvalent metal salt used by this invention to following (Production example 1)-(production example 4) is illustrated, this invention is not limited by the following preparation example.

Preparation Example 1 Preparation of Compound No. 1

10.16 g (0.02 mol) of 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate sodium salt was dissolved in methanol, and 2.41 g (0.01 mol) of aluminum trichloride hexahydrate was stirred at 40 ° C. 50 ml of aqueous solution was added dropwise for 30 minutes. After completion of the dropwise addition, the mixture was stirred for 4 hours under reflux, cooled to room temperature, and then a pH of 6 was added by adding 3N aqueous sodium oxide solution. The product was filtered, washed and dried to give 9.63 g of a white powder having a melting point of 300 ° C. or higher.

The result of analysis of the obtained white powder (product) was as follows, and it confirmed that it was a target object.

Aluminum content: 2.75% (calculated: 266%)

Phosphorus content: 620% (calculated: 6.11%)

Infrared spectroscopic analysis

3400 cm ^-1 (υOH), 1470 cm ^-1 (υp-o), 1230 cm ^-1 , 1100 cm ^-1 and 940 cm ^-1 (υp-o)

Preparation Example 2 Preparation of Compound No. 2

9.36 g (0.02 mol) of 2,2'-methylenebis (4,6-dit-butylphenyl) acid phosphate was dissolved in toluene and 2.84 g (0.01 mol) of toluene solution of tetraisopropyl titaniumate was added. . After 2 hours of stirring at 80 ° C., 2 g of water was added and further stirred at 80 ° C. for 2 hours. After cooling to room temperature, the product was filtered and dried to obtain 9.68 g of a white powder having a melting point of 300 ° C. or higher.

The result of analysis of the obtained white powder (product) was as follows, and it confirmed that it was a target object.

Titanium Content: 4.58% (calculated: 4.55%)

Phosphorus content: 6.03% (calculated: 5.89%)

Infrared Spectroscopy (cm ^-1 )

3400 cm ^-1 (υOH), 1470 cm ^-1 (υp-o), 1260 cm ^-1 , 1100 cm ^-1 and 920 cm ^-1 (υp-o)

Preparation Example 3 Preparation of Compound No. 3

10.16 g (0.02 mol) of 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate sodium salt was dissolved in methanol and 4.04 g (0.01 mol) of tin tetrachloride octahydrate while stirring at 50 ° C. 50 ml of aqueous solution was added dropwise for 30 minutes. After the dropwise addition, the methane was stirred under reflux for 4 hours and cooled to room temperature. The product was filtered, washed and dried to give 10.44 g of a white powder having a melting point of 300 ° C. or higher.

The result of analysis of the obtained white powder (product) was as follows, and it confirmed that it was a target object.

Tin content: 10.10% (calculated: 10.57%)

Phosphorus flow rate: 5.65% (calculated: 5.52%)

Infrared spectroscopic analysis

3400 cm ^-1 (υOH), 1470 cm ^-1 (υp-o), 1220 cm ^-1 , 1060 cm ^-1 and 950 cm ^-1 (υp-o)

Preparation Example 4 Preparation of Compound No. 4

10.16 g (0.02 mol) of 2,2'-methylenebis (4,6-di-t-butyl phenyl) phosphate sodium salt was dissolved in methanol, and 3.22 g (0.01 mol) of zirconium dihydrochloride zirconia was stirred at 50 ° C. 50 ml of an aqueous solution) was added dropwise for 30 minutes. After completion of the dropwise addition, the methane was stirred under reflux for 4 hours and cooled to room temperature. The product was filtered, washed with water and dried to obtain 10.12 g of a white powder having a melting point of 300 ° C. or higher.

The result of analysis of the obtained white powder (product) was as follows, and it confirmed that it was a target object.

Zirconium content: 8.56% (calculated: 8.47%)

Phosphorus content: 5.70% (calculated: 5.76%)

Infrared spectroscopic analysis

3400 cm ^-1 (υOH), 1470 cm ^-1 (υp-o), 1230 cm ^-1 , 1080 cm ^-1 and 940 cm ^-1 (υp-o)

The cyclic organic phosphate ester basic polyvalent metal salt is not particularly limited in terms of its particle diameter. For example, an average particle diameter of 0.01 to 50 microns may be used, but in order to obtain uniform dispersion, It is preferable to grind | pulverize into microparticles | fine-particles below micron, especially 3 micron or less, and to use.

The amount of the cyclic organic phosphate ester polybasic metal salt added is 0.01 to 5 parts by weight, preferably 0.03 to 3 parts by weight based on 100 parts by weight of the crystalline synthetic resin.

Moreover, the ratio of the alkali metal salt compound of the said (a) component and the cyclic organophosphoric acid ester ether polyvalent metal salt of the said (b) component is not restrict | limited, Especially the addition amount of the said (a) component is said (b) The effect of this invention is remarkable when it is more than equivalence of component addition amount.

As the crystalline synthetic resin in the present invention, for example, α such as low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, polybutene-1, poly-3-methylbutyl, ethylene / propylene block or random copolymer -Olefin polymers; Thermoplastic straight chain polyesters such as polyethylene terephthalate polybutylene terephthalate and polyhexamethylene terephthalate; And linear polyamides such as polyphenylene sulfide, polycaprolactone and polyhexamethyleneadipoamide.

In particular, the present invention relates to crystalline α-olefin polymers, in particular polypropylene. It is useful when applied to polypropylene resins, such as an ylene / propylene copolymer and a mixture of these propylene polymers with another alpha-olefin polymer.

In addition, the present invention can be applied in spite of the intrinsic viscosity, isotactic pentad fraction, density, molecular weight distribution, melt flow rate, rigidity, and the like of these polypropylene resins, for example 63-37,148, 63-37,152, 63-90,552, 63-210,152, 63-213,547, 63-243,150, 63-37 243,152, 63-260,943, 63-260,944, 63-264,650, JP-A-178,541, 2-49,047, JP The polypropylene resins such as those described in 2-102,242, 2-251,548, 2-279,746, 3-195,751 and the like can also be suitably used.

In the crystalline synthetic resin composition of the present invention, the method of adding each component is not particularly limited, and a method generally used, for example, a method of dry mixing a crystalline synthetic resin powder or a ferret with an additive powder, A master batch containing a high concentration of each component can be prepared, and a method of adding it to the crystalline synthetic resin can be used. Moreover, the crystalline synthetic resin composition of this invention can be used as various molded articles, a fiber, a biaxially stretched film, a sheet | seat, etc. by well-known processing methods, such as extrusion molding, injection molding, vacuum molding, blow molding, and crosslinked foam molding. .

In addition, the crystalline synthetic resin composition of the present invention may be subjected to various post-treatments, for example, to be used for sterilization by radiation such as medical use or food packaging, or to improve surface properties such as paintability. It can also be used for applications in which low-temperature plasma treatment is performed.

The crystalline synthetic resin composition of the present invention may also contain, if necessary, organophosphorus antioxidants such as phenolic antioxidants, organic phosphites or phosphonites, thioether antioxidants, ultraviolet light absorbers or hindered amines. By adding a light stabilizer such as a compound, the oxidation stability and the light stability can be further improved, and in particular, by using phenolic antioxidants and / or organophosphorus antioxidants together, it is possible to prevent the coloring and the mechanical properties of the underground during heat processing. Can be.

As said phenolic antioxidant, 2, 6- di- t- butyl- p- cresol, 2, 6- diphenyl-4- octadecyloxy phenol, stearyl (3, 5- di-t- butyl) are mentioned, for example. 4-hydroxyphenyl) propionate, distearyl (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate, thiodiethylenebis [(3,5-di-t-butyl -4-hydroxyphenyl) propionate], 4,4'-thiobis (6-t-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-t- Butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-t-butylphenol), bis [3,3-bis (4-hydroxy-3- t-butyl phenyl) butyric acid] glycol ester, 4,4'-butylidenebis (6-t-butyl-m-cresol), 2,2'-ethylidene bis (4,6-di-t-butyl Phenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butyl phenyl) butane, bis [2-t-butyl-4-methyl-6- (2-hydroxy-3 -t-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butyl benzyl) isocyanurate, 1,3, 5-tree number (3,5-di-t- Butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxy benzyl) -2,4,6-trimethylbenzene, 1,3 , 5-tris [(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-t-butyl- 4-hydroxyphenyl) pyrropiionate] methane, 2-t-butyl-4-methyl-6- (2-acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane-bis [β- (3-t-butyl-4-hydroxy-5 -Butylphenyl) propionate], triethylene glycol bis [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], and the like.

The amount of the phenolol-based antioxidant added is preferably 0.01 to 5 parts by weight, more preferably 0.01 to 3 parts by weight based on 100 parts by weight of the synthetic resin.

Examples of the organophosphorus antioxidant include trisnonylphenyl phosphite, tris (mono and dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and di (tridecyl) penta. Erythritol diphosphite, distearylpentaerythritol diphosphite, bis (2,4-di-t-butyl phenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butyl phenyl) pentaerythritol diphosphite, Tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidene bis (2-t-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (3-t-butyl-4-hydroxy-5-methylphenyl) butanetriphosphite, 2,2'-methylenebis (4,6-di-t-butyl phenyl) octyl force Pite, 2,2'-methylenebis (4,6-di-t-butylphenyl) octadecylphosphite, 2,2'-medylenebis (4,6-di-t-butylphenyl) fluorophosphite , Tetrakis (2,4-di-butylphenyl ) Biphenylene diphosphite, 9,10-dihydro-9-oxa-10-phosphapfenanthrene-10-oxide, and the like.

The amount of the organophosphorus antioxidant added is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 3 parts by weight based on 100 parts by weight of the crystalline synthetic resin.

Examples of the thioether antioxidants include dialkyl thio dipropionates and pentaerythritol tetra (β-dodecyl) such as dilauryl, dimyrisyl, myristyl stearyl, and distearyl ester of thiodipropionic acid. (Beta) -alkyl mercaptopropionic acid ester which is a polyol, such as mercaptopropionate).

As said ultraviolet absorber, 2, 4- dihydroxy benzophenone, 2-hydroxy-4- methoxy benzophenone, 2-hydroxy-4- octoxy benzophenone, 5, 5'- methylenebis (2-hydroxy 2-hydroxybenzophenones, such as 4-methoxy benzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3.5-di-t-butyl phenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3 -t-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzo triazole, 2,2'-methylenebis (4-t-octyl 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of -6-benzotriazolyl) phenol and 2- (2-hydroxy-3-t-butyl-5-carboxyphenyl) benzotriazole: Phenylsalicylate, resorcinol monobenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t Bezoates such as -butyl-4-hydroxybenzoate; Substituted oxo nilides, such as 2-ethyl-2'-ethoxy oxinilide and 2-ethoxy-4'-dodecyl oxinilide; Cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

As a light stabilizer, such as the said hindered amine compound, it is 2,2,6,6- tetramethyl-4- piperidyl stearate, 1,2,2,6,6,-pentamethyl-4- piperi, for example. Dilstearate, 2,2,6, 6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-pyrididyl) sebacate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane tetracarboxylate, tetrakis (1, 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-t -Butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl polycondensation 뭍, 1,6-bis (2,2,6,6-tetraethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 16-bis (2,2,6,6- Tramedyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis- (2,2,6,6-tetramethyl-4 -Piperidylamino) hexane / 2,4-dichloro-6-t-octylimino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl- N / 2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8 , 12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperi) Dill) amino) -s-triazin-6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-penta) Hindered amine compounds such as methyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane.

In addition, in the crystalline synthetic resin fired product of the present invention, a nonionic, cationic or ohmic antistatic agent, aluminum-pt-butyl benzoate, dibenzylidene sorbitol, and bis (4-methylbenzyl) may be used as necessary. Other nucleating agents such as lithium dendrite) sorbitol, hydrotarcites, alkaline earth metal salts of aliphatic carboxylic acids, pigments, dyes, fillers, blowing agents, flame retardants, lubricants, processing aids and the like can be added.

In the following, the crystalline synthetic resin composition of the present firing will be described in more detail by Examples. However, the present invention is not limited at all by these examples.

Example 1

The blend of <mixture> was then mixed for 5 minutes with a mixer, and then pelletized using a compressor under a temperature of 230 ° C. and a speed of 20 rpm. Using this pellet, it shape | molded at 250 degreeC and die silver at 60 degreeC with the injection molding machine, and produced the test piece of thickness 1mm. About this test piece, the haze value was measured based on the method of ASTMD-1003-61 (original). Moreover, also about the test piece after immersing in hot water of 8 degreeC for 36 hours, haze (haze value) was similarly measured. The results are shown in Table 1 below. In addition, the "comparative compound" of Table 1 is a compound shown below.

<Combination> Weight part

Ethylene / Propylene Random Copolymer 100

(Ethylene content: 3 wt%, MFR 5.0 g / 10 min)

Tetrakis [methylene-3- (3,5-di-t-butylphenylpropionate] methane 0.1

Tris (2,4-di-t-butylphenyl) phosphite 0.1

Sample Compound (see Table 1) 0.1

Lithium Laurate 0.1

Comparative Compound

TABLE 1

Example 2

The blend of <mixture> was then mixed with a mixer for 5 minutes and then pelletized using an extruder under conditions of a temperature of 230 ° C. and a rotation speed of 20 rpm. Using this pellet, it shape | molded at 250 degreeC and die temperature of 60 degreeC with the injection molding machine, and the test piece of thickness 1mm was created. This test piece was measured under the same conditions as in Example 1 (haze value).

Moreover, according to ASTM D-256, the IZOD impact strength (kg * cm / cm <2>, Table 2 only shows in "impact strength") in 20 degreeC was measured. The results are shown in Table 2 below.

<Combination> Weight part

Crystalline Ethylene-Propylene Random Copolymer 100

(Ethylene content: 2.5 wt%, MFR: 7.0 g / 10 min)

2,6-di-t-butyl-4-methylphenol 0.2

Stearyl-β- (3,5-di, t-butyl-4-hydroxyphenyl) propionate 0.1

Hydro Tar Sight (Kyogawa Chemical Co., Ltd.: DHT-4A) 0.05

Cyclic organophosphate ester basic polyvalent metal salt

(Compound No. 1) 0.2

Sample Compound (see Table 2) (see Table 2)

TABLE 2

* 1: The comparative compound was used instead of compound NO.1.

* 2: No compound No.1

Example 3

The mixture of <Formulation> was then mixed with a mixer for 5 minutes, and then pelletized using an extruder at a temperature of 240 ° C. and a rotational speed of 20 rpm. The pellet was formed at an injection molding machine at 250 ° C. and a mold temperature of 60 ° C. The test piece of thickness 1mm was created. Using this test piece, the degree of haze was measured by the same operation as in Example 1.

In the same manner, a test piece having a thickness of 3.5 mm was prepared, and 5 megawatt gamma rays were irradiated with cobalt 60 as a source. Izod impact strength at 23 degreeC was measured according to JlS K-7110 about the test piece heated at 100 degreeC after gamma ray irradiation for 10 days, and the test piece before gamma ray irradiation. The results are shown in Table 3 below.

<Combination> Weight part

Propylene Homopolymer (MFR 6 g / 10 min) 100

Bis (2,6-di-t-butyl-4-methylphenyl) 0.05

Pentaerythritol diphosphite 1,6,11-tris [2, r4-bis0.1

(N-butyl-N- (2.2,6,6-tetramethyl-4-piperidyl) amino)

-S-triazine-6-ylamino] undecane

Sample Compound (see Table 3) 0.2

Lithium Stearate 0.15

TABLE 3

Example 4

0.2 parts by weight of sodium stearate and 0.15 parts by weight of a sample compound (see Table 4) were mixed with respect to 100 parts by weight of polyethylene terephthalate having an intrinsic viscosity of 0.66, and pellets were prepared using a twin screw extruder. This pellet was put into the differential calorimeter, it heated up at 10 degree-C / min, and the crystallization temperature at the time of temperature rising was measured.

Furthermore, after melting at 280 ° C for 10 minutes, the crystallization temperature when the temperature was lowered at 5 ° C / min was measured, and the ratio H / W between the height H of the endothermic peak at the time of temperature reduction and the width W at H / 2 was determined. It was.

The lower the crystallization temperature at elevated temperature, the less the molded article having a higher crystallization temperature when molded into a low-temperature mold, the higher the crystallization temperature at lower temperature, and the larger the H / W, the higher the crystallization rate. The results are shown in Table 4 below.

TABLE 4

From the Natinan results in Tables 1 to 4, the following items can be seen.

That is, when the alkali metal salts of carboxylic acids or the cyclic organic phosphate ester basic polyvalent metal salts are used alone, the mechanical strength, crystallization rate, and the like of the crystalline synthetic resin are somewhat improved, but the effect is practically satisfactory. It is not. In particular, the effect of improving transparency is insufficient. Moreover, when the alkaline-earth metal salt of carboxylic acid or the mole of alkali metal hydroxide and cyclic organic phosphate ester basic polyvalent metal salt are used together, or the polybasic cyclic organic phosphoric acid of the alkali metal salt of carboxylic acid and (b) component of this invention. Even in the case of using an ester metal salt in combination, the improvement effect is insufficient.

On the other hand, the composition of this invention which used the alkali metal salt compound and the cyclic organic phosphate ester basic polyvalent metal salt together not only improves mechanical strength further, but also improves transparency which was conventionally insufficient, and the effect of this invention is extremely It is obvious that it is specific.

Claims (8)

0.01 to 5 parts by weight of one or more selected from the group consisting of (a) an alkali metal salt of carboxylic acid, an alkali metal salt of β-diketonate and an alkali metal salt of β-ketoacetic acid ester And (b) 0.01-5 parts by weight of at least one cyclic organic phosphate ester basic polyvalent metal salt represented by the following general formula (I). (Wherein R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 atomic atoms, R ₂ and R ₃ each represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M represents aluminum, titanium, tin or Zirconium, X represents HO- when M is aluminum, and O = or (HO) ₂ -when M is titanium, tin or zirconium.) The crystalline synthetic resin composition according to claim 1, wherein the component (a) is an alkali metal salt of carboxylic acid. The crystalline synthetic resin composition according to claim 2, wherein the alkali metal salt of carboxylic acid is an aliphatic carboxylic acid alkali metal salt. The crystalline synthetic resin composition according to claim 3, wherein the alkali metal is lithium. The crystalline synthetic resin composition according to claim 1, wherein the component (b) is a compound in which M is aluminum and X is HO- in General Formula (I). The crystalline synthetic resin composition according to claim 1, wherein the crystalline synthetic resin is a polyolefin. The crystalline synthetic resin composition according to claim 6, wherein the polyolefin is polypropylene. The crystalline synthetic resin composition according to claim 6, wherein the polyolefin is an ethylene / propylene copolymer.