JP2008007593A - Polyester resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin composition excellent in crystallization rate. <P>SOLUTION: The polyester resin composition includes a polyester resin (a), and a compound (b) having a barbituric acid structure. Favorably, the composition includes 100 pts.mass of the polyester (a), and 0.01-10 pts.mass of the compound having the barbituric acid structure formulated therewith. Favorably, the composition includes at least one polyester resin (a) selected from the group consisting of polyethylene terephtalate, polytetramethylene terephtalate, polybutylene terephtalate, and polylactic acid. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polyester resin composition having a high crystallization rate and excellent moldability.

  Polyester resins such as polyethylene terephthalate, polymethylene terephthalate, and polylactic acid are excellent in heat resistance, chemical resistance, mechanical properties, electrical properties, etc., and are excellent in cost / performance. Since it is used industrially and has good gas barrier properties, hygiene, and transparency, it is widely used in beverage bottles, cosmetic / pharmaceutical containers, detergent / shampoo containers, and the like.

  However, for injection molding, polyester resin, especially polyethylene terephthalate, is a crystalline resin, but its crystallization speed is very slow, so the range of molding conditions is extremely narrow and it is difficult to improve the processing cycle. The use of molding materials is still limited.

  As a method for improving the crystallization speed of polyethylene terephthalate, it is generally known to add a nucleating agent, and there are minerals, metal salts of organic acids, inorganic salts, metal oxides, etc. Examples of typical compounds include metal salts such as sodium benzoate, aluminum p-tert-butylbenzoate, and aromatic phosphate metal salts, and compounds such as dibenzylidene sorbitol. A method of blending resin oligomers is also known for the purpose of improving fluidity at the processing temperature of the resin.

For example, Patent Document 1 proposes a method of adding a metal salt of an abietic acid compound for the purpose of accelerating the crystallization speed of polyester. Patent Document 2 discloses a method of adding 4-aminobenzenesulfonamide to an olefin resin. Furthermore, Patent Document 3 proposes a method of adding a phosphate ester metal salt and an aliphatic carboxylic acid metal salt to a crystalline polymer.
Japanese Patent Laid-Open No. 08-059968 US Pat. No. 3,756,997 JP 2005-162867 A

  However, the effect of improving the crystallization rate of the polyester resin with conventionally known additives has not been satisfactory yet. Further, in the method of adding an oligomer of a resin such as ethylene glycol, the mechanical strength of the obtained molded product may be lowered although it contributes to the crystallization rate of the resin to some extent. If the molding cycle of the polyester resin can be improved by improving the crystallization speed, the absolute amount of molded products that can be manufactured with existing equipment can be increased, so the development of higher performance nucleating agents is desired. .

  Accordingly, an object of the present invention is to provide a polyester resin composition having an excellent crystallization speed by solving the above-described problems in the prior art.

  As a result of intensive studies, the present inventors have found that the above object can be achieved by adopting the following configuration, and have completed the present invention.

  That is, the polyester resin composition of the present invention is characterized by containing (b) a compound having a barbituric acid structure with respect to (a) the polyester resin.

（式（１）中、Ｒ¹、Ｒ²およびＲ³はそれぞれ独立して、水素原子、炭素原子数１〜１０の分岐や置換基を有してもよいアルキル基、炭素原子数１〜１０の分岐や置換基を有してもよいアルコキシ基、炭素原子数３〜３０の置換基を有してもよい環状基若しくは−ＮＨ−Ｒ⁴（Ｒ⁴はＲ¹と同じもの、または炭素原子数２〜２０のカルボン酸誘導体を表す）、または、これらの基の組合せを表し、Ｌは酸素原子または硫黄原子を表す）

（式（２）中、Ｒ¹、Ｒ²、Ｒ³およびＬは、上記一般式（１）中と同じものを表し、Ｒ⁵およびＲ⁶はそれぞれ独立して、水素原子、炭素原子数１〜１０の分岐や置換基を有してもよいアルキル基、炭素原子数１〜１０の分岐や置換基を有してもよいアルコキシ基、炭素原子数３〜３０の置換基を有してもよい環状基若しくは−ＮＨ−Ｒ⁴（Ｒ⁴はＲ¹と同じもの、または炭素原子数２〜２０のカルボン酸誘導体を表す）、または、これらの基の組合せを表す） In the present invention, as the compound (b) having a barbituric acid structure, a compound having a group represented by the following general formula (1) or (2) can be preferably used.

(In the formula (1), independently R ^1, R ² and R ³ are each a hydrogen atom, an optionally branched alkyl group having or substituent having 1 to 10 carbon atoms, 1 to 10 carbon atoms An alkoxy group which may have a branch or a substituent, a cyclic group which may have a substituent having 3 to 30 carbon atoms, or —NH—R ⁴ (R ⁴ is the same as R ¹ , or a carbon atom Represents a carboxylic acid derivative of 2 to 20), or represents a combination of these groups, and L represents an oxygen atom or a sulfur atom)

(In the formula (2), R ¹ , R ² , R ³ and L represent the same as those in the general formula (1), and R ⁵ and R ⁶ are each independently a hydrogen atom, carbon number 1 An alkyl group which may have 10 to 10 branches or substituents, an alkoxy group which may have 1 to 10 carbon atoms branches or substituents, and a substituent which has 3 to 30 carbon atoms A good cyclic group or —NH—R ⁴ (R ⁴ represents the same as R ¹ or a carboxylic acid derivative having 2 to 20 carbon atoms) or a combination of these groups)

（式（３）中、Ｒ¹、Ｒ²およびＲ³はそれぞれ独立して、水素原子、炭素原子数１〜１０の分岐や置換基を有してもよいアルキル基、炭素原子数１〜１０の分岐や置換基を有してもよいアルコキシ基、炭素原子数３〜３０の置換基を有してもよい環状基若しくは−ＮＨ−Ｒ⁴（Ｒ⁴はＲ¹と同じもの、または炭素原子数２〜２０のカルボン酸誘導体を表す）、または、これらの基の組合せを表し、Ｌは酸素原子または硫黄原子を表し、Ｍは水素原子または金属原子を表し、Ｍが水素原子または価数１の金属原子である場合には、ｐは１、ｑは０を表し、Ｍが価数２の金属原子である場合には、ｑは０または１の整数、ｐは２−ｑを表し、Ｍが価数３の金属原子である場合には、ｑは０〜２の整数、ｐは３−ｑを表し、Ｍが価数４の金属原子である場合には、ｑは０〜３の整数、ｐは４−ｑを表す）

（式（４）中、Ｒ¹、Ｒ²、Ｒ³、Ｌ、Ｍ、ｐおよびｑは上記一般式（３）と同じものを表し、Ｒ⁵およびＲ⁶はそれぞれ独立して、水素原子、炭素原子数１〜１０の分岐や置換基を有してもよいアルキル基、炭素原子数１〜１０の分岐や置換基を有してもよいアルコキシ基、炭素原子数３〜３０の置換基を有してもよい環状基若しくは−ＮＨ−Ｒ⁴（Ｒ⁴はＲ¹と同じもの、または炭素原子数２〜２０のカルボン酸誘導体を表す）、または、これらの基の組合せを表す）

（式（５）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁵およびＬは、上記一般式（４）と同じものを表す） In the present invention, a polyester resin composition containing at least one compound represented by the following general formula (3), (4) or (5) as the compound having the (b) barbituric acid structure, It can be particularly preferably used.

(In the formula (3), and each of R ^1, R ² and R ³ independently represents a hydrogen atom, an optionally branched alkyl group having or substituent having 1 to 10 carbon atoms, 1 to 10 carbon atoms An alkoxy group which may have a branch or a substituent, a cyclic group which may have a substituent having 3 to 30 carbon atoms, or —NH—R ⁴ (R ⁴ is the same as R ¹ , or a carbon atom Or a combination of these groups, L represents an oxygen atom or a sulfur atom, M represents a hydrogen atom or a metal atom, and M represents a hydrogen atom or a valence of 1 P is 1, q is 0, and when M is a valence 2 metal atom, q is 0 or an integer of 1, p is 2-q, M Is a valence 3 metal atom, q is an integer from 0 to 2, p is 3-q, M is a valence 4 metal atom, That in the case, q is an integer of 0 to 3, p is 4-q)

(In the formula ^{(4), R 1, R} 2, R 3, L, M, p and q are the same as those in the above general formula (3), R ⁵ and R ⁶ are each independently a hydrogen atom, An alkyl group that may have a branch or substituent having 1 to 10 carbon atoms, an alkoxy group that may have a branch or substituent having 1 to 10 carbon atoms, or a substituent that has 3 to 30 carbon atoms. A cyclic group which may have or —NH—R ⁴ (R ⁴ represents the same as R ¹ or a carboxylic acid derivative having 2 to 20 carbon atoms) or a combination of these groups)

(In the formula (5), R ¹ , R ² , R ³ , R ⁵ and L represent the same as those in the general formula (4)).

（式（６）中、Ｒ¹、Ｒ²およびＲ³はそれぞれ独立して、水素原子、炭素原子数１〜１０の分岐や置換基を有してもよいアルキル基、炭素原子数１〜１０の分岐や置換基を有してもよいアルコキシ基、炭素原子数３〜３０の置換基を有してもよい環状基若しくは−ＮＨ−Ｒ⁴（Ｒ⁴はＲ¹と同じもの、または炭素原子数２〜２０のカルボン酸誘導体を表す）、または、これらの基の組合せを表し、Ｌは酸素原子または硫黄原子を表し、Ｍは水素原子または金属原子を表し、ｎは１〜４の整数を表す）

（式（７）中、Ｒ¹、Ｒ²、Ｒ³、Ｌ、Ｍおよびｎは上記一般式（６）と同じものを表し、Ｒ⁵およびＲ⁶はそれぞれ独立して、水素原子、炭素原子数１〜１０の分岐や置換基を有してもよいアルキル基、炭素原子数１〜１０の分岐や置換基を有してもよいアルコキシ基、炭素原子数３〜３０の置換基を有してもよい環状基若しくは−ＮＨ−Ｒ⁴（Ｒ⁴はＲ¹と同じもの、または炭素原子数２〜２０のカルボン酸誘導体を表す）、または、これらの基の組合せを表す）

（式（５）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁵およびＬは、上記一般式（７）と同じものを表す） Furthermore, a polyester resin composition containing at least one compound represented by the following general formula (6), (7) or (5) is also suitable as the compound having the barbituric acid structure.

(In the formula (6), and each of R ^1, R ² and R ³ independently represents a hydrogen atom, an optionally branched alkyl group having or substituent having 1 to 10 carbon atoms, 1 to 10 carbon atoms An alkoxy group which may have a branch or a substituent, a cyclic group which may have a substituent having 3 to 30 carbon atoms, or —NH—R ⁴ (R ⁴ is the same as R ¹ , or a carbon atom Or a combination of these groups, L represents an oxygen atom or a sulfur atom, M represents a hydrogen atom or a metal atom, and n represents an integer of 1 to 4. To express)

(In the formula ^{(7), R 1, R} 2, R 3, L, M and n represent the same as above the general formula (6), R ⁵ and R ⁶ are each independently a hydrogen atom, a carbon atom An alkyl group that may have a branch or substituent of 1 to 10, an alkoxy group that may have a branch or substituent of 1 to 10 carbon atoms, or a substituent of 3 to 30 carbon atoms A cyclic group or —NH—R ⁴ (R ⁴ represents the same as R ¹ or a carboxylic acid derivative having 2 to 20 carbon atoms) or a combination of these groups)

(In the formula (5), R ¹ , R ² , R ³ , R ⁵ and L are the same as those in the general formula (7)).

  More preferably in the present invention, in the general formula (3) or (4), (b) barbiturin wherein M represents an alkali metal atom, particularly a sodium atom, p is 1 and q is 0. A compound having an acid structure can be used.

  In the present invention, as the (a) polyester resin, at least one selected from the group consisting of polyethylene terephthalate, polytetramethylene terephthalate, polybutylene terephthalate and polylactic acid can be suitably used.

  According to the present invention, a polyester resin composition having a high crystallization speed and excellent moldability can be realized by blending a barbituric acid compound as a crystal nucleating agent with respect to a polyester resin.

The polyester resin composition of the present invention will be described in detail below.
As the polyester resin used in the polyester resin composition of the present invention, a normal thermoplastic polyester resin is used and there is no particular limitation. For example, an aromatic polyester such as polyalkylene terephthalate such as polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, polycyclohexane dimethylene terephthalate, or polyalkylene naphthalate such as polyethylene naphthalate or polybutylene naphthalate; Other acid components and / or glycol components (for example, acid components such as isophthalic acid, adipic acid, sebacic acid, glutaric acid, diphenylmethanedicarboxylic acid, dimer acid, hexamethylene glycol, bisphenol A, neopentyl glycol alkylene oxide adduct Polyether ester resins copolymerized with glycol components such as polyhydroxybutyrate, polycaprolactone, polybuty Degradable aliphatic polyesters such as polysuccinate, polyethylene succinate, polylactic acid resin, polymalic acid, polyglycolic acid, polydioxanone, poly (2-oxetanone); aromatic polyester / polyether block copolymer, aromatic polyester / polylactone Broadly defined polyester resins such as block copolymers and polyarylate are also used. Among these, polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate and polylactic acid are preferably used.

  The thermoplastic polyester resin may be used alone or as a blend of a plurality of resins (for example, a blend of polyethylene terephthalate and polybutylene terephthalate), or a copolymer thereof (for example, a copolymer of polybutylene terephthalate and polytetramethylene glycol). Polymer, etc.). In particular, those having a melting point of 200 ° C. to 300 ° C. are preferably used because they exhibit heat resistance.

In the general formula, examples of the alkyl group having 1 to 10 carbon atoms which may have a branch represented by R ^{1 to} R ⁶ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second Butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, decyl and the like, and any —CH ₂ — in such an alkyl group May be substituted with —O—, —CO—, —COO— or —SiH ₂ —, wherein some or all of the hydrogen atoms are substituted with halogen atoms such as fluorine, chlorine, bromine, iodine, or cyano groups. May be.

In the above general formula, examples of the alkoxy group having 1 to 10 carbon atoms which may have a branch represented by R ^{1 to} R ⁶ include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, 2-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy , 2-ethylhexyloxy, nonyloxy, decyloxy and the like, and any —CH ₂ — in the alkoxy group may be substituted with —O—, —CO—, —COO— or —SiH ₂ —. , Some or all of the hydrogen atoms are fluorine, salt Bromine, it may be substituted by a halogen atom or a cyano group iodine.

In the general formula, the cyclic group having 3 to 30 carbon atoms which may have a substituent represented by R ^{1 to} R ⁶ may be a monocyclic ring, a polycyclic ring, a condensed ring, or an aggregate ring. Well, it can be used without distinction between an aromatic cyclic group and a saturated aliphatic cyclic group, and the ring carbon atom may be substituted with an oxygen atom, nitrogen atom, sulfur atom, etc., and a part of the ring hydrogen atom Or all may be substituted by the C1-C5 alkyl group and the C1-C5 alkoxy group. Examples of the cyclic group having 3 to 30 carbon atoms include pyrrole, furan, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine, morpholine, phenyl, Naphthyl, anthracene, biphenyl, triphenyl, 2-methylphenyl (o-tolyl, cresyl), 3-methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 4-chlorophenyl, 4-hydroxyphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethyl) (Hexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl (xylyl), 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5 -Dimethylphenyl, 2,4-ditertiarybutylphenyl, 2,5-ditertiarybutylphenyl, 2,6-ditertiarybutylphenyl, 2,4-ditertiarypentylphenyl, 2,5-ditertiary Triamylphenyl, 2,5-ditertiary octylphenyl, benzene, 2,4-dicumylphenyl, cyclohexylphenyl, 2,4,5-trimethylphenyl (mesityl), 4-aminophenyl, 5-dimethylaminonaphthyl, 6-ethoxy-benzothiazolyl, 2,6-dimethoxy-4-pyrimidyl, 5-methyl-1,3,4-thiadiazol-2-yl , 5-methyl-3-isoxazole-yl, and the like.

In the general formula, the carboxylic acid derivative having 2 to 20 carbon atoms represented by R ⁴ may be substituted with an amino acid or a hydroxy group, and the alkyl group, the alkoxy group, or the cyclic group is combined. Examples of the carboxylic acid derivatives having 2 to 20 carbon atoms include, for example, acetate, acrylate, malonate, succinate, maleate, fumarate, benzoate, 2-naphthoate, phthalate, isoterephthalate, terephthalate. , Nicotinate, isonicotinate, 2-furoate, formate, propionate, propiolate, butyrate, isobutyrate, methacrylate, palmitate, stearate, oleate, oxalate, glutarate, adipate, cinnamate, glycolater , Lactate, glycerate, tartrate, citrate, glyoxylate, Birubato, acetoacetate, Benjirato, anthranilate, ethylenediamine tetraacetate, and the like.

  In the above general formula, examples of the metal atom represented by M include alkali metals, alkaline earth metals, transition metals, base metals, noble metals, heavy metals, light metals, metalloids, rare metals, and the like. , Lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, barium, radium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium , Palladium, silver, aluminum, zinc, gold, platinum, iridium, osmium, mercury, cadmium, arsenic, tungsten, tin, bismuth, boron, silicon, germanium, tellurium, boronium, gallium, germanium, rubidium, indium , Antimony, cesium, hafnium, tantalum, rhenium, etc., lithium, sodium, potassium, magnesium, calcium, strontium, barium, titanium, manganese, iron, aluminum, zinc, silicon, zirconium, yttrium, barium, hafnium Preferably used.

  In the above general formula, examples of the alkali metal atom represented by M include lithium, sodium, and potassium. In particular, sodium is preferably used because the effect of the present invention is remarkable.

  Preferable specific examples of the compound having a group represented by the general formula (1) or (2) and the compounds represented by the general formulas (3) to (7) are as follows. 1-No. However, the present invention is not limited to these compounds.

Compound No. 1

Compound No. 2

Compound No. 3

Compound No. 4

Compound No. 5

Compound No. 6

Compound No. 7

Compound No. 8

Compound No. 9

Compound No. 10

Compound No. 11

Compound No. 12

Compound No. 13

Compound No. 14

  The compound having a barbituric acid structure according to the present invention is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and most preferably 0.1 to 3 parts, per 100 parts by mass of the polyester resin. A part by mass is blended. When the blending amount is less than 0.01 parts by mass, the effect of addition is insufficient, and when it is more than 10 parts by mass, a phenomenon such as the above-described compound jetting on the surface of the polyester resin composition occurs.

  Moreover, as long as the effect of this invention is not impaired, you may add the other additive normally used to a polyester resin composition as needed.

  Examples of the other additive include, for example, an antioxidant made of phenol, phosphorus, sulfur, etc .; a light stabilizer made of HALS, UV absorber, etc .; hydrocarbon, fatty acid, aliphatic alcohol, fat Lubricants such as aliphatic ester compounds, aliphatic amide compounds, aliphatic carboxylic acid metal salts or other metal soaps; heavy metal deactivators; antifogging agents; cationic surfactants, anionic surfactants, nonionic surfactants Antistatic agent composed of surfactant, amphoteric surfactant, etc .; halogen compound; phosphate ester compound; phosphate amide compound; melamine compound; fluorine resin or metal oxide; flame retardant; glass fiber, calcium carbonate And the like; pigments; silicic acid-based inorganic additives; crystal nucleating agents and the like. In particular, antioxidants composed of phenols and phosphorus are preferably used because they have an effect of preventing coloration of the polyester resin composition.

  Examples of phenolic antioxidants include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxy). Phenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5- Ditertiary butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tertiarybutyl-m-cresol), 2-octylthio-4,6-di (3,5-ditertiarybutyl- 4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3-bis 4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-ditert-butylphenol), 4,4′-butylidenebis (6-tert-butyl-3- Methylphenol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2 Tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4 -Tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris ( , 5-Ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] Isocyanurate, tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3) -Tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2, 4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propi Onate] and the like.

  Examples of phosphorus antioxidants include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (2,5-ditert-butylphenyl) phosphite, and tris (nonylphenyl). Phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2′-methylenebis (4,6-ditert-butylphenyl) octyl phosphite, Diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyldiisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, Dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyl diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphos Phyto, bis (2,5-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumyl) Phenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidenediphenyl phosphite, bis [2,2'-methylenebis (4,6-dia) Milphenyl)] ・ I Propyridene diphenyl phosphite, tetratridecyl-4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5-tert Tributyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7,9-tetrakis tert-butyldibenzo [ d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2 -Butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite and the like.

  Examples of sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). (beta) -alkyl mercaptopropionic acid ester is mentioned.

  Examples of the HALS include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6- Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1 -Octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-piperidyl methacrylate , Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2, , 6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) bis (tridecyl) -1, 2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 3,9-bis [1,1- Dimethyl-2- (tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy) ethyl] -2,4,8,10-tetraoxaspiro [5.5] un Can, 3,9-bis [1,1-dimethyl-2- (tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy) ethyl] -2,4,8 , 10-tetraoxaspiro [5.5] undecane, 1,6-bis (2,2,6,6-tetramethyl-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-tert-octylamino-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-tetraaza Dodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6 Yl] -1,5,8,12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) ) Amino) -s-triazin-6-ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) ) Amino) -s-triazin-6-ylamino] undecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-pi Rijiruamino) hexane / dibromoethane polycondensate, and the like.

  Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5 -Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5- Dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tertiary o Acetyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2- Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzo Riazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) ) Phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyl) Oxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl ] 2- (2-hydroxyphenyl) such as benzotriazole Benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl -1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy- 4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl)- , 6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3,5- 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3,5-diter Tributyl-4-hydroxybenzoate, octyl (3,5-ditert-butyl-4-hydroxy) benzoate, dodecyl (3,5-ditert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-ditert Tributyl-4-hydroxy) benzoate, hexadecyl (3,5-ditert-butyl-4-hydroxy) benzoate, octadecyl (3,5-ditert-butyl) Benzoates such as ru-4-hydroxy) benzoate and behenyl (3,5-ditert-butyl-4-hydroxy) benzoate; 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyloxy Substituted oxanilides such as zanilides; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts Alternatively, metal chelates, particularly nickel or chromium salts or chelates may be mentioned.

  Examples of the aliphatic amide compound used as a lubricant include monofatty acid amides such as lauric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, and 12-hydroxystearic acid amide; N, N ′ -Ethylene bis lauric acid amide, N, N'-methylene bis stearic acid amide, N, N'-ethylene bis stearic acid amide, N, N'-ethylene bis oleic acid amide, N, N'-ethylene bis behenic acid amide N, N′-ethylenebis-12-hydroxystearic acid amide, N, N′-butylene bisstearic acid amide, N, N′-hexamethylene bisstearic acid amide, N, N′-hexamethylene bisoleic acid amide N, N′-bis-fats such as N, N′-xylylene bis-stearic acid amide Acid amides; stearic acid monomethylolamide, palm oil fatty acid monoethanolamide, alkylolamides such as stearic acid diethanolamide; N-oleyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl stearic acid amide, N-substituted fatty acid amides such as N-stearyl oleic acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide; N, N′-dioleyl adipic acid amide, N, N′-distearyl adipic acid amide N, N′-N, N′-dioleyl sebacic acid amide, N, N′-distearyl sebacic acid amide, N, N′-distearyl terephthalic acid amide, N, N′-distearyl isophthalic acid amide, etc. -Substituted dicarboxylic acid amides. You may use these by 1 type or a 2 or more types of mixture.

Examples of the flame retardant include phosphorus such as triphenyl phosphate, phenol / resorcinol / phosphorus oxychloride condensate, phenol / bisphenol A / phosphorus oxychloride condensate, 2,6-xylenol / resorcinol / phosphorus oxychloride condensate, etc. Acid esters; Phosphoric amides such as aniline / phosphorus oxychloride condensate, phenol / xylylenediamine / phosphorus oxychloride condensate; phosphazenes; halogen flame retardants such as decabromodiphenyl ether and tetrabromobisphenol A; melamine phosphate, phosphorus Phosphate of nitrogen-containing organic compounds such as acid piperazine, melamine pyrophosphate, piperazine pyrophosphate, melamine polyphosphate, piperazine polyphosphate; red phosphorus and red phosphorus encapsulated in surface treatment or microencapsulation; antimony oxide, zinc borate, etc. Flame retardant aids Tetrafluoroethylene, anti-drip agents such as silicone resin.

  Examples of the silicate inorganic additive include hydrotalcite, fumed silica, fine particle silica, silica, diatomaceous earth, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, Examples include meteorite, attapulgite, talc, mica, minnesite, pyrophyllite, and silica.

  Examples of the crystallization agent include dibenzylidene sorbitol, bis (p-methylbenzylidene) sorbitol, bis (p-ethylbenzylidene) sorbitol, disodium bicyclo [2.2.1] heptane-2,3-dicarboxylate. Etc.

  In the polyester resin composition of the present invention, a compound having a barbituric acid structure, specifically the compounds according to the general formulas (1) to (7), and other additives as desired, with respect to the polyester resin. The method of blending is not particularly limited, and can be performed by a conventionally known method. For example, the polyester resin powder or pellets and a compound may be mixed by dry blending, or a part of the compound or the like may be preblended and then dry blended with the remaining components. After dry blending, for example, mixing may be performed using a mill roll, a Banbury mixer, a super mixer, or the like, and kneading may be performed using a single screw or twin screw extruder. This kneading is usually performed at a temperature of about 200 to 350 ° C. Moreover, the method of adding a compound etc. in the polymerization stage of a polyester resin, the masterbatch which contains a compound etc. in high concentration, the method of adding this masterbatch to a polyester resin, etc. can also be used.

  The polyester resin composition of the present invention is mainly used as a molding material for various molded products in the same manner as general plastics.

  When molding the polyester resin composition of the present invention, it is possible to perform extrusion molding, injection molding, blow molding, vacuum molding, compression molding and the like similar to general plastics, such as sheets, bars, bottles, containers, etc. These various molded products can be easily obtained.

  Moreover, the polyester resin composition of this invention is good also as a fiber reinforced plastic by mix | blending glass fiber, carbon fiber, etc.

  Hereinafter, the present invention will be described more specifically with reference to production examples and examples. However, the present invention is not limited to the following examples. In addition, a manufacture example is a manufacturing method of the resin composition which concerns on this invention, and an Example represents evaluation of the obtained resin composition.

(Production example)
1 part by mass of each of the compounds described in Table 1 below was mixed with 100 parts by mass of a polyethylene terephthalate resin (manufactured by Polyplastics Co., Ltd .; TR8550). It dried under reduced pressure at 140 degreeC for the time, and knead | mixed with the cylinder temperature of 270 degreeC and the screw speed of 150 rpm using the single screw extruder (Toyo Seiki Co., Ltd. product; Labo Plast Mill mu), and obtained the pellet. The obtained pellets were dried at 140 ° C. for 3 hours, and then evaluated as follows.

(Example)
(Crystallization temperature)
The obtained pellet was heated to 300 ° C. at a rate of 50 ° C./min in a nitrogen scanning atmosphere (20 ml / l) with a differential scanning calorimeter (Diamond; manufactured by Perkin Elmer) for 10 minutes. After the holding, it was cooled to 100 ° C. at −10 ° C./min to determine the crystallization temperature. The results are also shown in Table 1 below.

＊１）コントロール：結晶核剤未配合
＊２）比較化合物１：４−アミノベンゼンスルホンアミド
＊３）比較化合物２：ヒドロキシ（ジ第３ブチル安息香酸）アルミニウム
＊４）比較化合物３：ベンゼンスルホンアミド
＊５）比較化合物４：ミラード３９８８；ミリケン社製 結晶核剤
＊６）比較化合物５：タルク（Ｐ−６；日本タルク（株）製）
＊７）比較化合物６：メチレンビス（２，４−ジ第三ブチル−フェニル）ホスフェートナトリウム塩
＊８）比較化合物７：酸化亜鉛（１種；三井金属工業（株）製）
＊９）比較化合物８：安息香酸ナトリウム塩
＊１０）比較化合物９：リコモントＮａＶ１０１；クラリアント社製 結晶核剤

* 1) Control: Crystal nucleating agent not blended * 2) Comparative compound 1: 4-aminobenzenesulfonamide * 3) Comparative compound 2: hydroxy (di-tert-butylbenzoic acid) aluminum * 4) Comparative compound 3: benzenesulfonamide * 5) Comparative compound 4: Millard 3988; crystal nucleating agent manufactured by Milliken * 6) Comparative compound 5: talc (P-6; manufactured by Nippon Talc Co., Ltd.)
* 7) Comparative compound 6: Methylene bis (2,4-ditert-butyl-phenyl) phosphate sodium salt * 8) Comparative compound 7: Zinc oxide (1 type; manufactured by Mitsui Kinzoku Co., Ltd.)
* 9) Comparative compound 8: benzoic acid sodium salt * 10) Comparative compound 9: Recommont NaV101; Crystal nucleating agent manufactured by Clariant

  From the results of Table 1 above, the polyester resin composition of the example blended with the compound having a barbituric acid structure has a better crystallization temperature compared to the polyester resin composition of the comparative example blended with other components. It is clear that there is.

  As described above, according to the present invention, it was confirmed that a polyester resin composition having a high crystallization temperature and excellent crystallization promotion can be obtained by using a compound having a barbituric acid structure in the polyester resin. Moreover, in this invention, in the shaping | molding process of this polyester resin composition, the advantage that a moldability becomes favorable can also be acquired.

Claims (8)

  (A) A polyester resin composition comprising (b) a compound having a barbituric acid structure with respect to the polyester resin. The polyester resin composition according to claim 1, wherein the compound (b) having a barbituric acid structure has a group represented by the following general formula (1) or (2).

(In the formula (1), independently R ^1, R ² and R ³ are each a hydrogen atom, an optionally branched alkyl group having or substituent having 1 to 10 carbon atoms, 1 to 10 carbon atoms An alkoxy group which may have a branch or a substituent, a cyclic group which may have a substituent having 3 to 30 carbon atoms, or —NH—R ⁴ (R ⁴ is the same as R ¹ , or a carbon atom Represents a carboxylic acid derivative of 2 to 20), or represents a combination of these groups, and L represents an oxygen atom or a sulfur atom)

(In the formula ^{(2), R 1, R} 2, R 3 and L represent the same as above the general formula (1) Medium, independently R ⁵ and R ⁶ are each a hydrogen atom, carbon atom 1 An alkyl group which may have 10 to 10 branches or substituents, an alkoxy group which may have 1 to 10 carbon atoms branches or substituents, and a substituent which has 3 to 30 carbon atoms A good cyclic group or —NH—R ⁴ (R ⁴ represents the same as R ¹ or a carboxylic acid derivative having 2 to 20 carbon atoms) or a combination of these groups) The polyester resin composition according to claim 1, comprising at least one compound represented by the following general formula (3), (4) or (5) as the compound (b) having a barbituric acid structure.

(In the formula (3), and each of R ^1, R ² and R ³ independently represents a hydrogen atom, an optionally branched alkyl group having or substituent having 1 to 10 carbon atoms, 1 to 10 carbon atoms An alkoxy group which may have a branch or a substituent, a cyclic group which may have a substituent having 3 to 30 carbon atoms, or —NH—R ⁴ (R ⁴ is the same as R ¹ , or a carbon atom Or a combination of these groups, L represents an oxygen atom or a sulfur atom, M represents a hydrogen atom or a metal atom, and M represents a hydrogen atom or a valence of 1 P is 1, q is 0, and when M is a valence 2 metal atom, q is 0 or an integer of 1, p is 2-q, M Is a valence 3 metal atom, q is an integer from 0 to 2, p is 3-q, M is a valence 4 metal atom, That in the case, q is an integer of 0 to 3, p is 4-q)

(In the formula (4), R ¹ , R ² , R ³ , L, M, p and q are the same as those in the general formula (3), and R ⁵ and R ⁶ are each independently a hydrogen atom, An alkyl group that may have a branch or substituent having 1 to 10 carbon atoms, an alkoxy group that may have a branch or substituent having 1 to 10 carbon atoms, or a substituent that has 3 to 30 carbon atoms. A cyclic group which may have or —NH—R ⁴ (R ⁴ represents the same as R ¹ or a carboxylic acid derivative having 2 to 20 carbon atoms) or a combination of these groups)

(In the formula (5), R ¹ , R ² , R ³ , R ⁵ and L represent the same as those in the general formula (4)). The polyester resin composition according to claim 1, comprising at least one compound represented by the following general formula (6), (7) or (5) as the compound (b) having a barbituric acid structure.

(In the formula (6), and each of R ^1, R ² and R ³ independently represents a hydrogen atom, an optionally branched alkyl group having or substituent having 1 to 10 carbon atoms, 1 to 10 carbon atoms An alkoxy group which may have a branch or a substituent, a cyclic group which may have a substituent having 3 to 30 carbon atoms, or —NH—R ⁴ (R ⁴ is the same as R ¹ , or a carbon atom Or a combination of these groups, L represents an oxygen atom or a sulfur atom, M represents a hydrogen atom or a metal atom, and n represents an integer of 1 to 4. To express)

(In the formula (7), R ¹ , R ² , R ³ , L, M and n are the same as those in the general formula (6), and R ⁵ and R ⁶ are each independently a hydrogen atom or a carbon atom. An alkyl group that may have a branch or substituent of 1 to 10, an alkoxy group that may have a branch or substituent of 1 to 10 carbon atoms, or a substituent of 3 to 30 carbon atoms A cyclic group or —NH—R ⁴ (R ⁴ represents the same as R ¹ or a carboxylic acid derivative having 2 to 20 carbon atoms) or a combination of these groups)

(In the formula (5), R ¹ , R ² , R ³ , R ⁵ and L are the same as those in the general formula (7)).   The polyester resin composition according to claim 3, wherein M in the general formula (3) represents an alkali metal atom, p is 1, and q is 0.   The polyester resin composition according to claim 3, wherein M in the general formula (4) represents an alkali metal atom, p is 1, and q is 0.   The polyester resin according to any one of claims 1 to 6, wherein 0.01 to 10 parts by mass of the compound (b) having a barbituric acid structure is blended with respect to 100 parts by mass of the (a) polyester resin. Composition.   The polyester resin composition according to any one of claims 1 to 7, wherein the (a) polyester resin contains at least one selected from the group consisting of polyethylene terephthalate, polytetramethylene terephthalate, polybutylene terephthalate, and polylactic acid. object.