JP2006124451A - Modifier for polyester resin and molded article produced by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent draw-down trouble in the melt-molding of a polyester resin, especially a crystalline polyester resin comprising polyethylene terephthalate (PET) flake regenerated from used PET bottle and realize high impact resistance while preventing the lowering of the molecular weight of the molded article. <P>SOLUTION: The modifier for a polyester resin contains (I) an amorphous polyester resin, (II) a reactive compound containing two or more glycidyl groups and/or isocyanate groups in one molecule and having a weight average molecular weight of ≥200 and ≤500,000 and (III) a lubricant. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a modifier suitable for polyester. Specifically, the molding properties in injection molding, extrusion molding, profile extrusion molding, direct blow molding, and calendar processing molding using PET flakes recycled from polyester resins, especially used polyethylene terephthalate (PET) bottles that are crystalline polyester resins. The present invention relates to a modifier that achieves an improvement in mechanical properties and excellent mechanical properties, and a polyester molded article using the same.

  In recent years, PET bottles have grown rapidly in various soft drinks such as mineral water. On the other hand, the PET bottle disposal problem accompanying this has attracted attention, and PET bottle scrap processing has become a social problem as an environmental problem. From such a background, recycling of used PET bottles has been intensively studied.

  In recycling PET bottles, after collecting used PET bottles, they are pulverized and washed to form recycled PET flakes, which are used as raw materials to manufacture products and pelletized from the melt extrusion process. In some cases, a product is manufactured through melt molding.

  This recycled PET flake is difficult to be molded because it has a low molecular weight due to heat history, etc., contains a large amount of moisture by the washing process, and is flaky, so it is difficult to mold into the molding machine. Only can yield products that are unstable and brittle in quality. In addition, PET is usually susceptible to hydrolysis, and when molded in an undried state, hydrolysis is accelerated, molecular weight is reduced when melted, and mechanical properties such as impact resistance are greatly reduced. The performance required for plastic products is not satisfied.

  In particular, in extrusion molding and profile extrusion molding, in the case of PET, since the drawdown at the time of molding is severe, the molding process is difficult. In particular, since recycled PET has a low molecular weight due to thermal history, etc., the melt viscosity is lowered, and the drawdown during molding becomes even more severe, so it is possible to obtain a product that requires a complicated shape and fine dimensional accuracy. difficult.

  As a study so far, as a method of obtaining a product having good impact resistance from recycled PET flakes whose molecular weight has been reduced through a thermal history, a method of blending an effective impact modifier in polyester and melt-molding has been performed. ing. An impact modifier effective for polyester is disclosed in Patent Document 1. A rubbery polymer obtained by grafting or copolymerizing a compound with a chemical reaction with polyester is used. Particularly effective are polymers based on olefinic and styrene block polymers.

  Patent Document 2 shows that the drawdown at the time of molding is improved by blending a polytetrafluoroethylene-containing mixed powder composed of polytetrafluoroethylene and an organic polymer with respect to the polyester resin. Yes. Patent Document 3 discloses that impact resistance is improved by blending polypropylene and an unsaturated carboxylic acid-modified ethylene-based or styrene-based polymer. Patent Document 4 and Patent Document 5 show that impact resistance is improved by blending a rubber-based resin as a thickener and an ethylene-based or styrene-based elastomer as a polymerizing agent.

  However, the kneading of the impact resistance improver and the recycled PET flakes as described above causes a decrease in molecular weight due to re-extrusion, so that the impact resistance is not sufficient with the addition of a small amount of the impact resistance improver. Further, when the blending amount of the impact resistance improver is increased, the compatibility with PET is poor in the pelletizing step, so that the molten state is not stable, and strand cutting becomes very difficult. In the molding process, fluidity is lowered and the shape of the product is not stable. For this reason, there has been a demand for a polyester modifier that can achieve high impact resistance in a state where molecular weight reduction is prevented, and can prevent drawdown during molding, particularly for recycled PET flakes that are crystalline polyester resins. However, it has not been proposed yet.

Japanese Examined Patent Publication No.59-28223 (Pages 2-4) JP-A-11-269360 (pages 1 and 2) JP 2001-114995 A (pages 2 to 3) JP 2002-146167 A (pages 2 to 3) JP 2002-249649 A (pages 2 to 4)

  The object of the present invention is to provide melt molding, particularly injection molding, extrusion molding, profile extrusion molding, direct blow molding, using PET flakes regenerated from used polyethylene terephthalate (PET) bottles which are polyester resins, particularly crystalline polyester, An object of the present invention is to provide a polyester modifier that can prevent a draw-down preventing molecular weight from being lowered during molding and realize high impact resistance, and a polyester molded product using the same.

  As a result of diligent research to achieve the above problems, the present inventors have found that the above problems can be solved by blending a specific modifier with a polyester resin, particularly recycled PET flakes, and completing the present invention. . That is, the present invention relates to an amorphous polyester resin (I), a reactive compound (II) containing two or more glycidyl groups and / or isocyanate groups per molecule and having a weight average molecular weight of 200 to 500,000, and a lubricant ( It relates to a modifier for polyester resin characterized by containing III).

  The present invention also relates to a resin composition containing the modifier and a polyester resin, a molded product containing the modifier and a polyester resin, and a method for producing a molded product in which the modifier and the polyester resin are mixed and melt-molded.

  Improve moldability in melt molding, especially injection molding, extrusion molding, profile extrusion molding, direct blow molding, calendering molding by blending the modifier of the present invention with polyester resin, especially recycled PET flakes which are crystalline polyester And excellent mechanical properties.

  The modifier for a polyester resin of the present invention, and a molded article using the same, has a non-crystalline polyester resin (I), glycidyl group and / or isocyanate group per molecule for a polyester resin, particularly recycled PET flakes. It is desirable to include a reactive compound (II) containing two or more and having a weight average molecular weight of 200 to 500,000 and a lubricant (III). The lubricant referred to in the present invention includes an additive called a release agent in a broad sense.

  When the above-mentioned modifier is added to this prescription, that is, recycled PET flakes, since the lubricant (III) is blended, injection mold, profile extrusion sizing mold, direct blow molding mold, calendar processing molding It is possible to prevent the resin from adhering to the roll or the like, and to prevent the sheet surface from being uneven in the die during T-die extrusion molding. Furthermore, when the reduced viscosity before and after molding is compared, the reduced viscosity increases after molding, and the molecular weight can be prevented from lowering during melt molding, so the drawdown properties during various moldings can be improved, and the moldability and dimensional stability are improved. Etc. can be improved dramatically. Furthermore, the addition of the amorphous polyester resin allows the matrix to become amorphous and become a flexible material, and mechanical properties such as impact resistance can be improved. At the same time, in the case of profile extrusion molding, the resin discharged from the mold is prevented from being drawn down, and `` the resin discharged through the extrusion process and profile mold process adheres to the sizing mold and the resin clogging occurs. "Problems to stop continuous production", "Problems to deteriorate the dimensional accuracy of the product shape in the sizing process", "Battery (streaks parallel to the progress method) on the surface of the molded product due to the resin melting characteristics in the sizing mold "Problem to cause", "problem in which product warpage occurs in the direction of profile extrusion molding" and the like can be improved.

In the polyester resin modifier of the present invention, the lubricant (III) is preferably at least one compound selected from the group consisting of montanic acid ester wax, polyethylene wax and amide wax. A montanic acid ester wax is a linear monounsaturated monocarboxylic acid having a length of 28 to 30 carbon atoms as an acid component, and ethylene glycol, butylene glycol, and glycerin as glycol components. Formed from aliphatic polyols such as It is more preferable that a metal salt is formed in the montanic acid ester wax from the viewpoint of mold releasability during molding. Furthermore, a mixed wax of a montanic acid esterified product and a saponified product of montanic acid and calcium hydroxide is most preferable.
The polyethylene wax can be used without any problem as long as it is a polyethylene wax polymerized by a Ziegler catalyst. Furthermore, it is preferably a polyethylene wax that has been oxidized in order to enhance compatibility with polar plastics. The melt viscosity is preferably 3000 mPa · s or less at 140 ° C.
Further, as the amide wax, any wax of the N, N′-ethylenebisstearic acid amide type can be used without any problem.

  The polyester resin modifier of the present invention is preferably one in which the lubricant (III) contains one or more of glycerin compounds, sorbitan compounds, propylene glycol compounds and higher alcohol compounds.

  In other words, it is very compatible with polyester in the molten state by containing one or more of glycerin compounds, sorbitan compounds, propylene glycol compounds and higher alcohol compounds as modifiers for polyester resins. And the friction between the resins in the cylinder of the extruder or the like is reduced, so that shear heat generation of the resin can be prevented. At this time, since the resin temperature discharged from the die is lower than in the case where the above-described lubricant is not blended, the apparent melt strength of the resin is improved. Accordingly, it is possible to increase the temperature setting of only the cylinder tip and the die portion and to give the surface gloss of the extrusion-molded product at a level that can prevent the resin discharged from the die from being drawn down. Further, since the resin temperature discharged from the die is lowered, the resin adhesiveness at the time of melting is reduced.

  Furthermore, due to the synergistic effect of being very compatible with the amorphous polyester (I) in the molten state and being able to suppress the shear heat generation of the resin, the screw torque is reduced and the discharge amount is increased. realizable.

  As a result, for example, the adhesiveness to the sizing mold in the profile extrusion molding can be reduced, so that continuous production is possible and the production amount is increased. In addition, because of excellent resin fluidity in the sizing mold, fine dimensional accuracy is realized, and the product surface smoothness is realized by the excellent sizing mold lubricity due to the resin adhesive reduction effect. Furthermore, the sizing mold wall surface The product warpage problem can be solved from the effects of uniform and reduced resin wettability and adhesiveness.

  The glycerin compound, sorbitan compound, propylene glycol compound, and higher alcohol compound used in the present invention are not particularly limited, but glycerin organic acid ester, polyglycerin organic acid ester, sorbitan organic acid ester, propylene glycol organic acid Preferred are esters and higher alcohol organic acid esters, and more preferred are glycerin fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, and higher alcohol fatty acid esters. The glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, and higher alcohol fatty acid ester are most preferably derived from fatty acids having less than 40 carbon atoms.

  Among the additives, specific examples of preferable compounds include stearic acid monoglyceride, citric acid saturated fatty acid monoglyceride, sorbitan stearate, propylene glycol monostearate, stearyl stearate, and polyglyceryl stearate.

  The crystalline polyester referred to in the present invention is heated at a rate of 20 ° C./min from −100 ° C. to 300 ° C. using a differential scanning calorimeter (DSC), and then at a rate of 50 ° C./min to −100 ° C. Subsequently, in the two temperature rising processes in which the temperature is increased from −100 ° C. to 300 ° C. at a rate of 20 ° C./min, the one showing a clear melting peak in one of the temperature increasing processes. Conversely, amorphous polyester refers to a polyester that does not show a melting peak in either.

  As the polyester resin used for the modification in the present invention, any resin can be used regardless of crystallinity and non-crystallinity as long as it is composed of a dicarboxylic acid component and a glycol component. Polylactic acid and polycaprolactone can be used without any problem. Particularly, the polyester modifier in the present invention is preferably used as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), and the most effective polyester is recycled polyethylene terephthalate (PET). This is because in the case of recycled PET, the melt viscosity has already been greatly reduced, and the moldability is improved by recovering or further improving the melt viscosity with the present modifier.

  Any amorphous polyester resin (I) can be used as long as it comprises a dicarboxylic acid component and a glycol component.

  As the amorphous polyester resin (I) used in the present invention, it is desirable that an aromatic dicarboxylic acid having 8 to 14 carbon atoms and an aliphatic or alicyclic glycol having 2 to 10 carbon atoms are the main components. As used herein, the main component refers to 50 mol% or more, preferably 60 mol%, and more preferably 65 mol% or more of each component when the total acid component and glycol component are each 100 mol%. When both components are less than 50 mol%, the elongation and mechanical properties of the molded product may be lowered.

  Further, the aromatic dicarboxylic acid having 8 to 14 carbon atoms in the amorphous polyester resin (I) is preferably terephthalic acid and / or isophthalic acid. When these dicarboxylic acids are used, the elongation and mechanical properties of the molded product are further improved. Preferably, the terephthalic acid is preferably contained in an amount of 50 mol% or more, more preferably 60 mol% or more, and more preferably contains both terephthalic acid and isophthalic acid.

  The polyester resin may be copolymerized with other polycarboxylic acids other than the above-mentioned terephthalic acid and isophthalic acid, such as orthophthalic acid, naphthalenedicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, decanoic acid, Known compounds such as dimer acid, cyclohexanedicarboxylic acid, trimellitic acid can be used.

  The amorphous polyester resin (I) used in the present invention is mainly composed of an aliphatic or alicyclic glycol having 2 to 10 carbon atoms, and further, the aliphatic or alicyclic group having 2 to 10 carbon atoms. The glycol is at least selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, and 2-methyl-1,3-propanediol. One or more types are preferable from the viewpoint of improving the versatility of obtaining raw materials, cost, compatibility, and impact resistance.

  Among these, ethylene glycol and neopentyl glycol (60/40 to 90/10 (molar ratio)), ethylene glycol and 1,4-cyclohexanedimethanol (60/40 to 90/10 (molar ratio)), ethylene glycol and 1 , 2-propanediol (90/10 to 10/90 (molar ratio)), it is easy to achieve both melt molding processability and transparency of the molded product.

  The amorphous polyester resin (I) is composed of the above-mentioned ethylene glycol, diethylene glycol, neopentyl glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3. -Polyhydric alcohol components other than propanediol may be copolymerized, such as 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3 -Methyl-1,5-pentanediol, hexanediol, nonanediol, dimerdiol, ethylene oxide adduct or propylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 2-butyl-2-ethyl -1,3-propa Diol, tricyclodecane dimethanol, neopentyl hydroxypivalic acid ester, 2,2,4-trimethyl-1,5-pentanediol, trimethylolpropane and the like can be used.

  The amorphous polyester resin (I) used in the present invention has a polyfunctional compound having three or more carboxyl groups, hydroxyl groups or ester forming groups thereof (for example, trimellitic acid, pyromellitic acid, glycerin, trimethylolpropane). Etc.) is preferably included in order to improve the moldability.

  The reduced viscosity of the amorphous polyester resin (I) used in the present invention is preferably 0.4 to 1.50 dl / g, more preferably 0.50 to 1.20 dl / g, and still more preferably 0.60. 1.00 dl / g. When the reduced viscosity is less than 0.40 dl / g, the strength of the molded product is insufficient due to insufficient resin cohesive strength, and the resulting product may become brittle and cannot be used. On the other hand, if it exceeds 1.50 dl / g, the melt viscosity is excessively increased, so that the optimum temperature for molding is also increased, and as a result, molding processability may be deteriorated.

The acid value of the amorphous polyester resin (I) used in the present invention is preferably 100 equivalents / 10 ⁶ g or less, more preferably 50 equivalents / 10 ⁶ g or less, and even more preferably 40 equivalents / 10 ⁶ g or less. is there. On the other hand, the lower the lower limit, the better. When the acid value exceeds 100 equivalents / 10 ⁶ g, hydrolysis of the resin is further accelerated when the resin is heated during melt processing, and the mechanical strength of the finished molded product is lowered.

  The reactive compound (II) used in the present invention is capable of adjusting the melt strength by expanding the processing condition management range for expressing the “melt strength enhancing effect” depending on the increase in molecular weight due to the reaction with the polyester resin. The weight average molecular weight is 200 or more and 500,000 or less, and the preferable lower limit is 500 or more, more preferably, in order to satisfy the control and the bending whitening resistance of the product and the suppression of bleed out of the unreacted product to the product surface layer. 700 or more, most preferably 1000 or more. On the other hand, a preferable upper limit is preferably 300,000 or less, more preferably 100,000 or less, and most preferably 50,000 or less. When the weight average molecular weight of the reactive compound is less than 200, the unreacted reactive compound may bleed out on the surface of the product, which may cause a decrease in product adhesion and surface contamination. On the other hand, if it exceeds 500,000, even if it is bent, voids may occur due to poor compatibility between the reactive compound and the amorphous polyester, which may lead to deterioration of the whitening property of the molded product.

  The reactive compound (II) used in the present invention has two or more functional groups that can react with the hydroxyl group or carboxyl group of the polyester per molecule in terms of introducing a partial cross-link into the entire resin. preferable. Due to the effect of the reactive compound, when a reaction product of the hydroxyl group or carboxyl group of the polyester and the reactive compound is generated at the time of melt extrusion, an effect of improving the melt strength can be obtained by partially forming a crosslinked product. It is.

  Specific examples of the functional group possessed by the reactive compound (II) are preferably a glycidyl group or an isocyanate group from the speed of reaction.

Any form of the functional group (II) in the reactive compound is possible. For example, those having a functional group in the main chain of the polymer, those existing in the side chain, and those existing in the terminal are all possible.
Specific examples include styrene / methyl methacrylate / glycidyl methacrylate copolymer, bisphenol A type, cresol novolac, phenol novolac type epoxy compound, isocyanate compound, etc., and any of these may be used. Of course, it can be used.

  In particular, the reactive compound (II) includes (X) 20 to 99% by weight of vinyl aromatic monomer, (Y) 1 to 80% by weight of hydroxyalkyl (meth) acrylate and / or glycidylalkyl (meth). A copolymer comprising acrylate and (Z) 0 to 40% by weight of alkyl (meth) acrylate is preferred. More preferably, the resin comprises (X) of 25 to 90% by weight, (Y) of 10 to 75% by weight, and (Z) of 0 to 35% by weight, most preferably (X) of 30 to 85% by weight. %, (Y) is 15 to 70% by weight, and (Z) is 0 to 30% by weight. Since these compositions affect the functional group concentration contributing to the reaction with the polyester resin system, it is necessary to appropriately control them as described above. When it deviates from the above-mentioned composition, there is a possibility that the reactivity with the polyester resin is lowered and the molding processability is lowered.

    As a method for producing the modifier of the present invention, the reactive compound (II) and the lubricant (III) are pressed into the amorphous polyester resin (I) at the time of melt extrusion, and added to the polyester resin pellets before extrusion. A method of blending and melt-kneading can be considered, and any method can be used. However, a method of adding to a polyester resin pellet before extrusion and melt-kneading is preferable. The temperature at that time is preferably about 150 to 270 ° C. from the viewpoint of appropriately promoting the reaction between the amorphous polyester resin (I) and the reactive compound (II).

  The addition amount of the amorphous polyester resin (I) is preferably 40% by weight or more and 99.8% by weight or less when the whole modifier is 100 parts by weight, the lower limit is 50% by weight or more, and the upper limit is 98% by weight. The following is more preferable. If it is less than 40% by weight, compatibility with the polyester resin and resin fluidity may not be exhibited, and if it is added in excess of 99.8% by weight, the modification effect described later may not be obtained.

  The addition amount of the reactive compound (II) can be selected individually depending on the molecular weight and the number of introduced functional groups, but is preferably 0.1% by weight or more and 50% by weight or less when the total modifier is 100 parts by weight, More preferably, the lower limit is 1% by weight or more and the upper limit is 40% by weight or less. If it is less than 0.1% by weight, the effect as a target modifier may not be exhibited, and if it exceeds 50% by weight, the mechanical properties of the product may be affected.

  The addition amount of the lubricant (III) is preferably 0.1% by weight or more and 50% by weight or less when the whole modifier is 100 parts by weight, the lower limit is 1% by weight or more, and the upper limit is more preferably 40% by weight or less. . If it is less than 0.1% by weight, the targeted release effect on the mold or the like may not be exhibited, and if it exceeds 40% by weight, the mechanical properties of the product may be affected.

  The modifier of the present invention or the polyester resin composition using the same is oxidized in order to suppress thermal degradation of the polyester resin during processing (to prevent resin coloring and resin dripping due to thermal degradation). It is desirable to mix and use an inhibitor. As the antioxidant, for example, a phenol-based antioxidant, an organic phosphite-based compound and the like are suitable.

  Specific examples of the phenolic antioxidant used in the present invention include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,6-di-tert. -Butyl 4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,4,6-tri-tert-butylphenol, 2-tert-butyl-4-methoxyphenol, 3-methyl-4-isopropyl Phenol, 2,6-di-tert-butyl-4-hydroxymethylphenol, 2,2-bis (4-hydroxydiphenyl) propane, bis (5-tert-butyl-4-hydroxy-2-methylphenyl) sulfide, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 1,1- (3-tert-butyl-4-hydroxy-5-methylphenyl) butane, bis (3-tert-butyl-2-hydroxy-5-methylphenyl) methane, 2,6-bis (2-hydroxy-3- tert-butyl-5-methylbenzyl) -4-methylphenol, bis (3-tert-butyl-4-hydroxy-5-methylbenzyl) sulfide, bis (3-tert-butyl-5-ethyl-2-hydroxydiphenyl) Methane, bis (3,5-di-tert-butyl 4-hydroxydiphenyl) methane, bis (3-tert-butyl-2-hydroxy-5-methylphenyl) sulfide, 1,1-bis (4-hydroxyphenyl) Cyclohexane, ethylenebis [3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate Bis [2- (2-hydroxy-3-tert-butyl5-methylbenzyl) -4-methyl-6-tert-butylphenyl] terephthalate, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) ) -2-Methylpropane, 4-methoxyphenol, cyclohexylphenol, p-phenylphenol, catechol, hydroquinone, 4-tert-butylpyrocatechol, ethyl gallate, propyl gallate, octyl gallate, lauryl gallate, cetyl gallate, β-naphthol 2,4,5-trihydroxybutyrophenone, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanate, 1,3,5-trimethyl-2,4,6-tris (3,5- Di-tert-butyl-4-hydroxydibenzyl) , 1,6-bis [2- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] hexane, tetrakis [3- (3,5-di-tert-butyl-4-hydroxydiphenyl) ) Propionyloxymethyl] methane, bis (3-cyclohexyl-2-hydroxy-5-methylphenyl) methane, bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] sulfide, n-otatadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [3- (3,5-di-tert-butyl 4-hydroxydiphenyl) propionylamino] hexane, 2, 6-bis (3-tert-butyl-2-hydroxy-5-methylphenyl) -4-methyl Enol, bis [S- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)] thioterephthalate, tris [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy Ethyl] isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,1,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butane, etc. Is mentioned. These compounds may be used alone or in combination of two or more.

  The blending amount of the phenolic antioxidant is preferably 1.0 part by weight or less, particularly preferably 0.8 part by weight or less, when the total composition after blending the modifier is 100 parts by weight. On the other hand, the preferred lower limit is 0.01 parts by weight or more, particularly preferably 0.02 parts by weight or more. If the blending amount is less than 0.01 parts by weight, it is difficult to obtain the effect of suppressing heat deterioration during processing, and if it exceeds 1.0 part by weight, the effect of suppressing heat deterioration is saturated and not economical.

  Specific examples of the organic phosphite compound used in the present invention include, for example, triphenyl phosphite, tris (methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tris (2-ethylhexyl). Phosphite, Tris (nonylphenyl) phosphite, Tris (octylphenyl) phosphite, Tris [decylpoly (oxyethylene) phosphite, Tris (cyclohexylphenyl) phosphite, Tricyclohexylphosphite, Tri (decyl) thiophosphite , Triisodecyl thiophosphite, phenyl bis (2-ethylhexyl) phosphite, phenyl diisodecyl phosphite, tetradecyl poly (oxyethylene) bis (ethylphenyl) phosphato, phenyl Dicyclohexyl phosphite, phenyl diisooctyl phosphite, phenyl di (tridecyl) phosphite, diphenyl cyclohexyl phosphite, diphenyl isooctyl phosphite, diphenyl 2-ethylhexyl phosphite, diphenyl isodecyl phosphite, diphenyl・ Cyclohexylphenyl phosphite, diphenyl (tridecyl) thiophosphite, nonylphenyl ditridecyl phosphite, phenyl p-tert-butylphenyl dodecyl phosphite, diisopropyl phosphite, bis [otadecyl poly (oxyethylene)] phosphite , Octyl poly (oxypropylene) tridecyl poly (oxypropylene) phosphite, monoisopropyl phosphite, diisode Ruphosphite, diisooctyl phosphite, monoisooctyl phosphite, didodecyl phosphite, monododecyl phosphite, dicyclohexyl phosphite, monocyclohexyl phosphite, monododecyl poly (oxyethylene) phosphite, bis (cyclohexylphenyl) phosphite Monocyclohexyl phenyl phosphite, bis (p-tert-butylphenyl) phosphite, tetratridecyl 4,4′-isopropylidene diphenyl diphosphite, tetratridecyl 4,4′-butylidene bis (2-tert -Butyl-5-methylphenyl) diphosphite, tetraisooctyl-4,4′-thiobis (2-tert-butyl-5-methylphenyl) diphosphite, tetrakis (nonylphenyl) Poly (propyleneoxy) isopropyl diphosphite, tetratridecyl propyleneoxypropyl diphosphite, tetratridecyl 4,4'-isopropylidene dicyclohexyl diphosphite, pentakis (nonylphenyl) bis [poly (propylene Oxy) isopropyl] triphosphite, heptakis (nonylphenyl) tetrakis [poly (propyleneoxy) isopropyl] pentaphosphite, heptakis (nonylphenyl) tetrakis (4,4′-isopropylidenediphenyl) pentaphosphite, decachys (nonyl) Phenyl) ・ heptakis (propyleneoxyisopropyl) octaphosphite, decaphenyl heptakis (propyleneoxyisopropyl) octaphosphite, bis (butoxycal) Ethyl) · 2,2-dimethylene-trimethylenedithiophosphite, bis (isooctoxycarbomethyl) · 2,2-dimethylenetrimethylenedithiophosphite, tetradodecyl · ethylenedithiophosphite, tetradodecyl · hexamethylenedithio Phosphite, tetradodecyl 2,2'-oxydiethylenedithiophosphite, pentadodecyl di (hexamethylene) trithiophosphite, diphenyl phosphite, 4,4'-isopropylidene-dicyclohexyl phosphite, 4,4'- Isopropylidene diphenyl alkyl (C12-C15) phosphite, 2-tert-butyl-4- [1- (3-tert-butyl-4-hydroxydiphenyl) isopropyl] phenyldi (p-nonylphenyl) phosphite, di Ridecyl 4,4'-butylidenebis (3-methyl-6-tert-butylphenyl) phosphite, dioctadecyl 2,2-dimethylene trimethylene diphosphite, tris (cyclohexylphenyl) phosphite, hexatridecyl 4,4 ′, 4 ″ -1,1,3-butanetriyl-tris (2-tert-butyl-5-methylphenyl) triphosphite, tridodecylthiophosphite, decaphenyl heptakis (propyleneoxyisopropyl) octabosphite Dibutyl pentakis (2,2-dimethylenetrimethylene) diphosphite, dioctylpentakis (2,2-dimethylenetrimethylene) diphosphite, didecyl-2,2-dimethylenetrimethylenediphosphite and their lithium and sodium , Potassium, magnesium, caldium, barium, zinc and aluminum metal salts. These compounds may be used alone or in combination of two or more.

  The blending amount of the organic phosphite compound is preferably 3.0 parts by weight or less, particularly preferably 2.0 parts by weight, when the total composition after blending the modifier is 100 parts by weight. The lower limit is preferably 0.01 parts by weight or more, particularly preferably 0.02 parts by weight or more. If the blending amount is less than 0.01 parts by weight, it is difficult to obtain the effect of suppressing thermal deterioration during processing, and if it exceeds 3.0 parts by weight, the effect of suppressing thermal deterioration is saturated and not economical.

  Note that it is preferable to use a phenolic antioxidant and an organic phosphite ester compound in combination because the effect of suppressing thermal deterioration is further improved.

  In the present invention, in order to further improve the heat resistance, impact resistance, dimensional stability, surface smoothness, rigidity, and other mechanical properties of the resin composition, the following resins can be added. For example, polyolefin resin such as polyethylene, polypropylene, ethylene-ethyl acrylate copolymer (EEA), or elastomer, polybutadiene, polyisoprene, butadiene-polyisoprene copolymer, acrylonitrile-isoprene copolymer, acrylate ester-butadiene Conjugated diene polymers such as copolymers, acrylate-butadiene-styrene copolymers, acrylate-isoprene copolymers; hydrogenated conjugated diene polymers; ethylene-propylene copolymers, etc. Olefin rubbers; Acrylic rubbers such as polyacrylates; Polyorganosiloxanes; Thermoplastic elastomers; Thermoplastic elastomers having epoxy groups, carboxyl groups, isocyanate groups, etc .; Ethylene ionomers Coalescence is like, they may comprise one or, is used in two or more kinds. Among them, an acrylic rubber, a conjugated diene copolymer, or a hydrogenated product of a conjugated diene copolymer is preferable. Further, ethylene-vinyl acetate copolymer, ethylene-butene-1 copolymer, ethylene-propylene-ethyldennorbornene copolymer, ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-1,4 hexadiene Copolymer, ethylene-butene-1-dicyclopentadiene copolymer, ethylene-butene-1-1,4 hexadiene copolymer, acrylonitrile-chloroprene copolymer (NCR), styrene-chloroprene copolymer (SCR) , Butadiene-styrene copolymer (BS), ethylene-propylene ethylidene copolymer, styrene-isoprene rubber, styrene-ethylene copolymer, poly (α-methylstyrene) -polybutadiene-poly (α-methylstyrene) copolymer Coalescence (α-MES-B-α-MES), poly (α A resin such as -methylstyrene) -polyisoprene-poly (α-methylstyrene) copolymer or an elastomer can be added to the polyester resin composition.

  Further, preferably, the following multilayer structure polymer particles can be blended. Multi-layered polymer particles generally have a layer structure called a core / shell, that is, an inner / outer layer structure in which an inner layer is covered by an outer layer, and are composed of two or three layers. However, it may be composed of four or more layers. In the case of a two-layer structure, a rubber layer (center layer) / hard layer (outermost layer) structure is preferable. In the case of a three-layer structure, a hard layer (center layer) / rubber layer (intermediate layer) / hard Layer (outermost layer), rubber layer (center layer) / hard layer (intermediate layer) / hard layer (outermost layer) or rubber layer (center layer) / rubber layer (intermediate layer) / hard layer (outermost layer) Those having a four-layer structure are preferably, for example, rubber layer (intermediate layer) / hard layer (intermediate layer) / rubber layer (intermediate layer) / hard layer (outermost layer). However, the multilayer structure polymer particles are not limited to the above-described ones. The embodiment in which the inner layer is partially encased in the outer layer, microvoids (microvoids, voids, cavities in the inner layer or particles). Including one or more microvoids in the inner layer or in the particle, and including one or more passages connected to the space outside the particle. . The term “particle” used in the present specification completely encompasses the concept that the term “particle” generally has in polymer chemistry.

  The inner layer of the multi-layered polymer particles used in the present invention is rubber to improve impact resistance described later, sizing mold workability during profile extrusion, mold releasability during injection molding, etc. Is preferable. The polymer constituting the rubber layer is not particularly limited, but preferred polymers include polybutadiene, polyisoprene, butadiene-polyisoprene copolymer, acrylonitrile-isoprene copolymer, acrylate ester-butadiene copolymer, Conjugated diene polymers such as acrylate-butadiene-styrene copolymers and acrylate-isoprene copolymers; hydrogenated conjugated diene polymers; olefin rubbers such as ethylene-propylene copolymers; Acrylic rubber such as polyacrylic acid ester; polyorganosiloxane; thermoplastic elastomer; thermoplastic elastomer having epoxy group, carboxyl group, isocyanate group, etc .; ethylene ionomer copolymer, etc. With two or more It is use. Of these, acrylic rubbers, conjugated diene copolymers, or hydrogenated products of conjugated diene copolymers can be preferably used. Examples of the acrylic ester used in the polymerization to obtain the above acrylic rubber include acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and the like. Examples include esters.

  In the polymerization of a monomer system comprising an acrylate ester and / or a conjugated diene compound to obtain the above acrylate rubber or conjugated diene polymer, other monofunctional polymerizable monomers are copolymerized. be able to. Other polymerizable monomers that can be copolymerized include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, Methacrylic acid esters such as octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, isobornyl methacrylate; aromatic vinyl compounds such as styrene and α-methylstyrene; Examples include acrylonitrile. The amount of these other monofunctional polymerizable monomers is desirably 20% by weight or less based on the total polymerizable monomers forming the rubber layer.

  The rubber layer constituting a part of the multilayer structure polymer particles preferably has a cross-linked molecular chain structure in order to develop rubber elasticity, and the molecular chain of the rubber layer and the adjacent layer Molecular chains may be grafted by chemical bonds. For this purpose, it may be desirable to use a small amount of a polyfunctional polymerizable monomer as a crosslinking agent or a grafting agent in the monomer-based polymerization for forming the rubber layer. The polyfunctional polymerizable monomer is a monomer having two or more carbon-carbon double bonds in the molecule. For example, unsaturated carboxylic acid such as acrylic acid, methacrylic acid, cinnamic acid and allyl Examples include esters with unsaturated alcohols such as alcohol and methacrylic alcohol or glycols such as ethylene glycol and butanediol; esters of dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and maleic acid with the above unsaturated alcohols. Specifically, allyl acrylate, methallyl acrylate, allyl methacrylate, methallyl methacrylate, allyl cinnamate, methallyl cinnamate, diallyl maleate, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, divinylbenzene, ethylene glycol (Meth) acrylate, butanediol ) Acrylate, hexanediol (meth) acrylate and the like. The term “di (meth) acrylate” means a general term for “diacrylate” and “dimethacrylate”. The polyfunctional polymerizable monomer can be used alone or in combination. Among these, butanediol diacrylate, hexanediol acrylate, allyl methacrylate, and the like are preferably used. However, when a polyfunctional polymerizable monomer is used, if the amount of the polyfunctional polymerizable monomer is too large, the performance as a rubber in the multilayer structure polymer particles is lowered, for example, by profile extrusion. When performing profile extrusion sizing mold processing, polyester resin sizing mold adhesion reduction formulation improves profile extrusion continuous productivity improvement, profile extrusion product dimensional accuracy improvement, surface smoothness improvement (removal of chatter), continuous production Since the effect of improving the shape accuracy of product corners and edges between dies and sizing by improving product warpage and resin sag improvement during profile extrusion may be reduced, The amount of the monomer used is preferably 10% by weight or less based on the entire polymerizable monomer forming the rubber layer. In addition, in the case of using a polymerizable monomer having a conjugated diene compound as a main component, since it functions as a crosslinking point or a grafting point, it is not always necessary to use a polyfunctional polymerizable monomer in combination. Also good.

  The polymer constituting the skin layer of the multilayer structure polymer particle used in the present invention is not particularly limited as long as Tg is higher than 25 ° C., but is used for forming the skin layer. Common polymerizable monomers include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, methacrylic acid. Methacrylic acid esters such as octyl acid, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, isobornyl methacrylate; aromatic vinyl compounds such as styrene and α-methylstyrene; Nitrile, and the like. Among these polymerizable monomers, a polymer composed of acrylic acid (derivative) and / or methacrylic acid (derivative) is preferable, and one or more methyl methacrylate or styrene is used alone, or two or more of them are used as a main component. It is also preferable to use it in the form of a combination of these radically polymerizable monomers. The content of the rubber layer in the multilayer polymer particles is not necessarily limited, but is preferably in the range of 25 to 90% by weight, and more preferably in the range of 40 to 80% by weight. If the amount of the polymer part forming the rubber layer is too small, the flexibility is insufficient, and the sizing mold processability improvement, that is, the mold adhesion reduction effect is insufficient when the polyester resin composition is subjected to profile extrusion molding. Thus, continuous productivity may be inferior. In addition, if the amount of the hard polymer forming the outermost layer is too small, the compatibility with the polyester resin system is lowered, it is difficult to uniformly disperse in the polymer matrix, and it may be unevenly distributed to deteriorate the surface smoothness of the product. is there.

  There is no restriction | limiting in particular about the polymerization method for manufacturing the above-mentioned multilayered structure polymer particle in this invention, For example, a spherical multilayered structure polymer particle can be obtained with a normal emulsion polymerization method. In the emulsion polymerization method, a chain transfer agent such as octyl mercaptan or lauryl mercaptan can be used as necessary according to known means. In addition, after emulsion polymerization, separation and acquisition of the multilayer structure polymer particles from the polymer latex can be performed by, for example, coagulation drying according to a known method. Further, the form of the produced multilayer structure polymer particles is not particularly limited, and may be, for example, pellets in a state of being fused to each other at the outermost layer part, and may be powdery or granulated, Even in this case, it can be used for the production of the polyester resin composition of the present invention.

  In the present invention, other components can be appropriately added to the resin composition of the modifier and the polyester depending on the application. For example, impact resistance improvers, fillers, UV absorbers, surface treatment agents, lubricants, light stabilizers, pigments, antistatic agents, antibacterial agents, crosslinking agents, sulfur-based antioxidants, flame retardants, plasticizers, processing Auxiliaries, foaming agents and the like are listed. In particular, it is preferable to add talc in terms of promoting crystallization. The preferable addition amount of talc is 0.01 to 50 parts by weight, and preferably 0.1 to 10 parts by weight.

  As conditions for melt-molding the polyester resin and the modifier of the present invention, the polyester resin and the modifier pellets, or the polyester resin flakes and the modifier can be blended and melt-molded as they are. Also, a means for melt-kneading the polyester resin and the modifier with a uniaxial extruder, a biaxial extruder, etc. to form pellets, and melt-molding the kneaded polymer again can be used without any problem. As the temperature condition, there is no problem at any temperature as long as the polyester resin and amorphous polyester resin (I) used for extrusion can be melt-flowed, but on the nature of the polyester resin, it is considered to be 100 ° C. or higher and 350 ° C. or lower, More preferably, the temperature is 150 ° C. or higher and 300 ° C. or lower. If the temperature is too low, the polymer cannot be fed out or an excessive load is applied to the extruder. Conversely, if the temperature is too high, the polymer will be thermally deteriorated, which is not preferable.

  The modifier of the present invention can be improved in moldability and mechanical properties by blending with polyester resin, preferably recycled polyethylene terephthalate flakes, melt-kneading and molding. It is a feature. If recycled polyethylene terephthalate, reactive compound (II) and lubricant (III) are dry blended (mixed with pellets, powder, etc., the same applies hereinafter), put into a hopper of a molding machine such as an extruder and melt-kneaded and molded as it is Then, the tendency of thickening of the melt is remarkably difficult to control, and in the worst case, gelation may occur during melting (for example, in an extruder). In addition, when the tendency of thickening of the melt is remarkable, it is difficult to adjust it to the optimum conditions at the molding site, and eventually molding becomes difficult. On the other hand, when the modifier as in the present invention is manufactured in advance, it can be easily blended with recycled polyethylene terephthalate at the molding site, and the optimum molding conditions can be simply adjusted by checking the molding condition for the blending ratio. Can be selected. The advantages of each molding method will be specifically described below.

In the case of injection molding, if recycled polyethylene terephthalate, reactive compound (II) and lubricant (III) are simply melt-kneaded as they are, kneadability in the cylinder of the injection molding machine is often insufficient, and reactive compound (II) Reaction to the polyester matrix and dispersibility may be insufficient. Moreover, reaction may advance excessively and it may gelatinize. For this reason, the melt viscosity of the plasticizing process and the injection process during continuous production may fluctuate and the mass production stability deteriorates, so that it becomes difficult to stabilize the shape of the molded product.
On the other hand, in the case of the method using the modifier of the present invention, pellets are produced by suppressing a rapid reaction when a modifier composed of amorphous polyester (I) and reactive compound (II) is produced in advance. Can be In addition, the lubricant (III) is dispersed in good condition. When this is mixed as pellets with recycled polyethylene terephthalate during injection molding and melted, the compatibility is good and the reaction can be allowed to proceed slowly. The effect of the lubricant can be fully expressed.
In addition, in the process of searching for molding conditions for producing an injection molded product of recycled polyethylene terephthalate, resin melting characteristics suitable for product shape and runner design may be required. In this case, the pellets obtained by simply melting and kneading the recycled polyethylene terephthalate, the reactive compound (II) and the lubricant (III) can be controlled only by the injection conditions such as processing temperature, back pressure and injection pressure. However, in the case of the present invention, since it can be easily mixed by dry blending with recycled polyethylene terephthalate as a modifier, the resin having a desired product shape can be obtained by changing the melt viscosity characteristics by adjusting the blending amount. The composition can be easily determined.

In the case of profile extrusion molding, if the recycled polyethylene terephthalate resin, reactive compound (II) and lubricant (III) are simply melt-kneaded, the kneadability in the profile extrusion molding machine cylinder is often insufficient, and the reactive compound ( Reaction of II) to the polyethylene terephthalate matrix and dispersibility may be insufficient. Moreover, reaction may advance excessively and it may gelatinize. For this reason, the melt viscosity of the melt discharged from the mold during continuous production may fluctuate. Therefore, “the discharged resin that has passed through the extrusion process and the deformed mold process adheres to the sizing mold and the resin clogging occurs. "Problem to stop continuous production", "Problem to deteriorate dimensional accuracy of product shape in sizing process", "Problem to generate chatter on the surface of molded product" On the other hand, it becomes very difficult to suppress the “problem of product warping”.
On the other hand, in the case of the method using the modifier of the present invention, when producing a modifier composed of the amorphous polyester (I) and the reactive compound (II), the rapid reaction is suppressed and pelletized. it can. In addition, the lubricant (III) is kneaded in a good state. When mixed with recycled polyethylene terephthalate at the time of profile extrusion, the compatibility is good and the reaction can be allowed to proceed slowly, so that it is sufficiently kneaded in the profile extrusion cylinder and the dispersibility is also good. The effect of the mold release agent / lubricant can be fully expressed.
In the case of the present invention, since it can be easily mixed with a recycled polyethylene terephthalate resin as a modifier by dry blending, the resin composition that changes the melt viscosity property by adjusting the blending amount and becomes the desired product shape Determining things is easy.

In the case of direct blow molding, if the recycled polyethylene terephthalate resin, the reactive compound (II) and the lubricant (III) are simply melt-kneaded, the kneadability in the direct blow molding machine cylinder is often insufficient, and the reactive compound ( Reaction of II) to the polyethylene terephthalate matrix and dispersibility may be insufficient. Moreover, reaction may advance excessively and it may gelatinize. For this reason, since the melt viscosity of the melt discharged from the die during continuous production may fluctuate, the parison formation state becomes unstable and the continuous production stability decreases. As product physical properties, the reduced viscosity fluctuates, and mechanical property improvement effects such as impact resistance may vary depending on the product. As a result, the bottle strength improvement effect when the contents are filled in the bottle container varies, and the problem of the protrusion of the contents due to rupture at the time of dropping cannot be completely solved.
On the other hand, in the case of the method using the modifier of the present invention, when a modifier composed of amorphous polyester (I) and reactive compound (II) is produced in advance, the rapid reaction is suppressed and the pellet Can be In addition, the lubricant (III) is dispersed in good condition. When this is mixed with recycled polyethylene terephthalate at the time of direct blow molding, compatibility is good and the reaction can be allowed to proceed slowly, so that it is sufficiently kneaded in the direct blow molding machine cylinder and the dispersibility is also good. The effect of the lubricant can be sufficiently exhibited.
In the case of the present invention, since it can be easily mixed with the recycled polyethylene terephthalate resin as a modifier by dry blending, by adjusting the blending amount, the melt viscosity property is changed, and adjusted to an appropriate parison shape, Since it can blow in a metal mold | die, the resin composition determination for obtaining the target product shape becomes easy.

  In the case of calendering molding, if the recycled polyethylene terephthalate resin, reactive compound (II) and lubricant (III) are simply melt-kneaded, thickening occurs over time on the calender roll, so the material feed rate, reaction progress, film It is difficult to control the pick-up speed. Moreover, reaction may advance excessively and it may gelatinize. Eventually, during continuous operation, the reaction state changes between the film produced in the early stage and the film produced in the later stage, so that the problem arises that the film properties differ depending on the location. On the other hand, in the case of the method using the modifier of the present invention, the reaction between the non-crystalline polyester resin (I) and the reactive compound (II) proceeds to some extent, so that the reaction with the recycled polyethylene terephthalate becomes mild. It is easy to control, can ensure stable productivity, and can stabilize film properties at a high level. Further, the dispersibility of the lubricant (III) is also improved, and the effect of the lubricant can be sufficiently exhibited.

  Although the above has been described with recycled polyethylene terephthalate, it is natural that the same effect can be expected even when ordinary polyethylene terephthalate, polybutylene terephthalate, or amorphous polyester resin is used.

  As a processing method of the resin composition of the polyester resin, the amorphous polyester resin (I), the reactive compound (II), and the lubricant (III) (that is, the modifier of the present invention), the above-described injection molding and extrusion are used. There are no particular restrictions on methods other than molding, profile extrusion molding, direct blow molding, and calendar molding. Blow compression molding, stretch blow molding, thermoforming (including vacuum and pressure molding), reaction injection molding, foam molding, compression molding. , Powder molding (including rotation / stretch molding), lamination molding, casting, melt spinning, and the like.

  When the polyester resin is modified using the modifier of the present invention, the blending ratio is preferably in the range of 0.1 to 50% by weight of the modifier and 99.9 to 50% by weight of the polyester resin. If the modifier is 0.1% by weight or less, the moldability improving effect may not be recognized. On the other hand, when it exceeds 50% by weight, the physical properties of the molded product may be deteriorated. The final composition ratio of the reactive compound (II) is that the polyester resin is 55 to 99.945% by weight, contains two or more glycidyl groups and / or isocyanate groups per molecule, and has a weight average molecular weight of 200 to 500,000. Is preferably 0.005 to 30% by weight, and the lubricant (III) is contained in 0.05 to 15% by weight. The polyester resin is preferably composed of two or more kinds of crystalline and amorphous polyester resins. Further, the polyester resin preferably contains 50% by weight or more of recycled polyethylene terephthalate.

  In order to describe the present invention in more detail, examples are given below, but the present invention is not limited to the examples. The measurement value described in the synthesis example is measured by the following method.

  Reduced viscosity: 0.1 g of a sample for measurement was dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane (weight ratio 6/4), and the insoluble portion was removed by filtration.

  Weight average molecular weight: measured by Waters gel permeation chromatography using tetrahydrofuran as solvent and polystyrene as assay standard.

Resin composition: The composition of the amorphous polyester resin was determined from its integral ratio by performing ¹ H-NMR analysis using a nuclear magnetic resonance analyzer (NMR) Gemini-200 manufactured by Varian in a deuterated chloroform solvent.

  Glass transition temperature, melting point: It was determined by measuring at a heating rate of 20 ° C./min using a differential scanning calorimeter (DSC) DSC-220 manufactured by Seiko Instruments Inc.

<Synthesis Example of Crystalline Polyester Resin (A)>
In a reaction vessel equipped with a stirrer, a thermometer, and an outflow condenser, 530 parts by weight of terephthalic acid, 85 parts by weight of isophthalic acid, 203 parts by weight of adipic acid, 928 parts by weight of 1,4-butanediol, 0. 4 parts of tetrabutyl titanate. 34 parts by weight was added, and an esterification reaction was performed at 170 to 220 ° C. for 2 hours. After completion of the esterification reaction, the reaction system was heated from 220 ° C. to 250 ° C., while the pressure inside the system was slowly reduced to 500 Pa over 60 minutes. Further, a polycondensation reaction was performed at 130 Pa or lower for 55 minutes to obtain a polyester resin (A).

As a result of NMR analysis, the crystalline polyester resin (A) has a composition in which the dicarboxylic acid component is 63 mol% terephthalic acid, 10 mol% isophthalic acid, 27 mol% adipic acid, and the diol component is 100 mol% 1,4-butanediol. Had. The glass transition temperature was −6 ° C., the number average molecular weight was 35,000, and the acid value was 28 equivalents / 10 ⁶ g.

  The crystalline polyester resins (B) and (C) were produced in the same manner as the crystalline polyester resin (A). The composition and measurement results are shown in Table 1. (Figures are mol% in resin)

<Synthesis Example of Amorphous Polyester (D)>
960 parts by weight of dimethyl terephthalate, 527 parts by weight of ethylene glycol, 156 parts by weight of neopentyl glycol, 0.34 parts by weight of tetrabutyl titanate were added to a reaction vessel equipped with a stirrer, a thermometer, and an outlet cooler. The transesterification was carried out at 2 ° C. for 2 hours. After completion of the transesterification reaction, the temperature of the reaction system was raised from 220 ° C. to 270 ° C., while the pressure in the system was slowly reduced to 500 Pa over 60 minutes. Further, a polycondensation reaction was performed at 130 Pa or less for 55 minutes to obtain amorphous polyester (D).

As a result of NMR analysis, the amorphous polyester resin (D) had a composition in which the dicarboxylic acid component was 100 mol% terephthalic acid, the diol component was 70 mol% ethylene glycol, and 30 mol% neopentyl glycol. The glass transition temperature was 78 ° C. and the acid value was 30 equivalents / 10 ⁶ g.

  Amorphous polyester resins (E) to (I) were produced in the same manner as amorphous polyester (D). The composition and measurement results are shown in Table 1. (Figures are mol% in resin)

<Synthesis Example of Reactive Compound (J)>
A reactor equipped with a stirrer, a thermometer, a reflux device and a quantitative dropping device was charged with 50 parts of methyl ethyl ketone, heated to 70 ° C., 36.4 parts by weight of styrene, 37.3 parts by weight of glycidyl methacrylate, 26. A solution obtained by dissolving 3 parts by weight of the mixture and 2 parts of azobisdimethylvaleronitrile in 50 parts of methyl ethyl ketone was added dropwise to the methyl ethyl ketone in the reactor at 1.2 ml / min, and stirring was continued for another 2 hours. Thereafter, by reducing the pressure, methyl ethyl ketone was removed from the reactor to obtain a reactive compound (J).

  As a result of NMR analysis, this reactive compound (J) had a composition of 40 mol% styrene, 30 mol% glycidyl methacrylate, and 30 mol% methyl methacrylate. The glass transition temperature was 50 ° C. and the weight average molecular weight was 25,000.

<Synthesis Example of Reactive Compound (K)>
Prepared by emulsion polymerization in a 3 liter round bottom flask equipped with stirrer, cooler and heating mantle. The flask was initially charged with a solution consisting of 1800 parts deionized water, 0.4 part acetic acid, 0.01 part FeSO ₄ , and 0.12 part ethylenediaminetetraacetic acid sodium salt dihydrate. The solution was sparged with nitrogen gas and heated to 75 ° C. At 75 ° C, 366.1 parts of styrene, 14.4 parts of hydroxyethyl methacrylate, and 95.5 parts of butyl methacrylate monomer emulsified with 5.4 parts of sodium dodecylbenzenesulfonate in 150 parts of water are added to the flask. Then, 0.45 parts of sodium persulfate was added as an initiator. The reaction was then allowed to proceed for about 2 hours or until more than 99.9% of the monomer was replaced by investigation of solids content. After completion of the reaction, the emulsion was cooled to room temperature and then spray dried to obtain a white powder.

  As a result of NMR analysis, this reactive compound (K) had a composition of monomer components of 77 mol% styrene, 3 mol% hydroxyethyl methacrylate, and 20 mol% butyl methacrylate. The glass transition temperature was 50 ° C., and the weight average molecular weight was 200,000.

<Synthesis Example of Reactive Compound (L)>
The monomer component was synthesized by the same method as the reactive compound (K), and as a result of NMR analysis, the monomer component had a composition of styrene 75 mol%, glycidyl methacrylate 4 mol%, and butyl methacrylate 21 mol%. The weight average molecular weight was 300,000.

<Release agent / Lubricant>
(X-1) Partially saponified ester wax of montanic acid ester
: Rico wax OP (manufactured by Clariant)
(X-2) Montanic acid sodium salt: Recommont NaV101 (manufactured by Clariant)
(Y-1) Polyethylene wax: Recolbe H12 (manufactured by Clariant)
(Y-2) Amide wax: Recolb FA1 (manufactured by Clariant)
(Z-1) Glycerol monostearate: Riquester M100 (manufactured by Riken Vitamin Co., Ltd.)
(Z-2) Propylene glycol monostearate: “Riquemar PS100” (manufactured by Riken Vitamin)
(Z-3) Citric acid saturated fatty acid monoglyceride: “Poem K30” (manufactured by Riken Vitamin Co., Ltd.)

<Example 1>
Polyester resin (D) 90 wt%, reactive compound (J) 9 wt%, montanic acid wax (Licowax OP) 1.0 wt%, bis [S- (4-tert-butyl-3- Hydroxy-2,6-dimethylbenzyl)] thioterephthalate (1.0 part by weight) and talc (10 parts by weight) were mixed, and the mixture was an extruder (L / D = 30) set at a rotation speed of 30 rpm and a total barrel temperature of 220 ° C. The polyester resin modifier was obtained by melt kneading at a screw diameter of 20 mm, full flight, compression ratio of 2.0), extruding into a string from a nozzle, and cutting into pellets by cutting with a cutter in water.

[Evaluation by injection molding]
30 parts by weight of the above polyester resin modifier and 70 parts by weight of polyester (A) are dry blended, and the cylinder temperature is 230 ° C. and the mold temperature in an injection molding machine (Toshiba IS-100E: mold clamping force 100 tons). A test piece for a physical property test at 30 ° C. and a back pressure of 20 kg / cm ² was produced. Using this, evaluation was performed by the following method. The results are shown in Table 2.

Reduced viscosity increase / decrease tendency:
◎: Reduced viscosity increased by 15% or more ○: Reduced viscosity not increased ×: Reduced reduced viscosity

Continuous productivity:
○: “Injection time, injection pressure, etc. are stable, dimensional accuracy of the product is good, and surface smoothness is good”,
X: “Injection time, injection pressure, etc. are unstable, dimensional accuracy of the product varies, surface smoothness, gloss, etc. are not stable”.

Mold releasability:
○: “Good releasability from mold”
×: “Removability from the mold is poor”
It was.

Impact resistance test: Notched Izod impact strength (ASTM D-256)
(Test temperature: 23 ° C)
○: 40 J / m or more Δ: 25 J / m or more and less than 40 J / m ×: less than 25 J / m

[Evaluation by profile extrusion molding]
30 parts by weight of the above modifier for polyester resin and 70 parts by weight of polyester (A) are dry blended, the cylinder temperature is set to 210 ° C., and a single screw extruder (L / D = 25, full flight screw, screw) A die lip for producing the molded product shown in FIG. 1 is attached to the diameter 65 mm), and then a sizing die for determining the final dimension of the profile extrusion product is attached to the tip of the cooling water tank, and a take-up machine is equipped via the water tank. Molding was performed using a profile extrusion molding facility, and the sizing mold processing status, product dimensional accuracy, surface smoothness, and presence of product warpage of the molded product were evaluated according to the following criteria. The results are shown in Table 2.

Sizing mold processing status (continuous productivity):
○: “There was no resin adhesion in the sizing mold, the workability was smooth, and the edge shape accuracy of the molded product between the die and the sizing was high.”
×: “Resin adhesion occurred in the sizing mold, and it was not possible to move to the sizing process. Or, the sizing process had poor processability, the edge accuracy of the molded product was low, and the continuous productivity deteriorated.” did.

Product dimensional accuracy: Profile extrusion molding with a die lip for manufacturing the molded product shown in FIG. 1 was performed, and the product dimensional accuracy of the molded product was evaluated.
○: Product dimensions are as designed △: Product dimensions deviate from the design value by less than 0.3 mm ×: Product dimensions deviate from the design value by 0.5 mm or more

Surface smoothness: The outer surface unevenness state of the molded product was measured using an ultra-deep surface shape measuring microscope (VK-8500 manufactured by Keyence), and the following evaluation was performed.
○: Maximum height of uneven surface is less than 100 μm Δ: Maximum height of uneven surface is 100 μm or more and less than 200 μm ×: Maximum height of uneven surface is 200 μm or more

Product warpage evaluation: With respect to the extrusion molding direction of the profile extruded product, the presence or absence of warpage in the vertical and horizontal directions was evaluated as follows.
Existence: Up / down / left / right warpage with respect to the extrusion molding direction No: Up / down / left / right warpage with respect to the extrusion molding direction Table 2 shows the results of evaluation of the melt strength of the resin.

[Evaluation by direct blow molding]
30 parts by weight of the above modifier for polyester resin and 70 parts by weight of polyester (A) are dry-blended to produce a direct blow molding machine (single screw extruder: L / D = 25, full flight screw, screw diameter 65 mm). Cylinder temperature was set to 180-230 degreeC, and the direct blow molding bottle shown in FIG. 2 was manufactured. A parison forming die lip was attached to the tip of the cylinder, and blow air was sealed in the mold to continuously produce bottles. At this time, the parison holding state, product dimensional accuracy, and transparency were evaluated according to the following criteria.

Parison holding state:
○: The drawdown is very small and the shape is maintained. △: The drawdown is large and the shape collapses, but it can be blown somehow.

Product accuracy:
○: Small burr and uniform thickness ×: Large burr and uneven thickness

[Evaluation by calendar molding]
30 parts by weight of the polyester resin modifier and 70 parts by weight of polyester (A) were dry blended and kneaded on two 6 inch test rolls set at 200 ° C. Remove the resin adhering to the test roll with an occasional spatula, mix and mix for 5 minutes, then set the roll spacing to 0.3 mm (sheet thickness set to 0.3 mm), take the molten sheet to a distance of 30 cm from the roll, The take-up property of the sheet was evaluated by visually observing the sagging at that time. Moreover, the sheet peelability from the roll at that time was also evaluated. The evaluation criteria are as follows.

Sheet peelability:
○: Good peelability from rolls △: Strong stickiness to rolls, and sometimes difficult to peel off, making stable mass production ×: Strong stickiness to rolls, difficult to peel off, collecting normal sheets Can not

Sheet take-up property ◎: No sagging occurs ○: Slight sagging occurs, but there is no problem in practical use △: Sheet production is possible by adjusting the roll temperature conditions, etc., but stable mass production is not possible ×: Molten sheet is sagged by its own weight , Normal sheet can not be collected

<Examples 2 to 12, Comparative Examples 1 to 16>
When the polyester resin was a crystalline resin under the same conditions as in Example 1 using the raw materials listed in Tables 2 and 3, various melt moldings were performed at a temperature 30 ° C. higher than the melting point. When the polyester resin is an amorphous resin, various melt moldings were performed at 180 to 250 ° C. In addition, about Comparative Examples 1-6, the stabilizer was added to each polyester resin, various shaping | molding was performed, and it evaluated. In Comparative Examples 7 to 9, an impact resistance improver and a polyester resin were dry blended (blend of pellets and compound on powder) and molded. In Comparative Example 10, the reactive compound (II) and the polyester resin were dry blended and molded. In Comparative Example 11, a polyester resin and amorphous polyester (I) were dry blended and molded. In Comparative Example 12, a polyester resin, a reactive compound (II), and a lubricant (III) were dry blended and molded. Comparative Example 13 was a dry blend of polyester resin, reactive compound (II) and lubricant (III) in a total amount, and an extruder (L / D = 30, screw diameter = 20 mm, rotation speed set to 30 rpm, total barrel temperature 220 ° C. The polyester resin composition was melt-kneaded at full flight with a compression ratio of 2.0), extruded from a nozzle into a string, cut with a cutter in water and pelletized, and various types of molding were performed using the pellets. In Comparative Example 14, a polyester resin, amorphous polyester (I), reactive compound (II), and lubricant (III) were dry blended and molded. In Comparative Examples 15 and 16, dry polyethylene terephthalate resin, reactive compound (II) and lubricant (III) were first dry blended at a ratio of 47.5 / 5 / 47.5 parts by weight. Melted and kneaded with an extruder (L / D = 30, screw diameter = 20 mm, full flight, compression ratio 2.0) set at a barrel temperature of 270 ° C., extruded into a string from a nozzle, cut with a cutter in water and pelleted The resulting polyester resin composition was further dry-blended with a recycled polyethylene terephthalate resin at a ratio of 20/80 parts by weight, and various moldings were performed.
The evaluation results are also shown in Tables 2 and 3.

In addition, the stabilizers described in Tables 2 and 3 mean the following compounds.
M: Bis [S- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)] thioterephthalate

In Tables 2 and 3, the following were used as PET, PBT, and recycled PET.
PET: Polyethylene terephthalate Toyobo Co., Ltd. RE530
PBT: Polybutylene terephthalate Mitsubishi Engineering Plastics Nova Duran 5010R3
Recycled PET flake: YPR flake manufactured by Yono PET Bottle Recycle Co., Ltd.

  The mixing ratios in Tables 2 and 3 are {polyester resin + amorphous polyester resin (I) + reactive compound (II), mold release agent / lubricant (III)} at a weight ratio of 100, stabilizer, added The agent was expressed as the amount added relative to its 100 weight ratio.

As can be seen from Tables 2 and 3, in Examples 1 to 12, improvements in injection moldability, continuous productivity, and mechanical properties were realized. Concerning the profile extrusion processability, continuous productivity was improved. Increased dimensional accuracy and surface smoothness (removal of chatter) of extruded products, improved product warpage during continuous production, and improved resin sag during profile extrusion processing. Product corner and edge shape accuracy between die and sizing. It is excellent to improve.
In direct blow molding, the holding of the parison is excellent, and the product accuracy is also improved, so that the stability during continuous production and the yield rate of non-defective products are greatly improved.
In calendering molding, the melt strength of the polyester resin composition is greatly improved, so that the sheet peelability from the roll and the sheet take-off property are improved, and a sheet with excellent dimensional accuracy and surface properties is stably produced. I can do things.

On the other hand, Comparative Examples 1 to 6 do not contain the reactive compound (II) and the lubricant (III), and thus are outside the scope of the present invention. Since Comparative Example 10 does not contain amorphous polyester resin (I) and lubricant (III), it is out of the scope of the present invention. Comparative Example 11 is outside the scope of the present invention because it does not contain reactive compound (II) or lubricant (III). Since Comparative Examples 12 and 13 do not contain the amorphous polyester resin (I), they are out of the scope of the present invention. Moreover, since Comparative Examples 10-14 are not used as modifiers, they are outside the scope of the present invention. Comparative Examples 15 and 16 are out of the scope of the present invention because the modifier was prepared from polyethylene terephthalate without using the amorphous polyester resin (I).
Further, Comparative Example 10 has a tendency to prevent resin sag by adding a reactive compound, slightly improve product dimensional accuracy, and to prevent adhesion to molds, metal rolls, etc. due to the release agent / lubricant (III). However, since the dry blend molding is performed, the quantitative amount of the added amount is lowered, the dispersibility becomes unstable, and various qualities are adversely affected. In Comparative Examples 7 to 9, adhesion to a mold, a metal roll or the like was improved, but continuous productivity was deteriorated. In addition, although the resin fluidity in the sizing mold is slightly improved, it is not stable, so that the dimensional accuracy and surface smoothness of the profile extrusion product deteriorate, and further, the problem of product warpage occurs and the profile extrusion product is not suitable. Appropriate status. In direct blow molding, the parison retention is slightly improved, but the melt characteristics are not stable, so the product accuracy is lowered. In calendar molding, the sheet formability is slightly improved, but the take-off property is deteriorated. In Comparative Example 12, as a result of various moldings using pellets obtained by melt-kneading all the amorphous polyester resin (I), the reactive compound (II), and the release agent / lubricant (III), Although the viscosity increased, the reactivity suddenly occurred and the surface property deteriorated due to the generation of a gel-like material. In addition, since the tendency of the melt viscosity to gradually increase during continuous production, the desired product dimensions could not be obtained in injection molding, profile extrusion molding, direct blow molding, calendar processing molding, and the like. In Comparative Examples 15 and 16, there is a tendency to prevent adhesion to molds, metal rolls, etc., but because of the modifier based on unused PET, crystallization at the time of injection molding is fast, and the sink of the molded product Etc. could not be suppressed, and continuous productivity deteriorated. In addition, the resin fluidity in the sizing mold is slightly improved, but it is not stable, so the dimensional accuracy and surface smoothness of the profile extrusion product deteriorate, and further the problem of product warpage occurs, making it inappropriate as a profile extrusion product. It became a state. In addition, since the effect of delaying crystallization in the product cooling process is small, there is a problem that the dimensional accuracy of the product after passing through the sizing die changes with time. In direct blow molding, the parison retention is slightly improved, but the melt characteristics are not stable, so the product accuracy is lowered. In calendar molding, the sheet formability is slightly improved, but the take-off property is deteriorated.

  Improved molding properties in melt molding, especially injection molding, extrusion molding, profile extrusion molding, direct blow molding, and excellent mechanical properties by blending with polyester resins, particularly recycled PET flakes, using the modifier of the present invention It is possible to express improvements in the industry and contribute greatly to the industry.

It is sectional drawing of the profile extrusion molded product which evaluated. It is the figure of the direct blow molded product which evaluated.

Claims (19)

  Including amorphous polyester resin (I), reactive compound (II) containing two or more glycidyl groups and / or isocyanate groups per molecule and having a weight average molecular weight of 200 to 500,000, and lubricant (III) A modifier for polyester resin.   The polyester resin modifier according to claim 1, wherein the lubricant (III) is at least one compound selected from the group consisting of montanic acid ester wax, polyethylene wax and amide wax.   The polyester resin modifier according to claim 2, wherein the montanic acid ester wax is a metal salt.   The polyester resin according to claim 1, wherein the lubricant (III) is at least one compound selected from the group consisting of a glycerin compound, a sorbitan compound, a propylene glycol compound and a higher alcohol compound. Modifier.   The lubricant (III) is at least one compound selected from the group consisting of glycerin organic acid ester, polyglycerin organic acid ester, sorbitan organic acid ester, propylene glycol organic acid ester and higher alcohol organic acid ester. The modifier for polyester resins according to claim 1.   6. The polyester resin modifier according to claim 5, wherein the organic acid is a fatty acid having less than 40 carbon atoms.   The polyester resin modifying agent according to any one of claims 1 to 6, wherein the polyester resin for modification is polyethylene terephthalate (PET) or polybutylene terephthalate (PBT).   The polyester resin modifying agent according to any one of claims 1 to 6, wherein the polyester resin for modification is recycled polyethylene terephthalate.   Reactive compound (II) is (X) 20-99 wt% vinyl aromatic monomer, (Y) 1-80 wt% hydroxyalkyl (meth) acrylate or glycidylalkyl (meth) acrylate, and (Z) The modifier for a polyester resin according to any one of claims 1 to 8, which is a copolymer comprising 0 to 40% by weight of an alkyl (meth) acrylate.   Amorphous polyester resin (I) is 50 mol% or more of an aromatic dicarboxylic acid having 8 to 14 carbon atoms as an acid component, and 50 mol% or more of an aliphatic or alicyclic glycol having 2 to 10 carbon atoms as a glycol component. The modifier for polyester resins according to claim 1, wherein the modifier is contained.   The modifier for polyester resin according to claim 10, wherein the aromatic dicarboxylic acid having 8 to 14 carbon atoms is terephthalic acid and / or isophthalic acid.   Aliphatic or alicyclic glycols having 2 to 10 carbon atoms are ethylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol and 2-methyl-1,3-propane. The modifier for polyester resins according to claim 10 or 11, wherein the modifier is at least one selected from the group consisting of diols.   Amorphous polyester resin (I) contains 0.001 to 5 mol% of a polyfunctional compound unit having three or more carboxyl groups, hydroxyl groups or ester-forming groups thereof in the acid component and / or glycol component of the polyester. The modifier for polyester resins according to any one of claims 1 to 12, wherein:   A reactive compound (II) containing 40 to 99.8% by weight of the amorphous polyester resin (I), containing two or more glycidyl groups and / or isocyanate groups per molecule and having a weight average molecular weight of 200 to 500,000. The modifier for polyester resins according to any one of claims 1 to 13, comprising 0.1 to 50% by weight and lubricant (III) in an amount of 0.1 to 50% by weight.   Reactive compound in which the total amount of the crystalline polyester resin and the amorphous polyester is 55 to 99.945% by weight, contains 2 or more glycidyl groups and / or isocyanate groups per molecule, and has a weight average molecular weight of 200 to 500,000 A resin composition containing (II) in a range of 0.005 to 30% by weight and lubricant (III) in a range of 0.05 to 15% by weight.   The resin composition according to claim 15, wherein the crystalline polyester resin is a recycled polyethylene terephthalate resin.   The resin composition containing the modifier and polyester resin in any one of Claims 1-14.   The molded product containing the modifier and polyester resin in any one of Claims 1-14.   The manufacturing method of the molded article which mixes the modifier and polyester resin in any one of Claims 1-14, and melt-molds.

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