JP4737422B2 - Thermoplastic resin - Google Patents

Description

  The present invention relates to a novel thermoplastic resin excellent in heat resistance, mechanical properties and transparency.

  Polyester stretched films and sheets represented by polyethylene terephthalate are excellent in mechanical strength and heat resistance, and are used in a wide range of fields such as industrial materials, magnetic memory materials, optical materials, information materials, and packaging materials.

  However, the stretched polyester film / sheet may be damaged due to suddenly strong force, and improvement in impact resistance is desired.

  Thus, attempts have been made to improve impact resistance by blending an elastomer or the like with a polyester resin. For example, a composition in which a polyester elastomer is blended with a polyester resin to improve elongation at break and impact resistance has been proposed ( For example, see Patent Documents 1 and 2.)

JP-A-8-269911 JP 2004-18742 A

  However, the compositions proposed in Patent Documents 1 and 2 are insufficient in the impact resistance improvement effect.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a thermoplastic resin using a specific aromatic amide unit in the hard segment is excellent in heat resistance, mechanical properties, and transparency. It came to complete.

That is, the present invention provides (a) one or more selected from the group consisting of an aromatic amide unit represented by the following general formula (1) and (b) an aliphatic polyester, an aliphatic polycarbonate, or a copolymer thereof. The present invention relates to a thermoplastic resin comprising a unit and (c) one or more aromatic polyester units selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate .

（ここで、Ｒ^１およびＲ^２は、それぞれ独立して炭素数１〜２０の二価のオキシアルキレン基、アルキレンカルバモイル基、またはアリーレンカルバモイル基を示す。）
以下に本発明を詳細に説明する。

(Here, R ¹ and R ² each independently represent a divalent oxyalkylene group having 1 to 20 carbon atoms, an alkylenecarbamoyl group, or an arylenecarbamoyl group.)
The present invention is described in detail below.

  The thermoplastic resin of the present invention is one or more selected from the group consisting of (a) an aromatic amide unit represented by the general formula (1) and (b) an aliphatic polyester, an aliphatic polycarbonate, or a copolymer thereof. And (c) a thermoplastic resin comprising an aromatic polyester unit.

Here, R ¹ and R ² in the aromatic amide unit represented by the general formula (1) constituting the thermoplastic resin are each independently a divalent oxyalkylene group having 1 to 20 carbon atoms, alkylene It is a carbamoyl group or an arylenecarbamoyl group, and R ¹ and R ² may be the same or different, and may be linear or branched.

  Examples of the oxyalkylene group include unsubstituted oxyalkylene groups such as oxyethylene group, oxytrimethylene group, oxytetramethylene group, oxypentamethylene group and oxyhexamethylene group, or alkyl substitution such as methyl group and ethyl group. Group or one or more aryl substituents such as phenyl group bonded thereto. Furthermore, two or more of the above unsubstituted oxyalkylene group units and alkyl or aryl-substituted oxyalkylene group units may be bonded together, and one or more of these may be used. Of these, an oxyethylene group and an oxypropylene group are preferable. In addition, it is preferable that oxygen in these oxyalkylene groups is directly bonded to the benzene ring in the general formula (1).

  Examples of the alkylenecarbamoyl group include a methylenecarbamoyl group, an ethylenecarbamoyl group, a trimethylenecarbamoyl group, a tetramethylenecarbamoyl group, a pentamethylenecarbamoyl group, a 2,2-dimethyltrimethylenecarbamoyl group, a neopentylcarbamoyl group, and a hexamethylenecarbamoyl group. , 3-methylpentamethylenecarbamoyl group, 2-methylheptamethylenecarbamoyl group, heptamethylenecarbamoyl group, octamethylenecarbamoyl group, nonamethylenecarbamoyl group, decamethylenecarbamoyl group, 1,4-cyclohexylenecarbamoyl group, etc. One or more of these can be used. Of these, an ethylenecarbamoyl group is preferable.

  Examples of the arylenecarbamoyl group include 2-benzylcarbamoyl group, 3-benzylcarbamoyl group, 4-benzylcarbamoyl group, 1,2-phenylenecarbamoyl group, 1,3-phenylenecarbamoyl group, 1,4-phenylenecarbamoyl group and the like. One or more of these may be used.

  The one or more units selected from the group consisting of (b) aliphatic polyesters, aliphatic polycarbonates or copolymers thereof constituting the thermoplastic resin of the present invention are not particularly limited as long as they are known.

  The aliphatic polyester can be obtained, for example, by condensation polymerization of an aliphatic dicarboxylic acid or an aliphatic dicarboxylic acid anhydride and a short chain polyol. Examples of the aliphatic dicarboxylic acid or aliphatic dicarboxylic acid anhydride include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid and the like, and one or more of these are used. . On the other hand, examples of the short-chain polyol include aliphatic, alicyclic, aromatic, substituted aliphatic or heterocyclic dihydroxy compounds; trihydroxy compounds; tetrahydroxy compounds, and the like. For example, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, butenediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,10- Decamethylenediol, 2,5-dimethyl-2,5-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanedimethanol, 2-methyl-1,8-octanediol, 1,9-nonanediol, tri Methylolpropane, glycerin, 2-methylpropane-1,2,3-triol, 1 2,6-hexane triol and the like, one or more of these can be used.

  As another method for obtaining the aliphatic polyester, for example, β-propiolactone, pivalolactone, δ-valerolactone, β-methyl-δ-valerolactone, ε-caprolactone, methyl-ε-caprolactone, dimethyl-ε-caprolactone, It is also possible to use a method in which one or more lactone compounds such as trimethyl-ε-caprolactone are reacted with a hydroxy compound.

  Examples of the aliphatic polycarbonate include those obtained by a transesterification method of one or more hydroxy compounds and a carbonate compound such as diallyl carbonate, dialkyl carbonate, and ethylene carbonate. Examples of the polycarbonate include poly (1,6-hexamethylene carbonate) and poly (2,2′-bis (4-hydroxyhexyl) propylene carbonate). Moreover, as another method of obtaining an aliphatic polycarbonate, it can also obtain by what is called a phosgene method.

  The (c) aromatic polyester unit constituting the thermoplastic resin of the present invention is not particularly limited as long as it is a known one.

  The aromatic polyester unit can be obtained, for example, by subjecting an aromatic dicarboxylic acid component and a glycol component to a polycondensation reaction. Here, examples of the aromatic dicarboxylic acid component include terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodiumsulfonedicarboxylic acid, and phthalic acid. Can be mentioned. Examples of the glycol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Aliphatic glycols such as hexanediol and neopentyl glycol; polyoxyalkylene glycols such as diethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol; alicyclic glycols such as cyclohexanedimethanol; aromatics such as bisphenol A and bisphenol S And glycols. Among these, as the aromatic dicarboxylic acid component, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and isophthalic acid are preferable, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferable. As the glycol component, ethylene glycol, 1,3-propanediol, 1,4-butanediol, polytetramethylene glycol and the like are preferable.

  Specific examples of the aromatic polyester unit (c) include one or more units selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate.

  (A) an aromatic amide unit represented by the general formula (1), (b) one or more units selected from the group consisting of aliphatic polyesters, aliphatic polycarbonates or copolymers thereof, ) Among the aromatic polyester units, a thermoplastic resin having excellent heat resistance can be obtained. Therefore, (a) the aromatic amide unit represented by the general formula (1), (b) the aliphatic polyester unit, and (c) It is preferably composed of an aromatic polyester unit, and in particular, (a) an aromatic amide unit represented by the general formula (1), (b) a poly (ε-caprolactone) unit, (c) polyethylene terephthalate, polybutylene terephthalate, polyethylene It is preferably composed of one or more units selected from the group consisting of -2,6-naphthalate.

  The thermoplastic resin of the present invention is one or more selected from the group consisting of (a) an aromatic amide unit represented by the general formula (1) and (b) an aliphatic polyester, an aliphatic polycarbonate, or a copolymer thereof. The unit of (c) may be directly bonded to the aromatic polyester unit, or may contain other compound residues. Examples of other compound residues include bifunctional halide compounds, difunctional isocyanate compounds, difunctional carbonate compounds, bifunctional ester compounds, bifunctional acyllactam compounds, bifunctional epoxy compounds, and bifunctional tetra compounds. The compound residue derived from a carboxylic anhydride etc. is mentioned, These 1 type (s) or 2 or more types may be contained.

  Examples of the compound residue derived from a bifunctional halide compound include oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, pimelic acid dichloride, suberic acid dichloride, azelaic acid dichloride, and sebacic acid. Compound residues derived from bifunctional acid chlorides such as dichloride, dodecanoic acid dichloride, terephthalic acid dichloride, isophthalic acid dichloride, phthalic acid dichloride; oxalic acid dibromide, malonic acid dibromide, succinic acid dibromide, glutaric acid dichloride Bromide, adipic acid dibromide, pimelic acid dibromide, suberic acid dibromide, azelaic acid dibromide, sebacic acid dibromide, dodecanoic acid dibromide, terephthalate Compound residues derived from bifunctional acid bromides such as dibromide, isophthalic acid dibromide, diphthalide phthalate, etc. are mentioned. Among them, it is excellent in reactivity, and a thermoplastic resin can be obtained efficiently. Compound residues derived from acid dichloride are preferred.

  Examples of the compound residue derived from the bifunctional isocyanate compound include diphenylmethane-4,4′-diisocyanate, toluene diisocyanate, phenylene diisocyanate, xylene diisocyanate, xylylene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Examples include compound residues derived from naphthalene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, norbornene diisocyanate, etc. These may be used alone or in combination of two or more It may be use. Among them, a compound residue derived from diphenylmethane-4,4′-diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and the like is preferable because of excellent reactivity and efficient production of a thermoplastic resin. In particular, a compound residue derived from hexamethylene diisocyanate is preferably used.

  As the compound residue derived from a bifunctional carbonate compound, for example, a compound residue derived from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, etc., among them excellent in reactivity, A compound residue derived from dimethyl carbonate, diphenyl carbonate or the like is preferable because a thermoplastic resin can be obtained efficiently.

  Examples of the compound residue derived from the bifunctional ester compound include diphenyl terephthalate, diphenyl isophthalate, diphenyl phthalate, diphenyl 2,6-naphthalenedicarboxylate, diphenyl 2,7-naphthalenedicarboxylate, 4,4- Diphenyl biphenyl dicarboxylate, dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl 2,7-naphthalenedicarboxylate, dimethyl 4,4-biphenyldicarboxylate, diethyl terephthalate, isophthalic acid Compound residues derived from diethyl, diethyl phthalate, diethyl 2,6-naphthalenedicarboxylate, diethyl 2,7-naphthalenedicarboxylate, diethyl 4,4-biphenyldicarboxylate, etc. Excellent refractoriness, since the efficiency Netsukaso resin is obtained, diphenyl terephthalate, dimethyl terephthalate, diphenyl isophthalate, compound residues derived from isophthalic acid dimethyl, etc. are preferred.

  Examples of the compound residue derived from a bifunctional acyllactam compound include terephthaloyl bis (ε-caprolactam), isophthaloyl bis (ε-caprolactam), adipyl bis (ε-caprolactam), succinyl bis (ε-caprolactam). ) And the like. Among them, a compound residue derived from terephthaloyl bis (ε-caprolactam) is preferable because it is excellent in reactivity and can efficiently obtain a thermoplastic resin.

  Examples of the compound residue derived from a bifunctional epoxy compound include a compound residue derived from an aromatic dicarboxylic acid diglycidyl ester such as terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and phthalic acid diglycidyl ester; Compound residue derived from aromatic diglycidyl ether such as p-phenylene diglycidyl ether; Compound residue derived from aliphatic dicarboxylic acid diglycidyl ester such as diethylene glycol diglycidyl ester; Aliphatic such as diethylene glycol diglycidyl ether Examples thereof include a compound residue derived from dicarboxylic acid diglycidyl ether.

  Examples of the compound residue derived from a bifunctional tetracarboxylic anhydride include pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3 ′, 4, Examples thereof include compound residues derived from 4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the like.

  Since the thermoplastic resin of the present invention is flexible and excellent in stretchability, (b) units selected from the group consisting of aliphatic polyesters, aliphatic polycarbonates or copolymers thereof, and (c) the number of aromatic polyester units. The average molecular weight is preferably in the range of 200 to 10,000, and particularly preferably in the range of 300 to 5,000.

  The content of the aromatic amide unit represented by the general formula (1) in the thermoplastic resin of the present invention is not particularly limited, and a thermoplastic resin excellent in flexibility, heat resistance and transparency can be obtained. The content of the aromatic amide unit is preferably in the range of 2 to 95% by weight, particularly preferably in the range of 2 to 50% by weight, and more preferably in the range of 5 to 40% by weight.

  The content of the unit selected from the group consisting of (b) aliphatic polyester, aliphatic polycarbonate or copolymers thereof in the thermoplastic resin of the present invention is not particularly limited, and is a thermoplastic resin excellent in flexibility and heat resistance. Therefore, the content of units selected from the group consisting of (b) aliphatic polyesters, aliphatic polycarbonates or copolymers thereof is preferably in the range of 10 to 90% by weight, particularly 20 to 80%. The range is preferably in the range of wt%, and more preferably in the range of 25 to 80 wt%.

  The content of the (c) aromatic polyester unit in the thermoplastic resin of the present invention is not particularly limited, and a thermoplastic resin excellent in flexibility and transparency can be obtained. The content is preferably in the range of 0.1 to 70% by weight, particularly preferably in the range of 0.5 to 60% by weight, and more preferably in the range of 5 to 60% by weight.

  The thermoplastic resin of the present invention preferably has a number average molecular weight in terms of standard polymethyl methacrylate measured by gel permeation chromatography (hereinafter referred to as GPC) of 5,000 to 1,000,000, particularly 10,000 to 500,000. It is preferable that it is preferably 10,000 to 100,000. The thermoplastic resin preferably has a type A durometer hardness (JIS K6253: 1997) of 50 to 99, particularly preferably 65 to 99, and more preferably 70 to 99. Is preferred.

  The method for producing the thermoplastic resin of the present invention is selected from the group consisting of (a) an aromatic amide unit represented by the general formula (1) and (b) an aliphatic polyester, an aliphatic polycarbonate, or a copolymer thereof. Any method may be used as long as it is possible to produce a thermoplastic resin composed of one or more units and (c) an aromatic polyester unit. For example, (a) a fragrance represented by the general formula (1) A monomer having an amide unit and having a carboxylic acid group or a hydroxyl group at both ends; and (b) an aliphatic polyester, an aliphatic polycarbonate or a copolymer thereof containing a hydroxyl group or a carboxylic acid group at both ends. (C) a method of directly reacting a compound containing one or more units and (c) a compound containing an aromatic polyester unit; And a monomer having a hydroxyl group at both ends and (b) an aliphatic polyester, an aliphatic polycarbonate or a copolymer thereof containing a hydroxyl group at both ends. When reacting the above unit with a compound containing (c) an aromatic polyester unit, a bifunctional halide compound, a bifunctional isocyanate compound, a bifunctional carbonate compound, a bifunctional ester compound, a bifunctional acyllactam A method of reacting in the presence of one or more chain extender units selected from the group consisting of a compound, a bifunctional epoxy compound, a bifunctional tetracarboxylic anhydride, etc .; (a) represented by the general formula (1) A monomer containing an aromatic amide unit and having a hydroxyl group at both ends is reacted with (b) a cyclic ester compound such as ε-caprolactone. After obtaining the polymer, (c) a method of adding a compound containing an aromatic polyester unit and carrying out a transesterification reaction, and then adding and reacting one or more chain extenders described above; (a) General formula (1) (B) After reacting a monomer having a hydroxyl group at both ends with an aromatic amide unit and a cyclic ester compound such as ε-caprolactone to obtain a prepolymer, one or more chain extenders described above are added. Examples of the method include (c) a method of adding a compound containing an aromatic polyester unit and causing a transesterification reaction after the reaction. Among them, since a thermoplastic resin having an increased molecular weight can be easily obtained, (a) a monomer containing an aromatic amide unit represented by the general formula (1) and having hydroxyl groups at both ends, and (b) ε-caprolactone A method of reacting a cyclic ester compound such as (c) adding a compound containing an aromatic polyester unit, causing a transesterification reaction, and then adding one or more chain extenders as described above to react. (A) a monomer having an aromatic amide unit represented by the general formula (1) and having hydroxyl groups at both ends and a cyclic ester compound such as (b) ε-caprolactone were reacted to obtain a prepolymer, which was described above. A method in which one or more chain extenders are added and reacted, and then (c) a compound containing an aromatic polyester unit is added and subjected to a transesterification reaction, is particularly excellent in transparency. (A) a monomer having an aromatic amide unit represented by the general formula (1) and having hydroxyl groups at both ends and (b) a cyclic ester compound such as ε-caprolactone are reacted with each other. After obtaining the prepolymer, (c) a method in which a compound containing an aromatic polyester unit is added and subjected to a transesterification reaction, and then one or more chain extenders described above are added and reacted. Examples of the polymerization method in the above method include a solution polymerization method, a melt polymerization method, an interfacial polymerization method, a solid phase polymerization method, and the like. Among them, since a thermoplastic resin having an increased molecular weight can be easily obtained, it is preferable to perform melt condensation after performing the solution polymerization method.

  In the production of the thermoplastic resin of the present invention, it is preferable to use a catalyst in order to further promote the reaction efficiency. The catalyst is generally used in a ring-opening polymerization reaction of a lactone compound or generally in the production of a polyester. Those used in the transesterification reaction can be used, and examples include compounds such as inorganic bases, inorganic acids, alkali metals, alkaline earth metals, lanthanoids, and the like. For example, lithium, sodium, potassium, rubidium, cesium, magnesium, Metal oxides such as calcium, barium, strontium, zinc, aluminum, titanium, zirconium, cobalt, germanium, tin, lead, antimony, arsenic, cerium, boron, cadmium, manganese, tungsten, and molybdenum; organic metals containing these metals Compounds; halogens of these metals Products; alkoxides of these metals and the like, particularly low toxicity, reactivity, non-coloring property, and catalyst excellent balance 耐安 qualitative, organic tin compounds, organic titanium compounds or the like are preferable.

  Specific examples of the organic tin compound include tin tetraacetate, monobutyltin hydroxide oxide, monobutyltin tri-2-ethylhexanoate, dibutyltin oxide, dibutyltin dilaurate, tin dioctanoate and the like. Specific examples of the organic titanium compound include tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate. When manufacturing a thermoplastic resin, the said catalyst can be used individually or can use 2 or more types together.

  The amount of catalyst used is not particularly limited as long as a thermoplastic resin can be obtained. Among them, the reaction efficiency is particularly excellent, and the obtained thermoplastic resin is excellent in hue and thermal stability. 0.0001-0 with respect to the total amount of the aromatic amide unit represented by 1) and one or more units selected from the group consisting of (b) aliphatic polyesters, aliphatic polycarbonates or copolymers thereof. It is preferably 2% by weight, particularly preferably 0.0005 to 0.05% by weight.

  A pentavalent phosphorus compound may be added to the thermoplastic resin of the present invention in order to improve thermal stability, heat resistance, etc. during processing. As the pentavalent phosphorus compound, a pentavalent phosphorus compound may be added. Any of them may be used, and among these, a pentavalent phosphorus compound represented by the general formulas (2) to (4) is preferable because a thermoplastic resin excellent in heat resistance can be obtained.

（ここで、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０およびＲ^１１は、それぞれ独立して水素原子もしくは炭素数１〜３０の有機基を示す。）。

(Here, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or an organic group having 1 to 30 carbon atoms. ).

Here, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ in the pentavalent phosphorus compound represented by the general formulas (2) to (4) are: Each is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and may be the same or different, and may be linear or branched. Examples of the organic group having 1 to 30 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, decyl, isodecyl, dodecyl, and octadecyl. A cycloalkyl group such as a cyclohexyl group or a cyclooctyl group; an aryl group such as a phenyl group, a benzyl group, or a naphthyl group; or one having one or more alkyl substituents, aryl substituents, halogen substituents, or the like bonded thereto Is mentioned.

  Specific examples of pentavalent phosphorus compounds include inorganic acids such as phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, and polyphosphoric acid; dimethylphosphinic acid, diethylphosphinic acid, diisobutylphosphinic acid, and dibenzyl. Phosphinic acid such as phosphinic acid, diphenylphosphinic acid, dicyclohexylphosphinic acid, di (4-methylphenyl) phosphinic acid; methylphosphonic acid, ethylphosphonic acid, isopropylphosphonic acid, isobutylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, cyclohexylphosphone Acids, phosphonic acids such as 4-methylphenylphosphonic acid; acid esters or partial ester compounds such as dodecyl phosphate, octadecyl phosphate, didodecyl phosphate, dioctadecyl phosphate, etc. Among them, excellent in heat resistance Thermoplastic Since the resin is obtained, pentavalent phosphorus compound represented by the following general formula (5),

（ここで、Ｒ^１２は、水素原子もしくは炭素数１〜３０の有機基、Ｒ^１３は、炭素数１〜３０の有機基を示す。）
ジフェニルホスフィン酸、フェニルホスホン酸、リン酸等が好ましく、特に一般式（５）で示される５価のリン化合物が好ましい。これらの５価のリン化合物は１種または２種以上が使用される。

(Here, R ¹² represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R ¹³ represents an organic group having 1 to 30 carbon atoms.)
Diphenylphosphinic acid, phenylphosphonic acid, phosphoric acid and the like are preferable, and a pentavalent phosphorus compound represented by the general formula (5) is particularly preferable. One or two or more of these pentavalent phosphorus compounds are used.

Here, R ¹² in the pentavalent phosphorus compound represented by the general formula (5) is a hydrogen atom or an organic group having 1 to 30 carbon atoms, and R ¹³ is an organic group having 1 to 30 carbon atoms. Each may be the same or different, and may be linear or branched. Examples of the organic group having 1 to 30 carbon atoms in R ¹² and R ¹³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, 2-ethylhexyl group, decyl group, isodecyl group, dodecyl group, An alkyl group such as an octadecyl group; a cycloalkyl group such as a cyclohexyl group or a cyclooctyl group; an aryl group such as a phenyl group, a benzyl group, or a naphthyl group; or an alkyl substituent, an aryl substituent, or a halogen substituent. The thing etc. which couple | bonded or more are mentioned. Among these phosphorus compounds represented by the general formula (5), a phosphorus compound having an octadecyl group is particularly preferably used.

  The content of the pentavalent phosphorus compound used for the thermoplastic resin of the present invention is preferably 0.001 to 2.0 parts by weight, particularly preferably 0.001 to 1.0 parts by weight based on 100 parts by weight of the thermoplastic resin. Part by weight, more preferably 0.05 to 0.2 part by weight.

  The pentavalent phosphorus compound used for the thermoplastic resin of the present invention can be added at any stage, and among them, the ring-opening polymerization reaction or the transesterification reaction is substantially completed when producing the thermoplastic resin. It is preferable to add at a stage or a later stage. Particularly, since a thermoplastic resin having good dispersibility and excellent heat resistance of a pentavalent phosphorus compound can be obtained, ring-opening polymerization reaction or transesterification reaction at the time of solution polymerization It is more preferable to add at a stage where is substantially completed.

  In order to improve long-term heat resistance and the like, one or more reactive compounds selected from the group consisting of carbodiimide compounds, oxazoline compounds, and epoxy compounds may be added to the thermoplastic resin of the present invention, and carbodiimide compounds, oxazolines. The one or more reactive compounds selected from the group consisting of compounds and epoxy compounds are not particularly limited, and known compounds can be used.

  The carbodiimide compound may be any compound having one or more carbodiimide groups in the molecule. For example, N, N′-diisopropylcarbodiimide, N, N′-di (o-toluyl) carbodiimide, N, Monofunctional carbodiimide compounds such as N′-dicyclohexylcarbodiimide, N, N′-bis (2,6-diisopropylphenyl) carbodiimide; p-phenylene-bis (2,6-xylylcarbodiimide), p-phenylene-bis ( Bifunctional carbodiimide compounds such as t-butylcarbodiimide), p-phenylene-bis (mesitylcarbodiimide), tetramethylene-bis (t-butylcarbodiimide), cyclohexane-1,4-bis (methylene-t-butylcarbodiimide) ; Multifunctional carbodiimidization Goods and the like, polyfunctional carbodiimide compound among them is preferable. Examples of the polyfunctional carbodiimide compound are generally known under trade names such as Carbodilite LA-1 (Nisshinbo Co., Ltd.), Carbodilite HMV-8CA (Nisshinbo Co., Ltd.), and Elasto Stub H01 (Nisshinbo Co., Ltd.). A polyfunctional carbodiimide compound is mentioned. One or more of these carbodiimide compounds can be used.

  The oxazoline compound may be any compound as long as it has one or more oxazoline rings in the molecule. For example, 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5 Monofunctional oxazoline compounds such as dimethyl-2-oxazoline and 2,4-diphenyl-2-oxazoline; 2,2 ′-(1,3-phenylene) -bis (2-oxazoline), 2,2 ′-( 1,2-ethylene) -bis (2-oxazoline), 2,2 ′-(1,4-butylene) -bis (2-oxazoline), 2,2 ′-(1,4-phenylene) -bis (2 -Oxazoline) and the like, and monofunctional oxazoline compounds are preferable, and 2-phenyl-2-oxazoline is particularly preferable.These can be used alone or in combination of two or more.

  When using an oxazoline compound, it is preferable to use a catalyst for the purpose of promoting the reaction with the carboxyl group contained in the thermoplastic resin. Examples of the catalyst include organic phosphites such as triphenyl phosphite, p-toluenesulfonic acid, dimethyl sulfate, boron trifluoride etherate, anhydrous aluminum chloride, vanadium trichloride, vanadyl chloride, and organic halides. These catalysts can be used alone or in combination of two or more. The catalyst may be added all at once or dividedly. The amount of the catalyst added is preferably 3.0 parts by weight or less, particularly preferably 0.1 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin. 0001 to 2.0 parts by weight.

  The epoxy compound may be any compound having one or more epoxy groups in the molecule, for example, monofunctionality such as phenyl glycidyl ether, lauryl glycidyl ether, phenoxy polyethylene glycol glycidyl ether, benzoic acid glycidyl ether, etc. Epoxy compound; terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, p-phenylene diglycidyl ether, diethylene glycol diglycidyl ester, diethylene glycol diglycidyl ether, 2,2-bis (4-glycidyloxyphenyl) Examples thereof include bifunctional epoxy compounds such as propane and bisphenol A type epoxy resins. Among them, bifunctional epoxy compounds are preferable, and 2,2-biphenyl compounds are particularly preferable. (4-glycidyloxy phenyl) propane is preferred. These can be used alone or in combination of two or more.

  When using an epoxy compound, it is preferable to use a catalyst for the purpose of promoting the reaction with a carboxyl group contained in the thermoplastic resin. Examples of the catalyst include amines, phosphorus compounds, group 1 or group 2 metal salts selected from the periodic table of monocarboxylic acids and / or dicarboxylic acids having 10 or more carbon atoms, among them. Trivalent phosphorus compounds such as tributylphosphine and triphenylphosphine; metal salts of stearic acid such as calcium stearate and sodium stearate are preferred. These catalysts can be used alone or in combination of two or more. The catalyst may be added all at once or dividedly. The amount of the catalyst added is preferably 3.0 parts by weight or less, particularly preferably 0.1 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin. 0001 to 2.0 parts by weight.

  Among the one or more reactive compounds selected from the group consisting of these carbodiimide compounds, oxazoline compounds and epoxy compounds, a thermoplastic resin having excellent long-term heat resistance can be obtained, so that a multifunctional carbodiimide compound, 2,2- It is preferably at least one compound selected from the group consisting of bis (4-glycidyloxyphenyl) propane and 2-phenyl-2-oxazoline.

  Moreover, the functional group equivalent of a carbodiimide compound, an oxazoline compound, and an epoxy compound is preferably 50 to 1000 g / eq, and particularly preferably 100 to 500 g / eq, because a thermoplastic resin having excellent long-term heat resistance is obtained.

  The compounding amount of one or more reactive compounds selected from the group consisting of carbodiimide compounds, oxazoline compounds and epoxy compounds used in the thermoplastic resin of the present invention is not particularly limited, and among them, a thermoplastic resin having excellent long-term heat resistance can be obtained. Therefore, 0.01 to 5 parts by weight is preferable with respect to 100 parts by weight of the thermoplastic resin, and 0.05 to 3 parts by weight is particularly preferable.

  Further, a stabilizer may be added to the thermoplastic resin of the present invention to improve heat resistance, particularly heat discoloration, and examples of the stabilizer include phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, Phosphorus compounds such as phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, dialkylbisphenol A diphosphite; hindered phenolic compounds; hydroxydioxaphosphapine compounds; hydroxyacrylate compounds Sulfur-containing compounds such as thioether, dithioate, mercaptobenzimidazole, thiocarbanilide, and thiodipropionate; tin compounds such as tin malate and dibutyltin monoxide; lactone compounds; hydroxylamine compounds Vitamin E compounds; Allylamine compounds; Amine-ketone compounds; Aromatic secondary amine compounds; Monophenol compounds; Bisphenol compounds; Polyphenol compounds; Benzimidazole compounds; Dithiocarbamic acid compounds; Organic thioic acid compounds and the like, and the addition amount of the stabilizer is not particularly limited, and 0.0001 to 10 parts by weight is preferably used with respect to 100 parts by weight of the thermoplastic resin.

  Furthermore, the thermoplastic resin of the present invention has, for the purpose of improving molding processability, metal soaps such as calcium stearate, zinc stearate, barium stearate, zinc laurate; stearic acid ester; silicon oil; waxes; A lubricant such as ethylene bisstearylamide can also be added. There is no restriction | limiting in particular in these addition amount, 0.05-5 weight part is used preferably with respect to 100 weight part of thermoplastic resins.

  Examples of the thermoplastic resin of the present invention include dyes; organic pigments or inorganic pigments; inorganic reinforcing agents; plasticizers; light stabilizers such as hindered amine compounds and benzoate compounds; benzotriazole compounds, triazine compounds, and benzophenone compounds. UV absorbers such as compounds, phenyl silicate compounds, phenyl acrylate compounds; foaming agents; antistatic agents; conductive agents; crystal nucleating agents; plasticizers; mold release agents; hydrolysis inhibitors such as carbodiimides; Known additives such as can be added.

  For example, wax such as paraffin wax, petroleum wax, natural wax, synthetic wax; thermoplastic resin; thermoplastic elastomer; rubber; thermosetting resin; etc. can be added to the thermoplastic resin of the present invention. The properties of the resin can be modified and used.

  The thermoplastic resin of the present invention can be molded by ordinary thermoplastic resin molding methods such as injection molding, extrusion molding, transfer molding, inflation molding, blow molding, heat molding, compression molding, vacuum molding, etc. It can be used in a wide range of applications such as plastic modifiers for paints such as fibers, films, sheets, and polyethylene terephthalate, paints, and adhesives.

  The present invention can provide a novel thermoplastic resin excellent in heat resistance, mechanical properties, and transparency.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. The reagents used were commercially available unless otherwise noted.

  The equipment and methods used for evaluation and analysis are shown below.

-Measurement of number average molecular weight of thermoplastic resin-
The column temperature was 40 ° C. and the flow rate was 0.6 ml by a GPC apparatus (trade name HLC-8120GPC, manufactured by Tosoh Corporation) equipped with a column (trade name TSK-GEL super AWM-H, 2 manufactured by Tosoh Corporation). The measurement was performed using a 10 mmol / L sodium trifluoroacetate / 2,2,2-trifluoroethanol solution as an eluent under the conditions of / min and calculated in terms of standard polymethyl methacrylate.

-Measurement of aromatic amide unit, aliphatic polyester unit, aromatic polyester unit content in thermoplastic resin-
Using a nuclear magnetic resonance measuring apparatus (manufactured by JEOL, trade name: JNM-GSX270 type), ¹³ C-NMR was measured at room temperature in deuterated trifluoroacetic acid and calculated from the peak intensity ratio of each unit.

-Melting point measurement of thermoplastic resin-
A differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd., trade name DSC200) was used, and the temperature was measured at a temperature rising rate of 10 ° C./min and in the range of −100 to 300 ° C.

〜Type A durometer hardness of thermoplastic resin〜
Type A durometer hardness (JIS K6253: 1997) was measured using a 2 mm thick sheet obtained by compression molding a thermoplastic resin.

~ Tensile strength (TB) of thermoplastic resin ~
In accordance with JIS K 6251 (1993), a 2 mm thick sheet was punched into a JIS-3 dumbbell. The tensile speed was 200 mm / min.

~ Haze of thermoplastic resin ~
In accordance with JIS K7136 (2000), a 1 mm thick sheet was used as the test piece.

Synthesis Example 1 (Synthesis of dihydroxy aromatic amide compound ((a) monomer having an aromatic amide unit represented by general formula (1) and having hydroxyl groups at both ends))
In a 10 L four-necked flask equipped with a nitrogen inlet tube, a thermometer, and a stirring blade, 763 g (7.0 mol) of p-aminophenol and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) are added under a nitrogen atmosphere. ) 2.1 L and 1.4 L of toluene were added and the temperature was raised to 50 ° C. to obtain a uniform solution. Separately, 710 g (3.5 mol) of terephthalic acid dichloride, 0.3 L of NMP, and 1.4 L of toluene were added to a 3 L dropping funnel equipped with a nitrogen introduction tube to obtain a uniform solution. This solution was dropped into the previous solution over 30 minutes while maintaining 80 ° C., and further reacted at 80 ° C. for 2 hours.

  After cooling to room temperature, the solid content was collected by suction filtration and washed with 7 L of methanol twice to obtain N, N′-bis (4-hydroxyphenyl) -1,4-benzenedicarboxamide.

  Subsequently, 1045 g (3 of N, N′-bis (4-hydroxyphenyl) -1,4-benzenedicarboxamide was added to a 10 L four-necked flask equipped with a nitrogen introduction tube, a thermometer and a stirring blade under a nitrogen atmosphere. 0.0 mol), 555 g (6.3 mol) of ethylene carbonate, 0.95 g (9.0 mmol) of sodium carbonate as a catalyst, and 6.0 L of NMP were added and reacted at 180 ° C. for 3 hours. After cooling to room temperature, the solid content was collected by suction filtration, washed by stirring twice with NMP5L and then with 7.5L of methanol, and N, N′-bis (4- (2-hydroxyethoxy) phenyl) -1,4- 1110 g (yield 85%) of benzenedicarboxamide was obtained. Its structural formula is shown below. This compound is referred to as (A).

実施例１（熱可塑性樹脂の合成）
窒素導入管を備えた１５Ｌのオートクレーブに、窒素雰囲気下で化合物（Ａ）１０２４ｇ（２．３モル）、ε−カプロラクトン２１４１ｇ（１８．８モル）、ヒンダードフェノール系化合物として１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン［チバ・スペシャルティ・ケミカルズ（株）製、商品名イルガノックス１３３０］３．４７ｇ、ＮＭＰ３１６５ｇを仕込み、２００℃に昇温した後、テトラブチルチタネート０．３２ｇ（０．９４ミリモル）を加え、２００℃で１時間開環重合を行い、（ａ）一般式（１）で示される芳香族アミド単位と、（ｂ）脂肪族ポリエステル単位とのプレポリマーを得た。

Example 1 (Synthesis of thermoplastic resin)
In a 15 L autoclave equipped with a nitrogen inlet tube, 1024 g (2.3 mol) of compound (A), 2141 g (18.8 mol) of ε-caprolactone, and 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene [Ciba Specialty Chemicals Co., Ltd., trade name Irganox 1330] 3.47 g, NMP 3165 g were charged. After raising the temperature to 200 ° C., 0.32 g (0.94 mmol) of tetrabutyl titanate was added, ring-opening polymerization was carried out at 200 ° C. for 1 hour, and (a) an aromatic amide unit represented by the general formula (1) And (b) a prepolymer with an aliphatic polyester unit was obtained.

  Subsequently, as a compound containing an aromatic polyester unit, 415 g of polyethylene terephthalate [manufactured by Teijin Chemicals Ltd., trade name PET resin TR8550T] was added and reacted at 200 ° C. for 2 hours. Thereafter, 836 g (2.3 mol) of terephthaloyl bis (ε-caprolactam) was added and reacted at 200 ° C. for 2 hours. Thereafter, while raising the internal temperature to 240 ° C., NMP and ε-caprolactam as a by-product were distilled off under reduced pressure over 2 hours, and further reacted at 240 ° C. for 1 hour. Subsequently, after the inside of the system was pressurized with nitrogen, the molten polymer was extracted as a strand from the lower part of the autoclave and cut to obtain 3500 g of thermoplastic resin pellets.

  The obtained thermoplastic resin had a number average molecular weight of 17,000, a melting point of 187 ° C., a type A durometer hardness of 97, an aromatic amide unit of 30% by weight, an aliphatic polyester unit of 57% by weight, and an aromatic polyester unit of 13% by weight. .

  Subsequently, using a compression molding machine set at 250 ° C., compression molding was performed on a sheet having a thickness of 2 mm and 1 mm, and TB and haze were measured. TB57 MPa, haze 50%, excellent mechanical properties and transparency.

Example 2 (Synthesis of thermoplastic resin)
In a 15 L autoclave equipped with a nitrogen inlet tube, 875 g (2.0 mol) of compound (A), 1831 g (16.0 mol) of ε-caprolactone and 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene [manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Irganox 1330] 2.97 g and NMP 2706 g were charged. The temperature was raised to 200 ° C., 0.27 g (0.80 mmol) of tetrabutyl titanate was added, ring-opening polymerization was performed at 200 ° C. for 1 hour, and (a) an aromatic amide unit represented by the general formula (1) And (b) a prepolymer with an aliphatic polyester unit was obtained.

  Subsequently, as a compound containing an aromatic polyester unit, 1370 g of polyethylene terephthalate [manufactured by Teijin Chemicals Ltd., trade name PET resin TR8550T] was added and reacted at 200 ° C. for 2 hours. Thereafter, 715 g (2.0 mol) of terephthaloyl bis (ε-caprolactam) was added and reacted at 200 ° C. for 2 hours. Thereafter, while raising the internal temperature to 250 ° C., NMP and ε-caprolactam as a by-product were distilled off under reduced pressure over 2 hours, and further reacted at 250 ° C. for 1 hour. Subsequently, after the inside of the system was pressurized with nitrogen, the molten polymer was extracted as a strand from the lower part of the autoclave and cut to obtain 3900 g of thermoplastic resin pellets.

  The resulting thermoplastic resin had a number average molecular weight of 18000, a melting point of 177 ° C., a type A durometer hardness of 94, an aromatic amide unit of 24% by weight, an aliphatic polyester unit of 35% by weight, and an aromatic polyester unit of 41% by weight. .

  Subsequently, using a compression molding machine set at 250 ° C., compression molding was performed on a sheet having a thickness of 2 mm and 1 mm, and TB and haze were measured. TB55 MPa, haze 32%, and excellent mechanical properties and transparency.

Example 3 (Synthesis of thermoplastic resin)
In a 15 L autoclave equipped with a nitrogen inlet tube, 704 g (1.6 mol) of compound (A), 1472 g (12.9 mol) of ε-caprolactone and 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene [Ciba Specialty Chemicals Co., Ltd., trade name Irganox 1330] 2.39 g and NMP 2176 g were charged. The temperature was raised to 200 ° C., 0.22 g (0.65 mmol) of tetrabutyl titanate was added, ring-opening polymerization was performed at 200 ° C. for 1 hour, and (a) the aromatic amide unit represented by the general formula (1) And (b) a prepolymer with an aliphatic polyester unit was obtained.

  Subsequently, 575 g (1.6 mol) of terephthaloyl bis (ε-caprolactam) was added and reacted at 200 ° C. for 2 hours. Thereafter, 2570 g of polyethylene terephthalate [manufactured by Teijin Chemicals Ltd., trade name PET resin TR8550T] as a compound containing an aromatic polyester unit was added and reacted at 200 ° C. for 1 hour. Thereafter, while raising the internal temperature to 260 ° C., NMP and ε-caprolactam as a by-product were distilled off under reduced pressure over 2 hours, and further reacted at 260 ° C. for 1 hour. Subsequently, after the inside of the system was pressurized with nitrogen, the molten polymer was extracted as a strand from the lower part of the autoclave and cut to obtain 4500 g of thermoplastic resin pellets.

  The resulting thermoplastic resin had a number average molecular weight of 13,000, a melting point of 247 ° C., a type A durometer hardness of 99, an aromatic amide unit of 17% by weight, an aliphatic polyester unit of 29% by weight, and an aromatic polyester unit of 54% by weight. .

  Subsequently, using a compression molding machine set at 270 ° C., compression molding was performed on a sheet having a thickness of 2 mm and 1 mm, and TB and haze were measured. TB40 MPa, haze 65%, and excellent mechanical properties and transparency.

Example 4 (Synthesis of thermoplastic resin)
In a 15 L autoclave equipped with a nitrogen introduction tube, 607 g (1.4 mol) of compound (A), 2380 g (20.8 mol) of ε-caprolactone, and 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene [Ciba Specialty Chemicals Co., Ltd., trade name Irganox 1330] 3.17 g, NMP 3644 g are charged. After raising the temperature to 180 ° C., 1.42 g (4.2 mmol) of tetrabutyl titanate was added, ring-opening polymerization was carried out at 180 ° C. for 1 hour, and (a) an aromatic amide unit represented by the general formula (1) And (b) a prepolymer with an aliphatic polyester unit was obtained.

  Subsequently, as a compound containing an aromatic polyester unit, 370 g of polyethylene-2,6-naphthalate [manufactured by Teijin Kasei Co., Ltd., trade name Neotex TN8756] was added and reacted at 180 ° C. for 2 hours. Thereafter, 495 g (1.4 mol) of terephthaloyl bis (ε-caprolactam) was added and reacted at 180 ° C. for 2 hours. Thereafter, while raising the internal temperature to 250 ° C., NMP and ε-caprolactam as a by-product were distilled off under reduced pressure over 2 hours, and further reacted at 250 ° C. for 1 hour. Subsequently, after the inside of the system was pressurized with nitrogen, the molten polymer was extracted as a strand from the lower part of the autoclave and cut to obtain 3000 g of thermoplastic resin pellets.

  The obtained thermoplastic resin had a number average molecular weight of 18000, a melting point of 150 ° C., a type A durometer hardness of 88, an aromatic amide unit of 18% by weight, an aliphatic polyester unit of 62% by weight, and an aromatic polyester unit of 20% by weight. .

  Subsequently, using a compression molding machine set at 250 ° C., compression molding was performed on a sheet having a thickness of 2 mm and 1 mm, and TB and haze were measured. TB60 MPa, haze 38%, excellent mechanical properties and transparency.

Example 5 (Synthesis of thermoplastic resin)
In a 15 L autoclave equipped with a nitrogen introduction tube, 470 g (1.1 mol) of compound (A), 2456 g of ε-caprolactone (21.5 mol) and 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene [manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Irganox 1330] 3.07 g and NMP 2821 g were charged. After raising the temperature to 180 ° C., 1.46 g (4.3 mmol) of tetrabutyl titanate was added, ring-opening polymerization was performed at 180 ° C. for 1 hour, and (a) an aromatic amide unit represented by the general formula (1) And (b) a prepolymer with an aliphatic polyester unit was obtained.

  Subsequently, 1367 g of polyethylene terephthalate [manufactured by Teijin Chemicals Ltd., trade name PET resin TR8550T] as a compound containing an aromatic polyester unit was added and reacted at 180 ° C. for 1 hour. Thereafter, 383 g (1.1 mol) of terephthaloyl bis (ε-caprolactam) was added and reacted at 180 ° C. for 2 hours. Thereafter, while raising the internal temperature to 250 ° C., NMP and ε-caprolactam as a by-product were distilled off under reduced pressure over 2 hours, and further reacted at 250 ° C. for 1 hour. Subsequently, after the inside of the system was pressurized with nitrogen, the molten polymer was extracted as a strand from the lower part of the autoclave and cut to obtain 3900 g of thermoplastic resin pellets.

  The obtained thermoplastic resin had a number average molecular weight of 14,000, a melting point of 135 ° C., a type A durometer hardness of 78, an aromatic amide unit of 12% by weight, an aliphatic polyester unit of 48% by weight, and an aromatic polyester unit of 40% by weight. .

  Subsequently, using a compression molding machine set at 250 ° C., compression molding was performed on a sheet having a thickness of 2 mm and 1 mm, and TB and haze were measured. TB58 MPa, haze 20%, and excellent mechanical properties and transparency.

Example 6 (Synthesis of thermoplastic resin)
In a 15 L autoclave equipped with a nitrogen inlet tube, 875 g (2.0 mol) of compound (A), 1831 g (16.0 mol) of ε-caprolactone and 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene [manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Irganox 1330] 2.97 g and NMP 2706 g were charged. The temperature was raised to 200 ° C., 0.27 g (0.80 mmol) of tetrabutyl titanate was added, ring-opening polymerization was performed at 200 ° C. for 1 hour, and (a) an aromatic amide unit represented by the general formula (1) And (b) a prepolymer with an aliphatic polyester unit was obtained.

  Subsequently, 715 g (2.0 mol) of terephthaloyl bis (ε-caprolactam) was added and reacted at 200 ° C. for 2 hours. Thereafter, 1370 g of polyethylene terephthalate [manufactured by Teijin Kasei Co., Ltd., trade name PET resin TR8550T] was added as a compound containing an aromatic polyester unit, and reacted at 200 ° C. for 1 hour. Thereafter, while raising the internal temperature to 250 ° C., NMP and ε-caprolactam as a by-product were distilled off under reduced pressure over 2 hours, and further reacted at 250 ° C. for 1 hour. Subsequently, after the inside of the system was pressurized with nitrogen, the molten polymer was extracted as a strand from the lower part of the autoclave and cut to obtain 3900 g of thermoplastic resin pellets.

  The resulting thermoplastic resin had a number average molecular weight of 17,000, a melting point of 235 ° C., a type A durometer hardness of 97, an aromatic amide unit of 24% by weight, an aliphatic polyester unit of 39% by weight, and an aromatic polyester unit of 37% by weight. .

  Subsequently, using a compression molding machine set at 270 ° C., compression molding was performed on a sheet having a thickness of 2 mm and 1 mm, and TB and haze were measured. TB40 MPa, haze 66%, excellent mechanical properties and transparency.

Example 7 (Synthesis of thermoplastic resin)
In a 15 L autoclave equipped with a nitrogen inlet tube, 1024 g (2.3 mol) of compound (A), 2141 g (18.8 mol) of ε-caprolactone, and 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene [Ciba Specialty Chemicals Co., Ltd., trade name Irganox 1330] 3.47 g, NMP 3165 g were charged. After raising the temperature to 200 ° C., 0.32 g (0.94 mmol) of tetrabutyl titanate was added, ring-opening polymerization was carried out at 200 ° C. for 1 hour, and (a) an aromatic amide unit represented by the general formula (1) And (b) a prepolymer with an aliphatic polyester unit was obtained.

  Subsequently, as a compound containing an aromatic polyester unit, 415 g of polybutylene terephthalate [manufactured by Polyplastics Co., Ltd., trade name: PBT resin Duracon 2002] was added and reacted at 200 ° C. for 2 hours. Thereafter, 836 g (2.3 mol) of terephthaloyl bis (ε-caprolactam) was added and reacted at 200 ° C. for 2 hours. Thereafter, while raising the internal temperature to 240 ° C., NMP and ε-caprolactam as a by-product were distilled off under reduced pressure over 2 hours, and further reacted at 240 ° C. for 1 hour. Subsequently, after the inside of the system was pressurized with nitrogen, the molten polymer was extracted as a strand from the lower part of the autoclave and cut to obtain 3400 g of thermoplastic resin pellets.

  The resulting thermoplastic resin had a number average molecular weight of 18000, a melting point of 185 ° C., a type A durometer hardness of 97, an aromatic amide unit of 29% by weight, an aliphatic polyester unit of 56% by weight, and an aromatic polyester unit of 15% by weight. .

  Then, it compression-molded into the sheet | seat of thickness 2mm using the compression molding machine set to 250 degreeC, and measured TB. TB58 MPa and excellent mechanical properties.

Comparative Example 1 (Synthesis of a compound comprising (a) an aromatic amide unit represented by the general formula (1) and (b) an aliphatic polyester unit (hereinafter referred to as an aromatic amide block copolymer)
In a 15 L autoclave equipped with a nitrogen introduction tube, 759 g (1.7 mol) of compound (A), 1588 g (13.9 mol) of ε-caprolactone and 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (manufactured by Chiba Gaigi, trade name Irganox 1330) 2.57 g and NMP 4560 g were charged, and the temperature was raised to 180 ° C. Thereafter, 0.95 g (2.8 mmol) of tetrabutyl titanate was added, and ring-opening polymerization was performed at 180 ° C. for 1 hour. Subsequently, 620 g (1.7 mol) of terephthaloyl bis (ε-caprolactam) was added and reacted at 180 ° C. for 2 hours. Thereafter, while raising the internal temperature to 240 ° C., NMP and ε-caprolactam as a by-product were distilled off under reduced pressure over 2 hours, and further reacted at 240 ° C. for 1 hour. Subsequently, after the inside of the system was pressurized with nitrogen, the molten polymer was extracted as a strand from the lower part of the autoclave and cut to obtain 2100 g of aromatic amide block copolymer pellets.

  The obtained aromatic amide block copolymer had a number average molecular weight of 12,000, a melting point of 195 ° C., a type A durometer hardness of 98, and an aromatic amide unit of 34% by weight.

Subsequently, using a compression molding machine set at 250 ° C., compression molding was performed on a sheet having a thickness of 2 mm and 1 mm, and TB and haze were measured. TB51MPa and mechanical properties were excellent, but haze was 80% and poor transparency.

Claims (3)

(A) an aromatic amide unit represented by the following general formula (1); (b) one or more units selected from the group consisting of aliphatic polyesters, aliphatic polycarbonates or copolymers thereof; and (c). A thermoplastic resin comprising one or more aromatic polyester units selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, and polyethylene-2,6-naphthalate .

(Here, R ¹ and R ² each independently represent a divalent oxyalkylene group having 1 to 20 carbon atoms.) The thermoplastic resin according to claim 1, comprising (a) an aromatic amide unit represented by the general formula (1), (b) an aliphatic polyester unit, and (c) an aromatic polyester unit. . (B) The thermoplastic resin according to claim 1, wherein the aliphatic polyester unit is made of poly (ε-caprolactone).