JP2008031482A - Method for producing polyethylene terephthalate-based graft copolymer resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve such the problems that the utilization of a polyethylene terephthalate (PET)-based polyester as general-purpose plastics such as a polyolefin is limited because of small absolute molecular weight and melt viscosity, and narrow molecular weight distribution, and gel and fisheye are generated as byproducts under long-term operation although conventionally improvements of the molecular weight and the melt viscosity have been carried out by a modifier comprising an epoxy resin of a low-molecular weight liquid and a binding reaction catalyst. <P>SOLUTION: The production method involves converting a mixture constituted of (a) 100 pts.wt. PET-based polyester, (b) 0.01-2 pts.wt. mixture of a polymer-type polyfunctional epoxy resins as a binder, (c) 0.01-1 pt.wt. metal salt complex of an organic acid as a binding catalyst and (d) 0-100 pts.wt. aromatic polyester of a sub material into the PET-based graft copolymer resin having a huge molecular weight and a molecular weight distribution regulated so as not to become large by a reactive extrusion method. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention is a modified material comprising a polyethylene terephthalate (hereinafter abbreviated as PET) resin having a relatively low molecular weight as a main raw material and an aromatic polyester as a secondary raw material, comprising a polymeric polyfunctional epoxy binder and an organic acid catalyst. Polyethylene terephthalate-based graft copolymer resin that has improved the molding processability and resin physical properties by increasing the molecular weight and melt viscosity and controlling the expansion of the molecular weight distribution by adding a mass agent and causing a uniform binding reaction. It relates to the manufacturing method.
More specifically, the present invention relates to a low molecular weight PET-based resin after polycondensation, a medium to high molecular weight PET-based resin after solid-phase polymerization, or a PET recovered by reducing the molecular weight and physical properties by using them. In the reactive extrusion method, a modifier composed of a polymer-type polyfunctional epoxy binder and an organic acid metal catalyst is added to an aromatic polyester containing a carboxyl group in the aromatic core, and an aromatic polyester containing an aromatic nucleus. By forming a uniform binding reaction over a long period of time, there is no by-product of gel or fish eye, and molecular weight distribution is increased and molecular weight distribution is controlled by increasing molecular weight and melt viscosity. The present invention relates to providing a method for producing a polyethylene terephthalate-based graft copolymer resin that is improved on a periodic basis.

  Conventional aromatic saturated polyesters have excellent physical properties as thermoplastic resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene-2,6-naphthalenedicarboxylate (PEN), and the like. Widely used as fiber, film, plastic, etc. In the plastic field, molded products are widely used in bottles, sheets, containers, daily necessities, automobiles, machine parts, electrical / electronic materials, building materials, various industrial products, and the like.

  In recent years, from the viewpoint of resource conservation and environmental conservation, the need for reuse of used plastic products collected from the factory production process and general consumer market has been recognized globally, especially polyethylene terephthalate. The collection and reuse of bottles and films are actively promoted. Polyethylene terephthalate contains a small amount of isophthalic acid in addition to terephthalic acid, and in recent years, polyesters containing cyclohexanedimethanol such as PETG are also mixed. Such a crystalline PET-based polyester causes a significant decrease in molecular weight due to self-hydrolysis with a trace amount of water after a thermal history of the molding process. In this case, an increase in the number of free carboxyl groups at the molecular end due to the cleavage of the ester bond is a problem in practical use, which has been an obstacle for developing a recycling technology for recovered bottles and sheets. Since the used recovered PET bottle has a molecular weight lower than that of a new pellet, for example, the molecular weight of recovered PET bottle flakes (crushed material) derived from a large amount is almost halved. When it is reused as a raw material resin, the molding processability is poor, it does not become an original PET bottle, but only a single fiber or egg pack sheet that can be molded even with a low molecular weight, and its reuse is limited to a narrow range.

Solutions for these problems include methods for recovering molecular weight by solid-phase polymerization of PET polyester, methods for reacting chain extenders with hydroxyl groups or carboxylic acid groups of polyester end groups, elastomers to supplement mechanical properties, etc. Methods such as adding other resins are known.
As the chain extender, use of a compound having a functional group such as isocyanate, oxazoline, epoxy, aziridine, carbodiimide has been proposed. However, there are strong restrictions from reactivity, heat resistance, safety, stability, etc., and those with practicality are limited.
Among these, the epoxy compound is relatively useful, such as a combination of a monoepoxy compound [Patent Document 1] JP-A 57-161124, a combination of a diepoxy compound [Patent Document 2] JP-A 7-166419, [Patent Document 3] Japanese Patent Publication No. 48-25074, [Patent Document 4] Japanese Patent Publication No. 60-35944, etc., but the reaction rate, gel by-product, melt viscosity, compatibility, thermal stability, There were many problems in physical properties.

On the other hand, a method of melting and mixing the recovered PET polyester with a bifunctional epoxy resin and a sterically hindered hydroxyphenylalkylphosphonic acid ester to increase the molecular weight of the polyester [Patent Document 5] Japanese Patent Publication No. 8-508877 Proposed. Although this method has a relatively fast reaction rate, the resin produced is a linear structure similar to that of conventional PET, so the increase in melt viscosity is small and the effect of improving moldability is small. Further, the sterically hindered cedoxyphenylalkylphosphonic acid ester to be used is expensive, and there is a problem in practicality in the industry where low cost recovery and recycling costs are required. In addition, methods of blending rubber and elastomer with polyester have been proposed, but in those cases, there are problems in compatibility, heat resistance, elastic modulus and the like.
The present inventors previously added a bifunctional and trifunctional mixed epoxy resin (low molecular weight liquid) and an organic acid metal based catalyst to the PET polyester, and melt-mixed by a reactive extrusion method to form a long chain branched structure. A method of increasing the molecular weight of PET polyester in a short time [Patent Document 6] 3503952 has been proposed. However, gel and fisheye (FE) by-product problems caused by heterogeneous local reactions in a high-speed binding reaction for several minutes occurred.
Next, a method in which a bifunctional and trifunctional mixed epoxy resin (low molecular weight liquid) and an organic acid metal catalyst are homogeneously reacted with a master batch obtained by diluting with PET polyester about 1/10 [Patent Document 7] WO 2001-94443 was proposed. This greatly improved the by-product of gel and fish eye (FE) in the high-speed binding reaction for several minutes by the reactive extrusion method. Even in this masterbatch method, it is difficult in principle to uniformly mix a small amount of low-viscosity liquid epoxy resin with a high-viscosity resin in a reactive extruder. Needed. Also, in long-term operation of several days or more, the completeness of the reaction is uneven, the melt viscosity (MFR) of the pellet fluctuates, and a small amount of gel or Fisheye (FE) by-product tended to increase over time.

Problems to be solved by the invention

  In the present invention, when a PET resin having a molecular weight and a melt viscosity increased by a reactive extrusion method by adding a modifier comprising a binder and a catalyst to a PET polyester resin having a relatively low molecular weight, A method for producing a PET-based polyester resin that is free from by-product formation of gel and fish eye (FE) even when uniformly reacted for a period of time, and has dramatically improved molding processability and resin physical properties compared to conventional PET The purpose is to provide.

Means to try to solve the problem

  As a result of intensive research to solve the above-mentioned problems, the present inventors have added a modifier comprising a binder and a catalyst to a PET polyester resin having a relatively low molecular weight as a main raw material, and reactive extrusion. When a PET resin is produced by increasing the molecular weight and melt viscosity by the method, it replaces the conventional low-molecular-weight liquid 2-3 functional (up to 6 functional) mixed epoxy resin binder and is a multifunctional high molecular weight solid. By using an epoxy-based binder and a mixture thereof, there is no by-product of gel and fish eye (FE) even after a long-term uniform binding reaction, and the conventional low molecular weight liquid has 2-3 functionalities (up to 6). Functional) How to make PET polyester resin with dramatically improved molding processability compared to mixed epoxy resin binder and drastically improved resin physical properties by using aromatic polyester together It found that industrially advantageous manner the object can be achieved by, and have completed the present invention. Further, when a small amount of the modifier of the present invention is used, it has been found that it acts as a crystal nucleating agent for PET resin and sheet, and the present invention has been completed.

  The present invention first includes (A) 100 parts by weight of a polyethylene terephthalate polyester, (B) a molecular weight of 1,000 to 300,000 of a skeletal resin as a binder, and 7 to 100 epoxy groups in the molecule. 0.01 to 2 parts by weight of a polymeric polyfunctional epoxy compound, (C) 0.01 to 1 part by weight of a metal salt of an organic acid as a coupling reaction catalyst, and (D) an aromatic system containing a carboxyl group in an aromatic nucleus Provided is a method for producing a polyethylene terephthalate-based graft copolymer resin characterized in that a mixture composed of 0 to 100 parts by weight of a polyester is uniformly reacted at a temperature of 250 ° C. or higher to increase the melt viscosity. .

  The present invention secondly includes (A) 100 parts by weight of a polyethylene terephthalate polyester, (B) a molecular weight of the backbone resin as a binder of 1,000 to 300,000, and 7 to 100 epoxy groups in the molecule. 0.01 to 2 parts by weight of a polymer type polyfunctional epoxy compound, (C) 0.01 to 1 part by weight of a metal salt of an organic acid as a coupling reaction catalyst, and (D) an aromatic system containing a carboxyl in an aromatic cough Special teaching that a mixture composed of 0 to 100 parts by weight of polyester is uniformly reacted at a temperature of 250 ° C. or higher by a reactive extrusion method to 280 ° C. by a JIS method and 50 g / 10 min or less at a load of 2.16 kg. A method for producing a polyethylene terephthalate graft copolymer resin pellet is provided.

  In the present invention, thirdly, the polyethylene terephthalate-based polyester (A) contains at least one of polyethylene terephthalate having an intrinsic viscosity of 0.60 to 1.25 dl / g or a recycled product of recovered polyethylene terephthalate cedar products. It provides the manufacturing method of the polyethylene terephthalate type graft copolymer resin characterized by containing.

  Fourthly, the present invention provides two types of polymer-type polyfunctional epoxy compounds (B) having a molecular weight of 1,000 to 300,000 of the backbone resin and 7 to 100 epoxy groups in the molecule as binders. The present invention provides a method for producing a polyethylene terephthalate-based graft copolymer resin, which specializes in controlling the molecular weight distribution by using a mixture.

  According to the present invention, fifthly, the organic acid metal salt (C) contains at least one member selected from the group consisting of an alkali metal carboxylate and an alkaline earth metal carboxylate. The present invention provides a method for producing a graft copolymer resin.

  In the present invention, sixthly, an aromatic polyester (D) containing carboxyl in an aromatic cough is obtained from amorphous ethylene glycol, cyclohexanedimethanol, terephthalic acid (PETG), polyester elastomer and crystalline polybutylene terephthalate. The present invention provides a method for producing a polyethylene terephthalate-based graft copolymer resin, which contains at least one member selected from the group consisting of:

  The present invention sixthly includes (A) 100 parts by weight of a polyethylene terephthalate polyester, (B) a molecular weight of the skeleton resin as a binder of 1,000 to 300,000, and 7 to 100 epoxy groups in the molecule. A mixture composed of 0.01 to 0.3 parts by weight of a polymeric polyfunctional epoxy compound and (C) 0.01 to 0.3 parts by weight of a metal salt of an organic acid as a binding reaction catalyst is obtained by a reactive extrusion method. Polyethylene terephthalate-based graft copolymer resin sheet characterized by producing a polyethylene terephthalate-based graft copolymer resin by uniformly reacting at a temperature of ℃ or higher, and then molding it into a high-speed crystalline sheet by casting at that temperature The manufacturing method of this is provided.

The invention's effect

  According to the present invention, by adding a modifier comprising a polymer type polyfunctional epoxy binder and a catalyst to a PET polyester resin having a relatively low molecular weight as a main raw material and an aromatic polyester resin as a secondary raw material, reactive extrusion is performed. When producing PET resin by increasing the molecular weight and melt viscosity by the method, unlike the conventional low molecular weight liquid 2-3 functional (up to 6 functional) mixed epoxy binder, By using a functional (7-100 functional) epoxy-based binder and a mixture thereof, there is no by-product of gel and fish eye (FE) even when uniformly bonded for a long period of time, and it is extremely difficult with conventional PET. As a result, it has become possible to produce a PET-based polyester resin with dramatically improved molding processability and physical properties of the PET resin.

Hereinafter, the present invention will be described in detail.
(Polyethylene terephthalate polyester)
The polyethylene terephthalate polyester of component (A) used as the main raw material in the present invention is synthesized from a dicarboxylic acid component and a glycol component. Examples of the dicarboxylic acid component include aromatic and alicyclic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid. Of these, aromatic dicarboxylic acids, particularly terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferred.
Examples of the glycol component include ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, and cyclohexanedimethanol.
Of these, ethylene glycol is preferred.
Specific examples of the PET polyester to which the present invention can be applied include polyethylene terephthalate (PET), low-melting point PET obtained by copolymerizing a small amount of isophthalic acid, polyethylene-2,6-naphthalate (PEN), and the like. Polyethylene terephthalate (PET) is particularly preferred.

The PET-based polyester used in the present invention has an intrinsic viscosity of 0.60 dl / g or more measured at 25 ° C. by dissolving in a 1,1,2,2-tetrachloroethane / phenol (1: 1) mixed solvent. Is more preferable, and 0.70 dl / g or more is more preferable. When the intrinsic viscosity is less than 0.60 dl / g, it is difficult to achieve high differentiation according to the present invention, and the obtained polyester resin may not necessarily have excellent mechanical strength. The upper limit of the intrinsic viscosity is not particularly limited, but is usually 0.90 dl / g or less, preferably 0.80 dl / g or less, which is relatively inexpensive. The upper limit for the availability of commercially available PET is an intrinsic viscosity of 1.25 dl / g, but when used alone, the molding processability deteriorates. In the present invention, the intrinsic viscosity is 0.60-0.80 dl / g. It is preferable to use a mixture.
When a PET-based polyester recovered product is used, it is usually lower than the intrinsic viscosity of the molded product, and is generally 0.60 to 0.80 dl / g, particularly 0.65 to 0.00. It is about 75 dl / g. When the collected PET-based polyester molded product is used, the shape of the molded product may be any of a fiber, a film, a sheet, a bottle, and other molded products. In the polyester, other polymers such as, for example, Even if it contains a small proportion of polyolefin, polyacrylate, etc., it does not interfere with the reactive extrusion method. Also, those containing a small amount of additives such as fillers, pigments and dyes can be used. In particular, since PET bottles are being collected and a social environment for recirculation use is being prepared, and the polyester of the bottle has a composition suitable for reuse, it is suitable as the raw material polyester of the present invention.

(Polymer type multifunctional binder)
In the binder of the component (B) of the present invention, the molecular weight of the skeleton resin is 1,000 to 300,000, and a polymer type polyfunctional epoxy compound containing 7 to 100 epoxy groups in the molecule is used alone. Or it can use as a 2 or more types of mixture. Commercially available products in which a glycidyl group containing an epoxy ring is suspended in a high molecular weight resin or in a molecule containing an epoxy group, such as “Modiper” A series, “Nophalloy” IE series, “Blemmer”, “Falpack”, “Marproof” series, “Epofriend” series of Daicel Chemical Industries, Ltd., “Bond First” of Sumitomo Chemical Co., Ltd., etc. can also be used.
The skeleton resin is more preferably an acrylic resin type than a polyolefin type (PP, PS, PE). This is because the solubility parameters of the resin are: raw material PET 10.7, epoxy resin 10.8, polymethyl acrylate 10.2, polyethyl acrylate 9.4, polypropylene (PP) 9.3, polyethyl methacrylate 9 0.0, polystyrene (PS) 8.9, polyethylene (PE) 8.0, and the closer the numerical value, the better the mixing property.
In addition, even if the polyolefin type is mixed at 1-2%, the PET resin film / sheet is clouded, so it is not suitable when the molded product requires transparency. However, since the foam and the pipe or the high heat-resistant container are white, they can be used for applications that do not require transparency.

The present inventors have used a compound containing 2 to 3 or 4 to 6 epoxy groups in the molecule by a conventional method. For example, compounds having two epoxy groups in the molecule are typically aliphatic ethylene glycol diglycidyl ether (molecular weight 174, epoxy equivalent 135 g / eq., Number of functional groups 2 / molecule) or aromatic. Bisphenol A · diglycidyl ether (molecular weight: about 1,000, epoxy equivalent: 135 g / eq., Number of functional groups: 2 / molecule) and the like.
The compound having an average of 3 epoxy groups in the molecule was trimethylolpropane triglycidyl ether (molecular weight 288, epoxy equivalent 150 g / eq., Number of functional groups 3 / molecule) as a representative example. Furthermore, polyfunctional compounds having an average of 3 or more epoxy groups in the molecule are typically epoxidized soybean oil (molecular weight of about 1,000, epoxy equivalent of 232 g / eq., Number of functional groups of 4 / molecule) and Epoxidized linseed oil (molecular weight: about 1,000, epoxy equivalent: 176 g / eq., Number of functional groups: 6 / molecule).
PET has an intrinsic viscosity (IV value) of 0.7 dl / g, a number average molecular weight of about 12,000, a small absolute molecular weight, and a molecular weight distribution of Mw / Mn2-3 which is extremely narrow. Therefore, the molecular weight of the product obtained by the conventional coupling reaction was 24,000 (bifunctional), 36,000 (trifunctional) and at most 72,000 (hexafunctional), while polyolefin resin was In general, the number average molecular weight is as large as 100,000 to 1,000,000, and the molecular weight distribution is very wide as Mw / Mn5-20. For example, PET is the Eiffel tower type, and the polyolefin resin is Mt. Fuji. Therefore, the former is difficult for the moldability and the latter is extremely easy.

The greatest feature of the present invention is that the use of a polymer-type polyfunctional epoxy compound alone or a mixture of two or more types results in a large number average molecular weight of 100,000 to 1,000,000 and a molecular weight distribution as in polyolefin resins. An object of the present invention is to provide a method for producing a polyethylene terephthalate graft copolymer resin containing an extremely wide reaction product. This is to make the molding processability of PET polyester extremely easy like polyolefin resin.
The molecular weight distribution expansion control method is, for example, as a polymer-type polyfunctional epoxy compound, for example, 100% of a skeleton resin having a molecular weight of 10,000 having 15 epoxy groups in the molecule and 30 epoxy groups in the molecule. By using a mixture consisting of 50% product and 25% product having 60 epoxy groups in the molecule, it is possible to graft from a raw PET with a molecular weight of 12,000 to a molecular weight of 190,000, a molecular weight of 370,000 and a molecular weight of 730,000. The coalescence can be carried out by producing them at their charging ratio and blending amount. However, although the polyolefin resin is a linear structure, the resin model is different because the product of the present invention is a graft copolymer. Generally, PET-based polyesters are usually synthesized so that both ends are hydroxyl groups. However, since one end also has an aromatic carboxylic acid group, the polyester-based polyester undergoes a binding reaction with the epoxy compound of the present invention. Therefore, the model image of the product of the present invention is a sea of unreacted raw material PET having a molecular weight of 12,000 (the hydroxyl groups at both ends do not react), for example, having a molecular weight of 190,000, a molecular weight of 370,000, and a molecular weight of 730,000. It is a state in which chestnut crushed graft copolymers are dispersed at respective charging ratios.

(B) The compounding quantity of the polymeric polyfunctional epoxy compound of a component is 0.01-2 weight part with respect to 100 weight part of PET polyester of the (A) component. For applications such as blown film, foam, and pipe that require an increase in the molecular weight and melt viscosity of the main raw material polyester polyester (A) and auxiliary raw material polyester (D), 0.1 to 2 parts by weight, particularly 0. 4 to 1 part by weight is preferred. If it is less than 0.1 parts by weight, the effect of increasing the molecular weight and melt viscosity is insufficient, the molding processability is insufficient, and the basic physical properties and mechanical properties of the molded product are inferior. On the other hand, if it exceeds 2 parts by weight, the moldability deteriorates, and the resin is yellowed and colored, and by-produces gel and FE.
On the other hand, when the polymer type polyfunctional epoxy compound of component (B) is used as a “crystallization nucleating agent” for a specific use sheet and board, B) 0.01 to 0.3 parts by weight of a polymer type polyfunctional epoxy compound is used together with 0.01 to 0.3 parts by weight of (C) a binding reaction catalyst. If it is 0.01 parts by weight or less, the crystallization speed of the sheet and the board is slow, and if it is 0.3 parts by weight or more, the transparency of the sheet is lowered. 0.05-0.15 weight part is preferable.
In the present invention, as the blending amount of the polymer-type polyfunctional epoxy compound increases, the melt tension and the extension viscosity of the main raw material PET-based polyester (A) and the auxiliary raw material polyester (D) increase. Greatly improved. Further, since the polymer-type polyfunctional epoxy compound and the carboxylic acid metal salt-based catalyst act as a “molecular size crystal nucleating agent”, the crystallization speed of the PET-based polyester resin is increased. As an effect in the molding process, for example, the injection molding cycle is shortened, and the productivity is improved. Inflation / film molding stabilizes the bubble and reduces the uneven thickness of the film. In T-die / film forming, horizontal extrusion is possible, neck-in is reduced, and film yield is improved. In sheet molding, the drawdown property is improved and stable molding becomes possible. In particular, foam molding can be easily performed with a PET polyester resin having a large swell and melt tension. Since horizontal extrusion is possible, pipes and profile extrusion can be formed.
A major feature of resin production by the reactive extrusion method of the present invention is that the melt viscosity of the raw material PET (A) and (D) and the polymer type polyfunctional epoxy “solid” is almost the same, so that the mixing property in the extruder is particularly good. The problem of yellowing / coloration and gel or FE by-product caused by the use of the conventional low molecular weight epoxy “liquid” is eliminated.

(Binding reaction catalyst)
(1) Alkali metal organic acid salt, carbonate and bicarbonate, (2) Alkaline earth metal organic acid salt, (3) Aluminum, zinc Or a catalyst containing at least one selected from the group consisting of manganese organic acid salts. As the organic acid salt, carboxylate, acetate and the like can be used, but stearates are particularly preferable among the carboxylates. The metal that forms the metal salt of the carboxylic acid can be an alkali metal such as lithium, sodium and potassium; an alkaline earth metal such as magnesium, calcium, strontium and barium.
The compounding amount of the carboxylate as the binding reaction catalyst is 0.01 to 1 part by weight with respect to 100 parts by weight of the PET polyester as the component (A). In particular, the amount is preferably 0.1 to 0.5 part by weight. If it is less than 0.01 parts by weight, the catalytic effect is small, the reaction is not achieved, and the molecular weight may not be increased sufficiently. If the amount exceeds 1 part by weight, problems such as gel generation due to local reactions and troubles in the extruder due to rapid increase in melt viscosity due to acceleration of hydrolysis are caused.

(Aromatic polyester containing carboxyl in the aromatic nucleus)
The aromatic polyester containing carboxyl in the aromatic nucleus of the component (D) used as an auxiliary material in the present invention is amorphous ethylene glycol, cyclohexane dimethanol, terephthalic acid (PETG), polyester elastomer and crystallinity. It is selected so as to contain any one or more of the group consisting of polybutylene terephthalate (PBT). Since the modified PET resin has almost the same physical properties as commercially available PET since almost 99% is raw material PET, it can be used in new applications such as inflation film, adhesive film, fusing shrink film, foam and Development of applications such as pipes is difficult.
Co-polymerization with the auxiliary material of the present invention enables the development of new applications. Regarding the improvement of PET resin, amorphous ethylene glycol, cyclohexanedimethanol, terephthalic acid (PETG) contributes to, for example, the moldability and transparency of blown film, the shrinkability of blown shrink film, and the like. The polyester elastomer contributes to, for example, adhesiveness of an adhesive film, impact resistance of containers, foams and pipes, and flexibility of an inflation film. Crystalline polybutylene terephthalate (PBT) contributes to the promotion of recrystallization during the molding of containers, foams and pipes.
The blending amount of the aromatic polyester containing carboxyl in the aromatic nucleus of the component (D) is 0 to 100 parts by weight, preferably 2 to 80 parts by weight with respect to 100 parts by weight of the polyethylene terephthalate polyester of the component (A). Part. Each of these amounts is selected depending on the application. A part of practical examples will be shown in the examples described later, but the present invention is not limited thereto.

  In the polyester resin composition of the present invention, in addition to the polyester as the component (A), the epoxy group-containing compound as the component (B), the catalyst as the component (C), and the aromatic polyester as the component (D), a spreading material, Lubricants, antioxidants, stabilizers, UV absorbers, colorants, viscosity modifiers, antistatic agents, conductive agents, fluidity-imparting agents, mold release materials, and fillers such as talc, calcium carbonate, calcium oxide, kaolin, Alumina, aluminum hydroxide, etc., glass fibers, carbon fibers, aramid fibers, whiskers, etc. as reinforcing materials, carbon black, antimony oxide, molybdenum disulfide, titanium oxide, etc., may be optionally blended as pigments.

(Formulation method, binding reaction)
Next, a method for blending the polyester resin of the present invention will be described. As the PET-based polyester as the component (A), those having an arbitrary shape such as ordinary virgin chips, recovered flakes, granules, powders, and chips can be used. Drying is also optional. In general, it is preferable to dry the main component PET-based polyester. The same applies to the aromatic polyester as the component (D). Each component is mixed with a mixer such as a tumbler or a Henschel mixer, and then supplied to the extrusion apparatus. It is desirable from the viewpoint of the reactive extrusion method that the temperature for melting by heating is from 250 ° C. to 300 ° C. of the melting point of the polyester. In particular, it is preferably 280 ° C. or lower, particularly preferably 265 ° C. If it exceeds 300 ° C, the polyester may be discolored or thermally decomposed. In addition to the method of mixing each component at the same time, it is also possible to previously mix the component (A) and / or the component (D) (B) and then add the component (C) in an arbitrary step. It is also possible to mix the component (A) and / or the component (D) and the component (C) first, and then add the component (B) in an arbitrary step.

  As the reaction apparatus for heating and melting, a single-screw extruder, a twin-screw extruder, a combination two-stage extruder, or the like can be used. Inflation method film, adhesive film, blown shrink film, foam molding, pipe, sheet and board molding, hollow molding, injection molding, etc., when pre-formed by offline extrusion equipment Pellets can be used. On the other hand, the raw material mixture obtained by dry blending the above 3 to 4 components can be directly supplied to the hopper of the reaction extrusion apparatus and immediately molded by the in-line method. However, in the case of a single screw extruder, a specially structured screw with good mixing properties and a vacuum line where the resin does not vent up are required. It is important to select an optimum blending composition in consideration of the number of stages of the screw kneading process and heating conditions. In the case of a twin screw extruder, a screw structure with good mixing properties and a vacuum line where the resin does not vent up are required.

Hereinafter, the present invention will be described with reference to examples and comparative examples. The analytical instruments and measurement conditions used for measuring physical properties are shown below.
(1) The molecular weight was measured by the GPC method.
Showa Denko SYSTEM-21, column (both sample and reference side) Shodex KF-606M (2), solvent hexafluoroisopropyl alcohol, column temperature 40 ° C., flow rate 0.6 ml / min, polymer concentration 0.15% by weight , Detector Shodex RI-74, molecular weight conversion standard PMMA (Shodex M-75), injection volume 20 μl
(2) The melt flow rate (MFR) was measured according to JIS K6760 under conditions of a temperature of 280 ° C. and a load of 2.16 kg.
(3) The swell uses a melt indexer for MFR. The swell runs under the conditions of a temperature of 280 ° C. and a load of 2.16 kgg, cut when the sample hangs 2.0 cm, and measures the diameter at 5.0 mm from the lower end. It was calculated by the following formula. In practice, the diameter was measured several times and the average value was adopted. The numerical value “2.095” in the following formula is the nozzle diameter of the MFR melt indexer.
Swell (%) = [(average diameter−2.095) /2.095] × 100
(3) Intrinsic viscosity (IV value) was measured using a Canon Fenceke viscometer at 25 ° C. using a mixed solvent of equal weight of 1,1,2,2-tetrachloroethane and phenol.

Examples 1-10

[Method for Producing High Melt Viscosity Resin Pellets P1 ^to P10 from Recovered PET Bottle Flakes Using Polymer Type Polyfunctional Epoxy Only]
As PET-based polyester (A), recovered PET bottle flakes (Yono PET Bottle Recycle Co., Ltd., intrinsic viscosity 0.73 dl / g, MFR 56 g / 10 min, terminal carboxyl group amount 30 meq / kg) at 120 ° C. 100 parts by weight (400 g / time for each example, moisture content 150 ppm) dried in hot air for 12 hours, B1 (Falpack 200S, manufactured by NOF Corporation, PS skeleton MW6,000, epoxy equivalent) as a polymer type epoxy compound WPE 148 g / eq., 41 functional groups / molecule), B2 (Blemmer C P-30S, manufactured by NOF Corporation, PS skeleton MW 9,000, WPE 530 g / eq., 17 functional groups / molecule), B3 (Blemmer) CP-50M, manufactured by NOF Corporation, acrylic skeleton MW10,000, WPE310g / eq., 32 functional groups / Child), B4 (Blenmer CP-50S, Nippon Oil & Fats Co., Ltd., PS skeleton MW20,000, WPE 310 g / eq., Functional group 65), B5 (Marproof G-01100, Nippon Oil & Fat Co., Ltd., acrylic skeleton MW12, 000, WPE 1,700 g / eq., 71 functional groups / molecule), B6 (Malproof G-2050M, Nippon Oil & Fats Co., Ltd., acrylic skeleton MW 250,000, WPE 340 g / eq., 662 functional groups / molecule) Each predetermined weight part, 0.2 parts by weight of calcium stearate / sodium / lithium (50/25/25 weight ratio) composite as a binding reaction catalyst, 0.1 part by weight of Ciba Geykey IRGANOX B225 as a stabilizer, and 0.1 parts by weight of liquid paraffin as a spreading agent was manually mixed in a polyethylene bag.

  Using the same direction twin screw extruder (KZW15-30MG, screw diameter 25 mmΦ, L / D = 30, rotation speed 100 rpm, 1 vent type) manufactured by Technobel Co., Ltd., setting of screw and die of this extruder The temperature was set to 240 to 280 ° C., and the above-mentioned flake mixture was put into a hopper while being evacuated with a dry system pump, and fed at a predetermined speed with a feeder to carry out reactive extrusion. The strand is continuously extruded into water from a nozzle with a diameter of 3 mmΦ at a speed of about 2 m / min, cut with a rotary cutter to produce a transparent resin pellet, and the hot resin pellet is immediately dried with hot air at 140 ° C. for 4 hours. Later, it was stored in a moisture-proof bag or moisture-proof container.

  The reaction conditions, resin number, MFR (280 ° C., load 2.16 kg) and the like are shown in Table 1. The resin pellets of the present invention are characterized in that the MFR is controlled to a high melt viscosity of about 0.2 to 25 g / 10 min and the swell is as large as about 40 to 200%. However, the macromolecular weight of about 420,000 (P1-P2) is dispersed, the macromolecular weight of about 180,000 (P3) is dispersed, and the macromolecular weight is about 330,000 (P4-P6). Is dispersed, the macromolecular weight is approximately 660,000 (P7-P8) is dispersed, the macromolecular weight is approximately 720,000 (P9) is dispersed, and the macromolecular weight is approximately 6,630,000 (P10). A melt fracture occurred, and the surface was rough.

Examples 11-16

[Manufacturing Method of High Melt Viscosity Resin Pellets P11 to P16 with Expanded Molecular Weight Distribution Controlled from Collected PET / Bottle Flakes by Polymer Type Polyfunctional Epoxy Mixture]
Recovered PET bottle flakes (Yono PET Bottle Recycle Co., Ltd., intrinsic viscosity 0.73 dl / g, MFR 56 g / 10 min, terminal carboxyl group amount 30 meq / kg) as PET polyester (A) at 120 ° C. BM1 (B2: B3: B5 = 4: 2: 1), BM2 having a blend shown in Table 2 as a polymer-type epoxy compound in 100 parts by weight (400 g for each example, moisture content 150 ppm) dried with hot air for 12 hours (B2: B3: B5 = 10: 3: 1), BM3 (B2: B3: B5 = 20: 5: 1), BM4 (B2: B3: B5 = 100: 10: 1) 0.2 parts by weight of calcium stearate / sodium / potassium (50/25/25 weight ratio) composite as a binding reaction catalyst, Ciba Geyky IRGANOX B as a stabilizer 0.1 part by weight of 225 and 0.1 part by weight of liquid paraffin as a spreading agent were manually mixed in a polyethylene bag.

  Using the same direction twin screw extruder (KZW15-3MG, screw diameter 25 mmΦ, L / D = 30, rotation speed 100 rpm, 1 vent type) manufactured by Technobel Co., Ltd., setting of screw and die of this extruder While the temperature was set to 240 to 280 ° C., the above-mentioned flake mixture was put into a hopper while evacuating with a dry system pump, and the strand subjected to the binding reaction by supplying at a predetermined speed with a feeder had a diameter of 3 mmΦ. Continuous extruding into water at a speed of about 2 m / min from a nozzle, cutting with a rotary cutter to produce transparent resin pellets, hot resin pellets are immediately dried with hot air at 140 ° C. for 4 hours, Stored in moisture-proof container.

The reaction conditions, resin number, MFR (280 ° C., load 2.16 Kg), etc. are shown in Table 2. The resin pellets of the present invention are characterized in that the MFR is controlled to a high melt viscosity of about 12 to 34 g / 10 min, and the molding is generally stable without causing melt fracture of the strands.
In Example 13, the raw material PET is not a collected PET / bottle flake, but a new PET pellet (Mitsubishi Chemical, B2570, IV 0.78 dl / g, MFR 45 g / 10 min) is used. Since PET is manufactured to have fewer terminal carboxyl groups, the efficacy of the binder is slightly reduced to MFR 23.7, which is twice as large as MFR 12.7 of the produced pellet P12 of Example 12 using the recovered raw material PET. It is had.
As a general tendency, a resin from a mixture containing a large amount of a high-molecular-weight epoxy compound having a large number of functional groups is suitable for profile extrusion and foam molding. Surprisingly, the mixture BM1 containing the polymer epoxy compound B5 having the highest number of functional groups 71 and the highest ratio had good strand forming stability, and no gel or FE was generated on the press film.

Examples 17-18

[Inline inflation method film forming evaluation of high melt viscosity resins P17 to P18 in which molecular weight distribution is controlled from recovered pet bottle flakes, etc., with a high molecular weight polyfunctional epoxy mixture]
(Example 17): Recovered PET bottle flake (Kyoei Sangyo Co., Ltd., intrinsic viscosity 0.78 dl / g, MFR 45 g / 10 min) as PET-based polyester (A) was hot-air dried at 120 ° C. for 12 hours 50 Parts by weight (200 g, moisture content 150 ppm), new pellets (Mitsubishi Chemical Co., Ltd., intrinsic viscosity 0.80 dl / g, BK2170) 25 parts by weight (200 g), high molecular weight new pellets (Italy M & G, intrinsic viscosity 1. 25 dl / g, MFR 2.0 g / 10 min, COBITECH, for foaming) 25 parts by weight (200 g), BM5 (B2: B3: B5 = 1: 1: 1) 0.40 part by weight as a polymer type epoxy compound , 0.2 parts by weight of calcium stearate / sodium / lithium (50/25/25 weight ratio) composite as a binding reaction catalyst, Liquid paraffin 0.1 parts by weight of 0.1 parts by weight of a spreading agent of Chibagaiki Co. IRGANOX B225 were mixed manually in a polyethylene bag Te.
Co-directional twin-screw extruder (KZW15-30MG, screw diameter 25 mmΦ, L / D = 30, rotation speed 150 rpm) manufactured by Technobel Co., Ltd., round die (35 mm diameter, Lip Gap 0.8 mm), air blow machine and diameter A 200 mm external air cooling ring was installed. The extruder and screw have a set temperature of 240 to 280 ° C., the above flake mixture is put into a hopper and fed at a predetermined speed with a feeder, and at the same time, a binding reaction is carried out. The film was continuously extruded in a horizontal direction from a round die having a diameter of 35 mm. The blow-up ratio was adjusted, and an in-line inflation method film molding having a thickness of 30 to 70 μm was performed while externally cooling.
The film was transparent and uniform, had no gel / FE, and demonstrated the superiority of the resin production method of the present invention.

(Example 18): PET bottle flake (Kyoei Sangyo Co., Ltd., intrinsic viscosity 0.78 dl / g, MFR 45 g / 10 min) as PET polyester (A) was dried with hot air at 120 ° C. for 12 hours 100 Part by weight (300 g, moisture content 150 ppm), new PETG pellets (Eastman) 40 parts by weight (120 g), polyester elastomer new pellets (Teijin Chemicals Co., Ltd., Nouvelan, TRB-ELA) To 20 parts by weight (60 g) of the dried product, 0.90 part by weight of the mixture BM5 (B2: B3: B5 = 1: 1: 1) as a polymer type epoxy compound and calcium stearate / sodium / same lithium as a binding reaction catalyst ( 50/25/25 weight ratio) 0.2 parts by weight of the composite, 0 of IRGANOX B225 as a stabilizer 1 part by weight and 0.1 part by weight of liquid paraffin as a spreading agent were manually mixed in a polyethylene bag.
In the same manner as in Example 17, in-line inflation method film formation with a thickness of 30 to 70 μm was performed. The film was transparent and uniform, had no gel / FE, and further demonstrated the superiority of the resin production method of the present invention.

Comparative Example 1

  Only PET bottle flake (Kyoei Sangyo Co., Ltd., intrinsic viscosity 0.78 dl / g, MFR 45 g / 10 min) was molded under the same conditions as PET polyester (A), but the melt viscosity was low, and the film Molding was extremely difficult.

[Examples of mass production of high melt viscosity resin P19, whose molecular weight distribution is controlled to be expanded from recovered pet bottle flakes, etc., with a polymer type polyfunctional epoxy mixture]
100 parts by weight (water content 150 ppm) of PET bottle (Parisson) recovered from hot air at 120 ° C. for 12 hours, collected PET bottle parison (component A, Kyoei Sangyo Co., Ltd., intrinsic viscosity 0.738 dl / g, MFR 45 g / 10 min) Ingredients, Eastman, MFR 110 g / 10 min) dried by hot air at 70 ° C. for 4 hours, 10 parts by weight (water content 100 ppm), polyester elastomer (component D, Teijin Chemicals, PET red brown rubber TRB-ELA) 120 5 parts by weight (moisture content 120 ppm) dried at 50 ° C. for 4 hours to 50.80 parts by weight of a polymer type epoxy compound BM (component B, Nippon Oil & Fats Co., Ltd., Blemmer CP30S: molecular weight 9,000, epoxy) Radix 17 / molecule, Bremma CP50M: 10,000, 32, Marplop G01100: 12 71, weight ratio BM5 (B2: B3: B5 = 1: 1: 1), lithium stearate, sodium stearate, calcium stearate mixed powder as reaction catalyst 0.30 parts by weight (weight ratio 1: 1) : 2) 0.1 part by weight of IRGANOX B225 as a stabilizer and 0.05 part by weight of liquid paraffin as a spreading agent were mixed with a tumbler for 10 minutes.

A single-screw extruder made by Hoshi Plastic Co., Ltd. (screw diameter 65 mmΦ, compression screw, with mixing zone, L / D = 50, rotation speed 100 rpm, 1 vent type) The set temperature of the die was set to 240 to 280 ° C., and the above-mentioned parison mixture was put into a hopper while being evacuated with a dry system pump, and the extrusion was performed by feeding at a predetermined speed with a feeder. Five strands were continuously extruded into water from a die, cooled, cut with a rotary cutter, and transparent resin pellets were granulated at a rate of 80 kg / hour. About 500 kg of the heat-resistant heat-fusion resin pellets P19 (MFR 25 g / 10 minutes) thus obtained was dried in hot air at 120 ° C. for 12 hours, and then stored in a moisture-proof bag or moisture-proof container.
A film that can stably form a film having a thickness of 25 to 40 μm and a folding diameter of 400 mm in a polyethylene inflation film forming apparatus is transparent and uniform, has no gel and FE, and has a resin production method of the present invention. We were able to further demonstrate excellence.

  When reusing PET polyester resin recovered from the general consumer market as a main raw material, the field of use was limited due to the inevitable decrease in molecular weight. It can be restored to a polymer with good properties and physical properties, greatly contributing to the effective use of recycled resources. Also, it can be applied to a new PET polyester resin in the same manner, and has a macromolecular weight and a molecular weight distribution controlled to be expanded according to the present invention.・ Manufacturing of processed products such as boards, foams, pipes and profile extrusions has become possible, while by co-polymerizing aromatic polyester containing carboxyl in the aromatic core as an auxiliary material, Practical use of blown shrink film, adhesive film, impact-resistant foam, containers and pipes, which was impossible with PET polyester resin, has become possible.

Claims (7)

(A) 100 parts by weight of a polyethylene terephthalate-based polyester, (B) a polymer type polyfunctional epoxy compound having a molecular weight of 1,000 to 300,000 as a binder and 7 to 100 epoxy groups in the molecule 0.01 to 2 parts by weight, (C) 0.01 to 1 part by weight of an organic acid as a coupling reaction catalyst, and (D) 0 to 100 parts by weight of an aromatic polyester containing carboxyl in an aromatic cough A method for producing a polyethylene terephthalate-based graft copolymer resin, characterized in that a mixture thus formed is uniformly reacted at a temperature of 250 ° C. or higher to increase the melt viscosity. (A) 100 parts by weight of a polyethylene terephthalate-based polyester, (B) a polymer type polyfunctional epoxy compound having a molecular weight of 1,000 to 300,000 as a binder and 7 to 100 epoxy groups in the molecule 0.01 to 2 parts by weight, (C) 0.01 to 1 part by weight of a metal salt of an organic acid as a binding reaction catalyst, and (D) 0 to 100 parts by weight of an aromatic polyester containing a carboxyl in an aromatic nucleus. The polyethylene terephthalate-based graft coordinating the homogenous reaction of the composed mixture at a temperature of 250 ° C. or higher by the reactive extrusion method to 50 g / 10 min or less at 280 ° C. and a load of 2.16 kg by the JIS method. Production method of polymerized resin pellets. The polyethylene terephthalate-based polyester (A) contains at least one of polyethylene terephthalate having an intrinsic viscosity of 0.60 to 1.25 dl / g or a recycled product of recovered polyethylene terephthalate cedar products. The manufacturing method of the polyethylene terephthalate type graft copolymer resin of Claim 1. The molecular weight of the backbone resin is 1,000 to 300,000 as a binder and the molecular weight of the polymer type polyfunctional epoxy compound (B) containing 7 to 100 epoxy groups in the molecule is mixed and used. The method for producing a polyethylene terephthalate-based graft copolymer resin according to claim 1 or 2, wherein the distribution is expanded and controlled. The polyethylene according to claim 1 or 2, wherein the organic acid metal salt (C) contains at least one of the group consisting of an alkali metal carboxylate and an alkaline earth metal carboxylate. A method for producing a terephthalate graft copolymer resin. Aromatic polyester (D) containing carboxyl in the aromatic nucleus is any one of the group consisting of amorphous ethylene glycol, cyclohexanedimethanol, terephthalic acid (PETG), polyester elastomer, and crystalline polybutylene terephthalate. The method for producing a polyethylene terephthalate-based graft copolymer resin according to claim 1, comprising the above. (A) 100 parts by weight of a polyethylene terephthalate-based polyester, (B) a polymer type polyfunctional epoxy compound having a molecular weight of 1,000 to 300,000 as a binder and 7 to 100 epoxy groups in the molecule Uniform reaction of a mixture composed of 0.01 to 0.3 parts by weight and (C) 0.01 to 0.3 parts by weight of a metal salt of an organic acid as a bonding reaction catalyst at a temperature of 250 ° C. or higher by a reactive extrusion method. A method for producing a polyethylene terephthalate-based graft copolymer resin sheet, characterized in that a polyethylene terephthalate-based graft copolymer resin is produced and then formed into a high-speed crystalline sheet by casting at the temperature.