JP2008069339A - Dendritic polyester, method for producing the same, and thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dendritic polyester and a thermoplastic resin composition blended with the same, wherein the resin can be remarkably improved in thin-wall fluidity, rigidity, gas barrier properties and the like and also to provide a thermoplastic resin composition containing such a dendritic polyester. <P>SOLUTION: The dendritic polyester contains at least one constituent unit selected from an aromatic oxycarbonyl unit (P), an aromatic and/or aliphatic dioxy unit (Q) and an aromatic dicarboxy unit (R), and a tri- or more-functional organic residue (B) and the content of (B) relative to the total monomers constituting the dendritic polyester is within the range of 7.5-50 mol%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention has a large number of functional groups controlled sterically, and by blending with a thermoplastic resin, the thin wall fluidity of the thermoplastic resin can be improved, and the thickness and weight can be reduced by improving gas barrier properties and rigidity. The present invention relates to a dendritic polyester capable of imparting effects such as

  In recent years, there has been an increasing demand for higher performance of plastics, and many polymers with various new performances have been developed and put on the market. Among them, optically anisotropic liquid crystals characterized by parallel arrangement of molecular chains Liquid crystalline polymers such as water-soluble polyesters are attracting attention because of their excellent moldability and mechanical properties, and demand is growing for injection molded products, mainly for electrical and electronic parts.

  However, the magnitude of anisotropy of liquid crystalline polymers often becomes a problem, and when used alone or in combination with other thermoplastic resins, the extremely large anisotropy is molded. This may limit the use and design of the product and may limit its use.

  Therefore, for the purpose of reducing anisotropy, it has been studied to introduce a branch by blending a trifunctional or tetrafunctional compound with a liquid crystalline polyester by copolymerization or kneading. (See Patent Document 1).

  In addition, it has been studied to introduce a similar branched structure in order to balance weld strength and moldability (see Patent Documents 2 and 3).

  Further, polyamides having a dendritic structure have been studied, and improvement of fluidity by blending these with thermoplastic resins has been studied (see Patent Documents 4 and 5).

  Patent Document 1 describes that the flow anisotropy is improved by introducing a small amount of a branched structure. However, when a crosslinking point is introduced into the liquid crystalline resin, the ordered structure of the liquid crystalline resin is destroyed. Therefore, the addition of a small amount of 1 to 3% has little effect, and the addition of 6% has deteriorated mechanical properties, the cross-linking point disturbs the liquid crystal structure, and the effect is well balanced. I can't say that.

  In Patent Document 2, a tri- and tetrafunctional structural unit is copolymerized with a liquid crystalline resin to study a high degree of polymerization, and although mechanical properties and weld strength are improved, it is not cross-linked. On the other hand, even if the molecular weight is the same, the melt viscosity is large and the fluidity is not improved.

  In Patent Document 3, a polyester oligomer having a four-branched structure is blended with a liquid crystalline resin to improve releasability and a good balance of mechanical properties and the like. It does not react positively, and if the amount added is increased, the performance is degraded by the decomposition gas, and this is not sufficient from the viewpoint of giving a branched structure to the liquid crystalline resin.

In Patent Documents 4 and 5, dendritic polymers having a heteroatom as a branch point are studied. However, when the heteropolymer has a branch point, thermal stability is not sufficient and sufficient performance cannot be obtained. .
JP-B-5-38007 (Pages 1, 2) JP-A-3-275715 (first page) JP-A-6-340797 (first page) JP-T-2005-513186 (1st page) JP 2000-264965 A (first page)

  The present invention improves the anisotropy, which is a characteristic of the liquid crystalline resin and is also a problem characteristic, has a high shear response, and has a large number of functional groups that are sterically controlled. However, because it is rich in reactivity and compatibility with various thermoplastic resins, blending it with thermoplastic resins improves the thin-wall fluidity of thermoplastic resins, and also improves gas barrier properties, rigidity, and weight reduction. It is an object of the present invention to provide a dendritic polyester that can be imparted with the following.

  As a result of intensive studies to solve the above-described problems, the present inventors have found that a dendritic polyester having a new structure and exhibiting liquid crystallinity can be obtained, and the present invention has been achieved.

  That is, the present invention relates to at least one structural unit selected from an aromatic oxycarbonyl unit (P), an aromatic and / or aliphatic dioxy unit (Q), and an aromatic dicarboxy unit (R) and a trifunctional group. It is a dendritic polyester containing the above organic residue (B) and having a B content in the range of 7.5 to 50 mol% with respect to all monomers constituting the dendritic polyester.

  Moreover, this invention contains the thermoplastic resin composition formed by mix | blending said dendritic polyester with a thermoplastic resin.

  The present invention also provides a monomer containing at least one structural unit selected from the structural unit represented by the following formula R1, and a single unit containing at least one structural unit selected from the structural unit represented by the following formula R2. A method for producing a dendritic polyester comprising reacting a monomer, a monomer containing at least one structural unit selected from structural units represented by the following formula R3, and a trifunctional or higher polyfunctional monomer: And a method for producing a dendritic polyester in which the addition amount (mol) of the polyfunctional compound is 7.5 mol% or more based on the addition amount (mol) of all monomers constituting the dendritic polyester.

    The dendritic polyester of the present invention has small anisotropy, excellent shear response, and has a large number of reactive functional groups, so by blending with a thermoplastic resin, thin-walled fluidity and rigidity, Gas barrier properties and the like can be significantly improved.

  The thermoplastic resin composition blended with the dendritic polyester of the present invention has excellent surface appearance (color tone) and mechanical properties, heat resistance, flame retardancy by a molding method such as normal injection molding, extrusion molding, and press molding. Can be processed into a molded article, sheet, pipe, film, fiber or the like having Among them, it is useful for a huge molded product having a thin wall portion, a fuel tank having a gas barrier property, and the like.

  The dendritic polyester of the present invention comprises at least one structural unit selected from an aromatic oxycarbonyl unit (P), an aromatic and / or aliphatic dioxy unit (Q), and an aromatic dicarboxy unit (R). It is a dendritic polyester which contains a trifunctional organic residue (B) and whose B content is in the range of 7.5 to 50 mol% with respect to all monomers constituting the dendritic polyester.

  Here, the aromatic oxycarbonyl unit (P), the aromatic and / or aliphatic dioxy unit (Q), and the aromatic dicarboxy unit (R) are structural units represented by the following formula (1), respectively. Preferably there is.

Here, R1 and R3 are each an aromatic residue. R2 is an aromatic residue or an aliphatic residue. R1, R2, and R3 may each include a plurality of structural units.

  Examples of the aromatic residue include a substituted or unsubstituted phenylene group, naphthylene group, and biphenylene group. Examples of the aliphatic residue include ethylene, propylene, and butylene. R1, R2 and R3 are preferably at least one or more structural units selected from structural units represented by the following formulas.

  In the formula, Y is at least one selected from a hydrogen atom, a halogen atom and an alkyl group. Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. In the formula, n is an integer of 2 to 8.

  In the dendritic polyester of the present invention, the trifunctional organic residue (B) is directly linked to each other by an ester bond and / or an amide bond, or via a structural unit selected from the above-mentioned P, Q and R which are branch structure parts. The basic skeleton is a three-branch branched structure that is bonded together. It is not necessary for all of the polymers to be composed of the basic skeleton, and other structures may be included at the ends, for example, for end-capping. The dendritic polyester may contain a structure in which all three functional groups of B are reacted, a structure in which only two are reacted, and a structure in which only one is reacted. Preferably, the structure in which all three functional groups of B have reacted is preferably 15 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more based on the entire B. B is preferably an organic residue of a trifunctional compound.

  The above three-branch basic skeleton is schematically represented by the formula (2).

  The dendritic polyester of the present invention preferably exhibits molten liquid crystallinity. The term “showing molten liquid crystallinity” means that the liquid crystal state is exhibited in a certain temperature range when the temperature is raised from room temperature. The liquid crystal state is a state showing optical anisotropy under shear.

  In order to exhibit molten liquid crystallinity, the basic skeleton in the case of three branches is composed of a structural unit in which the organic residue (B) is selected from P, Q and R as shown in the following formula (4) It is preferable that they are connected via the branch structure portion D.

  The trifunctional organic residue B is preferably an organic residue of a compound containing a functional group selected from a carboxyl group, a hydroxyl group and an amino group. For example, aliphatic compounds such as glycerol, 1,2,3-tricarboxypropane, diaminopropanol, diaminopropionic acid, trimesic acid, trimellitic acid, 4-hydroxy-1,2-benzenedicarboxylic acid, phloroglucinol, resorcin Residues of aromatic compounds such as acid, tricarboxynaphthalene, dihydroxynaphthoic acid, aminophthalic acid, 5-aminoisophthalic acid, aminoterephthalic acid, diaminobenzoic acid and melamine are preferably used. A residue of an aromatic compound represented by the following formula (3) is more preferable.

  Specific examples of the above trifunctional organic residues include residues such as phloroglucinol, trimesic acid, trimellitic acid, trimellitic anhydride, α-resorcylic acid, 4-hydroxy-1,2-benzenedicarboxylic acid Are preferred, more preferred are residues of trimesic acid and α-resorcylic acid, and most preferred are residues of trimesic acid.

  The aromatic hydroxycarbonyl unit (P), aromatic and / or aliphatic dioxy unit (Q), and aromatic dicarboxy unit (R) of the dendritic polyester constitute a branch structure portion between branches of the dendritic polyester. Unit. p, q and r are the average contents (molar ratio) of the structural units P, Q and R, respectively, and preferably in the range of p + q + r = 1 to 10 moles with respect to 1 mole of the content b of B. . p + q + r is more preferably in the range of 2 to 6 moles. If the branch length is too long, an effect such as shear responsiveness based on a rigid and detailed dendritic structure is reduced, which is not preferable.

  The values of p, q and r are determined by, for example, dissolving dendritic polyester in a mixed solvent of 50% by weight of pentafluorophenol and 50% by weight of deuterated chloroform, and performing nuclear magnetic resonance spectrum analysis of proton nuclei at 40 ° C. It can obtain | require from the peak intensity ratio derived from a structural unit. The average content is calculated from the peak area intensity ratio of each structural unit, and the three decimal places are rounded off. From the area intensity ratio with the peak corresponding to the content b of the branched structure B, the average chain length of the branched structure portion is calculated and set as the value of p + q + r. In this case, the three decimal places are rounded off.

  The ratio of p to q and the ratio of p to r (p / q, p / r) are preferably in the range of 5/95 to 95/5, more preferably 10/90 to 90/10, It is preferably 20/80 to 80/20. If it is this range, liquid crystallinity is easy to express and it is preferable. It is preferable to set the ratio of p / q and p / r to 95/5 or less because the melting point of the dendritic polyester can be within an appropriate range. Further, it is preferable that p / q and p / r be 5/95 or more because the melted liquid crystallinity of the dendritic polyester can be expressed.

  q and r are preferably substantially equimolar, but either component can be added in excess to control the end groups. The ratio of q / r is preferably in the range of 0.7 to 1.5, more preferably 0.9 to 1.1. Equimolar here means that the molar amount in the repeating unit is equal and does not include the terminal structure. Here, the term “end structure” means the end of the branch structure portion, and when the end is blocked, it means the end of the branch structure portion closest to the end.

  In the general formula (1), R1 is a structural unit derived from an aromatic oxycarbonyl unit, and specific examples thereof include a structural unit generated from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. . A structural unit derived from p-hydroxybenzoic acid is preferred, and a structural unit derived from 6-hydroxy-2-naphthoic acid can be used in combination. Further, a structural unit derived from an aliphatic hydroxycarboxylic acid such as glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid and the like may be contained as long as the effects of the present invention are not impaired.

  R2 is a structural unit derived from an aromatic and / or aliphatic dioxy unit, such as 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl. , T-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, ethylene glycol, Examples include structural units derived from 1,3-propylene glycol, 1,4-butanediol and the like. Preferably, it is a structural unit derived from 4,4′-dihydroxybiphenyl, hydroquinone and ethylene glycol, and includes a structural unit derived from 4,4′-dihydroxybiphenyl and hydroquinone or 4,4′-dihydroxybiphenyl and ethylene glycol. This is preferable from the viewpoint of controlling liquid crystallinity.

  R3 is a structural unit derived from an aromatic dicarbonyl unit such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4. , 4′-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid. A structural unit derived from terephthalic acid or isophthalic acid is preferred, and when both are used in combination, the melting point can be easily adjusted. A part of the structural unit derived from aliphatic dicarboxylic acid such as sebacic acid or adipic acid may be contained.

  The branch structure portion of the dendritic polyester of the present invention is preferably mainly composed of a polyester skeleton, but it is also possible to introduce a carbonate structure, an amide structure, a urethane structure, etc. to such an extent that the characteristics are not greatly affected. Among them, it is preferable to introduce an amide structure. By introducing such another bond, compatibility with a wide variety of thermoplastic resins can be adjusted, which is preferable. As a method for introducing an amide bond, p-aminobenzoic acid, m-aminobenzoic acid, p-aminophenol, m-aminophenol, p-phenylenediamine, m-phenylenediamine, tetramethylenediamine pentamethylenediamine, hexamethylene Diamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xyl Range amine, p-xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-Aminocyclohexyl Aliphatic, alicyclic or aromatic such as methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine It is preferable to copolymerize such an amine compound. Of these, copolymerization of p-aminophenol or p-aminobenzoic acid is preferred.

  Specific examples of the branch structure portion of the dendritic polyester include structural units derived from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, structural units derived from p-hydroxybenzoic acid, 6-hydroxy-2 A structural unit derived from naphthoic acid, a structural unit derived from 4,4′-dihydroxybiphenyl and a structural unit derived from terephthalic acid, a structural unit derived from p-hydroxybenzoic acid, a structure derived from 4,4′-dihydroxybiphenyl Units, structural units derived from terephthalic acid and structural units derived from isophthalic acid, structural units derived from p-hydroxybenzoic acid, structural units derived from 4,4′-dihydroxybiphenyl, structural units derived from hydroquinone, derived from terephthalic acid And a structural unit derived from isophthalic acid, p-hydroxy A structural unit derived from benzoic acid, a structural unit derived from ethylene glycol and a structural unit derived from terephthalic acid, a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from ethylene glycol, derived from 4,4′-dihydroxybiphenyl Structural units and structural units derived from terephthalic acid, structural units derived from p-hydroxybenzoic acid, structural units derived from hydroquinone, structural units derived from 4,4′-dihydroxybiphenyl, structural units derived from terephthalic acid, and 2, Consists of structural units derived from 6-naphthalenedicarboxylic acid, structural units derived from p-hydroxybenzoic acid, structural units derived from 6-hydroxy-2-naphthoic acid, structural units derived from hydroquinone and structural units derived from terephthalic acid Things.

  Particularly preferably, the branch structural part is composed of the following structural units (I), (II), (III), (IV) and (V), or the following structural units (I), (II): , (VI) and (IV).

  When the branch structure part is composed of the structural units (I), (II), (III), (IV) and (V), the content p of the structural unit (I) 30-70 mol% is preferable with respect to total p + q + r, More preferably, it is 45-60 mol%.

  Further, the content q (II) of the structural unit (II) is preferably 60 to 75 mol%, more preferably 65 to 73 mol% with respect to the total content q of the structural units (II) and (III). is there. Further, the content r (IV) of the structural unit (IV) is preferably 60 to 92 mol%, more preferably 60 to 70 mol%, with respect to the total content r of the structural units (IV) and (V). More preferably, it is 62-68 mol%.

  In such a case, it is preferable because the effects of the present invention, such as shear responsiveness and the addition effect to the thermoplastic resin, are remarkably exhibited.

  As described above, the total content q of the structural units (II) and (III) and the total content r of (IV) and (V) are preferably substantially equimolar. An excess may be added.

  When the branch structure part is composed of the structural units (I), (II), (VI) and (IV), the content p of the structural unit (I) is 30 to 90 with respect to p + q + r. The mol% is preferable, and 40 to 80 mol% is more preferable. Moreover, 70-5 mol% is preferable with respect to the total content q of (II) and (VI), and, as for content q (VI) of structural unit (VI), 60-8 mol% is more preferable. As described above, the content r of the structural unit (IV) is preferably substantially equimolar to the total content q of the structural units (II) and (VI). May be added.

  The terminal of the dendritic polyester of the present invention is preferably a carboxyl group, a hydroxyl group, an amino group, or a derivative thereof. Examples of the hydroxyl derivative or carboxylic acid derivative include alkyl esters such as methyl ester and aromatic esters such as phenyl ester and benzyl ester. It is also possible to end-block using a monofunctional epoxy compound, an oxazoline compound, an acid anhydride compound, or the like. The end-capping method includes adding a monofunctional organic compound in advance when synthesizing the dendritic polyester, or adding a monofunctional organic compound when the dendritic polyster skeleton is formed to some extent. The method etc. are mentioned.

  Specifically, when blocking the hydroxyl terminal or acetoxy terminal, benzoic acid, 4-t-butylbenzoic acid, 3-t-butylbenzoic acid, 4-chlorobenzoic acid, 3-chlorobenzoic acid, 4- It is possible by adding methylbenzoic acid, 3-methylbenzoic acid, 3,5-dimethylbenzoic acid, and the like.

  When blocking the carboxyl group end, acetoxybenzene, 1-acetoxy-4-t-butylbenzene, 1-acetoxy-3-t-butylbenzene, 1-acetoxy-4-chlorobenzene, 1-acetoxy-3 -It is possible by adding chlorobenzene, 1-acetoxy-4-cyanobenzene or the like.

  Theoretically, the end-capping is possible by adding an amount of the organic compound used for end-capping corresponding to the end group to be capped. It is preferable to use 1.005 times equivalent or more, more preferably 1.008 times equivalent or more of the organic compound used for terminal blocking with respect to the equivalent amount of the terminal group to be blocked. Moreover, it is preferable that the addition amount of the organic compound used for terminal blockage is 1.5 times equivalent or less.

  If the amount of the organic compound used for terminal blocking is too small, the terminal blocking is not sufficient. On the other hand, if the addition amount is too large, excess additives remain in the system, which is not preferable because the reaction rate is reduced or gas is generated.

  Further, the content of the organic residue B is 7.5 mol% or more with respect to the content of all monomers constituting the dendritic polyester, more preferably 10 mol% or more, still more preferably 20 mol%. That's it. In such a case, the chain length of the branch structure portion is preferable because the dendritic polyester is suitable for taking a dendritic form. The upper limit of the content of the organic residue B is 50 mol% or less, preferably 45 mol% or less, and more preferably 40 mol% or less.

  The dendritic polyester of the present invention may have a partially crosslinked structure as long as the properties are not affected.

  In the present invention, the method for producing the dendritic polyester is not particularly limited, and can be produced according to a known polyester polycondensation method. A monomer containing at least one structural unit selected from the structural unit represented by R1, a monomer containing at least one structural unit selected from the structural unit represented by R2, and R3 A method of reacting a monomer containing at least one structural unit selected from structural units and a trifunctional monomer, wherein the addition amount (mol) of the trifunctional monomer is dendritic. The method of manufacturing as 7.5 mol% or more with respect to all the monomers (mol) which comprise polyester is preferable. The addition amount of the trifunctional monomer is more preferably 10 mol% or more, and further preferably 20 mol% or more.

  In the above reaction, an embodiment in which a trifunctional monomer is reacted after acylating a monomer containing at least one structural unit selected from structural units represented by R1, R2, and R3 is also preferable. Also preferred is a mode in which a polymerization reaction is carried out after acylating a monomer containing at least one structural unit selected from structural units represented by R1, R2 and R3 and a trifunctional monomer.

A preferable production method will be described by taking as an example the production of a dendritic polyester composed of the structural units (I), (II), (III), (IV) and (V) and a trimesic acid residue. .
(1) After synthesizing a liquid crystalline polyester oligomer from p-acetoxybenzoic acid, 4,4'-diacetoxybiphenyl, diacetoxybenzene, terephthalic acid and isophthalic acid by deacetic acid condensation polymerization reaction, trimesic acid is added to remove acetic acid A method for producing by polymerization reaction.
(2) A method of producing from p-acetoxybenzoic acid, 4,4′-diacetoxybiphenyl, diacetoxybenzene, terephthalic acid, isophthalic acid and trimesic acid by a deacetic acid condensation polymerization reaction.
(3) p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid and isophthalic acid are reacted with acetic anhydride to acylate the phenolic hydroxyl group, and then the liquid crystalline polyester is subjected to deacetic acid polycondensation reaction. A method in which an oligomer is synthesized and further trimesic acid is added and subjected to a deacetic acid polymerization reaction.
(4) Acetic anhydride is reacted with p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid and trimesic acid to acylate the phenolic hydroxyl group, and then by deacetic acid polycondensation reaction. How to manufacture.
(5) After synthesizing a liquid crystalline polyester oligomer from a phenyl ester of p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid diphenyl ester and isophthalic acid diphenyl ester by dephenol polycondensation reaction, trimesic acid was added. In addition, a method of producing by dephenol polycondensation reaction.
(6) A method of producing from phenyl ester of p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl, hydroquinone, diphenyl ester of terephthalic acid, diphenyl ester of isophthalic acid and phenyl ester of trimesic acid by dephenol polycondensation reaction.
(7) After reacting p-hydroxybenzoic acid, terephthalic acid, isophthalic acid, and trimesic acid with diphenyl carbonate to form phenyl esters, respectively, 4,4′-dihydroxybiphenyl and hydroquinone are added, and dephenol polycondensation reaction is performed. How to manufacture.

  Of these, the production methods (1) to (5) are preferred, the methods (3) and (4) are more preferred, and the production method (3) is most preferred from the viewpoint of chain length control and steric regulation.

  In the production method of (3), the amount of acetic anhydride used is preferably 0.95 equivalents or more and 1.10 equivalents or less, and 1.00 equivalents or more and 1.10 equivalents or less in terms of chain length control. The amount is more preferably 08 equivalents or less, and most preferably 1.02 equivalents or more and 1.05 equivalents or less. It is possible to control the terminal group by controlling the amount of acetic anhydride or adding an excess of either a dihydroxy monomer or a dicarboxylic acid monomer.

  In order to increase the molecular weight, an amount corresponding to the amount of carboxylic acid of trimesic acid is added in excess of dihydroxy monomer such as hydroquinone or 4,4′-dihydroxybiphenyl to the dicarboxylic acid monomer, and the carboxylic acid in all monomers is increased. The acid and the hydroxyl equivalent are preferably combined. On the other hand, when the carboxylic acid is intentionally left in the terminal group, it is preferable not to add the dihydroxy monomer as described above excessively. Furthermore, when the hydroxyl group is intentionally left at the terminal, the dihydroxy monomer is added in excess of the carboxylic acid equivalent of trimesic acid, and the amount of acetic anhydride used is less than 1.00 equivalent of the phenolic hydroxyl group. preferable.

  By these methods, the dendritic polyester of the present invention can be selectively provided with a terminal group structure rich in reactivity with various thermoplastic resins. However, depending on the thermoplastic resin used as the matrix, the dispersion state may be more easily controlled by blocking the ends with a monofunctional epoxy compound or the like in order to suppress excessive reactivity.

  When the deacetic acid polycondensation reaction is performed, a melt polymerization method in which the reaction is carried out at a temperature at which the dendritic polyester melts, optionally under reduced pressure, to distill a predetermined amount of acetic acid and to complete the polycondensation reaction, is preferable. For example, in a reaction vessel equipped with a predetermined amount of p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid and acetic anhydride, equipped with a stirring blade and a distillation pipe, and provided with a discharge port at the bottom. Prepare. The mixture is heated with stirring under a nitrogen gas atmosphere to acetylate the hydroxyl group, and then heated to 200 to 350 ° C. to perform a deacetic acid polycondensation reaction to distill acetic acid. When acetic acid is distilled to 50% of the theoretical distillation amount, a predetermined amount of trimesic acid is added and acetic acid is further distilled to 91% of the theoretical distillation amount to complete the reaction.

  As conditions for acetylation, the reaction temperature is preferably in the range of 130 to 170 ° C, more preferably in the range of 135 to 155 ° C. The reaction time is preferably 0.5 to 6 hours, more preferably 1 to 2 hours.

  The polycondensation temperature is a temperature at which the dendritic polyester is melted, and is preferably a melting point of the dendritic polyester + 10 ° C. or higher. Specifically, for example, it is in the range of 200 to 350 ° C, and preferably 240 to 280 ° C. The atmosphere for polycondensation is satisfactory even under atmospheric pressure nitrogen, but a reduced pressure is preferable because the reaction proceeds faster and the residual acetic acid in the system decreases. The degree of vacuum is preferably 0.1 mmHg (13.3 Pa) to 200 mmHg (26600 Pa), more preferably 10 mmHg (1330 Pa) to 100 mmHg (13300 Pa). Note that acetylation and polycondensation may be carried out continuously in the same reaction vessel, or acetylation and polycondensation may be carried out in different reaction vessels.

After the polycondensation reaction is completed, the reaction vessel is kept at a temperature at which the dendritic polyester melts, and is pressurized to, for example, 0.01 to 1.0 kg / cm ² (0.001 to 0.1 MPa), and the bottom of the reaction vessel The dendritic polyester is discharged in a strand form from the discharge port provided in. A mechanism that opens and closes intermittently is provided at the discharge port, and it is also possible to discharge liquid droplets. The discharged dendritic polyester is cooled by passing through air or water, and then cut or pulverized as necessary.

  The obtained pellet-like, granular or powdery dendritic polyester further removes water, acetic acid and the like by heat drying or vacuum drying, if necessary. Further, in order to finely adjust the degree of polymerization, or to further increase the degree of polymerization, solid phase polymerization can also be performed. In the solid phase polymerization, for example, the dendritic polyester obtained as described above is subjected to a temperature range of a melting point of the dendritic polyester of −5 ° C. to a melting point of −50 ° C. (for example, 200 to 300 ° C.) under a nitrogen stream or under reduced pressure. And heating for 1 to 50 hours.

  The polycondensation reaction of the dendritic polyester proceeds even without catalyst, but metal compounds such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and magnesium metal can also be used.

  The dendritic polyester of the present invention preferably has a number average molecular weight of 1,000 to 40,000, more preferably 1,000 to 20,000, still more preferably 1,000 to 10,000, Preferably it is the range of 1,000-5,000. The number average molecular weight is a value measured as an absolute molecular weight by a GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which the dendritic polyester is soluble.

  The melt viscosity of the dendritic polyester in the present invention is preferably 0.01 to 30 Pa · s, more preferably 0.5 to 20 Pa · s, and particularly preferably 1 to 10 Pa · s. In addition, this melt viscosity is a value measured by a Koka flow tester under the condition of a shear rate of 100 / s under the condition of the liquid crystal starting temperature of the dendritic polyester + 10 ° C.

  The dendritic polyester of the present invention thus obtained exhibits melt liquid crystallinity, has high shear response, and exhibits high elastic modulus and high gas barrier properties, so that it can be used alone as a resin material, coating agent and the like.

  Moreover, unlike the conventional liquid crystalline polyester, the dendritic polyester of the present invention has a large number of terminal groups. Therefore, when blended in a thermoplastic resin, it can be well dispersed in the thermoplastic resin and impart properties such as high shear response, high elastic modulus and high gas barrier properties without degrading the properties of the thermoplastic resin. it can.

  The thermoplastic resin used in the thermoplastic resin composition of the present invention is not particularly limited as long as it is a resin exhibiting thermoplasticity. For example, styrene resin, fluororesin, polyoxymethylene, polyamide polyester polyimide, polyamideimide, Vinyl chloride, olefin resin, thermoplastic elastomer, polyacrylate, polyphenylene ether, polycarbonate, polyethersulfone, polyetherimide, polyetherketone, polyetheretherketone, polyarylene sulfide such as polyphenylene sulfide, cellulose acetate, cellulose acetate butyrate Examples thereof include cellulose derivatives such as rate, ethyl cellulose, liquid crystal resins, and the like, and one or more blends thereof.

  Examples of styrene resins include PS (polystyrene), HIPS (high impact polystyrene), AS (acrylonitrile / styrene copolymer), AES (acrylonitrile / ethylene / propylene / non-conjugated diene rubber / styrene copolymer), ABS (acrylonitrile / Butadiene / styrene copolymer), MBS (methyl methacrylate / butadiene / styrene copolymer), and the like.

  Examples of the olefin resin include polypropylene, polyethylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / propylene / nonconjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / methacrylic acid. Examples thereof include glycidyl copolymers, ethylene / vinyl acetate / glycidyl methacrylate copolymers and ethylene / propylene-g-maleic anhydride copolymers, methacrylic acid / methyl methacrylate / glutaric anhydride copolymers, and the like.

  Examples of the thermoplastic elastomer include a polyester polyether elastomer, a polyester polyester elastomer, a thermoplastic polyurethane elastomer, a thermoplastic styrene butadiene elastomer, a thermoplastic olefin elastomer, and a thermoplastic polyamide elastomer.

  Polyamides include nylon 6 (polycaproamide), nylon 66 (polyhexamethylene adipamide), nylon 12 (polydodecanamide), nylon 610 (polyhexamethylene sebacamide), nylon 6/66 copolymer (polycapro). Amide / polyhexamethylene adipamide copolymer) and the like. Also, nylon 6T / 66 copolymer (polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer), nylon 6T / 6I copolymer (polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer), nylon 6T / M5T copolymer (poly Hexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer), nylon 6T / 12 copolymer (polyhexamethylene terephthalamide / polydodecanamide copolymer), nylon 66 / 6T / 6I copolymer (polyhexamethylene adipamide / Polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer) and nylon 6T / 6 copolymer (polycaproamide / polyhexamene) Copolymer having hexamethylene terephthalamide units such terephthalamide copolymer) is also preferred. Furthermore, it is also practically preferable to use a plurality of these polyamide resins as a mixture depending on required properties such as impact resistance and molding processability.

  The degree of polymerization of these polyamide resins is not particularly limited, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is in the range of 1.5 to 7.0. Nylon in the range of 2.0 to 6.0 is particularly preferable.

  When the polyamide resin is a copolymer having hexamethylene terephthalamide units, it is preferable because of high heat resistance. In this case, the melting point is preferably 200 ° C. or higher from the viewpoint of heat resistance, more preferably 250 ° C. or higher, and particularly preferably 280 ° C. or higher. Further, when the melting point exceeds 340 ° C., decomposition is likely to occur during melt processing. Therefore, the melting point is preferably 340 ° C. or less, more preferably 330 ° C. or less, and particularly preferably 320 ° C. or less. In this case, the dicarboxylic acid component is preferably composed of 40 to 100 mol% of terephthalic acid component units, and an aromatic dicarboxylic acid component other than terephthalic acid and / or 0 to 60% of aliphatic dicarboxylic acid units.

  For the polyamide resin, a copper compound is preferably used as an additive for improving long-term heat resistance. Of these, monovalent copper compounds, particularly monovalent copper halide compounds are preferred, and cuprous acetate, cuprous iodide, and the like can be exemplified as particularly suitable copper compounds. The addition amount of the copper compound is preferably 0.01 to 2 parts by weight, more preferably 0.015 to 1 part by weight with respect to 100 parts by weight of nylon. If the amount added is too large, liberation of metallic copper occurs during melt molding, and the value of the product is reduced by coloring. It is also possible to add an alkali halide in combination with a copper compound. As examples of the alkali halide compound, potassium iodide and sodium iodide are particularly preferable.

  The polyester is preferably a polymer or copolymer having a main structural unit of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative. Among them, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, Aromatic polyester resins such as polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, and polybutylene terephthalate / naphthalate are particularly preferred, and polybutylene terephthalate is most preferred. In these polymers, the ratio of the terephthalic acid unit to the total dicarboxylic acid is preferably 30 mol% or more, and more preferably 40 mol% or more.

  Further, the polyester may contain one or more selected from hydroxycarboxylic acids or ester-forming derivatives thereof and lactones. Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, and 6-hydroxy-2-naphthoic acid. Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Examples of the polymer or copolymer having these as a structural unit include aliphatic polyester resins such as polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, polyhydroxybutyric acid / β-hydroxybutyric acid / β-hydroxyvaleric acid. It is done.

  The melting point of the polyester is not particularly limited, but is preferably 120 ° C or higher, more preferably 180 ° C or higher, further preferably 200 ° C or higher, and 220 ° C or higher in terms of heat resistance. It is particularly preferred. Although an upper limit is not specifically limited, It is preferable that it is 300 degrees C or less, and it is more preferable that it is 280 degrees C or less. The melting point of the polyester is a value measured with a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min.

  The amount of the carboxyl terminal group of the polyester is not particularly limited, but is preferably 50 eq / t or less, more preferably 30 eq / t or less, in terms of fluidity, hydrolysis resistance and heat resistance, and 20 eq / It is more preferably t or less, and particularly preferably 10 eq / t or less. The lower limit is 0 eq / t. In the present invention, the carboxyl end group amount of the (A) polyester resin is a value measured by dissolving in o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.

  The viscosity of the polyester is not particularly limited as long as melt kneading is possible, but in terms of moldability, the intrinsic viscosity when the o-chlorophenol solution is measured at 25 ° C. is in the range of 0.36 to 1.60 dl / g. And is more preferably in the range of 0.50 to 1.25 dl / g.

  The molecular weight of the polyester resin is not particularly limited, but in terms of heat resistance, the weight average molecular weight (Mw) is preferably in the range of 50,000 to 500,000, more preferably in the range of 100,000 to 300,000. More preferably, it is in the range of 150,000 to 250,000. In the present invention, the molecular weight of the polyester is a value measured by gel permeation chromatography (GPC).

  The method for producing the polyester is not particularly limited, and can be produced by a known polycondensation method or ring-opening polymerization method. Either batch polymerization or continuous polymerization may be used, and any of transesterification and direct polymerization can be applied.

  Among these resins, those classified as engineering plastics are preferable, and specifically, polyamide, polyester, polycarbonate, polyarylene sulfide, and the like are preferable. Particularly preferred are nylon 6, nylon 66, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyphenylene sulfide and the like.

  Since the resin selected from polyamide and polyester has reactivity with the terminal functional group of the dendritic polyester, it is preferable because a good effect is exhibited.

  The melt viscosity of the thermoplastic resin is not limited, but is preferably 10 to 300 Pa · s, more preferably 15 to 200 Pa · s, and particularly preferably 20 to 100 Pa · s. When the melt viscosity of the thermoplastic resin is too low, it is difficult to cause a shearing force sufficient to cause a volume change of the dispersed dendritic polyester, and the effect is hardly exhibited. On the other hand, when the melt viscosity of the thermoplastic resin is too high, the dispersion in the resin becomes insufficient, and the effect is hardly exhibited. The melt viscosity is a value measured by a Koka flow tester under the condition of the melting point of the thermoplastic resin + 10 ° C. and the shear rate of 1000 / s.

  In the thermoplastic resin composition of the present invention, the amount of the dendritic polyester based on 100 parts by weight of the thermoplastic resin is preferably 0.01 to 99 parts by weight, more preferably 0.1 to 50 parts by weight, and still more preferably. 0.5 to 20 parts by weight. When the blending amount is in the above range, the effect of the present invention is remarkably obtained, which is preferable.

  In the thermoplastic resin composition of the present invention, a filler can be further blended in order to impart mechanical strength and other characteristics. Any filler such as fibrous, plate-like, powdery, granular, etc. can be used. As the filler, any of a fibrous filler and a non-fibrous filler can be used. Fiber fillers include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone Examples include koji fiber and metal fiber. Non-fibrous fillers include silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, silicon oxide, magnesium oxide, alumina, zirconium oxide, Metal compounds such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate, water Examples thereof include hydroxides such as calcium oxide, magnesium hydroxide and aluminum hydroxide, glass flakes, glass powder, carbon black and silica, and graphite. Also, smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, and various clay minerals such as vermiculite, halloysite, kanemite, kenyaite, zirconium phosphate, and titanium phosphate, Li-type fluorine teniolite, Na-type fluorine Layered silicates represented by swellable mica such as teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica are also used.

  Among these fillers, glass fiber, talc, wollastonite, montmorillonite and synthetic mica are preferable. Glass fiber having a large effect of improving mechanical strength is particularly preferably used. Moreover, a filler can also be used in combination of 2 or more types.

  The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like. Also, weakly alkaline glass fibers are excellent in terms of mechanical strength and can be preferably used. The glass fiber is preferably treated with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, an epoxy-based, urethane-based, acrylic-based coating or sizing agent, and preferably with an epoxy-based sizing agent. Particularly preferred. The glass fiber is preferably treated with a silane-based or titanate-based coupling agent or other surface treatment agent, and an epoxysilane-based or aminosilane-based coupling agent is particularly preferable.

  The blending amount of the filler is preferably 0.01 to 400 parts by weight, more preferably 0.05 to 150 parts by weight, and particularly preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin. .

  The thermoplastic resin composition of the present invention further includes an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites, and substituted products thereof), an ultraviolet absorber (for example, resorcinol, salicylate), and a flame retardant. (Bromine, phosphorus, metal hydroxide, etc.), impact resistance improver (olefin elastomer, polyester elastomer, etc.), anti-coloring agent (phosphite, hypophosphite, etc.), lubricant and release agent Mold additives (stearic acid, montanic acid and their metal salts, etc.), coloring agents, conductive agents or usual additives such as carbon black, crystal nucleating agents, plasticizers and antistatic agents as coloring agents, or thermoplastic resins Polymers other than can be blended.

  The method for producing the thermoplastic resin composition of the present invention is preferably by melt kneading. A known method can be used for melt kneading. For example, using a Banbury mixer, rubber roll machine, kneader, single screw or twin screw extruder, the resin composition can be obtained by melt-kneading at a temperature equal to or higher than the melting temperature of the thermoplastic resin. Among these, a method using a twin screw extruder is preferable.

  As kneading methods, 1) a method of kneading thermoplastic resin, dendritic polyester, optional fillers and other additives at once, and 2) a thermoplastic resin containing a high concentration of other additives in the thermoplastic resin. A method of preparing a resin composition (master pellet) and then adding a liquid thermoplastic resin, a dendritic polyester, an optional filler, and the remaining additives to a specified concentration (master pellet method), 3 ) Split addition method that kneads a part of thermoplastic resin and dendritic polyester and other additives, and then adds the remaining thermoplastic resin, dendritic polyester, optional filler and remaining additive, etc. Any method can be used.

  The thermoplastic resin composition of the present invention thus obtained has a good dispersion state between the thermoplastic resin and the dendritic polyester, and has a thin-walled fluidity, rigidity, and gas barrier properties without deteriorating the properties of the thermoplastic resin. These properties are imparted to the thermoplastic resin.

  The thermoplastic resin composition of the present invention is a molded article having excellent surface appearance (color tone) and mechanical properties, sheet, pipe, film, fiber, etc., by a molding method such as normal injection molding, extrusion molding, or press molding. Can be processed. Among them, it is useful for large injection molded products such as automobile parts, huge injection molded products having a thin part having a thickness of 0.01 to 1.0 mm, and fuel tanks having gas barrier properties.

  The thermoplastic resin composition thus obtained is used for electrical / electronic parts, household / office electrical product parts, building parts, fishery-related parts, civil engineering-related parts, automotive underhood parts, automotive interior parts, automotive use. Useful as exterior parts, various automotive connectors, machine parts, agricultural components, sanitary products, medical supplies, containers / packaging, clothing, interior goods, etc. Especially useful as automotive interior parts, automotive exterior parts, and automotive connectors It is.

  Specifically, examples of electrical / electronic components include a relay case, a coil bobbin, an optical pickup chassis, a motor case, a laptop computer housing, and internal components. Examples of home / office electrical product parts include VTR parts, TV parts, lighting parts, refrigerator parts, air conditioner parts, and the like. Examples of building members include sash doors, blind curtain parts, piping joints, curtain liners, and the like. Examples of fishery-related members include fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags, and the like. Examples of civil engineering-related members include vegetation nets, vegetation mats, grass barrier bags, grass barrier nets, curing sheets, and slope protection sheets. Examples of underhood parts for automobiles include air flow meters, air pumps, various cases, various tubes, various tanks, and the like. Examples of automotive interior parts include torque control levers, safety belt parts, register blades, and washer levers. Examples of exterior parts for automobiles include roof rails, fenders, bumpers, door mirror stays, and door handles. Examples of various automobile connectors include wire harness connectors, SMJ connectors, PCB connectors, and door grommet connectors.

  The thermoplastic resin composition of the present invention and a molded product comprising the same can be recycled. For example, a resin composition obtained by pulverizing a resin composition and a molded product comprising the resin composition, preferably powdered, and then adding additives as necessary, is used in the same manner as the resin composition of the present invention. It can also be a molded product.

  Hereinafter, although an example explains the present invention still in detail, the gist of the present invention is not limited only to the following example.

Example 1
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 66.3 g (0.48 mol) of p-hydroxybenzoic acid, 8.38 g (0.045 mol) of 4,4′-dihydroxybiphenyl, and terephthalic acid 7. 48 g (0.045 mol), 14.41 g (0.075 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 62.48 g of acetic anhydride (1.00 equivalent of total phenolic hydroxyl groups) The reaction was conducted at 145 ° C. for 2 hours with stirring under a nitrogen gas atmosphere. Thereafter, 31.52 g (0.15 mol) of trimesic acid was added, the temperature was raised to 260 ° C., and the mixture was stirred for 3 hours. When 91% of acetic acid was distilled from the theoretical distillate, heating and stirring were stopped. The object was discharged into cold water.

  The obtained dendritic polyester (A-1) was subjected to nuclear magnetic resonance spectrum analysis. As a result, the content p of p-oxybenzoate units was 2.66, 4,4′-di with respect to the trimesic acid residue. The content q of oxybiphenyl units and ethylene oxide units was 0.66, the content r of terephthalate units was 0.66, and p + q + r = 4. At the end, carboxylic acid and acetyl groups were present in a ratio of 64:36.

  In addition, the degree of branching was calculated as the ratio of the three functional groups of trimesic acid that had reacted with all three.

  For the nuclear magnetic resonance spectrum, the sample was dissolved in a mixed solvent of 50% pentafluorophenol: 50% deuterated chloroform and measured at 40 ° C., and the nuclear magnetic resonance spectrum analysis of the proton nucleus was performed. 7.44 ppm and 8.16 ppm peaks derived from p-oxybenzoate units, 7.04 ppm, 7.70 ppm peaks derived from 4,4′-dioxybiphenyl units, 8.31 ppm peaks derived from terephthalate units, ethylene oxide units A peak at 4.75 ppm derived from 9.25 ppm derived from trimesic acid was detected. The content ratio of each structural unit was calculated from the area intensity ratio of each peak, and the three decimal places were rounded off. From the ratio of the peak area intensity derived from the branch structure parts P, Q and R and the peak area intensity derived from the organic residue B, the contents p, q, r and the content of the branch point B were calculated. Moreover, the presence or absence of the reaction of carboxylic acid was determined from the peak shift of three protons of trimesic acid, the degree of branching was calculated, and the three decimal places were rounded off.

  The obtained dendritic polyester had a melting point Tm of 185 ° C., a liquid crystal starting temperature of 159 ° C., and a number average molecular weight of 2300. The melt viscosity measured using a Koka flow tester at a temperature of 189 ° C. and a shear rate of 100 / s was 12 Pa · s.

  In addition, melting | fusing point (Tm) is Tm1 + 20 degreeC temperature after observation of the endothermic peak temperature (Tm1) observed when dendritic polyester is measured on the temperature increase conditions from room temperature in 20 degreeC / min in differential calorimetry. For 5 minutes, once cooled to room temperature under a temperature drop condition of 20 ° C./min, and again as an endothermic peak temperature (Tm) observed when measured under a temperature rise condition of 20 ° C./min.

  The liquid crystal starting temperature is measured with a shear stress heating device (CSS-450) at a shear rate of 100 (1 / second), a heating rate of 5.0 ° C./min, and an objective lens 60 times, and the temperature at which the entire field of view starts to flow. It was.

  The molecular weight was measured by GPC-LS (gel permeation chromatography-light scattering) method using pentafluorophenol which is a solvent in which the dendritic polyester is soluble, and the number average molecular weight was determined.

The obtained dendritic polyester was evaluated in (1) to (3). The results are shown in Table 2.
(1) Shear responsiveness Using a Koka flow tester, at a liquid crystal starting temperature of + 30 ° C., a melt viscosity (η ₁₀₀ ) measured at a shear rate of 100 / s and a melt viscosity measured at a shear rate of 1,000 / s (η ₁₀₀₀ ) ratio (η ₁₀₀ / η ₁₀₀₀ ) was evaluated. The greater the shear response, the richer the liquid crystallinity, the fewer burrs, and the low pressure molding becomes possible.
(2) Rigidity Using a FANUC 30α-C injection molding machine, dendritic polyester was molded at a liquid crystal starting temperature of + 30 ° C. at a single pressure to obtain a test piece having a thickness of 1 mm × width 6.2 mm × length 40 mm. . About the obtained test piece, the storage elastic modulus in 25 degreeC was measured by the double-end bending test (frequency 1Hz) method using the dynamic-viscoelasticity measuring apparatus (vibron).

As for anisotropy, a test piece having a thickness of 1 mm × width of 6.2 mm × length of 40 mm cut out in the flow direction from a square plate having a thickness of 1 mm × 40 mm square molded in the same manner using the above molding machine and a right angle The storage elastic modulus of a test piece having a thickness of 1 mm, a width of 6.2 mm, and a length of 40 mm cut out in the direction was measured, and the ratio was evaluated.
(3) Gas barrier property GTR-10 (manufactured by Yanaco Analytical Industries) is used for the gas barrier property of a square plate having a thickness of 1 mm × 60 mm square molded in the same manner using the above molding machine in accordance with the JISK7126 A method (differential pressure method). And measured at 35 ° C. Hydrogen was used as the gas.

Example 2
Raw material monomers were p-hydroxybenzoic acid 58.01 g (0.42 mol), 4,4′-dihydroxybiphenyl 23.46 g (0.126 mol), hydroquinone 5.95 g (0.054 mol), terephthalate Acid 19.44 g (0.117 mol), isophthalic acid (0.063 mol), acetic anhydride 79.63 g (1.00 equivalent of total phenolic hydroxyl groups) and trimesic acid 31.52 g (0.15 mol) Except that, dendritic polyester was obtained in the same manner as in Example 1. The obtained dendritic polyester was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 3
The raw material monomers were p-hydroxybenzoic acid 58.01 g (0.42 mol), 4,4′-dihydroxybiphenyl 65.36 g (0.351 mol), hydroquinone 5.95 g (0.054 mol), terephthalate Changed to 19.44 g (0.117 mol) of acid, isophthalic acid (0.063 mol), 83.61 g of acetic anhydride (1.05 equivalent of total phenolic hydroxyl groups) and 31.52 g (0.15 mol) of trimesic acid Except that, dendritic polyester was obtained in the same manner as in Example 1. The obtained dendritic polyester was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 4
The raw material monomers were p-hydroxybenzoic acid 58.01 g (0.42 mol), 4,4′-dihydroxybiphenyl 70.95 g (0.381 mol), hydroquinone 5.95 g (0.054 mol), terephthalate Changed to 19.44 g (0.117 mol) of acid, isophthalic acid (0.063 mol), 75.65 g of acetic anhydride (0.95 equivalent of total phenolic hydroxyl groups) and 31.52 g (0.15 mol) of trimesic acid Except that, dendritic polyester was obtained in the same manner as in Example 1. The obtained dendritic polyester was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 5
Raw material monomers were p-hydroxybenzoic acid 60.50 g (0.44 mol), 6-hydroxy-2-naphthoic acid 30.49 g (0.162 mol), 4,4-dihydroxybiphenyl 18.62 g (0 .10 mol), 61.25 g of acetic anhydride (1.00 equivalent of the total phenolic hydroxyl group) and 31.52 g (0.176 mol) of trimesic acid Got. The obtained dendritic polyester was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 6
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 58.01 g (0.42 mol) of p-hydroxybenzoic acid, 23.46 g (0.126 mol) of 4,4′-dihydroxybiphenyl, 5.95 g of hydroquinone. (0.054 mol), 19.44 g (0.117 mol) of terephthalic acid, isophthalic acid (0.063 mol) and 79.63 g of acetic anhydride (1.00 equivalent of total phenolic hydroxyl groups) were charged in a nitrogen gas atmosphere. The reaction was allowed to proceed at 145 ° C. for 2 hours with stirring. Thereafter, 31.52 g (0.15 mol) of trimesic acid was added, the temperature was raised to 260 ° C., the mixture was stirred for 3 hours, and the pressure was further reduced to 26600 Pa. When 93% of the theoretical distillation amount of acetic acid was distilled, heating and stirring were stopped, and the contents were discharged into cold water. The obtained dendritic polyester was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 7
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 58.01 g (0.42 mol) of p-hydroxybenzoic acid, 23.46 g (0.126 mol) of 4,4′-dihydroxybiphenyl, 5.95 g of hydroquinone. (0.054 mol), 19.44 g (0.117 mol) of terephthalic acid, isophthalic acid (0.063 mol) and 79.63 g of acetic anhydride (1.00 equivalent of total phenolic hydroxyl groups) were charged in a nitrogen gas atmosphere. The reaction was allowed to proceed at 145 ° C. for 2 hours with stirring. Thereafter, 31.52 g (0.15 mol) of trimesic acid was added, the temperature was raised to 260 ° C., the mixture was stirred for 3 hours, and the pressure was further reduced to 13300 Pa. When 96% of the theoretical distillation amount of acetic acid was distilled, heating and stirring were stopped, and the contents were discharged into cold water. The obtained dendritic polyester was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 8
Raw material monomers were p-hydroxybenzoic acid 58.01 g (0.42 mol), 4,4′-dihydroxybiphenyl 23.46 g (0.126 mol), hydroquinone 5.95 g (0.054 mol), terephthalate Acid 19.44 g (0.117 mol), isophthalic acid (0.063 mol), acetic anhydride 79.63 g (1.00 equivalent of total phenolic hydroxyl groups) and trimesic acid 15.13 g (0.072 mol) Except that, dendritic polyester was obtained in the same manner as in Example 1. The obtained dendritic polyester was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 9
Raw material monomers were p-hydroxybenzoic acid 58.01 g (0.42 mol), 4,4′-dihydroxybiphenyl 23.46 g (0.126 mol), hydroquinone 5.95 g (0.054 mol), terephthalate The acid was changed to 19.44 g (0.117 mol), isophthalic acid (0.063 mol) and 79.63 g of acetic anhydride (1.00 equivalent of the total phenolic hydroxyl group), and α-resorcylic acid 23 instead of trimesic acid A dendritic polyester was obtained in the same manner as in Example 1 except that .12 g (0.15 mol) was used. The obtained dendritic polyester was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 10
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 58.01 g (0.42 mol) of p-hydroxybenzoic acid, 65.368 g (0.351 mol) of 4,4′-dihydroxybiphenyl, 5.95 g of hydroquinone. (0.054 mol), terephthalic acid 19.44 g (0.117 mol), isophthalic acid (0.063 mol), trimesic acid 31.52 g (0.15 mol) and acetic anhydride 83.61 g (total phenolic hydroxyl groups) And stirred at 145 ° C. for 2 hours with stirring under a nitrogen gas atmosphere. Thereafter, the temperature was raised to 280 ° C., and the mixture was stirred for 3 hours. When 91% of acetic acid was distilled out, 12.2 g of benzoic acid (0.100 mol; 1.000 times the theoretical acetoxy terminal) When acetic acid was distilled off to 100%, heating and stirring were stopped, and the contents were discharged into cold water. The obtained dendritic polyester was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 11
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 66.30 g (0.48 mol) of p-hydroxybenzoic acid, 8.38 g (0.045 mol) of 4,4′-dihydroxybiphenyl, and terephthalic acid 7. 48 g (0.045 mol), 14.40 g (0.075 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, 42.72 g (0.28 mol) of α-resorcillic acid, and acetic anhydride 78 .26 g (1.08 equivalent of the total of phenolic hydroxyl groups) was charged and reacted at 145 ° C. for 2 hours with stirring under a nitrogen gas atmosphere. Thereafter, the temperature was raised to 260 ° C., and the mixture was stirred for 3 hours. When 91% of acetic acid was distilled out, 25.6 g of benzoic acid (0.21 mol; 1.000 times the theoretical acetoxy terminal). When acetic acid was distilled off to 100%, heating and stirring were stopped, and the contents were discharged into cold water. The obtained dendritic polyester was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Comparative Example 1
Raw material monomers were 66.3 g (0.48 mol) of p-hydroxybenzoic acid, 8.38 g (0.045 mol) of 4,4′-dihydroxybiphenyl, 7.48 g (0.045 mol) of terephthalic acid, The inherent viscosity was changed to 14.41 g (0.075 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 62.48 g of acetic anhydride (1.00 equivalent of the total phenolic hydroxyl group), and trimesic acid was added. A polyester (B-1) was obtained in the same manner as in Example 1 except that it was not present. The obtained polyester was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Comparative Example 2
Raw material monomers were 66.3 g (0.48 mol) of p-hydroxybenzoic acid, 8.38 g (0.045 mol) of 4,4′-dihydroxybiphenyl, 7.48 g (0.045 mol) of terephthalic acid, 14.41 g (0.075 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, 62.48 g of acetic anhydride (1.00 equivalent of the total of phenolic hydroxyl groups) and 6.62 g of trimesic acid (0. Except for changing to 032 mol), a dendritic polyester (B-2) was obtained in the same manner as in Example 1. The obtained dendritic polyester was evaluated in the same manner as in Example 1. The results are shown in Tables 1 and 2.

  As is clear from Tables 1 and 2, the dendritic polyester of the present invention exhibits excellent liquid crystallinity due to its specific dendritic structure. In addition, because of excellent shear response, low-pressure and high-speed molding is possible, and burrs are difficult to occur. Furthermore, since it is easily oriented by shearing, the elastic modulus is also increased by press molding, and the obtained molded product is highly packed, and thus has excellent gas barrier properties. Moreover, although the liquid crystallinity is shown, the obtained molded product has small anisotropy.

(Reference Example) Thermoplastic resin C-1 Nylon 6 (N6) “Amilan” CM1010 manufactured by Toray (melting point: 225 ° C.),
C-2 nylon 66 (N66) “Amilan” CM3001-N (melting point 262 ° C.) manufactured by Toray,
C-3 Polybutylene terephthalate (PBT) “Toraycon” 1100S manufactured by Toray (Intrinsic viscosity 0.89 dl / g, melting point 223 ° C.)
C-4 Polyethylene terephthalate (PET) Toray T-704 (inherent viscosity 1.20 dl / g, melting point 260 ° C.)
C-5 Polyphenylene sulfide (PPS) Toray M2100 (melting point 283 ° C.)
C-6 polylactic acid (PLA) LACEA H-100 (melting point: 168 ° C.) manufactured by Mitsui Chemicals, Inc.
C-7 Modified polyphenylene ether (modified PPE) Noryl GTX6011 manufactured by GE (processing temperature 280 ° C)
C-8 Copolymer of methacrylic acid / methyl methacrylate / glutaric anhydride unit (processing temperature 260 ° C.)
In a stainless steel autoclave equipped with a 20 liter baffle and a foudra-type stirring blade, 0.1 part by weight of a polyvinyl alcohol suspension (“Poval PVA-117” manufactured by Kuraray Co., Ltd.) is added to 165 parts by weight of ion-exchanged water. The dissolved solution was supplied, and the system was bubbled with nitrogen gas at a flow rate of 10 l / min for 15 minutes while stirring at 400 rpm. The dissolved oxygen concentration of the aqueous solution at this time was 2.5 ppm. Next, nitrogen gas was flowed at a flow rate of 5 liters / minute, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 65 ° C.
Methacrylic acid: 30 parts by weight Methyl methacrylate: 70 parts by weight t-dodecyl mercaptan: 0.4 parts by weight Lauryl peroxide: 0.3 parts by weight Next, the time when the internal temperature reached 65 ° C. was used as the polymerization start time. The temperature was kept at 65 ° C. for 210 minutes, then the temperature was raised to 85 ° C., and the internal temperature was kept at 85 ° C. for 60 minutes to complete the polymerization. Thereafter, the reaction system was cooled, and the polymer was separated, washed and dried to obtain a bead-shaped acrylic resin precursor. The polymerization rate of this acrylic resin precursor was 98%, and the mass average molecular weight was 130,000.

Into 100 parts by weight of the obtained acrylic resin precursor, 0.2 parts by weight of lithium acetate as a catalyst was blended, and this was mixed with a 38 mm diameter biaxial / single screw composite continuous kneading extruder HTM38 (manufactured by CTE, L / D = 47.5, 2 vent portions). While purging nitrogen from the hopper at a flow rate of 10 liters / minute, an intramolecular cyclization reaction is carried out at a screw rotation speed of 75 rpm, a raw material supply rate of 10 kg / h, and a cylinder temperature of 290 ° C. to form pellets of methacrylic acid / methyl methacrylate / A copolymer of glutaric anhydride units was obtained. In this copolymer, the glutaric anhydride unit was 32% by weight, the methyl methacrylate unit was 65% by weight, and the methacrylic acid unit was 3% by weight.
C-9 Acrylonitrile / butadiene / styrene copolymer (ABS) Toray T-100 (processing temperature 220 ° C.)
C-10 Polycarbonate resin (PC) Idemitsu Petrochemical Toughlon A1900 (processing temperature 300 ° C)
Examples 12-35, Comparative Examples 3-15
Using a TEM35B type twin screw extruder manufactured by Toshiba Machine, thermoplastic resins (C-1 to C-10), the dendritic polyesters (A-1 to A-11) obtained in Examples 1 to 9, or Comparative Example 1, The polyesters (B-1, B-2) obtained in Step 2 were dry blended at the blending ratios shown in Tables 3 and 4 and charged from the hopper. Meanwhile, fillers (GF: D-1 Nippon Electric Glass ECS03T747H (diameter 10.5 μm), D-2 Nittobo CS3J948 (diameter 10 μm), D-3 Nippon Electric Glass T-289 (diameter 13 μm), D -4 Nippon Electric Glass T-249 (diameter 13 μm)) was added from the side feeder at the mixing ratio shown in Tables 3 and 4, and the melting point of the thermoplastic resin + 10 ° C. (C-7 is 280 ° C., C-8 Were melt-kneaded at 260 ° C., C-9 at 220 ° C., and C-10 at 300 ° C.) to obtain pellets of a thermoplastic resin composition.

The obtained pellets were dried with hot air and then subjected to a FANUC α30C injection molding machine (manufactured by FANUC CORPORATION). Each test piece was molded as shown in (4) to (6) below, and the thermoplastic resin composition was evaluated. went.
(4) Thin wall fluidity The resin temperature during injection molding is set to the same temperature as during kneading, the injection speed is set to 300 mm / s, the injection pressure is set to 50 MPa, the mold temperature is 80 ° C., 150 mm length × 3.2 mm. Using a rod flow test piece mold having a width of 0.3 mm, the rod flow length at a holding pressure of 0 was measured.
(5) Storage elastic modulus The resin temperature at the time of injection molding is set to the same temperature as at the time of kneading, the injection speed is set to 300 mm / s, the injection pressure is set to the lower limit pressure + 1 MPa, the mold temperature is 80 ° C., and ASTM No. 1 dumbbell test A piece was molded. Using a dynamic viscoelasticity measuring device (Vibron), the storage elastic modulus at 25 ° C. was measured by a double-end bending test (frequency 1 Hz) method.
(6) Gas barrier property The resin temperature during injection molding is set to the same temperature as during kneading, the injection speed is set to 300 mm / s, the injection pressure is set to the lower limit pressure + 1 MPa, the mold temperature is 80 ° C., 1 mm thickness × 40 mm square A square plate specimen was molded. According to JISK7126 A method (differential pressure method), it measured at 35 degreeC using GTR-10 (made by Yanako Analytical Industry). Hydrogen was used as the gas.

  As is clear from Tables 3 and 4, the thermoplastic resin composition containing the dendritic polyester of the present invention is excellent in thin-wall fluidity and can be molded at a low pressure, so that burrs are hardly formed. In addition, it is clear that the rigidity and gas barrier properties are improved as compared with those blended with polyester having few branches. Moreover, it turns out that it is also possible to adjust the effect with respect to various resin by controlling the reactivity by terminal blockage.

Example 36
The thermoplastic resin composition obtained in Example 26 and the thermoplastic resin composition obtained in Comparative Example 9 were subjected to the temperature of the pack and the base by a spinner equipped with a sand pack and a spinning device in a twin-screw extruder. The temperature at which the pack pressure was 100 MPa was evaluated. In the thermoplastic resin composition of Example 26, the temperature at which the pack pressure was 100 MPa was 282 ° C., and in the thermoplastic resin composition of Comparative Example 9, the temperature at which the pack pressure was 100 MPa was 310 ° C. Obviously, the thermoplastic resin composition of the present invention has a low viscosity and excellent workability.

Example 37
The thermoplastic resin composition obtained in Example 26 and the thermoplastic resin composition obtained in Comparative Example 9 were connected via a die plate to a TEX30 twin screw extruder manufactured by Nippon Steel Works having a vent mechanism. A gear pump and a polymer filter of 15 μmφ were connected via a pipe having a uniform thickness, and the film was prepared for a film forming apparatus in which a T die was connected. A screw is rotated at 150 rpm, while a vent is pulled, the supply amount is kept constant with a gear pump, and a molten thermoplastic resin composition is discharged from a T-die provided with a stay portion with a lip opening of 0.5 mm to produce a film. The T-die internal pressure at that time was evaluated. The temperature was 290 ° C. in all parts. The thermoplastic resin composition of Example 26 had a T-die internal pressure of 65 MPa, and the thermoplastic resin composition of Comparative Example 9 had a T-die internal pressure of 142 MPa. Obviously, the thermoplastic resin composition of the present invention is excellent in processability.

  The dendritic polyester of the present invention has low anisotropy, excellent shear response, and has a large number of reactive functional groups, and thus has high reactivity and compatibility with various thermoplastic resins. Therefore, by blending the dendritic polyester of the present invention into a thermoplastic resin, the thin-wall fluidity, rigidity, gas barrier property, etc. can be remarkably improved.

  The thermoplastic resin composition blended with the dendritic polyester of the present invention has excellent surface appearance (color tone) and mechanical properties, heat resistance and flame retardancy by a molding method such as normal injection molding, extrusion molding, or press molding. Can be processed into a molded article, sheet, pipe, film, fiber or the like having Among them, it is useful for a huge molded product having a thin wall portion, a fuel tank having a gas barrier property, and the like.

Claims (14)

At least one structural unit selected from an aromatic oxycarbonyl unit (P), an aromatic and / or aliphatic dioxy unit (Q), and an aromatic dicarboxy unit (R), and a trifunctional or higher functional organic residue ( B) and a dendritic polyester in which the content of B is in the range of 7.5 to 50 mol% with respect to all monomers constituting the dendritic polyester. The aromatic oxycarbonyl unit (P), the aromatic and / or aliphatic dioxy unit (Q), and the aromatic dicarboxy unit (R) are each selected from structural units represented by the following formula (1): 2. A structural unit, and the contents p, q and r of P, Q and R are in the range of p + q + r = 1 to 10 moles when the content of B is 1 mole. Dendritic polyester.

(Here, R1, R2 and R3 are each at least one structural unit selected from structural units represented by the following formula.)

(Wherein, Y is at least one selected from a hydrogen atom, a halogen atom and an alkyl group. In the formula, n is an integer of 2 to 8.) The dendritic polyester according to claim 1 or 2, comprising a basic skeleton represented by the formula (2).

(Here, B is an organic residue of a trifunctional compound, and BB is bonded directly by an ester bond and / or an amide bond, or bonded through a structural unit selected from P, Q and R. Yes.) The dendritic polyester according to any one of claims 1 to 3, which exhibits a melt liquid crystallinity. The dendritic polyester according to any one of claims 1 to 4, wherein the organic residue B is an organic residue of an aromatic compound. The dendritic polyester according to any one of claims 1 to 5, wherein the organic residue B is an organic residue of a compound represented by the formula (3).

The dendritic polyester according to any one of claims 1 to 6, wherein the content (mole) of the organic residue B is 10 mol% or more with respect to all monomers constituting the dendritic polyester. The dendritic polyester according to any one of claims 1 to 9, wherein the dendritic polyester has a number average molecular weight of 1000 to 5000. The dendritic polyester according to any one of claims 1 to 8, wherein a terminal functional group of the dendritic polyester is blocked with a monofunctional organic compound. The thermoplastic resin composition formed by mix | blending the dendritic polyester in any one of Claims 1-9 with a thermoplastic resin. The thermoplastic resin composition of Claim 10 containing 0.01-99 weight part of dendritic polyester with respect to 100 weight part of thermoplastic resins. A molded article comprising the thermoplastic resin composition according to any one of claims 10 to 11. A monomer containing at least one structural unit selected from structural units represented by the following formula R1, a monomer containing at least one structural unit selected from structural units represented by the following formula R2, A method for producing a dendritic polyester comprising reacting a monomer containing at least one structural unit selected from structural units represented by R3, and a trifunctional or higher polyfunctional monomer, the polyfunctional compound The method for producing a dendritic polyester in which the addition amount (mol) is 7.5 mol% or more with respect to the addition amount (mol) of all monomers constituting the dendritic polyester.

(Wherein, Y is at least one selected from a hydrogen atom, a halogen atom and an alkyl group. In the formula, n is an integer of 2 to 8.) The method for producing a dendritic polyester according to claim 13, wherein a monofunctional organic compound is further added.