TW201619263A - Polyester resin composition containing aminotriazine derivative and carboxylic amide - Google Patents

Abstract

To provide a polyester resin composition containing an aminotriazine derivative and a carboxylic acid amide. A polyester resin composition containing 100 parts by mass of polyester resin, 0.01-10 parts by mass of 2-amino-1,3,5-triazine derivative represented by formula [1], and 0.01-10 parts by mass of aliphatic carboxylic acid amide. (In the formula, R1 and R2 each independently represent -C(=O)R5, -C(=O)OR6, -C(=O)NR7R8, or -SO2R9, and R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1-6 carbon atoms, -C(=O)R5, -C(=O)OR6, -C(=O)NR7R8, or -SO2R9. Herein, R5, R6, and R9 each independently represent an alkyl group having 1-20 carbon atoms or a phenyl group optionally substituted by an alkyl group having 1-6 carbon atoms, and R7 and R8 each independently represent a hydrogen atom, an alkyl group having 1-20 carbon atoms, or a phenyl group optionally substituted by an alkyl group having 1-6 carbon atoms).

Description

Polyester resin composition containing an aminotriazine derivative and a guanamine carboxylic acid

The present invention relates to a polyester resin composition, and more particularly to a polyester resin composition comprising an aminotriazine derivative and a carboxylic acid guanamine.

The polyester resin is excellent in heat resistance, chemical resistance, mechanical properties, electrical properties, and the like, and is excellent in cost and performance. Therefore, it has been widely used as a fiber or a film in the industry. In addition, in recent years, from the viewpoint of natural environmental protection, research on aliphatic polyester which can be biodegraded in the natural environment is being vigorously carried out. In addition, for example, a polylactic acid resin has a high melting point of 160 to 180 ° C and is excellent in transparency, and is expected to be a fibrous material such as a packaging material such as a container or a film, a clothing material, a mat, and an automotive interior material. Forming materials for housings or parts of electrical and electronic products.

However, the polyester resin including a polylactic acid resin is a crystalline resin, but generally the crystallization rate is extremely slow. Therefore, the crystallization of the molded product is particularly carried out by injection molding without stretching. The degree of conversion tends to be low, and the temperature of the glass transitions before and after 60 ° C At the time, it becomes a disadvantage that it is easy to soften. In order to increase the degree of crystallization, attempts have been made to increase the temperature of the mold during injection molding and to lengthen the cooling time in the mold. However, in this method, the molding cycle becomes long, and productivity is a problem. In order to manufacture a polyester resin molded article with high productivity and to be used for a wide range of applications, it is necessary to attempt to increase the crystallization rate and the degree of crystallization and to improve the formability or heat resistance.

In general, as a method of increasing the crystallization rate of the polyester resin, a method of adding a crystal nucleating agent is known. The crystal nucleating agent is a primary nucleus of a crystalline polymer and promotes crystal growth, thereby refining the crystal size and increasing the crystallization rate. For example, as a crystal nucleating agent for a polyester resin, a metal salt of an organic acid such as potassium benzoate or magnesium stearate, an inorganic compound such as talc, vermiculite or calcium sulfate has been conventionally proposed. In addition, as a crystal nucleating agent of a polylactic acid resin, inorganic particles composed of talc or boron nitride having a specific particle diameter or less (Patent Document 1) and a guanamine compound represented by a specific formula (patent) have been disclosed. Document 2, Patent Document 3), a sorbitol-based derivative represented by a specific formula (Patent Document 4), a phosphate metal salt represented by a specific formula (Patent Document 5), and the like. Further, a specific phosphonic acid compound metal salt specifically discloses that zinc phenylphosphonate exhibits excellent properties (Patent Document 6).

[Previous Technical Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. Hei 8-3432

Patent Document 2: Japanese Patent Laid-Open No. Hei 10-87975

Patent Document 3: JP-A-2011-6654

Patent Document 4: Japanese Patent Laid-Open No. Hei 10-158369

Patent Document 5: Japanese Laid-Open Patent Publication No. 2003-192883

Patent Document 6: International Publication No. 2005/097894

As described above, in order to increase the crystallization rate and the degree of crystallization of the polyester resin, various crystal nucleating agents have been proposed, but in recent years, in order to achieve higher moldability or heat resistance of the polyester resin, more efficient crystallization is desired. Development of nuclear agents.

In particular, when a polyester resin composition of a crystal nucleating agent proposed in the prior art is blended and crystallized, the transparency of the polyester resin is impaired, and it is desirable to provide transparency even after crystallization. High resin molded body.

An object of the present invention is to provide a polyester resin composition containing a crystal nucleating agent capable of producing a polyester resin which promotes crystallization of a polyester resin while maintaining high transparency after crystallization, with high productivity. It is a molded product and can be used in a wide range of applications.

In order to solve the above problems, the inventors of the present invention have found through intensive studies that a specific 2-amino-1,3,5-triazine derivative and an aliphatic carboxylic acid amide are used in combination to improve the polyester resin. The same crystallization speed In the meantime, a molded article having excellent transparency after crystallization can be obtained to complete the present invention.

In other words, the first aspect of the present invention relates to a polyester resin composition comprising 100 parts by mass of a polyester resin and a 2-amino-1,3,5-triazine derivative represented by the formula [1]. 0.01 to 10 parts by mass and 0.01 to 10 parts by mass of the aliphatic carboxylic acid amide

(wherein R ¹ and R ² each independently represent -C(=O)R ⁵ , -C(=O)OR ⁶ , -C(=O)NR ⁷ R ⁸ , or -SO ₂ R ⁹ ,R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, -C(=O)R ⁵ , -C(=O)OR ⁶ , -C(=O)NR ⁷ R ⁸ , or -SO ₂ R ^9; thereto, R ^5, R ⁶ and R ⁹ each independently represent lines 1 to 20 carbon atoms of alkyl group, or an alkyl group having a carbon number of 1 to 6 substituted by phenyl, R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms).

The polyester resin composition according to the first aspect, wherein the R ³ and R ⁴ represent a hydrogen atom.

The polyester resin composition according to the first aspect or the second aspect, wherein the R ¹ and the R ² are simultaneously represented by -C(=O)R ⁵ (the R ⁵ groups independently represent the number of carbon atoms) An alkyl group of 1 to 20, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms).

The polyester resin composition of the third aspect, wherein the R ⁵ is an alkyl group having 1 to 8 carbon atoms.

A polyester resin composition according to the fourth aspect, wherein the R ⁵ is an ethyl group or a propyl group.

The polyester resin composition according to any one of the first aspect to the fifth aspect, wherein the aliphatic carboxylic acid decylamine is an aliphatic dicarboxylic acid decylamine.

According to a seventh aspect, the polyester resin composition of the sixth aspect, wherein the aliphatic carboxylic acid decylamine is decyl ethyl bismuth decanoate, decyl ethyl oleate, and ethyl bis-hard At least one selected from the group consisting of decylamine hydrochloride and N,N'-extended ethyl bis(nonyl 12-hydroxystearate).

The polyester resin composition according to any one of the first aspect to the seventh aspect, wherein the polyester resin is a polylactic acid resin.

The ninth aspect relates to a polyester resin molded article comprising the crystallization of the polyester resin composition according to any one of the first aspect to the eighth aspect.

The polyester resin composition of the present invention can promote the crystallization of the polyester resin by using a specific 2-amino-1,3,5-triazine derivative and an aliphatic carboxylic acid decylamine as a crystallization nucleating agent. Further, it is possible to provide a polyester resin composition excellent in heat resistance and moldability.

In particular, the polyester resin composition of the present invention provides a leaps in transparency after crystallization compared to a resin composition in which a conventional crystal nucleating agent is formulated. A resin composition excellent in properties.

Fig. 1 is a view showing the ¹ H NMR spectrum of DPM obtained in Production Example 1.

[Best Practice for Carrying Out the Invention]

Hereinafter, the present invention will be described in detail.

The polyester resin composition of the present invention comprises a polyester resin and a 2-amino-1,3,5-triazine derivative represented by the formula [1] (hereinafter also referred to as a derivative of the formula [1] And a composition of an aliphatic carboxylic acid decylamine.

[2-Amino-1,3,5-triazine derivative]

The 2-amino-1,3,5-triazine derivative used in the polyester resin composition of the present invention has a structure represented by the following formula [1].

The 2-amino-1,3,5-triazine derivative is suitable for use as a crystallization nucleating agent,

In the above formula, R ¹ and R ² each independently represent -C(=O)R ⁵ , -C(=O)OR ⁶ , -C(=O)NR ⁷ R ⁸ , or -SO ₂ R ⁹ ,R. lines ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to ^{6, -C (= O) R 5} , -C (= O) OR 6, -C (= O) NR 7 R 8, Or -SO ₂ R ⁹ .

Further, R ⁵ , R ⁶ and R ⁹ each independently represent an alkyl group having 1 to 20 carbon atoms or a phenyl group which may be substituted by an alkyl group having 1 to 6 carbon atoms, and R ⁷ and R ⁸ are each independently independent. It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms.

The alkyl group having 1 to 20 carbon atoms may be any of a linear chain, a branched chain or a cyclic alkyl group.

Examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, and an n-fluorenyl group. N-fluorenyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-ten Heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, and the like.

Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like.

The cyclic alkyl group is, for example, a group having a cyclopentyl ring or a cyclohexyl ring structure.

Further, examples of the alkyl group having 1 to 6 carbon atoms and the linear, branched or cyclic alkyl group exemplified above include those having 1 to 6 carbon atoms.

Further, as the above phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, for example, a phenyl group, a p-tolyl group, a 4-isopropylphenyl group, a 4-butylphenyl group, a trimethylphenyl group (for example) Mesityl) and so on.

In the 2-amino-1,3,5-triazine derivative represented by the above formula [1], R ³ and R ^{4 are} preferably a hydrogen atom.

Further, in the above formula [1], R ¹ and R ^{2 are} preferably -C(=O)R ⁵ (R ⁵ is synonymous with the above), and among them, R ^{5 is} preferably an alkane having 1 to 8 carbon atoms. Further, R ^{5 is} particularly preferably an ethyl group or a propyl group.

As a particularly preferable one, N,N'-(6-amino-1,3,5-triazine-2,4-diyl)dipropanamide represented by the formula [2] can be mentioned.

The polyester resin composition of the present invention may further contain a 1,3,5-triazine derivative represented by the following formula [3], within the range which does not impair the effects of the present invention.

In the above formula, R ¹ to R ⁴ are synonymous with those defined in the formula [1].

R ¹⁰ represents -C(=O)R ⁵ , -C(=O)OR ⁶ , -C(=O)NR ⁷ R ⁸ or -SO ₂ R ⁹ , and R ¹¹ represents a hydrogen atom and a carbon atom alkyl of 1 to ^{6, -C (= O) R 5} , -C (= O) oR 6, -C (= O) NR 7 R 8, or -SO ₂ R ^9. Further, R ⁵ to R ⁹ are synonymous with those defined in the formula [1].

a 2-amino-1,3,5-triazine derivative represented by the formula [1], The production method is not particularly limited, and for example, melamine, a carboxylic acid or the activated compound (halide halide, acid anhydride, hydrazine azide, active ester, etc.), a halogenated formate, an isocyanate, or a sulfonic acid or the like is activated. The body (sulfonic acid halide, sulfonic acid anhydride, etc.) can be easily obtained by a guanidination reaction, a urethanization reaction, an amine formate reaction or a sulfonylation reaction according to a conventional method. .

Specifically, for example, it can be manufactured by the structure shown in the formula [4] to the formula [7].

In the formula [4] to the formula [7], R ⁵ to R ⁷ and R ⁹ are synonymous with the above, R ^{5 '} and R ⁵ , R ^6' and R ⁶ , R ^7' and R ⁷ , R ^9' and R ^{9 is} represented by the same meaning, and may be the same base or a different base. In addition, X is not particularly limited as long as it can form a desired bond (melamine bond or sulfonamide bond), and examples thereof include a halogen atom such as a chlorine atom or a bromine atom. And, R ^{5 'and} R ^5, R ^6' and R ^6, R ⁷ when ^'and R ^7, R ^9' and R ⁹ is different is of the group, one after the first reaction can then make the other reaction, also Allow both parties to react at the same time.

[aliphatic carboxylic acid guanamine]

The aliphatic carboxylic acid guanamine used in the present invention is not particularly limited as long as it has an aliphatic carboxylic acid called a bond of a general guanamine bond and/or a derivative of an aliphatic amine.

Examples of such aliphatic carboxylic acid amides include decyl laurate, decyl palmitate, decyl stearate, decyl 12-hydroxystearate, decyl ricinoleate, decyl oleate, hawthorn. An aliphatic monocarboxylic acid amide such as decylamine or erucamide; N-stearyl sulphate decylamine, N-stearyl decyl oleate, N-stearyl succinate Amine, N-oleyl palmitate, decyl N-oleyl stearate, decyl N-oleyl oleate, decyl hydroxymethyl stearate, decyl hydroxymethyl behenate N-substituted aliphatic monocarboxylic acid decylamine; methylene double hard Decylamine decylamine, decylamine bis-decanoate, decylamine dilaurate, decylamine ethyl bis-stearate, decylamine ethyl bis-isostearate, ethyl oleic acid Indoleamine, exoethyl bis-indole decylamine, ethyl erucic acid decylamine, N, N'-extended ethyl bis(12-hydroxystearic acid decylamine), tetramethylene bis-stearic acid Indoleamine, hexamethylene bis-stearate decylamine, N,N'-hexamethylene bis(nonyl 12-hydroxystearate), hexamethylenebisoleate amide, m-phthalic acid Aliphatic dicarboxylic acid decylamine such as bis-stearate, N,N'-(m-phthaldimethyl) bis(12-hydroxystearic acid decylamine); N,N'-distearyl醯 base acid amide, N, N'-distearyl decyl decanoate, N, N'-dioleyl decyl amide, N, N'-dioleyl sebacate N-substituted aliphatic carboxylic acid bis-amines such as N,N'-distearone isophthalic acid decylamine, N,N'-distearate terephthalic acid decylamine; N- Butyl-N'-stearylcarbazide, N-propyl-N'-stearylcarbazide, N,N'-bisstearylcarbazide, N-phenyl-N'-stearylsulfonyl Urea, hexamethylenebisstearylcarbazide, benzodiazepine Urea, methyl acyl-phenylene bis stearyl urea, diphenylmethane-bis-lauryl urea, diphenylmethane bis stearyl acyl urea N- substituted ureas, etc. and the like.

Among these, for example, when the polyester resin described later is a polylactic acid resin, the aliphatic dicarboxylic acid decylamine is preferred, the ethyl bis-decanoate decylamine, the ethyl bis-oleic acid decylamine, and the ethyl bis-hard Preferably, decylamine amide, N,N'-extended ethyl bis(nonyl 12-hydroxystearate) is preferred.

These aliphatic carboxylic acid amides may be used alone or in combination of two or more.

[polyester resin]

The polyester resin used in the present invention may, for example, be polyglycolic acid (PGA), polylactic acid (PLA), poly(3-hydroxybutyrate) (PHB), or poly((3-hydroxybutyrate). )-co-(3-hydroxyvalerate)) (PHBV), poly((3-hydroxybutyrate)-co-(3-hydroxyhexanoate)) (PHBH), poly((3-hydroxybutyrate) Polyhydroxy fatty acid esters (PHA) such as -co-(4-hydroxybutyrate)) (P3/4HB); polyethylene naphthalate (PEN), polyethylene succinate Ester, polyethylene succinate/adipate, polyethylene terephthalate (PET), polybutylene adipate/terephthalate, polybutylene naphthalate Ester, polybutylene succinate (PBS), polybutylene succinate/adipate, polybutylene succinate/carbonate, polybutylene terephthalate (PBT) a polycondensate of a diol and a dicarboxylic acid; a polycaprolactone or the like. These polyester resins may be used alone or in combination of two or more.

Among them, polylactic acid resin is preferred.

<polylactic acid resin>

The above polylactic acid resin may comprise a homopolymer or a copolymer of polylactic acid. When the polylactic acid resin is a copolymer, the arrangement pattern of the copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer.

Further, it may be a polymer blended with other resins, which is a homopolymer or a copolymer of polylactic acid. The other resin is, for example, a biodegradable resin other than the polylactic acid resin to be described later, a general-purpose thermoplastic resin, and a general-purpose thermoplastic engineering plastic.

The polylactic acid is not particularly limited, for example, ring-opening polymerization of lactide For example, poly-L-lactic acid (PLLA), poly-D-lactic acid (PDLA), or the like, such as a poly-L-lactic acid (PLLA) or a poly-D-lactic acid (PDLA), may be used. The number average molecular weight of polylactic acid is generally about 10,000 to 500,000. Further, the polylactic acid resin may be crosslinked by a crosslinking agent using heat, light, radiation, or the like.

Examples of the biodegradable resin other than the polylactic acid resin which can be used as the above polymer blend are, for example, polyglycolic acid (PGA), poly(3-hydroxybutyrate) (PHB), poly((3-hydroxybutyrate). Acid ester)-co-(3-hydroxyvalerate) (PHBV), poly((3-hydroxybutyrate)-co-(3-hydroxyhexanoate)) (PHBH), poly((3- Polyhydroxyalkanoates (PHA) of hydroxybutyrate)-co-(4-hydroxybutyrate)) (P3/4HB); polybutylene succinate (PBS), polysuccinic acid Butylene glycol ester/adipate, polybutylene succinate/carbonate, polybutylene adipate/terephthalate, polyethylene succinate, polybutylene a polycondensate of a glycol such as acid glycol ester/adipate and an aliphatic dicarboxylic acid; polycaprolactone; polyvinyl alcohol; modified starch; cellulose acetate; chitin, chitin; Quality and so on.

Further, examples of the general-purpose thermoplastic resin which can be used as the above polymer blend include, for example, polyethylene (PE), polyethylene copolymer, polypropylene (PP), polypropylene copolymer, and polybutene (PB). Polyolefin resin such as ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), poly(4-methyl-1-pentene), etc.; polystyrene (PS), high enthalpy Polystyrene (HIPS), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), etc. Polystyrene resin; acrylic resin such as polymethyl methacrylate (PMMA); polyvinyl chloride resin; polyurethane resin; phenol resin; epoxy resin; amine resin; unsaturated polyester resin Wait.

Examples of general-purpose engineering plastics include, for example, polyamide resin; polyimine resin; polycarbonate resin; polyphenylene ether resin; denatured polyphenylene ether resin; polyethylene terephthalate (PET), polyester resin such as polybutylene terephthalate (PBT); polyacetal resin; polyfluorene resin; polyphenylene sulfide resin.

[Resin composition]

The polyester resin composition of the present invention contains the 2-amino-1,3,5-triazine derivative represented by the formula [1] in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the above-mentioned polyester resin. . When the amount of addition is 0.01 parts by mass or more, a sufficient crystallization rate can be obtained. Moreover, even if it exceeds 10 mass parts, the crystallization rate does not become faster, and it is economically advantageous to use 10 mass parts or less.

The derivative of the above formula [1] is contained in an amount of 0.1 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the polyester resin.

When the 1,3,5-triazine derivative represented by the above formula [3] is contained in the polyester resin composition of the present invention, the ratio is about 0.5 part by mass or less based on 100 parts by mass of the polyester resin. The inclusion is better.

The polyester resin composition of the present invention contains the aforementioned aliphatic carboxylic acid guanamine relative to 100 parts by mass of the above polyester resin. 0.01 to 10 parts by mass. When the amount of addition is 0.01 parts by mass or more, a sufficient crystallization rate can be obtained. Moreover, even if it exceeds 10 mass parts, the crystallization rate does not become faster, and it is economically advantageous to use 10 mass parts or less.

The amount of the above-mentioned polyester resin is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the above-mentioned polyester resin.

In the present invention, the method of blending the derivative of the formula [1] and the aliphatic carboxylic acid decylamine with respect to the polyester resin is not particularly limited and can be carried out by a conventional method.

For example, the polyester resin, the derivative of the formula [1], and the aliphatic carboxylic acid decylamine and various additives described later may be mixed by using a single agitator, and may be kneaded by using a uniaxial or biaxial extruder or the like. The kneading is usually carried out at a temperature of about 150 to 220 °C. Further, a method of adding a masterbatch having a high concentration of each component to the polyester resin can be also produced. Further, a derivative of the formula [1] and an aliphatic carboxylic acid decylamine may be added to the polymerization stage of the polyester resin.

A known inorganic filler can also be used as the polyester resin composition of the present invention. Examples of the inorganic filler include glass fiber, carbon fiber, talc, mica, vermiculite, kaolin, clay, ash, glass beads, glass flakes, potassium titanate, calcium carbonate, magnesium sulfate, and titanium oxide. The shape of the inorganic filler may be any of a fibrous shape, a granular shape, a plate shape, a needle shape, a spherical shape, and a powder. These inorganic fillers can be used within 300 parts by mass based on 100 parts by mass of the polyester resin.

As the polyester resin composition of the present invention, a conventional flame retardant can also be used. Examples of the flame retardant include halogen-based flame retardants such as bromine or chlorine; antimony-based flame retardants such as antimony trioxide and antimony pentoxide; and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, and polyoxonium compounds. Phosphorus-based flame retardant; red phosphide, phosphate ester, ammonium polyphosphate, azo phosphate, etc.; melamine, melam, melem, melamine, melamine cyanurate, melamine phosphate, melamine pyrophosphate, a melamine-based flame retardant such as melamine polyphosphate, polymelamine polyphosphate-melamine-melamine complex salt, alkylphosphonic acid melamine, phenylphosphonic acid melamine, melamine sulfate, methanesulfonic acid melam or the like; polytetrafluoroethylene A fluororesin such as (PTFE). These flame retardants can be used within 200 parts by mass based on 100 parts by mass of the polyester resin.

Further, in addition to the above components, a thermal stabilizer, a light stabilizer, an ultraviolet absorber, an antioxidant, a rinse improver, an antistatic agent, a pigment, a colorant, a release agent, a slip agent, a plasticizer, and a compatibilizing agent may be used in combination. Various coupling agents such as agents, foaming agents, perfumes, antibacterial and antifungal agents, decane, titanium, aluminum, etc., various other fillers, other crystal nucleating agents, etc., usually used in the manufacture of general synthetic resins. Various additives used.

In the present invention, a polyester resin molded body composed of the above-mentioned polyester resin crystallized material is also targeted.

The polyester resin composition of the present invention can be easily produced into various molded articles by a conventional molding method such as general injection molding, blow molding, vacuum molding, compression molding, or extrusion molding.

The polyester resin molding system of the present invention comprises the crystallized polyester resin, which is composed of the 2-amino-1,3,5-triazine derivative represented by the above formula [1] and an aliphatic carboxylic acid decylamine. It is composed of a crystal nucleating agent.

The polyester resin molded article of the present invention can be obtained, for example, by using the polyester resin composition of the present invention and crystallizing the polyester resin contained therein. The method of crystallizing the polyester resin is not particularly limited. For example, in the step of molding the polyester resin composition into a specific shape, it may be heated to a temperature higher than the temperature at which the polyester resin composition can be crystallized. In the above-mentioned step, the polyester resin composition is heated to a melting point or higher and molded, and then rapidly cooled to form a molded body in an amorphous state, and then heated (annealed) or crystallized.

The temperature at which the polyester resin is crystallized is usually appropriately selected from the temperature above the glass transition temperature of the resin to the temperature below the melting point. For example, when a polylactic acid resin is used as the polyester resin, the heating (annealing) temperature is, for example, 60 to 170 °C. Among them, it is preferably 70 to 130 ° C, more preferably 80 to 120 ° C. By setting it as 60 ° C or more, crystallization can be performed for a more practical time. In addition, by setting it to 170 ° C or less, it is possible to have more spherulites having a smaller crystal grain size, that is, a molded article having more excellent transparency.

Since the spherulite diameter of the polyester resin molded article of the present invention is small and uniform, it can be excellent in transparency, heat resistance and mechanical strength.

[Examples]

Hereinafter, the present invention will be described more specifically by way of examples, but the invention is not limited thereto.

Further, the apparatus and conditions used in the analysis of the preparation and physical properties of the samples in the examples are as follows.

(1) ¹ H NMR spectrum

Device: Japan Electronics Co., Ltd. JNM-ECX300

Solvent: DMSO-d ₆ ((CD ₃ ) ₂ SO))

Reference peak: DMSO-d ₆ (2.49ppm)

(2) Measurement of melting point/sublimation point, 5% weight reduction temperature (Td _5% ) measurement

Device: (share) Thermoga EVO II TG8120 manufactured by Rigaku

Measurement conditions: in the air environment

Heating rate: 10 ° C / min (30 ~ 500 ° C)

(3) Melting and mixing

Device A: (share) LAYO PLASTOMILL MICRO KF6V manufactured by Toyo Seiki Co., Ltd.

(4) Hot pressing

Device: Tester sangyo (share) SA-302 desktop type experimental press

(5) Differential Scanning Thermal Measurement (DSC)

Device: (share) Diamond DSC manufactured by PerkinElmer Japan

(6) HAZE measurement

Device: HAZE meter NDH 5000 made by Nippon Denshoku Industries Co., Ltd.

(7) Film thickness measurement (micrometer)

Device: (share) Quick Micro (registered trademark) manufactured by Mitutoyo MDQ-30M

[Production Example 1] Production of N,N'-(6-amino-1,3,5-triazine-2,4-diyl)dipropeneamine (DPM)

Into a reaction flask equipped with a stirrer, 1.26 g (10 mmol) of melamine [manufactured by Nissan Chemical Industries Co., Ltd.] and 50 g of pyridine were charged and stirred. 2.86 g (22 mmol) of propionic anhydride [manufactured by Kanto Chemical Co., Ltd.] was added thereto, and the mixture was heated under reflux at a liquid temperature of 110 ° C for 4 hours. The reaction solution was cooled to room temperature (about 25 ° C), and the precipitate was filtered, washed three times with 50 g of methanol and washed three times with 50 g of acetone. The obtained wet product was dried under reduced pressure at 80 ° C for 8 hours to obtain 1.64 g of a white powder (yield 69%) of the intended DPM. The ¹ H NNR spectrum of DPM is shown in Figure 1.

¹ H NNR (DMSO-d ₆ ): δ 9.92 (s, 2H), 7.14 (s, 2H), 2.62 (q, J = 7.4 Hz, 4H), 1.00 (t, J = 7.4 Hz, 6H) ( Ppm)

Sublimation point: 272.6 ° C, Td _5% : 255.2 ° C

[Examples 1 to 3, Comparative Examples 1 to 4]

For 100 parts by mass of polylactic acid (PLA) resin [Ingeo Biopolymer 4032D manufactured by NatureWorks LLC], the amounts described in Table 1 (the description of "-" in the table means no addition.) Ammonium bis-stearate (EBS) [manufactured by Tokyo Chemical Industry Co., Ltd.] As a crystal nucleating agent, a polylactic acid resin composition was obtained by melt-kneading at 185 ° C and 50 rpm for 5 minutes.

This resin composition was placed (interval) with a polyimide film having a thickness of 130 μm while being sandwiched between two 180 mm × 120 mm × 2 mm thick brass plates, and hot pressed at 200 ° C, 25 kgf / cm ^{2 for} 1 minute. Immediately after hot pressing, the film-form resin composition was taken out from between the brass plates, and the other brass plates (the same size as the above-mentioned brass plates) at room temperature (about 25 ° C) were used. It was cooled and quenched to obtain a polylactic acid resin film-like formed body in an amorphous state containing a crystal nucleating agent.

The amorphous film-like formed body was cut into about 5 mg, and DSC was used to evaluate the crystallization behavior. When the temperature was raised to 90 ° C at 500 ° C /min and held at 90 ° C, the time from the arrival of 90 ° C from the crystallization of polylactic acid (crystallized 焓 ΔHc) reached a peak, This time was set to the half crystallization time (t _1/2 ). When the value of t _1/2 is small, the faster the crystallization rate under the same conditions, the superior effect as a crystal nucleating agent. The results are shown together in Table 1.

Next, the amorphous film-shaped formed body was cut into a rectangular shape of 40 mm × 25 mm. This film-form molded body was annealed on a hot plate at 90 ° C for 30 minutes to obtain a crystallized polylactic acid resin film-like molded body (about 130 μm thick).

The transparency of the obtained crystallized film-like formed body was evaluated. It was evaluated to measure HAZE of three different points of the film-like formed body, and the average value was calculated. In addition, the calculated value (average value) of the film-formed body was normalized by the following formula.

Normalized value = measured value × 130 ÷ film thickness [μm]

The results are shown together in Table 1. The smaller the HAZE, the higher the transparency.

As shown in Table 1, a resin composition (Examples 1 to 3) prepared by mixing DPM of a 2-amino-1,3,5-triazine derivative and EBS of an aliphatic carboxylic acid guanamine was obtained. The semi-crystallization time (t _1/2 ) is short, and the transparency after crystallization is also excellent.

On the other hand, the resin composition (Comparative Example 1) which does not contain any crystal nucleating agent, the half crystallization time (t _1/2 ) is 1 minute or more, the crystallization rate is slow, and crystallization is obtained. The transparency after the conversion is the result of poor. Further, in the resin composition in which the aliphatic carboxylic acid decylamine was not blended (Comparative Examples 2 to 4), the crystallization rate was slow, and the transparency after crystallization with the same crystal nucleating dose was poor. result.

Claims (9)

A polyester resin composition comprising 100 parts by mass of a polyester resin, 0.01 to 10 parts by mass of a 2-amino-1,3,5-triazine derivative represented by the formula [1], and an aliphatic carboxylic acid醯amine 0.01~10 parts by mass, (wherein R ¹ and R ² each independently represent -C(=O)R ⁵ , -C(=O)OR ⁶ , -C(=O)NR ⁷ R ⁸ , or -SO ₂ R ⁹ ,R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, -C(=O)R ⁵ , -C(=O)OR ⁶ , -C(=O)NR ⁷ R ⁸ , or -SO ₂ R ^9; thereto, R ^5, R ⁶ and R ⁹ each independently represent lines 1 to 20 carbon atoms of alkyl group, or an alkyl group having a carbon number of 1 to 6 substituted by phenyl, R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms). The polyester resin composition of claim 1, wherein the R ³ and R ⁴ represent a hydrogen atom. The polyester resin composition of claim 1 or claim 2, wherein the above R ¹ and R ² represent simultaneously -C(=O)R ⁵ (R ⁵ each independently represents an alkyl group having 1 to 20 carbon atoms; Or a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms). The polyester resin composition of claim 3, wherein the aforementioned R ⁵ represents an alkyl group having 1 to 8 carbon atoms. The polyester resin composition according to claim 4, wherein the R ⁵ is an ethyl group or a propyl group. The polyester resin composition according to any one of claims 1 to 5, wherein the aliphatic carboxylic acid decylamine is an aliphatic dicarboxylic acid decylamine. The polyester resin composition of claim 6, wherein the aliphatic carboxylic acid decylamine is decyl bis-decanoate, decyl ethyl oleate, ethyl bis-stearate, and At least one selected from the group consisting of N,N'-extended ethyl bis(nonyl 12-hydroxystearate). The polyester resin composition according to any one of claims 1 to 7, wherein the polyester resin is a polylactic acid resin. A polyester resin molded body comprising the crystallized product of the polyester resin composition of any one of Claims 1 to 8.