WO2017026486A1 - Polyester resin composition containing aminotriazine derivative and fatty acid - Google Patents

Abstract

[Problem] To provide a nucleating agent-containing polyester resin composition that accelerates crystallization of a polyester resin, that enables production of, at high productivity without causing a plate-out, a polyester resin molding capable of maintaining high transparency even after crystallization, and that can be used in a wide range of use applications. [Solution] A polyester resin composition containing 100 parts by mass of a polyester resin, 0.01-10 parts by mass of a 2-amino-1,3,5-triazine derivative represented by formula [1], and 0.01-10 parts by mass of a fatty acid having 14-30 carbon atoms, and a polyester resin molded object obtained through crystallization of the polyester resin composition (in the formula: R¹ and R² each independently represent -C(=O)R⁵, -C(=O)OR⁶, -C(=O)NR⁷R⁸, or -SO₂R⁹; 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; R⁵, R⁶, and R⁹ each independently represent an alkyl group having 1-20 carbon atoms or a phenyl group optionally substituted with 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 with an alkyl group having 1-6 carbon atoms).

Description

Polyester resin composition containing aminotriazine derivative and fatty acid

The present invention relates to a polyester resin composition, and more particularly to a polyester resin composition containing an aminotriazine derivative and a fatty acid.

Polyester resins are widely used industrially as fibers and films because they are excellent in heat resistance, chemical resistance, mechanical properties, electrical properties, etc., and are excellent in cost / performance. In recent years, research on aliphatic polyesters that can be biodegraded in the natural environment has been vigorously conducted from the viewpoint of protecting the natural environment. Among them, polylactic acid resin, for example, has a high melting point of 160 to 180 ° C. and is excellent in transparency. Therefore, packaging materials such as containers and films, textile materials such as clothing, floor mats, automobile interior materials, and electrical / electronic products. It is expected as a molding material for housings and parts.

However, since polyester resins, including polylactic acid resins, are generally crystalline resins, the crystallization speed is generally very slow. However, the glass transition temperature tends to be low, and the glass transition temperature around 60 ° C. tends to be softened. In order to increase the crystallinity, an attempt has been made to increase the mold temperature at the time of injection molding and to increase the cooling time in the mold. Has a problem. In order to produce a polyester resin molded product with high productivity and use it in a wide range of applications, attempts have been made to increase the crystallization speed and the degree of crystallization, and improve the molding processability and heat resistance.

Generally, a method of adding a crystal nucleating agent is known as a method for improving the crystallization speed of a polyester resin. The crystal nucleating agent serves as a primary crystal nucleus of the crystalline polymer, and functions to promote crystal growth and refine the crystal size and increase the crystallization speed. As such a polyester resin crystal nucleating agent, for example, 2-amino-1,3,5-triazine derivatives are known (Patent Document 1).

By the way, an additive called a lubricant is appropriately added to the polyester resin in order to improve moldability such as fluidity and releasability (removability from the molding machine surface such as a mold and a metal roll). However, since the lubricant easily adheres (plates out) to the molding machine surface during molding, various methods for suppressing the plate out of the lubricant have been proposed. Specifically, specific fatty acids have been disclosed as lubricants that are difficult to plate out (Patent Documents 2 and 3).

International publication 2014/148555 pamphlet JP 2003-191266 A Japanese Patent Laid-Open No. 2003-277592

The crystal nucleating agent disclosed in Patent Document 1 promotes crystallization of the polyester resin, and a polyester resin molded product that can maintain high transparency even after crystallization is obtained. However, there is a problem that the crystal nucleating agent is not a little plate-out.
In addition, Patent Document 2 and Patent Document 3 only disclose a lubricant for a specific use of a polyethylene terephthalate-based resin composition having a specific composition for calendar molding, and in injection molding of a polyester resin including polylactic acid. There is no specific mention of crystallization acceleration or plate-out phenomenon.
The present invention promotes the crystallization of a polyester resin and can produce a polyester resin molded product that can maintain high transparency even after crystallization with high productivity without plate-out, and can be used in a wide range of applications. An object is to provide a polyester resin composition containing a nucleating agent.

As a result of intensive studies to solve the above problems, the present inventors have found that the combined use of a specific 2-amino-1,3,5-triazine derivative and a specific fatty acid increases the crystallization speed of the polyester resin. The present inventors have found that it is possible to realize a molded article having excellent transparency after crystallization, and to realize high moldability capable of suppressing the plate-out of the crystal nucleating agent.

That is, as a first aspect, the present invention provides 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 14 to 14 carbon atoms. The present invention relates to a polyester resin composition comprising 0.01 to 10 parts by mass of 30 fatty acids.

Wherein R ¹ and R ² are each independently —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 ) Represents NR ⁷ R ⁸ or —SO ₂ R ⁹ , wherein R ⁵ , R ⁶ and R ⁹ are each independently an alkyl group having 1 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms. Represents a phenyl group which may be substituted with a group, and R ⁷ and R ⁸ are each independently substituted with a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Represents an optionally substituted phenyl group.)
As a second aspect, the present invention relates to the polyester resin composition according to the first aspect, wherein the fatty acid is a fatty acid having 14 to 19 carbon atoms.
As a third aspect, the present invention relates to the polyester resin composition according to the second aspect, wherein the fatty acid is at least one selected from the group consisting of palmitic acid, stearic acid, and 12-hydroxystearic acid.
As a fourth aspect, the R ³ and R ⁴ represents a hydrogen atom, to a polyester resin composition according to any one of the first aspect to the third aspect.
As a fifth aspect, R ¹ and R ² are both —C (═O) R ⁵ (R ⁵ is independently an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Represents a phenyl group which may be substituted with a), and relates to the polyester resin composition according to any one of the first to fourth aspects.
As a sixth aspect, the present invention relates to the polyester resin composition according to the fifth aspect, wherein R ⁵ represents an alkyl group having 1 to 8 carbon atoms.
As a seventh aspect, the present invention relates to the polyester resin composition according to the sixth aspect, in which R ⁵ represents an ethyl group or a propyl group.
As an eighth aspect, the present invention relates to the polyester resin composition according to any one of the first aspect to the seventh aspect, in which the polyester resin is a polylactic acid resin.
As a 9th viewpoint, it is related with the polyester resin molded object formed by crystallizing the polyester resin composition as described in any one of a 1st viewpoint thru | or an 8th viewpoint.

In the polyester resin composition of the present invention, crystallization of the polyester resin was promoted by using a specific 2-amino-1,3,5-triazine derivative as a crystal nucleating agent and further using a fatty acid as a plate-out inhibitor. Thus, it is possible to provide a polyester resin composition that is excellent in heat resistance and particularly excellent in moldability and capable of suppressing the plate-out of the crystal nucleating agent during the molding process.
In particular, the polyester resin composition of the present invention has a resin composition in which the transparency after crystallization is remarkably improved and the plate-out of the crystal nucleating agent is suppressed compared to a resin composition containing a conventional crystal nucleating agent. Things can be provided.

1 is a diagram showing a ¹ H NMR spectrum of DPM obtained in Production Example 1. FIG.

Hereinafter, the present invention will be described in detail.
The polyester resin composition of the present invention comprises a polyester resin, a 2-amino-1,3,5-triazine derivative represented by the formula [1] (hereinafter also referred to as a derivative of the formula [1]), the number of carbon atoms It is a composition containing 14 to 30 fatty acids.

[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].
This 2-amino-1,3,5-triazine derivative is preferably used as a crystal nucleating agent.

In the above formula, R ¹ and R ² are each independently —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 ) Represents NR ⁷ R ⁸ or —SO ₂ R ⁹ .
Also independently each R ^5, R ⁶ and R ⁹ represents an alkyl group, or an alkyl phenyl group which may be substituted with a group having a carbon number of 1 to 6 carbon atoms 1 to 20, R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group optionally substituted with an alkyl group having 1 to 6 carbon atoms.

The alkyl group having 1 to 20 carbon atoms may be a linear, branched, or cyclic alkyl group.
Examples of the linear alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl. Group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group Group, n-eicosyl group and the like.
Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. Examples of the cyclic alkyl group include groups having a cyclopentyl ring and a cyclohexyl ring structure. Can be mentioned.
Examples of the alkyl group having 1 to 6 carbon atoms include those having 1 to 6 carbon atoms among the linear, branched or cyclic alkyl groups mentioned above. .
Examples of the phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms include a phenyl group, a p-tolyl group, a 4-isopropylphenyl group, a 4-butylphenyl group, and a mesityl group. Can be mentioned.

In the 2-amino-1,3,5-triazine derivative represented by the above formula [1], R ³ and R ⁴ are preferably hydrogen atoms.
In the above formula [1], R ¹ and R ² are preferably —C (═O) R ⁵ (R ⁵ is as defined above). Among them, R ⁵ has 1 to 8 carbon atoms. An alkyl group is preferred, and R ⁵ is particularly preferably an ethyl group or a propyl group.

Among these, N, N ′-(6-amino-1,3,5-triazine-2,4-diyl) dipropionamide (DPM) represented by the formula [2] is particularly preferable. .

The polyester resin composition of the present invention may contain a 1,3,5-triazine derivative represented by the following formula [3] as long as the effects of the present invention are not impaired.


In the above formula, R ¹ to R ⁴ have the same meaning as defined in 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, carbon It represents an alkyl group having 1 to 6 atoms, —C (═O) R ⁵ , —C (═O) OR ⁶ , —C (═O) NR ⁷ R ⁸ , or —SO ₂ R ⁹ . R ^{5 to} R ⁹ have the same meaning as defined in formula [1].

The production method of the 2-amino-1,3,5-triazine derivative represented by the formula [1] is not particularly limited. For example, melamines and carboxylic acids or activated products thereof (acid halides, acid anhydrides) Product, acid azide, active ester, etc.), halogenated formic acid ester, isocyanate, or sulfonic acid or its activated form (sulfonic acid halide, sulfonic anhydride, etc.), etc., in accordance with a conventionally known method It can be easily obtained by urethanization reaction, carbamidation reaction or sulfonamidation reaction.
Specifically, for example, it can be produced by the scheme shown in Formula [4] to Formula [7].

In the formulas [4] to [7], R ^{5 to} R ⁷ and R ⁹ represent the same meaning as described above, R ^{5 ′} represents R ⁵ , R ^{6 ′} represents R ⁶ , and R ^{7 ′} represents R ⁷ . , R ^{9 ′} represent the same meaning as R ^9, and may be the same group or different groups. X is not particularly limited as long as it is a group capable of generating a desired bond (amide bond, sulfonamide bond), and examples thereof include a halogen atom such as a chlorine atom and a bromine atom. When R ⁵ and R ^{5 ′} , R ⁶ and R ^{6 ′} , R ⁷ and R ^{7 ′} , and R ⁹ and R ^{9 ′} are different groups, one is reacted first and then the other is reacted. Alternatively, both may be reacted at the same time.

[C14-C30 fatty acid]
The fatty acid used in the present invention is not particularly limited as long as it has 14 to 30 carbon atoms.
Examples of such fatty acids include myristic acid, pentadecylic acid, palmitic acid, 2-hexyldecanoic acid, palmitoleic acid, margaric acid, stearic acid, 2-octyldecanoic acid, 2- (4-methylhexyl) -8-methyldecane. Acid, 2- (4,4-dimethylpentan-2-yl) -5,7,7-trimethyloctanoic acid, 12-hydroxystearic acid, oleic acid, vaccenic acid, linoleic acid, (9,12,15)- Linolenic acid, (6,9,12) -linolenic acid, eleostearic acid, arachidic acid, 2- (6-methylpentan-2-yl) -5,9-dimethyldecanoic acid, arachidonic acid, behenic acid, lignoserine Examples include acid, nervonic acid, serotic acid, montanic acid, and melicic acid.
Among these, fatty acids having 14 to 19 carbon atoms are preferable. In particular, for example, when the polyester resin described later is a polylactic acid resin, palmitic acid, stearic acid, and 12-hydroxystearic acid are more preferable.
These fatty acids may be used alone or in combination of two or more.

[Polyester resin]
Examples of the polyester resin used in the present invention include polyglycolic acid (PGA), polylactic acid (PLA), poly (3-hydroxybutyrate) (PHB), and poly ((3-hydroxybutyrate) -co- ( 3-hydroxyvalerate)) (PHBV), poly ((3-hydroxybutyrate) -co- (3-hydroxyhexanoate)) (PHBH), poly ((3-hydroxybutyrate) -co- (4 -Hydroxybutyrate)) (P3 / 4HB) and other polyhydroxyalkanoic acids (PHA); polyethylene succinate, polyethylene succinate / adipate, polybutylene succinate (PBS), polybutylene succinate / adipate, polybutylene succin Dehydration of diols such as nates / carbonates and aliphatic dicarboxylic acids Polycondensates of diols and aromatic dicarboxylic acids such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polybutylene adipate / terephthalate, polybutylene naphthalate, etc .; polycaprolactone, etc. Can be mentioned. These polyester resins may be used alone or in combination of two or more.
Among these, non-aromatic polyester resins, polyhydroxyalkanoic acids (PHA), polycondensates of diols and aliphatic dicarboxylic acids, and polycaprolactone are preferred, and polyhydroxyalkanoic acids (PHA) are preferred. Is more preferable. Of these, polylactic acid resin is more preferable.

<Polylactic acid resin>
The polylactic acid resin may include a homopolymer or copolymer of polylactic acid. When the polylactic acid resin is a copolymer, the arrangement pattern of the copolymer may be any of random copolymer, alternating copolymer, block copolymer, and graft copolymer.
Further, it may be a blend polymer with another resin mainly composed of polylactic acid homopolymer or copolymer. Examples of the other resin include biodegradable resins other than the polylactic acid resin described later, general-purpose thermoplastic resins, and general-purpose thermoplastic engineering plastics.
The polylactic acid is not particularly limited, and examples thereof include those obtained by ring-opening polymerization of lactide and those obtained by direct polycondensation of D-form, L-form, racemate, etc. of lactic acid. Examples thereof include lactic acid (PLLA), poly (D-lactic acid) (PDLA), and stereocomplexes thereof. The number average molecular weight of polylactic acid is generally about 10,000 to 500,000. A polylactic acid resin obtained by crosslinking with a crosslinking agent using heat, light, radiation, or the like can also be used.

Examples of biodegradable resins other than the polylactic acid resin that can be used as the blend polymer include polyglycolic acid (PGA), poly (3-hydroxybutyrate) (PHB), and poly ((3-hydroxybutyrate)- co- (3-hydroxyvalerate)) (PHBV), poly ((3-hydroxybutyrate) -co- (3-hydroxyhexanoate)) (PHBH), poly ((3-hydroxybutyrate) -co Polyhydroxyalkanoic acids (PHA) such as (4-hydroxybutyrate)) (P3 / 4HB); polybutylene succinate (PBS), polybutylene succinate / adipate, polybutylene succinate / carbonate, polybutylene adipate / Terephthalate, polyethylene succinate, polyethylene succinate / Polycondensates of diols and aliphatic dicarboxylic acids such as adipate; polycaprolactone, polyvinyl alcohol, modified starch; cellulose acetate; chitin, chitosan; lignin and the like.

Examples of general-purpose thermoplastic resins that can be used as the blend polymer include polyethylene (PE), polyethylene copolymer, polypropylene (PP), polypropylene copolymer, polybutylene (PB), ethylene-vinyl acetate copolymer (EVA), Polyolefin resins such as ethylene-ethyl acrylate copolymer (EEA) and poly (4-methyl-1-pentene); polystyrene (PS), high impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS), Polystyrene resins such as acrylonitrile-butadiene-styrene copolymer (ABS); acrylic resins such as polymethyl methacrylate (PMMA); polyvinyl chloride resins; polyurethane resins; phenol resins; epoxy resins; amino resins; Such as butter, and the like.
General-purpose engineering plastics include, for example, polyamide resins; polyimide resins; polycarbonate resins; polyphenylene ether resins; modified polyphenylene ether resins; polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT); Examples thereof include polyphenylene sulfide resin.

[Resin composition]
The polyester resin composition of the present invention comprises 0.01 to 10 parts by mass of the 2-amino-1,3,5-triazine derivative represented by the formula [1] with respect to 100 parts by mass of the polyester resin described above. Include in quantity. By making the addition amount 0.01 parts by mass or more, a sufficient crystallization rate can be obtained. Moreover, even if it exceeds 10 parts by mass, the crystallization rate does not increase further, so that it is economically advantageous to use it at 10 parts by mass or less.
Preferably, the derivative of the formula [1] is contained in an amount of 0.1 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the polyester resin.
When the 1,3,5-triazine derivative represented by the above-mentioned formula [3] is included in the polyester resin composition of the present invention, it is about 0.5 parts by mass or less with respect to 100 parts by mass of the polyester resin. It is preferable to include by a ratio.

The polyester resin composition of the present invention contains the fatty acid in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyester resin described above. By setting the addition amount to 0.01 to 10 parts by mass, a sufficient plate-out suppressing effect can be obtained.
Preferably, the fatty acid is contained in an amount of 0.1 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, with respect to 100 parts by mass of the polyester resin.

In the present invention, the blending method of the derivative of the formula [1] and the fatty acid into the polyester resin is not particularly limited and can be performed by a known method.
For example, a polyester resin, a derivative of formula [1], a fatty acid, and various additives described later may be mixed with various mixers and kneaded using a single screw or twin screw extruder. Kneading is usually performed at a temperature of about 150 to 220 ° C. Moreover, the method of producing | generating the masterbatch which contains each component in high concentration, and adding this to a polyester resin is also possible. Further, the derivative of the formula [1] and a fatty acid can be added at the polymerization stage of the polyester resin.

A well-known inorganic filler can also be used for the polyester resin composition of this invention. Examples of the inorganic filler include glass fiber, carbon fiber, talc, mica, silica, kaolin, clay, wollastonite, glass beads, glass flake, potassium titanate, calcium carbonate, magnesium sulfate, titanium oxide and the like. . The shape of these inorganic fillers may be any of fiber, granule, plate, needle, sphere, and powder. These inorganic fillers can be used within 300 parts by mass with respect to 100 parts by mass of the polyester resin.

A known flame retardant can also be used for the polyester resin composition of the present invention. Examples of the flame retardant include halogen flame retardants such as bromine and chlorine; antimony flame retardants such as antimony trioxide and antimony pentoxide; inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide and silicone compounds. Phosphorus flame retardants such as red phosphorus, phosphate esters, ammonium polyphosphate, phosphazene, etc .; melamine, melam, melem, melon, melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine / melam Melamine flame retardants such as melem double salt, melamine alkylphosphonate, melamine phenylphosphonate, melamine sulfate and melam methanesulfonate; fluororesins such as polytetrafluoroethylene (PTFE). These flame retardants can be used within 200 parts by mass with respect to 100 parts by mass of the polyester resin.

In addition to the above components, heat stabilizers, light stabilizers, UV absorbers, antioxidants, impact modifiers, antistatic agents, pigments, colorants, release agents, lubricants, plasticizers, compatibilizers, foaming Commonly used in the production of general synthetic resins such as agents, fragrances, antibacterial and antifungal agents, various coupling agents such as silane, titanium, and aluminum, other various fillers, and other crystal nucleating agents Various additives can also be used in combination.

[Resin molding]
The present invention is also directed to a polyester resin molded article obtained by crystallizing the above-described polyester resin composition.
The polyester resin composition of the present invention can be easily produced into various molded articles by applying conventional molding methods such as general injection molding, blow molding, vacuum molding, compression molding, extrusion molding, and calendar molding. it can. Among these, injection molding, blow molding, vacuum molding, compression molding, and extrusion molding are preferable, and extrusion molding is more preferable as a method for obtaining a sheet.
The polyester resin molded article of the present invention comprises the crystallized polyester resin, a crystal nucleating agent comprising a 2-amino-1,3,5-triazine derivative represented by the formula [1], and a fatty acid. .

The polyester resin molded body 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. There is no restriction | limiting in particular as a method to crystallize a polyester resin, For example, in the process of shape | molding a polyester resin composition in a specific shape, what is necessary is just to heat the polyester resin composition above the temperature which can crystallize. Further, in the above process, the polyester resin composition can be crystallized by heat-molding at a melting point or higher and then rapidly cooling to form an amorphous molded body, which is heated (annealed).

The temperature at which the polyester resin is crystallized is usually appropriately selected from temperatures not lower than the glass transition temperature and lower than the melting point of the resin. For example, when a polylactic acid resin is used as the polyester resin, the heating (annealing) temperature may be 60 to 170 ° C. Among these, 70 to 130 ° C is preferable, and 80 to 120 ° C is more preferable. By setting the temperature to 60 ° C. or higher, crystallization proceeds in a more practical time. Moreover, by setting it as 170 degrees C or less, more spherulites with a small crystal diameter exist, ie, it becomes a molded object which was more excellent in transparency.

The polyester resin molded article of the present invention has excellent transparency, heat resistance and mechanical strength because the spherulite diameter is small and uniform.

EXAMPLES Hereinafter, although an Example is given and this invention is described more concretely, this invention is not limited by the following description.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.
(1) ¹ H NMR spectrum apparatus: JNM-ECX300 manufactured by JEOL RESONANCE
Solvent: DMSO-d ₆ ((CD ₃ ) ₂ SO))
Reference peak: DMSO-d ₆ (2.49 ppm)
(2) Melting point / sublimation point measurement, 5% weight loss temperature (Td _5% ) measurement Device: Thermo plus EVO2 TG8120 manufactured by Rigaku Corporation
Measurement conditions: Under air atmosphere Temperature rising rate: 10 ° C / min (30-500 ° C)
(3) Melting and kneading equipment: Labo Plast Mill Micro KF6V manufactured by Toyo Seiki Seisakusho Co., Ltd.
(4) Hot press machine: SA-302 desktop test press (5) Differential scanning calorimetry (DSC) manufactured by Tester Sangyo Co., Ltd.
Device: Diamond DSC manufactured by PerkinElmer Japan
(6) HAZE measurement device: Nippon Denshoku Industries Co., Ltd. Haze meter NDH 5000

The meanings of the abbreviations used are as follows.
FSIL: fumed silica [AEROSIL (registered trademark) 200 manufactured by Nippon Aerosil Co., Ltd.]
HSTE: 12-hydroxystearic acid [manufactured by Tokyo Chemical Industry Co., Ltd.]
ISTE: 2- (4,4-Dimethylpentan-2-yl) -5,7,7-trimethyloctanoic acid [Fine oxocol (registered trademark) isostearic acid manufactured by Nissan Chemical Industries, Ltd.]
LAU: Lauric acid [manufactured by Tokyo Chemical Industry Co., Ltd.]
LAUOH: Lauryl alcohol [manufactured by Tokyo Chemical Industry Co., Ltd.]
MYR: Myristic acid [manufactured by Tokyo Chemical Industry Co., Ltd.]
PAM: Palmitic acid [manufactured by Tokyo Chemical Industry Co., Ltd.]
STE: Stearic acid [Lunac (registered trademark) S-98 manufactured by Kao Corporation]

[Production Example 1] Production of N, N '-(6-amino-1,3,5-triazine-2,4-diyl) dipropionamide (DPM) Melamine [Nissan Chemical Co., Ltd.] was placed in a reaction flask equipped with a stirrer. Industrial Co., Ltd.] 1.26 g (10 mmol) and 50 g of pyridine were charged and stirred. To this, 2.86 g (22 mmol) of propionic anhydride [manufactured by Kanto Chemical Co., Inc.] was added and heated to reflux at a liquid temperature of 110 ° C. for 4 hours. After the reaction solution was cooled to room temperature (approximately 23 ° C.), the precipitate was filtered and washed 3 times with 50 g of methanol and 3 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 the intended DPM as a white powder (yield 69%). The ¹ H NNR spectrum of DPM is shown in FIG.
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 = 7.4Hz, 6H) (ppm)
Sublimation point: 272.6 ° C., Td _5% : 255.2 ° C.

[Examples 1 to 5, Comparative Examples 1 to 4]
To 100 parts by mass of polylactic acid (PLA) resin [Ingeo Biopolymer 4032D manufactured by NatureWorks LLC], 0.5 parts by mass of DPM produced according to Production Example 1 as a crystal nucleating agent and 0.5 parts by mass of fatty acids listed in Table 1 were added. The polylactic acid resin composition was obtained by melt-kneading at 185 ° C. and 50 rpm for 5 minutes.
This resin composition was sandwiched between two 180 mm × 120 mm × 2 mm thick brass plates together with a 130 μm thick polyimide film (spacer), and hot pressed at 200 ° C. and 25 kgf / cm ² for 1 minute. Immediately after hot pressing, the resin composition in the form of a film is taken out from between the brass plates, sandwiched between two other brass plates (same size as the above-mentioned brass plate) at about room temperature (about 23 ° C.), and rapidly cooled to obtain crystals. An amorphous (amorphous) state polylactic acid resin film-like molded article containing a nucleating agent was obtained.

The amorphous film-shaped molded body was sandwiched between two 120 mm × 80 mm hard chrome plated metal plates and allowed to stand in an oven at 100 ° C. for 24 hours. After cooling to room temperature (approximately 23 ° C.), the surface of the metal plate to which the film had adhered was visually observed, and plate-out was evaluated according to the following criteria. The results are also shown in Table 1.
[Plate-out evaluation criteria]
A: No deposits were observed on the hard chrome plated metal plate, and there was no plate-out.
C: There is a deposit on the hard chrome plated metal plate, and the DPM is plated out.

Moreover, about 5 mg was cut out from the amorphous film-like molded product, and the crystallization behavior was evaluated using DSC. The evaluation is that when the temperature is raised to 90 ° C. at 500 ° C./min and kept at 90 ° C. until the exotherm derived from crystallization of polylactic acid (crystallization enthalpy ΔHc) reaches a peak. Time was measured as semi-crystallization time (t _1/2 ). The smaller the value of t1 _{/ 2,} the faster the crystallization rate under the same conditions, indicating that the crystal nucleating agent has an excellent effect. The results are also shown in Table 1.

Next, the amorphous film-like molded body was cut into a 40 mm × 25 mm rectangle. This film-shaped molded body was annealed for 30 minutes on a 90 ° C. hot plate to obtain a crystallized polylactic acid resin film-shaped molded body (approximately 130 μm thick).
The obtained crystallized film-like molded body was measured for HAZE, and the transparency was evaluated according to the following criteria. The results are also shown in Table 1.
[Transparency evaluation criteria]
A: 0 ≦ HAZE <10
B: 10 ≦ HAZE <50
C: 50 ≦ HAZE

As shown in Table 1, the resin composition containing DPM which is a 2-amino-1,3,5-triazine derivative and a fatty acid having 14 or more carbon atoms is a plate-out of DPM which is a crystal nucleating agent. To prevent the result obtained. That is, it was confirmed that the resin composition of the present invention does not contaminate the mold surface during molding. Furthermore, in this result, the addition of the fatty acid (Examples 1 to 5) shortened the half crystallization time as compared with Comparative Example 1 described later using a crystal nucleating agent alone, and not only suppressed the plate-out. As a result, the effect of promoting crystallization was also obtained.
On the other hand, a resin composition containing only a crystal nucleating agent (Comparative Example 1), a resin composition containing a fatty acid having 12 carbon atoms (Comparative Example 2), a composition containing a higher alcohol (Comparative Example 3), The resin composition containing the silica particles used as a lubricant (Comparative Example 4) obtained a result of occurrence of DPM plate-out on the metal surface.

Claims (9)

1. 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 0.01 to 10 parts by mass of a fatty acid having 14 to 30 carbon atoms A polyester resin composition comprising:
   

   

   
   
   Wherein R ¹ and R ² are each independently —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 ) Represents NR ⁷ R ⁸ or —SO ₂ R ⁹ , wherein R ⁵ , R ⁶ and R ⁹ are each independently an alkyl group having 1 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms. Represents a phenyl group which may be substituted with a group, and R ⁷ and R ⁸ are each independently substituted with a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. Represents an optionally substituted phenyl group.)
2. The polyester resin composition according to claim 1, wherein the fatty acid is a fatty acid having 14 to 19 carbon atoms.
3. The polyester resin composition according to claim 2, wherein the fatty acid is at least one selected from the group consisting of palmitic acid, stearic acid, and 12-hydroxystearic acid.
4. The polyester resin composition according to any one of claims 1 to 3, wherein R ³ and R ⁴ represent a hydrogen atom.
5. R ¹ and R ² are both —C (═O) R ⁵ (R ⁵ is independently substituted with an alkyl group having 1 to 20 carbon atoms or an alkyl group having 1 to 6 carbon atoms. The polyester resin composition according to claim 1, which represents a good phenyl group.
6. The polyester resin composition according to claim 5, wherein R ⁵ represents an alkyl group having 1 to 8 carbon atoms.
7. The polyester resin composition according to claim 6, wherein R ⁵ represents an ethyl group or a propyl group.
8. The polyester resin composition according to claim 1, wherein the polyester resin is a polylactic acid resin.
9. The polyester resin molding formed by crystallizing the polyester resin composition as described in any one of Claims 1 thru | or 8.

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